KR20220027237A - lubricating oil composition - Google Patents

Abstract

Disclosed is a lubricating oil composition comprising a large amount of oil of lubricating viscosity and a salicylic acid compound derived from an isomerized normal alpha olefin (NAO) having from about 10 to about 40 carbon atoms, wherein the TBN of the salicylic acid compound is 600 mg KOH/g on an active basis and wherein the lubricating oil composition contains from about 0.12 to about 0.17 weight percent calcium and is substantially free of magnesium. A method of lubricating an engine with the lubricating oil composition is also provided.

Description

lubricating oil composition

The present disclosure relates to lubricating oil compositions.

Because of the need to squeeze all fuel economy out of the engine, engine downsizing has become a major trend in the automotive industry. However, this can cause problems in certain cases through a phenomenon called low speed pre-ignition (LSPI). In some cases, it can cause catastrophic failures in engine hardware. Calcium present in lubricants Calcium from detergents has been found to play a largely detrimental role. However, calcium is used to provide cleaning and rust protection, and must be present in significant amounts to provide these benefits (ie >1800 ppm Ca). Many in the industry have lowered their calcium levels and replaced them with cleaner-containing magnesium to compensate for LSPI problems. Magnesium cleaners generally have better TBN retention, but are fairly weak at neutralizing acids. Also, crystals and gel formation occur which can sometimes be unwieldy. Accordingly, a need exists for a lubricant that is substantially magnesium free while providing adequate corrosion control. The inventors of the present application have found a solution to this problem.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a lubricating oil composition that is substantially free of magnesium while providing adequate corrosion control.

According to one embodiment of the present invention, there is provided a lubricating oil composition comprising:

(a) a major amount of oil of lubricating viscosity and

(b) Salicylic acid compounds derived from isomerized NAOs (generic alpha olefins) having from about 10 to about 40 carbon atoms (the TBN of the salicylic acid compounds is at least 600 mg KOH/g based on active agent)

The lubricating oil composition contains from about 0.12 to about 0.17 weight percent calcium and is substantially free of magnesium.

Also provided is an engine lubrication method comprising lubricating the engine with a lubricating oil composition comprising:

(a) oil with a large amount of lubricating viscosity and

(b) Salicylic acid compounds derived from isomerized NAOs (generic alpha olefins) having from about 10 to about 40 carbon atoms (the TBN of the salicylic acid compounds is at least 600 mg KOH/g based on active agent)

The lubricating oil composition contains from about 0.12 to about 0.17 weight percent calcium and is substantially free of magnesium.

In internal combustion engines equipped with an EGR control system, EGR gas is highly corrosive. In a situation where the engine oil temperature is low, moisture accumulates in the oil and comes into contact with the highly corrosive EGR gas to corrode engine parts. In one aspect of the present disclosure, the lubricating oil composition can prevent or reduce corrosion of an internal combustion engine equipped with an EGR control system.

In another aspect of the present disclosure, the lubricating oil composition can prevent or reduce corrosion of an internal combustion engine equipped with an EGR control system where low engine oil temperatures contact high corrosive EGR gases and lead to the accumulation of water that causes corrosion of engine parts.

While the present invention is susceptible to various modifications and alternative forms, specific embodiments of the invention are described in detail herein. However, the description of specific embodiments herein is not intended to limit the invention to the specific forms disclosed, but is intended to cover all modifications, equivalents and alternatives falling within the spirit and scope of the invention as defined by the appended claims. am.

To facilitate an understanding of the subject matter disclosed herein, a number of terms, abbreviations, or other abbreviations used herein are defined below. All terms, abbreviations, or abbreviations not defined are understood to have their ordinary meanings used by those skilled in the art upon the filing of this application.

Justice

As used herein, the following terms have the following meanings unless explicitly stated otherwise. In this specification, the following words and expressions have the following meanings when 'if' and 'if' are used.

* "Much" means greater than 50% by weight of the composition.

* "Minor" means less than 50% by weight of the composition expressed relative to the total mass of the stated additive and all additives present in the composition, counted as the active ingredient of the additive or additives.

* “Substantially free” means less than 50, less than 40, less than 30, less than 10, less than 50 wt. means less than ppm.

* "Active ingredient" or "active agent" or "oil free" refers to an additive material that is not a diluent or solvent.

* All percentages reported are weight percent based on active ingredient (ie irrespective of carrier or diluent oil) unless otherwise specified.

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

* TBN (Total Base Number: Total Number) was measured according to ASTM D2896.

* Metal—The term "metal" means an alkali metal, alkaline earth metal, or mixtures thereof.

* High temperature high shear (HTHS) viscosity at 150° C. was measured according to ASTM D4863.

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

* CCS (Cold Cranking Simulator) viscosity at -35°C was measured according to ASTM D5293.

* Olefins—The term “olefins” refers to a class of unsaturated aliphatic hydrocarbons having one or more carbon-carbon double bonds obtained through various processes. Those with 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 carbons. Examples are 1-octene and 1-octadecene used as starting points for intermediate biodegradable surfactants. Linear and branched olefins are also included in the definition of olefins.

* Generic Alpha Olefins—The term "generic alpha olefins" refers to olefins, which are straight chain, unbranched hydrocarbons with carbon-carbon double bonds at the beginning and end of the chain.

* Isomerized generic alpha olefins. As used herein, the term "general alpha olefin isomerized" refers to an alpha olefin that has undergone isomerization conditions that result in an alteration in the distribution of olefin species present and/or introduction of branching along the alkyl chain. The isomerized olefin product can 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, preferably from about 20 to about 24 carbon atoms.

All ASTM standards mentioned herein are the most current version as of the filing date of this application.

