DD295394A5 - IMPROVED ASHARM LUBRICANT COMPOSITIONS FOR INTERNAL COMBUSTION ENGINES - Google Patents

Abstract

According to the invention, there are provided ashless heavy duty diesel engine crankcase lubricating oil compositions comprising an oil lubricating oil composition as the main component and (A) at least 2% of at least one high molecular weight ashless dispersant, (B) an antioxidant effective amount of at least one ozone antioxidant and (C ) of a corrosion inhibiting effective amount of at least one organosulfuric azole or azoline compound, said lubricating oil being characterized by a total sulfated ash (SASH) value of less than 0.01%. {Ashless lubricant compositions for internal combustion engines; dispersant; Antioxidants; sulfur-organic azole or azoline compound}

Description

and 1,2,4-thiadiazole derivatives having the formula:

Y ¹ - (S) -CK

^W Il Il ο

N C- (S) ₂ - Y ^d

wherein Y ¹ and Y ^{2 are the} same or different and are H, a straight or branched alkyl, cyclic, alicyclic, aryl, alkaryl or aralkyl radical of 2 to 30 carbon atoms, and w and ζ are numbers between 1 and about 8, said Lubricating oil is characterized by a total value of sulphated ash (SASH value) of less than 0.01%.

31. The method according to claim 30, characterized in that the diesel engine can be operated with a normally liquid fuel having a sulfur content of less than 0.3%.

Field of application of the invention

The invention relates to lubricating oil compositions which have a marked reduction in carbon deposits in the engine. In particular, the invention relates to ashless lubricant compositions suitable for use in diesel engines which contain high molecular weight ashless dispersants, soluble antioxidants and sulfur organic anticorrosion agents.

Initial situation of the invention

The aim of the industry is to provide lubricating oil compositions which have improvements through minimized engine deposits and low rates of lubricating oil consumption, especially in diesel motor vehicles.

Among the conventionally used lubricating oil additives, zinc dihydrocarboxylic dithiophosphates exerts several functions in engine oil, such as oxidation inhibition, bearing corrosion inhibition, and extreme pressure anti-wear protection for the valve drive.

In prior patents, compositions utilizing polyisobutenyl succinimide dispersants in conjunction with zinc dialkyl dithiophosphates used in lubricating oil compositions with other conventional additives such as detergents, viscosity index improvers, rust suppressants, and the like, have been presented. Typical of these first disclosures are US Pat. Nos. 3,018,247, 3,018,291.

Since phosphorus is a catalyst poison for catalytic converters, and since zinc itself is a source of sulfated ash, the industry has sought to reduce or eliminate these zinc-phosphorus engine oil components.

Examples of known publications directed to the reduction of phosphorus-containing lubricant additives are U.S. Patents 4,147,640, 4,330,420, and 4,639,324.

U.S. Patent No. 4,147,740 relates to lubricating oils having improved antioxidant and antiwear properties obtained by reacting an olefinic hydrocarbon having from 6 to 8 carbon atoms and from about 1 to 3 olefinic double bonds concurrently with sulfur and hydrogen sulfide and then reacting the resulting reaction product with additional olefinic Hydrocarbon recovered. It is disclosed that these additives are generally used in conjunction with other conventional oil additives, metal cleaning washes, polyisobutenylsuccinimide dispersants and phenolic antioxidants. It is disclosed that although the amount of zinc supplement can be greatly reduced, resulting in a "low ash" or "no ash" lubricant composition, it is apparent that Applicant referred to zinc-derived ashes rather than the SASH totals Has.

U.S. Patent No. 4,330,420 relates to low ash and low phosphorus motor oils which have improved oxidative stability as a result of the inclusion of synergistic amounts of a dialkyldiphenylamine antioxidant and sulfurized polyolefin. It is disclosed that the synergism between these two additives compensates for the lower phosphorus levels in the form of zinc dithiophosphate. It is claimed that the finished engine oils contain from 2 to 10% ashless dispersant, from 0.5 to 5% listed magnesium or calcium cleaning salts (which provide at least 0.1% magnesium or calcium), between 0.5 and 2.0% zinc dialkyldithiophosphate, between 0.2 and 2.0% of a dialkyldiphenolamine antioxidant, between 0.2 and 4.0% sulfurized polyolefin antioxidant, from 2 to 10% of a first ethylene propylene VI improver, between 2 and 10% of a second vol Improver consisting of methacrylate polymer and containing oil base until balance.

U.S. Patent 4,639,324 discloses that while metal dithiophosphate salts are useful as antioxidants, they are also a source of ash, and disclose an ashless antioxidant consisting of a reaction product prepared by having at least one aliphatic, olefinically unsaturated hydrocarbon with 8 to 36 carbon atoms simultaneously with sulfur and at least one fatty acid ester to obtain a reaction intermediate, which is then reacted with additional sulfur and a dimer of cyclopentadiene or lower, C, -C ₄ alkyl substituted cyclopentadiene dimers. It is disclosed that these additives are generally used in lubricating compositions in conjunction with other conventional oil starches, such as neutral or overbased calcium or magnesium alkaryl sulfonates, dispersants and phenolic antioxidants. It is disclosed that when using the additives of this invention, the amount of zinc additives can be greatly reduced, resulting in a "low ash" or "no ash" lubricating composition. Also in this case, it is obvious that the Applicant referred to the zinc-derived ash and not to the total amount of SASH. Metal cleaners have heretofore been used in engine oils to help control varnish and corrosion, and thus the deleterious effects of varnish and corrosion on engine efficiency, by minimizing plugging of the tapered orifices and reducing the headroom of the moving parts Lower minimum.

U.S. Patent 4,089,791 relates to low ash mineral oil lubricant compositions consisting of a mineral oil base with minor amounts of an overbased alkaline earth metal compound, a zinc dihydrocarbyl dithiophosphate (ZDDP), and a substituted trialkanolamine compound wherein at least 50% of the ZDDP compounds consist of zinc dialkaryl dithicphosphates To give finished engine oil that passes the MS-IIC rust test and the L-38 bearing weight loss test. The patent illustrates three compositions containing overbased calcium detergent, ZDDP, trialkanolamine, and non-lubricated conventional lubricating oil additives to achieve viscosity index, antioxidant, dispersant, and antifoaming properties improvements, each having a SASH level of about 0.66% based on the stated Ca and Zn concentrations. No diesel engine oil compositions are illustrated.

U.S. Patent No. 4,153,562 relates to antioxidants particularly well disclosed for compounded lubricating oils intended for heavy duty use in relatively low ash vehicle crankcase compositions, the antioxidants being obtained by the condensation of phosphorodithioates of alkylphenol sulfides with unsaturated compounds such as styrene , getting produced. The antioxidants are exemplified in amounts of 0.33 and 1.25% in lubricating oil compositions (Example 3) which also contain about 2.65% borated polybutylene succinimide dispersant, about 0.06% Mg as the overbased magnesium sulfonate detergent inhibitor, and the like 0.10% Zn as a zinc dialkyl dithiophosphate antiwear agent (containing mixed C ₄ / C ₆ alkyl groups). U.S. Patent No. 4,157,772 states that the trend towards unleaded fuels and ashless lubricant compositions has necessitated the search for non-metallic (ashless) organometallic detergent replacements and relates to tetrahydropyrimidyl substituted compounds disclosed as useful as ashless bases and rust inhibitors. In the examples of this patent, the performance parameters of various lubricating oil compositions in a Ford V8 varnish test (Table I) and additional compositions, referred to as "low ash" or "ashless", in a moisture chamber rust test (Table II ) compared. The SASH levels of the "low ash content" compositions are not specified and can not be determined from the information given for the metal detergent and ZDDP components US Patent 4,165,292 discloses that overbased metal compounds provide effective rust inhibition Vehicle crankcase lubricants are guaranteed and rust formation becomes a serious problem when overbased additives are absent, such as with ashless oils, or when "minor amounts of additives are present, such as low ash" oils. These roster requirements are examined in the ASTM Sequence IIC engine tests. The patent does not disclose an ash-forming corrosion or rust inhibitor which consists of a combination of an oil-soluble, basic, organic nitrogen compound (of specified basic value) and an alkenyl- or alkyl-substituted succinic acid having 12 to 50 carbon atoms. The basic organic nitrogen compound and the carboxylic acid compound must be used together to achieve the desired anti-rust properties. It is disclosed that the best results are obtained when working with an excess of amine over the amount needed to form the neutral salts of the substituted succinic acid present.

U.S. Patent No. 4,502970 relates to improved crankcase lubricating oil compositions containing lubricating oil dispersants, overbased metal cleaners, zinc dialkyldithiophosphate antiwear additives, and polyisobutenyl succinic anhydride in amounts listed. Exemplary lubricating oil compositions comprising 3% polyisobutenylsuccinimide dispersant, polyisobutenyl succinic anhydride, overbased metal sulfonate or overbased sulfurized phenate detergent and zinc dialkyl dithiophosphate antiwear agent in the base oil in amounts of 3.0, 3.0, 2.0, and 1.0, respectively, are disclosed. 91.0% included.

EP 24146 relates to lubricating oil compositions containing copper antioxidants and gives examples of copper antioxidants in lubricating oil compositions which also contain 1.0% magnesium sulfonate 400TBN (containing 9.2% magnesium), 0.3% calcium phenate 250TBN (containing 9.3% calcium) and a zinc dialkyldithiophosphate in which the alkyl groups or a mixture of these groups have between 4 and 5 carbon atoms and by reaction of phosphorus (III) -P ₂ S ₆ with a mixture of about 65% isobutyl alcohol and 35% amyl alcohol to produce a phosphorus value of 1.0% in the lubricating oil compositions.

Published British Patent Application 2062672 relates to additive compositions consisting of sulfurized alkylphenol and an oil-soluble carboxylic dispersant containing a hydrocarbon-based radical having an average molecular weight of at least 1,300, which is disclosed in combination with ash-producing detergents.

However, it is extremely difficult to translate the developments in the lubricating oil field intended for passenger cars and light trucks, whether gasoline or light-duty diesel engines, to lubricating oils for use in heavy-duty diesel engines.

R. D. Hercamp reports in the SAE Technical Paper Series (Series Technical Contributions to SAE), article N ° 831720 (1983), on engine testing procedures to measure the relative ability of various lubricant compositions to control oil consumption in heavy duty diesel engines. The author states that laboratory analyzes of crown deposits on the pistons of diesel engines show that an organic binder containing high molecular weight esters is present, and the author speculates that oxidation products in the oil may be the precursors to the binder found in the deposits becomes. It is stated that better antioxidants could be the key to preventing premature loss of oil consumption.

AA Schetelich reports in the SAE Technical Paper Series, article N ⁰ 831722 (1983), on the effect of lubricating oil parameters on the performance of heavy duty diesel type PC-1 lubricating oil. It has been found that in the past thirty years in the heavy duty diesel industry there has been a tendency to reduce the sulphated ash content from 2.5% sulfated ash (SASH) in 1960 to the typical North American SASH value of 0.8 to reduce the D 2896 Alkaline Acidity (TBN) figure for heavy duty oils greater than 20 to the typical North American TBN values of 7 to 10. The author attributes these reductions in SASH and TBN values to improvements in the performance of ashless components, including ashless diesel detergents and ashless dispersants. In diesel engine tests, no significant correlation was found between the value of either piston deposits or oil consumption and SASH or TBN values at SASH values of approximately 1% to 2% and at TBN values of approximately 8% to 17%. On the other hand, a significant correlation was found between the value of the ashless component and the amount of piston deposits (at a confidence level of 92%) and oil consumption (at a confidence level of 98%). It is noted by the authors that this correlation is established for diesel fuels with an average sulfur content of less than about 0.5%. It is stated that the extent of ash accumulation is accelerated in hotter engine sections. The author concludes that, with a confidence level of 97%, there should be a correlation between oil consumption and piston deposits, especially upper surface deposits, which are believed to contribute to increased oil consumption due to two phenomena: (1) these deposits reduce the The amount of current flowing down the top surface resulting in reduced gas load behind the top ring of the piston, which in turn leads to higher oil consumption, and (2) the increased bore polishing of the piston cylinder liner by the head surface deposits, again by migration of the oil into the combustion chamber of the cylinder along the tracks of the polished bore contributes to a higher oil consumption. The paper therefore concludes that a reduced ash content of the oil should be sought in order to reduce head crop deposits and hence oil consumption.

This 1983 contribution by Schetelich indicates the composition of two test oils, each containing about 1% SASH and having a TBN of 10 and 9, respectively, each containing overbased metallic detergent along with a zinc source.

YES. McGeehan sums up in SAE-Beiirag N ° 831721, pp. 4848-4869 (1984), the results of a series of experiments with heavy duty diesel engines to study the effect of headspace deposits, sulfur content of the fuel and viscosity of the lubricant on the oil consumption of diesel engines and the polishing of the cylinder bore was performed. These authors also stated that excessive headspace deposits cause high oil consumption and heavy cylinder bore polishing, but they also add that polishing of the cylinder bore on high sulfur fuels is also caused by corrosion in low alkalinity oils. They therefore concluded that the oil should have sufficient alkalinity to minimize the corrosive aspect of polishing the cylinder bore. The authors reported that an experimental 0.01% sulfated ash oil tested in combination with a 0.2% sulfur fuel in a 120 hour AVL-Mack TZ675 test resulted in minimal headface deposits and very low oil consumption This latter component has not been further defined and, in addition, the data presented by the author in Figure 4 of this paper does not suggest that there are any benefits in terms of oil consumption when the ash value is lowered below 1%, as the oil consumption in the engine actually increased when the SASH content was reduced from 1% to 0.01%, reinforcing the author's view that a low but significant SASH value for a sufficient alkalinity is required to avoid oil consumption as a result of polishing the cylinder bore derived from the corrosive aspects of the oil.

McGeehan concludes that the deposits on the head surfaces are related to oil consumption but can not be directly related to the sulfated ash content in the lubricant and comments that these deposits are due to the composition of the oil for the oil Crankcase can be controlled.

-8- 295 394 Summary of the Invention

According to the present invention there are provided ashless heavy duty diesel lubricating oil compositions containing as main component an oil of lubricating viscosity and as minor component (A) at least 2% of at least one high molecular weight ashless dispersant, (B) an antioxidant effective amount of at least one oil. soluble antioxidant; and (C) a corrosion inhibiting effective amount of at least one organoaliphatic azole or azoline compound, wherein the lubricating oil is characterized by a total sulfated asher (SASH total) value of less than 0.01%.

The improved oils of the present invention are particularly valuable in diesel engines driven by low sulfur fuels. Therefore, the present invention also provides a method for improving the performance of a heavy duty diesel oil intended for use in a diesel engine having at least one dense top surface piston, and more preferably by a normally liquid fuel having a sulfur content of less than 1%, this method being to control the metal content of the oil to provide a total sulphated ash (SASH) value of less than 0.01% in this oil, and in diose oil (A). at least 2% of at least one high molecular weight, ashless dispersant, (B) an antioxidant effective amount of at least one oil soluble antioxidant, and (C) a copper corrosion inhibiting amount of at least one organosulfur azol or azoline compound, preferably having the formula:

N-N

Y ¹ - (s) _K S S C - / (s) _z -Y ² or the formula: -C- Y ¹ - \ N | i } - Y ²

wherein Y ¹ 'in Y ^{2 are the} same or different and are H, straight or branched alkyl, cyclic, alicyclic, aryl, alkylaryl or arylalkyl radicals having from 2 to about 30 carbon atoms, -C (O) R ⁶ , -P (O ) (OR ⁶ I ₂ and -C (S) N (R ⁶ I ₂ , where R ^{e is} a hydrocarbyl (eg C ₁ -C ₆ alkyl); and C ₁ -C ₆ alkylene groups substituted (e.g. end-substituted) with one or more carboxy, nitrophenyl, cyano, thiozyano, isocyanato, isothiozyano, alkylcarbonyl, thiocarbamyl, amino or aryl groups, and wherein one of the symbols Y ¹ and Y ² may contain the following component :

N-N

It Il η

₆ - (S) _w - CC - (S) ₅₅ - r '

or the component

- (C ₁ -C ₆ -alkyl) - (S) _w - C. N

N C- (S) - R ⁷ / ^Z

wherein R ⁷ is H or a C ₁ -C ₁ -hydrocarbyl; and w and ζ are the same or different and numbers are between 1 and about 9.

Detailed description of the invention Component A

Ashless, nitrogen or ester-containing dispersants useful in this invention include members selected from the group consisting of (i) oil-soluble salts, amides, imides, oxazolines and esters or mixtures thereof of long chain, substituted ( by hydrocarbons) mono- and dicarboxylic acids or their anhydrides or esters; (ii) long chain aliphatic hydrocarbons with a directly attached polyamine; (iii) Mannich condensation products prepared by condensing about one mole of a long chain hydrocarbyl substituted phenol with about 1 to 2.5 moles of formaldehyde and about 0.5 to 2 moles of polyalkylenepolyamine; and (A-4) Mannich condensation products formed by the reaction of long-chain hydrocarbyl substituted mono-

and dicarboxylic acids or their anhydrides or esters with an aminophenol, which may optionally be hydrocarbyl substituted, to produce a long chain hydrocarbyl substituted, amide or imide phenol intermediate, and by condensation of about one mole of the long chain hydrocarbyl substituted amide - or imide-containing phenol intermediate with about 1 to 2.5 moles of formaldehyde and about 0.5 to 2 moles of polyamine, said long-chain hydrocarbon group in (i), (ii) and (iii) a polymer of a C ₂ -C, ₀ monoolefin , z. A C ₂ -C ₅ monoolefin, wherein the polymer has an average molecular weight of about 300 to about 5,000. A (i). Oil-soluble salts, amides, imides, oxazolines and esters of long chain hydrocarbyl substituted mono- and dicarboxylic acids or esters or anhydrides with a nucleophilic reactant selected from the group consisting of amines, alcohols, aminoalcohols and mixtures thereof. The long chain hydrocarbyl polymer substituted mono- or dicarboxylic acid material, ie, the acid, anhydride or acid ester used in the invention, includes the reaction product of a long chain hydrocarbon polymer, generally a polyolefin, with a monounsaturated carboxylic reactant containing at least one member which is selected from the group consisting of (i) mono-unsaturated C 1 -C 4 -dicarboxylic acid [preferably wherein (a) the carboxyl groups are vizinyl (ie, located on adjacent carbon atoms) and (b) at least one, preferably both of these adjacent carbon atoms are part of this mono-unsaturation]; (ii) derivatives of (i) such as anhydrides or C) -C ₅ alcohol-derived mono- or diesters of (i); (iii) mono-unsaturated C ₃ to C ₁₀ monocarboxylic acid, wherein the carbon-carbon double bond is conjugated to the carboxyl group, ie, having the structure

Ii -C = C-C-;

and (iv) derivatives of (iii), such as C, -C _6, alcohol-derived monoesters of (iii). After the reaction with the polymer, the mono-unsaturation of the mono-unsaturated carboxylic reactant becomes saturated. For example, maleic anhydride becomes a polymer-substituted succinic anhydride, and acrylic acid becomes a polymer-substituted propionic acid. Typically, from about 0.7 to about 4.0 moles (e.g., 0.8 to 2.6 moles), preferably from about 1.0 to 2.0 moles, and most preferably from about 1.1 to about 1, 7 moles of this mono-unsaturated carboxyl reaction agent per mole of the introduced polymer in the reactor.

Normally, not all the polymer reacts with the mono-unsaturated carboxylic reactant and the reaction mixture contains non-acid, substituted polymer. The polyme, substituted mono- or dicarboxylic acid material (also referred to herein as a "functionalized" polymer or polyolefin), non-acid substituted polyolefin, and possible other polymeric by-products, eg, chlorinated polyolefin (also referred to herein as "non-functionalized" polymer), are summarized herein referred to as "product residue" or "product mixture". The non-acid substituted polymer is typically removed from the reaction mixture (since this elimination is difficult and not commercially feasible), and the product mixture from which all mono-unsaturated carboxylic reactants have been stripped is used for further reaction with the amine or alcohol as described below to prepare the dispersant. The characterization of the average number of moles of mono-unsaturated carboxylic reactants introduced into the reaction per mole of polymer charged (whether or not a reaction has occurred is not meant to be) is defined herein as functionality. This functionality is based on (i) determination of the saponification number of the resulting product mixture using potassium hydroxide and (ii) on the average molecular weight of the polymer fed, using the methods generally known in the art. Functionality is defined only with reference to the resulting product mixture. Although the amount of reacted polymer contained in the resulting product mixture is subsequently modified, i. h., can be increased or decreased by well-known techniques, these modifications do not alter functionality in the manner defined above. The terms "polymer-substituted monocarboxylic acid material" and "polymer-substituted dicarboxylic acid material" used herein refer to the product mixture regardless of whether or not they have undergone such modification.

