Patent Application
20080015126
The present invention provides a lubricant additive gel that control releases the components into a lubricant, which components are specifically formulated in the gel to meet desired performance requirements of the gels and the lubricant that the gel is releasing its desired additives into. The controlled release gel comprises:
The weight ratio of component 1 above i. e., ashless dispersant to component 2 above i. e., acid is about 0.1 to about 100 and in another embodiment about 1 to about 50.
The additive composition is in the form of a gel. The composition is a mixture of an ashless dispersant and an acid when combined form a gel. The controlled release gel is substantially free of ash producing components and in another embodiment has the absence of ash producing components. The weight ratio of the ashless dispersant to the acid is about 0.1 to about 100 and in another embodiment about 1 to about 50.
Gels are materials that comprise mixtures of two or more substances and which exist in a semi-solid state more like a solid than a liquid. The gel exists in a semi-solid state more like a solid than a liquid, see Parker, Dictionary of Scientific and Technical Terms, Fifth Edition, McGraw Hill,® 1994. See, also, Larson, “The Structure and rheology of Complex Fluids”, Chapter 5, Oxford University Press, New York, N.Y.,® 1999, each which is incorporated herein by reference. The rheological properties of a gel can be measured by small amplitude oscillatory shear testing. This technique measures the structural character of the gel and produces a term called the storage modulus which represents storage of elastic energy and the loss modulus which represents the viscous dissipation of that energy. The ratio of the loss modulus/storage modulus, which is called the loss tangent, or “tan delta”, is ≧1 for materials that are liquid-like and <1 for materials that are solid-like. The additive gels have tan delta values in one embodiment of about <0.75, in another embodiment of about <0.5 and in another embodiment of about <0.3. The gels have tan delta values in one embodiment of about ≦1, in one embodiment of about ≦0.75, in one embodiment of about ≦0.5 or in one embodiment of about ≦0.3.
The additive gel comprises at least two additives when combined form a gel. The additive gel includes combining a dispersant and an acid to form a gel. In one embodiment, the additive gel does not contain any ash containing detergents including, but not limited to, over based metal sulfonated detergents. In one embodiment, a gel which finds particular use are those in which gellation occurs through the combination of an acid and an ashless succinimide dispersant. In one embodiment, the ratio of the ashless dispersant to the acid is from about 1:1 to about 1:100, in another embodiment from about 100:1 to about 1:1 from about 4:1 to about 1:1 and in another embodiment from about 4:1 to about 2:1.
The ashless dispersant includes Mannich dispersants, polymeric dispersants, carboxylic dispersants, amine dispersants, and combinations and mixtures thereof, all of which are substantially free of forming ash to completely free of forming ash. In one embodiment the preferred dispersant is polyisobutenyl succinimide dispersant.
Ashless type dispersants are characterized by a polar group attached to a relatively high molecular weight hydrocarbon chain. Typical ashless dispersants include N-substituted long chain alkenyl succinimides, having a variety of chemical structures including typically:
wherein each R1 is independently an alkyl group, frequently a polyisobutyl group, with a molecular weight of 500-5000, and R2 are alkenylene groups, commonly ethylene (C2H4) groups. Succinimide dispersants are more fully described in U.S. Pat. No. 4,234,435 which is incorporated herein by reference. The dispersants described in this patent are particularly effective for producing a gel in accordance with the present invention.
The ashless dispersant includes, but is not limited to, an ashless dispersant such as a polyisobutenyl succinimide and the like. Polyisobutenyl succinimide ashless dispersants are commercially available products which are typically made by reacting together polyisobutylene having a number average molecular weight (“Mn”) of about 300 to 10,000 with maleic anhydride to form polyisobutenyl succinic anhydride (“PIBSA”) and then reacting the product so obtained with a polyamine typically containing 1 to 10 ethylene amino groups per molecule. The dispersant so obtained is typically formed from a mixture of different compounds and can be characterized by a variety of different variables including the degree of its amine substitution (i.e., the ratio of the equivalents of amino groups to carbonylic groups, or the N:CO ratio), its maleic anhydride conversion level (i.e., its molar ratio of maleic anhydride to PIB, as defined in U.S. Pat. No. 4,234,435, incorporated herein by reference), the Mn of its PIB group, and its mode of preparation (thermal assisted succination vs. Cl2-assisted succination). Analogous compounds made with other polyamines (e.g. polypropenyl) can also be used. Ashless dispersants of this type are described, for example, in U.S. Pat. No. 4,234,435, which is incorporated herein by reference.
Normally, the N:CO ratio of these polyisobutenyl succinimide ashless dispersants will be about 0.6 to 1.6 more typically about 0.7 to 1.4 or even 0.7 to 1.2. In addition or alternatively, the maleic anhydride conversion level of these polyisobutenyl succinimide ashless dispersants will normally be about 1.3, more typically at least 1.5 or even 1.6 or above. In addition or alternatively, the Mn of the polyisobutenyl segments of these polyisobutenyl succinimide ashless dispersants are normally ≧about 350, more typically at least 1200, at least about 1500 or even 1800 or above. In addition or alternatively, these polyisobutenyl succinimide ashless dispersants are also made using Cl2-assisted succination rather than thermal assisted succination, since this produces PISAs of higher conversion than thermally produced PIBSAs (the latter known as DA or direct addition PIBSAs).
