EP4025674A1 - Lubricating oil compositions - Google Patents
Lubricating oil compositionsInfo
- Publication number
- EP4025674A1 EP4025674A1 EP20768707.0A EP20768707A EP4025674A1 EP 4025674 A1 EP4025674 A1 EP 4025674A1 EP 20768707 A EP20768707 A EP 20768707A EP 4025674 A1 EP4025674 A1 EP 4025674A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lubricating oil
- alkylhydroxybenzoate
- lubricating
- oil composition
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M141/00—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential
- C10M141/08—Lubricating compositions characterised by the additive being a mixture of two or more compounds covered by more than one of the main groups C10M125/00 - C10M139/00, each of these compounds being essential at least one of them being an organic sulfur-, selenium- or tellurium-containing compound
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/14—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/144—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to carbon atoms of six-membered aromatic rings containing hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/26—Overbased carboxylic acid salts
- C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
- C10M2219/022—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of hydrocarbons, e.g. olefines
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/02—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds
- C10M2219/024—Sulfur-containing compounds obtained by sulfurisation with sulfur or sulfur-containing compounds of esters, e.g. fats
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
- C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
- C10M2219/106—Thiadiazoles
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/047—Thioderivatives not containing metallic elements
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/071—Branched chain compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/04—Detergent property or dispersant property
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/40—Low content or no content compositions
- C10N2030/45—Ash-less or low ash content
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/52—Base number [TBN]
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
Definitions
- a lubricating oil composition which comprises:
- a lubricating oil composition comprising:
- a “major amount” means in excess of 50 weight % of a composition.
- a “minor amount” means less than 50 weight % of a composition, expressed in respect of the stated additive and in respect of the total mass of all the additives present in the composition, reckoned as active ingredient of the additive or additives.
- ppm means parts per million by weight, based on the total weight of the lubricating oil composition.
- Total base number was determined in accordance with ASTM D2896.
- Metal refers to alkali metals, alkaline earth metals, or mixtures thereof.
- High temperature high shear (HTHS) viscosity at 150°C was determined in accordance with ASTM D4863.
- KV 100 Kinematic viscosity at 100°C
- CCS Cold Cranking Simulator
- Olefins refers to a class of unsaturated aliphatic hydrocarbons having one or more carbon-carbon double bonds, obtained by a number of processes. Those containing one double bond are called mono-alkenes, and those with two double bonds are called dienes, alkyldienes, or diolefins. Alpha olefins are particularly reactive because the double bond is between the first and second carbons. Examples are 1-octene and 1-octadecene, which are used as the starting point for medium-biodegradable surfactants. Linear and branched olefins are also included in the definition of olefins.
- Normal Alpha Olefins refers to olefins which are straight chain, non-branched hydrocarbons with carbon-carbon double bond present in beginning and end of the chain.
- Isomerized Normal Alpha Olefin refers to an alpha olefin that has been subjected to isomerization conditions which results in an alteration of the distribution of the olefin species present and/or the introduction of branching along the alkyl chain.
- the isomerized olefin product may be obtained by isomerizing a linear alpha olefin containing from about 10 to about 40 carbon atoms, preferably from about 20 to about 28 carbon atoms, and preferably from about 20 to about 24 carbon atoms.
- This disclosure describes lubricating oil compositions comprising a combination of alkylhydroxybenzoate detergents and ashless sulfur compounds wherein the combination synergistically controls oxidation of engine oils.
- the present disclosure is directed to a lubricating oil composition
- a lubricating oil composition comprising:
- a lubricating oil composition comprising:
- the TBN of the alkylhydroxybenzoate detergent derived from C 10 -C 40 isomerized NAO is from about 100 to about 700, such as from about 100 to about 650, from about 100 to about 600, from about 100 to about 500, from about 100 to about 400, from about 100 to 300, from about 150 to 250, from about 175 to about 250, from about 175 to about 225 mg KOH/gram on oil free-basis.
- the alkylhydroxybenzoate detergent is derived from C 10 -C 40 isomerized NAO and has a TBN of from about 10 to about 300, such as from about 50 to about 300, from about 100 to about 300, from about 150 to about 300, and from about 175 to about 250 mg KOH/gram on active basis.
- the alkylhydroxybenzoate detergent derived from C 10 -C 40 isomerized NAO is a Ca alkylhydroxybenzoate detergent.
- the alkylhydroxybenzoate detergent derived from C 10 -C 40 isomerized NAO can be an alkylated hydroxybenzoate detergent.
- the detergent can be a salicylate detergent.
- the alkylhydroxybenzoate derived from C 10 -C 40 isomerized NAO may be prepared as described in US Patent 8, 993,499 which is herein incorporated in its entirety.
- the alkylhydroxybenzoate detergent is made from an alkylphenol having an alkyl group derived from an isomerized alpha olefin having from about 10 to about 40 carbon atoms per molecules, such as from about 14 to about 28 carbon atoms per molecule, from about 20 to about 24 carbon atoms, from about 14 to about 18 carbon atoms, and from about 20 to about 28 carbon atoms per molecule.
- the alkylhydroxybenzoate derived from C 10 -C 40 isomerized NAO is made from an alkylphenol with an alkyl group derived from an isomerized NAO having an isomerization level (I) from about 0.10 to about 0.40, such as from about 0.10 to about 0.35, from about 0.10 to about 0.30, from about 0.12 to about 0.30 and from about 0.12 to about 0.20.
- I isomerization level
- the alkylhydroxybenzoate derived from C 10 -C 40 isomerized NAO is made from one or more alkylphenols with an alkyl group derived from C 10 -C 40 isomerized NAO and one or more alkylphenols with an alkyl group different from the C 10 -C 40 isomerized NAO.
- the isomerized NAO of the alkylhydroxybenzoate detergent has an isomerization level of about 0.16, and have from about 20 to about 24 carbon atoms.
- the isomerized NAO of the alkylhydroxybenzoate detergent has an isomerization level of about 0.26, and have from about 20 to about 24 carbon atoms.
- the alkylhydroxybenzoate detergents derived from C 10 -C 40 isomerized NAO may include alkali or alkaline earth metals (e.g., barium, sodium, potassium, lithium, calcium, and magnesium).
- alkali or alkaline earth metals e.g., barium, sodium, potassium, lithium, calcium, and magnesium.
- the most commonly used metals are calcium and magnesium, which may both be present in detergents used in a lubricant, and mixtures of calcium and/or magnesium with sodium.
- the lubricating oil composition comprises about 0.01 to about 2.0 wt.% in terms of Ca content of the alkylhydroxybenzoate derived from C 10 -C 40 isomerized NAO, such as from about 0.1 to about 1.0 wt. %, from about 0.05 to about 0.5 wt. %, and from about 0.1 to about 0.5 wt.%.
- the lubricating oil composition comprises about 0.01 to about 2.0 wt.% in terms of Mg content of the alkylhydroxybenzoate derived from C 10 -C 40 isomerized NAO, such as from about 0.1 to about 1.0 wt. % from about 0.05 to about 0.5 wt. %, and from about 0.1 to about 0.5 wt.%.
- the lubricating oil composition comprising the alkylhydroxybenzoate detergent derived from C 10 -C 40 isomerized NAO is an automotive engine oil composition, a gas engine oil composition, a dual fuel engine oil composition, a mobile gas engine oil composition, or a locomotive engine oil composition.
