KR20090127369A - Lubricating oil compositions having improved low temperature properties - Google Patents

Abstract

A lubricating base oil is disclosed comprising a mixture of gas-to-liquids (GTL) base stock/base oil, hydrodewaxed or hydroisomerized/catalytic (and/or solvent) dewaxed wax derived base stock/base oil and from about 1 to 95% by weight of an alkylated naphthalene or alkylated benzene synthetic oil having a pour point of 0°C or less. The pour point of the base oil is dramatically lowered by the addition of the synthetic oil.

Description

Lubricant composition with improved low-temperature properties {LUBRICATING OIL COMPOSITIONS HAVING IMPROVED LOW TEMPERATURE PROPERTIES}

The present invention relates to lubricants having improved low temperature properties, in particular viscosity, and low pour points, and methods of improving the low temperature properties, in particular viscosity, and lowering the pour point of gas-to-liquid (GTL) lubricants.

Lubricants and formulated lubricating oils used in most lubrication methods (ie, lubricating oils comprising a mixture of lubricating oil base stock / base oils and one or more performance additives) must be able to achieve lubricating performance at low temperatures, and they have low starting temperatures. Must be able to maintain or maintain a low operating temperature.

For this purpose, lubricating oils having better low temperature properties, in particular lower low viscosity, are preferred. It is important that these lubricants can flow to critical machine or engine parts even at very low temperatures to provide lubrication performance. This fluidity of the lubricated base stock or finished product, measured by pour point measurement, is one of the important low temperature properties and can easily be measured by standard pour point methods. Low pour point base stocks are preferred starting base stocks / base oils for lubricating oils, either using the lubricating oil as it is (i.e. without additives) or also as lubricating oil compositions (ie lubricating oils in combination with one or more performance additives) Use

The pour point of lubricating oil is traditionally defined as the temperature at which a certain amount of lubricating base stock / base oil or formulated lubricant does not move from the beaker when tilted. Pour point can be measured by standard method ASTM D-97 or similar automatic versions. Although the pour point of the base stock measures the lowest temperature at which the oil still flows, it is also an excellent indicator of low temperature properties. Lower pour points generally exhibit better low temperature properties or better low temperature viscosity.

The lubrication base stock / base oil pour point generally reflects the wax content of the base stock / base oil. Waxes are linear paraffins that mainly solidify at low temperatures. Thus, the pour point of the lubricant base stock / base oil can be lowered by removing the wax from the base stock / base oil. For some specially synthesized lubricated base stocks, such as polyalphaolefins, which do not contain crystallizable waxes, the pour point of the base stock is generally measured by the viscosity of the fluid at low temperatures. At very low temperatures, when the viscosity of the base stock has increased to a high level that stops flowing within the D97 test time frame, this temperature is recorded as the pour point even if no wax is formed in the base stock.

Historically and traditionally, the wax is removed from the lubricating base stock / base oil by the dewaxing method identified by the solvent dewaxing method or the catalytic dewaxing method.

In the solvent dewaxing process, a lubricating base stock / base oil containing a wax, followed by a “wax lubricating base stock” is added to a solvent such as methyl ethyl ketone (MEK) and / or methyl isobutyl ketone (MIBK) and / or Or contact with toluene or the like and lower the temperature during the contacting step to precipitate the wax as a solid. Then, the solid wax is removed from the cold oil / solvent mixture by decantation, centrifugation or filtration through the filter, and the oil / solvent is passed through the filter, whereby the wax is deposited on the filter as a filter compact. Subsequently, for example, it is scraped off to remove it from the filter element material. The recovered wax is known as slack wax.

Alternatively, a known solvent can be used as the autocooling solvent. Such solvents are liquefied propane and / or propylene and / or butane and / or butylene, which are mixed with waxy lubricating oil under pressure, and the pressure is subsequently reduced, which leads to a decrease in temperature of the entire mixture and precipitation of solid wax ( This then again separates from the oil, for example by decanting, centrifugation or filtration).

Solvent dewaxing consists of physically removing the wax from the waxy oil and then recovering the wax as a separate stream or product.

Catalytic dewaxing removes the wax from the waxy oil by converting the wax into smaller hydrocarbon materials. The substantially linear long chain paraffins (n-paraffins) that make up the wax decompose into paraffins with chain lengths as short as gas or non-lube range hydrocarbons or shorter chain paraffins with lower pour points.

Catalytic dewaxing physically changes the wax into shorter chain length molecules.

Another dewaxing method that also includes the use of a catalyst is hydrodewaxing or hydroisomerization. Either way, linear long chain paraffins or long chain paraffins containing some branches (ie isoparaffins) are converted to heavier branched isoparaffins by rearrangement (ie, isomerization with some limited degradation). In this way, the wax is not actually removed from the oil, but is converted to other forms of paraffin (ie isoparaffins) which have substantially lower pour points than linear long chain wax paraffins. Fluids of this type are often referred to as "chemically modified mineral oils."

In some cases, depending on the isomerization catalyst used, in order to further lower the pour point, the hydroisomerized lubricating oil removes the remaining long chain n-paraffins and only weakly branched isoparaffins via a subsequent solvent or catalytic dewaxing step. .

Another way to lower the pour point of the lubricating base stock / base oil is to use one or more pour point drop (PPD) performance additives.

Pour point depressant additives themselves are large molecules that act by hindering the solidification / solidification of linear long chain paraffins in waxy lubricants with lower temperatures.

PPD is generally used at reduced concentrations of 0.01 to about 3.0 weight percent of the lubricating base stock / base oil.

PPDs are typically high molecular weight polymerizable materials, polymethacrylates, polyalkylmethacrylates, alkylated naphthalenes, vinyl acetate-fumarate copolymers, polyarylamides, condensation products of haloparaffin waxes and aromatic compounds, vinyl Carboxylate polymers and terpolymers of dialkylfumarates, vinyl esters of fatty acids and allyl vinyl ethers.

The addition of too much pour point depressant has a detrimental effect on the oil being treated (for example, the pour point rises or the oil solidifies), so a limited amount of this pour point depressant is used.

U.S. Patent No. 3,396,114 discloses an amount of tricresyl phosphate, neutral calcium sulfate, poly (C _4-20 alkyl) methacrylate viscosity index improver (about 10,000 to 30,000 molecular weight), hindered phenolic antioxidant, about 0.5 to 2.0 vol A dual purpose lubricant is disclosed comprising% paraffin wax alkylated naphthalene lubricating oil pour point depressant, alkyl esters of chlorinated fatty acids, defoamers and petroleum lubricating base oils.

Pour point depressants are wax alkylated naphthalenes identified as well-known PPDs for lubricating oils, which are generally prepared by chlorinating paraffin wax and condensing chlorowax with naphthalene (see also US Pat. No. 1,815,022 and US Pat. No. 2,015,748). Reference).

U.S. Patent No. 2,671,051 discloses an aliphatic hydrocarbon chain in an amount of 75 to 150% by weight of the wax in a waxy hydrocarbon lubricating oil whose wax is primarily an n-aliphatic hydrocarbon wax (the chain averages n- by up to about 4 carbon atoms). Low pour point lubricants prepared by adding a pour point depressant, which is one or more foreign hydrocarbon waxes having cyclic end groups, on aliphatic hydrocarbon wax chain lengths). Pour point depressants can be one or more foreign naphthenic waxes having naphthenic end groups with aliphatic hydrocarbon side chains or foreign aromatic waxes with aromatic end groups having aliphatic hydrocarbon side chains, the aromatic end groups being bicyclic aromatic groups such as naphthalene.

U.S. Patent 4,753,745 discloses methylene linked aromatic pour point depressants of the formula:

Ar (R)-[Ar '(R')] _n -Ar "

Where

Ar, Ar 'and Ar "are independently aromatic moieties containing 1 to 3 aromatic rings, each aromatic moiety is substituted with 0 to 3 substituents,

(R) and (R ') are independently alkylene groups containing from about 1 to 100 carbon atoms, provided that at least one of (R) or (R') is CH ₂ ,

n is 0 to about 1000.

The material has a varying molecular weight of about 271 to about 300,000.

WO2004 / 081157 discloses a Fischer-Tropsch (FT) derived base oil obtained by a catalytic dewaxing step and having a pour point of -15 to -31 ° C. containing a pour point drop additive and at least 15% by weight of detergent inhibitor (DI ) A lubricant composition based on an additive package is disclosed. Suitable pour point depressants are alkylated naphthalene and phenolic polymers, polymethacrylates, maleate / fumarate copolymer esters, methacrylate vinyl pyrrolidone copolymers or vinyl acetate-fumarate copolymers. The preferred amount used is 0.1% by weight to preferably 0.3% by weight or less.

WO02 / 04578 discloses fused and / or multifused aromatic compositions alkylated with API II group and / or II group base stocks such as excellent additive solubility, heat-oxidation stability, hydrolysis stability and seal swelling properties. Disclosed is a composition comprising a blend of alkylated naphthalenes represented.

US Pat. No. 6,071,864 discloses a catalytic process for the preparation of arylated polyolefins for use as synthetic lubricants. The aryl moiety can be benzene, naphthalene, furan, thiophene, anthracene, phenanthrene and the like.

US 5,132,478 relates to alkylaromatic lubricating fluids. Aromatic compounds are alkylated with C ₂₀ -C ₁₃₀₀ olefin multimers using acidic alkylation catalysts to produce alkylated aromatic products that exhibit high viscosity indexes and low pour points. They are also disclosed to be useful as additives such as dispersants, detergents, VI improvers, extreme pressure / abrasion additives, antioxidants, pour point depressants, emulsifiers, demulsifiers, corrosion inhibitors, rust inhibitors, anti-staining additives, friction modifiers and the like.

U.S. Patent 5,602,086 discloses a lubricating composition comprising a mixture of polyalphaolefins and alkylated aromatic fluids. The alkyl aromatic may be alkylated naphthalene having a dynamic viscosity at 100 ° C. in the range of about 4 mm ² / s to about 30 mm ² / s. The mixture is characterized by improved oxidation resistance.

US Pat. No. 4,714,794 discloses mixtures of certain mono-alkylated naphthalenes as synthetic oils, having excellent oxidative stability and useful as thermal intermediate oils or as main components of synthetic lubricating oils. Certain mono-alkylated naphthalene mixtures can be incorporated into mineral oils and / or known lubricants in amounts that do not impair their high oxidative stability. Mineral oil and / or known lubricating oils may be added in an amount of up to 75% by weight, preferably up to 50% by weight, more preferably up to 25% by weight.

US Pat. No. 4,604,491 discloses a viscosity at 210 ° F. of 61 to 88 SUS, a viscosity index of 105 to 136 and a flash point of 508 ° F. to 560 ° F. (COC = Cleveland Open Cup), useful as synthetic oils for functional fluids and greases. A mixture of monoalkylated naphthalene and polyalkylated naphthalene with

Publication No. US2005 / 0077209 relates to a method for producing a lubricating base oil having an optimum branch.

The lubricant is characterized by having a low pour point and a very high viscosity index. Lubricants utilize form selective intermediate pore size molecular sieves to hydroisomerize the wax feed to produce intermediate oil isomers having a branching degree of less than 7 alkyl branches per 100 carbons, and solvent desoldering the intermediate oil isomers. To produce a lubricating oil having a branching degree of less than 8 alkyl branches per 100 carbon atoms and having less than 20% by weight of the alkyl branch in position 2, the lubricating base oil having a pour point below -8 ° C, about 3.2 dynamic viscosity at 100 ° C. of at least mm ² / s, with VI greater than the target VT as calculated below:

Target VI = 22 x ln (dynamic viscosity at 100 ° C)

This base oil is preferably less than 95% by weight of conventional Group I, II and III base stocks, isomerized petroleum wax oils, polyalpha olefins, poly internal olefins, diesters, polyol esters, phosphate esters, alkylated It is stated that it can be mixed with aromatics and mixtures thereof. Alkylated aromatics are identified as synthetic lubricants resulting from alkylation of aromatics with haloalkanes, alcohols or olefins in the presence of Lewis or Bronsted acid catalysts. Useful examples include alkylated benzenes and alkylated naphthalenes, which have good low temperature properties and can provide improved additive solubility.

