Stable colloidal suspensions and lubricating oil compositions containing same

专利摘要:
A stable collidal suspension comprising: (a) a dispersed phase comprising a majoramount of one or more dispersed hydrated polymeric compounds selected from the groupconsisting of polymolybdates, polytungstates, polyvanadates, polyniobates,polytantalates, polyuranates, and mixtures thereof; and, (b) an oil phase comprising oneor more dispersing agents and a diluent oil. Processes for preparing the stable colloidalsuspensions and their use in lubricating oil compositions are also provided.
公开号:EP1520905A1
申请号:EP04255532
申请日:2004-09-13
公开日:2005-04-06
发明作者:Kenneth D. Nelson；James J. Harrison
申请人:Chevron Oronite Co LLC；
IPC主号:C10M169-00

专利说明:
[0001] The present invention generally relates to stable colloidal suspensions useful aslubricating oil additives for lubricating oil compositions. 2. Description of the Related Art
[0002] Compositions containing molybdic acid have been used as lubricating oiladditives to control oxidation and wear of engine components. Since their discovery,such complexes have been widely used as engine lubricating oil additives in automotiveand diesel crankcase oils and as an additive in some two-cycle oils to prevent valvesticking. Generally, these compounds are added to a dispersant inhibitor (DI) packagethat is then added to the engine lubricating oils.
[0003] In general, such compositions can be, for example, complexes of molybdic acidand oil soluble basic nitrogen containing compounds made with an organic solvent duringa molybdenum-containing composition complexation step. The complexation step can befollowed by a sulfurization step as disclosed in U.S. Patent Nos. 4,263,152 and4,272,387, the contents of which are incorporated herein by reference.
[0004] A problem associated with these compounds is that they are dark in color,particularly after sulfurization; the sulfurized compositions are extremely dark in color.For instance, the sulfurized compositions are measured at about 5 triple dilute (DDD)using an ASTM D1500 or ASTM D6045 colorimetric test. Since reduced color lubricating oils are highly desired in the marketplace, these dark compositions can onlybe used in limited amounts because of the impact they have on the finished oil color.
[0005] It would therefore be desirable to provide a lubricating oil additive which not onlyexhibits good frictional properties, oxidation inhibition and anti-wear performance forlubricating oil compositions but also allows for lower color of the lubricating oils. SUMMARY OF THE INVENTION
[0006] In accordance with a first embodiment of the present invention, a stable colloidalsuspension is provided comprising (a) a dispersed phase comprising a major amount ofone or more dispersed hydrated polymeric compounds selected from the group consistingof polymolybdates, polytungstates, polyvanadates, polyniobates, polytantalates,polyuranates, and mixtures thereof; and, (b) an oil phase comprising one or moredispersing agents and a diluent oil.
[0007] In a preferred embodiment of the present invention, a stable colloidal suspensionis provided which comprises (a) a dispersed phase comprising a major amount of adispersed hydrated polymolybdate; and, (b) an oil phase comprising one or moredispersing agents selected from the group consisting of polyalkylene succinic anhydrides,non-nitrogen containing derivatives of a polyalkylene succinic anhydride and mixturesthereof, and a diluent oil.
[0008] In another embodiment of the present invention, a process for preparing a stablecolloidal suspension is provided comprising: mixing, under agitation, (a) an aqueous solution comprising one or morepolymeric compounds selected from the group consisting of polymolybdates, polytungstates, polyvanadates, polyniobates, polytantalates, polyuranates, and mixturesthereof; (b) one or more dispersing agents; and, (c) a diluent oil to form a microemulsion; and, heating the micro emulsion to a temperature to remove sufficient water so as toproduce a stable colloidal suspension comprising (a) a dispersed phase comprising amajor amount of one or more dispersed hydrated polymeric compounds selected from thegroup consisting of polymolybdates, polytungstates, polyvanadates, polyniobates,polytantalates, polyuranates, and mixtures thereof; and, (b) an oil phase comprising thedispersing agent and the diluent oil.
[0009] In yet another embodiment of the present invention, a process for preparing astable colloidal suspension is provided comprising: mixing, under agitation, (a) an aqueous solution comprising (i) one or moremonomeric compounds selected from the group consisting of molybdenum, tungsten, andvanadium containing compounds; and (ii) an effective amount of an acid capable of atleast partially polymerizing the one or more monomeric compounds; (b) one or moredispersing agents and (c) a diluent oil to form a micro emulsion; and, heating the micro emulsion to a temperature to remove sufficient water so as toproduce a stable colloidal suspension comprising (a) a dispersed phase comprising amajor amount of one or more dispersed hydrated polymeric compounds selected from thegroup consisting of polymolybdates, polytungstates and polyvanadates; and, (b) an oilphase comprising the dispersing agent and the diluent oil.
[0010] Still yet another embodiment of the present invention, a process for preparing astable colloidal suspension is provided comprising: mixing, under agitation, (a) an aqueous solution comprising one or moremonomeric compounds selected from the group consisting of niobium, tantalum, anduranium containing compounds; (b) one or more dispersing agents and (c) a diluent oil toform a micro emulsion; and, heating the micro emulsion to a temperature to remove sufficient water so as toproduce a stable colloidal suspension comprising (a) a dispersed phase comprising amajor amount of one or more dispersed hydrated polymeric compounds selected from thegroup consisting of polyniobates, polytantalates, and polyuranates and (b) an oil phasecomprising the dispersing agent and the diluent oil.
[0011] Yet another embodiment of the present invention is a lubricating oil compositioncomprising (a) a major amount of an oil of lubricating viscosity and (b) a minor effectiveamount of the foregoing stable colloidal suspensions.
[0012] The stable colloidal suspensions herein advantageously exhibit good frictionalproperties, oxidation inhibition and anti-wear performance when employed as alubricating additive for lubricating oil compositions. Additionally, the stable colloidalsuspensions herein possess low color. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0013] The stable colloidal suspension of the present invention may be generallycharacterized as comprising (a) a dispersed phase comprising a major amount of one ormore dispersed hydrated polymeric compounds selected from the group consisting of polymolybdates, polytungstates, polyvanadates, polyniobates, polytantalates,polyuranates, and mixtures thereof; and, (b) an oil phase comprising one or moredispersing agents and a diluent oil.
[0014] Each of these components in the colloidal suspension will be defined herein. THE DISPERSED HYDRATED POLYMERIC COMPOUNDS
[0015] Hydrated polymeric compounds useful in forming the dispersed hydratedpolymeric compounds of the dispersed phase of the colloidal suspensions of the presentinvention are hydrated polymeric compounds selected from the group consisting ofpolymolybdates, polytungstates, polyvanadates, polyniobates, polytantalates,polyuranates, and mixtures thereof. Generally, formation of the hydrated polymericcompounds is achieved by at least dissolving one or more monomeric compoundsselected from the group consisting of molybdenum, tungsten, vanadium, niobium,tantalum, and uranium containing compounds in a suitable medium, e.g., water, to form asolution. Suitable molybdenum, tungsten, vanadium, niobium, tantalum, and uraniumcontaining compounds include can be the simple oxides of such compounds. Forexample, the simple oxides of molybdenum and tungsten may have the followingchemical formulae: MoO₃, WO₃, Mo₂O₅, MoO₂, and WO₂. It is also contemplated thatknown other non-stoichiometric oxides can be used herein. For example, the so-called"blue oxides" of molybdenum and tungsten are examples of such non-stoichiometricoxides, and they contain both oxide and hydroxide groups. Although less is known aboutthe oxides and/or hydroxides of vanadium, niobium, tantalum, and uranium, thechemistry is similar and such compounds can be used herein.
[0016] In general, when dissolving the one or more molybdenum, tungsten, vanadium,niobium, tantalum, and uranium containing compounds, it is particularly advantageous toemploy a strong base such as, for example, hydroxides of alkali metal and alkaline earthmetals, ammonium, thallium, etc. While all of the hydroxides of alkali metal,ammonium, magnesium, and thallium form water soluble compounds with themolybdenum, tungsten, vanadium, niobium, tantalum, and uranium containingcompounds, other metal hydroxides such as, e.g., calcium, form water insolublecompounds with the molybdenum, tungsten, vanadium, niobium, tantalum, and uraniumcontaining compounds. Accordingly, it may be necessary to add a sufficient amount ofan acid effective to dissolve the water-insoluble metal hydroxide and molybdenum,tungsten, vanadium, niobium, tantalum, and uranium containing compounds. Watersoluble compounds are preferred herein with the sodium, potassium, ammonium, andmagnesium hydroxides being most preferred. Alternatively, compounds such as, forexample, sodium molybdates, are known and commercially available and can be directlyadded to the suitable medium.
[0017] The molybdenum containing compounds called molybdates, and the tungstencontaining compounds called tungstates, have the structures M₂MoO₄ and M₂WO₄respectively, where M is the alkali metal, alkaline earth metal, ammonium, magnesium,or thallium. The vanadates, niobates, tantalates, and uranates each behave similarly. Thewater soluble compounds can be dissolved in a suitable medium, e.g., water, to form asolution. On the other hand, the water-insoluble powders can be dissolved in a suitableacid and water to form a solution.