- the lubricating oil composition comprising the alkylhydroxybenzoate detergent derived from C 10 -C 40 isomerized NAO is a functional fluid for automotive and industrial applications, such as transmission oil, hydraulic oil, tractor fluid, gear oil, and the like.
- the lubricating oil composition comprising the alkylhydroxybenzoate detergent derived from C 10 -C 40 isomerized NAO is a multi-grade oil or mono-grade oil.
- the lubricating oil composition comprising the alkylhydroxybenzoate detergent derived from C 10 -C 40 isomerized NAO lubricates crankcases, gears, as well as clutches.
- the ashless sulfur compound is a sulfurized fatty ester.
- the sulfurized fatty acid esters are prepared by reacting sulfur, sulfur monochloride, and/or sulfur dichloride with an unsaturated fatty ester under elevated temperatures.
- Typical esters include C 1 -C 20 alkyl esters of C 8 -C 24 unsaturated fatty acids, such as palmitoleic, oleic, ricinoleic, petroselinic, vaccenic, linoleic, linolenic, oleostearic, licanic, paranaric, tariric, gadoleic, arachidonic, cetoleic, etc.
- mixed unsaturated fatty acid esters such as are obtained from animal fats and vegetable oils, such as tall oil, linseed oil, olive oil, castor oil, peanut oil, rape oil, fish oil, sperm oil, and so forth.
- Exemplary fatty esters include lauryl tallate, methyl oleate, ethyl oleate, lauryl oleate, cetyl oleate, cetyl linoleate, lauryl ricinoleate, oleyl linoleate, oleyl stearate, and alkyl glycerides.
- the ashless sulfur compound is a sulfurized olefin.
- Cross- sulfurized ester olefins such as a sulfurized mixture of C10 to C25 olefins with fatty acid esters of C10 to C25 fatty acids and C10 to C25 alkyl or alkenyl alcohols, wherein the fatty acid and/or the alcohol is unsaturated may also be used.
- Sulfurized olefins are usually derived from alpha olefins, isomerized alpha olefins, cyclic olefins, branched olefins, and polymeric olefins that are reacted with a sulfur source.
- olefins include but are not limited to; 1-butene, isobutylene, diisobutylene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and more with longer carbon chains up to C60 and beyond to polymeric olefins.
- NAOs non- normal alpha olefins
- sulfur sources include sulfur, hydrogen sulfide, sodium hydrogen sulfide, sodium sulfide, sulfur chloride, and sulfur dichloride.
- aromatic and alkyl sulfides such as dibenzyl sulfide, dixylyl sulfide, dicetyl sulfide, diparaffin wax sulfide and polysulfide, cracked wax-olefin sulfides and so forth.
- They can be prepared by treating the starting material, e.g., olefinically unsaturated compounds, with sulfur, sulfur monochloride, and sulfur dichloride.
- the paraffin wax thiomers described in U.S. Pat. No. 2,346,156.
- the ashless sulfur compound is a thiadiazole.
- Thiadiazoles include at least one of 2,5-dimercapto-1,3,4-thiadiazole; 2-mercapto-5-hydrocarbylthio-1,3,4- thiadiazoles; 2-mercapto-5-hydrocarbyldithio-1,3,4-thiadiazoles; 2,5-bis(hydrocarbylthio and 2.5-bis(hydrocarbyldithio)-1,3,4-thiadiazoles.
- Preferred compounds are the 1,3,4-thiadiazoles, especially the 2-hydrocarbyldithio-5-mercapto-1,3,4-dithiadiazoles and the
- 2.5-bis(hydrocarbyldithio)- 1,3,4-thiadiazoles a number of which are available as articles of commerce.
- Other preferred compounds include a non-polycarboxylate containing thiadiazole containing about 4.0 wt% 2,5-dimercapto-1,3,4-thiadiazole, which are commercially available as Hitec® 4313 from Afton Chemical (Richmond, Virginia) or Lubrizol® 5955A from Lubrizol Corporation (Wycliffe, Ohio).
- the ashless sulfur compound is an ashless dithiophosphate.
- suitable ashless dithiophosphates for use herein include those of represented by Formula (I): wherein R 11 and R 12 are independently an alkyl group having 3 to 8 carbon atoms.
- Suitable ashless dithiophosphates include VANLUBE ® 7611M which is commercially available from R.T. Vanderbilt Co., Inc.
- ashless dithiophosphates for use herein include dithiophosphoric acid esters of carboxylic acid such as IRGALUBE ® 63 which is commercially available from BASF.
- ashless dithiophosphates for use herein include triphenylphosphorothionates such as IRGALUBE ® TPPT commercially available from BASF.
- the ashless sulfur compound is a sulfurized hindered phenol.
- the sulfurized hindered phenols suitable for use in the present invention can be prepared by a number of known methods.
- the sulfurized hindered phenols are characterized by the type of hindered phenols used in their production and their final sulfur content. Hindered tert- butylphenols are preferred.
- the sulfurized hindered phenols may be chlorine-free, being prepared from chlorine-free sulfur sources such as elemental sulfur, sodium sulfide, or sodium polysulfide, or they may contain chlorine, being prepared from chlorinated sulfur sources such as sulfur monochiorxde and sulfur dichloride.
- Preferred sulfurized hindered phenols include those represented by Formula (II) .
- R is an alkyl group
- R 1 is an alkyl group or hydrogen
- one of Z or Z 1 is -OH group with the other being hydrogen
- one of Z 2 or Z 3 is -OH group with the other being hydrogen
- x is in the range of from 1 to 6
- y is in the range of from 0 to 2.
- Suitable chlorine-free, sulfurized hindered phenols may be prepared by the methods taught in U S. Patent No. 3,929,654 or may be obtained by (a) preparing a mixture of (i) at least one chlorine-free hindered phenol, (ii) a chlorine-free sulfur source, and (iii) at least one alkali metal hydroxide promoter, in a polar solvent, and (b) causing components (i), (ii) and (iii) to react for sufficient time and at a sufficient temperature so as to form at least one chlorine-free sulfurized hindered phenol, as taught in co-pending applications 08/657,141 filed June 3, 1996 and 08/877,533 filed February 19, 1997.
- Suitable sulfurized hindered phenol products prepared from a chlorinated sulfur source include those products taught in U.S. Patent Nos. 3,250,712 and 4,946,610, both of which are hereby incorporated by reference.
- sulfurized hindered phenols examples include 4,4'-thiobis(2,6-di-t-butylphenol), 4,4'-dithiobis(2,6-di-t-butylphenol), 4,4'-thiobis(2- t-butyl-6-methylphenol), 4,4'-dithiobis(2-t-butyl-6-methylphenol), 4,4'-thiobis(2-t-butyl-5- methylphenol), and mixtures of these.
- the sulfurized hindered phenols be a substantially liquid product.
- substantially liquid refers to compositions that are chiefly liquid.
- aged samples of the sulfurized hindered phenols may form a slight amount of crystallization, generally around the sides of the container where product comes in contact with air and the glass container surface.
- the sulfurized hindered phenols be chlorine-free, of low corrosivity and having a high content of monosulfide as described in co-pending applications 08/657,141 filed June 3, 1996 and 08/877,533 filed February 19, 1997.