Accordingly, the functionality of the polymer-substituted mono- and dicarboxylic acid material is typically at least about 0.5, preferably at least about 0.8, and most preferably at least about 0.9, and typically varies between about 0.5 and about 2.8 (e.g. 0.6 to 2), preferably between about 0.8 and about 1.4, and most preferably between about 0.9 and about 1.3.

Examples of these mono-unsaturated carboxylic reactants are fumaric acid, itaconic acid, maleic acid, maleic anhydride, chloromaleic acid, chloromaleic anhydride, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid and lower alkyl acid esters (e.g., C 1 -C 4 alkyl esters) of the above-mentioned, e.g. As methyl maleate, ethyl fumarate, Mothylfumarat etc.

Preferred olefin polymers for reaction with the mono-unsaturated Karboxylreaktionsmitteln to form reactant A are polymers comprising a major molar amount of C ₂ -C, ₀ monoolefin, z. C ₂ -C ₅ monoolefin. These olefins include ethylene, propylene, butylene, isobutylene, pentene, octene-1, styrene, etc. The polymers may be homopolymers such as polyisobutylene, as well as copolymers of two or more of these olefins, such as the copolymers of ethylene and propylene, butylene and Isobutylene, propylene and isopropylene, etc. Mixtures of polymers prepared by the polymerization of mixtures of isobutylene, butene-1 and butene-2, eg polyisobutylene wherein up to about 40% of the monomer units are derived from butene-1 and butene-2 are exemplary and preferred olefin polymers. Other copolymers include those in which a minor mole amount of the copolymer monomer, eg, 1 to 10 mole%, is a nonconjugated C ₄ -C _{8 8} diolefin, e.g. A copolymer of isobutylene and butadiene or a copolymer of ethylene, propylene and 1,4-hexadiene and the like.

In some cases, the olefin polymer may be completely saturated, for example, an ethylene-propylene copolymer prepared by a Ziegler-Natta synthesis using hydrogen as a molecular weight control moderator.

The olefin polymers employed in the formation of Reagent A generally have an average molecular weight in the range of from about 700 to about 5,000, preferably from about 900 to about 4,000, and most preferably from about 1,300 to about 3,000. Particularly suitable olefin polymers have an average molecular weight within the range of about 1500 to about 3000 with about one end double bond per polymer chain. A particularly useful. The starting material for high performance dispersant additives of the present invention is polyisobutylene wherein up to about 40% of the monomer units are derived from butene-1 and / or butene-2. The average molecular weight for these polymers can be determined by various known methods. A convenient method for such a determination is gel permeation chromatography (GPC), which additionally provides information on the molecular weight distribution, see W.W. Yau, J.J. Kirkland and D.D. Bly, "Modem Size Exclusion Liquid Chromatography", John Wilay and Sons, New York, 1979.

The olefin polymers generally have a molecular weight distribution (ratio of weight average molecular weight to number average molecular weight, ie, M _w / M ") of from about 1.0 to 4.5, and typically from about 1.5 to 3.0.

The polymer can be reacted with the mono-unsaturated carboxylic reactant in a variety of ways. For example, the polymer may first be chlorinated or brominated to about 1 to 8%, preferably 3 to 7% chlorine or bromine, based on the weight of the polymer, including the chlorine or bromine at a temperature of 6O ⁰ C to 25O ⁰ C. , preferably from 11O ⁰ C to 160 ⁰ C, for example from 12O ⁰ C to 14O ⁰ C, for a period of about 0.5 to 10 hours, preferably from 1 to 7 hours, is passed through the polymer. The halogenated polymer may then with a sufficient amount of the monounsaturated Karboxylreaktionsmit: el Lei 100 ⁰ C to 250 ⁰ C, in d ir typically about 18O ⁰ C to 235 ⁰ C for a period of about 0, ü to 10 hours, eg. 3 to 8 hours, so that the recovered product contains the desired number of moles of monounsaturated carboxylic reactant per mole of halogenated polymer. Processes of this general type are disclosed in U.S. Patent Nos. 3,087,436, 3,172,892, 3,227,276, and others. Alternatively, the polymer and monounsaturated carboxylic reactant may be mixed and heated and chlorine added to the hot material. Processes of this type are disclosed in U.S. Patent Nos. 3,215,707, 3,231,587, 3,912,764, 4,110,349, 4,244,435 and UK Patent 1,440,219. Alternatively, the polymer and the mono-unsaturated carboxylic reactant may be contacted at elevated temperature to initiate an "ene" thermal reaction. "" Thermal reactions have previously been described in US Patent Nos. 3,361,673 and 3,311,118, which are incorporated herein by reference Entity to be included as a reference. Preferably, the polymers used in this invention contain less than 5%, preferably less than 2%, and most preferably less than 14% of a polymer fraction consisting of polymer molecules having a molecular weight of less than about 300 as determined by high temperature gel permeation chromatography using appropriate reagents .hter polymer curves. These preferred polymers have been found to produce the production of reaction products having reduced deposits, particularly when using maleic anhydride as the unsaturated acid reactant. When the polymer prepared in the manner described above contains greater than about 5% of this low molecular weight polymer fraction, the polymer may first be treated by conventional means to remove the low molecular weight fraction to the desired level before initiating the "ene" reaction and, preferably, prior to contacting the polymer with the selected unsaturated carboxylic reactant (s). For example, the polymer, preferably with stripping by an inert gas (e.g., nitrogen), may be reduced to a higher pressure under reduced pressure The exact temperature, pressure and time values of such a heat treatment may be varied depending on such factors as the number-average molecular weight of the polymer, the amount of low molecular weight polymer to be removed and the temperature of the polymer molecular weight fraction, each used specific monomers and other factors to be very different. In general, a temperature between about 6O ⁰ C and 100 ⁰ C and a pressure between about 0.1 and 0.9at and a period of about 0.5 to / 0 hours (eg 2 to 8 hours) are sufficient.

In this process, the selected polymer and the mono-unsaturated carboxylic reactant and, if used, the halogen (eg, chlorine gas) are contacted for a time and under conditions effective in forming the desired polymer-substituted mono- or dicarboxylic acid material. Generally, the polymer and mono-unsaturated carboxylic reactant will be increased in an unsaturated carboxylic to unsaturated ratio of from about 0.7: 1 to about 4: 1, and preferably at a molar ratio of from about 1: 1 to about 2: 1 Temperature, generally between about 12O ⁰ C and 260 ⁰ C, preferably between about 16O ⁰ C and 240 ⁰ C, brought into contact with each other. The molar ratio of halogen to mono-unsaturated carboxylic reactant employed also varies and is generally between about 0.5: 1 and 4: 1, and more typically between about 0.7: 1 and 2: 1 (e.g., between about 0.9 and 1.4: 1). The reactions are generally carried out with stirring over a period of one to twenty hours, preferably from 2 to 6 hours.

The use of a halogen normally reacts with about 65 to 95% of the polyolefin, ζ. As the polyisobutylene, with the mono-unsaturated carboxylic acid reactant. When a heat reaction is carried out without the use of a halogen or a catalyst, only about 50 to 75% of the polyisobutylene usually react. Chlorination helps increase reactivity. For reasons of expediency, said functionality ratios are based on mono- or dicarboxylic acid-producing units to polyolefin, ζ. 1.1 to 1.8, etc., on the total amount of polyolefin, that is, the total amount of reacted and unreacted polyolefin used to make the product. The reaction is preferably conducted substantially without O ₂ and water (to avoid competing side reaction), and for this purpose may be carried out in an atmosphere of dry N ₂ -GaS or other gas which is inert under the reaction conditions. The reactants may be introduced into the reaction zone separately or together as a mixture, and the reaction may be carried out continuously, semi-continuously or in a batchwise manner. Although not generally required, the reaction can be carried out in the presence of a liquid diluent or solvent, e.g. A hydrocarbon diluent such as mineral lubricating oil, toluene, xylene, dichlorobenzene and the like. The polymer-substituted mono- or ω-carboxylic acid material thus formed can be recovered from the liquid reaction mixture, e.g. After stripping the reaction mixture, if desired, with an inert gas such as N ₂ to remove unreacted unsaturated carboxylic reactants.

When d " ¹ " is desired, a catalyst or promoter for the reaction of olefin polymer and mono-unsaturated carboxyynoxysiloxane (whether the olefin polymer and the mono-unsaturated carboxylic reactant in the presence or absence of a halogen (e.g. These catalysts or promoters include aloxides of Ti, Zr, V, and Al and nickel salts (eg, nickel acetoacetate and nickel iodide), which catalysts are generally present in an amount between about 1 and 5000 toilets / milliliter, basis weight, based on the mass of the reaction medium. Amine compounds useful as nucleophilic reactants for reaction with the hydrocarbyl substituted mono- and dicarboxylic acid compounds are those containing at least two reactive amino groups, ie , primary and secondary amino groups, including polyalkylon include polyamines having from about 2 to 60, preferably from 2 to 40 (e.g. E. To 20) carbon atoms in total and about 1 to 20, preferably 3 to 12 and at best 3 to 9 nitrogen atoms in the molecule. These amines can Hydrokarbylamine or Hydrokarbylamine including other groups, eg. Hydroxy groups, alkoxy groups, amide groups, nitriles, imidazoline groups and the like. Particularly suitable are hydroxyamines having 1 to 6 hydroxyl groups, preferably having 1 to 3 hydroxy groups. Preferred amines are aliphatic, saturated amines, including those having the general formula:

RN- (CH ₂ ) _a -R '

1- (CH ₂ ) _fl .

R ¹ "

-N-R R '

wherein R, R ', R "and R"' are independently selected from the group consisting of hydrogen, straight or branched C ₁ -C ₂ 5-alkyl radicals, C ₁ -C ₇ -alkyl-C ₁ -C ₄ -cycloalkyl, Alkylene radicals and Ci-C ^ -Alkylamino-Cz-Ce-Alkylenradikalun, and wherein R "'may additionally contain a component having the formula:

-N-

-H

(ID,

R ^f "

wherein R 'is as defined above and wherein s and s' may be the same or different numbers from 2 to 6, preferably from 2 to 4, and wherein t and t' may be the same or different and numbers between 0 and 10, v , preferably between 2 and 7, and at best between about 3 and 7, on the assumption that the sum of t and t 'is not greater than 15. To ensure a facile reaction, Fl, R ', R ", R"', s, s ', t and t' are preferably to be selected to provide compounds of Formula I, typically having at least one primary or secondary amine group , preferably at least two primary or secondary amine groups arise. This can be achieved by at least one of the R, R ', R "or R"' groups being hydrogen, or t in Formula I being at least one when R "'is H or when The most advantageous amines having the formula given above, which is represented by the formula I, contain at least two primary amine groups and at least one, preferably at least three, secondary amine groups.

Non-limiting examples of suitable amine compounds include: 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-dinminohexane, polyethyleneamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polypropylene amines such as 1,2-propylenediamine, Di (1,2-propylene) triamine, di- (1,3-propylene) triamine, N, N-dimethyl-1,3-diaminopropane, N, N-di (2-aminoethyl) ethylenediamine, N, N Di- (2-hydroxyethyl) -1,3-propylenediamine, 3-dodecyloxypropylamine, N-dodecyl-1,3-propanediamine, tris-hydroxymethyl-aminomethane (THAM), diisopropanolamine, diethanolamine, triethanolamine, mono-, di- and tritalgamines, Aminomorpholines such as N- (3-aminopropyl) morphopine and mixtures thereof. Other useful amine compounds include: alicyclic diamines, such as 1,4-di (aminomethyl) cyclohexane, and heterocyclic nitrogen compounds, such as imidzolines, and N-aminoalkyl piperazines of general formula (III):

h | NH- (ch.J

/ V ⁰¹ K

^CH 2 ^CH 2

NH-

-H

wherein P) and p _{2 are the} same or different and each are integers from 1 to 4 and πι, n ₂ and n _{3 are the} same or different and each are integers from 1 to 3. Non-limiting examples of these amines include 2-pentadezylimidazoline, N- (2-aminoethyl) piperazine, etc.

Advantageously, commercial mixtures of amine compounds can be used. For example, a process for the production of alkyleneamines involves the reaction of an alkylene dihalide (eg, an ethylene dichloride or propylene dichloride) with ammonia, resulting in a complex mixture of alkyleneamines in which nitrogen pairs are linked by alkylene compounds such that diethylenetriamine, triethylenetetramine, tetraethylenepentamine Cheap poly (ethyleneamine) compounds having an average of 5 to 7 nitrogen atoms per molecule are commercially available under such trade designations as "Polyamine H", "Polyamine 400", "Dow Polyamine E-100" and so on.

The useful amines also include polyoxyalkylenepolyamines, such as those having the formula:

Ethylene-W-alkylene-j

preferably has a value of from about 3 to 70 and preferably from 10 to 35, and having the formula:

, _R - (- alkylene M) -alkylene) _n ^NH 2 ^ a ^(v) <

wherein η has a value of about 1 to 40, provided that the sum of all η is about 3 to about 70, and preferably about 6 to 35, and R is a polyvalent, saturated hydrocarbon radical of up to ten carbon atoms, wherein the number the substituent on the R group is represented by the value a, which is a number between 3 and 6. The alkylene groups in both Formulas IV or V may be straight or straight chain with about 2 to 7 and preferably about 2 to 4 carbon atoms.

The polyoxyalkylene polyamines having the above formulas (IV) and (V), preferably polyoxyalkylenediamines and polyoxyalkylenetriamines, may have an average molecular weight of between about 200 and about 4,000, and preferably between about 400 and about 2,000. Preferred polyoxyalkylene polyoxyalkylene polyamines include the polyoxyethylene and polyoxypropylene diamines and the polyoxypropylene triamines having an average molecular weight between about 200 and 2000. The polyoxyalkylene polyamines are commercially available and can be obtained, for example, from Jefferson Chemical Company, Inc. under the trade designation "Jeffamine D-230, D" -400, D-1000, D-2000, T-403 "and so on.

Additional amines useful in the present invention are described in U.S. Patent 3,445,441, the disclosure of which is incorporated herein by reference in its entirety.

A particularly useful class of amines are polyamido and related amines, which are disclosed in copending application, No. 126,405, November 30, 1987, which consists of the reaction products of a polyamine and an alpha, beta-unsaturated compound having the following Formula consist of:

D ⁶ D ⁷ X

ι I il < ^vl >.

D ⁵ -C = CCY

wherein X is sulfur or oxygen, Y is -OD ⁸ , -SD ⁸ or ND ⁸ (D ⁹ ) and D ⁶ , D ⁶ , D ⁷ , D ⁸ and D ^{9 are the} same or different and are hydrogen or substituted or unsubstituted Hydrocarbyl are. Any polyamine, whether aliphatic, cycloaliphatic, aromatic, heterocyclic, etc., may be used, provided that it is attached to the acrylic double bond and amidated with, for example, the carbonyl group (-C (OH of the acrylate type compound of the formula VI or with the thiocarbonyl group (-C (S) -) of the chioacrylate-type compound having the formula VI ## STR5 ## If D ⁵ , D ⁶ , D ⁷ , D ⁸ or D ⁹ in the formula VI is a hydrocarbyl, these can Groups consisting of alkyl, cycloalkyl, aryl, alkaryl, aralkyl or a heterocyclic compound which may be substituted with groups which are substantially inert to any component of the reaction mixture under the conditions chosen for the preparation of the amidoamine Hydroxy, halide (e.g., Cl, F, I, Br), SH, and alkylthio groups When one or more of the values of D ⁵ to D ^{9 are} alkyl, this alkyl group may be en represents a straight or a branched chain, and they generally contain between 1 and 20, more often between 1 and 10 and preferably between 1 and 4 carbon atoms. Examples of these alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tridecyl, hexadecyl, octadecyl and the like. When one or more of the values of D ⁶ to D ^{9 are} aryl, the aryl groups generally contain from 6 to 10 carbon atoms (eg, phenyl, naphthyl).

When one or more of the values of D ⁵ to D ^{9 are} alkaryl, the alkaryl group generally contains between about 7 and 20 carbon atoms and preferably 7 to 12 carbon atoms. Examples of such alkaryl groups are ToIyI, m-ethylphenyl, o-ethyltolyl and m-hexyltolyl. When one or more of the values of D ⁵ to D ^{9 are} aralkyl, the aryl moiety is generally phenyl or C 1 -C 6 alkyl-substituted phenol, and the alkyl moiety generally contains from 1 to 12 carbon atoms, preferably from 1 to 6 carbon atoms , Examples of these aralkyl groups are benzyl, o-ethylbenzyl and 4-isobutylbenzyl. When one or more of the values of D ⁵ to D ^{9 are} cycloalkyl, the cycloalkyl group generally contains between 3 and 12 carbon atoms and preferably between 3 and 6 hydrocarbon atoms. Examples of these cycloalkyl groups are cyclopropyl, cyclobutyl, cyclohexyl, cyclooctyl and cyclododecyl. When one or more of the values of D ⁶ to D ^{9 is} a heterocyclic compound, the heterocyclic group generally consists of a compound having at least one ring of 6 to 12 members in which one or more carbon atoms of the ring is replaced by oxygen or nitrogen are. Examples of these heterocyclic groups are Fury I, Pranyl, Pyridiyl, Piperidyl, Dioxanyl, Tetrahydrofuryl, Pyrazinyl and 1,4-Oxazinyl

 The alpha, beta-ethylenically unsaturated carboxylate compounds used herein have the following formula:

D ⁶ D ⁷ 0

₅ (ι H ₈ «viii.

ΐ / - C = C - C - 0D ^a

wherein D ⁵ , D ⁶ , D ⁷ and D ^{8 are the} same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above. Examples of such alpha, beta-ethylenically unsaturated Kai boxylatverbindungen with the formula VII are acrylic acid, methacrylic acid, the methyl, ethyl, isopropyl, η-butyl and isobutyl before. Acrylic and methacrylic acid,

2-butenoic acid, hexene-2-acid, decene-2-acid, 3-methylhepten-2-acid, 3-methylbutene-2-acid, 3-phenyl-2-propenoic acid, 3-cyclohexylbutene-2-acid, 2-methylbutene-2-acid, 2-propylpropene-2-acid, 2-isopropylhexene-2-acid, 2,3-dimethylbutene-2-acid, S-cyclohexyl-methylene-pentene-1-acid, propene-2 acid, methyl 2-propenoate, methyl 2-methyl-2-propenoate, methyl 2-butenoate, ethyl 2-hexenoate, isopropyl 2-dezenoate, phenyl 2-pentenoate, tertiary butyl 2-propenoate, Octadecyl-2-propenoate, dodecyl-2-dezenoate, cyclopropyl-2,3-dimethyl-2-butenoate, methyl-3-phenyl-2-propenoate and the like.

