Lubricant Compositions Comprising Core-Shell Colloidal Zn-Containing Particles

Abstract

This invention relates to the use of colloids of a core of zinc containing compounds and a shell of metal containing surfactants, such as salicylates and or sulfonates, metal alkanoates, and or metal carboxylates, as additives in lubricant compositions having good anti-wear properties, especially for engine crankcase applications.

What is claimed is: 
     
         1 . A lubricating oil composition comprising or resulting from the admixing of:
 (A) from 1 to 99.99 wt. %, based upon the weight of the lubricating composition, of one or more base oils;   (B) at least one phosphorus-containing compound selected from detergents, friction modifiers or antiwear additives other than the colloidal particles described in (C);   (C) from 0.01 to 10 wt. %, based upon the weight of the composition, of colloidal particles comprising:   a) a core of one or more hydrocarbon insoluble zinc containing compounds, and   b) a shell of one or more of:   1) one or more metal containing surfactants, where the metal, M, comprises a group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal; and the surfactant comprises a hydrocarbyl-substituted sulfonate of Formula (I), or an hydrocarbyl-substituted salicylate group of Formula (II),   
       
         
           
           
               
               
           
         
         wherein each of R A  and R B  is, independently of each other, a linear, cyclic, or branched, saturated or unsaturated, aliphatic hydrocarbon group having from 1 to 70 carbon atoms, wherein, for n>1, the sum of the number of carbon atoms in the total of R A  groups in Formula (I) and the sum of the number of carbon atoms in the total of R B  groups in Formula (II) is 100 or less carbon atoms, and Ar is a mono- or polycyclic aromatic group; n is an integer from 1 to the maximum possible number of substitutions on Ar, with n=1 if m=0; m is an integer of 1 to 3, x is an integer from 1 to 5; y is an integer from 1 to 5, L is a ligand saturating the coordination sphere of M, and p is an integer from 0 to 8; 
         2) one or more metal alkanoates represented by the formula (III): 
       
       
         
           
           
               
               
           
         
         wherein M is a group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal; R C  is selected from a linear, cyclic, or branched, saturated or unsaturated, aliphatic hydrocarbon group having from 6 to 70 carbon atoms, or an aromatic or alkyl aromatic group with the aromatic group having from 6 to 20 carbon atoms and the alkyl group having 1 to 20 carbon atoms; x is an integer from 1 to 5, wherein for x>1 the R C  groups may be the same or different, y is an integer from 1 to 5, L is a ligand saturating the coordination sphere of M, and p is an integer from 0 to 8, 
         wherein the lubricating oil composition has a ratio of Zn to P (elemental mass basis as measured by ASTM D5185) of 1.1 to 5.0. 
       
     
     
         2 . The lubricating composition of  claim 1 , wherein the hydrocarbon insoluble zinc containing compound is selected from at least one of zinc, zinc oxide, zinc hydroxide, zinc carbonate, and zinc halides, or mixtures thereof. 
     
     
         3 . The lubricating composition of  claim 1 , wherein the colloidal particles have a mean particle diameter as determined by dynamic light scattering in the range of 5 nm to 1 μm. 
     
     
         4 . The lubricating composition of  claim 1 , wherein the metal M in Formula (I), (II), or (III) is selected from at least one of sodium, potassium, lithium, magnesium, calcium, barium, or mixtures thereof; or wherein the metal M is selected from at least one of gold, silver, palladium, platinum, zirconium, vanadium, molybdenum, nickel, copper, zinc, aluminum, or mixtures thereof. 
     
     
         5 . The lubricating composition of  claim 1 , wherein Ar in Formula (I) or Formula (II) is benzene or naphthalene. 
     
     
         6 . The lubricating composition of  claim 5 , wherein the surfactant of Formula (I) is a metal containing hydrocarbyl-substituted phenyl sulfonate surfactant of Formula (Ia), 
       
         
           
           
               
               
           
         
         wherein M is selected from calcium, magnesium, barium, or zinc, or combinations thereof, R A  is independently of each other a linear, cyclic, or branched, saturated or unsaturated, aliphatic hydrocarbon group having from 6 to 50 carbon atoms; n is an integer from 1 to 5, with n=1 if m=0; m is 0 to 3; the sum of the number of carbon atoms in the total of R A  groups is 60 or less carbon atoms; x is 2; y is 2; and, optionally, p is 0. 
       