[0018] As one skilled in the art would readily appreciate, the niobium, tantalum, anduranium compounds can be polymerized in basic solution. However, for themolybdenum, tungsten and vanadium containing compounds, polymeric compounds canonly be formed in an acid solution, e.g., a solution having a pH of between about 2 andabout 7 is preferred, with a pH between about 5 and about 7 being most preferred.Accordingly, it will be necessary to add an effective amount of an acid capable of at leastpartially polymerizing the molybdenum, tungsten and vanadium containing compounds.Suitable acids include, but are not limited to, nitric acid, nitric oxides, sulfuric acid, sulfurdioxide, sulfur trioxide, carbonic acid, carbon oxides, carbon dioxide, phosphoric acid,phosphorous acid, phosphoric oxides, polyphosphoric acid, polyphosphoric oxides, silicicacid, silicon monoxide, boric acid, boron oxides and the like with nitric acid, sulfuricacid, carbonic acid, phosphoric acid, pyrophosphoric acid, silicic acid, and boric acidbeing preferred. Generally, the amount of the acids employed in this step can varywidely, e.g., amounts ranging from about 0.1 to about 2 times the stoichiometric quantityrequired for neutralization and preferably from about 0.8 to about 1.2 times thetheoretical amount.
[0019] Generally, when the polymeric compound being formed is from a molybdenumcompound, these anions are called polymolybdates. The polymolybdates are generally oftwo types: the isopolymolybdates and their related anions, which contain onlymolybdenum, oxygen, and hydrogen, and the heteropolymolybdates and their relatedanions, which contain one or two atoms of another element in addition to themolybdenum, oxygen, and hydrogen. Similar behavior is observed for tungsten,vanadium, niobium, tantalum, and uranium compounds. These compounds will form polytungstates, polyvanadates, polyniobates, polytantalates, and polyuranates. Thesepolymeric compounds are also generally of two types: isopolytungstates and their relatedanions, isopolyvanadates and their related anions, isopolyniobates and their relatedanions, isopolytantalates and their related anions, isopolyuranates and their relatedanions, heteropolytungstates and their related anions, heteropolyvanadates and theirrelated anions, heteropolyniobates and their related anions, heteropolytantalates and theirrelated anions, and heteropolyuranates and their related anions.
[0020] The resulting polymeric compounds ordinarily contain a mixture of monomer,dimer, trimer, and higher polymers of the molybdenum, tungsten, vanadium, niobium,tantalum, and uranium containing compounds. The polymeric compounds can consist ofpolymeric acids in ionized form or in partially protonated form. They can also behydrated. The ionized polymeric compounds can also be bound with counter ions such asthose discussed above (e.g., alkali metals, ammonium ions, magnesium or thallium ions)depending on the base used to dissolve the molybdenum, tungsten, vanadium, niobium,tantalum, and uranium containing compounds. In addition, other salts may be present inthe structure of the polymeric compounds that result from the neutralization reaction ofthe aqueous solution with the acid for the vanadium, molybdenum, and tungstencompounds.
[0021] For the heteropolycompounds, one or more additional elements other than themolybdenum, tungsten, vanadium, niobium, tantalum, and uranium containingcompounds, oxygen, and hydrogen will be present. The additional element can be, forexample, phosphorus, boron, carbon, nitrogen, sulfur, arsenic, silicon, germanium, tin,titanium, zirconium, cerium, thorium, platinum, manganese, lead, nickel, tellurium, iodine, cobalt, aluminum, chromium, iron, rhodium, copper, selenium, and the like. Thepreferred additional elements are sulfur, boron and phosphorus. These additionalelements can be added at any time during the preparation of the polymeric compound.Preferably, these additional elements will be added to the aqueous solution of themolybdenum, tungsten, vanadium, niobium, tantalum, and uranium containingcompounds.
[0022] Any suitable compound of the additional element can be used in forming theheteropolycompounds such as, for example, the halide, pseudo halide, oxide, orhydroxide. Examples of such suitable compounds include, but are not limited to, boricacid, nitric acid, nitric oxides, sulfuric acid, sulfur dioxide, sulfur trioxide, carbonic acid,carbon oxides, carbon dioxide, phosphoric acid, phosphorous acid, phosphoric oxides,polyphosphoric acid, polyphosphoric oxides, silicic acid, silicon monoxide, aluminumoxides, germanium oxides, germanium dioxide, stannic acid, stannic oxides, stannousoxides, zinc oxides, plumbic acid, plumboplumbic oxides, plumbous oxides, titanic acid,titanium monoxide, titanium dioxide and the like. Most preferred of these compoundsare boric acid, sulfuric acid and phosphoric acid.
[0023] The reaction of the alkali metal hydroxides and the oxides of the molybdenum,tungsten, vanadium, niobium, tantalum, and uranium containing compounds is carried outat suitable temperatures and pressures, e.g., a temperature less than or equal to about100°C, and preferably from about 10°C to about 30°C and at atmospheric pressure, toform a solution. Subatmospheric to superatmospheric pressures can also be used herein.The reaction time for this step is typically in the range of from about 30 seconds to about1 hour. The oxide is ordinarily added to the hydroxide in an amount ranging from about 0.5 to about 3 times the theoretical amount required for reaction, preferably from about 1to about 2 times the theoretical quantity of oxide is employed, while the hydroxide ispresent in an amount ranging from about 0.3 to about 2 times the stoichiometric quantityand preferably about 0.5 to about 1 times the stoichiometric quantity. THE DISPERSING AGENT
[0024] The dispersing agents for use in forming the stable colloidal suspension of thepresent invention include, but are not limited to, polyalkylene succinic anhydrides, non-nitrogencontaining derivatives of a polyalkylene succinic anhydride and a basic nitrogencompound selected from the group consisting of succinimides, carboxylic acid amides,hydrocarbyl monoamines, hydrocarbyl polyamines, Mannich bases, phosphonoamides,thiophosphonamides and phosphoramides, and mixtures thereof. One other such groupsuitable for use herein as a dispersing agent includes copolymers which contain acarboxylate ester with one or more additional polar function, including amine, amide,imine, imide, hydroxyl, carboxyl, and the like. These products can be prepared bycopolymerization of long chain alkyl acrylates or methacrylates with monomers of theabove function. Such groups include alkyl methacrylate-vinyl pyrrolidinone copolymers,alkyl methacrylate-dialkylaminoethylmethacrylate copolymers and the like as well ashigh molecular weight amides and polyamides or esters and polyesters such astetraethylene pentamine, polyvinyl polystearates and other polystearamides. Preferably,the dispersing agent is a polyalkylene succinic anhydride, non-nitrogen containingderivative of a polyalkylene succinic anhydride or mixtures thereof.
[0025] The polyalkylene succinic anhydride dispersing agent is preferably apolyisobutenyl succinic anhydride (PIBSA). The number average molecular weight ofthe polyalkylene tail in the polyalkylene succinic anhydrides used herein will be at least350, preferably from about to about 750 to about 3000 and most preferably from about900 to about 1100.
[0026] In one embodiment, a mixture of polyalkylene succinic anhydrides is employed.In this embodiment, the mixture preferably comprises a low molecular weightpolyalkylene succinic anhydride component e.g., a polyalkylene succinic anhydridehaving a number average molecular weight of from about 350 to about 1000, and a highmolecular weight polyalkylene succinic anhydride component, e.g., a polyalkylenesuccinic anhydride having a number average molecular weight of from about 1000 toabout 3000. Still more preferably, both the low and high molecular weight componentsare polyisobutenyl succinic anhydrides. Alternatively, various molecular weightspolyalkylene succinic anhydride components can be combined as a dispersant as well as amixture of the other above referenced dispersants as identified above.
[0027] In general, the polyalkylene succinic anhydride is obtained from a reactionproduct of a polyalkylene such as polyisobutene with maleic anhydride. One can useconventional polyisobutene, or high methylvinylidene polyisobutene in the preparation ofsuch polyalkylene succinic anhydrides. The polyalkylene succinic anhydrides can beprepared using conventional techniques e.g., thermal, chlorination, free radical, acidcatalyzed, or any other process in this preparation that is within the purview of oneskilled in the art. Examples of suitable polyalkylene succinic anhydrides for use hereinare thermal PIBSA (polyisobutenyl succinic anhydride) described in U.S. Patent No. 3,361,673; chlorinated PIBSA described in U.S. Patent No. 3,172,892; a mixture ofthermal and chlorinated PIBSA described in U.S. Patent No. 3,912,764; high succinicratio PIBSA described in U.S. Patent No. 4,234,435; polyPIBSA described in U.S. PatentNos. 5,112,507 and 5,175,225; high succinic ratio polyPIBSA described in U.S. PatentNos. 5,565,528 and 5,616,668; free radical PIBSA described in U.S. Patent Nos.5,286,799, 5,319,030 and 5,625,004; PIBSA made from high methylvinylidenepolybutene described in U.S. Patent Nos. 4,152,499, 5,137,978 and 5,137,980; highsuccinic ratio PIBSA made from high methylvinylidene polybutene described inEuropean Patent Application Publication No. EP 355 895; terpolymer PIBSA describedin U.S. Patent No. 5,792,729, sulfonic acid PIBSA described in U.S. Patent No.5,777,025 and European Patent Application Publication No. EP 542 380; and purifiedPIBSA described in U.S. Patent No. 5,523,417 and European Patent ApplicationPublication No. EP 602 863, the contents of each of these references being incorporatedherein by reference.
[0028] Non-nitrogen containing derivatives of polyalkylene succinic anhydrides include,but are not limited to, succinic acids, Group I and/or Group II mono- or di-metal salts ofsuccinic acids, succinate esters formed by the reaction of a polyalkylene succinicanhydride, acid chloride, or other derivatives with an alcohol (e.g., HOR¹ wherein R¹ isan alkyl group of from 1 to 10 carbon atoms) and the like and mixtures thereof.
