JP7348077B2 - Low viscosity engine oil containing isomerized phenolic detergent - Google Patents

Description

This application claims priority and benefit from U.S. Provisional Application No. 62/527,119, filed June 30, 2017.

Background Engine oils are blended with various additives to meet various performance requirements. A well known way to increase fuel economy is to reduce the viscosity of the lubricating oil. However, this approach has now reached the limits of current equipment capabilities and specifications.

Boundary friction area is an important consideration in the design of low viscosity engine oils. Boundary friction occurs when the fluid film separating two surfaces becomes thinner than the height of the asperity above the surface. The resulting surface-to-surface contact creates undesirable high friction and poor fuel economy in the engine. Boundary friction in engines can occur under high loads, low engine speeds, and low oil viscosities. Lower viscosity engine oils make the engine more susceptible to operation in boundary friction conditions due to a thinner, less durable film of oil. Because additives, but not base oils, affect the coefficient of friction under boundary conditions, additives that demonstrate lower coefficients of friction under boundary conditions may give superior fuel economy for low viscosity oils in engines. (i.e. less than 20 SAE grade). Second, it is also of high importance to have additives with excellent low temperature performance to meet the demands of 0W-XX lubricants, which have more stringent low temperature pumping and cranking requirements.

Despite advances in lubricant formulation technology, a need exists for low viscosity engine oil lubricants that have the benefits described above.

SUMMARY OF THE DISCLOSURE The present disclosure generally relates to (a) a predominant amount of an oil of lubricating viscosity having a kinematic viscosity in the range of 1.5 to 6.0 mm ² /s at 100°C; and (b) superposition of an alkyl-substituted detergent. A lubricating oil composition having an HTHS viscosity ranging from about 1.3 to about 2.5 cP at 150° C., comprising: a basic metal salt.

DETAILED DESCRIPTION OF THE DISCLOSURE To facilitate an understanding of the subject matter disclosed herein, a number of terms, abbreviations or other shorthands used herein are defined below. It is understood that any terms, abbreviations, or shorthand not defined have the ordinary meaning used by one of ordinary skill in the art at the time of filing this application.

Definition:
As used herein, the following words and expressions, if and when used, have the meanings given below.

"Major amount" means more than 50% by weight of the composition.

"Minor amount" means less than 50% by weight of the composition, considered as the active ingredient of the additive, and expressed with respect to the total mass of all additives present in the composition and with respect to the listed additive.

"Active ingredient" or "active" refers to an additive material that is neither a diluent nor a solvent.

All percentages reported are by weight on an active ingredient basis (ie, ignoring carrier or diluent oil), unless otherwise specified.

The term "phenate" means a salt of phenol.

The abbreviation "ppm" means parts per million by weight, based on the total weight of the lubricating oil composition.

Total base number (TBN) was determined according to ASTM D2896.

High temperature high shear (HTHS) viscosity at 150°C was determined according to ASTM D4683.

Kinematic viscosity at 100° C. (KV ₁₀₀ ) was determined according to ASTM D445.

Cold cranking simulator (CCS) viscosity at −35° C. was determined according to ASTM D5293.

Noack volatility was determined according to ASTM D5800.

Boron, calcium, magnesium, molybdenum, phosphorus, sulfur, and zinc content were determined according to ASTM D5185.

Nitrogen content was determined according to ASTM D4629.

Metals - The term "metal" refers to alkali metals, alkaline earth metals, or mixtures thereof.

Olefins - The term "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 monoalkenes, 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 carbon. Examples are 1-octene and 1-octadecene, which are used as starting points for mesobiodegradable surfactants. Linear and branched olefins are also included within the definition of olefin.

Normal alpha olefin - The term "normal alpha olefin" refers to an olefin that is a straight chain unbranched hydrocarbon with a carbon-carbon double bond present in the alpha or first position of the hydrocarbon chain.

Isomerized normal alpha olefin - The term "isomerized normal alpha olefin" as used herein refers to isomerization conditions that result in the introduction of branching along the alkyl chain and/or a change in the distribution of olefin species present. refers to alpha olefins attached to The isomerized olefin product is a linear alpha containing about 10 to about 40 carbon atoms, preferably about 20 to about 28 carbon atoms, and preferably about 20 to about 24 carbon atoms. It can be obtained by isomerizing olefins.

C _10-40 Normal Alpha Olefins - This term defines a fraction of normal alpha olefins from which fewer than 10 carbons have been removed by distillation or other fractionation methods.

All ASTM standards referenced herein are current as of the filing date of this application.

In one aspect, what is offered is
(a) a major amount of an oil of lubricating viscosity with a kinematic viscosity in the range of 1.5 to 6.0 mm ² /s at 100°C; and (b) an overbased metal salt of an alkyl-substituted phenolic detergent:
A lubricating oil composition having an HTHS viscosity in the range of about 1.3 to about 2.5 cP at 150°C, comprising:
The alkyl group is derived from an isomerized normal alpha olefin having from about 10 to about 40 carbon atoms per molecule having a normal alpha olefin isomerization level (I) of from about 0.1 to about 0.4. , the aforementioned lubricating oil composition.

In one form, the metal salt is calcium, magnesium, or a combination thereof.

In one form, what is provided is
(a) a major amount of an oil of lubricating viscosity with a kinematic viscosity in the range of 1.5 to 6.0 mm ² /s at 100°C; and (b) an overbased metal salt of an alkyl-substituted phenolic detergent:
A lubricating oil composition having an HTHS viscosity in the range of about 1.3 to about 2.5 cP at 150°C, comprising:
the alkyl group is derived from an isomerized normal alpha olefin having from about 10 to about 40 carbon atoms per molecule having a normal alpha olefin isomerization level (I) of from about 0.1 to about 0.4;
Alkyl-substituted phenolic detergents are selected from sulfur-free phenates, sulfur-containing phenates, naphthenates, composite detergents, salixalates, carboxylates, salicylates, saligenins, calixarenes, sulfur-bridged alkylphenols, alkylene-bridged alkylphenols, and mixtures thereof. The above lubricating oil composition is selected from the group consisting of:

In one form, the metal salt is calcium, magnesium, or a combination thereof.