In one aspect, the present disclosure relates to a lubricating oil composition comprising:

(a) oil with a large amount of lubricating viscosity and

(b) Salicylic acid compounds derived from isomerized NAOs (generic alpha olefins) having from about 10 to about 40 carbon atoms (the TBN of the salicylic acid compounds is at least 600 mg KOH/g based on active agent)

The lubricating oil composition contains from about 0.12 to about 0.17 weight percent calcium and is substantially free of magnesium.

oil of lubricating viscosity

Oils of lubricating viscosity (sometimes referred to as “base stock” or “base oils”) are the major liquid components of lubricants, in which additives and other oils are mixed, for example, into the final lubricant (or lubricant composition). to create Base oils are useful for preparing concentrates as well as 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 and solvent treated mineral lubricants of the paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils of lubricating viscosity derived from coal or shale are also useful base oils.

Synthetic lubricants include polymerized and interpolymerized olefins such as polybutylene, polypropylene, propylene-isobutylene copolymer, chlorinated polybutylene, poly(1-hexene), poly(1-octene), poly(1-decene). hydrocarbon oils such as ); alkylbenzenes such as dodecylbenzene, tetradecylbenzene, dinonylbenzene, di(2-ethylhexyl)benzene, polyphenols such as biphenyl, terphenyl, alkylated polyphenols; and diphenyl ethers and alkylated diphenyl sulfides and derivatives, analogs and homologues thereof.

Other suitable classes of synthetic lubricating oils include esters of dicarboxylic acids, such as malonic acid, alkyl malonic acid, alkenyl malonic acid, succinic acid, alkyl succinic acid and alkenyl succinic acid, maleic acid, fumaric acid, azelaic acid, suberic acid, sebacic acid. Contains acetic acid, adipic acid, linoleic acid dimer, phthalic acid) and various alcohols (e.g. butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol) do. 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 complex ester formed by reacting 1 mole of sebacic acid with 2 moles of tetraethylene glycol and 2 moles of 2-ethylhexanoic acid.

Esters useful as synthetic oils also include those prepared from C ₅ to C ₁₂ monocarboxylic acids and polyols and polyol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol and tripentaerythritol. .

Base oils can be derived from Fischer-Tropsch synthetic hydrocarbons. Fischer-Tropsch synthetic hydrocarbons are produced from syngas containing H ₂ and CO using a Fischer-Tropsch catalyst. These hydrocarbons generally require further processing to be useful as a base oil. For example, hydrocarbons may be hydroisomerized using processes known to those skilled in the art; hydrocracking and hydroisomerization; dewax; or hydroisomerization and dewaxing.

Unrefined oils, refined oils and re-refined oils may be used in the present lubricating oil compositions. Unrefined oils are oils obtained directly from natural or synthetic sources without further refining treatment. For example, shale oil obtained directly from a retorting operation, petroleum directly obtained from distillation or ester oil obtained directly from an esterification process is a crude oil if used without further treatment. Refined oils are similar to unrefined oils except that they are further processed in one or more refining steps to improve one or more properties. Many purification techniques are known to those skilled in the art, such as distillation, solvent extraction, acid or base extraction, filtration and percolation.

The re-refined oil is obtained by a process similar to that used to obtain refined oil, which has been applied to refined oil already used in service. These re-refined oils, also referred to as reclaimed or reprocessed oils, are often further processed by techniques for approval of used additives and oil degradation products.

Accordingly, the base oil that may be used to prepare the lubricating oil composition of the present invention may be selected from any of the base oils of Groups I-V as specified in the American Petroleum Institute (API) Base Oil Interchangeability Guidelines (API Publication 1509). These base oil groups are summarized in Table 1 below.

base oil properties Group ^(a) saturates ^(b) , wt% Sulfur ^(c) , % by weight viscosity index ^(d) Group I <90 and/or >0.03 80 to <120 Group II ≥90 ≤0.03 80 to <120 Group III ≥90 ≤0.03 ≥120 Group IV Polyalphaolefin (PAO) Group V All other base stocks not included in Groups I, II, III or IV

(a) Groups I to III are mineral base oils.

(b) Measured according to ASTM D2007.

(c) Measured according to ASTM D2622, ASTM D3120, ASTM D4294 or ASTM D4927.

(d) Measured according to ASTM D2270.

Base oils suitable for use herein are various corresponding to API Group II, Group III, Group IV, Group V oils and combinations thereof, preferably Group III to Group due to their excellent volatility, stability, viscosity and cleanliness properties. is V.

Oils of lubricating viscosity for use in the lubricating oil compositions of the present disclosure, also referred to as base oils, are generally present in large amounts, such as greater than 50% by weight, and preferably about 70% by weight, based on the total weight of the composition. %, more preferably from about 80 to about 99.5 weight percent, and most preferably from about 85 to about 98 weight percent. As used herein, the expression "base oil" refers to a lubricant component that is produced by a single manufacturer to the same specifications (regardless of source or manufacturer's location), meets the specifications of the same manufacturer, and is identified by a unique formula, product identification number, or both. It is to be understood as meaning a phosphorus-based raw material or a mixture of base raw materials. Base oils for use herein are engine oils, marine cylinder oils, functional fluids such as hydraulic oils/gear oils/transmission oils, etc. of a currently known or later discovered lubricating viscosity used to formulate lubricating oil compositions for any and all applications. may be any oil. Additionally, base oils for use herein include viscosity index improvers such as polymeric alkylmethacrylates; olefin copolymers, such as ethylene-propylene copolymers or styrene-butadiene copolymers, and mixtures thereof.

As will be readily appreciated by those skilled in the art, the viscosity of the base oil is application dependent. Accordingly, the viscosity of base oils for use herein will generally range from about 2 to about 2000 centistokes (cSt) at 100 degrees Celsius. In general, the base oil individually used as the engine oil will have a kinematic viscosity at 100° C. of from about 2 cSt to about 30 cSt, preferably from about 3 cSt to about 16 cSt, most preferably from about 4 cSt to about 12 cSt. engine oil of the desired grade, such as 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.