US Pat. No. 6,627,779 discloses one or more high paraffin FT lubrication base stocks and one or more base stocks composed of alkyl aromatics, alkylcycloparaffins, and mixtures thereof to increase the yield of lubricating base oils from Fischer-Tropsch (FT) plants. An improved method of producing a blended lubricating base oil is disclosed. The alkyl aromatics, alkylcycloparaffins or mixtures thereof are present in an amount of about 1% to about 50% by weight. Alkylaromatics are alkyl aromatics boiling in the lubricating oil boiling range, and alkyltetralins of alkyl benzene, alkylnaphthalene and alkyl multinuclear aromatics. Preferably the alkyl aromatic is alkyl benzene. The product of the Fischer-Tropsch synthesis method is fractionally distilled to produce a C ₂₀ + fraction, a light aromatic fraction, and a light Fischer-Tropsch product fraction containing olefins, alcohols and mixtures thereof. The light aromatic fraction is alkylated using the light Fischer-Tropsch product fraction to produce alkyl aromatics.

Blended lubricating base oils are disclosed to have excellent viscosity and viscosity index properties. Only blends with alkyl benzenes or alkyl cyclohexanes are exemplified. No mention of pour point or low temperature viscosity for blends containing alkylbenzenes.

GTL base stocks generally have a pour point in the range of 0 ° C to -25 ° C. If it is desired to produce GTL derived base stocks having a pour point of less than -25 ° C, the lubricating oil yield of the process will be significantly lower, which is undesirable. Thus, a method has been found that can lower the pour point of GTL base stock / base oils by methods other than conventional solvent dewaxing or catalytic dewaxing or by not increasing the strength of hydrodewaxing or hydroisomerization methods. If possible, it will be a significant technological advance.

1 shows the pour point of the blend fluid versus the alkylnaphthalene fluid (AN), ester, low pour point alkylbenzene fluid (Ar PAO) and C ₂₀ -C ₂₄ alkylbenzene (C ₂₀₂₄ AB) (all 6cSt GTL bases) prepared according to the prior art. The weight percent of the stock (in GTL 6) is shown schematically. This graph shows the effect of alkylated naphthalene fluid and low pour point alkylbenzene (Ar PAO) on the pour point drop of the GTL base stock.

About 1 to 95% by weight, preferably 5 to 80% by weight, of GTL lubricated base stock / base oils or hydrodeleadized or hydroisomerized / catalyst (or solvent) dewaxed base stock / base oils, More preferably it relates to a method of lowering the pour point of such base stock / base oils by adding 5 to 60% by weight of alkylated aromatic synthesis fluid. When the alkyl aromatic synthesis fluid is an alkyl naphthalene, the alkylated naphthalene synthesis fluid is at about 100 mm from about 1.5 mm ² / s to about 600 mm ² / s, preferably from about 2 mm ² / s to about 300 mm ² / s, more preferably Is a dynamic viscosity at 100 ° C. in the range of about 2 mm ² / s to about 100 mm ² / s, 0 ° C. or less, preferably −15 ° C. or less, more preferably −25 ° C. or less, even more preferably −35 It has a pour point of about 0 ° C. or lower, and a viscosity index of about 0 to 200, preferably about 50 to 150, more preferably about 50 to 145.

When the synthetic alkyl aromatic fluid is alkyl benzene, the alkyl benzene synthesis fluid is about 1.5 mm ² / s to about 600 mm ² / s, preferably about 2 mm ² / s to about 300 mm ² / s, more preferably about 2 mm Dynamic viscosity from ² / s to about 100 mm ² / s, 0 ° C. or less, preferably −15 ° C. or less, more preferably −25 ° C. or less, even more preferably −35 ° C. or less, most preferably −60 It has a viscosity point in the range of about 0 to 200, preferably about 0 to 200, preferably about 70 to 200, more preferably about 80 to 180.

Dynamic viscosity (KV) is determined by ASTM D445. Pour point is determined by ASTM D97. Viscosity index (VI) is determined by ASTM D2270.

Base stock refers to lubricating oil produced by a single manufacturer to a specific specification and identified by a specific identification or number or code, regardless of the supply stock source, the manufacturer's location or the process used. Base oils are one or a mixture of base stocks that meet specific lubricating oil product specifications, eg, specific oil component requirements, such as specific engine oils, turbine oils, and finished product performance requirements.

GTL base stocks / base oils, as defined in more detail below, and hydrodewaxed or hydroisomerized / catalyzed (and / or solvent) wax-derived base stock / base oils have many excellent lubricating properties. . However, they are very paraffinic and nonpolar in nature, resulting in low solubility in polar additives used in many high quality, high performance lubricant blends. They also have low solubility and dispersibility for decomposition products or sludge formed in lubricating oils over long periods of use. Although esters have been used to improve dissolution and dispersibility, esters are expensive and have performance drawbacks.

The base stock / base oil solubility and dispersibility can be improved by combining certain alkylated aromatics selected from alkylated naphthalenes and / or low pour point alkylated benzenes or their hydrogenated homologs to the base stock / base oils, so that such bases It has been found that the pour point and low temperature properties of stock / base oils, in particular GTL base stock / base oils, can be improved.

The alkylated naphthalenes used in the process of the invention differ from the alkylated naphthalene pour point depressants disclosed in the prior art. The alkylated naphthalene used in the process of the invention is an alkyl naphthalene fluid having a dynamic viscosity at 100 ° C. in the range of 1.5 to 600 mm ² / s, a pour point below 0 ° C., and VI in the range of 0 to 200. These are liquids flowable at room temperature.

The fluid alkylated naphthalene used in the present invention has the formula

Where

n + m is 1 to 8, preferably 1 to 6, more preferably 1 to 5,

R is a C ₁ -C ₃₀ , preferably a C ₁ -C ₂₀ linear alkyl group, C ₃ -C ₃₀₀ , preferably C ₃ -C ₁₀₀ , more preferably a C ₃ -C ₃₀ branched alkyl group or It is a combination and the total number of carbons of R _m and R _n is preferably 4 or more.

Examples of typical alkyl naphthalenes are mono-, di-, tri-, tetra- or penta-C ₃ alkyl naphthalene, C ₄ alkyl naphthalene, C ₅ alkyl naphthalene, C ₆ alkyl naphthalene, C ₈ alkyl naphthalene, C ₁₀ alkyl naphthalene, C ₁₂ alkyl naphthalene, C ₁₄ alkyl naphthalene, C ₁₆ alkyl naphthalene, C ₁₈ alkyl naphthalene and the like, C ₁₀ -C ₁₄ mixed alkyl naphthalene, C ₆ -C ₁₈ mixed alkyl naphthalene, or mono-, di-, tri -, Tetra- or penta C ₃ , C ₄ , C ₅ , C ₆ , C ₈ , C ₁₀ , C ₁₂ , C ₁₄ , C ₁₆ , C ₁₈ alkyl monomethyl, dimethyl, ethyl, diethyl or methylethyl naphthalene Or mixtures thereof. The alkyl group may also be a branched alkyl group having C ₁₀ to C ₃₀₀ , for example C ₂₄ -C ₅₆ branched alkyl naphthalene, C ₂₄ -C ₅₆ branched alkyl mono-, di-, tri-, tetra- or Penta-C ₁ -C ₄ naphthalene. These branched alkyl group substituted naphthalenes or branched alkyl group substituted mono-, di-, tri-, tetra- or penta C ₁ -C ₄ naphthalene can be used as a mixture with the substances mentioned previously. These branched alkyl groups can be prepared from the multimerization of small olefins such as C ₅ to C ₂₄ alpha- or internal-olefins. If the branched alkyl group is very large (ie 8 to 300 carbons), typically only one or two of these alkyl groups are attached to the naphthalene core. Alkyl groups on the naphthalene ring may also be mixtures of such alkyl groups. Often these are advantageous because mixed alkyl groups provide more improvements in pour point and cold fluid properties. Fully hydrogenated fluid alkylnaphthalene can also be used for blending with GTL base stock / base oils, but alkyl naphthalene is preferred.

Typically, alkyl naphthalenes are prepared by alkylation of naphthalene or short-chain alkyl naphthalenes with olefins, alcohols or alkylchlorides having 6 to 24 carbon atoms on an acidic catalyst comprising a typical Friedel Crafts catalyst. Typical Friedel-Crafts catalysts are AlCl ₃ , BF ₃ , HT, zeolites, amorphous aluminosilicates, acid clays, acidic metal oxides or metal salts, USY and the like.

Methods of preparing alkylnaphthalenes suitable for use in the present invention are disclosed in US Pat. No. 5,034,563, US Pat. No. 5,516,954, US Pat. No. 6,436,882, and also in the references disclosed elsewhere and in those references. have. Since alkylated naphthalene synthesis techniques are well known in the literature and well known to those skilled in the art, these techniques will not be described further herein.

Naphthalene or mono- or di-substituted short chain alkyl naphthalenes can be derived from any conventional process, petrochemical process or coal process or source stream that produces naphthalene from petroleum. Naphthalene-power oil feeds can be prepared from aromatization of suitable streams available in the F-T process. For example, the aromatization of olefins or paraffins can produce naphthalene or naphthalene-containing components (DE84-3414705, US20060138024A1. Many of the medium or light cycle oils from petroleum refining processes have significant amounts of naphthalene, substituted naphthalene or naphthalene. In practice, substituted naphthalenes, no matter what source they are recovered from, may have up to about 3 alkyl carbons and can be used as raw material to produce alkylnaphthalenes for the present invention. Whatever was recovered from, alkylated naphthalene can be used in the present invention as long as it has dynamic viscosity, VI, pour point, and the like as described above.

Suitable alkylated naphthalenes are commercially available from ExxonMobil Chemical Company under the tradename Cinetic AN, or from King Industries under the tradename NA-Lube naphthalene-containing fluid.

As described above, the viscosity of 1.5 to 600 cS at 100 ° C, the VI of 0 to 200 and 0 ° C or less, preferably -15 ° C or less, more preferably -25 ° C or less, even more preferably -35 ° C or less, Most preferably alkylated benzenes of formula (II) having a pour point below −60 ° C. are useful for this purpose:

Where

x is 1-6, Preferably 1-5, More preferably, it is 1-4.

In the case of monoalkylated benzene, R is a linear C ₁₀ to C ₃₀ alkyl group or C ₁₀ -C ₃₀₀ branched alkyl group, preferably C ₁₀ -C ₁₀₀ branched alkyl group, more preferably C ₁₅ -C ₅₀ It may be a branched alkyl group. When n is 2 or more, one or two of the alkyl groups may be small alkyl radicals of the C ₁ to C ₅ alkyl groups, preferably C ₁ -C ₂ alkyl groups. The other alkyl group may be a linear C ₁₀ -C ₃₀ alkyl group or any combination of branched C ₁₀ to C ₃₀₀ alkyl groups, preferably C ₁₅ -C ₅₀ branched alkyl groups. These branched large alkyl radicals can be prepared from multimerization or polymerization of C ₃ to C ₂₀ internal or alpha-olefins or mixtures of these olefins. The total number of carbons in the alkyl substituents ranges from C ₁₀ to C ₃₀₀ . Preferred alkyl benzene fluids can be prepared according to US Pat. No. 6,071,864 or US Pat. No. 6,491,809 or European Patent No. 0,168,534.

According to the invention, alkylated benzene is preferably prepared by a process comprising the following steps:

(a) multimerizing one or more alpha olefins or internal olefins to form olefin dimers or some higher multimers; And

(b) arylation of the olefin multimers with benzene or short alkyl chains (C ₁ -C ₅ alkyl groups) mono or poly substituted benzene to produce alkylated benzene products.