The Mannich dispersant are the reaction products of alkyl phenols in which the alkyl group contains at least about 30 carbon atoms with aldehydes (especially formaldehyde) and amines (especially polyalkylene polyamines). Mannich bases having the following general structure (including a variety of different isomers and
the like) are especially interesting.
and/or
Another class of ashless dispersants is nitrogen containing carboxylic dispersants. Examples of these “carboxylic dispersants” are described in Patent U.S. Pat. No. 3,219,666.
Amine dispersants are reaction products of relatively high molecular weight aliphatic halides and amines, preferably polyalkylene polyamines. Examples thereof are described, in U.S. Pat. No. 3,565,804.
Polymeric dispersants are interpolymers of oil-solubilizing monomers such as decyl methacrylate, vinyl decyl ether and high molecular weight olefins with monomers containing polar substituents, e.g., amino alkyl acrylates or acrylamides and poly-(oxyethylene)-substituted acrylates. Examples of polymer dispersants thereof are disclosed in the following U.S. Pat. Nos. 3,329,658 and 3,702,300.
Dispersants can also be post-treated by reaction with any of a variety of agents. Among these are urea, thiourea, dimercaptothiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, expoxides, boron compounds, and phosphorus compounds.
The ashless dispersants can be used alone or in combination. The dispersant is present in the range from about 0.02 wt % to about 99.5 wt % gel, in another embodiment in the range from about 1 wt % to about 70 wt % gel, and in another embodiment in the range from about 5 wt % to about 50 wt % total weight of the gel.
The acid includes a polymer containing acidic groups in the backbone, for example, polymers derived from styrene and maleic anhydride, polymers derived from acrylates including acrylic acid, acrylic acid esters, methacrylic acid and its esters, polymers derived from high molecular weight (Cn wherein n≦12) esters and acids, polymers derived from esterified maleic anhydride styrene copolymers, polymers derived from esterified ethylene diene monomer copolymer; surfactants with acidic groups in the backbone; emulsifiers with acidic groups in the backbone; polyacidic compounds, for example, polyacidic surfactants and/or polyacidic dispersants; functionalized derivatives of each component listed herein and mixtures thereof.
In one embodiment, the acid is formed from the polymerization of styrene and maleic anhydride. In one embodiment, the copolymer is partially esterified with one or more C6 to C32 alcohol or mixture of alcohols and in another embodiment C8 to C18 alcohols. The equivalent ratio of alcohol to acid groups is from about 0.1wt % to about 0.99 wt % and in another embodiment about 0.45 wt % to about 0.95 wt %. In one embodiment, the polyacidic surfactants include a maleinated OCP (olefin copolymer of ethylene and propylene). In another embodiment, the polyacidic surfactants include di-isobutenyl succan from the reaction of di-isobutylene and maleic anhydride. In one embodiment, the polyacidic dispersants include a succinimide resulting from reaction of ≦1 equivalent of an ethylene diamine polyamine with the maleinated OCP. In another embodiment, the polyacidic dispersants include a succinimide resulting from reaction of ≦1 equivalent of an ethylene diamine polyamine with di-isobutenyl succan. The TAN is ≧1, in another embodiment the TAN is ≧3 (e.g. koH/g and the oil blend viscosity at about 10% oil is 75 cSTO 100 C and in another embodiment 10 cST o100 C. In one embodiment, the acid must have residual acid groups with a total acid number ≧1 and in another embodiment ≧3.
The acids can be used alone or in combination. The acid is present in the range from about 0.02 wt % to about 99.5 wt %, in one embodiment in the range from about 0.1 wt % to about 90 wt %, and in another embodiment in the range from about 1 wt % to about 80 wt %.
Typically, the additive gel further contains at least one desired additive for controlled release into the lubricant fluid. The additive gel desired components include viscosity modifier(s), friction modifier(s), ashless detergent(s), cloud point depressant(s), pour point depressant(s), demulsifier(s), flow improver(s), anti static agent(s), ashless dispersant(s), ashless antioxidant(s), antifoam(s), corrosion/rust inhibitor(s), extreme pressure/antiwear agent(s), seal swell agent(s), lubricity aid(s), antimisting agent(s), and mixtures thereof, resulting in a controlled release gel that over time releases the desired additive(s) into the lubricant when the gel is contacted with the lubricant. The desired additive component is further determined by the lubricant formulation, performance characteristics, function and the like and what additive is desired to be added for depleted additives and/or added new depending on the desired functions.
The desired additive optional components of the ashless detergent, ashless dispersant, and/or ashless antioxidants are compounds that contain a base component which is an acid neutralizing component that is free of ash containing components. Examples include, but are not limited to, high nitrogen to carbonyl (≧1:1) dispersants; nitrogen containing antioxidants such as substituted biphenyl amines, organic amines such as C 5 to C 36 amines, ethoxylated amines and the like. The ashless detergents, ashless dispersants and/or ashless antioxidants have a TBN which is ≧1, in another embodiment the TBN is ≧10 and in another embodiment the TBN is ≧50.