The alpha, beta-ethylenically unsaturated carboxylate thioester compounds used herein have the following formula:

D ⁶ D ⁷ 0

c I I Il ο (vim,

W - C = C - C - SD

wherein D ⁵ , D ⁶ , D ⁷ and D ^{8 are the} same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above. Examples of these alpha, beta-ethylenically unsaturated carboxylate thioesters of the formula VIII are methylmercapto-2-butenoate, ethylmercapto-2-hexenoate, isopropylmercapto-2-dezenoate, phenylmercapto-2-pentenoate, tertiary butylmercapto-2-propenoate, octadecylmercapto -2-propenoate, dodecylmercapto-2-dezenoate, cyclopropylmercapto-2,3-dimethyl-2-butenoate, methylmercapto-3-phenyl-2-propenoate, methylmercapto-2-propenoate, methylmercapto-2-methyl-2-propenoate and similar

 The alpha, beta-ethylenically unsaturated carboxyamide compounds used herein have the formula:

D ⁶ D ⁷ 0

ς 1 I Il QQ < ^IX >'

Y? -C = CC-ND (D *)

wherein D ⁵ , D ⁶ , D ⁷ , D ⁸ and D ^{a are the} same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above. Examples of these alpha, beta-ethylenically unsaturated carboxyamides of formula IX are 2-butenamide, 2-hexenam; 2-Dezenamide, 3-methyl-2-hepteneamide, 3-methyl-2-butenamide, 3-phenyl-2-propenamide, 3-cyclohexyl-2-butenamide, 2-methyl-2-butenamide, 2-propyl-2 propenamide, 2-isopropyl-2-hexenamide, 2,3-dimethyl-2-butenamide, 3-cyclohexyl-2-methyl-2-pentenamide, N-methyl-2-butenamide, N-methyl-2-butenamide, N, N-diethyl-2-hexenamide, N-isopropyl-2-decenamide, N-phenyl-2-pentenamide, N-tertiary-butyl-2-propenamide, N-octadecyl-2-propenamide, NN-didoezyl-2-decenamide, N -Cyclopropyl-2,3-dimethyl-2-butenamide, N-methyl-3-phenyl-2-propenamide, 2-propenamide, 2-methyl-2-propenamide, 2-ethyl-2-propenamide and the like

 The alpha, beta-ethylenically unsaturated thiocarboxylate compounds used herein have the following formula:

D ⁶ D ⁷ S

5 i \ H ₈ < ^x »'

D - C = C - C - OD

wherein D ⁵ , D ⁶ , D ⁷ and D ^{8 are the} same or different and are hydrogen or substituted or unsubstituted hydrocarbyl as defined above. Examples of alpha, beta-ethylenically unsaturated thiocarboxylate compounds having the formula X are 2-butenedionic acid, 2-hexenedionic acid, 2-decenthionic acid, 3-methyl-2-heptenthionic acid, 3-methyl-2-butenedionic acid, 3-phenyl-2-propenoionic acid , 3-cyclohexyl-2-butethionic acid, 2-methyl-2-butethionic acid, 2-propyl-2-propionionic acid, 2-isopropyl-2-hexenoic acid, 2,3-dimethyl-2-butenedionic acid, 3-cyclohexyl-2-methyl 2-pentenoic acid, 2-propionic acid, methyl 2-propenoioate, methyl 2-methyl-2-propenoioate, methyl 2-butenedioate, ethyl 2-hexenedioate, isopropyl 2-decethioate, phenyl 2-pentenedioate, tertiary Butyl 2-propenoioate, octadecyl 2-propenoioate, dodezyl 2-decenoioate, cyclopropyl-2,3-dimethyl-2-butenedioate, methyl 3-phenyl-2-propenoioate, and the like. The alpha, beta-ethylenically unsaturated dithionic acid and acid ester compounds used herein have the formula:

D ⁶ D ⁷ S

c- I ι Il ο ^(XI) <

D - C = C - C - SD °

wherein D ^s , D ⁶ , D ⁷ and D ^{8 are the} same or different and are hydrogen or a substituted or unsubstituted hydrocarbyl as defined above. Examples of alpha-, beta-ethylenically unsaturated dithionic acids and acid esters of the formula XI are 2-butenedithionic acid, 2-hexendithionic acid, 2-decendithionic acid, 3-methyl-2-heptendithionic acid, 3-methyl-2-butenedithionic acid, 3-phenyl- 2-propendithionic acid, 3-cyclohexyl-2-butenedithione acid, 2-methyl-2-butenedithione acid, 2-propyl-2-propendithionic acid, 2-isopropyl-2-hexendithionic acid, 2,3-dimethyl-2-butenedithionic acid, 3-cyclohexyl 2-methyl-2-pentenedithioic acid, 2-propenpendithionic acid, methyl 2-propenedithioate, methyl 2-methyl-2-propenedithioate, methyl 2-butenedithioate, ethyl 2-hexene dithioate, isopropyl 2-decithedioate, phenyl-2 pentenedithioate, tertiary butyl 2-propenedithioate, octadecyl 2-propenedithioate, dodecyl 2-decithedioate, cyclopropyl-2,3-dimethyl-2-butenedithioate, methyl 3-phenyl-2-propenedithioate and the like.

-14- 29F3a4

The alpha, beta-ethylenically unsaturated thiocarboxyamide compounds used herein have the following formula:

D ⁶ D ⁷ S

ς H I H ο q <Xt <> -

DC = CC-ND (D ³ )

wherein D ⁵ , D ⁶ , D ⁷ , D ⁹ and D ^{9 are the} same or different and are hydrogen or a substituted or unsubstituted hydrocarbyl as defined above. Examples of alpha-, beta-ethylenically unsaturated thiokarboxyamides of the formula XII are 2-butenethioamide, 2-hexenedioamide, 2-decenthioamide, 3-methyl-2-heptenthioamide, 3-methyl-2-butenedioamide, 3-phenyl-2-propenylthioamide , 3-cyclohexyl-2-butenedioamide, 2-methyl-2-butenedioamide, 2-propyl-2-propenedioamide, 2-isopropyl-2-hexenedioamide, 2,3-dimethyl-2-butenedioamide, 3-cyclohexyl-2-methyl 2-pentenedioamide, N-methyl-2-butenedioamide, N, N -diethyl-2-hexenedioamide, N-isopropyl-2-decenthioamide, N-phenyl-2-pentene thioamide, N-tertiary butyl 2-propeno-thioamide, N- Octadecyl-2-propenediamide, NN-didodecyl-2-decenthioamide, N-cyclopropyl-2,3-dimethyl-2-butenethioamide, N-methyl-3-phenyl-2-propeno-thioamide, 2-propeno-thioamide, 2-methyl-2- propenthioamide, 2-ethyl-2-propenthioamide and the like. Preferred compounds for the reaction with the polyamines according to the present invention are lower alkyl esters of acrylic acid and (by a lower alkyl) s ibstituierter acrylic acid. Exemplary of such preferred compounds are compounds having the formula:

D ⁷ 0

I, j (XiIl),

CH ₂ = C - COD ⁸

wherein D ^{7 is} hydrogen or a C 1 -C ₄ alkyl group, such as methyl; and D ^{8 is} hydrogen or a C 1 -C ₄ alkyl group. which can be removed to form an amido group, such as methyl, ethyl, propyl, isopropyl, butyl, sec -butyl, tert -butyl, aryl, hexyl, etc. In the preferred embodiments, these compounds are acrylic and methacrylic esters such as Methyl or ethyl acrylate, methyl or ethyl methacrylate.

When the selected alpha, beta-unsaturated compound is a compound of formula VI wherein X is oxygen, the resulting reaction product with the polyamine contains at least one amido linker (-C (O) N <), and these materials are referred to herein as " Similarly, when the selected alpha, beta-unsaturated compound of formula VI is a compound wherein X is sulfur, the resulting reaction product with the polyamine contains a thioamide linkage (-C (S) N <), and these Substances are referred to herein as "thioamidoamine". For convenience, the following discussion will cover the preparation and use of amidoamines, but it will be understood that these embodiments are also applicable to thioamidoamines.

The type of amidoamine formed varies with the reaction conditions. For example, a more linear amidoamine is formed when substantially equimolar amounts of the unsaturated carboxylate and the polyamine are reacted. The presence of an excess of ethylenically unsaturated reactant of formula VI tends to form an amidoamine that is more crosslinked than an amido-amine obtained using substantially equimolar amounts of the reactants. If, for economic or other reasons, a crosslinked amidoamine is desired using excess amine, generally a molar excess of ethylenically unsaturated reactant of at least about 10%, for example 10 to 300%, or more, for example 25 to 200%, is used. In order to achieve a more effective cross-linking, it is preferable to use an excess of carboxylated material, because then a cleaner reaction results, for example with a molar excess of about 10-100% or more, such as 10 to 50%, but preferably an excess of 30-50% of the carboxylated material. On request, you can work with a larger excess.

In summary, without consideration of other factors, equimolar amounts of reactants tend to produce a more linear amidoamine, while an excess of the reactant rrit of formula VI gives a more crosslinked amidoamine. It should be noted that the higher the polyamine is (that is, the greater the number of amino groups on the molecule), the greater the statistical probability of crosslinking, since, for example, a tetraalkylenepentamine, such as tetraethylenepentamine

HI

has more labile hydrogens than ethyldiamine.

These amidoamine adducts thus formed are characterized by both amido and amino groups. In the simplest embodiments, they may be represented by units having the following idealized formula (XIV):

D ^{10 d1} ° D ¹⁰ ü

ON

₂ -n ₄

I II

CH ₂ -CH-C-

wherein ^D10 values, which may be the same or different, are hydrogen or a substituted group such as a hydrocarbon group, for example, alkyl, alkenyl, alkynyl, aryl, etc., and A "is a component of the polyamine, for example, aryl, cycloalkyl , Alkyl, etc., and n <is an integer such as 1 to 100 or greater The above simplified formula represents a linear amidoamine polymer. However, crosslinked polymers can also be formed using certain conditions because the polymer is labile water ^r has atoms that can be further reacted with the unsaturated component by adding at the double bond, or by a carboxylate group with Amidieiung.

Preferably, however, the amidoamines used in this invention are not substantially cross-linked, and preferably are substantially linear.

Preferably, the polyamine reactant contains at least one primary amine (preferably 2 to 4 primary amines) per molecule and the polyamine and the unsaturated reactant of formula VI are present in an amount of about 1 to 10, preferably about 2 to 6 and most preferably about 3 to 5, equivalents of the primary amine in the polyamine reactant per mole of the unsaturated roughening agent having the formula Vl brought into contact with each other. The reaction between the selected polyamine and the acrylate-type compound is carried out at a suitable temperature. It can be worked with temperatures up to the decomposition point of the reactants and products. In practice, the reaction is generally by heating the reaction medium is carried out at a temperature below 100 ⁰ C, for example at 80 ° C-90 ° C, for a suitable period, for example several hours. When working with an ester of the acrylic type, the progress of the reaction can be assessed by the removal of the alcohol in the formation of the amide. During the part of the reaction, alcohol is readily removed below 100 ° C. in the case of low-boiling alcohols, such as methanol or ethanol. As the reaction slows, the temperature is raised to complete the polymerization and the temperature can be raised to 150 ° C towards the end of the reaction. The removal of the alcohol is an expedient method of assessing the progress and completion of the reaction, which is generally carried out until no more alcohol is released.On the basis of alcohol removal, yields are generally stoichiometric Reactions are generally achieved in yields of at least 95% It is also understood that the reaction of an ethylenically unsaturated carboxylate thioester of Formula VIII releases the corresponding HSD ⁸ compound (eg, H ₂ S when D ^{8 is} hydrogen) as a byproduct and the reaction of an ethylenically unsaturated carboxyamide of Formula IX releases the corresponding HND ⁸ (D ⁹ ) compound (eg, ammonia when D ⁸ and D ^{9 are} each hydrogen), which is by-produced.

The amine is readily reacted with the Dikarbonsäurematerial, including alkenyl succinic acid anhydride, by heating an oil solution containing 5 to 95% of Dikarbonsäurematerial to about 100 ⁰ C to 200 ⁰ C, preferably 125 ° C to 175 ⁰ C, generally for a period of 1 up to 10 hours, eg B. 2 to 6 hours, reacts until the desired amount of water is removed. The heating is preferably carried out to promote the formation of imides or mixtures of imides and amides, not amides and salts. The reaction ratios of dicarboxylic acid material to equivalents of amine, as well as other nucleophilic reactants described herein, can vary widely depending on the reactants and the type of bonds formed. In general, between 0.1 and 1.0, preferably between about 0.2 and 0.6, for example 0.4 to 0.6 moles of the content of Dikarbonsäurekompononte (eg polymerized maleic anhydride) per equivalent of the nucleophilic reactant ,? .. As amines used. For example, an amount of about 0.8 mole of a pentamine (having two primary amino groups and 5 nitrogen equivalents per molecule) is preferably used to recover the product obtained by the reaction of one mole (J'm'in with a sufficient amount of maleic anhydride, to add 1.6 moles of succinic anhydride groups per mole of olefin is formed to convert to a mixture of amides and imides, ie, the pentamine is preferably used in an amount sufficient to be about 0.4 mole (ie, 1.6 / (0 , 8 χ 5) moles of the succinic anhydride component per nitrogen equivalent of the amine.

Tris (hydroxymethyl) aminomethane (THAM) can be reacted with the above acidic material to form amides, imides, or ester type additives as described in UK Patent 984409, or to form oxazoline compounds and borated oxazoline compounds such as for example, in U.S. Patents 4,102,798, 4,116,876 and 4,131,639. The adducts may also be esters derived from the above-mentioned long chain hydrocarbon substituted dicarboxylic acid material and such hydroxy compounds as monohydric and polyhydric alcohols, or aromatic compounds such as phenols and naphthols, etc. The polyhydric alcohols are most preferred as hydroxy compounds. Suitable polyol compounds which may be employed include aliphatic polyhydric alcohols having up to 100 carbon atoms and from about 2 to about 10 hydroxyl groups. These alcohols may be quite different in structure and chemical composition, for example they may be substituted or unsubstituted, hindered or unobstructed, branched chain or straight chain, etc. as desired. Typical alcohols are alkylene glycols such as ethylene glycol, propylene glycol, trimethylene glycol, butylene glycol and polyglycol such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, dibutylene glycol, tributylene glycol and other alkylene glycols and polyalkylene glycols wherein the alkylene radical contains between two and about eight carbon atoms. Other useful polyhydric alcohols include glycerol, monomethyl ethers of glycerol, pentaerythritol, dipentaerythritol, tripentaerythritol, 9,10-dihydroxystearic acid, the ethyl esters of 9,10-dihydroxystearic acid, 3-chloro-1,2-propanediol, 1,2-butanediol , 1,4-butanediol, 2,3-hexanediol, pinacol, tetrahydroxypentane, erythritol, arabitol, sorbitol, mannitol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,4- (2-hydroxyethyl) cyclohexane, 1, 4-dihydroxy-2-nitrobutane, 1,4-di (2-hydroxyethyl) benzene, the carbohydrates such as glucose, rhamnose, mannose, glyceraldehyde and galactose and the like, amino alcohols such as di (2-hydroxyethyl) amine, tri (3-hydroxypropyl) amine, N, N-di (hydroxyethyl) amine, tri- (3-hydroxypropylamine, N, N-di (hydroxyethyl) ethylenediamine, copolymer of allyl alcohol and styrene, N, N-di- (2-) HydroxyethyDglyzin and their esters with lower mono- and polyhydric aliphatic alcohols, etc. In the group of aliphatic alcohols include the alkane polyols, the ether group n, such as polyethylene oxide repeating group, as well as the polyhydric alcohols containing at least three hydroxyl groups, at least one of which has been esterified with a monocarboxylic acid having from eight to about 30 carbon atoms, such as octanoic acid, oleic acid, stearic acid, linoleic acid, dodecanoic acid or tallow acid. Examples of such partially esterified polyhydric alcohols are the monooleate of sorbitol, the monooleate of glycerol, the monostearate of glycerol, the distearate of sorbitol and the didodecanoate of erythritol.

A preferred class of ester-containing adducts are those prepared from aliphatic alcohols having up to 20 carbon atoms and especially those having from 3 to 15 carbon atoms. This class of alcohols includes glycerol, erythritol, pentaerythritol, dipentaerythritol, tripentaerythritol, gluconic acid, glyceraldehyde, glucose, arabinose, 1,7-heptanediol, 2,4-heptanediol, 1,2,3-hexanthriol, 1,2,4- Hexanetriol, 1,2,5-hexanetriol, 2,3,4-hexanetriol, 1,2,3-butanetriol, 1,2,4-butanetriol, quinic acid, 2,2,6,6-tetrakis (hydroxyme'hyl ) cyclohexanol, 1,10-decanediol, digitalose and the like. Particularly preferred are the esters prepared from aliphatic alcohols having at least three hydroxyl groups and up to 15 carbon atoms. A particularly preferred class of polyhydric alcohols for the preparation of the ester products used as starting materials in the present invention are the polyhydric alkenols containing from 3 to 15, especially from 3 to 6, carbon atoms and having at least three hydroxyl groups. Such alcohols are exemplified in the above specifically mentioned alcohols and are exemplified by glycerol, erythritol, pentaerythritol, mannitol, sorbitol, 1,2,4-hexanetriol and tetrahydroxypentane and others.

The ester adducts may be diesters of succinic or acidic esters, ie, partially esterified succinic acids, and partially esterified polyhydric alcohols or phenols, ie, esters with free alcohols or phenolic hydroxyl groups. Mixtures of the above-mentioned esters are also provided in the context of the present invention. The ester adduct may be prepared by one of several known methods such as described in US Pat. No. 3,381,022. The ester adduct may also be borated, similar to the nitrogen-containing adduct, as described herein. The hydroxyamines which can be reacted with the said long chain hydrocarbyl substituted dicarboxylic acid groups to form adducts include 2-amino-2-methyl-1-propanol, p- (betahydroxyethyl) aniline, 2-amino-1-propanol , 3-amino-1-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, N- (beta hydroxypropyl) -N ^r - (beta-aminoethyl) piperazine , Tris (hydroxymethyl) aminomethane (also known as trimethylolaminomethane), 2-amino-1-butanol, ethanolamine, diethanolamine, triethanolamine, beta (beta-hydroxyethoxy) ethylamine, and the like. It is also possible to use mixtures of these or similar amines. The above description of nucleophilic reactants suitable for reaction with the hydrocarbyl-substituted dicarboxylic acid or anhydride includes amines, alcohols, and mixed amine compounds and hydroxy-containing reactive functional groups, ie, aminoalcohols. As the nitrogen-containing dispersants, adducts of the group (A-2) above in which a nitrogen-containing polyamine is directly attached to the long-chain aliphatic hydrocarbon (as disclosed in US Pat. Nos. 3,275,554 and 3,565,804) are also suitable in this invention, the disclosures of which are here is fully incorporated by reference) wherein the halogen group on the halogenated hydrocarbon is replaced by various alkylene polyamines. Another class of nitrogenous dispersants in this invention are the adducts of the above group (A-3) containing Mannich bases or Mannich condensation products as known in the art. Such Mannich condensation products (A-3) are generally prepared by condensing about 1 mole of a high molecular weight, hydrocaryl-substituted hydroxy aromatic compound (e.g., having a number average molecular weight of 700 or above) with about 1 to 2.5 moles of an aldehyde such as formaldehyde or paraformaldehyde, and about 0.5 to 2 moles of a polyalkylenepolyamine, as disclosed, for example, in U.S. Patent Nos. 3,442,802, 3,649,229, and 3,798,165 (the disclosures of which are incorporated herein by reference in their entirety). Such Mannich condensation products (A-3) may include a long chain, high molecular weight hydrocarbon on the phenolic group, or may be reacted with a compound containing such a hydrocarbon, eg, polyalkenyl succinic anhydride, as shown in U.S. Patent 3,442,808.

The optionally substituted aromatic hydroxy compounds used in the preparation of Mannich base products (A-3) include compounds having the formula:

R ² 'aryl- (OH),

(XV)

wherein aryl stands for, 20

or

wherein u is 1 or 2, R ^{21 is} a long chain hydrocarbon, R ^{20 is} a hydrocarbon or a substituted hydrocarbon radical of 1 to about 3 carbon atoms or a halogen radical such as a bromide or chloride radical, y is an integer of 1 to 2 is, χ is an integer from 0 to 2 and ζ is an integer from 1 to 2.

Examples of such aryl groups are phenylene, biphenylene, naphthylene and the like.

The long chain hydrocarbyl substituents R ²¹ are olefin polymers as described above for the olefin polymers used to form the reactant A-1.

Methods for the substitution of aromatic hydroxy compounds with the olefin polymer are known in the art and can be represented as follows (Equation 1):

yR

wherein R ²⁰ , R ² ', y and χ are as defined above and BF 3 is an alkylation catalyst. Methods of this type are described, for example, in U.S. Patent Nos. 3,539,633 and 3,649,229, and their disclosures are hereby incorporated by reference in their entirety.

Representative hydro carbyl-substituted aromatic hydroxy compounds which are useful in the present invention include, but are not limited to, 2-polypropylene phenol, 3-propylene phenol, 4-polypropylene phenol, 2-polybutylene phenol, 3-polyisobutylene phenol , 4-polyisobutylenephenol, 4-polyisobutylene-2-chlorophenol, 4-polyisobutylene-2-methylphenol and the like.

Suitable hydrocarbyl-substituted aromatic polyhydroxy compounds include the polyolefin catechols, the polyolefin resorcinols and the polyo-in-hydroquinones, e.g. 4-polyisobutylene-1,2-dihydroxybenzene, 3-polypropylene-1,2-dihydroxybenzene, 5-polyisobutylene-1,3-dihydroxybenzene, 4-polyamylene-1,3-dihydroxybenzene and the like.

Suitable hydrocarbyl-substituted naphthols include 1-polyisobutylene-5-hydroxynaphthalene, i-polypropylene-3-hydroxynaphthalenes and the like.

The preferred long-chain hydrokibyl-substituted aromatic compounds used in the preparation of a Mannich base (A-3) for use in the present invention can be illustrated by the following formula:

OH

(XVI)

wherein R ^{22 is} a hydrocarbyl of 50 to 300 carbon atoms and preferably a polyolefin derived from a C ₂ -C ₁₀ monoalphaolefin (eg, a C ₂ -C ₅ mono-alpha-olefin).