The alpha-olefins or internal olefins are multimerized in the presence of a catalyzed catalyst to form mainly olefin dimers and higher multimers. Once the reaction is complete, an aromatic composition containing one or more aromatic compounds is reacted with the multimer in the presence of the same catalyst to produce an alkylated aromatic lubricating base stock in high yield.

In a preferred embodiment, the alpha-olefin has 6 to about 20 carbon atoms. In a more preferred embodiment, the alpha-olefin has about 8 to about 16 carbon atoms. In a particularly preferred embodiment, the alpha-olefins have about 8 to about 14 carbon atoms.

According to the present invention, one or more alpha-olefins are multimerized to form predominantly olefin dimers and some trimers or more multimers are formed. In a preferred embodiment, the olefin multimer has about 20 to about 36 carbon atoms, more preferably about 20 to about 28 carbon atoms. In another embodiment, the one or more internal olefins, by themselves or mixed with alpha-olefins, to multimerize to form multimers, which can be further alkylated with aromatic compounds. Preferred internal olefin starting materials are C8 to C30 internal olefins, preferably C10 to C20, more preferably C12 to C18 internal olefins.

The aromatic moiety is either benzene or short-chain (C ₁ -C ₅ alkyl group) or hydroxy, alkoxy, hydroxy alkylthio or arylthio mono or poly substituted benzene, preferably C ₁ -C ₅ alkyl group mono or poly substituted Benzene, more preferably toluene, o-, m- or p-xylene, ethylene benzene, di-ethyl benzene, n- or iso-propyl benzene, di-n- or di-isopropyl benzene, n-iso or tert-butyl benzene, di-no- or di-iso or di-tert butylbenzene.

Catalysts used are Lewis acid catalysts such as BF ₃ , AlCl, triflic acid, BCl ₃ , AlBr ₃ , SnCl ₄ , GaCl ₃ , acid clay catalysts or acidic zeolites such as zeolite beta, USY, mordenite, mont Morillonite or other acidic layered, open structure zeolites such as MCM-22, MCM-56 or solid superacids such as sulfurized zirconia and activated Wo _x / ZrO ₂ . In a particularly preferred embodiment, the catalyst is BF ₃ or AlCl ₃ or an accelerated version thereof.

Catalysts as disclosed herein are known to be used advantageously with accelerators. Suitable promoters for use with the catalyst in the present invention include those known in the art, such as water, alcohols or esters or acids.

Preferred catalyst is MCM-56. MCM-56 is a member of the MCM-22 group useful in the present invention, and the MCM-22 group includes MCM-22, MCM-36, MCM-49 and MCM-56. MCM-22 is disclosed in US Pat. No. 4,954,325. MCM-36 is disclosed in US Pat. No. 5,250,277 and MCM-36 (combined form) is disclosed in US Pat. No. 5,292,698. MCM-49 is disclosed in US Pat. No. 5,236,575 and MCM-56 is disclosed in US Pat. No. 5,362,697.

Catalysts as mixed metal oxide superacids include oxides of Group IVB metals, preferably zirconia or titania. Group IVB metal oxides are modified using oxyanions of group VIB metals, for example oxyanions of tungsten, for example tungstates. Modification of Group IVB metal oxides with oxyanions of Group VIB metals imparts acid functionality to the material. The combination of oxyanions of Group IVB metal oxides and Group VIB metals is thought to enter into actual chemical interactions, which in any case is a simple mixture of individually formed Group VIB metal oxides or individually formed IVB metal oxides mixed with oxyanions. It provides a composition having more acidic than.

Acidic solid materials useful as catalysts are disclosed in US Pat. Nos. 5,510,539 and 5,563,310. These solid materials include oxides of Group IVB metals, preferably zirconia or titania. Group IVB metal oxides are modified using oxyanions of Group IVB metals, for example oxyanions of tungsten, for example tungstates. Modification of Group IVB metal oxides with oxyanions of Group VIB metals imparts acid functionality to the material. Modification of group IVB metal oxides, in particular zirconia, with group VIB metal oxyanions, in particular tungstate, is disclosed in U.S. Patent Nos. 5,113,034, JP-A-1989-288339 and K. Arata and M. Hino in Proceeding 9th International Congress on Catalysis, Volume 4, pages 1727-1735 (1988). According to these documents, the tungstate is infiltrated onto the preformed solid zirconia material. This chemical interaction is described in [K. Arata and M. Hino in Proceeding 9th International Congress on Catalysis, Volume 4, pages 1727-1735 (1988), which also relates to the reaction of sulfates with some metals, such as hydroxides or oxides of Zr. It is proposed that a solid super acid is formed. These superacids are said to have the structure of the bidentate ligand ions ion-coordinated to a metal, for example Zr. The document also suggests that superacids can be formed when the tungstate reacts with hydroxides or oxides of Zr. The resulting tungstate modified zirconia material, including sulphate and zirconium, is theorized to have a structure similar to the superacids described above in which tungsten atoms replaced sulfur atoms in a bidentate ligand structure. It is also proposed to produce super acidic sites when tungsten oxide is combined with a zirconium oxide compound to form a tetragonal phase.

Although the catalyst of the present invention is described above [K. Arata and M. Hino in Proceeding 9th International Congress on Catalysis, Volume 4, pages 1727-1735 (1988), which are thought to contain the bidentate ligand structure, but modified with oxyanions of Group VIB metals. The specific structure of the catalytically active site of the Group IVB metal oxide of the invention has not been identified and is not intended to limit the present catalyst component to any particular structure.

Suitable sources of Group IVB metal oxides used to prepare the catalyst include compounds capable of producing such oxides, such as oxychloride, chloride, nitrate, oxynitrate, in particular of zirconium or titanium. Alkoxides of these metals may also be used as precursors or sources of Group IVB metal oxides. Examples of such alkoxides include zirconium n-propoxide and titanium i-propoxide. These sources of group IVB metal oxides, in particular zirconia, can form zirconium hydroxides, ie Zr (OH) ₄ , or hydrated zirconia as intermediate species upon precipitation from an aqueous medium in the absence of a reactive source of tungstate. The expression hydrated zirconia is intended to mean a material comprising a zirconium atom, ie, Zr-O-Zr, which is covalently bonded to another zirconium atom via a crosslinked oxygen atom, and which further comprises surface hydroxy groups. When hydrated zirconia is infiltrated with a suitable source of tungstate under sufficient conditions, it is believed that these available surface hydroxyl groups react with the source of tungstate to form an acidic catalyst. [K. As suggested in Arata and M. Hino in Proceeding 9th International Congress on Catalysis, Volume 4, pages 1727-1735 (1988), preliminary calcination of Zr (OH) ₄ at a temperature of about 100 ° C. to about 400 ° C. Using this produces species that interact more favorably with the tungstate. Such precalcination is believed to result in condensation of the ZrOH groups to form polymeric zirconia species with surface hydroxyl groups which may be referred to as one form of hydrated zirconia.

Suitable sources for oxyanions of Group VIB metals, preferably molybdenum or tungsten, include ammonium metatungstate or metamolybdate, tungsten or molybdenum chloride, tungsten or molybdenum carbonyl, tungstic acid or molybdate and Sodium tungstate or molybdate, including but not limited to.

The ratio of aromatic compound to alpha-olefin multimer is preferably from about 0.05: 1 to about 20: 1. In a more preferred embodiment, the ratio of aromatic compound to alpha-olefin multimer is from about 0.1: 1 to about 8: 1.

The method provides poly alpha-olefins arylated in higher yield than conventional alkylbenzene fluid synthesis, where 2 moles of alpha-olefin and 1 mole of aromatic compound are mixed with the catalyst.

The reaction temperature is typically in the range of about 20 to 100 ° C.

The alkylbenzene fluids used in the present invention have good low temperature properties, including good pour points. These pour points are generally below 0 ° C. Preferred alkyl methyl benzene fluids and those used in all tests are prepared according to the methods disclosed in US Pat. No. 6,071,864, in the multimerization of a mixture of C ₈ , C ₁₀ and C ₁₂ linear alpha olefins on an accelerated BF ₃ catalyst. Starting from to produce the product reacted with toluene on the same catalyst at the same reaction temperature. The product is isolated to produce a lubrication base stock having a viscosity and pour point (viscosity above 1.5 cS and pour point below 0 ° C.) that meet the requirements of the present invention. Unexpectedly, this alkylbenzene was found to synergistically lower the pour point of the GTL fluid.

Dialkylbenzenes (DAB) as disclosed in US Pat. No. 6491809 are also used with GTL lubricants to provide similar advantages. These types of DABs can be prepared by repeated alkylation of benzene, for example by alkylating benzene to produce monoalkylbenzenes, and then further alkylating this mono-alkylbenzene in the same reactor or in separate reactors. Alkylbenzenes that meet the requirements for the present invention can also be obtained from many detergent alkylbenzene processes. In these processes linear alkylbenzenes (LAB) are prepared by alkylating benzene on an alkylation catalyst. Mono-alkyl LAB is used as raw material for detergent production. This detergent LAB process also produces some heavier by-product streams, which contain a mixture of dialkylbenzenes and high alkylbenzenes or multimerized alkylated benzenes. These higher fractions often have properties that meet the present disclosure and are suitable for blending with GTL base stocks.

In contrast, conventional C ₂₀ -C prepared by isomerizing C ₂₀ -C ₂₄ linear alpha-olefins to rearrange double bonds from the alpha position to internal positions and then alkylating benzene with these C ₂₀ -C ₂₄ linear olefins. ₂₄ alkylbenzene fluids (US Pat. No. 6,627,779) have a pour point higher than 0 ° C. This type of fluid has no effect on the GTL pour point or actually raises the pour point.

In addition, hydrogenated homologs of the alkylated naphthalenes or alkylated benzenes disclosed above may also be used for GTL base stocks and for hydrodewaxed or hydroisomerized / catalyzed (catalyst and / or solvent) dewaxed base stocks / base oils. It has been found to be an effective pour point dropping fluid. It has also been found that alkylated naphthalene or alkylated benzene fluids can unexpectedly improve the oxidative stability of blends with GTL fluids. This improvement in oxidative stability can be demonstrated by longer RBOT (ASTM D2272 method) or other oxidation test method. It has also been found that alkylated naphthalene or alkylated benzene fluids can improve the polarity of blends with GTL fluids. This higher polarity of the blend indicates better solubility of the additive and other polar components formed during oil use. Thus, blends of GTL with these alkylated aromatic fluids can provide higher levels of finished lubrication performance.

Base stocks and / or base oils used in the present invention are derived from one or more mixtures of base stocks and / or base oils derived from one or more Gas-to-Liquid (GTL) materials, and also from natural waxes or waxy feeds. Hydrodewaxed or hydroisomerized / conventional catalyst (and / or solvent) dewaxed base stock and / or baseoil, mineral and / or non-mineral oil waxy feed stock, eg slack wax (natural Oils, mineral oils or synthetic oils, for example derived from wax dewaxing of Fischer-Tropsch feed stocks, natural waxes and waxy stocks such as gas oils, waxy fuel hydrocracker bottoms bottoms, wax raffinate, hydrocrackate, thermal decomposition products, foots oil or other minerals, mineral oils, or even non-petroleum oils The wax material, for example, include coal liquefaction or shale waxy materials, hydro-carbon atoms of 20 or more, preferably more than 30 linear or branched out from the flow path hydrocarbyl compound, and this base stock and / or a mixture of the base oil.

