Lubricating oil compositions with improved wear performance and engine cleanliness

Abstract

This invention relates to a diesel engine lubricating oil composition comprising or resulting from the admixing of: (i) base oil, (ii) a functionalized polymer, (iii) an overbased magnesium based detergent, and (iv) one or more, optionally borated, higher and/or lower molecular weight PIBSA-PAM dispersant. The composition has a total sulfated ash of less than or equal to 0.9 wt. %, a kinematic viscosity at 100° C. of 5 to 20 cSt, a total phosphorous level of less than or equal to 0.120 wt. %, and a total sulfur level of less than or equal to 0.35 wt. % and provides a Detroit DD-13 scuffing test result of at least 31 hours. Also provided are a method of making the composition, a method of lubricating a diesel engine, a method of improving wear performance and engine cleanliness and reducing emissions of a diesel engine, and a diesel engine oil additive concentrate composition.

What is claimed is: 
     
         1 . A lubricating oil composition comprising or resulting from the admixing of:
 an oil of lubricating viscosity at greater than 50 wt. % of the composition comprising a Group II base oil, a Group III base oil, a Group IV base oil, or combinations thereof;   a functionalized polymer at from 0.1 to 20 wt. %, of the composition comprising an amide, imide, and/or ester functionalized partially or fully saturated polymer comprising C 4-5  olefins having:   vii) an Mw/Mn of less than 2,   viii) a Functionality Distribution (Fd) value of 3.5 or less, and   iii) an Mn of 10,000 g/mol or more (GPC-PS) of the polymer prior to functionalization,   
       provided that, if the polymer prior to functionalization is a copolymer of isoprene and butadiene, then the Mn of the copolymer is greater than 25,000 g/mol (GPC-PS);
 an overbased calcium based detergent with a Total Base Number (KOH/g) greater than or equal to 9 and less than or equal to 500 and at treat level to deliver at least 500 ppm by weight of calcium to the composition; 
 an overbased magnesium based detergent with a Total Base Number (KOH/g) greater than or equal to 9 and less than or equal to 500 and at treat level to deliver at least 200 ppm by weight of magnesium to the composition; 
 optionally, one or more, optionally borated, higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn 1600 g/mol or more), and 
 one or more, optionally borated, lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn less than 1600 g/mol), wherein the treat level of the combination of the higher molecular weight PIBSA-PAM and lower molecular weight PIBSA-PAM is from 1.0 to 6.0 wt. % of the composition, and wherein the treat level of the higher molecular weight PIBSA-PAM is less than or equal to 4.0 wt. % of the composition; 
 the lubricating oil composition having a total sulfated ash of less than or equal to 0.9 wt. %, a kinematic viscosity at 100° C. of 5 to 20 cSt, a total phosphorous level of less than or equal to 0.120 wt. %, and a total sulfur level of less than or equal to 0.35 wt. %, and 
 wherein the lubricating oil composition provides a Detroit DD-13 scuffing (ASTM D8074-22) test result of at least 31 hours. 
 
     
     
         2 . The lubricating oil composition of  claim 1 , wherein the higher molecular weight PIBSA-PAM is borated, the lower molecular weight PIBSA-PAM is borated or a combination thereof, and is/are included at a treat level to deliver from 20 ppm to 700 ppm by weight of boron to the composition. 
     
     
         3 . The lubricating oil composition of  claim 1 , wherein the composition is substantially free of the higher molecular weight PIBSA-PAM. 
     
     
         4 . The lubricating oil composition of  claim 1 , wherein the oil of lubricating viscosity is at from 60 wt. % to 95 wt. % of the composition, comprises a Group II base oil, and is substantially free of the Group III base oil and the Group IV base oil. 
     
     
         5 . The lubricating oil composition of  claim 1 , wherein the overbased magnesium based detergent is a sulfonate, a salicylate, a phenate or combinations thereof. 
     
     
         6 . The lubricating oil composition of  claim 1 , wherein the overbased calcium based detergent is a sulfonate, a salicylate, a phenate or combinations thereof. 
     
     
         7 . The lubricating oil composition of  claim 1 , wherein the lubricating oil composition has a high temperature high shear viscosity at 150° C. (HTHS) as determined according to ASTM D4683-20 of greater than or equal to 2.6 mPa·s and less than or equal to 3.2 mPa·s, or wherein the lubricating oil composition has a HTHS of greater than or equal to 3.5 mPa·s. 
     
     
         8 . The lubricating oil composition of  claim 1 , wherein the lubricating oil composition results in a turbocharger #1 deposit rating of greater than or equal to 50 and a piston cleanliness rating of greater than or equal to 74 in the Daimler OM471 engine test (CEC L-118-21). 
     