The aldehyde material that can be used in the preparation of the Marsnich base (A-3) and (A-4) is represented by the formula:

R ²³ CHO (XVII)

wherein R ^{23 is} hydrogen or an aliphatic hydrocarbon radical! with 1 to 4 carbon atoms. Examples of suitable aldehydes include formaldehyde, paraformaldehyde, acetaldehyde and the like. Among the polyamines which can be used are the amines which have been mentioned above as being suitable for the preparation of Reagents A-1. Another class of nitrogenous dispersants useful in the present invention are adducts of the above group (A-4) containing Mannich base condensation products of the aminophenol type, as known in the art. These Mannich condensation products are generally prepared by reaction of about 1 mole of long chain hydrocarbyl substituted mono- and di-carboxylic acids or their anhydrides with about one mole of an amine-substituted aromatic compound (eg, aminorjhenol), which aromatic compound is also halogenated. or may be hydrocarbyl-substituted to form a long chain hydrocarbyl substituted amide or imide phenolic intermediate adduct (having a number average molecular weight of generally 700 or above), and by condensation of about one mole fraction of the long chain hydrocarbyl substituted amide or imide phenolic intermediate adduct about 1 to 2.5 moles of formaldehyde and about 0.5 to 2 moles of polyamine, e.g. B. polyalkyleneamine.

The optional hydrocarbyl-substituted aromatic hydroxy compounds used in the preparation of Mannich base products (A-4) include compounds having the formula:

Ar - (OH) I ^z

wherein Ar, R ²⁰ , χ and ζ are as defined above.

Preferred N- (hydroxyaryl) amine reactants which can be used in the preparation of a Mannich base product (A-4) for use in the present invention are aminophenols having the formula:

(XIX)

wherein T 'is hydrogen, an alkyl radical of 1 to 3 carbon atoms or a halogen radical, such as a chloride or bromide radical

Suitable aminophenols include 2-aminophenol, 3-aminophenol, 4-aminophenol, 4-amino-3-methylphenol, 4-amino-3-chlorophenol, 4-amino-2-bromophenol and 4-amino-3-ethylphenol.

Suitable amino substituted polyhydroxyaryls are the amino catechols, the amino resorcinols and the aminohydroquinones, e.g. 4-amino-1,2-dihydroxybenzene, 3-amino-1,2-dihydroxybenzene, 5-amino-1,3-dihydroxybenzene, 4-amino-1,3-dihydroxybenzene, 2-amino-1,4-dihydroxybenzene, 3-amino-1,4-dihydroxybenzene and the like.

Suitable aminonaphthols include 1-amino-5-hydroxynaphthalene, 1-amino-3-hydroxynaphthalene and the like.

The long chain hydrocarbyl substituted mono- or dicarboxylic acid or anhydride material that may be used for reaction with the amine-substituted aromatic compound to produce the amide or imide intermediates in the formation of Reagent A-4 may be any of the materials described above for the preparation of reagent A-1. The above adducts of the selected and amine-substituted compound can then be contacted with an aldehyde and an amine for the Mannich base reaction, as described above. Aldehyde and amine may be any of the above mentioned compounds which have been found suitable for the formation of Reagents A-3.

According to a preferred aspect of the invention, the dispersant adducts A-4 are prepared by reacting the olefin polymer-substituted mono- or dicarboxylic acid material with the N- (hydroxyarylamine) material to form a carbonylamine material containing at least one group in which a carbonyl ! Group is bound to a secondary or tertiary nitrogen atom. In the amide form, the carbonylamino material may contain one or two C (O) -NH groups, and in the imide form, the carbonylamino material contains -C (O) -N-C (O) groups. The carbonylamino material may therefore contain N- (hydroxyaryl) -polymer substituted dicarboxylic acid diamide, N- (hydroxyaryl) -polymeric substituted dicarboxylic acid imide, N- (hydroxyaryl) -polymer substituted monocarboxylic acid monoamide, N- (hydroxyaryl) -polypropylene-substituted dicarboxylic acid monoamide, or mixtures thereof.

In general, such amounts of olefin polymer substituted mono- or dicarboxylic acid material, such as olefin polymer-substituted succinic anhydride, and N- (hydroxyaryl) amine, such as p-aminophenol, ensure that about one equivalent of a dicarboxylic acid or anhydride component or monocarboxylic acid component per equivalent of Amine component are dissolved in a solvent (ie, a hydrocarbon solvent such as toluene, xylene or iso-octane) dissolved and reacted at a moderately elevated temperature to the reflux temperature of the solvent used for a time sufficient to prevent formation of the N- (hydroxyaryl) hydrocarbylamide or imide intermediate. When working with an olefin polymer-substituted monocarboxylic acid material, the resulting intermediate product that is formed generally contains amide groups. Also, the resulting intermediate generally contains imide groups when an olefin polymer-substituted dicarboxylic acid material is used, although amide groups may also be present in a portion of the carbonylamine material so formed. Subsequently, the solvent is removed under vacuum and at elevated temperature, generally at about 160 ° C.

Alternatively, the intermediate is prepared by combining sufficient amounts of the olefin polymer-substituted mono- or dicarboxylic acid material to provide about one equivalent of the dicarboxylic acid or anhydride component or the monocarboxylic acid component per equivalent of the amine component of the N- (hydroxyaryl) amine, with the N- (Hydroxyaryl) amine and heating the resulting mixture to a higher temperature under a nitrogen purge in the absence of a solvent.

The resulting N- (hydroxyaryl) polymer-substituted imides can be exemplified by succinimides represented by the following formula (XX):

wherein T 'is as defined above and wherein R ^{21 is} also as defined above. Similarly, when an olefin polymer-substituted monocarboxylic acid material is used, the resulting N- (hydroxyaryl) -polymer substituted amides can be represented by the propionamides of formula (XXI):

OR ²¹ - CH ₂ CH ₂ -C ^ -NH

wherein T 'and P ² ' are as defined above.

In a second step, the carbonylamino intermediate is reacted with an amine compound (or mixture of amine compounds), such as polyfunctional amine, along with an aldehyde (e.g., formaldehyde) in the Mannich base reaction. Generally, the reactants are mixed at elevated temperature and reacted until the reaction is complete. This reaction can be carried out in the presence of a solvent and in the presence of such an amount of mineral oil which is an effective solvent for the final Mannich base dispersant. This second step can be illustrated by the Mannich base reactants between the above N- (hydroxyphenyl) polymer succinimide intermediate, paraformaldehyde and ethylenediamine according to the following equation:

R ²¹ -CH C

CH ₂ -C

OH

+ CH ₂ O + H ₂ N (CH ₂ J ₂ NH-)

[CH ₂ (NH (CH ₂ ) ₂ NH-D ¹ ] _{a /}

(Equation 2) wherein a 'is an integer between 1 and 2, H ² ' and T 'are as defined above and D' is H or the following component:

OH O

wherein R ² 'and T' are as defined above. Also, this second step can be illustrated by the Mannich base reaction between the above-mentioned N-hydroxypheny-d-acrylamide intermediate, paraformaldehyde and ethylenediamine according to the following equation:

O J /

NH

+ CH ₂ O + H ₂ N (CH ₂ J ₂ NH ₂

_R 21 CH ₂ CH ₂ -

[CH ₂ (HH (CH ₂ J ₂ NH-D ^] ₃ /

(Equation 3) wherein a 'is an integer 1 or 2, R ² ' and T are as defined above, and D ^{2 is} H or a component

- R

²¹

T 'OH wherein R ² ' and T are as defined above.

In general, the reaction of one mole of the carbonylamino material, eg, an N (hydroxyaryl) polymersukinimide or amide intermediate, with two moles of the aldehyde and one mole of amine favors the formation of products having two components which has been bridged by an alk-amine-alk group, wherein the "alk" moieties are derived from the aldehyde (eg -CH ₇ - from CH ₂ O) -> ind and the "amine" moiety is a divalent bis-N-terminated amino group derived from the amine reactant (eg, from polyalkylene polyamine) Such products are exemplified by the equations 2 and 3 above, wein a 'is one, and D ^{1 is the} following component:

-CH

T'OH 0

and D ^{2 is the} following component:

NH-C-CH ^ CF-R ²¹

Il ^u '0

wherein T 'and R ^{21 are} as defined above.

Similarly, the reaction of substantially equimolar amounts of the carbonylamino, aldehyde and amine reactants favors the formation of products exemplified by Equations 2 and 3 wherein "a"'is one and D' and D ^{2 are} each H and the reaction of one mole of the carbonylamino material with two moles of aldehyde and two moles of the amine reactant allows the formation of larger amounts of the products illustrated by Equations 2 and 3, wherein "a"'is 2 and D' and D ^{2 are} each H are.

In the preparation of the reactants A-4, the order of reaction of the various reactants can be modified so that, for example, the N-hydroxynrylamine is first mixed with the amine material and the aldehyde in the Mannich base reaction and reacted to form an aminomethylhydroxyarylamine , Subsequently, the resulting intermediate adduct is reacted with the olefin polymer substituted mono- or dicarboxylic acid material to produce the desired dispersant. The sequence of reactions carried out in accordance with this aspect of the invention tends to produce different dispersant isomers since in the first Mannich base condensation step a variety of aromatic and primary and secondary nitrogen atoms are formed which are responsible for reaction with the Carboxy components of the mono- and dicarboxylic acid material are available.

The Mannich base intermediate adduct A-4 formed by the reaction of the N-hydroxyarylamine with the amine reactant and the formaldehyde may have at least one compound selected from the group consisting of: (a) adducts with the Structural formula (XXII):

Η-ί-Α'ίχ, -ΑΓ'Α'-Α-ΙΑΆΓ'ΑΆΙχ, -ΙΑΆΓΊχ, -Η

wherein X ₁ is 0 or 1, x _{2 is} an integer between 0 and 8, x ₃ is 0 or 1, A is a divalent bis-N-terminated amino group derived from the amine reactant and has an amine group with Containing 2 to 60 (preferably 2 to 40) carbon atoms and 1 to 12 (preferably 3 to 12) nitrogen atoms, and A 'comprises the group -CH (T ") - where T" is H or an alkyl of 1 to 9 carbon atoms and derived from the corresponding aldehyde reactant, and Ar 'has the component (XXIII):

OH T' \ /

-ar-

NH,

wherein R 'and Ar are as defined above for the N-hydroxyarylamines used in this invention, and (b) adducts having the structure (XXIV):

OH T'

NH _0-Ar- (A'-AH) _0,

wherein a ', T', A ', A and Ar are as defined above.

Preferred adducts of the above formula XXII are those in which Xi is 0, x ₂ gleichi to 3 and x ₃ is 1, and most adducts are preferred wherein T 'is H or an alkyl having 1 to 3 carbon atoms and Ar is phenylene. Preferred adducts of formula XXIV are those in which Ar is phenylene.

Preferably, the divalent "Α" -amino group contains -NH end groups as illustrated by the structures of the following formula (XXV):

-N- (CH ₂ ) _s -R '

• NK- (CH ₂ ) _pl

-N- (CH ₂ ) _S A N-

4

ι ι ι

, CH ₂ -CH;

-τ- Ν

CH ₂ -CH ₂

η _Ί

(CH ₉ ) -NH-

L ^ P ₂ J

n ₂ n ₃

4-alkylene (-O-alkylene -) - NH -) -

O ^J D ¹ X

I I II (C - C - C) -

wherein Z ^{s has} at least one member selected from the group consisting of the above-mentioned elements (XXV) (i), (ii) and (iii),

wherein R ', R "'," t "and" s "are as defined above in connection with formula I, p ,, p ₂ , n _{) r} n ₂ and n _{3 are} as defined above in connection with formula III, Alkylene "and" m "are as defined above in connection with formula IV and D ⁶ , D ⁷ and X are as defined above in connection with formula Vl.

Illustrative examples of adducts having the structure XXIV are given below in Table A.

Tabel'eA X, x? X ₃ Ar ' A ' A O 2 1 -Ph (OH) (NH ₂ ) - -CH ₂ - -NH (Et) NH (Et) NH- O 2 1 -Ph (OH) (NH ₂ ) - -CH ₂ - -NH (Et) (NH (EO) ₃ NH- O 1 O -Ph (OH) (NH ₂ ) - -CH ₂ - -NH (Et) NH (Et) NH- O O O -Ph (OH) (NH ₂ ) - -CH ₂ - -NH (Et) (NH (EO) ₃ NH- O 1 1 -Ph (OH) (NH ₂ ) - -CH ₂ - -NH (Et) NH (Et) NH- O 1 1 -Ph (OH) (NH ₂ ) - -CH ₂ - -NH (Et) (NH (EO) ₃ NH- 1 2 O -Ph (OH) (NH ₂ ) - -CH (CH ₃ ) - -NH (Et) NH (Et) NH- 1 O 1 -Ph (OH) (NH ₂ ) - -CH (CH ₃ ) - -NH (Et) (NH (EO) ₅ NH- 1 3 O -Ph (OH) (NH ₂ ) - -CH (CH ₃ H -NH (Et) (NH (EO) ₆ NH- 1 1 O -Ph (OH) (NH ₂ ) - -CH (CH ₃ H -NH (EO (NH (EO) ₆ NH- 1 1 1 -Ph (OH) (NH ₂ ) - , -CH (CH ₃ H -NH (Et) (NH (EO) ₆ NH- O 2 1 -Ph (OH) (NH ₂ ) - -CH (CH ₃ H -NH (Et) (NH (EO) ₆ NH-

(Ph = phenyl, Et = C ₂ H ₁ )

Illustrative examples of adducts having the structure XXIII are listed below in Table B, where Ar is tri- or tetrasubstituted phenyl:

Table B a T ' A ' A 1 H -CH ₂ - -NH (Et) NH (Et) NH- 2 CH ₃ -CH ₂ - -NH (Et) (NH (EO) ₃ NH- 1 CH ₃ -CH ₂ - -NH (Et) NH (Et) NH- 2 C ₂ H ₆ -CH ₂ - -NH (Et) (NH (EO) ₅ NH- 1 C ₃ H ₇ -CH ₂ - -NH (Et) NH (Et) NH- 2 C ₄ H ₉ -CH ₂ - -NH (Et (NH (Et) I ₆ NH- 1 H -CH (CH ₃ H -NH (Et) NH (Et) NH- 2 CH ₃ -CH (CH ₃ ) - -NH (Et) (NH (EO) ₆ NH-

For the purpose of illustration, this aspect of the invention may be represented by the following equations (in which R ² ', T' and a 'are as defined above):

Dikfubonsäurematerial

OH

T '.OH

+ a 'CH ₂ O + a' NH ₂ (CH ₂ CH ₂ ) NH ₂

OH

T '

- [CH ₂ NH (CH ₂ CH ₂ ) NH ₂ J ₃ /

[CH ₂ NH (CH ₂ CH ₂ ) NH ₂ J ₃ / +

(1 +

H ₂ NH (CH ₂ CH ₂ ) N '

OH

^ C

Monocarboxylic acid material

+ a 'CH ₂ O + a' NH ₂ (CH ₂ CH ₂ ) NH ₂

(CH ₂ NH (CH ₂ CH ₂₎ NH ₂ J ₃₁

[CH ₂ NH (CH ₂ CH ₂ ) NH ₂ J ₃ / +

C- CH R

CH

R ²¹ - CH ₂ CH ₂ C-NH

[C: -I ₂ NH (CH ₂ CH ₂ ) N -CH ₂ CH ₂ -R ²¹ J _a ,

OH

In one embodiment of the preparation of Reagents A-4, a carbonylamino material consisting of a polyisobutylene-substituted hydroxyarylsuczincimide prepared by first reacting a polyisobutylene succinic anhydride with an aminophenol to form an intermediate, with formaldehyde and a mixture of poly (ethylene amines) in the above Mannich base reaction reacted to produce reactant adducts A-4. In another embodiment, an aminophenol is first reacted with formaldehyde and a mixture of poly (ethylene amines) in the Mannich base reaction outlined above to produce an intermediate containing between one and three (polyamino) methyl-substituted aminohydroxyaryl groups per molecule, followed by reaction of this intermediate with a polyisobutylene succinic anhydride to form Mannich base adducts A-4. A preferred group of Mannich base adducts A-4 are the adducts formed by condensation of polymer with formaldehyde and polyethyleneamines, eg, tetraethylenepentamine, pentaethylene, hexamine, polyoxyethylene, and polyoxypropylene amines, e.g. As polyoxypropylenediamine, and their combinations are produced. A particularly preferred dispersant combination includes a condensation of (a ") polymer substituted succinic anhydride or propionic acid, (b") aminophenol, (c ") formaldehyde and (d") at least one (d "i) polyoxyalkylene polyamine, e.g., polyoxypropylenediamine, and a (d " _:) polyalkylenepolyamine, e.g. Polyethylenediamine and tetraethylenepentamine, using a mole ratio of a ": b": c ": d" of from 1: 1 to 8: 1: 0.1 to 10 and preferably from 1: 2 to 6: 1: 1 to 4 wherein the molar ratio of a ":( d" i) :( d " ₂ ) is 1: 0 to 5: 0 to 5 and preferably 1: 0 to 4: 1 to 4. When the aldehyde has formaldehyde (or a material forming formaldehyde in situ) and the amine contains a primary diamine (e.g., polyalkylenepolyamine), formaldehyde and diprimary amine are most preferably present in an amount of about 2 (q-1) moles of formaldehyde and about (q-1) moles diprimary amine per "q" molar equivalents supplied with the hydroxyaryl group.

The nitrogenous dispersants may also be treated by boriding as generally described in U.S. Patent Nos. 3,089,736 and 3,225,025 (the contents of which are incorporated herein by reference). This is readily accomplished by treating the selected acyl-nitrogen dispersant with a boron compound selected from the class consisting of boric oxide, boron halides, boric acids, and boric acid esters, the amount being selected to be about 0.1 atomic percent boron per each Moles of the azylated nitrogen compound yield up to about 20 atomic proportions of boron per atomic proportion of nitrogen of the acylated sticking composition. In general, the dispersants according to the invention in the combination contain about 0.05 to 2.0%, z. 0.05 to 0.7% boron based on the total weight of the borated acyl nitrogen compound. It is believed that boron, which is believed to be present in the product as dehydrated boric acid polymers (predominantly [HBO 2 I 3), binds to the imides and diimides of the dispersant in the form of amine salts, e.g. B. the metaborate salt of this diimide.

Treatment is simply by adding about 0.05 to 4, e.g. B. 1 to 3% (based on the weight of the Azylstickstoffverbindung) of said boron compound, preferably boric acid which w'rd usually added as a slurry to dieserAzylstickstoffverbindung and heating to 135 ° C to 190 ⁰ C, for example, 140 ⁰ C to 170 ° C, with stirring for 1 to 5 hours, followed by stripping the nitrogen in these temperature ranges. However, the Borbehandliing can also be carried out so that boric acid is added to the hot reaction mixture of dicarboxylic acid material and amine with the discharge of water.

In a preferred embodiment of the present invention, the dispersants used in this invention are the above-mentioned nitrogen-containing adducts of the group (A-1), i. that is, the adducts derived from a hydrocarbyl substituted mono- or di-carboxylic acid-forming material (acids and anhydrides) and reacted with polyamines. Particularly preferred adducts of this type are those derived from polyisobutylene-substituted succinic anhydride or propionic acid groups and reacted with polyethyleneamines, e.g. For example, tetraethylene pontamine, pentaethylenehexamine, polyoxyethylene, and polyoxypropylene amines, e.g. As polyoxypropylenediamine, Trismethylolaminoethan and their combination were reacted.

Another preferred group of ashless dispersants useful as component A in this invention are the dispersant additive mixtures consisting of (a) a first dispersant consisting of the reaction product of a polyolefin of from 1 500 to 5000 number average molecular weight, represented by 1, 05 to 1.25, preferably 1.06 to 1.20, eg 1.10 to 1.20, dicarboxylic acid-producing components (preferably acid or anhydride components) having been substituted with a first nucleophilic reactant consisting of any of the above amines, alcohols, amino alcohols and mixtures thereof, and (b) a second dispersant consisting of the reaction product of a second polyolefin having an average molecular weight of 700 to 1150 substituted with 1.2 to 2.0, preferably 1.3 to 1.8, e.g. B. 1.4 to 1.7, dicarboxylic acid-producing components (preferably acid or anhydride components) per polyolefin molecule, with a second nucleophilic reactant consisting of any of the above amines, alcohols, amino alcohols and mixtures thereof, wherein the weight ratio of a : b is between 0.1: 1 and 10: 1. These dispersant mixtures generally contain between about 10 and 90% of the dispersant (a) and between about 90 and 10% of the dispersant (b), preferably between about 15 and 70% of the dispersant (a) and between about 85 and 30% of the dispersant (B) and in particular between about 40 and 80% of the dispersant (a) and between about 20 and 60% of the dispersant (b), calculated as each active ingredient (eg excluding diluent oil, solvent or unreacted polyalkylene). Preferably, the weight: weight ratio of dispersant (a) to dispersant (b) ranges from about 0.2: 1 to 2.3: 1, and most preferably between about 0.25: 1 and 1.5: 1.