- the sulfur content of the sulfurized hindered phenol be in the range of about 4.0 wt. % to about 12.0 wt. % of the additive concentrate.
- the ashless sulfur compound is a phenothiazine.
- Phenothiazines useful in the practice of the invention include alkylated phenothiazine compounds represented by Fonnula (III):
- R 1 is a linear or branched group having from 4 to 24 carbon atoms, such as 4 to 10, carbon atoms and being an alkyl or alkylaryl group: and R 2 is, independently of R 1 , a linear or branched group having from 4 to 24 carbon atoms, such as 4 to 10 carbon atoms and being an alkyl or alkylenyl group, or is a hydrogen atom.
- R 1 is a nonyl group and R 2 is a hydrogen atom or a nonyl group.
- R 1 is preferably an alkyl group having 4 to 10 carbon atoms and R 2 is a hydrogen atom or an alkyl group having 4 to 10 carbon atoms.
- the alkylated phenothiazines preferably comprise mixtures of mono- and dialkylated phenothiazines, for example, wherein about 15 to about 85 mass % of the mixture is monalkylated.
- Alkylated phenothiazines are known in the art and may be prepared by methods known in the art.
- phenothiazine may be alkylated in the presence of an acid catalyst by reaction with a C 1 to C 10 olefin or mixture thereof, suitable such olefins including alpha olefins and internal olefins, for example isobutylene, diisobutylene, nonene and 1-decene.
- the lubricating oil composition of the present invention can further contain one or more overbased detergents having a TBN of about 10 to about 800, such as from about 10 to about 700, from about 30 to about 690, from about 100 to about 600, from about 150 to about 600, from about 150 to about 500, and from about 200 to about 450 mg KOH/g on an actives basis.
- overbased detergents having a TBN of about 10 to about 800, such as from about 10 to about 700, from about 30 to about 690, from about 100 to about 600, from about 150 to about 600, from about 150 to about 500, and from about 200 to about 450 mg KOH/g on an actives basis.
- Detergents that may be used include oil-soluble overbased sulfonate, non- sulfur containing phenate, sulfurized phenates, salixarate, salicylate, saligenin, complex detergents and naphthenate detergents and other oil-soluble alkylhydroxybenzoates of a metal, particularly the alkali or alkaline earth metals, e.g., barium, sodium, potassium, lithium, calcium, and magnesium.
- a metal particularly the alkali or alkaline earth metals, e.g., barium, sodium, potassium, lithium, calcium, and magnesium.
- the most commonly used metals are calcium and magnesium, which may both be present in detergents used in a lubricant, and mixtures of calcium and/or magnesium with sodium.
- Overbased metal detergents are generally produced by carbonating a mixture of hydrocarbons, detergent acid, for example: sulfonic acid, alkylhydroxybenzoate etc., metal oxide or hydroxides (for example calcium oxide or calcium hydroxide) and promoters such as xylene, methanol and water.
- detergent acid for example: sulfonic acid, alkylhydroxybenzoate etc.
- metal oxide or hydroxides for example calcium oxide or calcium hydroxide
- promoters such as xylene, methanol and water.
- the calcium oxide or hydroxide reacts with the gaseous carbon dioxide to form calcium carbonate.
- the sulfonic acid is neutralized with an excess of CaO or Ca(OH) 2 , to form the sulfonate.
- Overbased detergents may be low overbased, e.g., an overbased salt having a
- the TBN of a low overbased salt may be from about 30 to about 100. In another embodiment, the TBN of a low overbased salt may be from about 30 to about 80.
- overbased detergents may be medium overbased, e.g., an overbased salt having a TBN from about 100 to about 250.
- the TBN of a medium overbased salt may be from about 100 to about 200.
- the TBN of a medium overbased salt may be from about 125 to about 175.
- overbased detergents may be high overbased, e.g., an overbased salt having a TBN above about 250.
- the TBN of a high overbased salt may be from about 250 to about 800 on an actives basis.
- the detergent can be one or more alkali or alkaline earth metal salts of an alkyl-substituted hydroxyaromatic carboxylic acid.
- Suitable hydroxyaromatic compounds include mononuclear monohydroxy and polyhydroxy aromatic hydrocarbons having 1 to 4, and preferably 1 to 3, hydroxyl groups.
- Suitable hydroxyaromatic compounds include phenol, catechol, resorcinol, hydroquinone, pyrogallol, cresol, and the like.
- the preferred hydroxyaromatic compound is phenol.
- the alkyl substituted moiety of the alkali or alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid is derived from an alpha olefin having from about 10 to about 80 carbon atoms.
- the olefins employed may be linear, isomerized linear, branched or partially branched linear.
- the olefin may be a mixture of linear olefins, a mixture of isomerized linear olefins, a mixture of branched olefins, a mixture of partially branched linear or a mixture of any of the foregoing.
- the mixture of linear olefins that may be used is a mixture of normal alpha olefins selected from olefins having from about 10 to about 40 carbon atoms per molecule.
- the normal alpha olefins are isomerized using at least one of a solid or liquid catalyst.
- At least about 50 mole%, at least about 75 mole%, at least about 80 mole%, at least about 85 mole%, at least about 90 mole%, at least about 95 mole% of the alkyl groups contained within the alkali or alkaline earth metal salt of an alkyl- substituted hydroxyaromatic carboxylic acid such as the alkyl groups of an alkaline earth metal salt of an alkyl-substituted hydroxybenzoic acid detergent are a C 20 or higher.
- the alkali or alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid is an alkali or alkaline earth metal salt of an alkyl- substituted hydroxybenzoic acid that is derived from an alkyl-substituted hydroxybenzoic acid in which the alkyl groups are C 20 to about C 28 normal alpha-olefins.
- the alkyl group on at least one of the at least two alkyl phenols is derived from an isomerized alpha olefin.
- the alkyl group on the second alkyl phenol may be derived from branched or partially branched olefins, highly isomerized olefins or mixtures thereof.
- the alkali or alkaline earth metal salt of an alkyl- substituted hydroxyaromatic carboxylic acid is a salicylate derived from an alkyl group with about 20 to about 40 carbon atoms, preferably about 20 to about 28 carbon atoms, more preferably, isomerized NAO having about 20 to about 40 carbon atoms.
- Sulfonates may be prepared from sulfonic acids which are typically obtained by the sulfonation of alkyl substituted aromatic hydrocarbons such as those obtained from the fractionation of petroleum or by the alkylation of aromatic hydrocarbons. Examples include those obtained by alkylating benzene, toluene, xylene, naphthalene, diphenyl or their halogen derivatives.
- the alkyl group of the alkaryl sulfonates usually contain from about 9 to about 80 or more carbon atoms, preferably from about 16 to about 60 carbon atoms, preferably about 16 to about 30 carbon atoms, and more preferably about 20 to about 24 carbon atoms.
- Metal salts of phenols and sulfurized phenols which are sulfurized phenate detergents, are prepared by reaction with an appropriate metal compound such as an oxide or hydroxide. Neutral or overbased detergent products may be obtained by methods well known in the art.
- Sulfurized phenols may be prepared by reacting a phenol with sulfur or a sulfur containing compound such as hydrogen sulfide, sulfur monohalide or sulfur dihalide, to form products which are generally mixtures of compounds in which two or more phenols are bridged by sulfur containing bridges.