     
         9 . The lubricating oil composition of  claim 1 , wherein the lubricating oil composition results in an oxidation induction time of greater than or equal to 65 minutes in the pressure differential scanning calorimetry (PDSC) oxidative stability test (CEC L-85_T-99). 
     
     
         10 . The lubricating oil composition of  claim 1 , wherein the lubricating oil composition having a kinematic viscosity at 100° C. of 9 to 20 cSt results in a rocker arm mass loss of less than or equal to 100 mg in the Ford 6.7 L valve train wear test. 
     
     
         11 . The lubricating oil composition of  claim 1 , further including one or more of the following components: 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 other than the higher molecular weight PIBSA-PAM and the lower molecular weight PIBSA-PAM; one or more inhibitors, one or more antirust agents; one or more seal swell agents; and/or one or more anti-wear agents. 
     
     
         12 . The lubricating oil composition of  claim 11 , wherein the one or more anti-wear agents includes one or more zinc dialkyldithiophosphates (ZDDP) at a treat level to deliver less than or equal to 0.12% by weight of phosphorous to the composition. 
     
     
         13 . The lubricating oil composition of  claim 11 , wherein the one or more antioxidants includes one or more phenolic antioxidants, one or more sulfur based antioxidants, one or more aminic antioxidants or a combination thereof, and wherein the one or more antioxidants comprise from 1.0 to 6.0 wt. % of the composition. 
     
     
         14 . The lubricating oil composition of  claim 11 , wherein the one or more friction modifier includes a dimeric molybdenum dialkyldithiocarbamate (moly dimer), a trimeric molybdenum dialkyldithiocarbamate (moly trimer), or a combination thereof at a treat level to deliver from 12 ppm to 200 ppm by weight of molybdenum to the composition. 
     
     
         15 . The lubricating oil composition of  claim 1 , wherein the composition is substantially free of molybdenum. 
     
     
         16 . The lubricating oil composition of  claim 1 , wherein the functionalized polymer comprises at least 50% of 1,4-insertions of monomer. 
     
     
         17 . The lubricating oil composition of  claim 1 , wherein the functionalized polymer comprises a partially or fully saturated homopolyisoprene containing one or more pendant amine groups and having an Mn of 25,000 to 100,000 g/mol (GPC-PS) and at least 50% of 1,4-insertions prior to functionalization. 
     
     
         18 . The lubricating oil composition of  claim 1 , wherein styrene repeat units are absent in the functionalized polymer. 
     
     
         19 . The lubricating oil composition of  claim 1 , wherein butadiene repeat units are absent in the functionalized polymer. 
     
     
         20 . The lubricating composition of  claim 1 , wherein the functionalized polymer is not homo-polyisobutylene. 
     
     
         21 . The lubricating oil composition of  claim 1 , wherein the functionalized polymer is not a copolymer of isoprene and butadiene. 
     
     
         22 . The lubricating oil composition of  claim 1 , wherein the lubricating oil composition is a heavy-duty diesel oil, a light-duty diesel oil, a hydrogen engine oil, a spark ignition combustion engine oil or a natural gas engine oil. 
     
     
         23 . The lubricating composition of  claim 1 , wherein lubricating oil composition is an SAE grade selected from the group consisting of 0W-20, 0W-30, 5W-20, 5W-30, 10W-30, 15W-40, 5W-40 and 10W-40. 
     
     
         24 . The lubricating oil composition of  claim 1 , wherein the lubricating oil composition is a heavy-duty diesel oil meeting the API PC-12 specification. 
     
     
         25 . A concentrate comprising or resulting from the admixing of:
 from 1 to less than or equal to 50 wt. % of one or more base oils;   from 1 to 30 wt. %, such as 2 to 20 wt. %, based upon the weight of the concentrate, of one or more of the functionalized polymers of the composition comprising an amide, imide, and/or ester functionalized partially or fully saturated polymer comprising C 4-5  olefins having:
 vii) an Mw/Mn of less than 2, 
 viii) a Functionality Distribution (Fd) value of 3.5 or less, and 
 ix) an Mn of 10,000 g/mol or more (GPC-PS) of the polymer prior to functionalization, 
 provided that, if the polymer prior to functionalization is a copolymer of isoprene and butadiene, then the Mn of the copolymer is greater than 25,000 g/mol (GPC-PS); 
   from 2 to 20 wt. % of an overbased magnesium based detergent with a Total Base Number (KOH/g) greater than or equal to 9 and less than or equal to 500;   from 2 to 20 wt. % of an overbased calcium based detergent with a Total Base Number (KOH/g) greater than or equal to 9 and less than or equal to 500; and   from 2 to 40 wt. % of one or more, optionally borated, higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn 1600 g/mol or more), and/or one or more, optionally borated, lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn less than 1600 g/mol).   
     