[0029] If desired, the foregoing polyalkylene succinic anhydrides and/or non-nitrogen-containingderivatives thereof can be post-treated with a wide variety of post-treatingreagents. For example, the foregoing polyalkylene succinic anhydride and/or derivativesthereof can be reacted with a cyclic carbonate under conditions sufficient to cause reaction of the cyclic carbonates with a hydroxyl group. The reaction is ordinarilyconducted at temperatures ranging from about 0°C to about 250°C, preferably from about100°C to about 200°C and most preferably from about 50°C to about 180°C.
[0030] The reaction may be conducted neat, wherein both the polyalkylene succinicanhydride or non-nitrogen containing derivative of a polyalkylene succinic anhydridedispersant and the cyclic carbonate are combined in the proper ratio, either alone or in thepresent of a catalyst (e.g., an acidic, basic or Lewis acid catalyst). Examples of suitablecatalysts include, but are not limited to, phosphoric acid, boron trifluoride, alkyl or arylsulfonic acid, alkali or alkaline carbonate. The same solvents or diluents as describedabove with respect to the preparing the polyalkylene succinic anhydride may also be usedin the cyclic carbonate post-treatment.
[0031] A particularly preferred cyclic carbonate for use herein is 1,3-dioxolan-2-one(ethylene carbonate).
[0032] The basic nitrogen compound used to prepare the colloidal suspensions of thepresent invention must contain basic nitrogen as measured by ASTM D664 test orD2896. It is preferably oil-soluble. The basic nitrogen compounds are selected from thegroup consisting of succinimides, polysuccinimides, carboxylic acid amides, hydrocarbylmonoamines, hydrocarbon polyamines, Mannich bases, phosphoramides,thiophosphoramides, phosphonamides, dispersant viscosity index improvers, andmixtures thereof. These basic nitrogen-containing compounds are described below(keeping in mind the reservation that each must have at least one basic nitrogen). Any ofthe nitrogen-containing compositions may be post-treated with, e.g., boron, usingprocedures well known in the art so long as the compositions continue to contain basic nitrogen. These post-treatments are particularly applicable to succinimides and Mannichbase compositions.
[0033] The succinimides and polysuccinimides that can be used to prepare the colloidalsuspension of the present invention are disclosed in numerous references and are wellknown in the art. Certain fundamental types of succinimides and the related materialsencompassed by the term of art "succinimide" are taught in U.S. Pat. Nos. 3,219,666;3,172,892; and 3,272,746, the contents of which are incorporated by reference herein.The term "succinimide" is understood in the art to include many of the amide, imide, andamidine species which may also be formed. The predominant product, however, is asuccinimide and this term has been generally accepted as meaning the product of areaction of an alkenyl substituted succinic acid or anhydride with a nitrogen-containingcompound. Preferred succinimides, because of their commercial availability, are thosesuccinimides prepared from a hydrocarbyl succinic anhydride, wherein the hydrocarbylgroup contains from about 24 to about 350 carbon atoms, and an ethylene amine, saidethylene amines being especially characterized by ethylene diamine, diethylene triamine,triethylene tetramine, tetraethylene pentamine, and higher molecular weight polyethyleneamines. Particularly preferred are those succinimides prepared from polyisobutenylsuccinic anhydride of 70 to 128 carbon atoms and tetraethylene pentamine or highermolecular weight polyethylene amines or mixtures of polyethylene amines such that theaverage molecular weight of the mixture is about 205 Daltons.
[0034] Also included within the term "succinimide" are the co-oligomers of ahydrocarbyl succinic acid or anhydride and a polysecondary amine containing at least onetertiary amino nitrogen in addition to two or more secondary amino groups. Ordinarily, this composition has between 1,500 and 50,000 average molecular weight. A typicalcompound would be that prepared by reacting polyisobutenyl succinic anhydride andethylene dipiperazine.
[0035] If desired, the foregoing succinimides and polysuccinimides can be post-treatedwith a wide variety of post-treating reagents, e.g., with a cyclic carbonate. The resultingpost-treated product has one or more nitrogens of the polyamino moiety substituted witha hydroxy hydrocarbyl oxycarbonyl, a hydroxy poly(oxyalkylene) oxycarbonyl, ahydroxyalkylene, hydroxyalkylenepoly(oxyalkylene), or mixture thereof.
[0036] The cyclic carbonate post-treatment is ordinarily conducted under conditionssufficient to cause reaction of the cyclic carbonate with secondary amino groups of thepolyamino substituents. The reaction is ordinarily conducted at temperatures rangingfrom about preferably from about 0°C to about 250°C and preferably from 100°C toabout 200°C. Generally, best results are obtained at temperatures of from about 150°Cto 180°C.
[0037] The reaction may be conducted neat, and may or may not be conducted in thepresence of a catalyst (such as an acidic, basic or Lewis acid catalyst). Depending on theviscosity of the reactants, it may be desirable to conduct the reaction using an inertorganic solvent or diluent, e.g., toluene or xylene. Examples of suitable catalysts includephosphoric acid, boron trifluoride, alkyl or aryl sulfonic acid, and alkali or alkaline earthcarbonate.
[0038] A particularly preferred cyclic carbonate is 1,3-dioxolan-2-one (ethylenecarbonate) because it affords excellent results and also because it is readily availablecommercially.
[0039] The molar charge of cyclic carbonate employed in the post-treatment reaction ispreferably based upon the theoretical number of basic nitrogen atoms contained in thepolyamino substitutent of the succinimide. Thus, when one equivalent of tetraethylenepentamine is reacted with two equivalents of succinic anhydride, the resulting bis-succinimidewill theoretically contain three basic nitrogen atoms. Accordingly, a molarcharge ratio of 2 would require that two moles of cyclic carbonate be added for eachbasic nitrogen, or in this case 6 moles of cyclic carbonate for each mole equivalent ofsuccinimide. Mole ratios of the cyclic carbonate to the basic amine nitrogen are typicallyin the range of from about 1:1 to about 4:1; preferably from about 2:1 to about 3:1.
[0040] The foregoing succinimides and polysuccinimides, including the post-treatedcompositions described above, can also be reacted with boric acid or a similar boroncompound to form borated dispersants. In addition to boric acid, examples of suitableboron compounds include boron oxides, boron halides and esters of boric acid.Generally, from about 0.1 equivalent to about 1 equivalent of boron compound perequivalent of basic nitrogen or hydroxyl in the compositions of this invention may beemployed.
[0041] Carboxylic acid amide compounds are also useful nitrogen-containing compoundsfor preparing the colloidal suspensions of this invention. Typical of such compounds arethose disclosed in U.S. Patent No.3,405,064, the contents of which are incorporated byreference herein. These compounds are ordinarily prepared by reacting a carboxylic acidor anhydride or ester thereof, having at least 12 to about 350 aliphatic carbon atoms in theprincipal aliphatic chain and, if desired, having sufficient pendant aliphatic groups torender the molecule oil soluble with an amine or a hydrocarbyl polyamine, such as an ethylene amine, to give a mono or polycarboxylic acid amide. Preferred are those amidesprepared from (1) a carboxylic acid of the formula R²COOH, where R² is C_12-20 alkyl or amixture of this acid with a polyisobutenyl carboxylic acid in which the polyisobutenylgroup contains from 72 to 128 carbon atoms and (2) an ethylene amine, especiallytriethylene tetramine or tetraethylene pentamine or mixtures thereof.
[0042] Another class of useful nitrogen-containing compounds are hydrocarbylmonoamines and hydrocarbyl polyamines, preferably of the type disclosed in U.S. PatentNo. 3,574,576, the contents of which are incorporated by reference herein. Thehydrocarbyl group, which is preferably alkyl, or olefinic having one or two sites ofunsaturation, usually contains from 9 to 350, preferably from 20 to 200 carbon atoms.Particularly preferred hydrocarbyl polyamines are those which are derived, e.g., byreacting polyisobutenyl chloride and a polyalkylene polyamine, such as an ethyleneamine, e.g., ethylene diamine, diethylene triamine, tetraethylene pentamine,2-aminoethylpiperazine, 1,3-propylene diamine, 1,2-propylenediamine, and the like.
[0043] Yet another class of useful nitrogen-containing compounds are the Mannich basecompounds. These compounds are prepared from a phenol or C_9-200 alkylphenol, analdehyde, such as formaldehyde or formaldehyde precursor such as paraformaldehyde,and an amine compound. The amine may be a mono or polyamine and typicalcompounds are prepared from an alkylamine, such as methylamine or an ethylene amine,such as, diethylene triamine, or tetraethylene pentamine, and the like. The phenolicmaterial may be sulfurized and preferably is dodecylphenol or a C_80-100 alkylphenol.Typical Mannich bases which can be used in this invention are disclosed in U.S. PatentNos. 3,539,663, 3,649,229; 3,368,972 and 4,157,309, the contents of which are incorporated by reference herein. U.S. Patent No. 3,539,663 discloses Mannich basesprepared by reacting an alkylphenol having at least 50 carbon atoms, preferably 50 to 200carbon atoms with formaldehyde and an alkylene polyamine HN(ANH)_nH where A is asaturated divalent alkyl hydrocarbon of 2 to 6 carbon atoms and n is 1-10 and where thecondensation product of said alkylene polyamine may be further reacted with urea orthiourea. The utility of these Mannich bases as starting materials for preparinglubricating oil additives can often be significantly improved by treating the Mannich baseusing conventional techniques to introduce boron into the compound.