     
     
         7 . The lubricating composition of  claim 5 , wherein the surfactant of Formula (II) is a metal containing hydrocarbyl-substituted phenyl salicylate surfactant of Formula (IIa), 
       
         
           
           
               
               
           
         
         wherein M is selected from calcium, magnesium, barium, or zinc, or combinations thereof, R B  is independently of each other a linear, cyclic, or branched, saturated or unsaturated, aliphatic hydrocarbon group having from 6 to 50 carbon atoms; n is an integer from 1 to 4; the sum of the number of carbon atoms in the total of R B  groups is 60 or less carbon atoms; x is 2, y is 2; and, optionally, p is 0. 
       
     
     
         8 . The lubricating composition of  claim 1 , wherein M in Formula (I), (II), or (III) is selected from calcium, magnesium, or zinc, or combinations thereof. 
     
     
         9 . The lubricating composition of  claim 1 , wherein R in Formula (III) is a linear, cyclic, or branched, alkyl or alkenyl group having from 6 to 48 carbon atoms. 
     
     
         10 . The lubricating composition  claim 9 , wherein the metal alkanoate of Formula (III) is one or more of zinc neodecanoate, zinc neoundecanoate, zinc neododecanoate, zinc neotridecanoate, zinc neotetradecanoate, zinc neopentadecanoate, zinc neohexadecanoate, zinc neoheptadecanoate, zinc stearate, zinc neooctadecanoate, zinc oleate, zinc neononadecanoate, and zinc neoeicosanoate. 
     
     
         11 . The lubricating composition of  claim 9 , wherein the metal alkanoates have a quaternary carbon atom at the 2 position attached to the carboxylate group. 
     
     
         12 . The lubricating composition of  claim 10 , wherein the metal alkanoates have a quaternary carbon atom at the 2 position attached to the carboxylate group. 
     
     
         13 . The lubricating composition of  claim 1 , further comprising one or more components selected from the group consisting of one or more friction modifiers; one or more antioxidants; one or more pour point depressants; one or more anti-foaming agents; one or more viscosity modifiers; one or more dispersants; one or more inhibitors and/or anti-rust agents; and/or one or more anti-wear agents, other than those of component (C). 
     
     
         14 . The lubricating composition of  claim 1 , wherein:
 (A) the base oil is present at 50 to 99 wt. % based upon the weight of the lubricating composition;   (B) the at least one phosphorus-containing compound selected from detergents, friction modifiers, or antiwear additives other than the colloidal particles described in (C) is present in an amount of 0.001 to 5 wt. %;   C) the colloidal particles are present at from 0.01 to 10 wt. %, such as 0.01 to 6 wt. % based on total weight of the lubricating composition;   D) optionally, one or more friction modifiers other than those of component (B) are present at from 0.01 to 5 wt. %, based on total weight of the lubricating composition;   E) optionally, one or more antioxidants are present at from 0.01 to 10 wt. %, based on total weight of the lubricating composition;   F) optionally, one or more pour point depressants are present at from 0.01 to 5 wt. %, based on total weight of the lubricating composition;   G) optionally, one or more anti-foaming agents are present at from 0.001 to 5 wt. %, based on total weight of the lubricating composition;   H) optionally, one or more viscosity modifiers are present at from 0.001 to 6 wt. %, based on total weight of the lubricating composition;   I) optionally, one or more dispersants are present at from 0.01 to 20 wt. %, based on total weight of the lubricating composition;   J) optionally, one or more inhibitors and/or anti-rust agents are present at from 0.01 to 5 wt. %, based on total weight of the lubricating composition; and   K) optionally, one or more anti-wear agents, other than those of components (B) and (C), are present at from 0.001 to 5 wt. %, based on total weight of the lubricating composition;   L) optionally, one or more detergents, other than those of components (B) and in the colloidal particles described in (C) are present at from 0.1 to 20 wt. % based on total weight of the lubricating composition.   
     
     
         15 . The lubricating composition of  claim 1 , wherein the lubricating composition has an adhesive wear of 100 hours or more, as measured by ASTM D8074-16. 
     
     
         16 . The lubricating composition of  claim 1 , wherein a ratio of Zn to P (elemental mass basis) is 1.1 to 4.9 in the lubricating composition. 
     