In one form, what is provided is
(a) a major amount of an oil of lubricating viscosity having a kinematic viscosity in the range of 1.5 to 6.0 mm ² /s at 100°C; and (b) an alkyl-substituted phenolic detergent;
A lubricating oil composition having an HTHS viscosity in the range of about 1.3 to about 2.5 cP at 150°C, comprising:
The phenolic detergent is a carboxylate or salicylate detergent, and the alkyl groups are about 10 to about 10 per molecule having an isomerization level (I) of normal alpha olefins of about 0.1 to about 0.4. The aforementioned lubricating oil composition is derived from an isomerized alpha olefin having 40 carbon atoms.
In connection with the present invention, the following contents are further disclosed.
[1]
(a) a major quantity of oil of lubricating viscosity having a kinematic viscosity in the range 1.5 to 6.0 mm ² /s at 100°C; and
(b) Overbased metal salts of alkyl-substituted phenolic detergents:
A lubricating oil composition having an HTHS viscosity in the range of about 1.3 to about 2.5 cP at 150°C, comprising:
The alkyl group is derived from an isomerized normal alpha olefin having from about 10 to about 40 carbon atoms per molecule having a normal alpha olefin isomerization level (I) of from about 0.1 to about 0.4. , the aforementioned lubricating oil composition.
[2]
The alkyl-substituted phenolic detergent is selected from the group consisting of sulfur-free phenates, sulfur-containing phenates, naphthenates, composite detergents, salixalates, salicylates, saligenins, calixarenes, sulfur-bridged alkylphenols, alkylene-bridged alkylphenols, and mixtures thereof. The selected lubricating oil composition of [1].
[3]
The alkyl-substituted phenolic detergent is a carboxylate or salicylate detergent, the alkyl groups having an isomerization level (I) of normal alpha olefins of about 0.1 to 0.4, from about 10 to about 10 alkyl groups per molecule. The lubricating oil composition of [1], which is derived from an isomerized alpha olefin having 40 carbon atoms.
[4]
The alkyl-substituted phenolic detergent is an isomerized olefin phenate detergent, and the alkyl groups are about 10 to 10 per molecule having an isomerization level (I) of normal alpha olefins of about 0.1 to 0.4. The lubricating oil composition of [1], which is derived from an isomerized alpha olefin having about 40 carbon atoms.
[5]
The lubricating oil composition of [1], wherein the overbased metal salt is calcium, magnesium, or a combination thereof.
[6]
The lubricating oil composition of [1], wherein the lubricating oil composition is 0W-8, 0W-12, or 0W-16 SAE viscosity grade.
[7]
The lubricating oil composition of [1], wherein the oil of lubricating viscosity is a base oil selected from one or more of API Type II, III, IV, and V.
[8]
The lubricating oil composition of [1], wherein the isomerized normal alpha olefin has a normal alpha olefin isomerization level (I) of about 0.12 to about 0.3.
[9]
The lubricating oil composition of [1], wherein the isomerized normal alpha olefin has a normal alpha olefin isomerization level (I) of about 0.16.
[10]
The lubricating oil composition of [1], wherein the isomerized normal alpha olefin has a normal alpha olefin isomerization level (I) of about 0.26.
[11]
The lubricating oil composition of [1], wherein the normal alpha olefin mixture has about 14 to about 28 carbon atoms per molecule.
[12]
The overbased phenolic detergent of [1], wherein the normal alpha olefin mixture has from about 18 to about 24 carbon atoms per molecule.
[13]
The overbased phenolic detergent of [1], wherein the normal alpha olefin mixture has about 20 to about 24 carbon atoms per molecule.
[14]
The lubricating oil composition of [1], wherein the TBN of the detergent is 100 to 600 mg KOH/gram on an oil-free basis.
[15]
The lubricating oil composition of [1] further comprising an additional detergent selected from the group consisting of sulfonates, phenates, and salicylates.
[16]
The lubricating oil composition of [15], wherein the detergent is magnesium sulfonate.
[17]
The lubricating oil composition of [1], further comprising a polymethacrylate dispersant VII.
[18]
The lubricating oil composition according to [1], further comprising a primary or secondary zinc dithiophosphate compound or a mixture thereof.
[19]
The lubricating oil composition of [1], further comprising a friction modifier.
[20]
A method of lubricating an engine comprising lubricating the engine with a lubricating oil composition having an HTHS viscosity in the range of about 1.3 to about 2.5 cP at 150°C, the lubricating oil composition comprising: :
(a) a major quantity of oil of lubricating viscosity having a kinematic viscosity in the range 1.5 to 6.0 mm ² /s at 100°C; and
(b) an overbased metal salt of an alkyl-substituted phenolic detergent;
including;
Moreover, the alkyl group is derived from an isomerized normal alpha olefin having from about 10 to about 40 carbon atoms per molecule having an isomerization level (I) of the normal alpha olefin from about 0.1 to about 0.4. The method as described above.

Phenolic Alkyl Hydroxybenzoate Detergent In one aspect of the present disclosure, the phenolic alkyl hydroxybenzoate detergent is an isomerized olefin alkyl hydroxybenzoate detergent.

In one aspect of the present disclosure, the TBN of the alkyl hydroxybenzoate detergent derived from C ₁₀ -C ₄₀ isomerized NAO is 100-700, 100-650, 100-600, 100-500, 100 on an oil-free basis. -400, 100-300, 150-250, 175-250, 175-225mg KOH/gram.

In one aspect of the present disclosure, the alkyl hydroxybenzoate detergent is derived from C ₁₀ -C ₄₀ isomerized NAO and has a molecular weight of 10 to 300, preferably 50 to 300, more preferably 100 to 300, even more on an active basis. Preferably it has a TBN of 150-300, and most preferably 175-250 mg KOH/gram.

In one aspect of the present disclosure, the alkylhydroxybenzoate detergent derived from C ₁₀ -C ₄₀ isomerized NAO is a Ca alkylhydroxybenzoate detergent.

In one aspect of the present disclosure, the alkyl hydroxybenzoate detergent derived from C ₁₀ -C ₄₀ isomerized NAO can be an alkylated hydroxybenzoate detergent. In other forms, the detergent can be a salicylate detergent. In other forms, the detergent can be a carboxylate detergent.