Salicylic acid detergent compounds derived from C ₁₀ - C ₄₀ isomerized common alpha olefins (NAOs)

In one aspect of the present disclosure, the salicylic acid detergent compound derived from C ₁₀ -C ₄₀ isomerized NAO has a TBN of at least 600, 600-800, 600-750, 600-700 mgKOH/g on an active basis.

In one aspect of the present disclosure, a salicylic acid detergent derived from C ₁₀ -C ₄₀ isomerized NAO having a TBN of at least 600 mgKOH/g on an oil-free basis is prepared as described in U.S. Patent No. 8,993,499, incorporated herein in its entirety. can be

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

In one aspect of the present disclosure, the salicylic acid detergent derived from C ₁₀ -C ₄₀ isomerized NAO may be an alkylated hydroxybenzoate detergent. In one embodiment, the cleaning agent may be a salicylic acid cleaning agent. In another embodiment, the detergent may be a carboxylate detergent. In one aspect of the present disclosure, a salicylic acid detergent having a TBN of at least 600 mgKOH/g on an oil-free basis has an alkyl group derived from an isomerized alpha olefin having from about 14 to about 28 or from about 20 to about 24 carbon atoms per molecule. It is prepared from alkylphenols.

In one aspect of the present disclosure, the salicylic acid detergent derived from C ₁₀ -C ₄₀ isomerized NAO having a TBN of at least 600 mgKOH/g on an active agent basis comprises at least one alkylphenol having an alkyl group derived from the C ₁₀ -C ₄₀ isomerized NAO and prepared from C ₁₀ -C ₄₀ isomerized NAO and one or more alkylphenols having different alkyl groups. Preferably the at least one alkylphenol having an alkyl group different from the C ₁₀ -C ₄₀ isomerized NAO has a highly branched alkyl group of at least 9, 9 to 24 and 10 to 15 carbon atoms. In one aspect of the present disclosure, the lubricating oil composition comprises about 0.03 to 0.17 wt%, 0.04 to 0.17 wt%, in terms of Ca content of a salicylic acid detergent derived from C ₁₀ -C ₄₀ isomerized NAO having a TBN of 600 mgKOH/g or more on an active basis; 0.05 to 0.17% by weight, 0.06 to 0.17% by weight, preferably 0.07 to 0.1% by weight, preferably 0.08 to 0.16% by weight, preferably 0.09 to 0.16% by weight, preferably 0.10 to 0.16% by weight, preferably is 0.11 to 0.16% by weight, preferably 0.12 to 0.16% by weight, preferably 0.13 to 0.15% by weight, preferably 0.12 to 0.15% by weight, preferably 0.06 to 0.14, 0.07 to 0.14, 0.07 to 0.12, 0.08 -0.14% by weight.

In one aspect of the present disclosure, the total amount of calcium in the lubricating oil composition is 0.12 to 0.17% by weight, 0.13 to 0.17% by weight, 0.14 to 0.17% by weight, 0.12 to 0.16% by weight, 0.12 to 0.15% by weight, 0.12 to 0.14% by weight, 0.13 to 0.15% by weight, 0.13 to 0.14% by weight, 0.14 to 0.16% by weight and 0.14 to 0.15% by weight.

In one aspect of the present disclosure, a lubricating oil composition comprising salicylic acid derived from NAO that is C ₁₀ -C ₄₀ isomerized at least TBN 600 on an activity basis is selected from an automotive engine oil, a gas engine oil, a motorcycle oil, a dual fuel engine oil, a mobile gas engine oil or It is locomotive engine oil.

In another aspect of the present disclosure, the lubricating oil composition is for use in an internal combustion engine equipped with an EGR control system, a naturally aspirated engine, a hybrid engine oil, a turbocharged gasoline direct injection engine (GDI) oil.

In internal combustion engines equipped with an EGR control system, EGR gas is highly corrosive.

In a situation where the engine oil temperature is low, moisture accumulates in the oil and comes into contact with the highly corrosive EGR gas to corrode engine parts. In one aspect of the present disclosure the lubricating oil composition prevents or reduces corrosion of an internal combustion engine equipped with an EGR control system. In another aspect of the present disclosure, a lubricating oil composition prevents or reduces corrosion of an internal combustion engine equipped with an EGR control system where low engine oil temperatures contact high corrosive EGR gases and lead to accumulation of water that causes corrosion of engine parts. In particular, in the case of a hybrid vehicle, the vehicle may be driven by the driving force of the motor in a state in which fuel supply to the internal combustion engine is stopped. In a situation where EV driving is frequent, it is difficult to preheat the engine in a short time, and water in which EGR gas is dissolved tends to accumulate and accumulate. The metal-containing detergent in the lubricating oil composition of the present invention is generally an oily dispersion comprising a metal salt of an organic acid (generally referred to as a "soap component") and particles of a basic inorganic salt (eg, calcium carbonate particles) gathered around the metal salt of an organic acid in a base oil. available in the form. The soap content is based on 1 kg of oil.

1) Measurement of organic acid metal salt content (soap content): Mineral oil and low molecular weight compounds contained in metal-containing detergents were removed by conventional rubber membrane dialysis. Weigh the residue (A) remaining on the membrane. Separately, a quantitative analysis of metal elements is performed by measuring the content of carbon dioxide derived from carbonate in the metal-containing detergent. Calculate the amount (B) of an overbased component such as calcium carbonate or magnesium carbonate from the carbon dioxide content and the metal content. The soap content (ie the organic acid metal salt content) is calculated by subtracting (B) from (A). In one embodiment, the total SOAP content of the lubricating oil composition is less than 18 mM. In one embodiment, the total SOAP content of the lubricating oil composition is between 2 mM and 18 mM. In another embodiment, the total SOAP content of the lubricating oil composition is between 2 mM and 17 mM, between 2 mM and 16 mM, or between 3 mM and 16 mM.

additional cleaning agent

Additional calcium detergents may be present so that the total calcium in the final oil does not exceed 0.17% by weight.