- the reactants and reagents used in the present process may utilize all allotropic forms of sulfur.
- the sulfur can be employed either as molten sulfur or as a solid (e.g., powder or particulate) or as a solid suspension in a compatible hydrocarbon liquid.
- Other compatible calcium bases include, for example, calcium alkoxides.
- Suitable alkylphenols which can be used are those wherein the alkyl substituents contain a sufficient number of carbon atoms to render the resulting overbased sulfurized calcium alkylphenate composition oil-soluble. Oil solubility may be provided by a single long chain alkyl substitute or by a combination of alkyl substituents. Typically, the alkylphenol used will be a mixture of different alkylphenols, e.g., C 20 to C 24 alkylphenol.
- suitable alkyl phenolic compounds will be derived from isomerized alpha olefin alkyl groups having from about 10 to about 40 carbon atoms per molecule and having an isomerization level (1) of the alpha olefin between from about 0.1 to about 0.4.
- suitable alkyl phenolic compounds will be derived from alkyl groups which are branched olefinic propylene oligomers or mixture thereof having from about 9 to about 80 carbon atoms.
- the branched olefinic propylene oligomer or mixtures thereof have from about 9 to about 40 carbon atoms.
- the branched olefinic propylene oligomer or mixtures thereof have from about 9 to about 18 carbon atoms. In one embodiment, the branched olefinic propylene oligomer or mixtures thereof have from about 9 to about 12 carbon atoms.
- suitable alkyl phenolic compounds may be sourced from distilled cashew nut shell liquid (CNSL) or hydrogenated distilled cashew nut shell liquid.
- Distilled CNSL is a mixture of biodegradable meta-hydrocarbyl substituted phenols, where the hydrocarbyl group is linear and unsaturated, including cardanol. Catalytic hydrogenation of distilled CNSL gives rise to a mixture of meta-hydrocarbyl substituted phenols predominantly rich in 3-pentadecylphenol.
- the alkylphenols can be para-alkylphenols, meta-alkylphenols or ortho alkylphenols. Since it is believed that p-alkylphenols facilitate the preparation of highly overbased calcium sulfurized alkylphenate where overbased products are desired, the alkylphenol is preferably predominantly para alkylphenol with no more than about 45 mole percent of the alkylphenol being ortho alkylphenols; and more preferably no more than about 35 mole percent of the alkylphenol being ortho alkylphenol. Alkyl-hydroxy toluenes or xylenes, and other alkyl phenols having one or more alkyl substituents in addition to at least one long chained alkyl substituent can also be used. In the case of distilled cashew nut shell liquid, the catalytic hydrogenation of distilled CNSL gives rise to a mixture of meta- hydrocarbyl substituted phenols.
- the one or more overbased detergent can be a complex or hybrid detergent which is known in the art as comprising a surfactant system derived from at least two surfactants described above.
- the one or more overbased detergent can be a salicylate with an alkyl group having about 20 to about 28 carbon atoms, more preferably about 20 to about 24 carbon atoms.
- the one or more overbased detergent can be a salicylate with an alkyl group derived from C 14-18 NAO and contribute less than about 0.05 wt%, preferably less than about 0.025 wt%, more preferably less than about 0.01 wt% in terms of Ca content to the lubricating oil.
- the amount of the detergent can be from about 0.001 wt. % to about
- the lubricating oil composition disclosed herein can comprise one or more anti- wear agent.
- Anti -wear agents reduce wear of metal parts.
- Suitable anti-wear agents include dihydrocarbyl dithiophosphate metal salts such as zinc dihydrocarbyl dithiophosphates (ZDDP) of Formula (IV):
- R 1 and R 2 may be the same or different hydrocarbyl group having from 1 to 18 (e.g., 2 to 12) carbon atoms.
- Suitable hydrocarbyl groups include, but are not limited to, alkyl, alkenyl, aryl, arylalkyl, alkaryl and cycloaliphatic groups.
- Particularly preferred R 1 and R 2 groups include alkyl groups having from 2 to 8 carbon atoms (e.g., ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl.
- the zinc dihydrocarbyl dithiophosphate can therefore comprise zinc dialkyl dithiophosphates.
- the zinc dialkyl dithiophosphate is a primary, secondary zinc dialkyl dithiophosphate, or a combination thereof.
- ZDDP may be present at about 3 wt. % or less (e.g., about 0.1 to about 1.5 wt. %, or about 0.5 to about 1.0 wt %) of the lubricating oil composition.
- the lubricating oil composition containing the magnesium salicylate detergent described herein further comprises an antioxidant compound.
- the antioxidant is a diphenylamine antioxidant.
- the antioxidant is a hindered phenol antioxidant.
- the antioxidant is a combination of a diphenylamine antioxidant and a hindered phenol antioxidant.
- the lubricating oil composition disclosed herein can comprise one or more antioxidant.
- Antioxidants reduce the tendency of mineral oils to deteriorate during service. Oxidative deterioration can be evidenced by sludge in the lubricant, vamish-like deposits on the metal surfaces, and/or by viscosity growth.
- Suitable antioxidants include hindered phenols, aromatic amines, and sulfurized alkylphenols and alkali and alkaline earth metals salts thereof.
- the hindered phenol antioxidant often contains a secondary butyl and/or a tertiary butyl group as a sterically hindering group.
- the phenol group may be further substituted with a hydrocarbyl group (typically linear or branched alkyl) and/or a bridging group linking to a second aromatic group.
- a hydrocarbyl group typically linear or branched alkyl
- suitable hindered phenol antioxidants include 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: and 4-dodecyl-2,6-di-tert- butylphenol.
- antioxidants include 2, 6-di-alkyl-phenolic propionic ester derivatives such as IRGANOX ® L-135 from Ciba and bis-phenolic antioxidants such as 4.4 -bis(2.6-di -tert-butyl phenol) and 4,4'-methylenebis(2,6-di-tert-butylphenol).
- Typical aromatic amine antioxidants have at least two aromatic groups attached directly to one amine nitrogen.
- Typical aromatic amine antioxidants have alkyl substituent groups of at least 6 carbon atoms.
- Particular examples of aromatic amine antioxidants useful herein include 4,4'- dioctyldiphenylamine, 4,4'-dinonyldiphenylamine, N-phenyl-1-naphthylamine. N-(4-tert- octyphenyl)-1-naphthylamine, and N-(4-octylphenyl)-1-naphthylamine.
- Antioxidants may be present at about 0.01 to about 5 wt. % (e.g., about 0.1 to about 2 wt. %) of the lubricating oil composition.
- the lubricating oil composition disclosed herein can comprise one or more dispersant.
- Dispersants maintain in suspension materials resulting from oxidation during engine operation that are insoluble in oil, thus preventing sludge flocculation and precipitation or deposition on metal parts.
- Dispersants useful herein include nitrogen-containing, ashless (metal -free) dispersants known to effective to reduce formation of deposits upon use in gasoline and diesel engines.
- Suitable dispersants include hydrocarbyl succinimides, hydrocarbyl succinamides, mixed ester/amides of hydrocarbyl-substituted succinic acid, hydroxyesters of hydrocarbyl-substituted succinic acid, and Mannich condensation products of hydrocarbyl- substituted phenols, formaldehyde and polyamines. Also suitable are condensation products of polyamines and hydrocarbyl-substituted phenyl acids. Mixtures of these dispersants can also be used.