Base stocks and / or base oils derived from waxy feeds also suitable for use in the present invention may be selected from the group consisting of hydrodelead or hydroisomerization / catalysts of mineral oil, non-mineral oil, non-petroleum or natural source origin. And / or solvents) Dewaxed waxy feedstocks such as gas oils, slack waxes, waxy fuel hydrocracker bottoms, hydrocarbon raffinates, neutral waxes, hydrocracks, thermal decomposition products, putts oils, waxes from coal liquefaction , Waxes from shale oil, or other suitable mineral oils, non-mineral oils, non-petroleum or waxy materials derived from natural sources, linear or branched hydrocarbyl compounds having at least about 20 carbon atoms, preferably at least about 30 carbon atoms, and iso Paraffin oil of lubricating viscosity derived from a mixture of merate / isode waxate base stock and / or base oil A.

GTL materials include gaseous carbon-containing compounds, hydrogen-containing compounds and / or elements as feedstocks, for example hydrogen, carbon dioxide, carbon monoxide, water, methane, ethane, ethylene, acetylene, propane, propylene, propene, butane, butyl A substance derived through one or more synthesis, combination, conversion, rearrangement, and / or degradation / disassembly processes from len and butyne. GTL base stocks and / or base oils are generally lubricated from hydrocarbons, for example wax synthesized hydrocarbons derived from simpler gaseous carbon-containing compounds, hydrogen-containing compounds and / or elements as such feedstocks. GTL material with viscosity. GTL base stocks and / or base oils may be (1) distilled and subsequently subjected to a final waxing step (which includes either or both a catalytic dewaxing process or a solvent dewaxing process to produce a lubricating oil having a lower or lower pour point). Separated / divided from GTL material synthesized by; (2) synthetic wax isomerates comprising, for example, hydrodewaxed or hydroisomerized and then catalytically and / or solvent-lead synthesized waxes or waxy hydrocarbons; (3) Fischer-Tropsch (F-T) materials (i.e., hydrocarbons, waxy hydrocarbons, waxes and possibly similar oxygenates) after hydrodehydration or hydroisomerization followed by catalytic and / or solvent dewaxing; Preferably dehydrolead FT waxy hydrocarbons which are catalytically and / or solvent deleadated after hydrodehydration or hydroisomerization, or catalytic (or solvent) deleadated FT wax after hydrodeleadized or hydroisomerized or Oils boiling in the lubricating oil boiling range, including mixtures thereof.

GTL base stocks and / or base oils derived from GTL materials, in particular catalytic and / or solvent-dewaxed wax or waxy feeds, preferably FT material-derived base stocks and hydrode or hydroisomerized and And / or the base oil is typically from about 2 mm ² / s to about 50 mm ² / s, preferably from about 3 mm ² / s to about 50 mm ² / s, more preferably from about 3.5 mm ² / s to about 30 mm at 100 ° C. ^It is characterized by having a dynamic viscosity of ² / s (ASTM D445). They are further characterized as having typically a pour point of about -5 ° C to about -40 ° C or less (ASTM D97). They are also typically characterized as having a viscosity index (ASTM D2270) of about 80 to 140 or more.

In addition, GTL base stocks and / or base oils are typically very paraffinic (greater than 90% saturation) and may contain a mixture of monocycloparaffins and multicycloparaffins in combination with non-cyclic isoparaffins. The ratio of naphthene (ie cycloparaffin) content in this combination varies depending on the catalyst and temperature used. In addition, GTL base stocks and / or base oils and hydrodeleadized or hydroisomerized / catalyst (and / or solvent) deleadated base stocks and / or base oils typically have very low sulfur and nitrogen contents, generally about It contains less than 10 ppm, more typically less than about 5 ppm of each of these elements. The sulfur and nitrogen content of GTL base stocks and / or base oils, in particular F-T waxes, obtained from F-T materials are essentially free. In addition, the absence of phosphorus and aromatics makes this material particularly suitable for the combination of low sulfur, sulfurized ash and phosphorus (low SAP) products.

Base stocks and / or base oils derived from waxy feeds (which are also suitable for use in the present invention) are hydrodelead or hydroisomerized of mineral oil, non-mineral oil, non-petroleum or natural source origin. Waxed feedstocks, such as one or more gas oils, slack waxes, waxy fuel hydrocracker bottoms, hydrocarbon raffinates, natural waxes, hydrocracks, thermal crackers, Putts oil, wax from coal liquefaction or wax from shale oil, or other suitable mineral oil, non-mineral oil, non-petroleum or wax material derived from a natural source, linear at least about 20 carbon atoms, preferably at least about 30 carbon atoms, or Branched hydrocarbyl compounds and mixtures of these isomerate / isodesaxate base stocks and / or base oils Since the paraffin fluids of lubricating viscosity derived.

Slack wax is a wax recovered from any waxy hydrocarbon oil, including synthetic oils, such as F-T wax oils or petroleum oils, by solvent or autocold dewaxing. Solvent dewaxing utilizes cooled solvents such as methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), a mixture of MEK / MIBK, a mixture of MEK and toluene, and autocooling dewaxing is a pressurized liquefied low boiling hydrocarbon. For example, propane or butane is used.

Slack waxes obtained from synthetic wax oils such as F-T wax oils generally have a sulfur and / or nitrogen containing compound content of zero. Slack waxes obtained from petroleum may have sulfur and nitrogen containing compounds. Such heteroatomic compounds may be hydrotreated (not hydrocracked), for example hydrodesulfurization (HDS) and hydrodenitrogenation (HDN), to avoid subsequent poisoning / inactivation of the hydroisomerization catalyst. Should be removed by

The term GTL base stock and / or base oil and / or wax isomerate base stock and / or base oil is used to produce individual fractions of such materials in a wide range of viscosities recovered in the production process, and to produce blends that exhibit a target dynamic viscosity. It is understood to include mixtures of 1, 2 or more high viscosity fractions of 2, or more low viscosity fractions.

Hydrodewaxate or hydroisomerate / catalyst (or solvent) dewaxate base stocks and / or mixtures of base oils, GTL base stocks and / or base oils, or mixtures thereof, preferably GTL base stocks and / or Or a mixture of base oils may constitute all or part of the base oil.

In a preferred embodiment, the GTL material from which the GTL base stock and / or base oil is derived is an F-T material (ie hydrocarbons, waxy hydrocarbons, waxes).

The types and amounts of performance additives used in combination with the present invention in lubricating compositions are not limited by the examples shown herein by way of example.

Wear resistance  And EP  additive

Internal combustion engine lubricants require the presence of wear and / or extreme pressure (EP) additives to provide adequate wear protection for the engine. Surprisingly, specifications for engine oil performance indicate a trend towards improved wear resistance properties of oils. Wear and extreme pressure EP additives play this role by reducing friction and wear of metal parts.

There are many different types of antiwear additives, but for decades the main antiwear additives for internal combustion engine crankcase oils are metal alkylthiophosphates, more specifically metal dialkyldithiophosphates whose main metal component is zinc, or zinc dialkyl Dithiophosphate (ZDDP). ZDDP compounds generally have the general formula Zn [SP (S) (OR ¹ ) (OR ² )] ₂ , wherein R ¹ and R ² are C ₁ -C ₁₈ alkyl groups, preferably C ₂ -C ₁₂ alkyl Qi). These alkyl groups can be straight or branched chain. ZDDP is typically used in amounts of about 0.4 to 1.4 weight percent of the total lubricating oil composition, and more or less amounts may advantageously be used.

However, phosphorus from these additives can have a detrimental effect on catalysts in catalytic converters and also on oxygen sensors in automobiles. One way to reduce this effect is to replace some or all of the ZDDP with a phosphorus free antiwear additive.

Various non-phosphorus additives are also used as antiwear additives. Sulfurized olefins are useful as antiwear and EP additives. Sulfur-containing olefins can be prepared by sulfiding various organic materials including aliphatic, arylaliphatic or cycloaliphatic olefin hydrocarbons containing about 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms. The olefin compound contains one or more non-aromatic double bonds. Such compounds are defined by the formula R ³ R ⁴ C = CR ⁵ R ⁶ , wherein each of R ³ to R ⁶ is independently hydrogen or a hydrocarbon radical. Preferred hydrocarbon radicals are alkyl or alkenyl radicals. Any two of R ³ to R ⁶ may be linked to form a cyclic ring. Further information on sulfided olefins and their preparation can be found in US Pat. No. 4,941,984.

The use of polysulfides of thiophosphoric and thiophosphoric esters as lubricating additives is disclosed in US Pat. Nos. 2,443,264, 2,471,115, 2,526,497 and 2,591,577. Abrasion resistance, anti-oxidation and the addition of phosphorothionyl disulfide as EP additives are disclosed in US Pat. No. 3,770,854. Alkylthiocarbamoyl compounds (e.g. bis (e) in combination with phosphorus esters (e.g. dibutyl hydrogen phosphite) and molybdenum compounds (e.g. oxymolybdenum diisopropyl phosphorodithioate sulfide) Dibutyl) thiocarbamoyl) is disclosed in US Pat. No. 4,501,678. US 4,758,362 discloses the use of carbamate additives to provide improved wear and extreme pressure properties. The use of thiocarbamates as antiwear additives is disclosed in US Pat. No. 5,693,598. Thiocarbamate / molybdenum complexes such as molly-sulfur alkyl dithiocarbamate trimer complexes (R═C ₈ -C ₁₈ alkyl) are also useful antiwear agents. For the purpose of producing low SAP formulations, the use or addition of such materials should be kept to a minimum. Each of the foregoing patents is incorporated herein by reference in their entirety.

Esters of glycols can be used as antiwear agents. For example, mono-, di- and tri-oleate, mono-palmitate and mono-myristate can be used.

ZDDP is combined with other compositions that provide wear resistance. U.S. Patent No. 5,034,141 discloses that the combination of a thiodixanthogen compound (e.g. octylthiodiixanthogen) and a metal thiophosphate (e.g. ZDDP) can improve wear resistance. U.S. Patent No. 5,034,142 discloses that the use of metal alkyloxyalkyl xanthates (e.g. nickel ethoxyethyl xanthate) and dizantogen (e.g. It is disclosed to improve. Each of the foregoing patents is incorporated herein by reference in their entirety.

Preferred antiwear additives include phosphorus and sulfur compounds such as zinc dithiophosphate and / or sulfur, nitrogen, boron, molybdenum phosphorodithioate, molybdenum dithiocarbamate, and heterocyclic Various organic molybdenum derivatives such as dimercaptothiadiazoles, mercaptobenzothiadiazoles, triazines and the like, cycloaliphatic, amines, alcohols, esters, diols, triols, fatty acid amides and the like can also be used. . Such additives may be used in amounts of about 0.01 to 6% by weight, preferably about 0.01 to 4% by weight. ZDDP-type compounds provide significantly lower limited peroxide resolution than the compounds disclosed and claimed in the present patent exhibit, thus facilitating the production of low SAP formulations if they can be removed or maintained from the formulation. To maintain a minimum concentration.

Antioxidant

Antioxidants delay oxidative degradation of the base oil during use. This decomposition may result in deposits on the metal surface, resulting in the presence of sludge or increased viscosity in the lubricant. Those skilled in the art know a wide variety of oxidation inhibitors useful in lubricating oil compositions. See, for example, Klamann in Lubricants and Related Product, and US Pat. Nos. 4,798,684 and 5,084,197, which are hereby incorporated by reference in their entirety.