In one aspect of the present disclosure, alkyl hydroxybenzoates derived from C ₁₀ -C ₄₀ isomerized NAO can be prepared as described in US Pat. No. 8,993,499, incorporated herein in its entirety.

In one aspect of the disclosure, the alkyl hydroxybenzoate detergents have about 14 to about 28 carbon atoms per molecule, preferably about 20 to about 24 carbon atoms, or preferably about 14 to about 18 carbon atoms per molecule. of carbon atoms, or preferably from about 20 to about 28 carbon atoms per molecule, having alkyl groups derived from isomerized alpha olefins.

In one aspect of the present disclosure, the alkyl hydroxybenzoate derived from C ₁₀ -C ₄₀ isomerized NAO has a molecular weight of about 0.10 to about 0.40, preferably about 0.10 to about 0.35, preferably about 0 Alkyl derived from isomerized NAO having an isomerization level (I) of from .10 to about 0.30, preferably from about 0.12 to about 0.30, and more preferably from about 0.12 to about 0.20. Produced from alkylphenols with radicals.

In one aspect of the present disclosure, the alkyl hydroxybenzoate derived from C ₁₀ -C ₄₀ isomerized NAO comprises one or more alkylphenols with alkyl groups different from the C ₁₀ -C ₄₀ isomerized NAO and C ₁₀ -C ₄₀ Produced from one or more alkylphenols with alkyl groups derived from isomerized NAO.

In one aspect of the present disclosure, the isomerized NAO of the alkyl hydroxybenzoate detergent has an isomerization level of about 0.16 and has about 20 to about 24 carbon atoms.

In one aspect of the present disclosure, the isomerized NAO of the alkyl hydroxybenzoate detergent has an isomerization level of about 0.26 and has about 20 to about 24 carbon atoms.

In one aspect of the present disclosure, the lubricating oil composition has a Ca content of alkyl hydroxybenzoate derived from C ₁₀ -C ₄₀ isomerized NAO from about 0.01 to 2.0 wt%, preferably from 0.1 to It contains 1.0 wt%, more preferably 0.05 to 0.5 wt%, more preferably 0.1 to 0.5 wt%.

In one aspect of the present disclosure, lubricating oil compositions comprising alkyl hydroxybenzoate detergents derived from C ₁₀ -C ₄₀ isomerized NAO are used in automotive engine oil compositions, gas engine oil compositions, dual fuel engine oil compositions. a vehicle gas engine oil composition, or a locomotive engine oil composition.

In one aspect of the present disclosure, lubricating oil compositions comprising alkyl hydroxybenzoate detergents derived from C ₁₀ -C ₄₀ isomerized NAO are used in automotive and industrial applications, such as transmission oils, hydraulic oils, tractor fluids, gear oils, etc. It is a functional fluid.

In one aspect of the present disclosure, the lubricating oil composition comprising an alkylhydroxybenzoate detergent derived from C ₁₀ -C ₄₀ isomerized NAO is a multigrade oil or a monograde oil.

In one aspect of the present disclosure, a lubricating oil composition comprising an alkyl hydroxybenzoate detergent derived from C ₁₀ -C ₄₀ isomerized NAO lubricates not only clutches but also crankcases and gears.

Phenolic Phenate Detergent In one aspect of the present disclosure, the phenolic detergent is an isomerized olefin phenate detergent.

In one aspect of the present disclosure, the isomerized olefin phenate detergent is based on an oil-free basis, -425, 350-425, 350-400 mgKOH/gram.

In one aspect of the disclosure, the phenolic detergent is an alkylated phenate detergent, in which the alkyl group is derived from an isomerized normal alpha olefin having from about 10 to about 40 carbon atoms per molecule. Ru.

In one aspect of the disclosure, the phenolic detergent has a molecular weight between about 0.10 and about 0.40, preferably between about 0.10 and about 0.30, preferably between about 0.12 and about 0.30, and More preferably, it has a normal alpha olefin isomerization level (I) of about 0.22 to about 0.30.

In one aspect of the disclosure, the phenate detergent is a sulfurized phenate detergent.

In one aspect of the present disclosure, isomerized olefin phenate detergents can be prepared as described in US Pat. No. 8,580,717, which is incorporated herein in its entirety.

In one aspect of the disclosure, there are about 14 to about 30 alkyl groups, about 16 to about 30, about 18 to about 30, about 20 to about 28, 20 to about 24 alkyl groups per molecule. or from about 18 to about 28 carbon atoms.

In other forms, the alpha olefin has an isomerization level of about 0.26 and has about 20 to about 24 carbon atoms.

Oils of lubricating viscosity Oils of lubricating viscosity (sometimes referred to as "base stocks" or "base oils") are the main liquid components of lubricants, and include, for example, the final lubricant (or lubricant composition). Additives and possibly other oils are blended to produce the product. Base oils are useful not only for making concentrates, but also for making lubricating oil compositions therefrom, and can be selected from natural and synthetic lubricating oils and combinations thereof. .

Natural oils include hydrorefined, solvent-treated mineral lubricating oils of the paraffinic, naphthenic and mixed paraffinic-naphthenic types, as well as liquid petroleum, animal and vegetable oils. Oils of lubricating viscosity derived from coal or shale are also useful base oils.

Synthetic lubricating oils include hydrocarbon oils such as: polymerized and copolymerized olefins (e.g., polybutylene, polypropylene, propylene-isobutylene copolymers, chlorinated polybutylene, poly(1-hexene), poly(1-hexene), octene), poly(1-decene); alkylbenzenes (e.g. dodecylbenzene, tetradecylbenzene, dinonylbenzene, di(2-ethylhexyl)benzene); polyphenols (e.g. biphenyl, terphenyl, alkylated polyphenols); and alkylation Diphenyl ethers and alkylated diphenyl sulfides, and derivatives, analogs and homologs thereof.

