# US 9,434,906 B2 · Marine diesel engine lubricating oil compositions > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,434,906 B2 - Document ID: US9434906B2 - Status: Granted - Kind: B2 - Application number: 13/849,884 - Filed: 2013-03-25 - Published: 2014-09-25 - Granted: 2016-09-06 - Earliest claimed: 2013-03-25 - Assignees: Chevron Oronite Company LLC; Chevron Oronite Technology B.V. - Applicants: Ronald Theodorus Fake Jukes; Eugene E. Spala - Inventors: Ronald Theodorus Fake Jukes; Eugene E. Spala - Web page: https://patentgrep.com/patent/US9434906B2 ## CPC - C10M 169/044: {the additives being a mixture of non-macromolecular and macromolecular compounds} - C10M 159/22: containing phenol radicals - C10M 2203/1006: used as base material - C10M 2207/262: derived from hydroxy substituted aromatic acids, e.g. salicylates - C10M 2219/046: Overbased sulfonic acid salts - C10M 2219/089: Overbased salts - C10N 2010/04: Groups 2 or 12 - C10N 2020/02: Viscosity; Viscosity index - C10N 2030/02: Pour-point; Viscosity index - C10N 2030/04: Detergent property or dispersant property - C10N 2030/10: Inhibition of oxidation, e.g. anti-oxidants - C10N 2030/52: {Base number [TBN]} - C10N 2040/252: {Diesel engines} - C10N 2060/10: by sulfur or a compound containing sulfur - C10N 2070/00: Specific manufacturing methods for lubricant compositions - C10M: LUBRICATING COMPOSITIONS (well drilling compositions C09K8/02); USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION (mould release, i.e. separating, agents for metals B22C3/00, for plastics or substances in a plastic state, in general B29C33/56, for glass C03B40/02; textile lubricating compositions D06M11/00, D06M13/00, D06M15/00; immersion oils for microscopy G02B21/33) - C10N: INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS ## Abstract Disclosed herein are marine diesel engine lubricating oil compositions which comprises (a) a major amount of an oil of lubricating viscosity, and (b) about 3 wt. % to about 40 wt. %, based on the total weight of the marine diesel engine lubricating oil composition, of a sulfurized, alkaline earth metal alkylphenate detergent which is substantially free of polyol promoter oxidation products. ## Claims ### Claim 1 A marine diesel engine lubricating oil composition which comprises (a) a major amount of an oil of lubricating viscosity, and (b) about 3 wt. % to 14.19 wt. %, based on the total weight of the marine diesel engine lubricating oil composition, of a sulfurized, alkaline earth metal alkylphenate detergent which is substantially free of polyol promoter oxidation products, the sulfurized, alkaline earth metal alkylphenate detergent being prepared by a process comprising (i) contacting an alkylphenol having at least one alkyl substituent from 6 to 36 carbon atoms with sulfur, in the presence of a promoter acid selected from the group of alkanoic acids having 1 through 3 carbon atoms, mixtures of the alkanoic acids, alkaline earth metal salts of the alkanoic acids and mixtures thereof, and at least a stoichiometric amount of a calcium base sufficient to neutralize the alkylphenol and the promoter at a temperature of from about 130° C. to about 250° C. under reactive conditions in the absence of at polyol promoter or an alkanol having 1 to 5 carbon atoms for a sufficient period of time to react essentially all of the sulfur thereby yielding a calcium sulfurized alkylphenate essentially free of elemental sulfur; and (ii) contacting the reaction product of step (i) with carbon dioxide and additional calcium base, if required, to provide the desired TBN, in the presence of an alkylene glycol having 2 to 6 carbon atoms under reactive conditions at a temperature of from about 150° C. to about 260° C., wherein the marine diesel engine lubricating oil composition has a total base number (TBN) of from about 30 to about 70. ### Claim 2 (depends on 1) The marine diesel engine lubricating oil composition of claim 1, having a TBN of from about 40 to about 70. ### Claim 3 (depends on 1) The marine diesel engine lubricating oil composition of claim 1, having a kinematic viscosity at 100° C. of from about 12.5 to about 26.1 centistokes (cSt). ### Claim 4 (depends on 1) The marine diesel engine lubricating oil composition of claim 1, further comprising one or more alkaline earth metal sulfonates. ### Claim 5 (depends on 4) The marine diesel engine lubricating oil composition of claim 4, wherein