Useful antioxidants include hindered phenols. These phenolic antioxidants may be ashless (metal free) phenolic compounds or neutral or basic metal salts of some phenolic compounds. Typical phenolic antioxidant compounds are hindered phenols containing sterically hindered hydroxyl groups, which include derivatives of dihydroxy aryl compounds in which the hydroxyl groups are o- or p-positions relative to one another. Typical phenolic antioxidants include the C ₆ of the hindered phenol and these hindered phenol substituted with an alkyl + alkylene coupled derivatives. Examples of this type of phenolic material are 2-t-butyl-4-heptyl phenol, 2-t-butyl-4-octyl phenol, 2-t-butyl-4-dodecyl phenol, 2,6-di-t- Butyl-4-heptyl phenol, 2,6-di-t-butyl-4-dodecyl phenol, 2-methyl-6-t-butyl-4-heptyl phenol and 2-methyl-6-t-butyl-4- Dodecyl phenol. Other useful hindered mono-phenolic antioxidants may include, for example, hindered 2,6-di-alkyl-phenolic proprioric ester derivatives. Bis-phenolic antioxidants may also be advantageously used in combination with the present invention. Examples of ortho-coupled phenols are 2,2'-bis (4-heptyl-6-t-butyl-phenol), 2,2'-bis (4-octyl-6-t-butyl-phenol) and 2 , 2'-bis (4-dodecyl-6-t-butyl-phenol). Para-coupled bisphenols include, for example, 4,4'-bis (2,6-di-t-butyl phenol) and 4,4'-methylene-bis (2,6-di-t-butyl phenol) do.

Non-phenolic antioxidants that may be used include aromatic amine antioxidants, which may be used as such or in combination with phenols. Typical examples of non-phenolic antioxidants are alkylated aromatic amines and non-alkylated aromatic amines, for example the formula R ⁸ R ⁹ R ¹⁰ N, wherein R ⁸ is an aliphatic, aromatic or substituted aliphatic group, and R ⁹ Is an aromatic or substituted aromatic group, R ¹⁰ is H, alkyl, aryl or R ¹¹ S (O) _x R ¹² , wherein R ¹¹ is an alkylene, alkenylene or aralkylene group, and R ¹² is higher Alkyl groups or alkenyl, aryl or alkaryl groups, x being 0, 1 or 2). Aliphatic groups R ⁸ may contain from 1 to about 20 carbon atoms and preferably contain about 6 to 12 carbon atoms. Aliphatic groups are saturated aliphatic groups. Preferably both R ⁸ and R ⁹ are aromatic or substituted aromatic groups and the aromatic group is a fused ring aromatic group such as naphthyl. Aromatic groups R ⁸ and R ⁹ may be linked together with other groups such as S.

Typical aromatic amine antioxidants have alkyl substituent groups having about 6 or more carbon atoms. Examples of aliphatic groups include hexyl, heptyl, octyl, nonyl and decyl. Aliphatic groups generally do not contain more than about 14 carbon atoms. Common types of amine antioxidants useful in the compositions of the present invention include diphenylamine, phenyl naphthylamine, phenothiazine, imidodibenzyl and diphenyl phenylene diamine. Mixtures of two or more aromatic amines are also useful. Polymerizable amine antioxidants may also be used. Particular examples of aromatic amine antioxidants useful in the present invention include p, p'-dioctyldiphenylamine, t-octylphenyl-alpha-naphthylamine, phenyl-alphafinaptylamine and p-octylphenyl-alpha-naphthylamine Include.

Sulfurized alkyl phenols and their alkali or alkaline earth metal salts are also useful antioxidants.

Another class of antioxidants used in lubricating oil compositions are oil soluble copper compounds. Suitable copper compounds of any oiliness can be blended into the lubricant. Examples of suitable copper antioxidants include copper dihydrocarbyl thio- or dithio-phosphate and copper salts of (natural or synthetic) carboxylic acids. Other suitable copper salts include copper dithiacarbamate, sulfonate, phenate and acetylacetonate. Basic, neutral or acidic copper Cu (I) and / or Cu (II) salts or anhydrides derived from alkenyl succinic acids are known to be particularly suitable.

Preferred antioxidants include hindered phenols, arylamines. These antioxidants can be used individually or in combination with one another. Such additives may be used in amounts of about 0.01 to 5% by weight, preferably in amounts of about 0.01 to 1.5% by weight, more preferably in amounts of less than 0 to 1.5% by weight, most preferably in amounts of 0% by weight. .

Detergent

Detergents are commonly used in lubricating compositions. Typical detergents are anionic materials containing the long chain hydrophobic portion of the molecule and the smaller anionic or oleophobic hydrophilic portion of the molecule. The anionic portion of the detergent is typically derived from organic acids such as sulfuric acid, carboxylic acids, phosphoric acid, phenols or mixtures thereof. Counter ions are typically alkaline earth metals or alkali metals.

Salts containing substantially stoichiometric amounts of metal are disclosed as neutral salts and have a total base number of 0 to 80 (measured according to TBN, ASTM D2896). Many compositions are overbased and contain large amounts of metal bases obtained by reacting excess metal compounds (eg metal hydroxides or oxides) with acidic gases (eg carbon dioxide). Useful detergents may be neutral, mildly overbased, or very overbased.

It is desirable that at least some detergents be overbased. Overbased detergents help neutralize acidic impurities produced by the combustion process and trapped in oil. Typically, the overbased material has a ratio of metal ion to anionic portion of the detergent on an equivalent basis of about 1.05: 1 to 50: 1. More preferably, the ratio is about 4: 1 to about 25: 1. The resulting detergent is typically an overbased detergent having a TBN of about 150 or more, often about 250 to 450 or more. Preferably, the overbased cation is sodium, calcium or magnesium. Mixtures of detergents with different TBNs can be used in the present invention.

Preferred detergents include alkali or alkaline earth metal salts of sulfonates, phenates, carboxylates, phosphates and salicylates.

Sulfonates can be prepared from sulfonic acids, typically obtained by sulfonation of alkyl substituted aromatic hydrocarbons. Hydrocarbon examples include those obtained by alkylating benzene, toluene, xylene, naphthalene, biphenyl and halogenated derivatives thereof (eg chlorobenzene, chlorotoluene and chloronaphthalene). Alkylating agents typically have about 3 to 70 carbon atoms. Alkaryl sulfonates typically contain about 9 to about 80 or more carbon atoms, and more typically about 16 to 60 carbon atoms.

The aforementioned Klamann in Lubricants and Related Product disclose a number of overbased metal salts of various sulfonic acids useful as detergents and dispersants in lubricating oils. Book [Lubricant Additives], C. V. Smallheer and R. K. Smith, published by the Lezius-Hiles Co. of Cleveland, Ohio (1967) discloses a number of overbased sulfonates which are similarly useful as dispersants / detergents.

Alkaline earth phenates are another class of useful detergents. These detergents react alkaline earth metal hydroxides or oxides (eg CaO, Ca (OH) ₂ , BaO, Ba (OH) ₂ , MgO, Mg (OH) ₂ ) with alkyl phenols or sulfided alkylphenols. Can be prepared by Useful alkyl groups include straight or branched C ₁ -C ₃₀ alkyl groups, preferably C ₄ -C ₂₀ . Examples of suitable phenols include isobutylphenol, 2-ethylhexylphenol, nonylphenol, dodecyl phenol and the like. It should be noted that the starting alkylphenols may each contain one or more alkyl substituents, which may be straight or branched chain. If non-sulfurized alkylphenols are used, the sulfided products can be obtained by methods well known in the art. These methods include heating a mixture of alkylphenols and sulfiding agents (including sulfur elements, sulfur halides such as sulfur dichloride, etc.), and then reacting the sulfided phenols with alkaline earth metal bases. do.

Metal salts of carboxylic acids are also useful as detergents. These carboxylic acid detergents can be prepared by reacting a basic metal compound with one or more carboxylic acids and removing free water from the reaction product. These compounds may be overbased to produce the desired TBN level. Detergents made from salicylic acid are one preferred class of detergents derived from carboxylic acids. Useful salicylates include long chain alkyl salicylates. One useful class of compositions is the formula:

Where

R is a hydrogen atom or an alkyl group having 1 to about 30 carbon atoms,

n is an integer from 1 to 4,

M is an alkaline earth metal.

Preferred R groups are C ₁₁ or higher, preferably C ₁₃ or higher alkyl chains. R may optionally be substituted with substituents that do not interfere with the performance of the detergent. M is preferably calcium, magnesium or barium. More preferably, M is calcium.

Hydrocarbyl-substituted salicylic acid can be prepared from phenol by the Kolbe reaction. For further information on the synthesis of these compounds, see US Pat. No. 3,595,791. Metal salts of hydrocarbyl-substituted salicylic acid can be prepared by double decomposition of metal salts in polar solvents such as water or alcohols.

Alkaline earth metal phosphates are also useful as detergents.

Detergents may be simple detergents or may be those known as hybrid or complex detergents. The latter detergent can provide the properties of the two detergents without the need to blend separate materials. See, for example, US Pat. No. 6,034,039.

Preferred detergents include calcium phenate, calcium sulfonate, calcium salicylate, magnesium phenate, magnesium sulfonate, magnesium salicylate and other related ingredients (including borated detergent). Typically, the total detergent concentration is about 0.01 to about 6.0 weight percent, preferably about 0.1 to 0.4 weight percent.

Detergent

During engine operation, oil-insoluble oxidation by-products are produced. Dispersants help keep these byproducts in solution, thus reducing their deposition on the metal surface. Dispersants may be ashless in nature or may form ash. Preferably the dispersant is ashless. So-called ashless dispersants are organic materials that do not substantially form ash upon combustion. For example, non-metal containing or borated metal-free dispersants are considered ashless. In contrast, the metal-containing detergents discussed above form ash upon combustion.

Suitable dispersants typically contain polar groups attached to relatively high molecular weight hydrocarbon chains. Polar groups typically contain at least one element of nitrogen, oxygen or phosphorus. Typical hydrocarbon chains contain 50 to 400 carbon atoms.

Chemically, many dispersants can be considered phenates, sulfonates, sulfurized phenates, salicylates, naphthenates, stearates, carbamates, thiocarbamates, phosphorus derivatives. Particularly useful classes of dispersants are alkenylsuccinic acid derivatives which are typically produced by the reaction of long-chain substituted alkenyl succinic compounds, generally substituted succinic anhydrides with polyhydroxy or polyamino compounds. The long chain group constituting the lipophilic portion of the molecule that confers solubility in oil is generally a polyisobutylene group. Many examples of this type of dispersant are well known commercially and disclosed in the literature. Exemplary U.S. patents that disclose such dispersants are described in US Pat. 3,2145,707; 3,219,666; 3,316,177; 3,341,542; 3,444,170; 3,444,170; 3,454,607; 3,454,607; 3,541,012; 3,541,012; 3,630,904; 3,630,904; 3,632,511; 3,632,511; 3,787,374 and 4,234,435. Other types of dispersants include US Pat. No. 3,036,003; 3,200,107; 3,254,025; 3,254,025; 3,275,554; 3,438,757; 3,454,555; 3,454,555; 3,565,804; 3,565,804; 3,413,347; 3,697,574; 3,725,277; 3,725,480; 3,725,480; 3,726,882; 4,454,059; 3,329,658; 3,449,250; 3,449,250; 3,519,565; 3,519,565; 3,666,730; 3,687,849; 3,702,300; 4,100,082; 4,100,082; 5,705,458. Further description of the dispersant can be found, for example, in European Patent Publication No. 471 071.

Hydrocarbyl-substituted succinic acid compounds are popular dispersants. In particular, succinimides, succinate esters or succinate ester amides prepared by the reaction of at least one equivalent alkylene amine of a hydrocarbon-substituted succinic acid compound having at least 50 carbon atoms in a hydrocarbon substituent are particularly preferred. useful.

Succinimides are formed by condensation reactions between alkenyl succinic anhydrides and amines. The molar ratio can vary depending on the poly-amine. For example, the molar ratio of alkenyl succinic anhydride to TEPA can vary from about 1: 1 to about 5: 1. Representative examples include US Pat. No. 3,087,936; 3,172,892; 3,219,666; 3,272,746; 3,322,670; 3,652,616 and 3,948,800; And Canadian Patent 1,094,044.

Succinate esters are formed by the condensation reaction between alkenyl succinic anhydrides and alcohols or polyols. The molar ratio can vary depending on the alcohol or polyol used. For example, the condensation product between alkenyl succinic anhydride and pentaerythritol is a useful dispersant.