     
         26 . A method of lubricating an engine comprising supplying to the engine a lubricating oil composition of  claim 1 . 
     
     
         27 . The method of  claim 26 , further including providing a diesel fuel to the engine and combusting the diesel fuel in the engine, wherein the diesel fuel is a non-renewable diesel fuel, a renewable diesel fuel or a combination thereof, and wherein the engine is a diesel engine. 
     
     
         28 . The method of  claim 26 , further including providing a natural gas or hydrogen to the engine and combusting the natural gas or hydrogen in the engine, wherein the engine is a natural gas engine or a hydrogen engine. 
     
     
         29 . A method of improving wear performance and engine cleanliness and reducing emissions of an engine comprising supplying to the engine a lubricating oil composition of  claim 1 . 
     
     
         30 . The method of  claim 29 , further including providing a diesel fuel to the engine and combusting the diesel fuel in the engine, wherein the diesel fuel is a non-renewable diesel fuel, a renewable diesel fuel or a combination thereof, and wherein the engine is a diesel engine. 
     
     
         31 . The method of  claim 29 , further including providing a natural gas or hydrogen to the engine and combusting the natural gas or hydrogen in the engine, wherein the engine is a natural gas engine or a hydrogen engine. 
     
     
         32 . A method of making a lubricating oil composition comprising combining:
 (1) an oil of lubricating viscosity at greater than 50 wt. % of the composition comprising a Group II base oil, a Group III base oil, a Group IV base oil, or combinations thereof,   (2) a functionalized polymer at from 0.1 to 20 wt. %, of the composition comprising an amide, imide, and/or ester functionalized partially or fully saturated polymer comprising C4-5 olefins having:
 i) an Mw/Mn of less than 2, 
 ii) a Functionality Distribution (Fd) value of 3.5 or less, and 
 iii) an Mn of 10,000 g/mol or more (GPC-PS) of the polymer prior to functionalization, 
 provided that, if the polymer prior to functionalization is a copolymer of isoprene and butadiene, then the Mn of the copolymer is greater than 25,000 g/mol (GPC-PS); 
   (3) an overbased calcium based detergent with a Total Base Number (KOH/g) greater than or equal to 9 and less than or equal to 500 and at treat level to deliver at least 500 ppm by weight of calcium to the composition;   (4) an overbased magnesium based detergent with a Total Base Number (KOH/g) greater than or equal to 9 and less than or equal to 500 and at treat level to deliver at least 200 ppm by weight of magnesium to the composition;   (5) optionally, one or more, optionally borated, higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn 1600 g/mol or more), and   (6) one or more, optionally borated, lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn less than 1600 g/mol), wherein the treat level of the combination of the higher molecular weight PIBSA-PAM and lower molecular weight PIBSA-PAM is from 1.0 to 6.0 wt. % of the composition, and wherein the treat level of the higher molecular weight PIBSA-PAM is less than or equal to 4.0 wt. % of the composition; and   wherein the lubricating oil composition has a total sulfated ash of less than or equal to 0.9 wt. %, a kinematic viscosity at 100° C. of 5 to 20 cSt, a total phosphorous level of less than or equal to 0.120 wt. %, and a total sulfur level of less than or equal to 0.35 wt. %, and   wherein the lubricating oil composition provides a Detroit DD-13 scuffing (ASTM D8074-22) test result of at least 31 hours.   
     
     
         33 . The method of  claim 32 , wherein the higher molecular weight PIBSA-PAM is borated, the lower molecular weight PIBSA-PAM is borated or a combination thereof, and is/are included at a treat level to deliver from 20 ppm to 700 ppm by weight of boron to the composition. 
     
     
         34 . The method of  claim 32 , wherein the composition is substantially free of the higher molecular weight PIBSA-PAM. 
     
     
         35 . The method of  claim 32 , wherein the oil of lubricating viscosity comprises from 60 wt. % to 95 wt. %, based upon the weight of the composition, of Group II base oil, and is substantially free of Group III base oil and Group IV base oil. 
     
     
         36 . The method of  claim 32 , wherein the overbased magnesium based detergent is a sulfonate, a salicylate, a phenate or combinations thereof. 
     