Other suitable classes of synthetic lubricating oils include dicarboxylic acids (e.g. malonic acid, alkylmalonic acid, alkenylmalonic acid, succinic acid, alkylsuccinic acid and alkenylsuccinic acid, maleic acid, fumaric acid, azelaic acid, suberic acid, esters of sebacic acid, adipic acid, linoleic acid dimer, phthalic acid) with various alcohols (e.g., butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol). include. Specific examples of these esters include: dibutyl adipate, di(2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azelate, diisodecyl azelate, dioctyl phthalate. , didecyl phthalate, diicosyl sebacate, 2-ethylhexyl diester of linoleic acid dimer, and formed by reacting 1 mole of sebacic acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid. complex ester.

Esters useful as synthetic oils include those made from _C5 to _C12 monocarboxylic acids and polyols, and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, and tripentaerythritol. Also includes.

The base oil can be derived from Fischer-Tropsch synthetic hydrocarbons. Fischer-Tropsch synthetic hydrocarbons are produced 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 base oils. For example, hydrocarbons can be hydroisomerized; hydrocracked and hydroisomerized; dewaxed; or hydroisomerized and dewaxed using processes known to those skilled in the art. be done, be able to do.

Unrefined, refined, and rerefined oils can be used in the lubricating oil compositions of the present invention. Unrefined oils are those obtained directly from natural or synthetic sources without further purification treatment. For example, unrefined oils would be shale oils obtained directly from carbonization operations, petroleum oils obtained directly from distillation, or ester oils obtained directly from esterification processes and used without further treatment. Refined oils are similar to unrefined oils, except that they have been further processed in one or more refining steps to improve one or more properties. Many such purification techniques are known to those skilled in the art, such as distillation, solvent extraction, acid or base extraction, filtration and osmosis. Rerefined oil is obtained by a process similar to that used to obtain refined oil applied to refined oil already used in service. Such rerefined oils are also known as reclaimed oils or reprocessed oils, and are often further processed by techniques for approval of oil breakdown products and used additives.

Therefore, the base oil that can be used to make the lubricating oil compositions of the present invention may be any base oil from Group I to V as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines (API Publication 1509). You can choose from. Types (groups) of such base oils are summarized in Table 1 below:

Suitable base oils for use herein are any variety corresponding to API Group II, Group III, Group IV, and Group V oils and combinations thereof, preferably with their exceptional volatility, Class III to V oils due to their stability, viscosity and cleanliness characteristics.

The base oil constitutes the main component of the lubricating oil composition of the present invention and has a weight of 50 to (greater than) 99 wt. % (eg, 70-95 wt.%, or 85-95 wt.%).

The base oil can be selected from any of the synthetic or natural oils typically used as crankcase lubricants for spark ignition internal combustion engines. Base oils typically have a kinematic viscosity at 100° C. in the range 1.5-6 mm ² /s. When the kinematic viscosity at 100° C. of the lubricating base oil exceeds 6 mm ² /s, low-temperature viscosity characteristics may be reduced and sufficient fuel efficiency may not be obtained. At kinematic viscosities below 1.5 mm ² /s, the formation of an oil film at the lubrication points is insufficient; for this reason, lubrication is poor and evaporation losses of the lubricating oil composition can increase.

Preferably, the base oil has a viscosity index of at least 90 (eg, at least 95, at least 105, at least 110, at least 115, or at least 120). If the viscosity index is less than 90, not only the viscosity-temperature properties, thermal and oxidative stability, and volatilization prevention are reduced, but also the coefficient of friction tends to increase; the wear resistance also tends to decrease.

Lubricating Oil Composition The lubricating oil composition can be a multigrade oil recognized by the viscosity grade definition SAE 0W-X, where X represents any one of 8, 12, and 16. .

The lubricating oil composition has a temperature of 2.3 cP or less (e.g., 1.0 to 2.6 cP, or 1.3 to 2.3 cP), such as 2.0 cP or less (e.g., 1.0 to 2.0 cP, or 1.3 to 2.3 cP), or even 1.7 cP or less (eg, 1.0 to 1.7 cP, or 1.3 to 1.7 cP).

The lubricating oil composition has at least 135 (eg, 135-400, or 135-250), at least 150 (eg, 150-400, 150-250), at least 165 (eg, 165-400, or 165-250), It has a viscosity index of at least 190 (eg, 190-400, or 190-250), or at least 200 (eg, 200-400, or 200-250). If the viscosity index of the lubricating oil composition is less than 135, it may be difficult to improve fuel efficiency while maintaining HTHS viscosity at 150°C. If the viscosity index of the lubricating oil composition exceeds 400, the evaporation properties may be reduced and may cause defects due to poor solubility of sealant and sealant compatibility properties. be.

The lubricating oil composition is heated at 100° C. in the range of 3 to 12 mm ² /s (e.g., 3 to 8.2 mm ² /s, 3.5 to ^{8.2 mm 2} /s, or 4 to 8.2 mm ² /s). It has a kinematic viscosity of .

Generally, the level of sulfur in the lubricating oil compositions of the present invention will be about 0.7 wt., based on the total weight of the lubricating oil composition. % or less, for example, about 0.01 wt. % to about 0.70wt. %, 0.01-0.6wt. %, 0.01-0.5wt. %, 0.01-0.4wt. %, 0.01-0.3wt. %, 0.01-0.2wt. %, 0.01wt. %~0.10wt. %. of sulfur levels. In one form, the level of sulfur in the lubricating oil composition of the present invention is about 0.60 wt.%, based on the total weight of the lubricating oil composition. % or less, approximately 0.50wt. % or less, about 0.40wt. % or less, approximately 0.30wt. % or less, about 0.20wt. % or less, about 0.10wt. % or less.

In one form, the level of phosphorus in the lubricating oil composition of the present invention is about 0.12 wt.%, based on the total weight of the lubricating oil composition. % or less, for example, about 0.01 wt. % to about 0.12wt. % phosphorus level. In one form, the level of phosphorus in the lubricating oil composition of the present invention is about 0.11 wt.%, based on the total weight of the lubricating oil composition. % or less, for example, about 0.01 wt. % to about 0.11wt. % phosphorus level. In one form, the level of phosphorus in the lubricating oil composition of the present invention is about 0.10 wt., based on the total weight of the lubricating oil composition. % or less, for example, about 0.01 wt. % to about 0.10wt. % phosphorus level. In one form, the level of phosphorus in the lubricating oil composition of the present invention is about 0.09 wt.%, based on the total weight of the lubricating oil composition. % or less, for example, about 0.01 wt. % to about 0.09wt. % phosphorus level. In one form, the level of phosphorus in the lubricating oil composition of the present invention is about 0.08 wt.%, based on the total weight of the lubricating oil composition. % or less, for example, about 0.01 wt. % to about 0.08wt. % phosphorus level. In one form, the level of phosphorus in the lubricating oil composition of the present invention is about 0.07 wt., based on the total weight of the lubricating oil composition. % or less, for example, about 0.01 wt. % to about 0.07wt. % phosphorus level. In one form, the level of phosphorus in the lubricating oil composition of the present invention is about 0.05 wt.%, based on the total weight of the lubricating oil composition. % or less, for example, about 0.01 wt. % to about 0.05wt. % phosphorus level.