Ashless antioxidants include alkyl-substituted phenols such as 2,6-di-tertiary butyl-4-methyl phenol, phenate sulfides, phosphosulfurized terpenes, sulfurized esters, aromatic amines, diphenyl amines, alkylated diphenyl amines and hindered phenols, bis-nonylated diphenylamine, nonyl diphenylamine, octyl diphenylamine, bis-octylated diphenylamine, bis-decylated diphenylamine, decyl diphenylamine and mixtures thereof.
The ashless antioxidant function includes sterically hindered phenols and includes but is not limited to 2,6-di-tert-butylphenol, 4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol, 4-propyl-2,6-di-tert-butylphenol, 4-butyl-2,6-di-tert-butylphenol 2,6-di-tert-butylphenol, 4-pentyl-2-6-di-tert-butylphenol, 4-hexyl-2,6-di-tert-butylphenol, 4-heptyl-2,6-di-tert-butylphenol, 4-(2-ethylhexyl)-2,6-di-tert-butylphenol, 4-octyl-2,6-di-tert-butylphenol, 4-nonyl-2,6-di-tert-butylphenol, 4-decyl-2,6-di-tert-butylphenol, 4-undecyl-2,6-di-tert-butylphenol, 4-dodecyl-2,6-di-tert-butylphenol, 4-tridecyl-2,6-di-tert-butylphenol, 4-tetradecyl-2,6-di-tert-butylphenol, methylene-bridged sterically hindered phenols include but are not limited to 4,4-methylenebis(6-tert-butyl-o-cresol), 4,4-methylenebis(2-tert-amyl-o-cresol), 2,2-methylenebis(4-metyl-6-tert-butylphenol), 4,4-methylene-bis(2,6-di-tertbutylphenol) and mixtures thereof
Another example of an ashless antioxidant is a hindered, ester-substituted phenol, which can be prepared by heating a 2,6-dialkylphenol with an acrylate ester under based conditions, such as aqueous KOH.
Ashless antioxidants may be used alone or in combination. The antioxidants are typically present in the range of about 0.01 wt % to about 95 wt %, in one embodiment in the range from about 0.01 wt % to 95 wt %, and in another embodiment in the range from about 1 wt % to about 70 wt % and in another embodiment in the range from about 5 wt % to about 60 wt % total weight of the gel.
The extreme pressure/anti-wear agents include a sulfur or chlorosulphur EP agent, a chlorinated hydrocarbon EP agent, or a phosphorus EP agent, or mixtures thereof. Examples of such EP agents are amine salts of phosphorus acid acid, chlorinated wax, organic sulfides and polysulfides, such as benzyldisulfide, bis-(chlorobenzyl) disulfide, dibutyl tetrasulfide, sulfurized sperm oil, sulfurized methyl ester of oleic acid sulfurized alkylphenol, sulfurized dipentene, sulfurized terpene, and sulfurized Diels-Alder adducts; phosphosulfurized hydrocarbons, such as the reaction product of phosphorus sulfide with turpentine or methyl oleate, phosphorus esters such as the dihydrocarbon and trihydrocarbon phosphate, i.e., dibutyl phosphate, diheptyl phosphate, dicyclohexyl phosphate, pentylphenyl phosphate; dipentylphenyl phosphate, tridecyl phosphate, distearyl phosphate and polypropylene substituted phenol phosphate, metal thiocarbamates, such as zinc dioctyldithiocarbamate and barium heptylphenol diacid, such as zinc dicyclohexyl phosphorodithioate and the zinc salts of a phosphorodithioic acid combination may be used and mixtures thereof.
In one embodiment the antiwear agent/extreme pressure agent comprises an amine salt of a phosphorus ester acid. The amine salt of a phosphorus ester acid includes phosphoric acid esters and salts thereof, dialkyldithiophosphoric acid esters and salts thereof, phosphites; and phosphorus-containing carboxylic esters, ethers, and amides; and mixtures thereof.
In one embodiment the phosphorus compound further comprises a sulfur atom in the molecule. In one embodiment the amine salt of the phosphorus compound is ashless, i.e., metal-free (prior to being mixed with other components).
The amines which may be suitable for use as the amine salt include primary amines, secondary amines, tertiary amines, and mixtures thereof. The amines include those with at least one hydrocarbyl group, or, in certain embodiments, two or three hydrocarbyl groups. The hydrocarbyl groups may contain about 2 to about 30 carbon atoms, or in other embodiments about 8 to about 26 or about 10 to about 20 or about 13 to about 19 carbon atoms.
Primary amines include ethylamine, propylamine, butylamine, 2-ethylhexylamine, octylamine, and dodecylamine, as well as such fatty amines as n-octylamine, n-decylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine, n-octadecylamine and oleylamine. Other useful fatty amines include commercially available fatty amines such as “ArmeenOR” amines (products available from Akzo Chemicals, Chicago, Ill.), such as Armeen C, Armeen O, Armeen OL, Armeen T, Armeen HT, Armeen S and Armeen SD, wherein the letter designation relates to the fatty group, such as coco, oleyl, tallow, or stearyl groups.