The lubricating oil composition of the present invention is 10-800, 10-700, 30-690, 30-600, 50-600, 100-600, 150-600, 50-500, 150-500, 50-450, 200 based on the active agent. It may further contain one or more overbased detergents having a TBN of -450 mg KOH/g.

Detergents that may be used include oil-soluble overbased sulfonates, non-sulfur containing phenates, sulphated phenates, salisarates, salicylic acid, saligenin, complex detergents and naphthenic acid detergents and metals, especially alkali or alkaline earth metals. Other oil soluble salicylic acids (eg barium, sodium, potassium, lithium, calcium and magnesium). The most commonly used metals are calcium and magnesium, which may be present both in cleaning agents used in lubricants and in calcium and/or mixtures of magnesium and sodium.

Overbased metal cleaners are usually produced by carbonating a mixture of hydrocarbons, detergent acids (e.g. sulfonic acid, salicylic acid, etc.), metal oxides or hydroxides (e.g. calcium oxide or calcium hydroxide) and accelerators such as xylene, methanol and water. . For example, in carbonation to produce overbased calcium sulfate, calcium oxide or hydroxide reacts with gaseous carbon dioxide to form calcium carbonate. The sulfonic acid is neutralized with an excess of CaO or Ca(OH)z ₂ to form a sulfonate.

The overbased detergent may be an overbased salt with a low overbased, such as a TBN of less than 100 on an active basis. In one embodiment, the TBN of the low overbased salt may be from about 30 to about 100. In another embodiment, the TBN of the low overbased salt may be from about 30 to about 80. The overbased detergent may be a medium overbased salt, such as an overbased salt having a TBN of about 100 to about 250. In one embodiment, the TBN of the medium overbased salt may be from about 100 to about 200. In another embodiment, the TBN of the low overbased salt may be from about 125 to about 175. The overbased detergent may be a highly overbased salt, such as an overbased salt with a TBN of 250 or greater. In one embodiment, the TBN of the highly overbased salt may be from about 250 to about 800 based on active agent.

In one embodiment, the detergent may 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, preferably 1 to 3 hydroxyl groups. Suitable hydroxyaromatic compounds include phenol, catechol, resorcinol, hydroquinone, pyrogallol, cresol, and the like. A 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 used 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.

In one embodiment, the mixture of linear olefins that may be used is a mixture of common alpha olefins selected from olefins having from about 10 to about 40 carbon atoms per molecule. In one embodiment, the generic alpha olefin is isomerized using one or more of a solid or liquid catalyst.

In one embodiment, 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 contained alkyl groups are alkyl-substituted. C ₂₀ or higher in alkali or alkaline earth metal salts of alkyl-substituted hydroxyaromatic carboxylic acids, such as the alkyl group of alkaline earth metal salts of hydroxybenzoic acid detergents. In another embodiment, the alkali or alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid is an alkyl-substituted hydroxybenzoic acid derived from an alkyl-substituted hydroxybenzoic acid in which the alkyl group is a C ₂₀ to about C ₂₈ common alpha-olefin. It is an alkali or alkaline earth metal salt of hydroxybenzoic acid. In another embodiment, the alkyl group is derived from two or more alkylated phenols. At least one alkyl group of the two or more alkyl phenols is derived from an isomerized alpha olefin. The alkyl group of the second alkyl phenol may be derived from a branched or partially branched olefin, a highly isomerized olefin or mixtures thereof.

In another embodiment, the alkali or alkaline earth metal salt of an alkyl-substituted hydroxyaromatic carboxylic acid has from 20 to 40 carbon atoms, preferably from 20 to 28 carbon atoms, more preferably from 20 to 24 isomerized NAO. salicylic acid derived from an alkyl group.

Sulfonates can be prepared from sulfonic acids, which are generally obtained by sulfonation of alkyl substituted aromatic hydrocarbons such as those obtained from fractionation of petroleum or alkylation of aromatic hydrocarbons. Examples include those obtained by alkylation of benzene, toluene, xylene, naphthalene, diphenyl or halogen derivatives thereof. The alkylation may be carried out in the presence of a catalyst together with an alkylating agent having from about 3 to more than 70 carbon atoms. Alkaryl sulfonates generally contain from about 9 to about 80 carbon atoms per alkyl substituted aromatic moiety, preferably from about 16 to about 60 carbon atoms, preferably from about 16 to 30 carbon atoms, more preferably from 20 to 24 carbon atoms. contains the number of carbon atoms.

The sulfurized phenate detergent phenol and its metal salts are prepared by reaction with suitable metal compounds such as oxides or hydroxides, and neutral or overbased products can be obtained by methods well known in the art. Sulfurized phenols can be prepared by reacting a phenol with sulfur or a sulfur containing compound (such as hydrogen sulfide, sulfur monohalide or sulfur dihalogenide) to form a product, which is usually a mixture of compounds in which two or more phenols are crosslinked by a sulfur containing crosslinking. can

Additional details regarding the general preparation of sulfide phenates can be found, for example, in U.S. Patent Nos. 2,680,096; 3,178,368; 3,801,507; and 8,580,717, the contents of which are incorporated herein by reference.

Now, considering the reactants and reagents used in this process in detail, all allotropic forms of sulfur can be used first. Sulfur can be used as molten sulfur or as a solid (eg powder or particulate) or as a solid suspension in a compatible hydrocarbon liquid.

For example, it is preferred to use calcium hydroxide as the calcium base because it is easier to handle than calcium oxide and provides superior results. Other calcium bases such as calcium alkoxides may also be used.