Succinate ester amides are formed by the condensation reaction between alkenyl succinic anhydrides and alkanol amines. For example, suitable alkanol amines include ethoxylated polyalkylpolyamines, propoxylated polyalkylpolyamines and polyalkenylpolyamines such as polyethylene polyamines. One example is propoxylated hexamethylenediamine. Representative examples are shown in US Pat. No. 4,426,305.

The molecular weight of the alkenyl succinic anhydrides used in the previous paragraph will typically range from 800 to 2500. The product may be post-reacted with various reagents such as sulfur, oxygen, formaldehyde, carboxylic acids such as oleic acid and boron compounds such as borate esters or highly borated dispersions. The dispersant may be borated with about 0.1 to about 5 moles of boron per mole of dispersion reaction product.

Mannich base dispersants are prepared from the reaction of alkylphenols, formaldehyde and amines. See US Pat. No. 4,767,551, which is incorporated herein by reference. Processing aids and catalysts such as oleic acid and sulfonic acid may also be part of the reaction mixture. The molecular weight of the alkylphenols is in the range of 800 to 2500. Representative examples include US Pat. No. 3,697,574; 3,703,536; 3,704,308; 3,751,365; 3,756,953; 3,756,953; 3,798,165; 3,798,165; And 3,803,039.

Typical high molecular weight aliphatic acid modified Mannich condensation products useful in the present invention can be prepared from high molecular weight alkyl-substituted hydroxyaromatics or NH (R) ₂ group-containing reactants.

Examples of high molecular weight alkyl-substituted hydroxyaromatic compounds are polypropylphenols, polybutylphenols and other polyalkylphenols. These polyalkylphenols are alkylated with high molecular weight polypropylene, polybutylene and other polyalkylene compounds in the presence of an alkylation catalyst, for example BF ₃ , on the benzene ring of phenols having an average molecular weight of 600 to 100,000 molecular weight. It can be obtained by producing an alkyl substituent.

Examples of HN (R) ₂ group containing reactants are alkylene polyamines, mainly polyethylene polyamines. Other representative organic compounds containing one or more HN (R) ₂ groups suitable for use in the preparation of Mannich condensation products are well known and are mono- and di-amino alkanes, and substituted analogs thereof, such as ethyl Amines and diethanol amines; Aromatic diamines such as phenylene diamine, diamino naphthalene; Heterocyclic amines such as morpholine, pyrrole, pyrrolidine, imidazole, imidazolidine and piperidine; Melamine and substituted analogs thereof.

Examples of alkylene polyamide reactants include ethylenediamine, diethylene triamine, triethylene tetraamine, tetraethylene pentaamine, pentaethylene hexaamine, hexaethylene heptaamine, heptaethylene octaamine, octaethylene nonaamine, nonaethylene deca Amines and decaethylene undecaamines, and the alkylene polyamines in the previously mentioned formula H ₂ N- (Z-NH-) _n H _where Z is divalent ethylene and n is 1 to 10 Mixtures of such amines with a nitrogen content. Corresponding propylene polyamines such as propylene diamine and di-, tri-, tetra-, penta-propylene tri-, tetra-, penta- and hexaamines are also suitable reactants. Alkylene polyamines are generally obtained by reaction of ammonia with dihalo alkanes, for example dichloroalkanes. Thus, alkylene polyamines obtained from the reaction of 2 to 11 moles of ammonia with dichloroalkanes having 1 to 10 moles of 2 to 6 carbon atoms and chlorine on different carbons are suitable alkylene polyamine reactants.

Aldehyde reactants useful in the preparation of high molecular weight products useful in the present invention include aliphatic aldehydes such as formaldehyde (also as paraformaldehyde and formalin), acetaldehyde and aldol (β-hydroxybutyraldehyde). Formaldehyde or formaldehyde generating reactants are preferred.

Hydrocarbyl substituted amine ashless dispersing additives are well known to those skilled in the art, see for example US Pat. No. 3,275,554; 3,438,757; 3,565,804; 3,565,804; 3,755,433; See 3,822,209 and 5,084,197.

Preferred dispersants include borated succinimides and non-borined succinimides and include those derived from mono-succinimides, bis-succinimides and / or mixtures of mono- and bis-succinimides Wherein the hydrocarbyl succinimide is derived from a hydrocarbyl group such as polyisobutylene having a Mn of about 500 to about 5000 or a mixture of such hydrocarbyl groups. Other preferred dispersants include succinic acid-esters and amides, alkylphenol-polyamine-coupled Mannich adducts, capped derivatives thereof, and other related components. Such additives may be used in amounts of about 0.1 to 20% by weight, preferably about 0.1 to 8% by weight.

Supplementary Pour Point Depressant

If necessary, conventional pour point depressants, which are also known as lubricant flow improvers, may be added to the compositions of the present invention. These pour point depressants can be added to the lubricating composition of the present invention to lower the minimum temperature at which the fluid can flow or be poured. Examples of suitable pour point depressants are the polymethacrylates, polyacrylates, polyarylamides, condensation products of haloparaffin waxes and aromatic compounds, vinyl carboxylate polymers, and dialkylfumarates, vinyl esters of fatty acids and allyl vinyl ethers. Copolymers. US Patent No. 1,815,022; 2,015,748; 2,191,498; 2,387,501; 2,387,501; 2,655,479; 2,655,479; 2,666,746; 2,721,877; 2,721,877; 2,721,878; 2,721,878; And 3,250,715 disclose useful pour point depressants and / or their preparation. Such additives may be used in amounts of about 0.00 to 5% by weight, preferably about 0.01 to 1.5% by weight.

Corrosion inhibitor

Corrosion inhibitors are used to reduce the decomposition of metal parts in contact with the lubricating oil composition. Suitable corrosion inhibitors include thiadiazoles. See, for example, US Pat. No. 2,719,125; 2,719,126; 2,719,126; And 3,087,932. Such additives may be used in amounts of about 0.01 to 5% by weight, preferably about 0.01 to 1.5% by weight.

Sealing Compatibility Additives

Seal compatibilizers help the elastomeric seal to swell by causing a chemical reaction in the fluid or by causing a physical change in the elastomer. Suitable sealing compatibilizers for lubricating oils include organic phosphates, aromatic esters, aromatic hydrocarbons, esters (eg butylbenzyl phthalate) and polybutenyl succinic anhydrides. Such additives may be used in amounts of about 0.01 to 3 weight percent, preferably about 0.01 to 2 weight percent.

Antifoam

Advantageously an antifoaming agent can be added to the lubricating composition. These reagents delay the formation of stable foams. Silicones and organic polymers are typical antifoams. Polysiloxanes such as, for example, silicone oils or polydimethyl siloxanes provide antifoam properties. Defoamers are commercially available and can be used in conventional small amounts with other additives such as demulsifiers, and the amount of these additives combined is generally less than 1%, often less than 0.1%.

Inhibitors and Antirust Additives

Antirust additives (or corrosion inhibitors) are additives that protect lubricated metal surfaces from chemical attack by water or other contaminants. A wide variety of these are available commercially, and they can be referred to the above-mentioned Klamann in Lubricants and Related Products.

One type of antirust additive is a polar compound that preferentially wets the metal surface and protects it with an oil film. Another type of antirust additive absorbs water by incorporating water into the water-in-oil emulsion so that only the oil comes into contact with the metal surface. Another type of antirust additive chemically adheres to the metal to create a non-reactive surface. Examples of suitable additives include zinc dithiophosphate, metal phenolates, basic metal sulfonates, fatty acids and amines. Such additives may be used in amounts of about 0.01 to 5% by weight, preferably about 0.01 to 1.5% by weight.

friction Modifier

Friction modifiers are any materials that can change the coefficient of friction of the surface lubricated by any lubricant or fluid containing material. Friction modifiers, also known as friction reducers, lubricants or oilness agents, and such other drugs that change the ability of the base oil, formulated lubricating composition, or functional fluid to change the coefficient of friction of the lubricated surface, may be necessary. It can be effectively used in combination with the base oil or lubricating composition of the invention. Friction modifiers that reduce the coefficient of friction are particularly useful in combination with the base oils and lubricating compositions of the present invention. Friction modifiers may include metal containing compounds or materials, and ashless compounds or materials, or mixtures thereof. The metal-containing friction modifier may comprise a metal salt or a metal-ligand complex, where the metal may comprise an alkali, alkaline earth or transition group metal. Such metal containing friction modifiers may also have low ash properties. The transition metal may include Mo, Sb, Sn, Fe, Cu, Zn and the like. Ligands are alcohols, polyols, glycerol, partial ester glycerol, thiols, carboxylates, carbamates, thiocarbamates, dithiocarbamates, phosphates, thiophosphates, dithiophosphates, amides, imides, amines, thiazoles, thiadiias Hydrocarbyl derivatives of sol, dithiazole, diazole, triazole and other polar molecular functional groups containing an effective amount of O, N, S or P. In particular, Mo-containing compounds such as Mo-dithiocarbamate, Mo (DTC), Mo-dithiophosphate, Mo (DTP), Mo-amine, Mo (Am), Mo-alcolate, Mo-alcohol-amide and the like This is particularly effective. US Patent No. 5,824,627; US Patent No. 6,232,276; US Patent No. 6,153,564; US Patent No. 6,143,701; US Patent No. 6,110,878; US Patent No. 5,837,657; US Patent No. 6,010,987; US Patent No. 5,906,968; US Patent No. 6,734,150; US Patent No. 6,730,638; US Patent No. 6,689,725; US Patent No. 6,569,820; WO 99/66013; WO 99/47629; See WO 98/26030.

Ashless friction modifiers may also include lubricating materials that contain an effective amount of polar groups, such as hydroxyl-containing hydrocarbyl base oils, glycerides, partial glycerides, glyceride derivatives, and the like. The polar groups in the friction modifiers may include hydrocarbyl groups containing, individually or in combination, an effective amount of O, N, S or P. Other friction modifiers that may be particularly effective are, for example, salts of fatty acids (both ash-containing and ashless derivatives), fatty alcohols, fatty amides, fatty esters, hydroxyl-containing carboxylates, and comparable synthetic long chain hydrocarbyl Acids, alcohols, amides, esters, hydroxy carboxylates, and the like. In some instances, fatty organic acids, fatty amines and sulfided fatty acids can be used as suitable friction modifiers.

Useful concentrations of friction modifiers may range from about 0.01% to 10-15% or more, often with a preferred range of about 0.1% to 5% by weight. The concentration of molybdenum-containing material is often disclosed in terms of Mo metal concentration. Advantageous concentrations of Mo may range from about 10 ppm to 3000 ppm or more, often with a preferred range of about 20-2000 ppm, and in some cases a more preferred range of about 30-1000 ppm. All types of friction modifiers can be used alone or as a mixture with the materials of the present invention. Often a mixture of two or more friction modifiers or a mixture of friction modifiers with other surface active materials is also preferred.

COBASE STOCK ( cobasestock )

Cobasestock includes natural oils, synthetic oils and other non-traditional oils and mixtures thereof, which can be used unrefined, refined or refined (also known as recycled or reprocessed oils). have. Unrefined oils are those obtained directly from sources that are not natural, synthetic or customary and are used without further purification. These include, for example, shale oil obtained directly from the retort operation, oils derived from coal, petroleum directly obtained from the primary distillation and ester oils obtained directly from the esterification process. Refined oils are similar to those discussed for unrefined oils, except that the refined oils have undergone one or more refining or conversion steps to improve one or more lubricant properties. Those skilled in the art are familiar with many purification or conversion methods. These methods include, for example, solvent extraction, second distillation, acid extraction, base extraction, filtration, effusion, hydrogenation, hydrorefining, and hydrofinishing. The refined oil is obtained by a method similar to the refined oil, but using the oil previously used.