In one form, the sulfate ash level produced by the lubricating oil composition of the present invention is about 1.60 wt. as determined by ASTM D874. % or less, for example, from about 0.10 to about 1.60 wt.% as determined by ASTM D874. % sulfate ash level. In one form, the sulfate ash level produced by the lubricating oil composition of the present invention is about 1.00 wt. % or less, for example, from about 0.10 to about 1.00 wt.%, as determined by ASTM D874. % sulfate ash level. In one form, the sulfate ash level produced by the lubricating oil composition of the present invention is about 0.80 wt. as determined by ASTM D874. % or less, for example, from about 0.10 to about 0.80 wt.%, as determined by ASTM D874. % sulfate ash level. In one form, the sulfate ash level produced by the lubricating oil composition of the present invention is about 0.60 wt. as determined by ASTM D874. % or less, for example, from about 0.10 to about 0.60 wt.%, as determined by ASTM D874. % sulfate ash level.

Suitably, the lubricating oil compositions of the present invention have a total base number (TBN) of 4 to 15 mg KOH/g (e.g., 5 to 12 mg KOH/g, 6 to 12 mg KOH/g, or 8 to 12 mg KOH/g). ).

Viscosity modifier The lubricating oil composition can also include a viscosity modifier. Viscosity modifiers function to impart high and low temperature workability to the lubricating oil. The viscosity modifier used can have a single function or can be multifunctional. Multifunctional viscosity modifiers that also function as dispersants are also known. Suitable viscosity modifiers include: polyisobutylene, copolymers of ethylene and propylene and higher alpha-olefins, polymethacrylates, polyalkyl methacrylates, methacrylate copolymers, copolymers of unsaturated dicarboxylic acids and vinyl compounds. Polymers, copolymers of styrene and acrylic esters, and partially hydrogenated copolymers of styrene/isoprene, styrene/butadiene, and isoprene/butadiene, and partially hydrogenated homopolymers of butadiene and isoprene and isoprene/divinylbenzene. polymer. In one form, the viscosity modifier is a polyalkyl methacrylate. The topology of the viscosity modifier can include, but is not limited to, linear, branched, multibranched, star, or comb topology.

Suitable viscosity modifiers have a permanent shear stability index (PSSI) of 30 or less (eg, 10 or less, 5 or less, or even 2 or less). PSSI is a measure of the irreversible reduction in oil viscosity resulting from shear contributed by additives. PSSI is determined according to ASTM D6022. The lubricating oil compositions of the present disclosure exhibit stay-in-grade capabilities. Retention of kinematic viscosity at 100° C. within a single SAE viscosity grade classification by fresh oil (refined oil) and its sheared version is evidence of the oil's stay-in-grade ability.

The viscosity modifier may be 0.5 to 15.0 wt. based on the total weight of the lubricating oil composition. % (e.g., 0.5-10 wt.%, 0.5-5 wt.%, 1.0-15 wt.%, 1.0-10 wt.%, or 1.0-5 wt.%). can. In one form, viscosity modifiers are not present in the lubricating oil compositions described herein.

Additional Lubricating Oil Additives The lubricating oil compositions of the present disclosure can also contain other conventional additives that can improve or impart any desirable properties of the lubricating oil composition, including those additives are dispersed or dissolved. Any additive known to those skilled in the art can be used in the lubricating oil compositions disclosed herein. Some suitable additives are 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. For example, lubricating oil compositions can be blended with: antioxidants, antiwear agents, detergents such as metal detergents, rust inhibitors, defogging agents, demulsifiers, metal deactivators, friction modifiers. and mixtures thereof. Various additives are known and commercially available. These additives or their similar compounds can be used to prepare the disclosed lubricating oil compositions by conventional blending procedures.

In preparing lubricating oil formulations, from 10 to 100 wt. It is common practice to introduce additives in the form of % active ingredient concentrates.

Typically, these concentrates are diluted with 3 to 100 parts by weight of lubricating oil, such as 5 to 40 parts by weight, per part by weight of the additive package to form a finished lubricant, such as crankcase motor oil. can. The purpose of the concentrate is, of course, to make handling of the various materials less difficult and inappropriate, as well as to facilitate dissolution or dispersion in the final blend.

Each of the foregoing additives, when used, is used in a functionally effective amount to impart the desired properties to the lubricant. Thus, for example, if the additive is a friction modifier, the functionally effective amount of the friction modifier would be an amount sufficient to impart the desired friction modifying properties to the lubricant.

Generally, the concentration of each of the additives in the lubricating oil composition, when used, is about 0.001 wt.%, based on the total weight of the lubricating oil composition. %~about 20wt. %, about 0.01wt. % to about 15wt. %, or about 0.1 wt. % to about 10wt. %, about 0.005wt. % to about 5wt. %, or about 0.1 wt. % to about 2.5wt. %. Additionally, the total amount of additives in the lubricating oil composition is about 0.001 wt., based on the total weight of the lubricating oil composition. %~about 20wt. %, about 0.01wt. % to about 10wt. %, or about 0.1 wt. % to about 5wt. %.

The following examples are presented to illustrate the form of the disclosure and are not intended to limit the disclosure to the particular form set forth. All parts and percentages are by weight unless indicated to the contrary. All numbers are approximate. It should be understood that when numerical ranges are given, forms outside the stated ranges are still within the scope of the disclosure. Specific details described in each example should not be construed as necessary features of the disclosure. It will be understood that various modifications may be made to the form disclosed herein. Accordingly, the above description is merely an exemplification of preferred forms and should not be construed as limiting. For example, the features described above, which are implemented as the best mode for operating this disclosure, are for purposes of illustration only. Other arrangements and methods may be practiced by those skilled in the art without departing from the spirit and scope of this disclosure. Additionally, those skilled in the art will envision other modifications within the spirit and scope of the claims appended hereto.