[0044] Still yet another class of useful nitrogen-containing compounds are thephosphoramides and phosphonamides such as those disclosed in U.S. Patent Nos.3,909,430 and 3,968,157, the contents of which are incorporated by reference herein.These compounds may be prepared by forming a phosphorus compound having at leastone P--N bond. They can be prepared, for example, by reacting phosphorus oxychloridewith a hydrocarbyl diol in the presence of a monoamine or by reacting phosphorusoxychloride with a difunctional secondary amine and a mono-functional amine.Thiophosphoramides can be prepared by reacting an unsaturated hydrocarbon compoundcontaining from 2 to 450 or more carbon atoms, such as polyethylene, polyisobutylene,polypropylene, ethylene, 1-hexene, 1,3-hexadiene, isobutylene, 4-methyl-1-pentene, andthe like, with phosphorus pentasulfide and a nitrogen-containing compound as definedabove, particularly an alkylamine, alkyldiamine, alkylpolyamine, or an alkyleneamine,such as ethylene diamine, diethylenetriamine, triethylenetetramine,tetraethylenepentamine, and the like.
[0045] Another class of useful nitrogen-containing compounds includes the so-calleddispersant viscosity index improvers (VI improvers). These VI improvers are commonlyprepared by functionalizing a hydrocarbon polymer, especially a polymer derived fromethylene and/or propylene, optionally containing additional units derived from one ormore co-monomers such as alicyclic or aliphatic olefins or diolefins. Thefunctionalization may be carried out by a variety of processes which introduce a reactivesite or sites which usually has at least one oxygen atom on the polymer. The polymer isthen contacted with a nitrogen-containing source to introduce nitrogen-containingfunctional groups on the polymer backbone. Commonly used nitrogen sources includeany basic nitrogen compound especially those nitrogen-containing compounds andcompositions described herein. Preferred nitrogen sources are alkylene amines, such asethylene amines, alkyl amines, and Mannich bases. THE DETERGENT
[0046] If desired, a detergent can also be added to the colloidal suspension of the presentinvention. Suitable detergents for use herein include, but are not limited to, phenates(high overbased or low overbased), high overbased phenate stearates, phenolates,salicylates, phosphonates, thiophosphonates, ionic surfactants and sulfonates and the likewith sulfonates being preferred and with low overbased metal sulfonates and neutralmetal sulfonates being most preferred. Low overbased metal sulfonates typically have atotal base number (TBN) of from about 0 to about 30 and preferably from about 10 toabout 25. Low overbased metal sulfonates and neutral metal sulfonates are well knownin the art.
[0047] The low overbased or neutral metal sulfonate detergent is preferably a lowoverbased or neutral alkali or alkaline earth metal salt of a hydrocarbyl sulfonic acidhaving from about 15 to about 200 carbon atoms. The term "metal sulfonate" as usedherein is intended to encompass at least the salts of sulfonic acids derived from petroleumproducts. Such acids are well known in the art and can be obtained by, for example,treating petroleum products with sulfuric acid or sulfur trioxide. The acids obtainedtherefrom are known as petroleum sulfonic acids and the salts as petroleum sulfonates.Most of the petroleum product which become sulfonated contain an oil-solubilizinghydrocarbon group. Also, the meaning of "metal sulfonate" is intended to encompass thesalts of sulfonic acids of synthetic alkyl, alkenyl and alkyl aryl compounds. These acidsalso are prepared by treating an alkyl, alkenyl or alkyl aryl compound with sulfuric acidor sulfur trioxide with at least one alkyl substituent of the aryl ring being anoil-solubilizing group. The acids obtained therefrom are known as alkyl sulfonic acids,alkenyl sulfonic acids or alkyl aryl sulfonic acids and the salts as alkyl sulfonates, alkenylsulfonates or alkyl aryl sulfonates.
[0048] The acids obtained by sulfonation are converted to metal salts by neutralizationwith one or more basic reacting alkali or alkaline earth metal compounds to yield GroupIA or Group IIA metal sulfonates. Generally, the acids are neutralized with an alkalimetal base. Alkaline earth metal salts are obtained from the alkali metal salt bymetathesis. Alternatively, the sulfonic acids can be neutralized directly with an alkalineearth metal base. If desired, the sulfonates can then be overbased to produce the lowoverbased metal sulfonate. The metal compounds useful in making the basic metal saltsare generally any Group IA or Group IIA metal compounds (CAS version of the Periodic Table of the Elements). The Group IA metals of the metal compound include alkalimetals, e.g., sodium, potassium, lithium. The Group IIA metals of the metal base includethe alkaline earth metals such, for example, magnesium, calcium, barium, etc. Preferablythe metal compound for use herein is calcium. The metal compounds are ordinarilydelivered as metal salts. The anionic portion of the salt can be hydroxyl, oxide,carbonate, borate, nitrate, etc.
[0049] The sulfonic acids useful in making the low overbased or neutral salts include thesulfonic and thiosulfonic acids. Generally they are salts of sulfonic acids. The sulfonicacids include, for example, the mono- or polynuclear aromatic or cycloaliphaticcompounds. The oil-soluble sulfonates can be represented for the most part by one of thefollowing formulae: R₂ --T--(SO₃)_a and R₃ --(SO₃)_b, wherein T is a cyclic nucleus suchas, for example, benzene, naphthalene, anthracene, diphenylene oxide, diphenylenesulfide, petroleum naphthenes, etc.; R₂ is an aliphatic group such as alkyl, alkenyl,alkoxy, alkoxyalkyl, etc.; (R₂)+T contains a total of at least about 15 carbon atoms; andR₃ is an aliphatic hydrocarbyl group containing at least about 15 carbon atoms.Examples of R₃ are alkyl, alkenyl, alkoxyalkyl, carboalkoxyalkyl, etc. Specific examplesof R₃ are groups derived from petrolatum, saturated and unsaturated paraffin wax, and theabove-described polyalkenes. The groups T, R₂, and R₃ in the above Formulae can alsocontain other inorganic or organic substituents in addition to those enumerated abovesuch as, for example, hydroxy, mercapto, halogen, nitro, amino, nitroso, sulfide,disulfide, etc. In the above Formulae, a and b are at least 1. In one embodiment, thesulfonic acids have a substituent (R₂ or R₃) which is derived from one of theabove-described polyalkenes.
[0050] Illustrative examples of these sulfonic acids include monoeicosanyl-substitutednaphthalene sulfonic acids, dodecylbenzene sulfonic acids, didodecylbenzene sulfonicacids, dinonylbenzene sulfonic acids, cetylchlorobenzene sulfonic acids, dilaurylbeta-naphthalene sulfonic acids, the sulfonic acid derived by the treatment of polybutenehaving a number average molecular weight (M_n) in the range of about 350 to about 5000,preferably about 800 to about 2000, or about 1500 with chlorosulfonic acid,nitronaphthalene sulfonic acid, paraffin wax sulfonic acid, cetylcyclopentane, sulfonicacid, lauryl-cyclohexane sulfonic acids, polyethylenyl-substituted sulfonic acids derivedfrom polyethylene (M_n of from about 300 to about 1000, and preferably about 750), etc.Normally the aliphatic groups will be alkyl and/or alkenyl groups such that the totalnumber of aliphatic carbons is at least about 8, preferably at least 12 up to about 400carbon atoms, preferably about 250. Also useful are polyisobutene sulfonates, e.g., thosedisclosed in U.S. Patent No. 6,410,491, the contents of which are incorporated byreference herein.
[0051] Another group of sulfonic acids are mono- , di- , and tri-alkylated benzene andnaphthalene (including hydrogenated forms thereof) sulfonic acids. Illustrative ofsynthetically produced alkylated benzene and naphthalene sulfonic acids are thosecontaining alkyl substituents having from about 8 to about 30 carbon atoms, preferablyabout 12 to about 30 carbon atoms, and advantageously about 24 carbon atoms. Suchacids include di-isododecylbenzene sulfonic acid, polybutenyl-substituted sulfonic acid,polypropylenyl-substituted sulfonic acids derived from polypropene having an M_n offrom about 300 to about 1000 and preferably from about 500 to about 700,cetylchlorobenzene sulfonic acid, di-cetylnaphthalene sulfonic acid, di-lauryldiphenylether sulfonic acid, diisononylbenzene sulfonic acid,di-isooctadecylbenzene sulfonic acid, stearylnaphthalene sulfonic acid, and the like.
[0052] Specific examples of oil-soluble sulfonic acids are mahogany sulfonic acids;bright stock sulfonic acids; sulfonic acids derived from lubricating oil fractions having aSaybolt viscosity from about 100 seconds at 100°F. to about 200 seconds at 210°F.;petrolatum sulfonic acids; mono- and poly-wax-substituted sulfonic and polysulfonicacids of, e.g., benzene, naphthalene, phenol, diphenyl ether, naphthalene disulfide, etc.;other substituted sulfonic acids such as alkyl benzene sulfonic acids (where the alkylgroup has at least 8 carbons), cetylphenol mono-sulfide sulfonic acids, dilauryl betanaphthyl sulfonic acids, and alkaryl sulfonic acids such as dodecyl benzene "bottoms"sulfonic acids.
[0053] Dodecyl benzene "bottoms" sulfonic acids are the material leftover after theremoval of dodecyl benzene sulfonic acids that are used for household detergents. Thesematerials are generally alkylated with higher oligomers. The bottoms may bestraight-chain or branched-chain alkylates with a straight-chain dialkylate preferred.
[0054] Particularly preferred based on their wide availability are salts of the petroleumsulfonic acid, e.g., those obtained by sulfonating various hydrocarbon fractions such aslubricating oil fraction and extracts rich in aromatics which are obtained by extracting ahydrocarbon oil with a selective solvent, which extract may, if desired, be alkylatedbefore sulfonation by reacting them with olefins or alkyl chlorides by means of analkylation catalyst; organic polysulfonic acids such as benzene disulfonic acid which mayor may not be alkylated; and the like.
[0055] Other particularly preferred salts for use herein are alkylated aromatic sulfonicacids in which the alkyl radical or radicals contain at least about 6 carbon atoms andpreferably from about 8 to about 22 carbon atoms. Another preferred group of sulfonatestarting materials are the aliphatic-substituted cyclic sulfonic acids in which the aliphaticsubstituent or substituents contain a total of at least 12 carbon atoms such as, forexample, alkyl aryl sulfonic acids, alkyl cycloaliphatic sulfonic acids, the alkylheterocyclic sulfonic acids and aliphatic sulfonic acids in which the aliphatic radical orradicals contain a total of at least 12 carbon atoms. Specific examples of these oil-solublesulfonic acids include, but are not limited to, petroleum sulfonic acids; petrolatumsulfonic acids; mono- and poly-wax-substituted naphthalene sulfonic acids; substitutedsulfonic acids such as cetyl benzene sulfonic acids, cetyl phenyl sulfonic acids and thelike; aliphatic sulfonic acids such as paraffin wax sulfonic acids, hydroxy-substitutedparaffin wax sulfonic acids and the like; cycloaliphatic sulfonic acids; petroleumnaphthalene sulfonic acids; cyclopentyl sulfonic acid; mono- and poly-wax-substitutedcyclohexyl sulfonic acids and the like. The expression "petroleum sulfonic acids" asused herein shall be understood to cover all sulfonic acids that are derived directly frompetroleum products.