the one or more alkaline earth metal sulfonates are alkaline earth metal alkylaromatic sulfonates. ### Claim 6 (depends on 5) The marine diesel engine lubricating oil composition of claim 5, wherein the one or more alkaline earth metal alkylaromatic sulfonates are low overbased alkaline earth metal alkylaromatic sulfonates. ### Claim 7 (depends on 5) The marine diesel engine lubricating oil composition of claim 5, wherein the one or more alkaline earth metal alkylaromatic sulfonates are high overbased alkaline earth metal alkylaromatic sulfonates. ### Claim 8 (depends on 1) The marine diesel engine lubricating oil composition of claim 1, further comprising one or more alkali or alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid. ### Claim 9 (depends on 1) The marine diesel engine lubricating oil composition of claim 1, further comprising a marine diesel engine lubricating oil composition additive selected from the group consisting of an antioxidant, ashless dispersant, detergent, rust inhibitor, dehazing agent, demulsifying agent, metal deactivating agent, friction modifier, pour point depressant, antifoaming agent, co-solvent, package compatibiliser, corrosion-inhibitor, dyes, extreme pressure agent and mixtures thereof. ### Claim 10 A method for improving oxidative stability of a marine diesel engine lubricating oil composition used in a marine diesel engine, the method comprising adding about 3 wt. % to 14.19 wt. %, based on the total weight of the marine diesel engine lubricating oil composition, of a sulfurized, alkaline earth metal alkylphenate detergent which is substantially free of polyol promoter oxidation products to a marine diesel engine lubricating oil composition comprising a major amount of an oil of lubricating viscosity to form a marine diesel engine lubricating oil composition having a TBN of from about 30 to about 70, wherein the sulfurized, alkaline earth metal alkylphenate detergent is prepared by a process comprising (i) contacting an alkylphenol having at least one alkyl substituent from 6 to 36 carbon atoms with sulfur, in the presence of a promoter acid selected from the group of alkanoic acids having 1 through 3 carbon atoms, mixtures of the alkanoic acids, alkaline earth metal salts of the alkanoic acids and mixtures thereof, and at least a stoichiometric amount of a calcium base sufficient to neutralize the alkylphenol and the promoter at a temperature of from about 130° C. to about 250° C. under reactive conditions in the absence of a polyol promoter or an alkanol having 1 to S carbon atoms for a sufficient period of time to react essentially all of the sulfur thereby yielding a calcium sulfurized alkylphenate essentially free of elemental sulfur; and (ii) contacting the reaction product of step (i) with carbon dioxide and additional calcium base, if required, to provide the desired TBN, in the presence of an alkylene glycol having 2 to 6 carbon atoms under reactive conditions at a temperature of from about 150° C. to about 260° C. ### Claim 11 (depends on 10) The method of claim 10, wherein the marine diesel engine lubricating oil composition has a TBN of from about 40 to about 70. ### Claim 12 (depends on 10) The method of claim 10, wherein the marine diesel engine lubricating oil composition has a kinematic viscosity at 100° C. of from about 12.5 to about 26.1 cSt. ### Claim 13 (depends on 10) The method of claim 10, wherein the marine diesel engine lubricating oil composition further comprises one or more alkaline earth metal sulfonates. ### Claim 14 (depends on 13) The method of claim 13, wherein the one or more alkaline earth metal sulfonates are alkaline earth metal alkylaromatic sulfonates. ### Claim 15 (depends on 10) The method of claim 10, wherein the marine diesel engine lubricating oil composition further comprises one or more alkali or alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid. ### Claim 16 (depends on 10) The method of claim 10, wherein the marine diesel engine lubricating oil composition further comprises a marine diesel engine lubricating oil composition additive selected from the group consisting of an antioxidant, ashless dispersant, detergent, rust inhibitor, dehazing agent, demulsifying agent, metal deactivating agent, friction modifier, pour point depressant, antifoaming agent, co-solvent, package compatibiliser, corrosion-inhibitor, dyes, extreme pressure agent and mixtures thereof.