     
         17 . The lubricating composition of  claim 1 , wherein the ligand L is selected from the group consisting of water, hydroxide, halide, ammonia, amino, amido, alcoholate, and mixtures thereof. 
     
     
         18 . The lubricating composition of  claim 1 , wherein the colloidal particles have a molar ratio of metal to surfactant, MR, of at least 5. 
     
     
         19 . The lubricating composition of  claim 1 , wherein a total base number (TBN) of the composition is from 1 to 30 mgKOH/g, as measured by ASTM D2896. 
     
     
         20 . The lubricating composition of  claim 1 , having a zinc content of 500 ppm or more, as determined by ASTM D5185. 
     
     
         21 . The lubricating composition of  claim 1 , having a phosphorus content of not more than 2000 ppm, based on the total mass of the lubricating compositions, as measured by ASTM D5185. 
     
     
         22 . The lubricating composition of  claim 1  wherein the lubricating composition is a combustion engine oil or a gas turbine oil. 
     
     
         23 . The lubricating composition of  claim 1 , wherein the lubricating composition is transmission fluid or gear oil. 
     
     
         24 . The lubricating composition of  claim 1 , comprising more than 500 ppm of Zn and less than 500 ppm of P, wherein the lubricating composition has an adhesive wear of 100 hours or more, and optionally a total base number of 7 mgKOH/g or more. 
     
     
         25 . The lubricating composition of  claim 1 , comprising more than 1000 ppm of Zn and less than 1000 ppm of P, wherein the lubricating composition has an adhesive wear of 100 hours or more, and optionally a total base number of 7 mgKOH/g or more. 
     
     
         26 . The lubricating composition of  claim 1 , wherein zinc dialkyl dithiophosphates are present at 2 wt. % or less. 
     
     
         27 . The lubricating composition of  claim 1 , wherein the lubricating composition has a wear scar volume of less than 150 μm 3 , determined by HFRR method as described herein. 
     
     
         28 . A method to obtain an adhesive wear of 100 hours or more (ASTM D 8074-16) for a lubricating composition having 500 ppm of zinc or more, preferably 1000 ppm of zinc or more comprising:
 (i) providing to the lubricating composition of  claim 1  to a crankcase of an internal combustion engine;   (ii) providing a hydrocarbon fuel in the internal combustion engine; and   (iii) combusting the fuel in the internal combustion engine.   
     
     
         29 . A method of lubricating an internal combustion engine during operation of the engine comprising:
 (i) providing the lubricating composition of  claim 1  to a crankcase of the internal combustion engine;   (ii) providing fuel in the internal combustion engine; and   (iii) combusting the fuel in the internal combustion engine, wherein the fuel comprises hydrocarbon fuel derived from petroleum and or biological sources; hydrogen fuel, optionally combined with liquified natural gas; and or ammonia fuel.   
     
     
         30 . The method of  claim 29  wherein the engine is a diesel engine, a gas engine, or a marine engine. 
     
     
         31 . A concentrate composition comprising or resulting from the admixing of:
 (A) from 1 to less than 50 wt. % of one or more base oils, based upon the weight of the concentrate composition;   (B) at least one phosphorus-containing compound selected from detergents, friction modifiers or antiwear additives other than the colloidal particles described in (C);   (C) from 0.1 to 50 wt. %, based upon the weight of the composition, of colloidal particles comprising:   a) a core of one or more hydrocarbon insoluble zinc containing compounds, and   b) a shell of one or more of:   1) one or more metal containing surfactants, where the metal, M, comprises a group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal; and the surfactant comprises an hydrocarbyl-substituted sulfonate of Formula (I), or an hydrocarbyl-substituted salicylate group of Formula (II),   
       
         
           
           
               
               
           
         
         wherein each R A , and R B  is, independently of each other, a linear, cyclic, or branched, saturated or unsaturated, aliphatic hydrocarbon group having from 1 to 70 carbon atoms, wherein, for n>1, the sum of the number of carbon atoms in the total of R A  groups in Formula (I) and the sum of the number of carbon atoms in the total of R B  groups in Formula (II) is 100 or less carbon atoms, and Ar is a mono- or polycyclic aromatic group; n is an integer from 1 to the maximum possible number of substitutions on Ar, with n=1 if m=0; m is an integer of 0 to 3, x is an integer from 1 to 5; y is an integer from 1 to 5, L is a ligand saturating the coordination sphere of M, and p is an integer from 0 to 8; 
         2) one or more metal alkanoates represented by the formula (III): 
       