- Basic nitrogen-containing ashless dispersants are well-known lubricating oil additives and methods for their preparation are extensively described in the patent literature.
- Preferred dispersants are the alkenyl succinimides and succinamides where the alkenyl-substituent is a long -chain of preferably greater than about 40 carbon atoms. These materials are readily made by reacting a hydrocarbyl-substituted dicarboxylic acid material with a molecule containing amine functionality. Examples of suitable amines are polyamines such as polyalkylene polyamines, hydroxy-substituted polyamines and polyoxyalkylene polyamines.
- Particularly preferred ashless dispersants are the polyisobutenyl succinimides formed from polyisobutenyl succinic anhydride and a polyalkylene polyamine such as a polyethylene polyamine of Formula (V):
- the polyisobutenyl group is derived from polyisobutene and preferably has a number average molecular weight (M,,) in a range of about 700 to about 3000 Daltons (e.g., about 900 to about 2500 Daltons).
- M number average molecular weight
- the polyisobutenyl succinimide may be a bis-succinimide derived from a polyisobutenyl group having aM» of about 900 to about 2500 Daltons.
- the dispersants may be post-treated (e.g., with a boronating agent or a cyclic carbonate, ethylene carbonate etc).
- Nitrogen-containing ashless (metal-free) dispersants are basic, and contribute to the TBN of a lubricating oil composition to which they are added, without introducing additional sulfated ash. Dispersants may be present at about 0.1 to about 10 wt. % (e.g., about 2 to about 5 wt. %) of the lubricating oil composition.
- the lubricating oil composition disclosed herein can comprise one or more foam inhibitor that can break up foams in oils.
- suitable foam inhibitors or anti-foam inhibitors include silicone oils or polydimethylsiloxanes, fluorosilicones, alkoxylated aliphatic acids, polyethers (e.g., polyethylene glycols), branched polyvinyl ethers, alkyl acrylate polymers, alkyl methacrylate polymers, polyalkoxyamines and combinations thereof.
- the lubricating oil compositions of the present disclosure may also contain other conventional additives that can impart or improve any desirable property of the lubricating oil composition in which these additives are dispersed or dissolved.
- Any additive known to a person of ordinary skill in the art may be used in the lubricating oil compositions disclosed herein.
- Some suitable additives have been described in Mortier et al., “Chemistry and Technology of Lubricants”, 2nd Edition, London, Springer, (1996); and Leslie R. Rudnick, “Lubricant Additives: Chemistry and Applications”, New York, Marcel Dekker (2003), both of which are incorporated herein by reference.
- the lubricating oil compositions can be blended with antioxidants, anti-wear agents, detergents such as metal detergents, rust inhibitors, dehazing agents, demulsifying agents, metal deactivating agents, friction modifiers, pour point depressants, antifoaming agents, co-solvents, corrosion-inhibitors, ashless dispersants, multifunctional agents, dyes, extreme pressure agents and the like and mixtures thereof.
- detergents such as metal detergents, rust inhibitors, dehazing agents, demulsifying agents, metal deactivating agents, friction modifiers, pour point depressants, antifoaming agents, co-solvents, corrosion-inhibitors, ashless dispersants, multifunctional agents, dyes, extreme pressure agents and the like and mixtures thereof.
- detergents such as metal detergents, rust inhibitors, dehazing agents, demulsifying agents, metal deactivating agents, friction modifiers, pour point depressants, antifoaming agents, co-solvents, corrosion-inhibitors, ashless
- additives in the form of about 10 to about 100 wt. % active ingredient concentrates in hydrocarbon oil, e.g. mineral lubricating oil, or other suitable solvent.
- these concentrates may be diluted with about 3 to about 100, e.g., about 5 to about 40, parts by weight of lubricating oil per part by weight of the additive package in forming finished lubricants, e.g. crankcase motor oils.
- the purpose of concentrates is to make the handling of the various materials less difficult and awkward as well as to facilitate solution or dispersion in the final blend.
- Each of the foregoing additives when used, is used at a functionally effective amount to impart the desired properties to the lubricant.
- a functionally effective amount of this friction modifier would be an amount sufficient to impart the desired friction modifying characteristics to the lubricant.
- the concentration of each of the additives in the lubricating oil composition when used, may range from about 0.001 wt. % to about 20 wt. %, from about 0.01 wt. % to about 15 wt. %, or from about 0.1 wt. % to about 10 wt. %, from about 0.005 wt.% to about 5 wt.%, or from about 0.1 wt.% to about 2.5 wt.%, based on the total weight of the lubricating oil composition.
- the total amount of the additives in the lubricating oil composition may range from about 0.001 wt.% to about 20 wt.%, from about 0.01 wt.% to about 10 wt.%, or from about 0.1 wt.% to about 5 wt.%, based on the total weight of the lubricating oil composition.
- Oil of lubricating viscosity Oil of lubricating viscosity
- the oil of lubricating viscosity (sometimes referred to as “base stock” or “base oil”) is the primary liquid constituent of a lubricant, into which additives and possibly other oils are blended, for example to produce a final lubricant (or lubricant composition).
- a base oil is useful for making concentrates as well as for making lubricating oil compositions therefrom and may be selected from natural and synthetic lubricating oils and combinations thereof.
- Natural oils include animal and vegetable oils, liquid petroleum oils and hydrorefined, solvent-treated mineral lubricating oils of the paraffinic, naphthenic and mixed paraffinic -naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils.
- Synthetic lubricating oils include hydrocarbon oils such as polymerized and interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene-isobutylene copolymers, chlorinated polybutylenes, poly(1-hexenes), poly(1-octenes), poly(1-decenes); alkylbenzenes (e.g., dodecylbenzenes, tetradecylbenzenes, dinonylbenzenes, di(2- ethylhexyl)benzenes; polyphenols (e.g., biphenyls, terphenyls, alkylated polyphenols); and alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogues and homologues thereof.
- hydrocarbon oils such as polymerized and interpolymerized olefins (e.g
- Another suitable class of synthetic lubricating oils comprises the esters of dicarboxylic acids (e.g., malonic acid, alkyl malonic acids, alkenyl malonic acids, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, fumaric acid, azelaic acid, suberic acid, sebacic acid, adipic acid, linoleic acid dimer, phthalic acid) with a variety of alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol).
- dicarboxylic acids e.g., malonic acid, alkyl malonic acids, alkenyl malonic acids, succinic acid, alkyl succinic acids and alkenyl succinic acids, maleic acid, fumaric acid, azelaic acid, suberic acid, sebac
- esters include dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, the 2-ethylhexyl diester of linoleic acid dimer, and the complex ester formed by reacting one mole of sebacic acid with two moles of tetraethylene glycol and two moles of 2-ethylhexanoic acid.
- Esters useful as synthetic oils also include those made from C 5 to C 12 monocarboxylic acids and polyols, and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol.
- the base oil may be derived from Fischer-Tropsch synthesized hydrocarbons.
- Fischer-Tropsch synthesized hydrocarbons are made from synthesis gas containing H 2 and CO using a Fischer-Tropsch catalyst.
- Such hydrocarbons typically require further processing in order to be useful as the base oil.