These dispersant admixtures allow for better diesel performance and have better viscometric properties because they control the level of functionality and molecular weight of two disperse dispersant components produced individually. For these dispersant mixtures, the high level of functionality is in the low molecular weight dispersant components, and the low level of functionality is with the high molecular weight components, so it is not randomly distributed in the dispersant molecules. The dispersant mixtures are disclosed in copending application Ser. No. 95056 of Sep. 9, 1987, the contents of which are fully incorporated herein by reference.

Component B

Useful antioxidants include oil-soluble phenolic compounds, oil-soluble sulfurized organic compounds, oil-soluble amine antioxidants, oil-soluble organoborates, oil-soluble organophosphites, oil-soluble organophosphates, oil-soluble organodithiophosphates, and mixtures thereof. Preferably, these antioxidants are metal-free (i.e., free of metals that can produce sulfated ash) and, therefore, preferably ashless (containing siftered ash not more than 1% SASH).

Examples of oil-soluble phenol compounds are alkylated monophenols, alkylated hydroquinones, hydroxylated thiodiphenyl ethers, alkylidenebisphenols, benzyl compounds, azylaminophenols and esters and amides of hindered phenol-substituted alkanoic acids.

Examples of phenol antioxidants

1. Alkylated monophenols

2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2, 6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (a-methylcyclohexyl) -4,6-dimethylphenol, 2,6-dioctadezyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-ditertbutyl-4-methoxymethyl-otertbutylphenol.

2. Alkylated hydroquinones

2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl hydroquinone, 2,5-di-tertamyl-hydroquinone, 2,6-o-phenyl-4-octadecyl-oxyphenol.

3. Hydroxylated thiodiphenyl ethers

2,2'-Thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thiobis (6-tert-butyl-3-m3thylphenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol).

4. Alkylidenebisphenols

2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'-methylenebis [4-methyl-6- (amethylcyclohexylphenol], 2 , 2'-Methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (6-nonyl-4-methylphenol), 2,2'-methylenebis (4,6-di-tert-butylphenol), 2,2 'Ethyldienebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis [6- (a-methylbenzyl) -4-nonylphenol], 2,2 'Methylonebis (6- (a, a-dimethylbenzyl) -4-noriylphenol], 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4'-methylenebis (6-tert-butyl-2-methylphenol), 1 , 1-bis (5-tert-butyl-4-hydroxy-2-methylphenydbutane, 2,6-di (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5 tert -butyl-4-hydroxy-2-methylphenyl) -3-n-dodezylm3rkaptobutane, ethylene glycol bis [3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate), di (3-tert-butyl-4-hydroxy-5 -methylphenyl) dicyclopentadiene, di [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate.

5. Benzyl compounds

1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, di (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 3,5-di-tert-butyl-4 -hydroxybenzylmercaptoacetic acid isooctyl ester, bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, 1,3,5-trif (3,5-di-tert-butyl-4-hydroxybenzyl) -cycanourate, 1,3,5-tris ( 4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid dioctadecyl ester, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester calcium salt.

6. Azylaminophenols

4-Hydroxylauric anilide, 4-hydroxysteraric anilide, 2,4-bisoctylmercapto-6- (3,5-di-tert-butyl-4-hydroxyanilino) -s-triazine, N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamic acid octyl ester.

6. Esters of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols, e.g. with methanol, octadecanol, 1,6-H> 3xandiol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, di (hydroxyethyl) oxalic acid diamide.

8. Esters of ß- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono- or polyhydric alcohols, eg. B. with methanol, octadecanol, 1,6-hexanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate and di (hydroxyethyl) oxalsäurediamid.

9. Amides of p- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, e.g. N, N'-Di (s, t-ditertbutyl-4

hydroxyphenylpropionyl) hexamethylenediamine, N, N'-di (3,5-ditertbutyl-4-hydroxyphenylpropionyl) trimethylene-diamine, N ₁ N'-di (3,5-ditortbutyl-4-hydroxyphenylpropionyl) hydrazine.

A variety of sulfurized organic compounds can be used as component B in the compositions of the present invention, and these compounds can be generally represented by the formula (XXVI):

R ^3O S "R ³¹

wherein S is sulfur, X _{4 is} an integer from 1 to about 10, and R ³¹ and R ^{30 may be the} same or different organic groups. The organic groups may be hydrocarbon groups or substituted hydrocarbon groups which may contain alkyl, aryl, aralkyl, alkaryl, alkanoate, thiazole, imidazole, phosphorothionate, beta-ketoalkyl groups, etc. The substantially hydrocarbon groups may contain other substituents such as halogen, amino, hydroxyl, msrkapto, alkoxy, aryloxy, thio, nitro, sulfonic, carboxylic, carboxylic and the like.

Particular examples of types of sulfurized compositions suitable as component (B) in the compositions of this invention include aromatics, alkyl or alkenyl sulfides and polysulfides,

sulfurized olefins, sulphurised carboxylic acid esters, sulphurised esterolefins, sulfurized oil and mixtures thereof. The preparation of these oil-soluble, sulfurized compositions is described in the literature, and U.S. Patent No. 4,612,129 is incorporated herein by reference in its entirety to disclose such processes, including the type and amount of reactants and catalysts (or promoters), temperatures, and other process conditions and product purification and recovery techniques (eg, decolorization, filters, and steps to remove other solids and contaminants).

The sulfurized organic compounds used in the present invention may be aromatic and aryl sulfides such as dibenzyl sulfide, dixylyl sulfide, dicetyl sulfide, diparaffin wax sulfide and polysulfide, crack wax wax sulfides, etc.

Examples of dialkenyl sulfides suitable for the compositions of the present invention are described in U.S. Patent 2,442,072. Examples of sulfides of this type include 6,6'-dithiobis (5-methyl-4-nonene), 2-butenyl monosulfide and disulfide and 2-methyl-2-butenyl monosulfide and disulfide.

Sulfurized olefins that can be used as component (B) in the compositions of the present invention include sulfurized olefins formed by reaction of an olefin (preferably having 3 to 6 carbon atoms) or a lower molecular weight polyolefin derived therefrom with a sulfur-containing compound , such as sulfur, sulfur monochloride and / or sulfur dichloride, hydrogen sulfide, etc., are produced. Isobutene, propylene and their dimers, trimers and tetramers and mixtures thereof are particularly preferred olefin compounds. Isobutylene and diisobutylene are the most advantageous of these compounds because they are highly available and can be used to produce compositions having a particularly high sulfur content.

The sulfurized organic compounds employed in the compositions of the present invention can be sulfurized oils which can be prepared by treating natural or synthetic oils, including mineral oils, lard oil, carboxylic acid esters derived from aliphatic alcohols and fatty acids or aliphatic carboxylic acids (for example, myristyl oleate and oleyl oleate), whale oil and synthetic whale sperm substitutes, and unsaturated synthetic esters or glycerides.

The sulfurized fatty acid esters used in the compositions of the present invention can be prepared by reacting sulfur, sulfuric chloride and / or sulfur dichloride with an unsaturated fatty acid ester at elevated temperatures. Typical esters include C ₁ -C 20 alkyl esters and unsaturated C ₁ -C ₂ 4 fatty acids such as palmitoleinolein, ricinoleic, petroselin, vaccine, linoleic, linoleic, oleostearic, lycanoic acid, etc. Sulfurated fatty acid esters which are prepared from mixed unsaturated fatty acid esters, such as derived from animal fats and vegetable oils, such as tall oil, linseed oil, olive oil, castor oil, peanut oil, rapeseed oil, fish oil, sperm oil, etc., are also suitable. Specific examples of fatty acid esters that can be sulfurized include lauryl tolate, methyl oleate, ethyl oleate, lauryl oleate, cetyl oleate, cetyl linoleate, lauryl ricinoleate, oleolinoleate, oleostearate, and alkyl glycerides.

Another class of organic, sulfur-containing compounds that can be used as component (B) in the compositions of the present invention include sulfurized aliphatic esters of an olefinic monodicarboxylic acid. For example, aliphatic alcohols having 1 to 30 carbon atoms can be used to esterify monocarboxylic acids such as acrylic acid, methacrylic acid, 2,4-pentadienoic acid, etc., or fumaric acid, maleic acid, muconic acid, etc. The sulfurization of these esters is carried out with elemental sulfur, sulfur monochloride and / or sulfur dichloride.

Another class of sulfurized organic compounds that can be used in the compositions of the invention are the diester sulfides characterized by the following general formula (XXVII):

_-SXl [(CH ₂ ) "COOR ¹² ] ₂

wherein X _{6 is} between about 2 and about 5, x _{e is} between 1 and about 6, preferably between 1 and about 3, and R ^{32 is} an alkyl group of about 4 to about 20 carbon atoms. The R ³² group may be a straight or branched group which is sufficiently large to ensure the solubility of the compositions of the invention in oil. Typical diesters include butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, tridezyl, myristyl, pentadezyl, zetyl, heptadecyl, staryl, l-curyl and eicosyl diesters of thiodialcanic acids such as propionic, butanoic, pentanoic and hexanoic acid. A specific example of diester sulfides is dilauryl-3,3-thidipropionate.

In another preferred embodiment, the sulfurized organic compound (component (B)) is derived from a particular type of cyclic or bicyclic olefin which is a Diels-Alder adduct of at least one dienophile with at least one aliphatic conjugated diene Diels-Alder adducts can be prepared by the reaction of various sulfurized agents with the Diels-Alder adducts, as described in more detail below: Preferably, the sulfurizing agent is sulfur.

Dib "Jiels-Alder adducts are a well known class of compounds that are prepared by the diene synthesis of the L'iels-Alder reaction." A summary of the known publications on this class of compounds is in the Russian monograph "DienovyiS ^: ntes", lzdatelstwoAkademii Nauk SSSR, 1963, by A.S.Nenchenko. (Translated into English by L.Mandel, "Diene Synthesis", NY, Dani'jl Davey and Co., Inc., 1964) .This monograph and the references therein are incorporated by reference into the present specification Sulfurized composition used in the present invention (component (B)) may be at least one sulfurated terpene compound or a composition prepared by sulfurizing a mixture containing at least one terpene and at least one other olefinic compound.

The term "terpene compound" as used in the specification and claims is intended to include the various isomeric terpene hydrocarbons having the empirical formula CioHt6 as contained in turpentine, ciene oil and dipentenes, and the various synthetic and naturally occurring oxygenated ones ^de; vate In general, mixtures of the various compounds can be used, especially when natural products such as pine oil and turpentine are used pine oil, for example, the destructive distillation of pine with by waste wood..

superheated steam containing a mixture of terpene derivatives such as alpha-terpineol, beta-terpineol, alpha-fenchol, camphor, borneol / isoborneol, fenchone, estragole, dhydro-alpha-terpineol, anethole and other monoterpene hydrocarbons. The particular ratios and amounts of the various components in a given ciene oil will depend on the particular source and the degree of purification. A group of pine oil-derived products is commercially available from Hercules Incorporate. It has been found that the pine oil products, commonly referred to as terpene alcohols, available from Hercules Incorporated, are particularly suitable for the preparation of the sulfurized products used in the invention. Examples of these products include Alpha-Terpineo! containing from about 95 to 97% of alpha-terpineol, a mixture of high purity tertiary terpene alcohols, which typically contains 96.3% of tertiary alcohols; Terpineol 318 Prime, a mixture of isomeric terpineols obtained by dehydration of terpene hydrate containing about 60 to 65% alpha-terpineol and 15 to 20% beta-terpineol and 18 to 20% other tertiary terpene alcohols. Other blends and grades of suitable pine oil products are available from Hercules under such designations as Yarmor 302, Herco-Pine Oil, Yarmor 302 W, Yarmor F and Yarmor 60.

The slip compounds which may be employed in the compositions of the present invention may be sulfurized terpene compounds, sulfurized mixtures of terpene compounds, or mixtures of at least one terpene diol compound and at least one sulfurized terpene compound. Sulfurized terpene compounds can be prepared by sulfurizing terpene compounds with sulfur, sulfur halides, or mixtures of sulfur or sulfur dioxide with hydrogen sulfide, as described in more detail below. The sulfurization of various terpene compounds has also been described in the literature. For example, the sulfur of pine oil is described in US Patent No. 2012446.

The other olefinic compound which can be combined with the treparene compound can be any of the various olefinic compounds already described.

The other olefin used in combination with the terpan may be an unsaturated fatty acid, an unsaturated fatty acid ester, mixtures thereof, or mixtures thereof with the olefins described above. The term "fatty acid" is used herein to refer to acids derived from the hydrolysis of naturally occurring vegetable or animal fats or oils, which generally contain from 16 to 20 carbon atoms and are mixtures of saturated and unsaturated The unsaturated fatty acids, which are generally present in naturally occurring vegetable or animal fats and oils, may contain one or more double bonds, and these acids include palmitoleic acid, oleic acid, linoleic acid, linolenic acid and erucic acid The unsaturated fatty acids may be mixtures of acids as derived from naturally occurring animal and vegetable oils, such as lard oil, tall oil, peanut oil, soybean oil, cottonseed oil, sunflower oil or wheat germ oil Tall oil is a mixture of rosin acids, especially abietic acid, and unsaturated fatty acids, especially Olefinic and linoleic acid, tall oil is a by-product of the sulphate process for the production of mechanical pulp.

Particularly preferred uraturated fatty acid esters are the feit oils, i. h., naturally occurring esters of glycerol with the fatty acids mentioned above and synthetic proteins of similar structure. Examples of naturally occurring non-saturated fats and oils include animal fats such as beef claw oil, lard oil, depot fat, beef tallow, etc. Examples of naturally occurring vegetable oils include cottonseed oil, corn oil, poppy oil, safflower oil, sesame oil, soybean oil, sunflower oil and wheat germ oil.

The fatty acid esters which are suitable may also be prepared as aliphatic olefinic acids of the type described above, such as oleic acid, linoleic acid, linolenic acid and behenic acid, by reaction with alcohols and polyols. Examples of aliphatic alcohols that can be reacted with the acids listed above include monohydric alcohols such as methanol, ethanol, n-propanol, isopropanol, the butanols, etc., and polyhydric alcohols including ethylene glycol, propylene glycol, trimethylene glycol, neopentyl glycol, Glycerol etc.

Other olefinic compounds used in the preparation of the compositions after combination with the terpene compound include sulfurized derivatives of said olefinic compounds. Thus, the olefin can be formed by one or more of the above-mentioned olefinic compounds, their sulfurized derivatives or mixtures of these olefinic compounds and sulfurized derivatives. The sulfurized derivatives can be prepared by methods known in the art, with sulfurizing agents such as sulfur, sulfur halides, or mixtures of sulfur or sulfur dioxide with hydrogen sulfide. Examples of suitable amine antioxidants include phenyl-substituted and phenylene-substituted amines, N-nitrophenylhydroxylamine, isoindoline compounds, phosphinedithioic acid vinylcarboxylate adducts, phosphorodithioate ester-aldehyde reaction products, phosphorodithioate-alkylene oxide reaction products, silyl ethers of terephthalic acid, bis-1,3-alkylamino-2 -propanol, anthranilamide compounds, anthranilic acid esters, alpha-methylstyrenated aromatic amines, aromatic amines and substituted benzophenones, aminoguanidines, peroxide-treated phenothiazine, N-substituted phenothiazines and triazines, 3-tertiary alkyl-substituted phenothiazines, alkylated diphenylamines, 4-alkylphenyl-1-alkyl-2 naphthylamines, dibenzazepine compounds, fluorinated aromatic amines, alkylated polyhydroxybenzenoid compounds, substituted indanes, dimethyloctadezylphosphonate-aryliminodialkanol copolymers, and substituted benzodiazoborol.

Examples of amine antioxidants

N.N'-diisopropyl-p-phenylenediamine ^ N, N'-disecbuyl-p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl) -p-p-methylnediamine. N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine. N, N'-bis (1-methylheptyl) -p-phenylenediamine, Ν, Ν'-diphenyl-p-phenylenediamine, N, N'-di (naphthyl-2 -) - p-phenyleneditmin, N-isopropyl-N'-phenyl -p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-n-phenylenediamine, N- (1-methylheptyl) -N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl- p-phenylene,: amine, 4- (p-toluenesulfonamido) diphenylamine, N, N'-dimethylNiN'-disecbutylp-phenylenediamine diphenylamine, 4-isopropoxyphenylamine, N-phenyl-1-naphthylamine, N-phonyl-2-naphthylamine, octylated diphenylamine , 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanylaminophenol, di (4-methoxyphenyldamine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane,

4,4'-diaminophenylmethane, N, N, N ', N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-di [(2-methylphenyl) amino] ethane, 1,2-di (phenylamino) - propane, (o-tolyl) biguanide, di [4- (1 ', 3'-dimethylbutyl) phenyllamine, tert-octylated N-phenyl-1-naphthylamino, and mixtures of mono- and dialkylated tert-butyl N / teto-tyldiphenylamines.

The oil-soluble organoborates, phosphates and phosphites include alkyl and aryl substituted (and alkyl, aryl mixed substituted) borates, alkyl and aryl substituted (and mixed alkyl, aryl substituted) phosphates, alkyl and aryl substituted (and mixed alkyl) alkyl groups. and aryl substituted) phosphites and alkyl and aryl substituted (and mixed alkyl, aryl substituted) dithiophosphates such as OOS trialkyl dithiophosphates, OOS triaryl dithiophosphates and dithiophosphates with mixed substitution by alkyl and aryl groups, phosphorothionyl sulfide, phosphorus silane, polyphenylene sulfide, amine salts of phosphinic acid and Chino phosphates.

As component B of the compositions of the present invention, at least one sulfurized, alkyl-substituted hydroxyaromatic compound is preferred as the oxidation inhibiting agent. Sulfurized alkyl-substituted hydroxyaromatic compounds and their methods of preparation are known to those skilled in the art, for example, in the following US patents (incorporated herein by reference): 2139766, 2198828, 2230542, 2836565, 3328854, 3538166, 3844956, 3951830, and 4115287.

In general, the sulfurized alkyl-substituted hydroxyaromatic compounds can be prepared by reacting an alkyl-substituted hydroxyaromatic compound with a sulfurizing agent such as elemental sulfur, a sulfur halide (e.g., sulfur monochloride or sulfur dichloride), a mixture of hydrogen sulfide and sulfur dioxide or the like. The preferred sulfurizing agents are sulfur and the sulfur sharks, especially the sulfur chloride, with sulfur dichloride (SCI ₂ ) being particularly preferred.

The alkyl-substituted hydroxyaromatic compounds that are sulfurized to produce component B are generally compounds containing at least one hydroxy group (e.g., 1 to 3 hydroxy groups) and at least one alkyl radical (eg, 1 to 3 alkyl radicals) attached thereto are bound aromatic ring. The alkyl radical normally contains about 3 to 100 and preferably about 6 to 20 carbon atoms. The alkyl-substituted hydroxyaromatic compounds may contain more than one hydroxy group, as illustrated by alkylresorcinols, hydroquinones and catechols, or they may contain more than one alkyl radical; however, they usually contain only one of these components. Compounds in which the alkyl and hydroxy groups are in ortho, meta and para positions and mixtures of such compounds are also within the scope of the invention. Examples of alkyl-substituted hydroxyaromatic compounds are n-propylphenol, isopropylphenol, n-butylphenol, t-butylphenol, hexylphenol, heptylphenol, octylphenol, nonylphenol, n-dodezylphenol, (propentetramer) -substituted phenol, octadecylphenol, eicosylphenol, polybutene-substituted (molecular weight about 1,000) Phenol, n-Dodezylresorzinol and 2,4-di-t-butylphenol and the alkyl-substituted catechols corresponding to the above-mentioned compounds. Also included are methylene bridged alkyl-substituted hydroxyaromatic compounds of the type prepared by reaction of an alkyl-substituted hydroxyaromatic compound with formaldehyde or with a formaldehyde-yielding reagent such as trioxane or paraformaldehyde.

The sulfurized alkyl-substituted hydroxyaromatic compound is typically prepared by reaction of the alkyl-substituted hydroxyaromatic compound with the sulfurizing agent at a temperature in the range of about 100 ° C to 250 ⁰ C. The reaction may be carried out in a substantially inert diluent such as toluene, xylene, petroleum naphtha, mineral oil, cellosolve or the like. When the sulfurizing agent is a sulfur halide, and especially when no diluent is employed, it is often advantageous to remove acidic substances, such as hydrogen halides, by vacuum stripping the reaction mixture or blowing it with a gas such as nitrogen. When the sulfurizing agent is sulfur, it is often advantageous to blow the sulfurized product with a carrying gas such as nitrogen or air, so as to remove sulfurous oxides and the like.

Also suitable as component (B) in the present invention are the antioxidants referred to in the following U.S. patents, the disclosures of which are hereby incorporated by reference in their entirety: U.S. Patent Nos. 3,451,136,345,849, 3,487,099, 3,511,780, 3,687,848, 3,770,854, 3,850,822 , 3876733, 3929654, 4115287, 4136041, 4153562, 4367152 and 4737301.