[0056] Typical Group IIA metal sulfonates suitable for use herein include, but are notlimited to, the metal sulfonates exemplified as follows: calcium white oil benzenesulfonate, barium white oil benzene sulfonate, calcium dipropylene benzene sulfonate,barium dipropylene benzene sulfonate, calcium mahogany petroleum sulfonate, bariummahogany petroleum sulfonate, calcium triacontyl sulfonate, calcium lauryl sulfonate,barium lauryl sulfonate, and the like.
[0057] The acidic material used to accomplish the formation of the overbased metal saltcan be a liquid such as, for example, formic acid, acetic acid, nitric acid, sulfuric acid,etc, or an inorganic acidic material such as, for example, HCl, SO₂, SO₃, CO₂, H₂S, etc,with CO₂ being preferred. The amount of acidic material used depends in some respectsupon the desired basicity of the product in question and also upon the amount of basicmetal compound employed which will vary (in total amount) from about 1 to about 10,preferably from about 1.2 to about 8 and most preferably from about 1.7 to about 6.0equivalents per equivalent of acid. In the case of an acidic gas, the acidic gas is generallyblown below the surface of the reaction mixture that contains additional (i.e., amounts inexcess of what is required to convert the acid quantitatively to the metal salt) base. Theacidic material employed during this step is used to react with the excess basic metalcompound which may be already present or which can be added during this step.
[0058] The reaction medium used to prepare the low overbased metal sulfonate or neutralmetal sulfonate is typically an inert solvent. Suitable inert solvents that can be employedherein include oils, organic materials which are readily soluble or miscible with oil andthe like. Suitable oils include high boiling, high molecular weight oils such as, forexample, parrafinic oils having boiling points higher than about 170°C. Commerciallyavailable oils of this type known to one skilled in the art include, e.g., those availablefrom such sources as Exxon under the Isopar® tradenames, e.g., Isopar® M, Isopar® G,Isopar® H, and Isopar® V, and the Telura® tradename, e.g., Telura® 407, and CromptonCorporation available as carnation oil. Suitable organic solvents include unsubstituted orsubstituted aromatic hydrocarbons, ethoxylated long chain alcohols, e.g., thoseethoxylated alcohols having up to about 20 carbon atoms, and mixtures thereof. Useful unsubstituted or substituted aromatic hydrocarbons include high flash solvent naptha andthe like.
[0059] If desired, a promoter can also be employed in preparing the low overbased metalsulfonate or neutral metal sulfonate. A promoter is a chemical employed to facilitate theincorporation of metal into the basic metal compositions. Among the chemicals useful aspromoters are, for example, water, ammonium hydroxide, organic acids of up to about 8carbon atoms, nitric acid, sulfuric acid, hydrochloric acid, metal complexing agents suchas alkyl salicylaldoxime, and alkali metal hydroxides such as lithium hydroxide, sodiumhydroxide and potassium hydroxide, and mono- and polyhydric alcohols of up to about30 carbon atoms. Examples of the alcohols include methanol, ethanol, isopropanol,dodecanol, behenyl alcohol, ethylene glycol, monomethylether of ethylene glycol,hexamethylene glycol, glycerol, pentaerythritol, benzyl alcohol, phenylethyl alcohol,aminoethanol, cinnamyl alcohol, allyl alcohol, and the like. Especially useful are themonohydric alcohols having up to about 10 carbon atoms and mixtures of methanol withhigher monohydric alcohols. Amounts of promoter will ordinarily range from about 0%to about 25%, preferably from about 1.5% to about 20% and most preferably from about2% to about 16% of acid charge.
[0060] In general, the dispersant mixture will ordinarily contain the low overbased metalsulfonate or neutral metal sulfonate in an amount ranging from about 1 to about 20 andpreferably from about 5 to about 10 weight percent, based on the total weight of themixture. PROCESS FOR PREPARING THE COLLOIDAL SUSPENSION
[0061] In one embodiment of the present invention, the process for preparing the stablecolloidal suspension of the present invention involves mixing, under vigorous agitation, areaction mixture comprising an aqueous solution containing the foregoing polymericcompounds; and the foregoing dispersing agents, diluent oil and optional detergent toform a micro emulsion and then heating the micro emulsion to a temperature to removesufficient water so as to produce the stable colloidal suspension of the present invention.If desired, the foregoing dispersing agents and detergents can be added to the aqueoussolution as a pre-formed dispersant mixture or each alone can be added, eithersimultaneously or sequentially. Alternatively, the dispersing agent, diluent oil andoptional detergent can be added to the aqueous solution as an oil phase. A diluent oil isused to provide a suitable viscosity such that mixing is adequate to form a stableemulsion having an aqueous phase containing at least the polymeric compounds and anoil phase containing the dispersing agent(s), diluent oil and optionally detergent(s).Suitable diluents are known in the art and commercially available and include, forexample, lubricating oil and non-volatile liquid compounds containing only carbon andhydrogen.
[0062] In a second embodiment of the present invention, a process for preparing a stablecolloidal suspension involves at least mixing, under agitation, (a) an aqueous solutioncomprising (i) one or more monomeric compounds selected from the group consisting ofmolybdenum, tungsten, and vanadium containing compounds and (ii) an effective amountof an acid capable of at least partially polymerizing the one or more compounds, (b) oneor more dispersing agents, (c) a diluent oil and optionally (d) a detergent to form a micro emulsion and then heating the micro emulsion to a temperature to remove sufficientwater so as to produce the stable colloidal suspension of the present invention.
[0063] In yet another embodiment of the present invention, a process for preparing astable colloidal suspension involves at least mixing, under agitation, (a) an aqueoussolution comprising one or more monomeric compounds selected from the groupconsisting of niobium, tantalum, and uranium containing compounds, (b) one or moredispersing agents, (c) a diluent oil and optionally (d) a detergent to form a microemulsion and then heating the micro emulsion to a temperature to remove sufficientwater so as to produce the stable colloidal suspension of the present invention.
[0064] In the microemulsion, the polymeric compound or monomeric molybdenum,tungsten, vanadium, niobium, tantalum, or uranium containing compounds will generallybe present in the mixture in an amount ranging from about 5 to about 50 weight percentand preferably from about 10 to about 40 weight percent of the mixture. The dispersingagent is typically present in an amount of from about 1 to about 25 weight percent andpreferably from about 5 to about 15 weight percent, the water is present in an amountranging from about 20 to 60 weight percent, while the diluent oil is present in an amountranging from about 10 to about 70 weight percent. The detergent, if present, is employedin an amount of from about 1 to about 10 weight percent and preferably from about 2 toabout 5 weight percent.
[0065] Following the formation of the emulsion, it is particularly advantageous tosubstantially dehydrate the emulsion by heating to a temperature effective to removesufficient water to provide a stable colloidal suspension. If desired, the colloidalsuspension can be further dehydrated to remove additional water, i.e., an amount of from 0 to about 20 wt. % and preferably from about 5 to about 15 wt. %. However, additionaldehydration needs to be carefully controlled in order not to destabilize the colloidalsuspension. Accordingly, it is generally advantageous to at least partially dehydrate theproduct. Dehydration of the emulsion can also assist in polymerizing the molybdenum,tungsten, vanadium, niobium, tantalum, and uranium containing compounds to form thedispersed polymeric compounds.
[0066] Dehydration can occur in one step or more than one step including an initial stepof water removal that is initiated at a temperature of slightly over 100°C. This initial stepis followed by a slow increase in temperature whereupon the turbidity of the emulsionchanges from turbid to substantially clear. Accordingly, stable colloidal suspensions willordinarily have a turbidity of less than about 300 nephelometric turbidity units (ntu) andpreferably less than about 100 ntu (Turbidity of the finished oils was measured, neat, at20°C using a Hach Ratio Turbidimeter Model: 18900. The turbidimeter was calibratedwith 18 and 180 ntu Formazin primary standards). The temperature during thedehydration step will typically not exceed about 200°C and preferably is between about105°C to about 150°C to provide a low color stable colloidal suspension.
[0067] Dehydration may also be carried out under reduced pressure. The pressure maybe reduced incrementally to avoid problems with foaming. The reaction time sufficientto dehydrate the emulsion and form a stable colloidal suspension can vary widely, e.g., inthe range of from about 0.5 to about 3 hours and preferably from about 0.75 to about 1.5hours. The resulting colloidal suspension will ordinarily contain a dispersed phase and anoil phase containing at least one or more dispersing agents and a diluent oil. Thedispersed phase will normally contain at least a major amount of the dispersed hydrated polymeric compounds, e.g., about 50 wt. % to about 100 wt. % and preferably from about60 wt. % to about 95 wt. % and an oil phase containing at least one or more dispersingagents and a diluent oil.