Suitable alkylphenols that may be used are alkyl substituents containing a sufficient number of carbon atoms to render the resulting overbased calcium sulfide alkylphenate composition oil-soluble. Utility may be provided by a single long chain alkyl substituent or by a combination of alkyl substituents. In general, the alkylphenols used will be mixtures of different alkylphenols, such as C ₂₀ to C ₂₄ alkylphenols.

In one embodiment, 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 an isomerization level (1) of alpha olefins between about 0.1 and about 0.4. In one embodiment, suitable alkyl phenolic compounds will be derived from alkyl groups that are branched olefinic propylene oligomers having from about 9 to about 80 carbon atoms or mixtures thereof. In one embodiment, the branched olefinic propylene oligomer or mixture thereof has from about 9 to about 40 carbon atoms. In one embodiment, the branched olefinic propylene oligomer or mixture thereof has from about 9 to about 18 carbon atoms. In one embodiment, the branched olefinic propylene oligomer or mixture thereof has from about 9 to about 12 carbon atoms.

In one embodiment, suitable alkyl phenolic compounds include distilled cashew nut shell liquid (CNSL) or hydrogenated distilled cashew nut shell liquid. Distilled CNSL is a mixture of biodegradable meta-hydrocarbon substituted phenols, wherein the hydrocarbyl groups are linear and unsaturated with cardanol. Catalytic hydrogenation of distilled CNSL produces a mixture of meta-hydrocarbyl substituted phenols predominantly enriched in 3-pentadecylphenol.

The alkylphenol may be a para-alkylphenol, a meta-alkylphenol or an ortho alkylphenol. Since p-alkylphenols are believed to facilitate the preparation of highly overbased calcium sulfate alkylphenates where overbased products are desired, the alkylphenols preferably contain up to about 45 mole percent of the alkylphenols are ortho alkylphenols. para alkylphenol; More preferably up to about 35 mole percent of the alkylphenol is ortho alkylphenol. Alkyl-hydroxy toluene or xylene and other alkyl phenols having one or more alkyl substituents in addition to one or more long chain alkyl substituents may also be used. In the case of distilled cashew nut shell liquid, catalytic hydrogenation of distilled CNSL produces a mixture of meta-hydrocarbyl substituted phenols.

In one embodiment, the one or more overbased detergents may be complex or hybrid detergents known in the art to include surfactant systems derived from two or more surfactants described above.

In one embodiment, the one or more overbased detergents may be salicylic acid comprising an alkyl group having from 20 to 28 carbon atoms, more preferably from 20 to 24 carbon atoms. In another embodiment, the at least one overbased detergent may be salicylic acid having an alkyl group derived from C _14-18 NAO, less than 0.05% by weight, preferably less than 0.025% by weight, more preferably less than 0.025% by weight in terms of Ca content for the lubricating oil. contributes less than 0.01% by weight.

Generally, the amount of detergent is from about 0.001% to about 50% by weight, or from about 0.05% to about 25% by weight or from about 0.1% to about 20% by weight or from about 0.01 to 15% by weight, based on the total weight of the lubricating oil composition. It can be %.

anti-wear agent

The lubricating oil compositions disclosed herein may include one or more anti-wear agents. Anti-wear agents reduce wear on metal parts. Suitable antiwear agents include dihydrocarbyl dithiophosphate metal salts such as zinc dihydrocarbyl dithiophosphate (ZDDP) of formula (1):

In Formula 1,

R ¹ and R ² are different hydrocarbyl radicals having 1 to 18 (eg 2 to 12) carbon atoms and including radicals such as alkyl, alkenyl, aryl, arylalkyl, alkaryl and cycloaliphatic radicals. may be the same as Particularly preferred as R ¹ and R ² groups are alkyl groups having 2 to 8 carbon atoms, for example the alkyl radicals are ethyl, n-propyl, isopropyl, n-butyl, isobutyl, Sec-butyl, n-pentyl , isopentyl, n-hexyl, isohexyl, 2-ethylhexyl). To obtain oil solubility, the total number of carbon atoms (ie R ¹ +R ² ) must be at least 5. Thus zinc dihydrocarbyl dithiophosphate may comprise zinc dialkyl dithiophosphate. Zinc dialkyl dithiophosphates are primary and secondary zinc dialkyl dithiophosphates or combinations thereof. ZDDP may be present in up to 3% by weight of the lubricating oil composition (eg 0.1 to 1.5% or 0.5 to 1.0% by weight). In one embodiment, the lubricating oil composition containing the magnesium salicylic acid detergent described herein further comprises an antioxidant compound. In one embodiment, the antioxidant is a diphenylamine antioxidant. In another embodiment, the antioxidant is a hindered phenol antioxidant. In another embodiment, the antioxidant is a combination of a diphenylamine antioxidant and a hindered phenol antioxidant.

antioxidant

The lubricating oil compositions disclosed herein may include one or more antioxidants. Antioxidants reduce the tendency of mineral oils to deteriorate during use. Oxidative degradation can be evidenced by sludges of lubricants, varnish-like deposits on metal surfaces, and increased viscosity. Suitable antioxidants include hindered phenols, aromatic amines and sulfided alkylphenols and their alkali and alkaline earth metal salts.