     
         37 . The method of  claim 32 , wherein the overbased calcium based detergent is a sulfonate, a salicylate, a phenate or combinations thereof. 
     
     
         38 . The method of  claim 32 , wherein the lubricating oil composition has a HTHS of greater than or equal to 2.6 mPa·s and less than or equal 3.2 mPa·s, or wherein the lubricating oil composition has a HTHS of greater than or equal to 3.5 mPa·s. 
     
     
         39 . The method of  claim 32 , wherein the lubricating oil composition results in a turbocharger #1 deposit rating of greater than or equal to 50 and a piston cleanliness rating of greater than or equal to 74 in the Daimler OM471 engine test (CEC L-118-21). 
     
     
         40 . The method of  claim 32 , wherein the lubricating oil composition results in an oxidation induction time of greater than or equal to 65 minutes in the pressure differential scanning calorimetry (PDSC) oxidative stability test (CEC L-85 T-99). 
     
     
         41 . The method of  claim 32 , wherein the lubricating oil composition having a kinematic viscosity at 100° C. of 9 to 20 cSt results in a rocker arm mass loss of less than or equal to 100 mg in the Ford 6.7 L valve train wear test. 
     
     
         42 . The method of  claim 32 , further including one or more of the following components:
 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 other than the higher molecular weight PIBSA-PAM and the lower molecular weight PIBSA-PAM; one or more inhibitors, one or more antirust agents; one or more seal swell agents; and/or one or more anti-wear agents.   
     
     
         43 . The method of  claim 42 , wherein the one or more anti-wear agents includes one or more zinc dialkyldithiophosphates (ZDDP) at a treat level to deliver less than or equal to 0.12% by weight of phosphorous to the composition. 
     
     
         44 . The method of  claim 42 , wherein the one or more antioxidants includes one or more phenolic antioxidants, one or more sulfur based antioxidants, one or more aminic antioxidants or a combination thereof, and wherein the one or more antioxidants comprise from 1.0 to 6.0 wt. % of the composition. 
     
     
         45 . The method of  claim 42 , wherein the one or more friction modifier includes a dimeric molybdenum dialkyldithiocarbamate (moly dimer), a trimeric molybdenum dialkyldithiocarbamate (moly trimer), or a combination thereof at a treat level to deliver from 12 ppm to 200 ppm by weight of molybdenum to the composition. 
     
     
         46 . The method of  claim 32 , wherein the composition is substantially free of molybdenum. 
     
     
         47 . The method of  claim 32 , wherein the functionalized polymer comprises at least 50% of 1,4-insertions of monomer. 
     
     
         48 . The method of  claim 32 , wherein the functionalized polymer comprises a partially or fully saturated homopolyisoprene containing one or more pendant amine groups and having an Mn of 25,000 to 100,000 g/mol (GPC-PS) and at least 50% of 1,4-insertions prior to functionalization. 
     
     
         49 . The method of  claim 32 , wherein styrene repeat units are absent in the functionalized polymer. 
     
     
         50 . The method of  claim 32 , wherein butadiene repeat units are absent in the functionalized polymer. 
     
     
         51 . The method of  claim 32 , wherein the functionalized polymer is not homo-polyisobutylene. 
     
     
         52 . The method of  claim 32 , wherein the functionalized polymer is not a copolymer of isoprene and butadiene. 
     
     
         53 . The method of  claim 32 , wherein lubricating oil composition is a heavy-duty diesel oil, a light-duty diesel oil, a hydrogen engine oil, a spark ignition combustion engine oil or a natural gas engine oil. 
     
     
         54 . The method of  claim 32 , wherein the lubricating oil composition is an SAE grade selected from the group consisting of 0W-20, 0W-30, 5W-20, 5W-30, 10W-30, 15W-40, 5W-40 and 10W-40. 
     
     
         55 . The method of  claim 32 , wherein the lubricating oil composition is a heavy-duty diesel oil meeting the API PC-12 specification. 
     