Examples of suitable secondary amines include dimethylamine, diethylamine, dipropylamine, dibutylamine, diamylamine, dihexylamine, diheptylamine, methylethylamine, ethylbutylamine and ethylamylamine. The secondary amines may be cyclic amines such as piperidine, piperazine and morpholine.
The amine may also be a tertiary-aliphatic primary amine. The aliphatic group in this case may be an alkyl group containing about 2 to about 30, or about 6 to about 26, or about 8 to about 24 carbon atoms. Tertiary alkyl amines include monoamines such as tert-butylamine, tert-hexylamine, 1-methyl-1-amino-cyclohexane, tert-octylamine, tert-decylamine, tert-dodecylamine, tert-tetradecylamine, tert-hexadecylamine, tert-octadecylamine, tert-tetracosanylamine, and tert-octacosanylamine.
Mixtures of amines may also be used in the invention. In one embodiment a useful mixture of amines is “Primene® 81R” and “Primene® JMT.” Primene® 81R and Primene® JMT (both produced and sold by Rohm & Haas) are mixtures of C11 to C14 tertiary alkyl primary amines and C18 to C22 tertiary alkyl primary amines respectively.
Suitable hydrocarbyl amine salts of alkylphosphoric acid may be represented by the following formula:
wherein R3 and R4 are independently hydrogen or hydrocarbyl groups such as alkyl groups; for the phosphorus ester acid, at least one of R3 and R4 will be hydrocarbyl. R3 and R4 may contain about 4 to about 30, or about 8 to about 25, or about 10 to about 20, or about 13 to about 19 carbon atoms. R5, R6 and R7 may be independently hydrogen or hydrocarbyl groups, such as alkyl branched or linear alkyl chains with 1 to about 30, or about 4 to about 24, or about 6 to about 20, or about 10 to about 16 carbon atoms. These R5, R6 and R7 groups may be branched or linear groups, and in certain embodiments at least one, or alternatively two of R5, R6 and R7 are hydrogen. Examples of alkyl groups suitable for R5, R6 and R7 include butyl, sec-butyl, isobutyl, tert-butyl, pentyl, n-hexyl, sec-hexyl, n-octyl, 2-ethylhexyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, octadecenyl, nonodecyl, eicosyl groups and mixtures thereof.
In one embodiment the hydrocarbyl amine salt of an alkylphosphoric acid ester is the reaction product of a C14 to C18 alkylated phosphoric acid with Primene 81R™ (produced and sold by Rohm & Haas) which is a mixture of C11 to C14 tertiary alkyl primary amines.
Similarly, hydrocarbyl amine salts of dialkyldithiophosphoric acid esters of the invention used in the rust inhibitor package may be represented by the formula:
wherein the various R groups are as defined above, although typically both R groups are hydrocarbyl or alkyl. Examples of hydrocarbyl amine salts of dialkyldithiophosphoric acid esters include the reaction product(s) of hexyl, heptyl or octyl or nonyl, 4-methyl-2-pentyl or 2-ethylhexyl, isopropyl dithiophosphoric acids with ethylene diamine, morpholine, or Primene 81R™, and mixtures thereof.
In one embodiment the dithiophosphoric acid may be reacted with an epoxide or a glycol. This reaction product is further reacted with a phosphorus acid, anhydride, or lower ester. The epoxide includes an aliphatic epoxide or a styrene oxide. Examples of useful epoxides include ethylene oxide, propylene oxide, butene oxide, octene oxide, dodecene oxide, styrene oxide and the like. In one embodiment the epoxide is Propylene oxide. The glycols may be aliphatic glycols having from 1 to about 12, or from about 2 to about 6, or about 2 to about 3 carbon atoms. The dithiophosphoric acids, glycols, epoxides, inorganic phosphorus reagents and methods of reacting the same are described in U.S. Pat. Nos. 3,197,405 and 3,544,465. The resulting acids may then be salted with amines. An example of suitable dithiophosphoric acid is prepared by adding phosphorus pentoxide (about 64 grams) at about 58° C. over a period of about 45 minutes to about 514 grams of hydroxypropyl O,O-di(4-methyl-2-pentyl)phosphorodithioate (prepared by reacting di(4-methyl-2-pentyl)-phosphorodithioic acid with about 1.3 moles of propylene oxide at about 25° C. ). The mixture is heated at about 75° C. for about 2.5 hours, mixed with a diatomaceous earth and filtered at about 70° C. The filtrate contains about 11.8% by weight phosphorus, about 15.2% by weight sulfur, and an acid number of 87 (bromophenol blue).
The EP/antiwear agents are present in the range of about 0 wt % to about 50 wt %, in one embodiment in the range from about 0.25 wt % to about 25 wt % and in another embodiment in the range from about 0.5 wt % to about 10 wt % total weight of the gel.
The antifoams include organic silicones such as poly dimethyl siloxane, poly ethyl siloxane, polydiethyl siloxane, polyacrylates and polymethacrylates, trimethyl-triflouro-propylmethyl siloxane and the like.