EXAMPLES The following examples are intended for illustrative purposes only and do not limit the scope of this disclosure in any way.

The isomerization level was determined by NMR method.

Isomerization level (I) and NMR method The isomerization level (I) of the olefin was determined by hydrogen-1 (1H) NMR. NMR spectra were obtained on a Bruker Ultrashield Plus 400 in chloroform-d1 at 400 MHz using TopSpin 3.2 spectral processing software.

The isomerization level (I) is a methyl group (-CH ₃ ) (chemical shift 0.30-1.01 ppm) attached to a methylene backbone group (-CH ₂ -) (chemical shift 1.01-1.38 ppm). represents the relative amount of and is defined by equation (1) as shown below:
I=m/(m+n) Formula (1)
In the above formula, m is the NMR integral of the methyl group with a chemical shift between 0.30±0.03 and 1.01±0.03 ppm, and n is between 1.01±0.03 and 1 NMR integral of methylene group with chemical shift between .38±0.10 ppm.

Example A
Alkylated phenols and phenates were prepared in substantially the same manner as in US Pat. No. 8,580,717 using C _20-24 isomerized normal alpha olefins. The alpha olefin isomerization level was approximately 0.26. The resulting product calcium content was 9.66%; sulfur 3.41%, unreacted alkylphenol 8.2%, and had a kinematic viscosity at 100° C. of 319 cSt. Estimated TBN was approximately 400 mg KOH/g on an oil-free basis. Diluent oil is 35wt. %Met.

Comparative example A
Alkylated phenols and phenates were prepared using propylene tetramer available from Chevron Oronite. The resulting product calcium content was 9.66%; sulfur 3.41%, unreacted alkylphenol 8.2%, and had a kinematic viscosity at 100° C. of 319 cSt. TBN was 380 mg KOH/g on an active basis. Dilution oil is 31.4wt. %Met.

baseline 1
A lubricating oil composition containing a major amount of a base oil of lubricating viscosity and the following additives was prepared to provide a finished oil with a HTHS viscosity at 150° C. of 1.4 cP:
(1) Ethylene carbonate post-treated bis-succinimide;
(2) borate-treated bis-succinimide dispersant;
(3) Calcium content: 0.10wt. % overbased calcium sulfonate detergent;
(4) Regarding magnesium content: 0.05wt. % overbased magnesium sulfonate detergent;
(5) a mixture of primary zinc dialkyldithiophosphate and secondary zinc dialkyldithiophosphate at 770 ppm with respect to phosphorus content;
(6) Molybdenum sulfide succinimide complex;
(7) borate treated organic friction modifier;
(8) alkylated diphenylamine antioxidant;
(9) Foam suppressant;
(10) 2.5wt. % of a non-dispersible polyalkyl methacrylate comb viscosity modifier having a PSSI of 1; and (11) the remainder, Group II base oil (YUBASE® 2).

Example 1
Formulation Baseline 1 was supplemented with 0.04wt. for calcium content. % of the calcium phenate detergent of Example A was added.

Comparative example 1
Formulation Baseline 1 was supplemented with 0.04wt. for calcium content. % of the calcium phenate detergent of Comparative Example A was added.

baseline 2
A lubricating oil composition containing a major amount of a base oil of lubricating viscosity and the following additives was prepared to provide a SAE 0W-8 finished oil:
(1) Ethylene carbonate post-treated bis-succinimide;
(2) borate-treated bis-succinimide dispersant;
(3) Calcium content: 0.10wt. % overbased calcium sulfonate detergent;
(4) Regarding magnesium content: 0.05wt. % overbased magnesium sulfonate detergent;
(5) a mixture of primary zinc dialkyldithiophosphate and secondary zinc dialkyldithiophosphate at 770 ppm with respect to phosphorus content;
(6) Molybdenum sulfide succinimide complex;
(7) borate treated organic friction modifier;
(8) alkylated diphenylamine antioxidant;
(9) Foam suppressant;
(10) 3.0wt. % of a non-dispersible polyalkyl methacrylate viscosity modifier having a PSSI of 1; and (11) the remainder, Group II base oil (YUBASE® 3).

Example 2
Formulation Baseline 2 had 0.04 wt. % of the calcium phenate detergent of Example A was added.

Comparative example 2
Formulation Baseline 2 had 0.04 wt. % of the calcium phenate detergent of Comparative Example A was added.

baseline 3
A lubricating oil composition containing a major amount of a base oil of lubricating viscosity and the following additives was prepared to provide an SAE 0W-12 finished oil:
(1) Ethylene carbonate post-treated bis-succinimide;
(2) borate-treated bis-succinimide dispersant;
(3) Calcium content: 0.10wt. % overbased calcium sulfonate detergent;
(4) Regarding magnesium content: 0.05wt. % overbased magnesium sulfonate detergent;
(5) a mixture of primary zinc dialkyldithiophosphate and secondary zinc dialkyldithiophosphate at 770 ppm with respect to phosphorus content;
(6) Molybdenum sulfide succinimide complex;
(7) borate treated organic friction modifier;
(8) alkylated diphenylamine antioxidant;
(9) Foam suppressant;
(10) 2.0wt. % of a non-dispersible polyalkyl methacrylate viscosity modifier having a PSSI of 1; and (11) the remainder, Group III base oil (YUBASE® 4).

Example 3
Formulation Baseline 3 had 0.04 wt. % of the calcium phenate detergent of Example A was added.