[0068] The colloidal suspension will have a dispersed phase content ranging from about5 to about 60 and preferably from about 10 to about 50 weight percent of the suspension.The dispersed hydrated polymeric compound particles generally possess a mean particlesize of less than about 1 micron and preferably from about 0.01 microns to about 0.5microns.
[0069] Generally, the dehydration of the emulsion is carefully controlled (i.e. using aslow dehydration rate, employing a sweep gas, and the like) in order to avoidcondensation of water on the walls of the reaction chamber. Condensation can result inwater droplets that contaminate the composition which, in turn, can lead to undesiredprecipitate formation. Such precipitate formation typically results in large particles thatfall from suspension and have deleterious properties. THE LUBRICATING OIL COMPOSITION
[0070] The stable colloidal suspensions of the present invention are particularly useful asanti-wear agents when used in lubricating oil compositions. The lubricant composition ofthe present invention comprises a major amount of an oil of lubricating viscosity and aminor amount of the stable colloidal suspensions of the present invention. Thelubricating oil compositions containing the stable colloidal suspensions of this inventioncan be prepared by admixing, by conventional techniques, the appropriate amount of thestable colloidal suspensions with a suitable lubricating oil. The selection of the particular lubricating oil depends on the contemplated application of the lubricant and the presenceof other additives.
[0071] The lubricating oil compositions of the present invention ordinarily contain amajor amount of an oil of lubricating viscosity and a minor effective amount of theforegoing stable colloidal suspensions. The oils of lubricating viscosity are ordinarilypresent in an amount ranging from about 30 to about 70 weight percent and morepreferably from about 45 to about 55 weight percent of the lubricating oil compositionand the stable colloidal suspensions will be present in the lubricating oil compositions inan amount ranging from about 0.1 wt. % to about 10 wt. % and preferably from about 0.5wt. % to about 2.5 % wt. %, based on the total weight of the composition.
[0072] The lubricating oil which may be used in this invention includes a wide variety ofhydrocarbon oils, such as naphthenic bases, paraffin bases and mixed base oils as well assynthetic oils such as esters and the like. The lubricating oils may be used individually orin combination and generally have viscosity which ranges from 50 to 5,000 SayboltUniversal Seconds (SUS) and usually from 100 to 15,000 SUS at 40°C.
[0073] The lubricating oil employed may be any of a wide variety of oils of lubricatingviscosity. The base oil of lubricating viscosity used in such compositions may be mineraloils or synthetic oils. A base oil having a viscosity of at least about 2.5 centistokes (cSt)at 40°C and a pour point below about 20°C, preferably at or below about 0°C is desirable.The base oils may be derived from natural or synthetic sources. Mineral oils for use asthe base oil in this invention include, for example, paraffinic, naphthenic and other oilsthat are ordinarily used in lubricating oil compositions. Synthetic oils include, forexample, both hydrocarbon synthetic oils and synthetic esters and mixtures thereof having the desired viscosity. Hydrocarbon synthetic oils may include, for example, oilsprepared from the polymerization of ethylene or from the polymerization of 1-olefinssuch as polyalphaolefin or PAO, or from hydrocarbon synthesis procedures using carbonmonoxide and hydrogen gases such as in a Fisher-Tropsch process. Useful synthetichydrocarbon oils include liquid polymers of alpha olefins having the proper viscosity.Especially useful are the hydrogenated liquid oligomers of C₆ to C₁₂ alpha olefins such as1-decene trimer. Likewise, alkyl benzenes of proper viscosity, such as didodecylbenzene, can be used. Useful synthetic esters include the esters of monocarboxylic acidsand polycarboxylic acids, as well as mono-hydroxy alkanols and polyols. Typicalexamples are didodecyl adipate, pentaerythritol tetracaproate, di-2-ethylhexyl adipate,dilaurylsebacate, and the like. Complex esters prepared from mixtures of mono anddicarboxylic acids and mono and dihydroxy alkanols can also be used. Blends of mineraloils with synthetic oils are also useful.
[0074] Thus, the oil can be a refined paraffin type base oil, a refined naphthenic base oil,or a synthetic hydrocarbon or non-hydrocarbon oil of lubricating viscosity. The oil canalso be a mixture of mineral and synthetic oils.
[0075] The colloidal suspensions of the present invention (as described herein above) canalso be blended to form additive packages comprising such colloidal suspensions. Theseadditive packages typically contain from about 10 to about 75 weight percent of thecolloidal suspensions described above and from about 90 to about 15 weight percent ofone or more of conventional additives selected from the group consisting of ashlessdispersants (about 0-5%), detergents (about 0-2%), sulfurized hydrocarbons (about 0-30%),dialkyl hydrogen phosphates (about 0-10%), zinc dithiophosphates (about 0-20%), dialkyl hydrogen phosphates (about 0-10%), pentaerythritol monooleate (about 0-10%),2,5-dimercaptothiadiazole (about 0-5%), benzotriazole (about 0-5%), molybdenumsulfide complexes such as those described in U.S. Patent Nos. 4,263,152 and 4,272,387(about 0-5%), imidazolines (about 0-10%), and foam inhibitors (about 0-2%) and the likewherein each weight percent is based on the total weight of the additive package.
[0076] Fully formulated finished oil compositions of this invention can be formulatedfrom these additive packages upon further blending with an oil of lubricating viscosity.Preferably, the additive package described above is added to an oil of lubricatingviscosity in an amount of from about 5 to about 15 weight percent to provide for thefinished oil composition wherein the weight percent of the additive package is based onthe total weight of the composition. More preferably, added along with the oil oflubricating viscosity is a polymethacrylate viscosity index improver which is included ata level of about 0-12% and/or a pour point depressant at a level of about 0-1%, to form afinished oil wherein the weight percent of each of the viscosity index improver and pourpoint depressant is based on the total weight of the lubricant composition.
[0077] A variety of other additives can be present in lubricating oils of the presentinvention. Those additives include antioxidants, rust inhibitors, corrosion inhibitors,extreme pressure agents, antifoam agents, other viscosity index improves, other anti-wearagents, and a variety of other well-known additives in the art.
[0078] The following non-limiting examples are illustrative of the present invention. EXAMPLE 1Preparation of a Colloidal Suspension ContainingDispersed Hydrated Polymeric Molybdate
[0079] To a 1 liter glass beaker was added, 58.2g (0.240 mol) of sodium molybdatedihydrate, 15.21g (0.246 mol) of boric acid, and 150g deionized water. The mixture wasstirred and quickly formed a homogeneous aqueous solution with gentle heating.
[0080] To a 1 liter stainless steel blender flask was added 137.75g Exxon 150N oil (aGroup I base stock), 14.40g of a low overbased synthetic sulfonate having a Total BaseNumber (TBN) of 17mgKOH/g (as measured by ASTM D8296), and 30.00g of apolyisobutenyl succinic anhydride (PIBSA) having a saponification (SAP) number of118.6mgKOH/g (as measured by ASTM D93) and containing 92.8% actives. Thecomponents were mixed until a homogeneous solution was formed. The hot aqueoussolution was then added to the oil solution, over a time period of about 1 minute, whilethe oil solution was mixed on a Waring Laboratory blender with the blender speed beingslowly increased from 50% to 100% of the "high" setting during the 1 minute period toform an emulsion. The resulting emulsion was then mixed for 30 minutes on the "high"setting.
[0081] The emulsion was then partially dehydrated in a 1 liter glass beaker insulated withglass wool by heating the emulsion to a maximum temperature of 105°C with stirringunder a nitrogen sweep until an essentially clear colloidal oil suspension was obtained.The total dehydration time was about 1 hour. Next, a small amount of non-dehydratedemulsion was removed from the oil. The resulting product contained 7.8% Mo byInductively Coupled Plasma (ICP) and had a TBN of 88mgKOH/g. EXAMPLE 2Preparation of a Colloidal Suspension ContainingDispersed Hydrated Polymeric Molybdate
[0082] Using the same general procedure outlined in example 1, a dispersed hydratedsodium molybdate complex (the aqueous phase) was prepared by mixing 80.0g (0.331mol) of sodium molybdate dihydrate, 8.1g (0.083mol) of 96.8% sulfuric acid and 107.5gof deionized water. The pH of the aqueous phase was approximately neutral (using a pHtest strip). The oil phase was prepared using 119.9g of Exxon, 150N oil, and 50.1g ofPIBSA having a SAP number of 92mgKOH/g. An emulsion was prepared and partiallydehydrated in the same manner as example 1 to form a colloidal suspension. Totalheating time was about 1.5 hours to a maximum temperature of 105°C. The resultingproduct was filtered through anhydrous sodium sulfate; and contained 9.7% Mo and 4.6%Na by ICP. EXAMPLE 3Alternative Preparation Preparation of a Colloidal SuspensionContaining Dispersed Hydrated Polymeric Molybdate
[0083] To a 1 liter glass beaker 34.9g (0.242 mol) of molybdenum oxide, 19.2g (0.48mol) of sodium hydroxide, and 150g deionized water was added and gently heated andstirred to dissolve the reactants, and then 15.2g (0.246 mol) of boric acid was furtheradded. The mixture quickly formed a slightly turbid aqueous solution with heat andstirring.
[0084] To a 1 liter stainless steel blender flask was added 137.75g Exxon 150N oil (aGroup I base stock), 14.40g of a low overbased synthetic sulfonate having a TBN of 17mgKOH/g, and 30.00g of a PIBSA having a SAP number of 118.6mgKOH/g andcontaining 92.8% actives. The components were mixed until a homogeneous oil solutionwas formed. Next, the hot aqueous solution was added to the oil solution, over about 1minute, while the oil solution was mixed on a Waring Laboratory blender; with theblender speed being slowly increased from 50% to 100% of the "high" setting during the1 minute period to form an emulsion. The resulting emulsion was then mixed for 30minutes on the "high" setting.