The antifoams may be used alone or in combination. The antifoams are used in the range of about 0 wt % to about 20 wt %, in one embodiment in the range of about 0.02 wt % to about 10 wt % and in another embodiment in the range of 0.05 wt % to about 2.5 wt % total weight of the gel.
The viscosity modifier provides both viscosity improving properties and dispersant properties. Examples of dispersant-viscosity modifiers include vinyl pyridine, N-vinyl pyrrolidone and N,N′-dimethylaminoethyl methacrylate are examples of nitrogen-containing monomers and the like. Polyacrylates obtained from the polymerization or copolymerization of one or more alkyl acrylates also are useful as viscosity modifiers.
Functionalized polymers can also be used as viscosity modifiers. Among the common classes of such polymers are olefin copolymers and acrylate or methacrylate copolymers. Functionalized olefin copolymers can be, for instance, interpolymers of ethylene and propylene which are grafted with an active monomer such as maleic anhydride and then derivatized with an alcohol or an amine. Other such copolymers are copolymers of ethylene and propylene which are reacted or grafted with nitrogen compounds. Derivatives of polyacrylate esters are well known as dispersant viscosity index modifiers additives. Dispersant acrylate or polymethacrylate viscosity modifiers such as Acryloid™ 985 or Viscoplex™ 6-054, from RohMax, are particularly useful. Solid, oil-soluble polymers such as the PIB (polyisobutylene), methacrylate, polyalkystyrene, ethylene/propylene and ethylene/propylene/1,4-hexadiene polymers and maleic anhydride-styrene interpolymer and derivatives thereof, can also be used as viscosity index improvers. The viscosity modifiers are known and commercially available.
The viscosity modifiers may be used alone or in combination. The viscosity modifiers are present in the range of about 0 wt % to 80 wt %, in one embodiment in the range from about 0.25 wt % to about 50 wt % and in another embodiment in the range from about 0.5 wt % to about 10 wt % total weight of the gel.
The friction modifiers include organo-molybdenum compounds, including molybdenum dithiocarbamates, and fatty acid based materials, including those based on oleic acid, including glycerol mono-oleate, those based on stearic acid, and the like.
In one embodiment, the friction modifier is a phosphate ester or salt including a monohydrocarbyl, dihydrocarbyl or a trihydrocarbyl phosphate, wherein each hydrocarbyl group is saturated. In several embodiments, each hydrocarbyl group contains from about 8 to about 30, or from about 12 up to about 28, or from about 14 up to about 24, or from about 14 up to about 18 carbons atoms. In another embodiment, the hydrocarbyl groups are alkyl groups. Examples of hydrocarbyl groups include tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl groups and mixtures thereof.
In one embodiment, the phosphate salts may be prepared by reacting an acidic phosphate ester with an amine compound or a metallic base to form an amine or a metal salt. The amines may be monoamines or polyamines. Useful amines include those amines disclosed in U.S. Pat. No. 4,234,435 at Col. 21, line 4 to Col. 27, line 50.
Useful amines include primary ether amines, such as those represented by the formula, R″(OR′)x—NH2, wherein R′ is a divalent alkylene group having about 2 to about 6 carbon atoms; x is a number from one to about 150, or from about one to about five, or one; and R″ is a hydrocarbyl group of about 5 to about 150 carbon atoms.
The phosphate salt may be derived from a polyamine. The polyamines include alkoxylated diamines, fatty polyamine diamines, alkylenepolyamines, hydroxy containing polyamines, condensed polyamines, arylpolyamines, and heterocyclic polyamines.
The metal salts of the phosphorus acid esters are prepared by the reaction of a metal base with the acidic phosphorus ester. The metal base may be any metal compound capable of forming a metal salt. Examples of metal bases include metal oxides, hydroxides, carbonates, borates, or the like. Suitable metals include alkali metals, alkaline earth metals and transition metals. In one embodiment, the metal is a Group IIA metal, such as calcium or magnesium, Group IIB metal, such as zinc, or a Group VIIB metal, such as manganese. Examples of metal compounds which may be reacted with the phosphorus acid include zinc hydroxide, zinc oxide, copper hydroxide or copper oxide.
In one embodiment, the friction modifier is a phosphite and may be a monohydrocarbyl, dihydrocarbyl or a trihydrocarbyl phosphite, wherein each hydrocarbyl group is saturated. In several embodiments each hydrocarbyl group independently contains from about 8 to about 30, or from about 12 up to about 28, or from about 14 up to about 24, or from about 14 up to about 18 carbons atoms. In one embodiment, the hydrocarbyl groups are alkyl groups. Examples of hydrocarbyl groups include tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl groups and mixtures thereof.
In one embodiment, the friction modifier is a fatty imidazoline comprising fatty substituents containing from 8 to about 30, or from about 12 to about 24 carbon atoms. The substituent may be saturated or unsaturated, preferably saturated. In one aspect, the fatty imidazoline may be prepared by reacting a fatty carboxylic acid with a polyalkylenepolyamine, such as those discussed above. A suitable fatty imidazoline includes those described in U.S. Pat. No. 6,482,777.
The friction modifiers can be used alone or in combination. The friction reducing agents are present in the range of about 0 wt % to 60 wt %, or from about 0.25 wt % to about 40 wt %, or from about 0.5 wt % to about 10 wt % total weight of the gel.