Component C

Component C of the present invention is a copper corrosion inhibitor and is composed of at least one oil-soluble compound containing an azole or azoline polysulfide component containing at least one heterocyclic ring having at least one N atom and at least one S atom and at least one N = C group (and preferably two N = C ring groups). Examples of these are 2,5-dimercapto-1,3,4-thiadiazole derivatives having the formula (XXVIII):

N - N

-, il Il

γ ¹ _ (s) w - C C-

and3,5-dimercapto-1, il, 4-thiadiazole derivative of the formula (XXIX):

Y ¹ - (S) _n - C - N

N C- (S) _- Y ²

wherein Y ¹ and Y ^{2 are the} same or different and are H, straight or branched alkyl, cyclic, alicyclic. Aryl, alkylaryl or arylalkyl radicals having from 2 to about 30 carbon atoms are -C (O) R ⁶ , -P (O) (OR ⁸ I ₂ and -C (S) N (R ⁶ I ₂ wherein R ^{6 is} a Hydrocarbyl is (eg, C 1 -C 6 -alkyl) and C 1 -C 6 -alkylene groups containing one or more carboxy, nitrophenyl, cyano, thiozyano, isocyanato, isothiocyano, alkylcarbonyl, thiocarbamyl, Amino or aryl groups are substituted (eg end-substituted), and in which one of the values Y ¹ and Y ^{2 may have the} following component:

N - K - (C ₁ -C ₆ -AIlCyIe _n) - (S) _w - C C (S) _z - R. ⁷

or the component:

(C _r C ₆ alkylene) - (S) _w -CN

NC - (S) ₂ - R ⁷

s'

wherein R ⁷ is H or C 1 -C 4 -hydrocarbyl (e.g., C 4 -C ₁₀ alkyl) and w and ζ are the same or different and numbers from 1 to about 9. Preferably, Y ¹ and Y ^{2 are the} same or different and each have from about 4 to about 16 carbon atoms, and most preferably between about 8 and about 14 carbon atoms, and the values of "w" and "z" are preferably from 1 to 4 In general, the sum of "w" + "z" is at least 3 (eg, 3 to 6).

One class of preferred additives of component (C) are the 1,3,5-thiadiazole derivatives represented by formula (XXX):

N-N

Ii _Λ 1

Y - (S) _w - C C-SH

's

wherein Y 'and "w" are as defined above, most preferably when Y ^{1 is} a hydrocarbyl having 8 to 14 carbon atoms and "w" is an integer from 1 to 4. Particularly suitable are 1,3,4-thiadiazole derivatives having the above-mentioned formula (XXX) in which Y 'is an alkyl having 8 to 14 carbon atoms (for example, n-octyl, isooctyl, 2-ethylhexyl, 5.5- Dimethylhexyl, nonyl, decyl, dodezyl, tridecyl, tetradecyl and the like) and wherein "w" is a number 2 or 3.

The polysulfide-2,5-dimercapto-1,3,4-thiadiazole and -S-di-mercapto-1-M-thiadiazole derivatives described herein can advantageously be prepared by known methods. For example, 2,5-dimercapto-1,3,4-thiadiazole can be reacted with a suitable sulfenyl chloride, or the dimercaptan can react with chlorine and the resulting disulfenyl chloride below

N - II

Il

Cl-S-C C-S-Cl

react with a primary or tertiary mercaptan. Bistrisulfidderivate are prepared by reacting Dimerkaptan with a mercaptan and a sulfur chloride in molar ratios of 1: 4 at a temperature between about 120 ° F and 212 ⁰ F (about 39 ⁰ C to 100 ⁰ C): 2: 2 to 1: 2 , Higher polysulfides can be prepared by reaction of the Thiadiazoldi- or trisulfides with sulfur at temperatures between about 9O ⁰ C and 200 ⁰ C. Another method of making polysulfides of the present invention involves the reaction of 2,5-dimercapto-1,3,4-thiadiazole with a mercaptan and sulfur in a molar ratio of 1: 1: 1 to 1: 4: 16 at temperatures between about 70 ° C and about 15O ⁰ C. compounds which were prepared in accordance with the method described above, preferably are polysulfides of 1,3,4-thiadiazole-2,5-bis (alkyl di-, tri- or tetrasulfide) containing from two to about 30 carbon atoms. Desirable polysulfides include 1, 3,4-thiadiazole-2,5-bis (octyl disulfide), 1,3,4-thiadiazole-2,5-bis (octyl trisulfide), 1,3,4-thiadiazole-2,5 -bis (octyl tetrasulfide), 1,3,4-thiazole-2,5- (nonyl disulfide), 1,3,4-thiadiazole-2,5- (nonyl trisulfide), 1,3,4-thiadiazole-2,5- (nonyl tetrasulfide), 1,3,4-thiadiazole-2,5-bis (dodecyl disulfide), 1,3,4-thiadiazole-2,5-bis (dodecyl trisulfide), 1,3,4-thiadiazole-2,5- bis (dodecyltetrasulfide), 2-lauryldithia-5-thiaalphamethylstyryl-1,3,4-thiadiazole and 2-lauryltritia-5-thia-alphamethylstyryl-1,3,4-thiadiazole, and mixtures thereof. Preferred substances are the derivatives of 1,3,4-thiadiazoles as described in US Pat. Nos. 2,719,125, 2,719,126 and 3,037,932, more preferably the compound is 2,5-bis (t-octadithio) -1,3,4 thiadiazole, which is known commercially as Amoco 150, and the compound 2,5-bis (nonyldithio) -1,3,4-thiadiazole, commercially available as Amoco 158

 Examples of the component (C) are also the following 1,3,4-thiadiazole derivatives having the formula XXVIII:

ζ Y ¹ -29- 295 394 Y ² W 2 H- lsooktyl 1 2 H- octyl 1 2 H- nonyl 1 2 H- dodecyl 1 2 H- decyl 1 2 H- Undezyl 1 2 H- styryl 1 2 H- Alpha methylstyryl 1 2 H- octadecyl 1 2 H- -C (S) N (C ₄ H ₉ I ₂ 1 2 H- -C (S) N (C ₂ H ₅ ) ₂ 1 2 H- -P (O) (OC ₄ Hg) ₂ 1 2 H- -P (O) (OC ₂ H ₅ I ₂ 1 2 H- -C (O) C ₈ H ₁₇ 1 2 H- -CH (CH ₃ ) OC ₆ H ₁₃ 1 2 H- -CH ₂ N (H) Ar 1 2 H- -CH ₂ N (CH ₃ ) (C ₂ H ₅ ) 1 2 H- -CHrPiperidyl 1 2 lsooktyl lsooktyl 2 2 octyl octyl 2 2 nonyl nonyl 2 2 dodecyl dodecyl 2 2 decyl decyl 2 2 Undezyl Undezyl 2 2 styryl styryl 2 2 Alpha Methylstyral Alpha methylstyryl 2 2 octadecyl octadecyl 2 2 -C (S) N (C ₄ Hg) ₂ -C (S) N (C ₄ Hg) ₂ 2 2 -C (S) N (C ₂ H ₅ I ₂ -C (S) N (C ₂ H ₅ ) ₂ 2 2 -P (O) (OC ₄ Hg) ₂ -P (O) (OC ₄ Hg) ₂ 2 2 -P (O) (OC ₂ H ₅ I ₂ -P (Ci (OC ₂ Hs) ₂ 2 2 -C (O) C ₈ H ₁₇ -C (O) C ₈ H ₁₇ 2 2 -CH (CH ₃ ) OC ₆ H ₁₃ -CH (CH ₃ ) OC ₆ H ₁₃ 2 2 -CH ₂ N (H) Ar -CH ₂ N (H) Ar 2 2 -CH ₂ N (CH ₃ ) (C ₂ H ₅ ) -CH ₂ N (CH ₃ ) (C ₅ H ₅ ) 2 2 -CH ₂ -piperidyl -CH ₂ scholarship 2

Note: "Ar" is phenyl.

The preparation of the above-mentioned substances of component (C) is further described in U.S. Patent Nos. 2,658,588, 270,337,8, 270,337, 17,217,225, 27,112,227, 27,272,271, 27,259, 457, 276,231, 27,259, 457, 275, 289, 3087932, 36663561, 3676449, 3759830, 3775321, 3850548, 3929652, 3966623, 40094880, 4104179, 4351, 945, 4410436, and 4, 536, 189, the disclosures of which are incorporated herein by reference in their entirety.

Also suitable as the material for component (C) are the reaction products of each of the abovementioned substances with phosphoric acid (eg dithiophosphoric acid), dihydrocarbyldithiophylactic acids (for example dialkyldithiophosphoric acid), terpene compounds (for example alpha-pinene), epoxides (B Ethylene oxide, propylene oxide, 1,2-epoxybutane, dodecylglycidyl ether, octyl glycidyl ether, butyl glycidyl ether, 1,2-epoxyhexadecene, epichlorohydrin, phenylglycidyl ether, glycidyl 2-ethylhexanoate, glycidyl oleate, peroxides (eg hydrogen peroxide), amines (ζ, B! Polyolefinsukzinimide, Dodezylsukzinimide), aldehydes and mixture of olefin and sulfur dichloride.

The preparation and structures of these fabrics and related suitable materials for component (C) are described in U.S. Patent Nos. 3,914,241, 4,882,942, 4,224,171, 4,487,706, 4,706,542 and 4,761,482 and in European Patent Publication 209730, the disclosures of which are fully incorporated herein by reference be included.

lubricant compositions

Lubricating oil compositions, e.g. Automatic transmission fluids, heavy duty oils suitable for diesel engines (i.e., compression-ignition engines), etc. can be made with the additives of the invention. It is also possible to produce universal crankcase oils in which the same lubricating oil compositions can be used both for gasoline and for diesel engines. These lubricating oil preparations contain in the conventional case several different types of additives, which give characteristics as needed in the preparations. These types of additives include viscosity improvers, ashless antioxidants, ashless corrosion inhibitors, pour point depressants, ashless capping agents, etc., provided that the finished oil preparation meets the ashless SASH requirements of the invention.

In the manufacture of heavy duty diesel lubricating oil preparations, it is common practice to add 10 to 80%, e.g. 20 to 80% active ingredient concentrates in hydrocarbon oil, ζ. As mineral lubricating oil or other suitable solvent to use. In general, these concentrates with 3 to 100, z. B. 5 to 40 parts by weight of the lubricating oil per part of the additive package in the manufacture of finished lubricants, for. B. crankcase engine oils.

The purpose of the concentrates is, of course, to simplify the handling of the various materials and to facilitate the solution or dispersion in the finished waste. Thus, an ashless dispersant of component A would generally be employed in the form of a 40 to 50% concentrate, for example in a lubricating oil fraction. Components A, B and C of the present invention are generally employed in admixture with a lubricating oil base material consisting of an oil of lubricating viscosity and including natural and synthetic lubricating oils and mixtures thereof.

Components A, B and Π may be incorporated into a lubricating oil in any suitable manner. Thus, these mixtures can be added to the oil just below their dissolution or dispersion in the oil at the desired level of detergent inhibitor concentration or antiwear agent concentration, respectively. This blending into the additional lubricating oil can be done at room temperature or at elevated temperatures. Alternatively, components A, B and C may be blended with a suitable oil-soluble solvent and base oil to form a concentrate, and this concentrate then blended with the lubricating oil stock to make the finished preparation. These concentrates typically contain (based on the weight of the active ingredient, [AI basis]). Between about 10 and about 70%, and preferably between about 30 and about 60% of the additive component A, the ashless dispersant, in the typically about 3 to 40%, preferably about 10 to 30% of additive B, of the antioxidant, typically about 0.05 to 5% and preferably between about 0.6 and 3% of component C, of the copper corrosion inhibitor, and typical case between about 30 and 80%, preferably between about 40 and 60% of the base oil, based on the concentrate weight.

The compositions of the invention are also characterized as ashless, that is, by a concentration of total sulfate ash (SASH) concentration of less than 0.01% SASH, preferably substantially zero. By "total sulfated ash" is meant the total weight percent of ash determined for a given oil (based on the metal components of the oil) according to ASTM D874.

The lubricating oil base for components A, B and C is typically tuned to a selected function by the inclusion of additional additives to produce lubricating oil compositions (i.e., lubricating oil preparations). Natural oils include animal and vegetable oils (e.g., castor and lard oil), petroleum-based liquid oils, and pressurized hydrocarbon-refined, solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also suitable base oils.

Alkylene oxide polymers and interpolymers and their derivatives in which the end hydroxyl groups have been modified by esterification, etherification, etc. represent another class of known synthetic lubricating oils. Examples include polyoxyalkylene polymers formed by polymerization of ethylene oxide or propylene oxide, the alkyl and aryl ethers these polyoxyalkylene polymers (eg, an average molecular weight of 1 000 molecular weight methyl polyisopropylene glycol ethers, 500-1000 average molecular weight diphenyl ethers of polyethylene glycol, 1000-500 molecular weight diethyl ether of polypropylene glycol) and their mono- and polycarboxylic acid esters, for example the acetic acid ester, mixed with Cj-Cs fatty acid esters and C _{) 3-} oxoacetic acid diesters of tetraethylene glycol. Another suitable class of synthetic lubricating oils includes the esters of dicarboxylic acids (e.g., phthalic, succinic, alkyl succinic and alkenyl succinic, maleic, azelaic, suberic, sebacic, fumaric, adipic, linoleic, malonic, alkenylmanonic, alkylmalonic) acids with a variety of alcohols (eg, butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). Specific examples of these ethers include dibutyl adipate, de (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodisyl azelate, dioctyl phthalate, didecyl phthalate, dieikosyl sebacate, the 2-ethylhexyl diesters of linoleic acid dimer, and the complex ester prepared by reaction of one mole of sebacic acid with two moles of tetraethylene glycol and two moles of tetraethylene glycol and two moles of 2-thylhexansäure.

Esters useful as synthetic oils also include those made from Cs-C 1-4 monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylol propane, pentaerythritol, dipentaerythritol and tripentaerythritol. Silicon-based oils such as the polyalkyl, polyaryl, polyalkoxy or polyaryloxy siloxane oils and silicate oils form another useful class of synthetic lubricants; these include tetraethyl silicate, tetraisopropyl silicate, tetra (2-ethylhexyldsilicate, tetra (4-methyl-2-ethylhexyl) silicate, tetra (p-tert-butylphenyl) silicate, hexa- (4-methyl-2-pentoxy) disiloxane, poly ( Other synthetic lubricating oils include liquid esters of phosphorus-containing acids (eg, tricresyl phosphate, tioctyl phosphate, diethyl ester of decylphosphonic acid) and polymeric tetrahydrofurans.

Unrefined, refined and recycled oils can be used in the lubricants of the present invention. Non-refined oils are those which are used directly from a natural or synthetic source without further purification treatment. For example, a shale oil recovered directly from the retort smoldering process, a petroleum-based oil coming directly from distillation, or an ester oil derived directly from an esterification process and used without further purification, would be an unrefined oil. Refined oils are similar to unrefined oils but have been further treated in one or more purification steps to improve one or more properties. Many such purification methods, such as distillation, solvent extraction, acids or base extraction, filtering and percolation, are known to those skilled in the art. Recycled oils are recovered by similar procedures to those used in refined oils, except that they are used on oils that have already been used as refined oils. These remanufactured oils are also referred to as regenerated oils or reused oils, and are often additionally treated by methods for removing used additives and oil degradation products.

The novel compositions of the present invention can be used with viscosity improvers to produce multigrade lubricating oils for diesel engines. Viscosity modifiers give lubricating oils the ability to operate at high and low temperatures, and enable the oils to remain relatively viscous at relatively high temperatures and also to have adequate low temperature viscosity or flowability. Viscosity modifiers are generally high molecular weight hydrocarbon polymers, including

the polyester. The viscosity modifiers may also be derived to include other properties or functions, such as the addition of disperse sizing agents. These oil-soluble viscosity modifying polymers generally have an average molecular weight of from 10 ³ to 10 ⁶ , preferably from 10 ⁴ to 10 ^e , eg 20,000 to 250,000 as determined by gel permeation chromatography or osmometry.

Examples of suitable hydrocarbon polymers include homopolymers and copolymers of two or more monomers of OH ^ -olefins, * · B-Cz-Cg-olefins, including the alpha-olefins and ο-internal olefins, straight or branched, aliphatic, aromatic , alkylaromatic, cycloaliphatic, etc. may be. Often it is ethylene with Cr-Cso olefins, the copolymers of ethylene and propylene are particularly preferred. It is also possible to use other polymers such as polyisobutylenes, homopolymers and copolymers of C ₆ and higher alpha-olefins, atactic polypropylene, hydrieite polymers and copolymers and terpolymers of styrene, e.g. B. with isoprene and / or butadiene and their hydrogenated derivatives. The polymer may be reduced in molecular weight, for example by mastication, extrusion, oxidation or thermal degradation, and may be oxygenated and contain oxygen.

The preferred hydrocarbon polymers are ethylene copolymers containing between 15 and 90% of ethylene, preferably between 30 and 80% of ethylene, and 10 to 85%, preferably 20 to 70% of one or more C ₃ -C ₂₈ -alpha-olefins, preferably Cs-Cie Alpha-olefin, and especially Ca-Cg alpha-olefins. These copolymers, although not essential, preferably have a degree of crystallinity of less than 25%, as determined by X-ray examination and differential scanning calorimetry. Copolymers of ethylene and propylene are most preferred. Other alpha olefins which may be used in place of propylene to form the copolymer or may be used in conjunction with ethylene and propylene to form a yer polymer, a tetrapolymer, etc. include 1-butene, 1-pentene, 1-hexene , 1-heptene, 1-octene, 1 -none, 1-diene, etc., as well as branched alpha-olefins, such as 4-methyl-1-pentene, 4-methyl-1-hexene, 5-methylpentene-1, 4, 4-dimethyl-1-pentene and 6-methyl-hopten 1, etc., as well as their mixtures.

Also, terpolymers, tetrapolymers, etc. of ethylene, the Cj-C _2e- alpha-olefins and a non-conjugated diolefin or a mixture of these diolefins can be used. The amount of nichiconjugated diolefin is generally between about 0.5 and 20 mol%, preferably between about 1 and about 7 mol%, based on the total amount of ethylene and alpha-olefin present.

One class of preferred polymers used as viscosity modifiers is disclosed in U.S. Patents Nos. 4,540,753 and 4,804,494, the disclosures of which are incorporated herein by reference in their entireties.

Also included are nitrogen and ester-containing polymeric viscosity improvers dispersants which are derived polymers, such as the post-polymerized intermediate polymers of ethylene-propylene with an active monomer such as maleic anhydride which can be further reacted with an alcohol or an amine, e.g. An alkylenepolyamine or a hydroxyamine, see e.g. U.S. Patent Nos. 4,039,794,4160739, 4,137,185; or copolymers of ethylene and propylene which have been reacted or grafted with nitrogen compounds, as shown, for example, in U.S. Patent Nos. 4,068,056,406,805, 4,146,489 and 4,149,984.

The polyester viscosity improvers are generally polymers of esters of ethylenically unsaturated Ca-Cg mono- and di-carboxylic acids such as methacrylic and acrylic acids, maleic acid, maleic anhydride, fumaric acid, etc.

Examples of unsaturated esters that can be used include those of aliphatic, saturated monoalcohols having at least one carbon atom and preferably 12 to 20 carbon atoms, such as decyl acrylate, lauryl acrylate, stearyl acrylate, eicosanyl acrylate, docosanyl acrylate, decyl methacrylate, diamyl fumarate, lauryl methacrylate, cetyl methacrylate, stearyl methacrylate and similar, and their mixtures.

Other esters include the vinyl alcohol esters of C ₂ -C ₂₂ fatty or mono carboxylic acids, preferably saturated ones such as vinyl acetate, vinyl laurate, vinyl palmitate, vinyl stearate, vinyl oleate and the like, and mixtures thereof. Copolymers of vinyl alcohol esters with unsaturated acid esters, such as the copolymer of vinyl acetate with dialkyl fumarates, may also be used.

The esters may also be copolymerized with other unsaturated monomers, such as olefins, e.g. B. 0.2 to 5 moles of aliphatic or aromatic C 2 -C 20 olefin per mole of unsaturated ester or per mole of unsaturated acid or acid anhydride, followed by esterification. For example, copolymers of styrene with maleic anhydride esterified with alcohols and amines are known, see e.g. US-PS 3702300.