- the hydrocarbons may be hydroisomerized; hydrocracked and hydroisomerized; dewaxed; or hydroisomerized and dewaxed; using processes known to those skilled in the art.
- Unrefined, refined and re-refined oils can be used in the present lubricating oil composition.
- Unrefined oils are those obtained directly from a natural or synthetic source without further purification treatment.
- a shale oil obtained directly from retorting operations a petroleum oil obtained directly from distillation or ester oil obtained directly from an esterification process and used without further treatment would be unrefined oil.
- Refined oils are similar to the unrefined oils except they have been further treated in one or more purification steps to improve one or more properties. Many such purification techniques, such as distillation, solvent extraction, acid or base extraction, filtration and percolation are known to those skilled in the art.
- Re-refined oils are obtained by processes similar to those used to obtain refined oils applied to refined oils which have been already used in service. Such re-refined oils are also known as reclaimed or reprocessed oils and often are additionally processed by techniques for approval of spent additive and oil breakdown products.
- the base oil which may be used to make the present lubricating oil composition may be selected from any of the base oils in Groups I-V as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines (API Publication 1509).
- API American Petroleum Institute
- Base Oil Interchangeability Guidelines API Publication 1509
- Groups I-III are mineral oil base stocks. Determined in accordance with ASTM D2007. Determined in accordance with ASTM D2622, ASTM D3120, ASTM D4294 or ASTM
- Base oils suitable for use herein are any of the variety corresponding to API Group II, Group III, Group IV, and Group V oils and combinations thereof, preferably the Group III to Group V oils due to their exceptional volatility, stability, viscometric and cleanliness features.
- the oil of lubricating viscosity for use in the lubricating oil compositions of this disclosure is typically present in a major amount, e.g., an amount of greater than about 50 wt. %, preferably greater than about 70 wt. %, more preferably from about 80 to about 99.5 wt. % and most preferably from about 85 to about 98 wt. %, based on the total weight of the composition.
- base oil as used herein shall be understood to mean a base stock or blend of base stocks which is a lubricant component that is produced by a single manufacturer to the same specifications (independent of feed source or manufacturer's location); that meets the same manufacturer's specification; and that is identified by a unique formula, product identification number, or both.
- the base oil for use herein can be any presently known or later-discovered oil of lubricating viscosity used in formulating lubricating oil compositions for any and all such applications, e.g., engine oils, marine cylinder oils, functional fluids such as hydraulic oils, gear oils, transmission fluids, etc.
- the base oils for use herein can optionally contain viscosity index improvers, e.g., polymeric alkylmethacrylates; olefmic copolymers, e.g., an ethylene-propylene copolymer or a styrene -butadiene copolymer; and the like and mixtures thereof.
- viscosity index improvers e.g., polymeric alkylmethacrylates
- olefmic copolymers e.g., an ethylene-propylene copolymer or a styrene -butadiene copolymer; and the like and mixtures thereof.
- the viscosity of the base oil is dependent upon the application. Accordingly, the viscosity of a base oil for use herein will ordinarily range from about 2 to about 2000 centistokes (cSt) at 100° Centigrade (C.).
- the base oils used as engine oils will have a kinematic viscosity range at 100° C. of about 2 cSt to about 30 cSt, preferably about 3 cSt to about 16 cSt, and most preferably about 4 cSt to about 12 cSt and will be selected or blended depending on the desired end use and the additives in the finished oil to give the desired grade of engine oil, e.g., a lubricating oil composition having an SAE Viscosity Grade of 0W, 0W-8, 0W-12, 0W-16, 0W- 20, 0W-26, 0W-30, 0W-40, 0W-50, 0W-60, 5W, 5W-20, 5W-30, 5W-40, 5W-50, 5W-60, 10W, 10W-20, 10W-30, 10W-40, 10W-50, 15W, 15W-20, 15W-30, 15W-40, 30, 40 and the like.
- the level of sulfur in the lubricating oil compositions of the present invention is less than or equal to about 0.7 wt. %, based on the total weight of the lubricating oil composition, e.g., a level of sulfur of about 0.01 wt. % to about 0.70 wt. %, about 0.01 to about 0.6 wt.%, about 0.01 to about 0.5 wt.%, about 0.01 to about 0.4 wt.%, about 0.01 to about 0.3 wt.%, about 0.01 to about 0.2 wt.%, about 0.01 wt. % to about 0.10 wt. %.
- the level of sulfur in the lubricating oil compositions of the present invention is less than or equal to about 0.60 wt. %, less than or equal to about 0.50 wt. %, less than or equal to about 0.40 wt. %, less than or equal to about 0.30 wt. %, less than or equal to about 0.20 wt. %, less than or equal to about 0.10 wt. % based on the total weight of the lubricating oil composition.
- the levels of phosphorus in the lubricating oil compositions of the present invention is less than or equal to about 0.12 wt. %, based on the total weight of the lubricating oil composition, e.g., a level of phosphorus of about 0.01 wt. % to about 0.12 wt. %. In one embodiment, the levels of phosphorus in the lubricating oil compositions of the present invention is less than or equal to about 0.11 wt. %, based on the total weight of the lubricating oil composition, e.g., a level of phosphorus of about 0.01 wt. % to about 0.11 wt. %.
- the levels of phosphorus in the lubricating oil compositions of the present invention is less than or equal to about 0.10 wt. %, based on the total weight of the lubricating oil composition, e.g., a level of phosphorus of about 0.01 wt. % to about 0.10 wt. %. In one embodiment, the levels of phosphorus in the lubricating oil compositions of the present invention is less than or equal to about 0.09 wt. %, based on the total weight of the lubricating oil composition, e.g., a level of phosphorus of about 0.01 wt. % to about 0.09 wt. %.
- the levels of phosphorus in the lubricating oil compositions of the present invention is less than or equal to about 0.08 wt. %, based on the total weight of the lubricating oil composition, e.g., a level of phosphorus of about 0.01 wt. % to about 0.08 wt. %. In one embodiment, the levels of phosphorus in the lubricating oil compositions of the present invention is less than or equal to about 0.07 wt. %, based on the total weight of the lubricating oil composition, e.g., a level of phosphorus of about 0.01 wt. % to about 0.07 wt. %.
- the levels of phosphorus in the lubricating oil compositions of the present invention is less than or equal to about 0.05 wt. %, based on the total weight of the lubricating oil composition, e.g., a level of phosphorus of about 0.01 wt. % to about 0.05 wt. %.
- the level of sulfated ash produced by the lubricating oil compositions of the present invention is less than or equal to about 1.60 wt. % as determined by ASTM D 874, e.g., a level of sulfated ash of from about 0.10 to about 1.60 wt. % as determined by ASTM D 874. In one embodiment, the level of sulfated ash produced by the lubricating oil compositions of the present invention is less than or equal to about 1.00 wt. % as determined by ASTM D 874, e.g., a level of sulfated ash of from about 0.10 to about 1.00 wt. % as determined by ASTM D 874.
- the level of sulfated ash produced by the lubricating oil compositions of the present invention is less than or equal to about 0.80 wt. % as determined by ASTM D 874, e.g., a level of sulfated ash of from about 0.10 to about 0.80 wt. % as determined by ASTM D 874. In one embodiment, the level of sulfated ash produced by the lubricating oil compositions of the present invention is less than or equal to about 0.60 wt. % as determined by ASTM D 874, e.g., a level of sulfated ash of from about 0.10 to about 0.60 wt. % as determined by ASTM D 874.