     
         56 . A lubricating oil composition comprising or resulting from the admixing of:
 an oil of lubricating viscosity at greater than 50 wt. % of the composition comprising a Group I, Group II base oil, a Group III base oil, a Group IV base oil, or combinations thereof;   a functionalized polymer at from 0.1 to 20 wt. %, of the composition comprising an amide, imide, and/or ester functionalized partially or fully saturated polymer comprising C 4-5  olefins having:   v) an Mw/Mn of less than 2,   vi) a Functionality Distribution (Fd) value of 3.5 or less, and   iii) an Mn of 10,000 g/mol or more (GPC-PS) of the polymer prior to functionalization(GPC-PS);   an overbased calcium based detergent with a Total Base Number (KOH/g) greater than or equal to 9 and less than or equal to 500 and at treat level to deliver at least 500 ppm by weight of calcium to the composition;   an overbased magnesium based detergent with a Total Base Number (KOH/g) greater than or equal to 9 and less than or equal to 500 and at treat level to deliver at least 200 ppm by weight of magnesium to the composition;   one or more, optionally borated, higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn 1600 g/mol or more), and   one or more, optionally borated, lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn less than 1600 g/mol), wherein the treat level of the combination of the higher molecular weight PIBSA-PAM and lower molecular weight PIBSA-PAM is from 1.0 to 6.0 wt. % of the composition, and wherein the treat level of the higher molecular weight PIBSA-PAM is less than or equal to 4.0 wt. % of the composition;   the lubricating oil composition having a total sulfated ash of less than or equal to 0.9 wt. %, a kinematic viscosity at 100° C. of 5 to 20 cSt, a total phosphorous level of less than or equal to 0.120 wt. %, and a total sulfur level of less than or equal to 0.35 wt. %, and   wherein the lubricating oil composition provides the following: 1) a Detroit DD-13 scuffing (ASTM D8074-22) test result of at least 31 hours, 2) a high temperature high shear viscosity at 150° C. (HTHS) as determined according to ASTM D4683-20 of greater than or equal to 2.6 mPa·s and less than or equal to 3.2 mPa·s or wherein the lubricating oil composition has a HTHS of greater than or equal to 3.5 mPa·s, 3) a turbocharger #1 deposit rating of greater than or equal to 50 and a piston cleanliness rating of greater than or equal to 74 in the Daimler OM471 engine test (CEC L-118-21), 4) an oxidation induction time of greater than or equal to 65 minutes in the pressure differential scanning calorimetry (PDSC) oxidative stability test (CEC L-85_T-99), and 5) when the lubricating oil composition has a kinematic viscosity at 100° C. of 9 to 20 cSt results in a rocker arm mass loss of less than or equal to 100 mg in the Ford 6.7 L valve train wear test.   
     
     
         57 . The lubricating oil composition of  claim 1 , where the functionalized polymer is present at from 0.3 to 5 wt. %. 
     
     
         58 . The lubricating oil composition of  claim 56 , where the functionalized polymer is present at from 0.3 to 5 wt. %. 
     
     
         59 . A lubricating oil composition comprising or resulting from the admixing of:
 an oil of lubricating viscosity at greater than 50 wt. % of the composition comprising a Group I, Group II base oil, a Group III base oil, a Group IV base oil, or combinations thereof;   a functionalized polymer at from 0.1 to 20 wt. %, of the composition comprising an amide, imide, and/or ester functionalized partially or fully saturated polymer comprising C 4-5  olefins having:   iii) an Mw/Mn of less than 2,   iv) a Functionality Distribution (Fd) value of 3.5 or less, and   iii) an Mn of 10,000 g/mol or more (GPC-PS) of the polymer prior to functionalization,   
       provided that, if the polymer prior to functionalization is a copolymer of isoprene and butadiene, then the Mn of the copolymer is greater than 25,000 g/mol (GPC-PS);
 an overbased calcium based detergent with a Total Base Number (KOH/g) greater than or equal to 9 and less than or equal to 500 and at treat level to deliver at least 500 ppm by weight of calcium to the composition; 
 an overbased magnesium based detergent with a Total Base Number (KOH/g) greater than or equal to 9 and less than or equal to 500 and at treat level to deliver at least 200 ppm by weight of magnesium to the composition; 
 optionally, one or more, optionally borated, higher molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn 1600 g/mol or more), and 
 one or more, optionally borated, lower molecular weight polyisobutylene succinimide (PIBSA-PAM) dispersant (Mn less than 1600 g/mol), wherein the treat level of the combination of the higher molecular weight PIBSA-PAM and lower molecular weight PIBSA-PAM is from 1.0 to 6.0 wt. % of the composition, and wherein the treat level of the higher molecular weight PIBSA-PAM is from 0 to 4.0 wt. % of the composition; 
 the lubricating oil composition having a total sulfated ash of less than or equal to 0.9 wt. %, a kinematic viscosity at 100° C. of 5 to 20 cSt, a total phosphorous level of less than or equal to 0.120 wt. %, and a total sulfur level of less than or equal to 0.35 wt. %, and 
 wherein the lubricating oil composition provides a Detroit DD-13 scuffing (ASTM D8074-22) test result of at least 31 hours.