[0085] The emulsion was then partially dehydrated in a 1 liter glass beaker insulated withglass wool by heating the emulsion to a maximum temperature of 104°C with stirringunder a nitrogen sweep until an essentially clear colloidal oil suspension was obtained.The total dehydration time was about 1.5 hours. A small amount of non-dehydratedemulsion was removed from the oil. The product contained 8.0% Mo, 3.6% Na, and0.88% B by ICP, had a TBN of 86mgKOH/g, and an average particle size distribution of0.130 µm as measured using a Horiba LA-920 light scattering particle size analyzer. EXAMPLE 4Extended Dehydration of a Colloidal SuspensionContaining Dispersed Hydrated Polymeric Molybdate
[0086] Using the same general procedure outlined in example 2, a dispersed hydratedsodium molybdate complex was prepared from 81.5 (0.337 mol) of sodium molybdatedihydrate, 16.5g (0.168mol) of 96.2% sulfuric acid and 224.7g of deionized water to formthe aqueous phase; and 103.6g of Exxon 150N oil, 36.7g of PIBSA having a SAP numberof 68.1mgKOH/g, and 8.1g of an alkyl benzene sulfonic acid was used in the oil phase.An emulsion was then prepared and dehydrated in a similar manner as example 2. The total heating time was about 3 hours to a maximum temperature of 133°C. Water wasremoved from the suspension during this period as evidenced by evolution of steam. Aclear colloidal oil suspension was obtained after about 1.5 hours heating time to atemperature of 105°C with the product being hazy both before and after this point. Thefinal product was opaque. EXAMPLE 5Preparation of a Colloidal Suspension ContainingDispersed Hydrated Polymeric Molybdate
[0087] The preparation of the colloidal suspension described in example 1 was repeatedwith no significant changes. The resulting product contained 7.6% MO, 3.7% Na, and0.86% B by ICP, had a TBN of 90mgKOH/g, and an average particle size distribution of0.135 µm as measured using a Horiba LA-920 light scattering particle size analyzer. EXAMPLE 6Preparation of a Colloidal Suspension ContainingDispersed Hydrated Polymeric Molybdate
[0088] The preparation of the colloidal suspension described in example 3 was repeatedin essentially the same manner except that 18.45g of 85% of phosphoric acid was used inplace of boric acid. The resulting product contained 7.8% MO, 3.7% Na, and 1.7% P byICP, had a TBN of 76mgKOH/g, and an average particle size distribution of 0.129 µm asmeasured using a Horiba LA-920 light scattering particle size analyzer. EXAMPLE 7Automobile Engine Oil Formulated withColloidal Suspension of Example 1
[0089] A baseline automobile engine oil composition was formed containing a SAE 30Wautomobile engine oil with 6% of a bis-succinimide dispersant, 25mM/kg of a synthetichighly overbased calcium sulfonate detergent, 25mM/kg of a highly overbased calciumphenate detergent, 13mM/kg of a secondary zinc dialkyl dithiophosphate, and 5ppm of afoam inhibitor. The colloidal suspension of example 1 was formulated into this baselineautomobile engine oil composition at 1 weight percent such that the Mo concentrationwas 0.078%. COMPARATIVE EXAMPLE AAutomobile Engine Oil Formulated withMolybdenum Sulfide Complex
[0090] A baseline automobile engine oil composition was formed containing the samebase oil, additives and treat rate as described in Example 7. A commercially availablemolybdenum sulfide complex as prepared and described in U.S. Patent Nos. 4,263,152and 4,272,387 was formulated into this baseline automobile engine oil composition at1.2% by weight and the Mo concentration was 0.078%. Color Measurement by ASTM D1500
[0091] The automobile engine oils of Example 7 and Comparative Example A wereanalyzed for color by ASTM D1500. The automobile engine oil of Example 7 measured3.5 while the automobile engine oil of Comparative Example A measured greater than 8 (off scale by this method). These results demonstrate the preferred low color of thecolloidal suspensions of this invention. EXAMPLE 8Low Phosphorus Automobile Engine OilFormulated With Colloidal Suspension of Example 1
[0092] A baseline automobile engine oil composition was formed that contained about0.05% phosphorus (calculated from ZnDTP concentration). Thus, a SAE 5W-20automobile engine oil with 3% of a bis-succinimide dispersant, 6mM/kg of a syntheticlow overbased calcium sulfonate detergent, 55mM/kg of a highly overbased calciumphenate detergent, 7mM/kg of a secondary zinc dialkyl dithiophosphate ; 0.5% of anamine anti-oxidant, 0.2% of a phenolic anti-oxidant and 5% of an ethylene/propylenecopolymer viscosity index improver was prepared. The colloidal suspension of example1 was formulated into this baseline automobile engine oil composition at 1% by weight,and the Mo concentration was 0.078%. EXAMPLE 9Low Phosphorus Automobile Engine OilFormulated With Colloidal Suspension of Example 2
[0093] A baseline automobile engine oil composition was formed containing the samebase oil, additives and treat rate as described in Example 8. The colloidal suspension ofExample 2 was formulated into this baseline automobile engine oil composition at 1% byweight, and the Mo concentration was 0.097%. COMPARATIVE EXAMPLE BLow Phosphorus Automobile Engine Oil
[0094] A baseline automobile engine oil composition was formed that contained thesame base oil, additives and treat rate as described in Example 8, and no colloidalsuspension. COMPARATIVE EXAMPLE C0.1% Phosphorus Automobile Engine Oil
[0095] A baseline automobile engine oil composition was formed containing the samebase oil, additives and treat rate as described in Example 8 except that the 7mM/kg of asecondary zinc dialkyl dithiophosphate was replaced with 18mM/kg of the samesecondary zinc dialkyl dithiophosphate, and no colloidal suspension. 4-Ball Wear Test
[0096] The low phosphorous automobile engine oils of Examples 8 and 9 andComparative Examples B and C were tested for anti-wear performance using a four ballwear test performed in a manner similar to ASTM D-4172 (4-ball wear), as follows.These formulated test oils were aged in an oxidation bath, containing steel balls, for 48hours at 160°C with 15L/hour of airflow bubbled through the oil. These aged oils weretested on a 4-ball wear test apparatus using 100C6 steel balls; 90kg load was applied in 9stages starting from 10kg with 10kg increments at 1500 rotations per minute. The wearindex was calculated from movement of the load arm.
[0097] The wear test results are set forth below in TABLE 1. Oils with good anti-wearproperties exhibit a low wear index in this test. 4-Ball wear test results Sample 4-Ball Wear Index Result Example 8 29 Example 9 28 Comparative Example B 216 Comparative Example C 24
[0098] As these data demonstrate, a low phosphorus automobile engine oil havingdesirable anti-wear properties can be formulated with the colloidal suspensions of thisinvention. EXAMPLE 10Low Phosphorus Automobile Engine OilFormulated With Colloidal Suspension of Example 1
[0099] A baseline automobile engine oil composition was formed containing a SAE 5W-20automobile engine oil with 3% of a bis-succinimide dispersant, 6mNVkg of a syntheticlow overbased calcium sulfonate detergent, 55mM/kg of a highly overbased calciumphenate detergent, 7mM/kg of a secondary zinc dialkyl dithiophosphate, 0.5% of anamine anti-oxidant, 0.2% of a phenolic anti-oxidant and 5% of an ethylene/propylenecopolymer viscosity index improver. The colloidal suspension of example 1 wasformulated into this baseline automobile engine oil composition at 1.6% by weight, andthe Mo concentration was 0.125%. 4-Ball Load Wear Index Test
[0100] The automobile engine oils of Example 10 and Comparative Example B were evaluatedfor load carrying properties by ASTM D2783. The test measures a load wear index(LWI), reported in kilo-gram force (kgF), a measure of the properties of a lubricant underhigh pressure conditions. A high LWI is desirable. The load wear index test results areset forth below in TABLE 2. 4-Ball LWI Test Results Sample LWI (kgF) Example 10 41.7 Comparative B 30.0
[0101] The foregoing data further demonstrate the superior performance of theautomobile engine oils formulated with the colloidal suspensions of the present invention. EXAMPLE 11Preparation of a Colloidal Suspension ContainingDispersed Hydrated Polymeric Tungstate
[0102] To a 1-Liter beaker was added 56.1 g (0.242 mol) of Tungsten Oxide, 19.66 g(0.49 mol) of Sodium Hydroxide, and 168.39 g De-ionized water. The mixture was thenheated and stirred until all of the solids had gone into solution. Next, 15.17 g (0.245 mol)of Boric Acid was added to the beaker, heated and stirred until dissolved. To a stainlesssteel Waring lab blending flask was added a dispersant system containing 128.78 g Exxon 150N base oil, 17.02 g of a low overbased synthetic sulfonate with a TBN of 17mgKOH/g, and 38.97 g of a PIBSA having a SAP number of 118.8 mgKOH/g. Thedispersant system was mixed in the blending flask.
[0103] Once the system was thoroughly mixed, the heated aqueous solution prepared inthe beaker was slowly (over about 1 minute) blended into the flask using a Variaccontroller to increase the blend speed from 50% to 100% of the Waring Lab blender's"high" setting. The contents of the mixture were then mixed for an additional 30 minuteson the "high setting". Next, the contents of the blending flask were transferred to aninsulated 1-Liter Beaker where they were partially dehydrated in the same manner asexample 1. A maximum temperature 100°C was reached over a period of approximately2 hours. The process yielded a hazy, opaque product which contained 3.45% Sodium and0.802% Boron by ICP, and had a TBN of 81 mgKOH/g. The average particle size was0.135 µm as measured using a Horiba LA-920 light scattering particle size analyzer.
[0104] It will be understood that various modifications may be made to the embodimentsdisclosed herein. Therefore the above description should not be construed as limiting,but merely as exemplifications of preferred embodiments. For example, the functionsdescribed above and implemented as the best mode for operating the present inventionare for illustration purposes only. Other arrangements and methods may be implementedby those skilled in the art without departing from the scope and spirit of this invention.Moreover, those skilled in the art will envision other modifications within the scope andspirit of the claims appended hereto.