Hindered phenol antioxidants often contain secondary butyl and/or tertiary butyl groups as hindering groups. The phenol group may be further substituted with a hydrocarbyl group (usually a linear or branched alkyl) and/or a bridging group connected to a second aromatic group. Examples of suitable hindered phenol antioxidants include 2,6-di-but-butylphenol; 4-methyl-2,6-di-vert-butylphenol; 4-ethyl-2,6-di-vert-butylphenol; 4-propyl-2,6-di-but-butylphenol; 4-butyl-2,6-di-but-butylphenol; and 4-dodecyl-2,6-di-tert-butylphenol. Other useful hindered phenol antioxidants include 2,6-di-alkyl-phenolic propionic acid ester derivatives (eg, IRGANOX ^® L-135 from Ciba) and 4,4'-bis(2,6-di-vert-butylphenol). ) and bis-phenolic antioxidants such as 4,4'-methylenebis(2,6-di-but-butylphenol. Other useful hindered phenolic antioxidants include thio-ethylene-bis-('3- hindered phenols with sulfur antioxidants such as (3,5-di-tert-butyl-4-hydroxylphenyl) propionate (IRGANOX ^® L-115 from Ciba).

Common aromatic amine antioxidants have at least two aromatic groups attached directly to one amine nitrogen. Common aromatic amine antioxidants have an alkyl substituent of 6 or more carbon atoms. Specific examples of aromatic amine antioxidants useful herein are 4,4'-dioctyldiphenylamine, 4,4'-dinonyldiphenylamine, N-phenyl-1-naphthylamine, N-(4-tert- octiphenyl) )-1-naphthylamine and N-(4-octylphenyl)-1-naphthylamine. The antioxidant may be present in 0.01 to 5 weight percent (eg 0.1 to 2 weight percent) of the lubricating oil composition.

dispersant

The lubricating oil compositions disclosed herein may include one or more dispersants. The dispersant remains in the oil-insoluble suspension material due to oxidation during engine operation, preventing sludge agglomeration and precipitation or deposition of metal parts. Dispersants useful herein include nitrogen-containing, ashless (metal-free) dispersants that are known to be effective in reducing the formation of deposits when used in gasoline and diesel engines.

Suitable dispersants include hydrocarbyl succinimides, hydrocarbyl succinamides, mixed esters/amides of hydrocarbyl-substituted succinic acids, hydroxyesters of hydrocarbyl-substituted succinic acids and hydrocarbyl-substituted phenols, form Mannich condensation products of aldehydes and polyamines. Condensation products of polyamines with hydrocarbyl substituted phenyl acids are also suitable. Mixtures of these dispersants may also be used. Basic nitrogen-containing ashless dispersants are well known lubricant additives and methods for their preparation are extensively described in the patent literature. Preferred dispersants are alkenyl succinimides and succinamides in which the alkenyl-substituent is a long chain, preferably greater than 40 carbon atoms. Such materials are readily prepared by reacting a hydrocarbyl substituted dicarboxylic acid material with a molecule containing an amine functionality. Examples of suitable amines are polyamines such as polyalkylene polyamines, hydroxy-substituted polyamines and polyoxyalkylene polyamines.

A particularly preferred ashless dispersant is polyisobutenyl succinimide formed from polyisobutenyl succinic anhydride and a polyalkylene polyamine, such as a polyethylene polyamine of formula (II).

In Formula 2,

z is 1 to 11; The polyisobutenyl group is derived from polyisobutene and preferably has a number average molecular weight (M _n ) in the range of 700 to 3000 Daltons (eg 900 to 2500 Daltons). For example, the polyisobutenyl succinimide may be a bis-succinimide derived from a polyisobutenyl group having an M _n of 900 to 2500 Daltons. As is known in the art, the dispersant may be post-treated (eg, with a boronating agent or cyclic carbonate, ethylene carbonate, etc.).

The nitrogen-containing ashless (metal-free) dispersant is basic and contributes to the TBN of the lubricating oil composition being added without introducing additional sulphated ash. The dispersant may be present in 0.1 to 10% by weight of the lubricating oil composition (eg 2 to 5% by weight).

antifoam

The lubricating oil compositions disclosed herein may include one or more antifoam agents capable of breaking down foam in the oil. Non-limiting examples of suitable antifoam or antifoam inhibitors include silicone oils or polydimethylsiloxanes, fluorosilicones, alkoxylated aliphatic acids, polyethers such as polyethylene glycol, branched polyvinyl ethers, alkyl acrylate polymers, alkyl methacrylic late polymers, polyalkoxyamines, and combinations thereof.

Additional Co-Additives

The lubricating oil compositions of the present disclosure may contain other conventional additives that can impart or improve any desirable properties of the lubricating oil compositions in which these additives are dispersed or dissolved. Any additives known to those skilled in the art may 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, the lubricating oil composition may contain antioxidants, antiwear agents, cleaners such as metal cleaners, rust inhibitors, antifogging agents, emulsifiers, metal deactivators, friction modifiers, pour point depressants, defoamers, cosolvents, corrosion inhibitors, ashless dispersants, It can be blended with multifunctional agents, dyes, extreme pressure agents, and the like, and mixtures thereof. Various additives are known and commercially available. These additives or similar compounds thereof may be used in the preparation of the lubricating oil compositions of the present disclosure by conventional blending procedures.

In the manufacture of lubricating oil formulations it is common practice to introduce in the form of concentrates of 10 to 100% by weight active ingredient in hydrocarbon oils (eg mineral lubricating oils or other suitable solvents).

Typically these concentrates may be diluted to 3 to 100 (eg 5 to 40) parts by weight of lubricant oil per part by weight of the additive package when forming the final lubricant (eg crankcase motor oil). The purpose of the concentrate, of course, is to make the handling of various substances less difficult and less cumbersome and to facilitate solution or dispersion in the final blend.

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

Generally, the concentration of each additive in the lubricating oil composition, if used, is from about 0.001% to about 20% by weight, from about 0.01% to about 15% by weight, or from about 0.1% to about 10% by weight, based on the total weight of the lubricating oil composition. %, from about 0.005% to about 5% by weight or from about 0.1% to about 2.5% by weight. Further, the total amount of additives in the lubricating oil composition may range from about 0.001% to about 20% by weight, from about 0.01% to about 10% by weight, or from about 0.1% to about 5% by weight, based on the total weight of the lubricating oil composition. there is.