       
         
           
           
               
               
           
         
         wherein M is a group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal; R C  is selected from a linear, cyclic, or branched, saturated or unsaturated, aliphatic hydrocarbon group having from 6 to 70 carbon atoms, or an aromatic or alkyl aromatic group with the aromatic group having from 6 to 20 carbon atoms and the alkyl group having 1 to 20 carbon atoms; x is an integer from 1 to 5, wherein for x>1 the R C  groups may be the same or different, y is an integer from 1 to 5, L is a ligand saturating the coordination sphere of M, and p is an integer from 0 to 8; 
         wherein the concentrate composition has a ratio of Zn to P (elemental mass basis as measured by ASTM D5185) of 1.1 to 5.0. 
       
     
     
         32 . An antiwear additive comprising or resulting from the admixing of:
 (A) from 1 to less than 50 wt. % of one or more base oils, based upon the weight of the composition;   (B) at least one phosphorus-containing compound selected from detergents, friction modifiers or antiwear additives other than the colloidal particles described in (C);   (C) from 0.1 to 50 wt. %, based upon the weight of the composition, of colloidal particles comprising:   a) a core of one or more hydrocarbon insoluble zinc containing compounds, and   b) a shell of one or more of:   1) one or more metal containing surfactants, where the metal, M, comprises a group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal; and the surfactant comprises an hydrocarbyl-substituted aromatic sulfonate of Formula (I), or an hydrocarbyl-substituted salicylate group of Formula (II),   
       
         
           
           
               
               
           
         
         wherein each R A , and R B  is, independently of each other, a linear, cyclic, or branched, saturated or unsaturated, aliphatic hydrocarbon group having from 1 to 70 carbon atoms, wherein, for n>1, the sum of the number of carbon atoms in the total of R A  groups in Formula (I) and the sum of the number of carbon atoms in the total of R B  groups in Formula (II) is 100 or less carbon atoms, and Ar is a mono- or polycyclic aromatic group; n is an integer from 1 to the maximum possible number of substitutions on Ar, with n=1 if m=0; m is an integer of 0 to 3, x is an integer from 1 to 5; y is an integer from 1 to 5, L is a ligand saturating the coordination sphere of M, and p is an integer from 0 to 8; 
         2) one or more metal alkanoates represented by the formula (III): 
       
       
         
           
           
               
               
           
         
         wherein M is a group 1, 2, 4, 5, 6, 10, 11, 12, or 13 metal; R C  is selected from a linear, cyclic, or branched, saturated or unsaturated, aliphatic hydrocarbon group having from 6 to 70 carbon atoms, or an aromatic or alkyl aromatic group with the aromatic group having from 6 to 20 carbon atoms and the alkyl group having 1 to 20 carbon atoms; x is an integer from 1 to 5, wherein for x>1 the R C  groups may be the same or different, y is an integer from 1 to 5, L is a ligand saturating the coordination sphere of M, and p is an integer from 0 to 8; 
         wherein the composition has a ratio of Zn to P (elemental mass basis as measured by ASTM D5185) of 1.1 to 5.0. 
       
     
     
         33 . The composition of  claim 1 , wherein the colloidal particles have a mean particle diameter as determined by dynamic light scattering in the range of 20 to 200 nm;
 wherein M in Formula (I) or (II) is selected from calcium, magnesium, or combinations thereof,   wherein the metal alkanoate of Formula (III) is one or more of zinc neodecanoate, zinc neoundecanoate, zinc neododecanoate, zinc neotridecanoate, zinc neotetradecanoate, zinc neopentadecanoate, zinc neohexadecanoate, zinc neoheptadecanoate, zinc stearate, zinc neooctadecanoate, zinc oleate, zinc neononadecanoate, and zinc neoeicosanoate,   wherein the metal alkanoates have a quaternary carbon atom at the 2 position attached to the carboxylate group;   wherein the ratio of Zn to P (elemental mass basis) is 1.5 to 4.5, in the lubricating composition; and   wherein the colloidal particles have a molar ratio of metal to surfactant, MR, of 6 to 40.