The anti-misting agents include very high (≧100,000 Mn) polyolefins such as 1.5 Mn polyisobutylene (for example the material of the trades name Vistanex®), or polymers containing 2-(N-acrylamido), 2-methyl propane sulfonic acid (also known as AMPS®), or derivatives thereof, and the like.
The anti-misting agents can be used alone or in combination. The anti-misting agents are present in the range of about 0 wt % to 10 wt %, or from about 0.25 wt % to about 10 wt %, or from about 0.5 wt % to about 2.5 wt % total weight of the gel.
The corrosion inhibitors include alkylated succinic acids and anhydrides derivatives thereof, organo phosphonates and the like. The rust inhibitors may be used alone or in combination. The rust inhibitors are present in the range of about 0 wt % to about 20 wt %, and in one embodiment in the range from about 0.0005 wt % to about 10 wt % and in another embodiment in the range from about 0.0025 wt % to about 2.5 wt % total weight of the gel.
The ashless metal deactivators include derivatives of benzotriazoles such as tolyltriazole, N,N-bis(heptyl)-ar-methyl-1H-benzotriazole-1-methanamine, N,N-bis(nonyl)-ar-methyl-1H-Benzotriazole-1-methanamine, N,N-bis(decyl)ar-methyl-1H-Benzotriazole-1-methanamine, N,N-(undecyl)ar-methyl-1H-benzotriazole-1-methanamine, N,N-bis(dodecyl)ar-methyl-1H-Benzotriazole-1-methanamine N,N-bis(2-ethylhexyl)-ar-methyl-1H-Benzotriazole-1-methanamine and mixtures thereof. In one embodiment the metal deactivator is N,N-bis(1-ethylhexyl)ar-methyl-1H-benzotriazole-1-methanamine;1,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles; 2-alkyldithiobenzothiazoles; 2-N,N-dialkyldithio-carbamoyl)benzothiazoles;2,5-bis(alkyl-dithio)-1,3,4-thiadiazoles such as 2,5-bis(tert-octyldithio)-1,3,4-thiadiazole 2,5-bis(tert-nonyldithio)-1,3,4-thiadiazole, 2,5-bis(tert-decyldithio)-1,3,4-thiadiazole, 2,5-bis(tert-undecyldithio)-1,3,4-thiadiazole, 2,5-bis(tert-dodecyldithio)-1,3,4-thiadiazole, 2,5-bis(tert-tridecyldithio)-1,3,4-thiadiazole, 2,5-bis(tert-tetradecyldithio)-1,3,4-thiadiazole, 2,5-bis(tert-octadecyldithio)-1,3,4-thiadiazole, 2,5-bis(tert-nonadecyldithio)-1,3,4-thiadiazole, 2,5-bis(tert-eicosyldithio)-1,3,4-thiadiazole and mixtures thereof; 2,5-bis(N,N-dialkyldithiocarbamoyl)-1,3,4-thiadiazoles; 2-alkydithio-5-mercapto thiadiazoles; and the like.
The ashless metal deactivators may be used alone or in combination. The ashless metal deactivators are present in the range of about 0 wt % to about 50 wt %, or from about 0.0005 wt % to about 25 wt %, or from about 0.0025 wt % to about 10 wt % total weight of the gel.
The demulsifiers include polyethylene and polypropylene oxide copolymers and the like. The demulsifiers may be used alone or in combination. The demulsifiers are present in the range of about 0 wt % to about 20 wt %, or from about 0.0005 wt % to about 10 wt %, or from about 0.0025 wt % to about 2.5 wt % total weight of the gel.
The lubricity aids include glycerol mono oleate, sorbitan mono oleate and the like. The lubricity additives may be used alone or in combination. The lubricity additives are present in the range of about 0 wt % to about 50 wt %, or from about 0.0005 wt % to about 25 wt %, or from about 0.0025 wt % to about 10 wt % total weight of the gel.
The flow improvers include ethylene vinyl acetate copolymers and the like. The flow improvers may be used alone or in combination. The flow improvers are present in the range of about 0 wt % to about 50 wt %, or from about 0.0005 wt % to about 25 wt %, or from about 0.0025 wt % to about 5 wt % total weight of the gel.
The cloud point depressants include alkylphenols and derivatives thereof, ethylene vinyl acetate copolymers and the like. The cloud point depressants may be used alone or in combination. The cloud point depressants are present in the range of about 0 wt % to about 50 wt %, or from about 0.0005 wt % to about 25 wt %, or from about 0.0025% to about 5 wt % total weight of the gel.
The pour point depressants include alkylphenols and derivatives thereof, ethylene vinyl acetate copolymers and the like. The pour point depressant may be used alone or in combination. The pour point depressant are present in the range of about 0 wt % to about 50 wt %, or from about 0.0005 wt % to about 25 wt %, or from about 0.0025 wt % to about 5 wt % total weight of the gel.
The seal swell agents include organo sulfur compounds such as thiophene, 3-(decyloxy)tetrahydro-1,1-dioxide, phthalates and the like. The seal swell agents may be used alone or in combination. The seal swell agents are present in the range of about 0 wt % to about 50 wt %, or from about 0.0005 wt % to about 25 wt %, or from about 0.0025 wt % to about 5 wt % total weight of the gel.