Comparative example 3
Formulation Baseline 3 had 0.04 wt. % of the calcium phenate detergent of Comparative Example A was added.

baseline 4
A lubricating oil composition containing a major amount of a base oil of lubricating viscosity and the following additives was prepared to provide a finished oil with a HTHS viscosity at 150° C. of 1.4 cP:
(1) Ethylene carbonate post-treated bis-succinimide;
(2) borate-treated bis-succinimide dispersant;
(3) Regarding magnesium content: 0.05wt. % overbased magnesium sulfonate detergent;
(4) a mixture of primary zinc dialkyldithiophosphate and secondary zinc dialkyldithiophosphate at 770 ppm with respect to phosphorus content;
(5) alkylated diphenylamine antioxidant;
(6) Molybdenum sulfide succinimide complex;
(7) borate treated organic friction modifier;
(8) Foam suppressant;
(9) 2.5wt. % of a non-dispersible polyalkyl methacrylate viscosity modifier having a PSSI of 1; and (10) the remainder, Group II base oil (YUBASE® 2).

Example 4
Formulation Baseline 4 had 0.14 wt. % of the calcium phenate detergent of Example A was added.

Comparative example 4
Formulation Baseline 4 had 0.14 wt. % of the calcium phenate detergent of Comparative Example A was added.

baseline 5
A lubricating oil composition containing a major amount of a base oil of lubricating viscosity and the following additives was prepared to provide a SAE 0W-8 finished oil:
(1) Ethylene carbonate post-treated bis-succinimide;
(2) borate-treated bis-succinimide dispersant;
(3) Regarding magnesium content: 0.05wt. % overbased magnesium sulfonate detergent;
(4) a mixture of primary zinc dialkyldithiophosphate and secondary zinc dialkyldithiophosphate at 770 ppm with respect to phosphorus content;
(5) alkylated diphenylamine antioxidant;
(6) Molybdenum sulfide succinimide complex;
(7) borate treated organic friction modifier;
(8) Foam suppressant;
(9) 3.0wt. % of a non-dispersible polyalkyl methacrylate viscosity modifier having a PSSI of 1; and (10) the remainder, Group II base oil (YUBASE® 3).

Example 5
Formulation Baseline 5 had 0.14 wt. % of the calcium phenate detergent of Example A was added.

Comparative example 5
Formulation Baseline 5 had 0.14 wt. % of the calcium phenate detergent of Comparative Example A was added.

baseline 6
A lubricating oil composition containing a major amount of a base oil of lubricating viscosity and the following additives was prepared to provide an SAE 0W-12 finished oil:
(1) Ethylene carbonate post-treated bis-succinimide;
(2) borate-treated bis-succinimide dispersant;
(3) Regarding magnesium content: 0.05wt. % overbased magnesium sulfonate detergent;
(4) a mixture of primary zinc dialkyldithiophosphate and secondary zinc dialkyldithiophosphate at 770 ppm with respect to phosphorus content;
(5) alkylated diphenylamine antioxidant;
(6) Molybdenum sulfide succinimide complex;
(7) borate treated organic friction modifier;
(8) Foam suppressant;
(9) 2.0wt. % of a non-dispersible polyalkyl methacrylate viscosity modifier having a PSSI of 1; and (10) the remainder, Group III base oil (YUBASE® 4).

Example 6
Formulation Baseline 6 had 0.14 wt. % of the calcium phenate detergent of Example A was added.

Comparative example 6
Formulation Baseline 6 had 0.14 wt. % of the calcium phenate detergent of Comparative Example A was added.

Example B
Alkylated phenols and alkyl hydroxybenzoates were prepared in substantially the same manner as US Pat. No. 8,993,499 using C _20-24 isomerized normal alpha olefins. The alpha olefin isomerization level was approximately 0.16. The additive was 6.4wt. % Ca and about 20 wt. % diluent oil and had a TBN of about 180 mg KOH/g and a basicity index of about 2.4. On an active basis, the TBN of this additive is approximately 225 mg KOH/g.

Comparative example B
The alkyl hydroxybenzoate contains at least 60 mol. % of alkylphenols with alkyl groups derived from C _14-18 normal alpha olefins. The wt% Ca in the alkyl hydroxybenzoate is approximately 6.4, with an active basis of 297 mg KOH/g TBN. The diluent oil was 41 wt%.

baseline 7
A lubricating oil composition containing a major amount of a base oil of lubricating viscosity and the following additives was prepared to provide a SAE 0W-8 finished oil:
(1) Ethylene carbonate post-treated bis-succinimide;
(2) borate-treated bis-succinimide dispersant;
(4) a mixture of primary zinc dialkyldithiophosphate and secondary zinc dialkyldithiophosphate at 770 ppm with respect to phosphorus content;
(5) alkylated diphenylamine;
(6) Molybdenum sulfide succinimide complex;
(7) borate treated organic friction modifier;
(8) 5 ppm foam suppressor with respect to silicon content;
(9) 0wt. % VII and 0.4wt. % PPD; and (10) the remainder, Group III base oil (YUBASE® 4).

Example 7
Formulation Baseline 7 contains 0.18 wt. % of the calcium alkyl hydroxybenzoate detergent of Example B was added.

Comparative example 7
Formulation Baseline 7 contains 0.18 wt. % of highly overbased calcium sulfonate detergent was added.

Comparative example 8
Formulation Baseline 7 contains 0.18 wt. % of the calcium alkyl hydroxybenzoate detergent of Comparative Example B was added.

ASTM D4684 Mini Rotary Viscometer Test (MRV)
In this test, the test oil is first heated and then cooled to the test temperature (-40° C. in this case) in a mini rotary viscometer cell. Each cell contains a calibrated rotor-stator set in which the rotor is rotated using strings attached to weights and wrapped around the rotor shaft. A series of increasing weights are applied to the string, starting with a 10g weight, until rotation occurs to determine the yield stress. Results are reported as yield stress as applied force in Pascals. A 150 g weight is then added to determine the apparent viscosity of the oil. It appears that the higher the apparent viscosity, the less continuously and fully the oil will be supplied to the oil pump inlet. Results are reported as viscosity in centipoise. The results of MRV testing for each lubricating oil composition are set forth in Table 2 below.