The following examples are presented to illustrate examples of the invention, but are not intended to limit the invention to the specific examples described. Unless otherwise indicated, all parts and percentages are by weight. All figures are approximate. When numerical ranges are given, it is to be understood that embodiments outside the stated ranges may still fall within the scope of the present invention. The specific details described in each embodiment should not be construed as essential features of the present invention.

Example

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

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) represents the relative amount of a methyl group (-CH3) (chemical shift 0.3-1.01 ppm) attached to the methylene backbone group (-CH2-) (chemical shift 1.01-1.38 ppm) and is defined by the following formula, ,

where m is the NMR integral for a methyl group with a chemical shift of 0.3±0.03 to 1.01±0.03 ppm, and n is the NMR integral for a methylene group with a chemical shift of 1.01±0.03 to 1.38±0.10 ppm.

The isomerization level (I) of the alpha olefin is 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.

In one embodiment, the isomerization level of NAO is about 0.16 and has from about 20 to about 24 carbon atoms.

In another embodiment, the isomerization level of NAO is about 0.26 and has from about 20 to about 24 carbon atoms.

Baseline Formulation 1

A 0W-16 lubricating oil composition containing a large amount of a base oil of lubricating viscosity and the following additives was prepared.

(1) ethylene carbonate post-treatment bis-succinimide;

(2) boric acid bis-succinimide;

(3) a mixture of primary and secondary zinc dialkyldithiophosphates in an amount of 0.077% by weight phosphorus, wherein the primary to secondary molar ratio is 9:1;

(4) diphenylamine antioxidants;

(5) PMA comb polymer;

(6) MoDTC compound in 0.085 wt % molybdenum;

(7) anti-foam; And

(8) The remaining Group III base oils.

detergent 1

Alkylated phenol and Ca salicylic acid were prepared in substantially the same manner as in US Pat. No. 8,993,499 using C _20-24 isomerized common alpha olefins. The level of isomerization of alpha olefins is about 0.16. The resulting salicylic acid composition has a TBN of about 630 and a Ca content of about 22.4% by weight on an oil-free basis.

Cleaner 2

An overbased calcium sulfonate having a TBN of 690, a Ca content of about 26 wt. % based on active agent, and an alkyl group derived from C _20-24 NAO.

detergent 3

Salicylic acid having an alkyl group derived from C _14-18 NAO and a TBN of about 300 and a Ca content of about 10.6 wt % on an oil-free basis was prepared.

detergent 4

Alkylated phenol and alkylated Ca salicylic acid were prepared in substantially the same manner as in US Pat. No. 8,993,499 using C _20-24 isomerized generic alpha olefins available from CP Chem. The level of isomerization of alpha olefins is about 0.16. The resulting alkylated salicylic acid composition has a TBN of about 225 mgKOH/gm and a Ca content of about 8% by weight on an oil-free basis.

Cleaner 5

Alkylated phenol and alkylated Ca salicylic acid were prepared in substantially the same manner as in US Pat. No. 8,993,499 using C _20-24 isomerized generic alpha olefins available from CP Chem. The level of isomerization of alpha olefins is about 0.16. The resulting alkylated salicylic acid composition has a TBN of about 120 mgKOH/gm and a Ca content of about 4.2% by weight on an oil-free basis.

detergent 6

Salicylic acid having an alkyl group derived from C _14-18 NAO and a TBN of about 520 and a Ca content of about 18.7 wt % on an oil-free basis was prepared.

Example 1

To the baseline formulation 1, 0.14 wt % was added based on the Ca content of detergent 1 (35 mM). The total SOAP of the detergent mixture is given in Table 2 below.

Example 2

Add 0.14 wt. % to Baseline Formulation 1 to the Ca content of the mixture of detergent 1 (15.0 mM), detergent 4 (10.0 mM) and detergent 5 (10.0 mM) in a mixture of about 1.5:1:1 based on mM of detergent did The total SOAP of the detergent mixture is given in Table 2 below.

Example 3

Add 0.14 wt. % to Baseline Formulation 1 to the Ca content of the mixture of Detergent 1 (23.0 mM), Detergent 4 (6.0 mM) and Detergent 5 (6.0 mM) in a mixture of about 3.83:1:1 based on mM of detergent did The total SOAP of the detergent mixture is given in Table 2 below.

Example 4

Add 0.12 wt % to Baseline Formulation 1 based on the Ca content of the mixture of detergent 1 (19.8 mM), detergent 4 (5.10 mM) and detergent 5 (5.10 mM) in a mixture of about 3.88:1:1 based on mM of detergent did The total SOAP of the detergent mixture is given in Table 3 below.

Example 5

Add 0.12 wt % to Baseline Formulation 1 relative to the Ca content of the mixture of detergent 1 (12.9 mM), detergent 4 (8.55 mM) and detergent 5 (8.55 mM) in a mixture of about 1.5:1:1 based on mM of detergent did The total SOAP of the detergent mixture is given in Table 3 below.

Example 6

Add 0.12 wt % to Baseline Formulation 1 relative to the Ca content of the mixture of detergent 1 (4.2 mM), detergent 4 (12.9 mM) and detergent 5 (12.9 mM) in a mixture of about 0.33:1:1 based on mM of detergent did The total SOAP of the detergent mixture is given in Table 3 below.

Example 7

To the baseline formulation 1, 0.16 wt% was added based on the Ca content of detergent 1 (40 mM). The total SOAP of the detergent mixture is given in Table 4 below.

Comparative Example A

0.14 wt % was added to the Ca content of detergent 2 (35 mM) to baseline formulation 1. The total SOAP of the detergent mixture is given in Table 2 below.

Comparative Example B

To the baseline formulation 1, 0.14% by weight was added based on the Ca content of detergent 3 (35 mM). The total SOAP of the detergent mixture is given in Table 2 below.