- the present disclosure provides lubricating oil compositions suitable for reducing friction in passenger car internal combustion engines, particularly spark-ignited, direct injection and/or port fuel injection engines.
- the engine may be coupled to an electric motor/battery system in a hybrid vehicle (e.g., a port fuel injection spark ignition engine coupled to an electric motor/battery system in a hybrid vehicle).
- the present disclosure provides lubricating oil compositions suitable for reducing friction in heavy duty diesel internal combustion engines.
- the isomerization level (I) of the olefin was determined by hydrogen-1 (1H) NMR.
- the NMR spectra were obtained on a Bruker Ultrashield Plus 400 at 400 MHz using TopSpin 3.2 spectral processing software.
- the NMR samples were dissolved in chloroform- dl.
- the isomerization level (I) represents the relative amount of methyl groups (- CH3) (chemical shift 0.3-1.01 ppm) attached to the methylene backbone groups (-CH2-) (chemical shift 1.01-1.38 ppm) and is defined by Equation (1) as shown below,
- I m/(m+n) Equation (I) where m is NMR integral for methyl groups with chemical shifts between 0.3 ⁇ 0.03 to 1.01 ⁇ 0.03 ppm, and n is NMR integral for methylene groups with chemical shifts between 1.01 ⁇ 0.03 to 1.38 ⁇ 0.10 ppm.
- the isomerizationlevel (I) of the alpha olefin is between from about 0.1 to about 0.4, preferably from about 0.1 to about 0.3, more preferably from about 0.12 to about 0.3.
- the isomerization level of the NAO is about 0.16, and having from about 20 to about 24 carbon atoms.
- the isomerization level of the NAO is about 0.26, and having from about 20 to about 24 carbon atoms.
- An alkylhydroxybenzoate was prepared from an alkylphenol with an alkyl group derived from C 14- 18 NAO and a TBN about 300 and Ca content about 10.6 wt. % on an oil-free basis.
- Example C is a sulfurized olefin namely sulfurized isobutylene.
- Example D is a sulfurized fatty ester which is (9-Octadecenoic acid (Z)-, isooctyl ester, reaction products with glycerol trioleate and sulfur).
- Example E is an ashless dithiocarbamate, namely methylenebis (dibutyldithiocarbamate) .
- Example F is a thiadiazole with the tradename Hitec 4313.
- Example G is an ashless dithiophosphate with the tradename Irgalube TPPT.
- Example H is a sulfurized phenol with a sulfur content of 15.8 wt.%.
- a 15W-40 lubricating oil composition was prepared that contained a major amount of a group II base oil of lubricating viscosity and the following additives:
- Example A To baseline 1 was added between 30 to 36 mM of Example A providing the lubricant with between 1200 to 1400 ppm of Ca. Also added was 0.29 wt.% of Example C providing the finished oil with approximately 1300 ppm of sulfur.
- Example A To baseline 1 was added between 30 to 36 mM of Example A providing the lubricant with between 1200 to 1400 ppm of Ca. Also added was 1.35 wt.% of Example D providing the finished oil with approximately 1300 ppm of sulfur.
- Example A To baseline 1 was added between 30 to 36 mM of Example A providing the lubricant with between 1200 to 1400 ppm of Ca. Also added was 0.375 wt.% of Example F providing the finished oil with approximately 1300 ppm of sulfur.
- Example A To baseline 1 was added between 30 to 36 mM of Example A providing the lubricant with between 1200 to 1400 ppm of Ca. Also added was 1.452 wt.% of Example G providing the finished oil with approximately 1300 ppm of sulfur.
- Example A To baseline 1 was added between 30 to 36 mM of Example A providing the lubricant with between 1200 to 1400 ppm of Ca. Also added was 0.854 wt.% of Example H providing the finished oil with approximately 1300 ppm of sulfur.
- Comparative Example 1 [00142] To baseline 1 was added between 30 to 36 mM of Comparative Example B providing the lubricant with between 1200 to 1400 ppm of Ca. Also added was 0.29 wt.% of Example C providing the finished oil with approximately 1300 ppm of sulfur.
- Example B To baseline 1 was added between 30 to 36 mM of Comparative Example B providing the lubricant with between 1200 to 1400 ppm of Ca. Also added was 1.35 wt.% of Example D providing the finished oil with approximately 1300 ppm of sulfur.
- Example A To baseline 1 was added between 30 to 36 mM of Example A providing the lubricant with between 1200 to 1400 ppm of Ca. Also added was 0.45 wt.% of Example E providing the finished oil with approximately 1300 ppm of sulfur.
- Example B To baseline 1 was added between 30 to 36 mM of Comparative Example B providing the lubricant with between 1200 to 1400 ppm of Ca. Also added was 0.45 wt.% of Example E providing the finished oil with approximately 1300 ppm of sulfur.
- Example I is prepared by a slurry of MgO (82 grams) in MeOH (81.4 grams) and xylene (500 grams) is prepared and introduced into a reactor. Then the hydroxybenzoic acid made from isomerized alpha olefin (C20-24, 0.16 isomerization level), (1774 grams, 43% active in xylene) is loaded into the reactor and the temperature kept at 40°C for 15 minutes. Then dodecenylanhydride (DDSA, 7.6 grams) followed by AcOH (37.3 grams) then H 2 O (69 grams) are introduced in the reactor over 30 minutes while the temperature is ramped up to 50°C. CO 2 is then introduced in the reactor under strong agitation (96 grams).
- DDSA dodecenylanhydride
- Example I To baseline 1 was added between 38 to 46 mM of Example I providing the lubricant with between 900 to 1200 ppm of Mg. Also added was 0.45 wt.% of Example E providing the finished oil with approximately 1300 ppm of sulfur.
- Example J To baseline 1 was added between 38 to 46 mM of Comparative Example J providing the lubricant with between 900 to 1100 ppm of Mg. Also added was 0.45 wt.% of Example E providing the finished oil with approximately 1300 ppm of sulfur.
- Example B To baseline 1 was added between 30 to 36 mM of Comparative Example B providing the lubricant with between 1200 to 1400 ppm of Ca. Also added was 0.375 wt.% of Example F providing the finished oil with approximately 1300 ppm of sulfur.
- Example B To baseline 1 was added between 30 to 36 mM of Comparative Example B providing the lubricant with between 1200 to 1400 ppm of Ca. Also added was 1.452 wt.% of Example G providing the finished oil with approximately 1300 ppm of sulfur.
- Example B To baseline 1 was added between 30 to 36 mM of Comparative Example B providing the lubricant with between 1200 to 1400 ppm of Ca. Also added was 0.854 wt.% of Example H providing the finished oil with approximately 1300 ppm of sulfur.
- Example K An alkylated phenol and Ca alkylhydroxybenzoate were prepared in substantially the same manner as in U.S. Patent No. 8,993,499 using a C 20-24 isomerized normal alpha olefin. The isomerization level of the alpha olefin is about 0.15. The resulting alkylhydroxybenzoate composition has a TBN of about 225 and Ca content of about 8 wt.% on an oil-free basis.