Groups I, II, III, IV, and V are based on base oil stocks developed and defined by the American Petroleum Institute (API Publication 1509; www.API.org) to create guidelines for lubricating base oils. It is a wide category. Group I base stocks generally have a viscosity index of about 80 to 120 and contain more than about 0.03% sulfur and less than about 90% saturates. Group II base stocks generally have a viscosity index of about 80 to 120 and contain up to about 0.03% sulfur and at least about 90% saturates. Group III stocks generally have a viscosity index of greater than about 120 and contain up to about 0.03% sulfur and more than about 90% saturates. Group IV contains polyalphaolefins (PAO). Group V base stocks include base stocks not included in Groups I through IV. Table A summarizes the properties of each of these five groups.

Base stock properties Saturated Water sulfur Viscosity index I group Less than 90% and / or Greater than 0.03% and 80 or more and less than 120 II group over 90 0.03% or less 80 or more and less than 120 III group over 90 0.03% or less More than 120 IV group Polyalphaolefin (PAO) V group All other base oil stocks not included in groups I, II, III or IV

Natural oils include animal oils, vegetable oils (eg castor oil and lard oil), and mineral oils. Animal and vegetable oils with desirable thermal oxidative stability can be used. Of the natural oils, mineral oils are preferred. Mineral oils are very broad depending on their crude source, for example depending on whether they are paraffinic, naphthenic or mixed paraffin-naphthenic. Oils derived from coal or shale are also useful in the present invention. Natural oils also vary depending on the method used for their preparation and refining, for example, on their distillation range and on whether they are straight run, cracked, hydrorefined or solvent extracted. Do.

Synthetic oils include hydrocarbon oils as well as non-hydrocarbon oils. Synthetic oils are chemical combinations (e.g., polymerization, multimerization, condensation, alkylation, acylation, etc.) in which substances consisting of smaller, simpler species are constructed (ie, synthesized) of substances consisting of larger and more complex molecular species. It can be derived from a process such as. Synthetic oils are hydrocarbon oils such as polymerized olefins and interpolymerized olefins (polybutylene, polypropylene, polyisobutylene (eg ["Polybutenes" JD Fotheringham, Synthetic Lubricants and High-Performance Functional Fluids "). 2nd Edition, ed.LR Rudnick and RL Shubkin, published by Marcel Dekker Inc., NY 1999, p. 357-391), propylene isobutylene copolymers, ethylene-olefin copolymers, ethylene-butene copolymers (eg WO2003 / 07655A1) and ethylene-alpha olefin copolymers) Polyalphaolefin (PAO) oil base stocks are commonly used synthetic hydrocarbon oils, for example C ₈ , C ₁₀ , C ₁₂ , PAOs derived from C ₁₄ olefins or mixtures thereof may be used, see US Pat. Nos. 4,956,122; 4,827,064; and 4,827,073.

The number average molecular weight of PAO, which is a known material and generally available on a commercial scale mainly from suppliers such as ExxonMobil Chemical Company, Chevron, Ineos, etc., can typically vary from about 250 to about 3000 or more, and PAO May be prepared with a viscosity of up to about 100 mm ² / s (100 ° C.). In addition, higher viscosity PAOs are commercially available and can be prepared with viscosities up to about 3000 mm ² / s (100 ° C.) or higher. PAO is typically relatively low molecular weight alpha-hydrogenated polymer or oligomer of an olefin (which does include from about C ₂ to about C ₃₂ alpha-olefins, but not limited to, about C ₈ to about C ₁₆ alpha olefin, e. 1-octene, 1-decene, 1-dodecene, etc. are preferable). Preferred polyalphaolefins are poly-1-octene, poly-1-decene and poly-1-dodecene and mixtures thereof and mixed olefin-derived polyolefins. However, higher oligomer multimers ranging from about C ₁₄ to C ₁₈ can be used to provide a low viscosity base stock of acceptable low volatility. Depending on the viscosity grade and the starting multimer, the PAO may be predominantly trimers and tetramers of the starting olefins and have small amounts of higher multimers having a viscosity in the range of about 1.5 to 12 mm ² / s.

PAO fluids are typically complexes of aluminum trichloride, boron trifluoride, or boron trifluoride with water, alcohols (eg ethanol, propanol or butanol), carboxylic acids or esters (eg ethyl acetate or ethyl propionate) It is prepared by polymerizing an alpha-olefin in the presence of a polymerization catalyst such as Friedel-Crafts catalyst comprising. For example, the methods disclosed in US Pat. No. 4,149,178 or US Pat. No. 3,382,291 can be conveniently used herein. Other disclosures for PAO synthesis are described in US Pat. No. 3,742,082; 3,769,363; 3,876,720; 4,239,930; No. 4,367,352; No. 4,413,156; No. 4,434,408; 4,910,355; No. 4,956,122; And 5,068,487. Dimers of C ₁₄ to C ₁₈ olefins are disclosed in US Pat. No. 4,218,330.

Other useful synthetic lubricating base stock oils can also be used, for example silicon-based oils or esters of phosphorus containing acids. Examples of other synthetic lubricating base stocks are described in "Synthetic Lubricants", Gunderson and Hart, Reinhold Publ. Corp., NY 1962.

Alkylene oxide polymers and interpolymers, and derivatives thereof containing modified terminal hydroxyl groups obtained by, for example, esterification or etherification, are useful synthetic lubricants. For example, these oils are dies of ethylene oxide or propylene oxide, alkyl and aryl ethers of these polyoxyalkylene polymers (methyl-polypropylene glycol ethers having an average molecular weight of about 1000, polyethylene glycols having a molecular weight of about 500 to 1000 phenyl ether, and from about 1000 to 1500 polypropylene glycol diethyl ether) or a mono having a molecular weight of - and poly-carboxylic acid ester (e.g. acidic acid esters, mixed C _{3 -8} fatty acid ester or tetraethylene glycol C ₁₃ oxo acid diester).

Esters include useful base stocks. Additive solubility and sealing compatibility characteristics can be ensured by the use of esters such as esters of dibasic acids with monoalkanols and polyol esters of monocarboxylic acids. Esters of the electronic type are for example dicarboxylic acids, for example phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azlaic acid, suberic acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, mal Esters with various alcohols such as lonic acid, alkyl malonic acid, alkenyl malonic phase, for example butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol and the like. Specific examples of these types of esters include dibutyl adipate, di (2-ethylhexyl) sebacate, di-n-hexyl fumarate, dioctyl sebacate, diisooctyl azlate, diisodecyl azlate, dioctyl Phthalates, diedecyl phthalates, diecosyl sebacates and the like.

Particularly useful synthetic esters include one or more polyhydric alcohols (preferably hindered polyols such as neopentyl polyols such as neopentyl glycol, trimethylol ethane, 2-methyl-2-propyl-1,3-propanediol , Trimethylol propane, pentaerythritol and dipentaerythritol) and alkanoic acid having at least about 4 carbon atoms (preferably C ₅ to C ₃₀ acids, for example caprylic acid, capric acid, lauric acid, myristic) Full or partial esters obtained by reacting saturated straight fatty acids, or corresponding branched or unsaturated fatty acids such as oleic acid), including acids, palmitic acid, stearic acid, arachnic acid and behenic acid.

Suitable synthetic ester components include esters with one or more monocarboxylic acids containing about 5 to about 10 carbon atoms of trimethylol propane, trimethylol butane, trimethylol ethane, pentaerythritol and / or dipentaerythritol. Include.

Silicon-based oils are another class of useful synthetic lubricants. These oils include polyalkyl-, polyaryl-, polyalkoxy- and polyaryloxy-siloxane oils and silicate oils. Examples of suitable silicon-based oils are tetraethyl silicate, tetraisopropyl silicate, tetra- (2-ethylhexyl) silicate, tetra- (4-methylhexyl) silicate, tetra- (p-tert-butylphenyl) silicate, hexyl- (4-methyl-2-pentoxy) disiloxane, poly (methyl) siloxane and poly- (methyl-2-methylphenyl) siloxane.

Another class of synthetic lubricants is esters of phosphorus-containing acids. These include, for example, tricresyl phosphate, trioctyl phosphate, diethyl ester of decanephosphonic acid.

Other classes of synthetic oils include polymerizable tetrahydrofuran, derivatives thereof, and the like.

Other useful fluids of lubricating viscosity include non- customary or non- customary base stocks that are processed, preferably catalytically processed, or synthesized to provide high performance lubrication properties.

Typical additive amount

If the lubricating oil composition contains one or more of the additives discussed above, the additive is blended into the composition in an amount sufficient to perform the intended function. Typical amounts of such additives useful in the present invention are shown in Table B below.

It should be noted that many additives are shipped from the manufacturer and used with a certain amount of base oil solvent in the formulation. Thus, the weights in the tables below, as well as the other amounts mentioned herein, relate to the amount of the active ingredient (ie, the non-solvent portion of the ingredient) unless otherwise indicated. The weight percentages indicated below are based on the total weight of the lubricating oil composition.

Typical amount of various lubricant components compound Approximate weight percent (useful amount) Approximate weight percent (preferred) Detergent 0.01 to 6 0.01 to 4 Dispersant 0.1 to 20 0.1 to 8 Friction reducer 0.01 to 5 0.01 to 1.5 Antioxidant 0.0 to 5 0.0 to 1.5 Corrosion inhibitor 0.01 to 5 0.01 to 1.5 Wear resistant additives 0.01 to 6 0.01 to 4 Supplementary Pour Point Depressant 0.0 to 5 0.01 to 1.5 Antifoam 0.001 to 3 0.001 to 0.15 Nose-Base Stock 0 to 90 0 to 50 Base oil Remainder Remainder

In the examples, the following fluid properties were measured according to standard ASTM methods:

(a) Dynamic viscosity at 40 ° C. and 100 ° C. by ASTM 445 method in cSt (mm ² / s). Herein, all fluid viscosities are 100 ° C. viscosities unless otherwise specified.

(b) Pour point by the ASTM D97 method or equivalent automated method.

(c) Aniline point by ASTM D611 method.

(d) Rotary Bomb Oxidation of Turbine Oil at 150 ° C. by ASTM D2272 Method.

(e) Oxidation tests were performed by purging oil samples with air at 325 ° C. for 40 hours in the presence of copper, iron and lead metals. Oxidative stability was assessed by viscosity increase, change in total acid value, sludge grade and lead loss amount.

(f) A thermal stability test was performed by heating a small amount of oil sample sealed inside a metal container for 24 hours to 300 ° C. or to an appropriate test temperature. Thermal stability was measured by the rate of viscosity reduction and the weight loss during thermal decomposition into volatile components.

The alkylated naphthalenes used in the examples below are described below. AN5 was prepared according to the method disclosed in US Patent 5034563.

Prepared by reacting naphthalene with 1-hexadecene olefin on a USY catalyst. AN12 was prepared by reacting naphthalene with 1-tetradecene using a catalytic amount of trifluoromethane sulfonic acid. Starting with multimerizing a mixture of C ₈ , C ₁₀ and C ₁₂ linear alpha olefins on a BF ₃ catalyst promoted according to the method disclosed in US Pat. No. 6,071,864 to produce the product, this is further the same catalyst as olefin multimerization. Alkylmethylbenzene was synthesized by reaction with toluene (methylbenzene) at the same reaction temperature in the phase. The product was isolated to produce a lubricating base stock fluid having the viscosity and pour point listed in the table below (which also shows the properties of C ₁₂ alkylbenzenes prepared according to Example 7).

Example 1

In the examples various base stocks were used to blend with alkyl naphthalene fluids, and these base stocks in combination with various amounts of alkylated naphthalene fluid AN5 show the effect on the pour point (reported in ° C.) in the table below. .