These ester polymers can be grafted with polymerizable, unsaturated, nitrogen-containing monomers or the copolymerized to give the viscosity improvers dispersibility. Examples of suitable unsaturated nitrogen-containing monomers are those containing from 4 to 20 carbon atoms, for example, amino-substituted olefins such as p- (beta-diethylaminoethyl) styrene, basic nitrogen-containing heterocycles bearing a polymerizable, ethylenically unsaturated substituent, e.g. the vinylpyridines and the vinylalkylpyridines, such as 2-vinyl-5-ethylpyridine, 2-methyl-5-vinylpyridine, 2-vinylpyridine, 4-vinylpyridine, 3-vinylpyridine, 3-methyl-5-vinylpyridine, 4-methyl-2 vinylpyridine, 4-ethyl-2-vinylpyridine and 2-butyl-1-1,5-vinylpyridine and the like.

Also suitable are N-vinyl lactams, z. N-vinylpyrrolidones or N-vinylpiperidones.

Preference is given to vinylpyrrolidones and examples of these include N-vinylpyrrolidone, N- (1-methylvinyl) pyrrolidone, N-vinyl-5-methylpyrrolidone, N-vinyl-3,3-dimethylpyrrolidone, N-vinyl-5-ethylpyrrolidone, etc.

These nitrogen and ester-containing polymeric viscosity index improving dispersants are generally employed in concentrations between about 0.05 and 10% in the finished oil, and preferably about 0.1 to 5%, and more preferably about 0.5 to 3% reduce the amount of the above-mentioned component (A), ashless dispersant (eg, to about 0.5%), which is used to ensure the required dispersibility of the oil preparation.

Other antioxidants useful in the present invention include oil-soluble copper compounds.

The copper may be mixed into the oil in the form of any suitable oil-soluble copper compound. By oil-soluble is meant that the compound is oil-soluble under normal mixing conditions in the oil or additive package. The copper compound may have a copper (I) or copper (II) form. The copper may be used in the form of copper dihydrocarbyl thio- or dithiophosphates wherein copper may be substituted for zinc in the above-described compounds and reactions wherein one mole of the copper (I) or copper (II) oxide is substituted with a metal oxide Two moles of dithiophosphoric acid can be reacted. Alternatively, the copper may be added as a copper salt to a synthetic or natural carboxylic acid

become. Examples of the _{C) 0-C)} include ₈ fatty acids such as stearic or palmitic acid, but unsaturated acids such as oleic acid or branched carboxylic acids such as naphthenic acids having a molecular weight of from 200 to 500, or synthetic carboxylic acids are due to better Handling and solubility properties of the resulting copper carboxylates are preferred. Also suitable are oil-soluble copper dithiocarbamates having the general formula (RFVNCSS) _n Cu, where η is 1 or 2 and R and R 'are the same or different hydrocarbyl radicals having from 1 to 18 carbon atoms and preferably from 2 to 12 carbon atoms, including such radicals as alkyl radicals. , Alkenyl, aryl, aralkyl, alkaryl and cycloaliphatic radicals. Particularly preferred values for the R and R 'groups are alkyl groups having 2 to 8 carbon atoms. For example, the radicals may be ethyl, n -propyl, i -propyl, η-butyl, i -butyl, sec -butyl, amyl, n -hexyl, i -hexyl, n -heptyl, n-octyl, decyl, dodecyl, octadecyl , 2-ethylhexyl, phenyl, butylphenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl, etc. In order to achieve oil solubility, the total number of carbon atoms (ie, R and R ') is generally about 5 or more. Also, copper sulfonates, phenates and acetylacetonates have been used. Examples of suitable copper compounds are copper salts (Cu ¹ and / or Cu "salts) of alkenyl succinic acids or anhydrides The salts themselves may be basic, neutral or acidic They may be prepared by reaction of (6a) one of the materials have been discussed above in the section on ashless dispersants and have at least one free carboxylic acid group (or carboxylic acid anhydride group) with (b) a reactive metal compound Suitable acid-reactive (or acid anhydride-reactive) metal compounds include such as copper (II) or copper (I) hydroxides, oxides, acetates, borates and carbonates or basic copper carbonate.

Examples of the metal salts of the present invention are Cu salts of polyisobutenyl succinic anhydride (hereinafter referred to as Cu-PIBSA) and Cu salts of polyisobutenyl succinic acid. Preferably, the selected metal that is employed is in the divalent form, e.g. For example, Cu ⁺² . The preferred substrates are polyalkenyl succinic acids in which the alkenyl group has an average number average molecular weight (M _n ) greater than about 700. The alkenyl group preferably has an M _n between about 900 and 1400 and up to 2500, with an M _n of about 950 being most favorable. Of the compounds listed above in the Dispersants section, polyisobutylene succinic acid (PIBSA) is most preferred. These substances can be advantageously dissolved in a solvent, such as a mineral oil, and heated in the presence of a water solution (or slurry) of the metal-bearing material. The heating can be carried out at 7O ⁰ C to about 200 ° C. Temperatures of 110 ° C to 14O ⁰ C are perfectly adequate. Depending on the salt produced, it may be necessary to increase the temperature to above about 140 ° C for a longer time, e.g. B. more than 5 hours, to avoid, otherwise a decomposition of the salt can occur.

The copper antioxidants (eg, Cu-PIBSA, Cu-oleate, or mixtures thereof) will generally be present in an amount of between about 50 and 500 particles / mill. the weight of the metal used in the finished lubricant or fuel composition.

The copper antioxidants used in this invention are inexpensive and effective at low concentrations so that they do not add significantly to the cost of the product. The results obtained are often better than those achieved with the previously used antioxidants, which are expensive and used in higher concentrations. At the amounts used, the copper compounds do not affect the performance of the other components of the lubricant composition.

Although it is possible to include in the lubricating oil composition any effective amount of the copper antioxidant, it is believed that effective amounts are sufficient which introduce into this lubricating oil composition an amount of copper antioxidant which is between about 5 and 500 (preferably 100 to 200.10 to 180 or at best 20 to 130 [eg 90 to 120]) particles / mill. of the added copper based on the weight of the lubricating oil composition. Of course, the preferred amount may be u.a. be dependent on the quality of the lubricating oil base material.

Part B components may also employ other oxidation inhibitors to help reduce, if desired, the tendency of mineral oils to deteriorate during use, and hence the formation of oxidation products such as sludge and varnish deposits on the metal surfaces lower and reduce the increase in viscosity. These other oxidation inhibitors include alkaline earth metal salts of alkylphenol thioesters having preferably C ₅ -C ₂ alkyl side chains (such as calcium nonylphenol sulfide, barium-t-octylphenyl sulfide, etc.). Other corrosion inhibitors, also called corrosion inhibitors, can be used in addition to component (C) to further reduce the degradation of the non-ferrous metal parts that come in contact with the lubricating oil composition. As examples of corrosion inhibitors may be mentioned phosphosulfurized hydrocarbons and the products made by reacting a phosphosulfurized hydrocarbon with an alkaline earth metal oxide or hydroxide, preferably in the presence of an alkylated phenol or an alkylphenol thioester, and preferably also in the presence of carbon dioxide. Phosphosulfurized hydrocarbons are formed by reacting a suitable hydrocarbon, such as a terpene, a heavy petroleum fraction of Cz-Ce-olefin polymer, such as polyisobutylene, with 5 to 30% of a phosphorous sulfide for 0.5 to 15 hours at a temperature in the range of 65 ° C to 32O ⁰ C, prepared. The neutralization of the phosphosulfurized hydrocarbon can be carried out as described in U.S. Patent No. 1,969,324.

Friction modifiers serve to impart corresponding frictional properties to lubricating oil compositions, such as automatic transmission fluids.

Representative examples of suitable friction modifiers are described in US Pat. No. 3,933,659, which discloses fatty acid esters and amides; U.S. Patent 4,174,074, which describes molybdenum complexes of polyisobutenyl succinic anhydride aminoalkanols; U.S. Patent 4,105,571 which discloses glycerol esters of dimerized fatty acids; U.S. Patent 3,774,928, which discloses alkane phosphonic acid salts; in U.S. Patent 3,778,375 which discloses reaction products of a phosphone with an oleamide; U.S. Patent 3,852,205 which discloses S-carboxyalkylene hydrocarbyl succinimide, S-carboxyalkylene hydrocarbyl succinic acid and mixtures thereof; U.S. Patent 3,879,306 which discloses N- (hydroxyalkyl) alkenylsuccinamic acids or succinimides; in US Pat. No. 3,932,290, which discloses reaction products of di (lower alky phosphites and epoxides, and US Pat

discloses the alkylene oxide adduct of phosphosulfurized N-hydroxyalkyD alkenylsuccinimides. The disclosures of the above patents are incorporated herein by reference. Most preferred as friction modifiers are glycerol mono- or dioleates and succinate esters or their metal salts of hydrocarbyl substituted succinic acids or anhydrides and thiobis alkanols as described in US Pat. No. 4,344,853.

Pour point depressants lower the temperature at which the flowing medium flows or can be poured. Such agents are well known. Typical of these additives suitable for optimizing the low temperature fluidity of the flowing medium are Cg-Cie dialkyl fumarate vinyl acetate copolymers, polymethacrylates and wax naphthalenes.

Foam control can be accomplished by a polysiloxane type antifoam agent, e.g. Silicone oil and polydimethylsiloxane.

Organic, oil-soluble compounds useful in this invention as rust inhibitors include nonionic surfactants such as polyoxyalkylene polyols and their esters, and anionic surfactants such as the salts of alkylsulfonic acids. Such antirust components are known and can be prepared in a conventional manner. Nonionic surfactants useful as anti-rust additives in the oleagenic compositions of this invention generally return their surfactant properties to a number of weak stabilizing groups, such as ether bonds. Nonionic rust inhibitors containing ether linkages can be prepared by alkoxylating organic substrates containing active hydrogen atoms with an excess of lower alkylene oxides (such as ethylene and propylene oxides) until the desired number of alkoxy groups have been introduced into the molecule.

The preferred rust inhibitors are polyoxyalkylene polyols and their derivatives. This class of materials is commercially available from several sources: Pluron polyols from Wyandotte Chemicals Corporation; Polyglycol 112-2, a liquid triol derived from ethylene oxide and propylene oxide, is available from Dow Chemical Co., and tergitol, dodecylphenol or monophenyl polyethylene glycol ethers, and Ucon, polyalkylene glycols and derivatives are both from Union Carbide Corp.

available. These are but a few of the commercial products that are useful as rust inhibitors in the improved compositions of the present invention.

In addition to the polyols themselves, their esters can be obtained by reaction of the polyols with various carboxylic acids and also be used. Acids useful in the preparation of these esters include lauric acid, stearic acid, succinic acid, and alkyl- or alkenyl-substituted succinic acids wherein the alkyl or alkenyl group contains up to about twenty carbon atoms.

The preferred polyols are prepared as block polymers. Thus, a hydroxy-substituted compound, R- (OH) _n (wherein η is 1 to 6 and R is the residue of a mono- or polyhydric alcohol, phenol, naphthol, etc.) is reacted with propylene oxide to form a hydrophobic base. This base is then reacted with ethylene oxide to form a hydrophilic portion which gives a molecule having hydrophobic and hydrophilic portions. Theelative size of these sections can be tuned by regulating the ratio of reactants, reaction time, etc., as will be apparent to those skilled in the art. Thus, it is known in the art to prepare polyols whose molecules are characterized by hydrophobic and hydrophilic components which are present in a proportion which makes rust inhibitors suitable for use in any lubricant composition, notwithstanding the differences in base oils and the presence of other additives ,

If greater oil solubility is required in a given lubricant composition, the hydrophobic portion may be increased and / or the hydrophilic portion may be reduced. If a greater oil-in-water break-through ability of the emulsion is required, the hydrophilic and / or hydrophobic portion can be tuned to accomplish this.

The compounds exemplified by R- (OH) _n include alkylene polyols such as the alkylene glycols, alkylene triols, alkylene tetrols, etc., such as ethylene glycol, propylene glycol, glycerol, pentaerythritol, sorbitol, mannitol, and the like. Aromatic hydroxy compounds such as alkylated mu. ^ O- and polyhydric phenols and naphthols can also be used / .. B.

Heptylphonol, dodecylphenol, etc.

Other suitable demulsifiers include the esters disclosed in U.S. Patents 3,098,827 and 2,674,619.

The liquid polyols available from Wyandotte Chemical Co. under the name Pluronic Polyols and other similar polyols are particularly suitable as rust inhibitors. These Pluronic polyols correspond to the formula:

HO- (CH ₂ CH ₂ O) _x (CHCH ₂ O) _y (CH ₂ CH ₂ O), H (XXXI),

wherein x, y and ζ are integers greater than one such that the -CH ₂ CH ₂ O groups account for about 10% to about 40% of the total molecular weight of the glycol, the average molecular weight of this glycol being between about 1 000 and about 5000 lies. These products are made by first condensing propylene oxide with propylene glycol to form the hydrophobic base

HOI-CH-CH ₂ -Oly-H (XXXII)

CH ₃

manufacture. This condensation product is then treated with ethylene oxide to add hydrophilic sections at both ends of the molecule. For best results, the ethylene oxide units should account for about 10% to about 40% of the weight of the molecule. Particularly useful are the products wherein the molecular weight of the polyol is between about 2,500 and 4,500 and the ethylene oxide units comprise about 10% to about 14% of the weight of the molecule. Polyols with a molecular weight of about 4000, of which about 10% are due to the (CH ₂ CH ₂ O) units, are particularly good. Also suitable are alkoxylated fatty acid amines, amides, alcohols and the like, including the alkoxylated fatty acid derivatives which are reacted with C ₉ -C ₁₆ alkyl-substituted phenols (such as mono- and diheptyl, octyl, nonyl, decyl, undecyl, dodecyl). and tridecylphenols), as described in US Pat. No. 3,849,501, which is incorporated herein by reference in its entirety.

These compositions of the present invention may also contain other additives such as those already described and other metal-containing additives, for example, barium and sodium containing.

Other suitable additives are the thio and polythiosulfenamides of thiadiazoles, as described in British Patent 1,560,030. When these compounds are included in the lubricant composition, they are preferably present in an amount of from 0.01 to 10%, especially from 0.1 to 5.0%, based on the weight of the composition.

Some of these numerous additives can cause the multiplicity of effects, e.g. B. a dispersant oxidation inhibitor. This method is well known and need not be further elaborated here.

When compositions containing these conventional additives are typically mixed in the base oil in such amounts that their normal characteristic function is achieved. Renräs'Mtative effective amounts of these additives (given as the corresponding active ingredients) in the finished oil are given below:

compositions Wt .-% A.I. Wt .-% A.I. (Prefers) (Wide Erber.) Component A 4-7 3-10 Component B 0.5-4 0.2-6 Component C 0.05-0.4 0.01-0.6 viscosity modifiers 0-4 0-12 Other corrosion inhibitor. 0.01-0.5 0-1.5 Other oxidation inhibitors. 0-1.5 0-5 pour point depressants 0.01-0.5 0.01-1.0 Anti-foaming agent 0.001-0.01 0.001-0.1 Non-metallic Ver schleißschutzmittel 0.001-1.5 0-5 friction modifiers 0.01-1.5 0-5 Schmi ;. -T'ttelgrundöl compensation compensation

When component (B) comprises a sulfurized, alkyl substituted hydroxyaromatic compound (e.g., sulfurized, alkyl substituted phenol), the sulfurized, alkyl substituted, hydroxyaromatic compound is preferably oil in an amount of about 2 to 6%, and especially used by about 2.2 to 4%. It is also possible to use lower amounts of the sulfurized, alkyl-substituted, hydroxyaromatic compound (for example, it may be used in amounts of between about 0.5 and 3%), if in the composition a mixture of such compounds and other oil-soluble antioxidants (such as which is set forth above) is used as component (B) (for example, mixtures with oil-soluble, sulfurized organic compounds, oil-soluble amino antioxidants, oil-soluble organoborates, oil-soluble organophosphites, oil-soluble organophosphates, oil-soluble oranodithiophosphates, and mixtures thereof). In addition, in these finished oils, the weight% concentrations of components A (wt.% _A ), B (wt.% _B ) and C (wt.% C) are chosen to be wt%. _A > (wt .-% _B + wt .-% _c ) and preferably wt .-% _A > wt .-% _B > wt .-% _c . When other additives are used, it may be desirable, although not necessary, to make additive concentrates having concentrated solutions or dispersions of the novel ashless dispersant-antioxidant thiadiazole corrosion inhibitor mixtures of this invention (in the concentrate levels described above) along with one or more of the other additives (where this concentrate, if it is an additive mixture, is referred to herein as an additive package) whereby several different additives can be added to the base oil simultaneously to form the lubricating oil composition. Dissolution of the additive concentrate in the lubricating oil can be facilitated by solvents and low heat mixing, but that is not essential. The concentrate or supplemental package is typically FsII-designed to contain the additives in the appropriate amounts to achieve the desired concentration in the final preparation when the additive package is combined with a specified amount of the lubricant base oil. Thus, the detergent-inhibitor antiwear compositions of the present invention may be added to small amounts of the base oil or other compatible solvents along with other desirable additives to form additive packages containing active ingredients in combined amounts of about 2.5 to about 90%, typically and from about 15 to about 75% in the preferred case and from about 25 to about "0% in the best case, as weight additives in the respective proportions while the remainder is base oil.

The finished preparations may typically contain about 10% of the additive package while the remainder is base oil. All% by weight given herein are based (unless otherwise indicated) on the active ingredient content in the additive and / or on the total weight of the supplemental pack or preparation, which is the sum of the weight of the active ingredient of each additive plus the weight of the additive whole oil or diluent.

The invention will be further described by reference to the following examples, all parts of which are by weight unless otherwise indicated and which include preferred embodiments of the invention.

Examples

A series of finished lubricating oils SAE 15W40 were prepared containing the components listed in Table I.

Table I Test preparations (Vol .-%)

comparison comparison example example A B 1 2 7.57 5.54 7.57 7.57 2.83 1.8 2.83 2.83 1.75 1.45 1.35 - 1.19 1.45 0.51 - - - - 0.25 8.82 - 8.20 8.50 compensation compensation compensation compensation 8.4 8.0 5.0 2.4 0.85 0.84 0.44 0

PIBSA-PAM dispersant "

Sulfurized alkylphenol antioxidant ² '

Zinc Dia Ikyldithiophosphate Anti Wear Agent ³¹

Overbased Mg sulfonate detergent inhibitor "

AlkylierterDithiazolkorrosionshemmstoff

Viscosity improver ⁶¹

Base oil ⁷¹

SASH ⁹¹

Anmorkungan

1 mixtures of 5.93VoI.% Polyisobutonylsuccinimide (1.58 wt% N, 950M _n PIB, SA: PIB molar ratio 1.0, 0.35% B, 51.5% active ingredient) and 1.64vol % Polyisobutonylsuccinimide, 1.46 wt% N, 1300M _n PIB, SA: PI8 molar ratio 1.2.0.32 wt% B, 50.8% active ingredient). By the SA: PIB molar ratio is meant the moles of succinic anhydride reacted per mole of polyisobutylene to form the polyisobutenyl succinic anhydride used to make the described succinimides.

2 Sulfurized nonylphenol (70% active ingredient, 7% S).

3 COMPARATIVE EXAMPLE A: MSVol ^ 'oZine dihydrocarbyldithiophosphate IZDDPj antiwear additive. Wobeidio alkyl groups containing carbon atoms prepared by reaction of P ₂ S ₅ with isooctyl alcohol to give a phosphorus content of about 7% by weight; 0.30vol% ZDDP anti-wear additive wherein the alkyl group was a mixture of these groups having between 4 and 5 carbon atoms, prepared by reacting P ₂ S ₅ with a mixture of about 65% isobutyl alcohol and 35% amyl alcohol to provide a phosphorus content of about 8%. Comparative Example B and Examples 1 and 2: 1.45% by volume ZDDP antiwear agent wherein the alkyl groups contained 8 carbon atoms, prepared by reaction of P ₂ S ₅ with isooctyl alcohol to give a phosphorus content of about 7%.

4 overbased Mg sulfonate (based on an alkyl tartaric acid), 400TBN, 51.7% active ingredient, 9.2% Mg).

5 2,5-bis (nonycithio) -1,3,4-thiadiazole (Amoco 158; Amoco Chemical Company).

6 Comparative Example A and Example 1 = Concentrate of Ethylene-Propylene-Copolymor Viscosity Enhancers (43% ethylene, Thickening Effect 2.8, 10% active ingredient).

7 Principally Base oil Solvent 150 Neutral.

8 total baseline number; ASTM D2896.

9 Total level of sulphated ash (ASTM D874).

The specimens are subjected to a field test Cummins NTC-400 (loads = cooling hanger, 80000 pounds gross vehicle weight), load factor about 80%; US mainland (except Alaska), the largest part of the Dallas transportation route to the Pacific Northwest, using diesel fuel with <0.3% sulfur.