- An alkylated phenol and Ca alkylhydroxybenzoate were prepared in substantially the same manner as in U.S. Patent No. 8,993,499 using a C 20-24 isomerized normal alpha olefin.
- the isomerization level of the alpha olefin is about 0.219.
- the resulting alkylhydroxybenzoate composition has a TBN of about 225 and Ca content of about 8 wt.% on an oil-free basis.
- An alkylated phenol and Ca alkylhydroxybenzoate were prepared in substantially the same manner as in U.S. Patent No. 8,993,499 using a C 20-24 isomerized normal alpha olefin.
- the isomerization level of the alpha olefin is about 0.23.
- the resulting alkylhydroxybenzoate composition has a TBN of about 225 and Ca content of about 8 wt.% on an oil-free basis.
- Example K To baseline 1 was added between 30 to 36 mM of Example K providing the lubricant with between 1200 to 1400 ppm of Ca. Also added was 0.29 wt.% of Example C providing the finished oil with approximately 1300 ppm of sulfur.
- Example L To baseline 1 was added between 30 to 36 mM of Example L providing the lubricant with between 1200 to 1400 ppm of Ca. Also added was 0.29 wt.% of Example C providing the finished oil with approximately 1300 ppm of sulfur.
- Example M To baseline 1 was added between 30 to 36 mM of Example M providing the lubricant with between 1200 to 1400 ppm of Ca. Also added was 0.29 wt.% of Example C providing the finished oil with approximately 1300 ppm of sulfur.
- the Oxidation-Nitration bench test demonstrates the capacity of lubricating oil to resist oxidation and nitration. This test is an additional tool to help determine the performance of oils as they relate to the actual service of lubricating engines that use natural gas as a fuel source. The lower the value for oxidation and nitration at the end of the test, the superior the product's performance.
- the Oxidation-Nitration bench test was designed to simulate Caterpillar 3500 series engine conditions as related to actual field performance of the Caterpillar 3516 model. Oxidation-Nitration tests were performed on Examples 1-8 and Comparative Examples 1-9.
- the lubricating oil compositions from these Examples were placed in a heated glassware bath and subjected to calibrated levels of nitrous oxide gas over a specific period of time. The tests were run on each sample in duplicate and the results are an average of the two runs. The samples were evaluated using differential infra-red spectroscopy before placing them in the heated glassware bath to determine a base line for each sample . The samples were reevaluated at the end of testing period. The differential between the base line data, absorbance units at 5.8 and 6.1 microns, and the data taken at the end of test cycle provides an indication of the oxidation-nitration resistance of the samples.
- Differential infra-red spectroscopy measures the amount of light that is absorbed by an oil sample and provides a unit of measure called an absorbance unit.
- DIR Differential Infrared
- spectra was determined by subtracting the fresh oil spectra from the used oil spectra to observe changes that have occurred due to oxidation, nitration, fuel dilution, soot accumulation, and or contamination.
- a 0.1 millimeter (mm) cell is used; however an ATR crystal setup may be used after determining its associated path length. If the instrument does not have software that determines path length, the path length may be back calculated by measuring oxidation with a calibrated 0.1 mm cell. The variation between ATR and vertical cell measurements is minimal if restricted to the narrow area of oxidation and nitration ( ⁇ 1725 to 1630 cm -1 ).
- Oxidation levels of 5.8 microns and Nitration levels of 6.1 microns were used as peak height comparisons.
- Examples 1-8 and Comparative Examples 1-9 were tested separately by using each one as a lubricant in the bench test.
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Abstract
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US201962896373P | 2019-09-05 | 2019-09-05 | |
PCT/IB2020/058193 WO2021044326A1 (en) | 2019-09-05 | 2020-09-03 | Lubricating oil compositions |
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EP (1) | EP4025674A1 (en) |
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US2346156A (en) | 1942-02-16 | 1944-04-11 | Standard Oil Co | Compounded lubricant |
US2680096A (en) | 1951-02-12 | 1954-06-01 | California Research Corp | Process for preparing sulfurized polyvalent metal phenates |
US3250712A (en) | 1959-07-24 | 1966-05-10 | Ethyl Corp | Sulfur-containing phenolic compounds |
US3178368A (en) | 1962-05-15 | 1965-04-13 | California Research Corp | Process for basic sulfurized metal phenates |
US3801507A (en) | 1972-08-18 | 1974-04-02 | Chevron Res | Sulfurized metal phenates |
GB1421108A (en) | 1973-09-07 | 1976-01-14 | Exxon Research Engineering Co | Sulphurised phenols |
GB2033923B (en) * | 1978-10-13 | 1982-12-22 | Exxon Research Engineering Co | Diesel lubricating oil compositions |
US4946610A (en) | 1989-08-03 | 1990-08-07 | Ethyl Petroleum Additives, Inc. | Sulfur-bridged phenolic antioxidants |
US6063741A (en) * | 1994-09-05 | 2000-05-16 | Japan Energy Corporation | Engine oil composition |
ATE491775T1 (en) * | 1999-09-13 | 2011-01-15 | Infineum Int Ltd | A METHOD OF LUBRICATION FOR TWO-STROKE MARINE DIESEL ENGINES |
US6656887B2 (en) * | 2001-01-24 | 2003-12-02 | Nippon Mitsubishi Oil Corporation | Lubricating oil compositions |
US8993499B2 (en) | 2007-12-28 | 2015-03-31 | Chevron Oronite Company Llc | Low temperature performance lubricating oil detergents and method of making the same |
US20100081591A1 (en) * | 2008-09-30 | 2010-04-01 | Chevron Oronite Company Llc | Lubricating oil compositions |
US8580717B2 (en) | 2009-11-24 | 2013-11-12 | Chevron Oronite Company Llc | Process for making an overbased, sulfurized salt of an alkylated hydroxyaromatic compound |
US8841243B2 (en) * | 2010-03-31 | 2014-09-23 | Chevron Oronite Company Llc | Natural gas engine lubricating oil compositions |
EP2420552B1 (en) * | 2010-08-19 | 2017-12-20 | Infineum International Limited | Use of phenothiazine derivatives in lubricating oil compositions in EGR equipped diesel engines |
EP3215592A1 (en) * | 2014-11-06 | 2017-09-13 | Chevron Oronite Technology B.V. | Marine diesel cylinder lubricant oil compositions |
CA2938020C (en) * | 2015-08-26 | 2023-07-04 | Infineum International Limited | Lubricating oil compositions |
US20190241829A1 (en) * | 2016-09-14 | 2019-08-08 | The Lubrizol Corporation | Lubricating composition comprising sulfonate detergent and ashless hydrocarbyl phenolic compound |
WO2018073268A1 (en) * | 2016-10-18 | 2018-04-26 | Chevron Oronite Technology B.V. | Marine diesel lubricant oil compositions |
JP7315482B2 (en) * | 2017-06-30 | 2023-07-26 | シェブロン・オロナイト・カンパニー・エルエルシー | Lubricating engine oil composition containing detergent compound |
SG11201913170VA (en) * | 2017-06-30 | 2020-01-30 | Chevron Oronite Co | Marine diesel lubricant oil compositions |
WO2019003178A1 (en) * | 2017-06-30 | 2019-01-03 | Chevron Oronite Company Llc | Lubricating oil compositions containing detergent compounds |
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WO2021044326A1 (en) | 2021-03-11 |
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