As shown, if alkylated naphthalene (AN5) is blended with API I or III group base stocks, there is no synergistic improvement of the pour point. The pour point of this blend is lower, but the lower amount is never lower than the pour point of the AN base stock. When combined with PAO, AN actually degrades pour point performance. However, when AN is blended with GTL-6 (having a pour point of −21 ° C.), the pour point improvement associated with the blend is not linear (see FIG. 1 and Table 3). The data in Table 3 demonstrated that the oxidative stability of the blended oils was also synergistically improved compared to pure GTL-6. When 5% An5 was added, the RBOT improved from 68 minutes to 102 minutes. When 20% AN5 was added, the RBOT improved to 132 minutes. This further proved the goodness of the blend.

Example 2

Various amounts of AN5 (disclosed above) were combined with GTL-14 (nominal dynamic viscosity of 14 mm ² / s at 100 ° C.). The results are shown in Table 4 below:

As can be seen, the pour point of the GTL was still synergistically improved by adding alkylated naphthalene fluid.

Example 3

Various amounts of AN12 (disclosed above) were combined with GTL-6. The results are shown in Table 5 below:

Again, the addition of alkylated naphthalene, in this case high viscosity AN to GTL (GTL-6), appears to produce a blend that exhibits a non-linear decrease in pour point. In addition, the oxidative stability of the blend was synergistically improved. When 20% by weight of AN12 was added, the RBOT increased from 68 minutes to 111 minutes.

Example 4

In this example AN5 was fully hydrogenated for 16 hours using 2 wt% nickel on a Kiselguhr catalyst in the presence of 800 psi H2 pressure to produce a hydrogenated AN5 fluid (alkyl cycloparaffin fluid). This fluid was blended with various amounts of GTL-6 and the results are reported in Table 6 below.

As shown, fully hydrogenated alkylcycloparaffinic fluids derived from alkyl naphthalene have the same effect on the pour point of the blend and the pour point of the blend is non-linearly reduced.

Example  5

Alkylmethylbenzene fluids (ArPAO) were prepared and combined with various amounts of GTL-6. Alkylmethylbenzene was prepared by first multimerizing a mixture of C ₈ , C ₁₀ and C ₁₂ linear alpha olefins to give a multimer on a promoted BF3 catalyst. After hydrogenation at 600 psi H ₂ pressure, 200 ° C. on a standard hydrogenation catalyst, diatomaceous earth catalyst, a high boiling fraction,> 750 ° F. (398.8 ° C.), was isolated as a high quality PAO base stock. Lighter multimers with boiling points below 750 ° F. were separated by distillation. This light fraction generally contains olefins having less than 24 carbons. These light olefin multimers were then further reacted with toluene on similar promoted BF ₃ catalysts such as those used in the multimer stage. The resulting alkylmethylbenzene fluid had excellent VI, pour point, thermal and oxidative stability. This alkylmethylbenzene fluid was combined with GTL-6 in various amounts. The results are shown in Table 7 and FIG. 1.

As shown, the pour point of GTL-6 was lowered by the addition of alkylmethylbenzene fluid.

Example 6

A hydrogenated version of the alkylmethylbenzene fluid of Example 5 was prepared by hydrogenating the fluid for 8 hours using 2 wt% nickel (50% nickel metal content) on a diatomaceous earth catalyst at 200 ° C., 800 psi H ₂ pressure. The hydrogenated alkylmethylbenzene fluid is combined with various amounts of GTL-6 and the results are shown in Table 8 below.

Again, a drop in the pour point of the GTL appears.

Example 7

Alkylbenzene fluids were prepared by alkylating benzene with 1-dodecene on zeolite MCM22 according to the general method as disclosed in US Pat. No. 4,962,256. The properties of this fluid are summarized in Table 1. This fluid was blended with GTL6 and the blend properties are shown in Table 9 below. Again, these data demonstrated that the low pour point alkylaromatic fluids mentioned in the present invention, when combined with GTL derived base stocks, improved the pour point of the blend stock.

Comparative Example 1

C ₂₀ -C ₂₄ alkyl benzene fluids were prepared according to the disclosure of US Pat. No. 6,627,779. C ₂₀ -C ₂₄ alkyl benzene was blended with GTL-6 and the pour points of the individual fluids and various blends are reported in Table 10 and FIG. 1 below.

As shown, C ₂₀ -C ₂₄ alkyl benzene of US Pat. No. 6,627,779 exhibited a high pour point, did not lower the pour point of the GTL fluid in any way, and all blends were compared with the data shown in Tables 6 and 7 It did not show any change in the pour point or significantly increased the pour point.

Comparative example  2

Ester (ester 5) having a nominal dynamic viscosity of 5 mm ² / s at 100 ° C. was blended with GTL-6 in various amounts and the results are shown in Table 11 and FIG. 1 below.

As shown, despite having a pour point of less than -61, ester 5 had substantially no effect on the pour point of GTL-6 at 5 and 20 wt% treatment levels, and treatment of 60 wt% ester 5 The fact that the pour point of GTL at the level was lowered from -21 ° C to -33 ° C clearly demonstrates that there is no significant pour point lowering effect and no synergistic effect as with alkylated naphthalene. Since only the second additional fluid has a low pour point, this does not automatically mean that adding such a low pour point fluid to a higher pour point fluid will produce a mixture with a significantly lower pour point than the high pour point fluid. Thus, the results of the present invention secured using alkylated naphthalene and alkylbenzene synthesis fluids as disclosed herein are truly surprising and unpredictable.

Claims (24)

Gas-to-Liquids (GTL) lubricated base stock / base oil, hydrodeleaded or hydroisomerized / catalyst (and / or solvent) deleadated waxy feed lubricated base stock / base oil or mixtures thereof at 100 ° C. GTL lubrication by adding about 1-95% by weight of a synthetic alkylated naphthalene fluid having a dynamic viscosity in the range of about 1.5 mm ² / s to about 600 mm ² / s, a pour point below 0 ° C., and a viscosity index in the range of 0 to 200 A method of lowering the pour point of a base stock / base oil, a hydrodewaxed or hydroisomerized / catalyzed (and / or solvent) waxed feed lubricating base stock / base oil or mixtures thereof. The method of claim 1, Low pour point base stock / base oil is GTL base stock / base oil. The method of claim 1, The low pour point base stock / base oil is a hydrodegreased Fischer-Tropsch wax lubricated base stock / base oil. The method of claim 1, Low pour point base stock / base oil is a hydroisomerized / catalyzed (and / or solvent) deleased Fischer-Tropsch wax lubricated base stock / base oil. The method according to any one of claims 1 to 4, Wherein the alkylated naphthalene has the formula Formula 1

Where n + m is an integer from 1 to 8, R is a C ₁ -C ₃₀ linear alkyl group, a C ₃ -C ₃₀₀ branched alkyl group, or a combination thereof, and the total number of carbons of R _m and R _n is 4 or more. The method of claim 5, wherein n + m is an integer from 1 to 6. The method of claim 5, wherein R is a C ₁ -C ₂₀ linear alkyl group, a C ₃ -C ₁₀₀ branched alkyl group, or a combination thereof. The method of claim 7, wherein R is a branched alkyl group containing at least 4 carbons and n + m is 1 or 2. The method according to any one of claims 1 to 4, Wherein the alkylated naphthalene is hydrogenated. The method of claim 7, wherein Alkylated naphthalene is mono-, di-, tri-, tetra- or penta-C ₃ alkyl naphthalene, C ₄ alkyl naphthalene, C ₅ alkyl naphthalene, C ₆ alkyl naphthalene, C ₈ alkyl naphthalene, C ₁₀ alkyl naphthalene, C ₁₂ Alkyl naphthalene, C ₁₄ alkyl naphthalene, C ₁₆ alkyl naphthalene, C ₁₈ alkyl naphthalene, mono-, di-, tri-, tetra- or penta-C ₃ alkyl monomethyl, dimethyl, ethyl, diethyl or methyl ethyl naphthalene, C ₄ alkyl monomethyl, dimethyl, ethyl, diethyl or methyl ethyl naphthalene, C ₅ alkyl monomethyl, dimethyl, ethyl, diethyl or methyl ethyl naphthalene, C ₆ alkyl monomethyl, dimethyl, ethyl, diethyl or Methyl ethyl naphthalene, C ₈ alkyl monomethyl, dimethyl, ethyl, diethyl or methyl ethyl naphthalene, C ₁₀ alkyl naphthalene, C ₁₂ alkyl monomethyl, dimethyl, ethyl, diethyl or methyl ethyl naphthalene, C ₁₄ al Cyl monomethyl, dimethyl, ethyl, diethyl or methyl ethyl naphthalene, C ₁₆ alkyl monomethyl, dimethyl, ethyl, diethyl or methyl ethyl naphthalene, C ₁₈ alkyl monomethyl, dimethyl, ethyl, diethyl or methyl ethyl Naphthalene, C ₂₄ -C ₅₆ branched alkyl naphthalene or C ₂₄ -C ₅₆ branched alkyl mono, di-, tri-, tetra- or penta-C ₁ -C ₄ naphthalene and mixtures thereof. The method of claim 10, Wherein the alkylated naphthalene is hydrogenated. Gas-to-Liquids (GTL) lubricated base stock / base oil, hydrodeleaded or hydroisomerized / catalyst (and / or solvent) deleadated waxy feed lubricated base stock / base oil or mixtures thereof at 100 ° C. GTL lubrication by adding about 1 to 95% by weight of an alkylated benzene synthesis fluid having a dynamic viscosity in the range of about 1.5 mm ² / s to about 600 mm ² / s, a pour point below 0 ° C., and a viscosity index in the range of 0 to 200 A method of lowering the pour point of a base stock / base oil, a hydrodewaxed or hydroisomerized / catalyzed (and / or solvent) waxed feed lubricating base stock / base oil or mixtures thereof. The method of claim 12, Low pour point base stock / base oil is GTL base stock / base oil. The method of claim 12, The low pour point base stock / base oil is a hydrodegreased Fischer-Tropsch wax lubricated base stock / base oil. The method of claim 12, Low pour point base stock / base oil is a hydroisomerized / catalyzed (and / or solvent) deleased Fischer-Tropsch wax lubricated base stock / base oil. The method according to any one of claims 12 to 15, Wherein the alkylated benzene has the formula Formula 2

Where x is an integer from 1 to 6, R is a C ₁₀ to C ₃₀ linear alkyl group, a C ₁₀ to C ₃₀₀ branched alkyl group or a combination thereof, If x is 2 or more, at least one of the R groups may be a C ₁ -C ₅ alkyl group provided that at least one additional alkyl group is a C ₁₀ to C ₃₀ linear alkyl group or a C ₁₀ to C ₂₀₀ branched alkyl group or combinations thereof have. The method of claim 16, x is an integer from 1 to 5. The method of claim 16, Alkylated benzene has a pour point below -35 ° C The method of claim 16, The alkylated benzene is an alkyl methyl benzene prepared by multimerizing a mixture of C ₈ , C ₁₀ and C ₁₂ linear alpha olefins on a catalyst to produce a multimer product, which is then arylated with toluene on the catalyst. At least one lubricant stock selected from a GTL lubricated base stock / base oil, a hydrodeleaded or hydroisomerized / catalyzed (and / or solvent) waxed feed lubricating base stock / base oil, and from about 1 to about at 100 ℃ of 95% by weight of about 1.5mm ² / s to about 600mm ² / s, the lubricating oil containing the alkylated benzene synthetic fluid having a kinematic viscosity, a pour point of 0 to 200 range below 0 ℃ viscosity index in the range of Base oil for the composition. The method of claim 20, Base oils where the lubricant stock is a GTL base stock / base oil. The method of claim 20, Base oil wherein the lubricating oil stock is a hydrodegreased Fisher-Tropsch wax lubricating base stock / base oil. The method of claim 20, Base oil wherein the alkylated benzene has a pour point below -35 ° C. The method of claim 20 or 23, Base oil wherein alkylated benzene is alkyl methyl benzene prepared by multimerizing a mixture of C ₈ , C ₁₀ and C ₁₂ linear alpha olefins on a catalyst to produce a multimer product, which is then arylated with toluene on the catalyst.

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