Optionally, other components can be added to the gel which includes base stock oils, inert carriers, dyes, bacteriostatic agents, solid particulate additives, and the like so long as these components do not have a detrimental effect on the gel.
In one embodiment the invention provides a method for lubricating a mechanical device. Typically the oil-soluble gel is delivered from within an oil filter, but any means by which the gel can be brought into contact with the lubricant can be used e.g., container/delivery device within the oil pan, or within a fluid by-pass loop.
The gel is positioned within the lubricating system, anywhere the gel will be in contact with the lubricant including, but not limited to, lubricating oil, motor oil, hydraulic fluid, transmission driveline fluid, metal working fluid and the like. The gel is positioned anywhere that the circulating lubricant contacts the gel such as full flow of oil, bypass of the oil in the reservoir or combinations therein. The location of the gel in the lubricating system includes, but is not limited to, a filter, drain pan, oil bypass loop, canister, housing, reservoir, pockets of a filter, canister in a filter, mesh in a filter, canister in a bypass system, mesh in a bypass system and the like. One or more locations can contain the gel. Further, if more than one gel is used it can be identical, similar and/or a different gel.
In one embodiment, the gel is positioned anywhere in the filter. The filter is a desirable location to place the gel because the gel and/or spent gel can easily be removed, and then replaced with a new and/or recycled gel.
The gel needs to be in contact with the engine oil, in one embodiment the gel is in contact with the oil in the range of about 100% to about 1% of the oil system, in another embodiment the gel is in contact with the oil in the range of about 75% to about 25% of the oil system and in another embodiment the gel is in contact with the oil in the range of about 50% of the oil system.
The release rate of the additive components in the gel is determined primarily by the gel formulation. The release rate is also dependent on the form of the gel and/or the mode of addition. The gel is positioned in a location desirable for the specified and desirable dissolution rate of the specified additives. The gel's formulation may be composed of one or more components that selectively dissolve completely or a portion of the components remain till the end of its service life or combinations thereof.
The gel is added to the lubrication system by any known method depending on the desired form of the gel, the desired speed of addition, the desired release rate, the desired mode of operation and/or any of the combinations of the above. In one embodiment the additive composition is a gel and is added to the lubricating system by means of an injector pump, or a container in the oil filter. In one embodiment the gel is added to the lubricating system by means of an addition device such as an auger system.
In one embodiment the properties imparted by the desired additives include dispersancy, antioxidance, corrosion inhibition, wear prevention, scuffing prevention, pitting prevention including micro and macro pitting, friction modifying properties including increased and/or decreased friction coefficients, detergency, viscosity control using viscosity modifiers, foam control or mixtures thereof.
In accordance with the present invention, a controlled release gel is provided for fluid conditioning devices. The present invention of a gel can be used in any fluid conditioning device including internal combustion engines which include mobile and stationary engines, natural gas engines, marine diesel engines, generators, on highway and/or off highway engines, hydraulic systems, automatic transmissions, gear boxes which include manual transmissions and differentials (e.g., front and rear drive axles and industrial speed increasers or reducers), metalworking fluids, pumps, suspension systems, other lubricated mechanical systems, industrial lubricated system and the like.
The controlled release of the ashless base-containing gel formulation has been demonstrated along with corresponding improvement in acid neutralization performance efficiency.
Gel 1 is formed of the following composition:
aDerived from Maleic anhydride-styrene copolymer (0.69 RSV)/C8–10 Alcohol/C12-18 Alcohol/MeSO4H(catalyst) (2.9:0.87:1.7:0.11) eq in SUAQ Oil to 60%, Total Acid Number = 23 meq KOH/g.
bDerived from alykylation of diphenylamine with nonene using AIC12 catalyst, Total Base Number = 156 meq KOH/g.
cDerived from 850–1600 Mn high vinylidene polyisobutylene, maleic anhydride and tetraethylene pentamine, Total Base Number = 100
The polymer and half of the antioxidant are mixed to form Component A. The dispersant and the other half of the antioxidant are mixed to form Component B. Component B was then added to Component A with stirring and the resulting mixture heated at about 100 C for about 12 hours. The resulting Gel (Gel 1) was used in Example 2 and 3.
The Gel 1 (about 50 g) was loaded into the bottom of a 1-L beaker and about 500 g of Valvoline 10 W-30 added. The resulting mixture was heated at about 100 C and oil samples were taken at regular intervals over 13 days and the total base number measured by ASTM Test Method D2896. The results are shown in Table 1.
These results show that controlled release of ashless base can be achieved using a gel of the composition described herein.
Gel 1 (about 71 g) was loaded into a cylindrical cup, with about 2 mm holes located on the top face. The container was placed at the crown end of an oil filter of the same size and fittings as a Fram PH3387A oil filter, and installed on a 2002 Pontiac Grand Prix. The car was then driven under normal stop-and-go conditions for about 500 miles, with oil samples taken at regular intervals and the total base number analyzed by ASTM D2896 and the total acid number analyzed by ATMS method D664A. The results are shown in Table 2.