权利要求:
Claims (48)
[1] A stable colloidal suspension comprising: (a) a dispersed phase comprising amajor amount of one or more dispersed hydrated polymeric compounds selected from thegroup consisting of polymolybdates, polytungstates, polyvanadates, polyniobates,polytantalates, polyuranates, and mixtures thereof; and, (b) an oil phase comprising oneor more dispersing agents and a diluent oil.
[2] The colloidal suspension of Claim 1, wherein the dispersed hydrated polymericcompound is a dispersed hydrated polymolybdate.
[3] The colloidal suspension of Claim 1, wherein the polymeric compound furthercomprises an alkali metal selected from the group consisting of lithium, sodium,potassium and rubidium.
[4] The colloidal suspension of Claim 3, wherein the alkali metal polymericcompound is sodium polymolybdate.
[5] The colloidal suspension of Claim 1, wherein the polymeric compound furthercomprises magnesium, calcium, ammonium or thallium.
[6] The colloidal suspension of Claim 1, wherein the polymeric compounds areselected from the group consisting of isopolymolybdates, isopolytungstates,isopolyvanadates, isopolyniobates, isopolytantalates, isopolyurantes,heteropolymolybdates, heteropolytungstates, heteropolyvanadates, heteropolyniobates,heteropolytantalates, and heteropolyurantes.
[7] The colloidal suspension of Claim 1, wherein the major amount of thedispersed hydrated polymeric compounds is from about 50 wt. % to about 100 wt. % ofthe dispersed phase.
[8] The colloidal suspension of Claim 1, wherein the major amount of thedispersed hydrated polymeric compounds is from about 60 wt. % to about 95 wt. % of thedispersed phase.
[9] The colloidal suspension of Claim 2, having a reduced color.
[10] The colloidal suspension of Claim 1, wherein the dispersed hydratedpolymeric compound possesses a mean particle size less than about 1 micron.
[11] The colloidal suspension of Claim 1, wherein the dispersed hydratedpolymeric compound possesses a mean particle size of about 0.01 microns to about 0.5microns.
[12] The colloidal suspension of Claim 1, wherein the dispersing agent is selectedfrom the group consisting of polyalkylene succinic anhydrides, non-nitrogen containingderivatives of a polyalkylene succinic anhydride and mixtures thereof.
[13] The colloidal suspension of Claim 12, wherein the polyalkylene succinicanhydride is a polyisobutylene succinic anhydride.
[14] The colloidal suspension of Claim 1, wherein the oil phase further comprisesa detergent.
[15] The colloidal suspension of Claim 14, wherein the detergent is a metalsulfonate.
[16] The colloidal suspension of Claim 15, wherein the metal sulfonate is a lowoverbased metal or neutral metal sulfonate.
[17] The colloidal suspension of Claim 15, wherein the metal sulfonate is acalcium sulfonate.
[18] A lubricant composition comprising a major amount of an oil lubricatingviscosity and a minor effective amount of the stable colloidal suspension of any one ofclaims 1 to 17.
[19] An additive package comprising about 10 to about 75 weight percent of thestable colloidal suspension of any one of claims 1 to 17.
[20] An additive package of Claim 40 further comprising one or more of additivesselected from the group consisting of ashless dispersants, detergents, sulfurizedhydrocarbons, dialkyl hydrogen phosphates, zinc dithiophosphates, polyol esters of fattyacids, 2,5-dimercaptothiadiazole, benzotriazole, molybdenum sulfide complexes,imidazolines, and foam inhibitors.
[21] A process for preparing a stable colloidal suspension comprising:
mixing under agitation, (a) an aqueous solution comprising one or more hydratedpolymeric compounds selected from the group consisting of polymolybdates,polytungstates, polyvanadates, polyniobates, polytantalates, polyuranates, and mixturesthereof; (b) one or more dispersing agents and (c) a diluent oil to form a microemulsion; and
heating the micro emulsion to a temperature to remove sufficient water so as toproduce a stable colloidal suspension comprising (a) a dispersed phase comprising amajor amount of one or more dispersed hydrated polymeric compounds selected fromthe group consisting of a polymolybdates, polytungstates, polyvanadates, polyniobates,polytantalates, polyuranates, and mixtures thereof; and (b) an oil phase comprising thedispersing agent and the diluent oil.
[22] The process of Claim 21, wherein the polymeric compound is apolymolybdate.
[23] The process of Claim 21, wherein the polymeric compound furthercomprises an alkali metal selected from the group consisting of lithium, sodium,potassium and rubidium.
[24] The process of Claim 23, wherein the alkali metal polymeric compounds issodium polymolybdate.
[25] The process of Claim 21, wherein the polymeric compound further comprisesmagnesium, calcium, ammonium or thallium.
[26] The process of Claim 21, wherein the polymeric compounds are selectedfrom the group consisting of isopolymolybdates, isopolytungstates, isopolyvanadates,isopolyniobates, isopolytantalates, isopolyuranates, heteropolymolybdates,heteropolytungstates, heteropolyvanadates, heteropolyniobates, heteropolytantalates andheteropolyuranates.
[27] A process for preparing a stable colloidal suspension comprising:
mixing, under agitation, an (a) aqueous solution comprising (i) one or moremonomeric compounds selected from the group consisting of molybdenum, tungsten,and vanadium containing compounds and (ii) an effective amount of an acid capable ofat least partially polymerising the one or more monomeric compounds; (b) one or moredispersing agents and (c) a diluent oil to form a micro emulsion; and,
heating the micro emulsion to a temperature to remove sufficient water so as toproduce a stable colloidal suspension comprising (a) a dispersed phase comprising amajor amount of one or more dispersed hydrated polymeric compounds selected fromthe group consisting of polymolybdates, polytungstates, and polyvanadates; and, (b) anoil phase comprising the dispersing agent and the diluent oil.
[28] The process of Claim 43, wherein the monomeric compound is a monomericmolybdenum containing compound.
[29] A process for preparing a stable colloidal suspension comprising:
mixing, under agitation, (a) an aqueous solution comprising one or moremonomeric compounds selected from the group consisting of niobium, tantalum, anduranium containing compounds; (b) one or more dispersing agents and (c) a diluent oilto form a micro emulsion; and,
heating the micro emulsion to a temperature to remove sufficient water so as toproduce a stable colloidal suspension comprising (a) a dispersed phase comprising amajor amount of a dispersed hydrated polymeric compound selected from the groupconsisting of: polymolybdates, polytungstates, polyvanadates, polyniobates,polytantalates, and polyuranates; and (b) an oil phase comprising the dispersing agentand the diluent oil.
[30] The process of Claim 27 or 29, wherein the aqueous solution in the step ofmixing, under agitation, further comprises a hydroxide selected from the groupconsisting of alkali metal hydroxides, alkaline earth metal hydroxides, ammoniumhydroxide and thallium hydroxide.
[31] The process of Claim 30, wherein the alkali metal hydroxide is selected fromthe group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide andrubidium hydroxide.
[32] The process of Claim 31, wherein the alkaline earth metal hydroxide ismagnesium hydroxide.
[33] The process of Claim 27, wherein the acid is selected from the groupconsisting of nitric acid, sufuric acid, carbonic acid, phosphoric acid, pyrophosphoricacid, silic acid, boric acid and mixtures thereof.
[34] The process of Claim 27, wherein the one or more monomeric compoundsselected from the group consisting of molybdenum, tungsten and vanadium containingcompounds further comprises an alkali metal.
[35] The process of Claim 29, wherein the one or more monomeric compoundsselected from the group consisting of niobium, tantalum, and uranium containingcompounds further comprise an alkali metal.
[36] The process of Claim 34 or 35, wherein the alkali metal is selected from thegroup consisting of lithium, sodium, potassium and rubidium.
[37] The process of Claim 29, wherein the one or more dispersed hydratedpolymeric compounds are selected from the group consisting of isopolyniobates,isopolytantalates, isopolyuranates, heteropolyniobates, heteropolytantalates andheteropolyuranates.
[38] The process of Claim 21, 27 or 29, wherein the dispersing agent is selectedfrom the group consisting of polyalkylene succinic anhydrides, non-nitrogen containingderivatives of a polyalkylene succinic anhydride and mixtures thereof.
[39] The process of Claim 38, wherein the polyalkylene succinic anhydride is apolyisobutylene succinic anhydride.
[40] The process of Claim 21, 27 or 29, wherein the step of mixing, underagitation further comprises a detergent.
[41] The process of Claim 40, wherein the detergent is a metal sulfonate.
[42] The process of Claim 41, wherein the metal sulfonate is a low overbasedmetal or neutral metal sulfonate.
[43] The process of Claim 42, wherein the metal sulfonate is a calcium sulfonate.
[44] The process of Claim 21, 27 or 29, wherein one or more dispersed hydratedpolymeric compounds possess a mean particle size less than about 1 micron.
[45] The process of Claim 21, 27 or 29, wherein the one or more dispersedhydrated polymeric compounds possess a mean particle size of about 0.01 microns toabout 0.5 microns.
[46] The process of Claim 21, 27 or 29, wherein the major amount of the dispersedhydrated polymeric compounds is from about 50 wt. % to about 100 wt. % of thedispersed phase.
[47] The process of Claim 21, 27 or 29, wherein the major amount of the dispersedhydrated polymeric compounds is from about 60 wt. % to about 95 wt. % of thedispersed phase.
[48] The process of Claim 21, 27 or 29, wherein the colloidal suspension has areduced color.

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同族专利:

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CA2482059C|2013-12-31|

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US7884058B2|2011-02-08|

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SG110154A1|2005-04-28|

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JP2005105274A|2005-04-21|

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EP1520905B1|2012-04-25|

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CA2482059A1|2005-03-30|

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US20050070445A1|2005-03-31|

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JP5221838B2|2013-06-26|

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优先权:

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申请号 | 申请日 | 专利标题

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US675631||2003-09-30||

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US10/675,631|US7884058B2|2003-09-30|2003-09-30|Stable colloidal suspensions and lubricating oil compositions containing same|

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