Comparative Example C

0.14% by weight relative to the Ca content of the mixture of detergent 1 (5 mM), detergent 4 (15 mM) and detergent 5 (15 mM) in a mixture of about 0.33:1:1 based on mM of detergent was added to baseline formulation 1 . The total SOAP of the detergent mixture is given in Table 2 below.

Comparative Example D

To the baseline formulation 1, 0.14 wt% was added based on the Ca content of detergent 6 (35 mM). The total SOAP of the detergent mixture is given in Table 2 below.

Ball Rust Test (BRT) - ASTM D6557

The ball rust test referred to herein is performed using the method of ASTM-D-6557. The Ball Rust Test (BRT) is a procedure that evaluates the corrosion protection ability of fluid lubricants. According to ASTM D6557, ball bearings are immersed in oil. Air saturated with acid contaminants is bubbled through the oil at 49 °C for 18 h. After an 18 hour reaction period, the balls are removed from the test oil and the amount of corrosion in the balls is quantified using a light reflection technique. The amount of reflected light is reported as the average gray value (AGV). A new, uncorroded ball has an AGV of about 140. The AGV result for a fully corroded ball is less than 20. Lubricating oil compositions that provide an average gray value (AGV) of 100 or greater pass the Ball Rust Test (BRT). Lubricating oil compositions that provide an average gray value (AGV) of less than 100 do not pass the Ball Rust Test (BRT).

BRT test results Example 1 Example 2 Example 3 comparison
Yes A comparison
Yes B comparison
Yes C comparison
yes D Calcium (wt%) 0.14 0.14 0.14 0.14 0.14 0.14 0.14 gun of detergent
SOAP (mM) 3.96 13.4 9.62 1.96 12.25 18.12 4.9 BRT 126 113 112 91 81 86 81

BRT test results Example 4 Example 5 Example 6 Calcium (wt%) 0.12 0.12 0.12 gun of detergent
SOAP (mM) 8.2 11.46 15.57 BRT 117 132 113

BRT test results Example 7 Calcium (wt%) 0.16 gun of detergent
SOAP (mM) 4.52 BRT 122

Claims (14)

A lubricating oil composition comprising:
(a) a large amount of oil of lubricating viscosity and
(b) a salicylic acid compound derived from an isomerized NAO (generic alpha olefin) having an isomerized level (I) of the alpha olefin of from about 0.1 to about 0.4 and having from about 10 to about 40 carbon atoms;
The TBN of the salicylic acid compound is 600 mg KOH/g or more based on the active agent,
wherein the lubricating oil composition contains from about 0.12 to about 0.17 weight percent calcium and is substantially free of magnesium and has a total organic acid metal salt (SOAP) content from all detergents of less than 18 mM;
The isomerization level (I) represents the relative amount of a methyl group (-CH3) (chemical shift 0.3-1.01 ppm) attached to a methylene backbone group (-CH2-) (chemical shift 1.01-1.38 ppm) and is defined by the following Equation 1 becomes,
[Equation 1]

wherein m is the NMR integral for a methyl group having a chemical shift of 0.3±0.03 to 1.01±0.03 ppm, and n is the NMR integral for a methylene group having a chemical shift of 1.01±0.03 to 1.38±0.10 ppm. According to claim 1,
A lubricating oil composition further comprising a zinc dithiophosphate compound. According to claim 1,
The lubricating oil composition further comprising molybdenum dithiocarbamate. According to claim 1,
and magnesium is present at less than 50 ppm. According to claim 1,
The lubricating oil composition reduces corrosion of an engine. According to claim 1,
wherein the engine is an internal combustion engine equipped with an EGR system. 6. The method of claim 5,
The engine is a hybrid engine or a turbo GDI engine. A method of lubricating an engine comprising the step of lubricating the engine with a lubricating oil composition, the method comprising:
(a) a large amount of oil of lubricating viscosity and
(b) a salicylic acid compound derived from an isomerized NAO (generic alpha olefin) having an isomerization level (I) of the alpha olefin of from about 0.1 to about 0.4 and having from about 10 to about 40 carbon atoms;
The TBN of the salicylic acid compound is 600 mg KOH/g or more based on the active agent,
wherein the lubricating oil composition contains from about 0.12 to about 0.17 weight percent calcium and is substantially free of magnesium and has a total organic acid metal salt (SOAP) content from all detergents of less than 18 mM;
The isomerization level (I) represents the relative amount of a methyl group (-CH3) (chemical shift 0.3-1.01 ppm) attached to a methylene backbone group (-CH2-) (chemical shift 1.01-1.38 ppm) and is defined by the following Equation 1 becomes,
[Equation 1]

where m is the NMR integral for a methyl group with a chemical shift of 0.3±0.03 to 1.01±0.03 ppm, and n is the NMR integral for a methylene group with a chemical shift of 1.01±0.03 to 1.38±0.10 ppm. A method of lubricating an engine comprising the steps of: 9. The method of claim 8,
and lubricating the engine with a lubricating oil composition, wherein the engine is a hybrid engine or a turbo GDI engine. 9. The method of claim 8,
and lubricating the engine with a lubricating oil composition, wherein the engine is an internal combustion engine equipped with an EGR system. 9. The method of claim 8,
and lubricating the engine with the lubricating oil composition, wherein the lubricating oil composition reduces corrosion of the engine. 9. The method of claim 8,
and lubricating the engine with the lubricating oil composition, wherein the lubricating oil composition further comprises a zinc dithiophosphate compound. 9. The method of claim 8,
and lubricating the engine with the lubricating oil composition, wherein the lubricating oil composition further comprises molybdenum dithiocarbamate. 9. The method of claim 8,
and magnesium is present at less than 50 ppm in the lubricating oil composition.