The following commercial trials also included the following commercial SAE 15W40 lubricating oils. These preparations contain ashless dispersant, overbased alkaline earth metal detergent inhibitors, and zinc dihydrocarbyl dithiophosphate wear protectants.

Test comparison oils Wt .-% SASH TBN (D 2896) OEIC 1.0 10 Oil D 1.1 12 Oil E 0.72 6.9 Oil F 1.0 10 Oil G 1.0 8th Oil H 1.0 8th Oil I 1.0 8th ÖIJ 0.9 7 Oil K 1.95 14

The data obtained are shown in Table III.

Table III

Comparative Examples

A B C D e F - G H I Unit Mileage 196K 207 K 175 K 195K 211K 189K ^# - 187K 173K 200K Avg. mud 9.84 9.78 9.76 9.83 9.75 9.81 - 9.76 9.75 9.74 TGF,% 67 40 40 70 56 - - 63 64 84 2.GF,% 39 39 34 49 85 - 513 73 40 47 3.GF,% 8th 5 0 1 15 - Ex. 6 5 6 4GMangel 0.59 1.29 0.32 0.67 1.86 - 2 0.63 0.71 0.21 Kopffiäche Heavy Coal,% 8th 9 24 10 7 15 7 22 43 Polished carbon,% 17 35 59 35 29 45 39 33 49 Clean, % 1 0 0 0 1 0 3 8th 0 Deficiencies total area 21.59 26.42 28.8 22.73 36.37 31.47 28,11 27,55 Deficiencies lower Ber. 5.13 5.44 1.88 3.51 10.00 3.19 4.19 3.69 Unweighted M., sat. 137 115 119 138 199 180 140 167 Rated M angel, sat. 987 1073 872 889 2144 1574 1022 1069 Ol economy, mile / quantity 524 473 609 1024 450 612 694 312 average Ex. J K commercial 1 oils

183K

9.73

2.21

35.14

4.88

185

1840

332

177K

9.73

0.7

20.4

2.0

137

703

613

190K

9.78

63

50

5.9

0.92

20.72

37.1

1.6

27.86

4.39

151.7

1217

536

Sigma (G)

12.8

0.04

19.8

4.4

0.66

17.6

11.0

2.6

5.4

2.31

29.0

471

203

168K

9.76

35

66

1.8

10

31

12

28.4

7.8

138

1355

359

186K 9.74 67 76

3.2

35.7 9.2 189 1757 349

Table III, continued

Comparative Examples

A B C D e F G H I working cylinder Max. Wear, inches 0.0015 0.0018 0.0028 0.0018 0.0023 0.0025 0.0008 0.0022 0.0017 Avg. Max. Wear, inches 0.0012 0.0012 0.0022 0.0012 0.0021 0.0023 0.0007 0.0015 0.0013 Wear rate, inches / 100 k-mile 0.0006 0.0006 0.0013 0.0006 0.0010 0.0012 0.0004 0.0009 0.0007 Obtained honey,% 83 93 95 95 92 92 88 94 92 Bore policies,% 7 7 2 2 8th 7 9 7 9 Annular gap, inch N ° 1 0,025 0.026 0.024 0.028 0.027 0.027 0,030 0.027 0,025 N ° 2 0.031 0,039 0.028 0,030 0.028 0.031 0, C28 0,030 0,030 N ° 3 0.024 0.027 0.023 0,029 0.026 0.028 0.028 0.027 0,025 N ° 4 0.024 0,020 0.019 0,020 0.019 0,025 0,025 0,020 0.019 Connecting rod bearing,% C4 pole 0 0 0 0 0 0 0 0 0 cap 0 0 0 0 0 0 0 0 0

* Values above piston deposits not available - Pistons cleaned and reused by service personnel.

K average Sigma (G) Ex. Bcisp. commercial 0.0006 1 2 oils 0.0005 0.0015 0.0003 0, OC15 0.0013 0.00185 4.9 0.0017 0.0018 0,00.3 0.0007 0.0015 2.5 0.0017 0.0018 0.0007 80 0.0003 0,002 0.0010 0 0010 93 9 90.6 0,002 80 td 7 0,022 6.7 0,002 9 10 0,025 0,029 0.026 0,003 Ο, ΟΪ2 12:02. ¹ 0.024 0.026 0,029 _ 0,02α 0,029 0.024 C.014 0.026 0.028 0,029 0,021 0 0,021 0,014 0.019 0 0 0 0 0 0 0 0 0

It can be seen from the data in Table III that the oils of Examples 1 and 2 provide better head cleanliness without affecting the other performance characteristics.

The ashless oils of the present invention are particularly suitable for heavy duty diesel engines with roller cam followers. The ashless oils of the invention are preferably used in heavy duty diesel engines normally associated with liquid fuels having a sulfur content of less than 1.0%, more preferably less than 0.5%, even better less than 0.3% (eg between about C, 1 and about 0.3%) and most preferably less than 0.1% (eg between 100 and 500 particles / million sulfur). These normally liquid fuels include hydrocarbonaceous petroleum distillate fuels such as diesel fuels or fuel oils as defined by ASTM Specification D396. Compressor ignition engines may normally burn liquid fuel compositions consisting of non-hydrocarbonaceous materials such as alcohols, ethers, nitroorgaric compounds, and the like (eg, methanol, ethanol, diethyl ether, methyl ethyl ether, nitromethane); Imagine the invention as liquid fuels derived from vegetable or mineral sources such as cereals, alfalfa, shale and coal. Also contemplated are normally liquid fuels which are mixtures of one or more hydrocarbonaceous fuels and one or more non-hydrocarbonaceous substances. Examples of such mixtures are combinations of diesel fuel and ether. Particularly preferred is the Diesekroftstoff N ° 2. The lubricating oils according to the invention are particularly suitable in the crankcase of diesel engines with cylinders (generally between one and eight or more cylinders per Mo'or), where for the cyclic, vertically reciprocating movement, a piston is housed, which with a tight-fitting Head face is provided, ie, cylinder, be ^! The distance between the head face of the piston and the cylinder jack is small in order to minimize the amount of particulates generated in the combustion chamber of the cylinder (where the fuel is burned to generate energy). Such close fitting head surfaces can ai ¹ h Krafistoffeffektivität improve and increase the effective compression ratio in the cylinder. The top surface comprises dan area of the generally cylindrical piston above the top piston ring groove, and the head face isi therefore generally by a circular cross section (along the longitudinal axis of the piston) in. The outer periphery of the head face may enclose a substantially vertical surface which is constructed to be substantially parallel to the vertical walls of the cylinder liner. (Such head flats are referred to herein as "cylindrical head surfaces.") However, the head surface may also be, and this is preferred, inwardly toward the center of the piston from the point where the head surface contacts the upper piston ring groove and the top surface of the piston. that is, the "crown" is adjacent, be conical. The distance between the top surface and the cylinder wall bushing, referred to herein as "head clearance", is preferably between about 0.010 and 0.030 inches (about 0.254 and 0.762 mm) for cylindrical top surfaces the point at which the head face joins the upper piston ring groove) is preferably about 0.005 to 0.030 inches (0.127 to 0.762mm), more preferably about 0.010 to 0.020 inches (0.254 to 0.508mm), and the top head clearance, ie, head head clearance Preferably, the piston crown is about 0.010 to 0.045 inches (0.254 to 1.143 mm), and more preferably about 0.015 to 0.030 inches (0.381 to 0.762 mm) The head clearance may be less than the dimensions given above (e.g., less than 0.105 Inch - 0.127 mm), if these smaller distances do not lead to undesirable contact of the top surface section of the piston with the cylinder logbook e during operation of the engine, which is not desirable due to the resulting damage to the socket. In general, the height of the head face (ie, the vertical distance from the bottom of the head face to the top of the head face measured along the cylinder wall bushing) is between about 0.1 and about 1.2 inches (2.54 and 30.48mm) In general, four-stroke diesel engines have between about 0.8 and 1.2 inches (20.32 and 30.48 mm) and between about 0.1 and 0.5 inches (2.54 and 12.7 mm) in two stroke diesel engines. The construction of diesel engines and pistons with such close-fitting head surfaces is within the known technical skills urd need not be further described here.

The term "oil" is used herein to mean that the additive or specified material is soluble, can be dissolved in oil with the aid of a suitable solvent, and is dispersible in a stable manner The term "oil-soluble" does not necessarily state that the additive or material is soluble (or dissolvable, miscible or suitable, suspendable) in oil in all proportions. However, it does mean that the additives, for example, are sufficiently soluble (or stably dispersible) in oil to exert the desired effect in the environment in which the oil is employed. In addition, the additional inclusion of other additives may also allow the inclusion of higher levels of a particular polymer adduct, if desired.

The principles, preferred embodiments, and modes of operation of the present invention have been described in the above-mentioned patent. The invention which is to be protected here, however, is not intended to be limited to the particular disclosed embodiments, as they are to be considered as illustrative and not restrictive. Those skilled in the art can make variations and variations without departing from the spirit of the invention.

CONSUMPTION ΛΝ OIL NTC-400

At interval centers

50 100

test hours

ο = oil preparation from example 3 • = reference oilCTCM-3

Claims (30)

An ashless lubricating oil composition for heavy duty diesel engine crankcase consisting of a major amount of an oil of lubricating viscosity and (A) at least 2% by weight of at least one high molecular weight, ashless dispersant, (B) an antioxidant effective amount of at least one oil soluble antioxidant, and (C ) a corrosion-inhibiting amount of at least one oil-soluble sulfur compound containing an azole or azole component having at least one N-ring atom and at least one S-ring atom and at least one N = C ring group, wherein the lubricating oil composition is denoted by a total value sulphated ash (SASH value) of less than 0.01% by weight. 2. A composition according to claim 1, characterized in that the oil-soluble sulfur compound has at least one member selected from the group consisting of 1,3,4-thiadiazole derivatives having the formula: N - N
Y ¹ - (S) _w - C 1 -C- (S) ₂ - Y ² and 1,2,4-thiadiazole derivatives having the formula: Y ¹ - (S) _w - C - N N C- (S) ₂ - Y ^ wherein Y ¹ and Y ^{2 are} identical or different and are H, straight or branched alkyl, cyclic, alicyclic, aryl, alkylaryl or arylalkyl radicals having from 2 up to about 30 carbon atoms, -C (O) R ⁶ , -P (O) (OR ⁶ ) ₂ and -C (S) N (R ⁶ J ₂ , wherein R ^{6 is} a hydrocarbyl, and are C ₁ -C ₆ -alkylene groups which are substituted by one or more carboxy, nitrophenyl, cyano, thiocyanato , Isocyanato, isothiocyanato, alkylcarbonyl, thiocarbamyl, amino or aryl groups, and in which one of Y ¹ and Y ^{2 may have} the following component: N-N Il Il 7 - (C ₁ -C ₆ -AhCyIe _n ) - (S) _w - C C- (S) ₂ -R ¹ V
or the component - (C 1 -C 4 -alkylene) - (S) -C-N M C- (S) ₇ - R ' wherein R ⁷ is H or C ₁ -C ₂₀ hydrocarbyl and w and ζ are the same or different and numbers from 1 to about 9.
A composition according to claim 2, characterized in that the ashless dispersant comprises at least one member selected from the group consisting of oil-soluble salts, amides, imides, oxazolines and esters or mixtures thereof of lany-chain hydrocarbyl substituted mono- and dicarboxylic acids or their acid anhydrides, wherein the long-chain hydrocarbon group is a polymer of a C ₂ -Cio-monoolefin and the polymer has an average molecular weight of about 1500 to 5000. 4. The composition according to claim 1, characterized in that the substituted by a long-chain hydrocarbyl mono- or Dikai bonsäurematerial consists of a polyolefin, which is substituted per mole of polyolefin with an average of about 0.8 to 2.0 moles of a substituent group, which consists of an alpha or beta unsaturated monounsaturated C ₄ -C ₁₀ dicarboxylic acid producing material. Composition according to Claim 4, characterized in that the alpha-unsaturated or mono-unsaturated, mono-unsaturated C 4 -C ₁₀ -dicarboxylic acid-producing material consists of a dicarboxylic acid or its anhydride or esters thereof. A composition according to claim 5, characterized in that the substituent group has a member selected from the group consisting of fumaric acid, itaconic acid, maleic acid, maleic anhydride, chloromaleic acid, dimethyl fumarate, chloromaleic anhydride, acrylic acid, methacrylic acid, crotonic acid and cinnamic acid. 7. A composition according to claim 1, characterized in that the ashless dispersant polyisobutenylsuccinimide of a polyalkylenepolyamine having an average of 2 to 60 carbon atoms and 1 to 12 nitrogen atoms per molecule of the polyamine, said polyisobutylene moiety of polyisobutylene having an average number average molecular weight between about 1300 and 3000 won becomes. 8. A composition according to claim 2, characterized in that the SASH value is substantially equal to zero. Composition according to Claim 1, characterized in that the ashless dispersant comprises at least one member selected from the group consisting of (i) oil-soluble salts, amides, imides, oxazolines and esters or mixtures thereof substituted by long chain hydrocarbons Mono- and di-carboxylic acids or their anhydrides or esters; (ii) a long chain aliphatic hydrocarbon having a directly attached polyamine; (iii) Mannich condensation products formed by condensing about one mole of a long chain hydrocarbyl substituted phenol with about 1 to 2.5 moles of formaldehyde and about 0.5 to 2 moles of polyalkylenepolyamine, and (A-4) Mannich condensation products which are formed by reaction of long chain hydrocarbon substituted mono- and dicarboxylic acids or their esters or anhydrides with an aminophenol which may optionally be hydroxy-carbyl substituted to form a long chain hydrocarbon substituted amide- <-> the imide-containing phenol intermediate adduct; by condensing about one mole of the long chain hydrocarbyl substituted amide- or imide-containing phenolic bisphenol adduct with about 1 to 2.5 moles of formaldehyde and about 0.5 to 2 polyamines, wherein the long chain hydrocarbon group in (i), (ii) and (iii) a polymer of a C ₂ -C ₀ monoolefin and this Olefinpolyme r has an average molecular weight of about 1,000 to about 5,000. 10. The composition according to claim 9, characterized in that the ashless dispersant consists of the product of (a) a hydrokarbylsubstituierten, monounsaturated C4-C ₁₀ -dikarbonsäure-producing material ₁₀ monoolefin average by reacting an olefin polymer of a C2-C with a Molecular weight of about 1,500 to 5,000 and a monounsaturated C ₄ -C ₁₀ acid material, the acid-producing material having on average at least 0.8 dicarboxylic acid-producing components per molecule of the olefin polymer present in the reaction mixture used to form the acid-producing material and (b) a nucleophilic reactant selected from the group consisting of amines, alcohol, aminoalcohols and mixtures thereof. 11. The composition according to claim 10, characterized in that the nucleophilic Reaktionsmittei comprises an amine. 12. The composition according to claim 11, characterized in that the amine contains 2 to 60 carbon atoms and 1 to 12 nitrogen atoms per molecule. 13. The composition according to claim 12, characterized in that the amine consists of a polyalkylenepolyamine, wherein the alkylene groups each contain 2 to 6 carbon atoms and the polyalkylenepolyamine contains 2 to about 9 nitrogen atoms per molecule. 14. The composition according to claim 13, characterized in that the amine consists of polyethylpolyamine. 15. A composition according to claim 10, characterized in that the hydrocarbyl substituted acid generating material contains between about 0.8 and about 2.0 moles of the succinic acid components per mole of the olefin polymer used in the reaction mixture. 16. A composition according to claim 15, characterized in that the reaction product contains between about 0.5 and 2.0% of boron. 17. A composition according to claim 16, characterized in that the olefin polymer consists of polybutylene. 18. A composition according to claim 1, characterized in that the ashless dispersant is borated and the reaction mixture contains boric acid. 19. A composition according to claim 18, characterized in that the olefin polymer consists of polyisobutylene. 20. The composition according to claim 19, characterized in that d ^r S is the number average molecular weight of the olefin polymer is between about 1800 bits, 3000, and the amine comprises a polyalkylene polyamine having an average of about 5 to 7 nitrogen atoms per molecule. 21. A composition according to claim 20, characterized in that the oil-soluble antioxidant comprises at least one member selected from the group consisting of oil-soluble phenol compounds, oil-soluble sulfurized organic compounds, oil-soluble amine antioxidants, oil-oil organoborates, oil-soluble organophosphites, oil-soluble organophosphates, oil-soluble Organodithiophosphaten and mixtures thereof. 22. The composition according to claim 20, characterized in that the oil-soluble antioxidant is substantially free of metal. 23. A composition according to claim 22, characterized in that the oil-soluble antioxidant is substantially ashless and is characterized by a value of sulfated ash of not more than 1%. 24. The composition according to claim 1, characterized in that the oil-soluble antioxidant comprises at least one alkyl-substituted, hydroxyaromatic compound containing at least one hydroxy group and at least one C ₆ -C ₂ alkyl group bonded to the same aromatic ring which is attached to a Temperature between about 100 ⁰ C and 250 ° C is reacted with a sulfurizing agent. 25. The composition according to claim 20, characterized in that the oil-soluble Antikoxydationsmittel is used in a concentration of about 2 to 6%. 26. An additive concentrate characterized in that it consists of (A) between about 10 and about 70% of at least one oil-soluble, high molecular weight, ashless dispersant, (B) between about 3 and about 40% of at least one oil-soluble antioxidant, (C) between about 0.05 and 5% of at least one organosulfur compound of the formula: N-N 1 Il ι! ο Y ¹ - (S) - C C - (S) _z - Y ^d . and 1,2,4-thiadiazole derivatives having the formula: γ ¹ _ (S) - G - N ^w h il 2 NC - (S) ₂ - Y ^ ν / wherein Y ¹ and Y ^{2 are the} same or different and are H, a straight or branched alkyl, cyclic, alicyclic, aryl, alkylaryl or arylalkyl radical having 2 to about 30 carbon atoms, w and ζ are numbers between 1 and about 8, and Sum of w and ζ is at least 3, and between about 30 and 80% base oil. -4- 292 394 27. An additive concentrate according to claim 26, characterized in that Y ¹ is H and Y ^{2 is} a straight or branched alkyl, cyclic, alicyclic, aryl, alkylaryl or arylalkyl having 2 to 30 carbon atoms. A method for improving the performance of a heavy duty crankcase lubricating oil intended for use in a diesel engine in conjunction with a normally liquid fuel having a sulfur content of less than 1%, characterized in that the metal content of the oil is controlled to give a total sulfated ash (SASH) value of less than 0.01% in the oil and (A) at least about 2% of a high molecular weight ashless dispersant, (B) an antioxidant an effective amount of at least one oil-soluble antioxidant and (C) a copper corrosion inhibiting amount of at least one organosulfur compound having the formula: N - N , Il Il ρ Y ¹ - (S) - C C - (S) ₂ , - Y / S / S
and 1,2,4-thiadiazole derivatives having the formula: Y ¹ - (S) _w - C - N ^w U Il? H c - (S) ₂ - Y ^ wherein Y ¹ and Y ^{2 are the} same or different and are H, a straight or branched alkyl, cyclic, alicyclic, aryl, alkaryl or aralkyl radical mt from 2 to 30 carbon atoms and w and ζ are numbers between 1 and about 8. A method for improving the performance of a heavy duty diesel crankcase lubricating oil intended for use in a diesel engine having at least one cylinder with a close-fitting top piston, characterized in that the metal content of the oil is controlled to provide a total of sulfated oil ( SASH value) of less than 0.01% in the oil and in the oil are present (A) at least about 2% of a high molecular weight ashless dispersant, (B) an antioxidant effective amount of at least one oil soluble antioxidant and ( C) a copper corrosion inhibiting amount of at least one organosulfur compound having the formula: N-N 1 'I Il ρ Y ¹ - (S) _w - G C - (S) ₂ , - Y ^d S
and 1,2,4-thiadiazole derivatives having the formula: Y ¹ . (S) - C - U H G- (S) ₂ - Y ^d wherein Y ¹ and Y ^{2 are the} same or different and are H, a straight or branched alkyl, cyclic, alicyclic, aryl, alkaryl or aralkyl radical having 2 to 30 carbon atoms and w and ζ are numbers between 1 and about 8. 29. The method according to claim 8, characterized in that the diesel engine can be operated with a normally liquid fuel having a sulfur content of less than 0.3%. 30. In a diesel engine having a lubricating crankcase and at least one close-fitting top piston, the improvement characterized by comprising in the crankcase a lubricating effective amount of an ashless lubricating oil composition consisting of a major amount of an oil of lubricating viscosity and (A) at least 2% of a high molecular weight, ashless dispersant, (B) an antioxidant effective amount of at least one oil soluble antioxidant, and (C) a copper corrosion inhibiting amount of at least one organosulfur compound of the formula: NN
Y ¹ - (S) _w - C C - (S) ₂ - Y ²