Scanning Brookfield Scanning Brookfield Viscosity: ASTM D5133 is used to measure the low temperature, low shear rate, viscosity/temperature dependence of engine oils. The low temperature, low shear viscosity behavior of engine oil determines whether the oil will flow to the sump inlet screen, then to the oil pump, immediately after a cold start, or eventually to the engine. Determine whether it will flow to locations in the engine that require lubrication in sufficient quantities to prevent damage. ASTM D5133, Scanning Brookfield Viscosity Technique, measures the Brookfield viscosity of a sample (which is cooled at a constant rate of 1° C./hour). Similar to MRV, ASTM D5133 is intended for low temperature oil pumpability. The test reports the temperature at which the sample reaches 40,000 cP or the viscosity at -40°C. The gelation index is also reported and is defined as the greatest rate of change in viscosity increase from -5°C to the lowest test temperature. The current API SL/ILSAC GF-5 specification for passenger car engine oils calls for a maximum gelling index of 12. The results are shown in Table 2 below.

Pour point (JIS K2269)
A 45 ml sample is warmed to 45° C. in a test tube and cooled by a specific method. Each time the temperature of the sample decreases by 2.5°C, the test tube is removed from the cooling bath, the temperature at which the sample remains fully motionless for 5 seconds is read, and 2.5°C is added to this value to determine its value. Consider the result as a pour point.

The data shows that formulations containing the phenate of Example A derived from isomerized normal alpha olefins are superior in one or more measurements compared to phenate detergents not derived from isomerized normal alpha olefins. It is clear that it exhibited low temperature characteristics. The higher the concentration of the detergent, the greater the effect.

Plint TE77 High Frequency Friction Machine Boundary friction coefficient measurements of the Examples and Comparative Examples were obtained using a Plint TE-77 High Frequency Friction Machine (commercially available from Phoenix Tribology). For each test, a 5 mL sample of test oil was placed in the device. The TE-77 was operated at 100° C. and a load of 56 N was placed on the specimen. The reciprocating speed was swept from 10 Hz to 1 Hz and coefficient of friction data was collected throughout the test. The friction coefficient measurements are shown in Table 3.

The friction coefficient data collected with these oils at reciprocating speeds of 1-2 Hz are in the boundary friction region.

Boundary friction area is an important consideration in the design of low viscosity engine oils. Boundary friction occurs when the fluid film separating two surfaces becomes thinner than the height of the asperity above the surface. The resulting surface-to-surface contact creates undesirable high friction and poor fuel economy in the engine. Boundary friction in engines can occur under high loads, low engine speeds, and low oil viscosities. Lower viscosity engine oils make the engine more susceptible to operation in boundary friction conditions due to a thinner, less durable film of oil. Additives, but not base oils, affect the coefficient of friction under boundary conditions, so the additives that exemplify the lower coefficient of friction under boundary conditions in TE-77 are an excellent choice for low viscosity oils in engines. would give fuel economy.

Based on the boundary friction area results from Example 7, it is clear that formulations containing alkyl hydroxybenzoates derived from isomerized normal alpha olefins are superior to those not derived from isomerized normal alpha olefins.

Claims (15)

(a) a major amount of oil of lubricating viscosity having a kinematic viscosity in the range of 1.5 to 6.0 mm ² /s at 100° C., determined according to ASTM D445, where “major amount” is 50% of the composition; and (b) an overbased metal salt of an alkyl-substituted phenolic detergent:
A lubricating oil composition having an HTHS viscosity in the range of 1.3 to 2.5 cP at 150°C determined according to ASTM D4683, comprising:
the alkyl group is derived from an isomerized normal alpha olefin having from 10 to 40 carbon atoms per molecule, with a normal alpha olefin isomerization level (I) of from 0.1 to 0.4;
The isomerization level (I) of the olefins was determined by hydrogen-1 (1H) NMR obtained on a Bruker Ultrashield Plus 400 in chloroform-d1 at 400 MHz using TopSpin 3.2 spectral processing software. ,
The isomerization level (I) is:
I=m/(m+n),
In the above formula, m is the NMR integral of the methyl group with a chemical shift between 0.30±0.03 and 1.01±0.03 ppm;
n is the NMR integral of methylene groups with chemical shifts between 1.01 ± 0.03 and 1.38 ± 0.10 ppm;
The alkyl-substituted phenolic detergent is a Ca alkyl hydroxybenzoate compound,
The lubricating oil composition comprises from 0.01 to 2.0 wt% with respect to the Ca content of the alkyl hydroxybenzoate compound.
The aforementioned lubricating oil composition. The alkyl-substituted phenolic detergent is a carboxylate or salicylate detergent, and the alkyl group contains 10 to 40 alkyl groups per molecule having an isomerization level (I) of normal alpha olefins of 0.1 to 0.4. The lubricating oil composition of claim 1, which is derived from an isomerized alpha olefin having carbon atoms. The lubricating oil composition of claim 1, wherein the lubricating oil composition is a 0W-8, 0W-12, or 0W-16 SAE viscosity grade. The lubricating oil composition of claim 1, wherein the oil of lubricating viscosity is a base oil selected from one or more of API Group II, Group III, Group IV, and Group V. The isomerized normal alpha olefin has an isomerization level (I) of normal alpha olefin of 0.12 to 0.3, or the isomerized normal alpha olefin has an isomerization level (I) of normal alpha olefin of 0.16 or 0.26. 2. The lubricating oil composition of claim 1, having a chemical level (I). The lubricating oil composition of claim 1, wherein the normal alpha olefin mixture has 14 to 28 carbon atoms per molecule. The lubricating oil composition of claim 1, wherein the normal alpha olefin mixture has 18 to 24 carbon atoms per molecule. The lubricating oil composition of claim 1, wherein the normal alpha olefin mixture has 20 to 24 carbon atoms per molecule. The lubricating oil composition of claim 1, wherein the detergent has a TBN of 100 to 600 mg KOH/gram on an oil-free basis, as determined according to ASTM D2896. The lubricating oil composition of claim 1 further comprising an additional detergent selected from the group consisting of sulfonates, phenates, and salicylates. 11. The lubricating oil composition of claim 10, wherein the detergent is magnesium sulfonate. The lubricating oil composition of claim 1 further comprising a polymethacrylate dispersant VII. The lubricating oil composition of claim 1 further comprising a primary or secondary zinc dithiophosphate compound or a mixture thereof. The lubricating oil composition of claim 1 further comprising a friction modifier. A method of lubricating an engine comprising lubricating the engine with a lubricating oil composition according to any one of claims 1 to 14.