These results show that controlled release of ashless base can be achieved in a vehicle under actual driving conditions using a gel of the composition described above.
In another specific embodiment, Gel 2 is formed pursuant to Example 1 but with the following components:
The polymer and half of the borate are mixed to form Component A. The dispersant and the other half of the borate are mixed to form Component B. Component B was then added to Component A with stirring and the resulting mixture heated at 100 C for 12 hours. The resulting Gel (Gel 2) was used in Example 5.
The Gel 5 (about 50g) was loaded into the bottom of a 1-L beaker and 500 g of Valvoline 10 W-30 added. The resulting mixture was heated and oil samples were taken at regular intervals over 13 days and the total base number measured by ASTM Test Method D2896. The results are shown in Table 3.
These results show that controlled release of ashless base can be achieved using a gel of the composition described herein.
Gel 2, (about 71 g,) was loaded into a cylindrical cup, with about 2 mm holes located on the top face. The container was placed at the crown end of an oil filter of the same size and fittings as a Fram 4967 oil filter, and installed on a 1998 4-cylinder Toyota Camry. The car was then driven under normal stop-and-go conditions for about 500 miles, with oil samples taken at regular intervals and the total base number analyzed by ASTM D4730 and the total acid number analyzed by ATMS method D664A. The results are compared to the same analyses for the car when driven without the gel in the filter (Comparative Example) and are shown in Table 4.
These results show that the controlled release ashless gel of the composition described in Example 5 reduces acid build-up in an engine under actual driving conditions.
In another specific embodiment, Gel 3 is formed of the composition below:
dMitsui Lucant A-5320H
by the mixing procedure used for Gel 2, Example 4.
The gel 3 (5 g) was loaded into a metal 2-oz jar cap and placed in the bottom of a 100-mL beaker and about 50 g of Valvoline 10 W-30 added. The resulting mixture was heated and oil samples were taken at regular intervals over 13 days and the total base number measured by ASTM Test Method D2896. The results are shown in Table 5.
These results show that controlled release of ashless base can be achieved using a gel of the composition described herein.
Gel 4 is formed by the following components:
hAkeda Saukuralube 100 friction modifier
iLiquid Corrosion Inhibitor
The components are mixed per the procedure used for Gel 2 in Example 6.
The gel (5 g) was loaded into a metal 2-oz jar cap and placed in the bottom of a 100-mL beaker and 50 g of Valvoline 10 W-30 added. The resulting mixture was heated and oil samples were taken at regular intervals over 8 days and the % Mo measure by inductively coupled plasma (ICP) analysis. The results are shown in Table 16. These results show that controlled release of Mo FM gel can be achieved using an ash less FM gel of the composition described in Table 16.
In another specific embodiment, an ash less DIS/AO gel is formed of the following component (Gel 5):
iLiquid Corrosion Inhibitor
jDerived from 850–1600 Mn high vinylidene
k2,6di-tert-butyl, 4-(3 butylpropanoyl) phenol
In another specific embodiment, an ash less VM gel is formed of the following components (Gel 6):
eEthylene-propylene copolymer, MW = 105–106.
The EPDM and the dil oil are mixed and half of the resulting solution is mixed with dispersant to form Component A. The other half of the EPDM/dil oil solution is mixed with MSC to form Component B. Component A and B are then mixed and the resulting mixture heated at lOOC for 12 hours. The resulting Gel 6 (VM Gel) was used in Example 9.
The above gel (Gel 6) (about 18 g) was loaded into a plastic cylinder 2 inch high and 1 inch in diameter with 18 equally spaced 0.25 inch square openings. The loaded gel container was placed in the bottom of a 250-mL beaker and about 90 g of Valvoline 10 W-30 oil added. The resulting mixture was heated at 100 C and oil samples were taken at regular intervals over 4 days and the kinematic viscosity measured at 100 C by ASTM Test Method D445—100. The results are shown in Table 9. These results show that controlled release of ashless viscosity modifier can be achieved using a gel of the composition described in Table 7 below.
In another specific embodiment, an ash less FM gel is formed from the following component.
The dispersants and the phenolic antioxidant are mixed with half of the diphenylamine antioxidant to form Component A. The MSC and the Saukuralube are mixed with the other half of the diphenylamine antioxidant to form Component B. Component A was then added to Component B with stirring and the resulting mixture heated at 100 C for 12 hours.
The resulting Gel (DIS/AO Gel) was used in Example 13.
The gel (5 g) was loaded into a metal 2-oz jar cap and placed in the bottom of a 100-mL beaker and 50 g of Valvoline 10 W-30 added. The resulting mixture was heated and oil samples were taken at regular intervals over 8 days and the % Mo measure by inductively coupled plasma (ICP) analysis. The results are shown in Table 8.
These results show that controlled release of the DIS/AO Gel components can be achieved using an ash less DIS/AO Gel of the composition described in example 12.
Although only a few embodiments of the present invention have been described above, it should be appreciated that many modifications can be made without departing from the spirit and scope of the invention. All such modifications are intended to be included within the scope of the present invention, which is to be limited only by the following claims:
