EP2132156B1 - Liquides lubrifiants alkylaromatiques - Google Patents

Liquides lubrifiants alkylaromatiques Download PDF

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EP2132156B1
EP2132156B1 EP08726928.8A EP08726928A EP2132156B1 EP 2132156 B1 EP2132156 B1 EP 2132156B1 EP 08726928 A EP08726928 A EP 08726928A EP 2132156 B1 EP2132156 B1 EP 2132156B1
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substituted
unsubstituted
alkylaromatic
process according
olefin
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EP2132156A1 (fr
EP2132156A4 (fr
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Beth A. Yoon
Margaret M. Wu
Christine N. Elia
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ExxonMobil Technology and Engineering Co
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ExxonMobil Research and Engineering Co
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/02—Well-defined hydrocarbons
    • C10M105/06—Well-defined hydrocarbons aromatic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M127/00—Lubricating compositions characterised by the additive being a non- macromolecular hydrocarbon
    • C10M127/06—Alkylated aromatic hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/06—Well-defined aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/06—Well-defined aromatic compounds
    • C10M2203/065—Well-defined aromatic compounds used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/22—Alkylation reaction products with aromatic type compounds, e.g. Friedel-crafts
    • C10M2205/223—Alkylation reaction products with aromatic type compounds, e.g. Friedel-crafts used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00—Specific manufacturing methods for lubricant compositions

Definitions

  • the present disclosure relates to novel alkylaromatic compositions useful as lubricant basestocks and additives. More particularly, the compositions of the present disclosure are quaternary-substituted alkylaromatic compositions that have improved thermo- and oxidative stability prepared by alkylating aromatics with vinylidene-containing olefins. The present disclosure also relates to processes for producing alkylaromatic compositions that employ acidic alkylation catalysts.
  • a lubricant is a substance capable of reducing friction, heat and wear when introduced as a film between solid surfaces.
  • Efforts to improve upon the performance of mineral oil based lubricants have been the focus of important research and development activities in the petrochemical industry for over 50 years. Maintenance of friction reducing properties, extended useful life in terms of thermal and oxidative stability and wear protection, improved viscosity index and pour point equal to or better than mineral oil are performance areas where research and development activities have occurred.
  • These efforts have led to the introduction of a number of synthetic fluids including polyalpha-olefin (PAO) synthetics primarily made by oligomerization of alpha-olefins or 1-alkenes.
  • PAO polyalpha-olefin
  • Synthetic fluids is a term that can describe materials useful as lubricants, heat transfer agents, and corrosion inhibition among other uses.
  • PAO synthetic fluids compositions are saturated hydrocarbons and thus are less polar than mineral oil based compositions that can contain polar moieties including aromatics.
  • a polar co-basestock is added to the composition to help dissolve polar additives of the composition and sludge during usage.
  • a polar co-basestock such as ester or alkylaromatics is used in amounts of about 3 to about 50 weight percent of the basestock composition.
  • polar co-basestock could introduce undesirable side effects such as hydrolytic instability if an ester co-basestock is used or poorer low temperature properties, reduced cleanliness properties if typical alkylaromatic co-basestocks are used.
  • Finished synthetic lubricants are often formulated with additives to enhance their properties for specific applications. Additives that are commonly used can include oxidation inhibitors, dispersants, detergents, rust inhibitors, antiwear agents, extreme pressure agents, metal passivators, pour point depressants, viscosity index (VI) improvers, and the like.
  • formulated fluids are compositions comprising a number of components, the largest volume component being the fluid basestock.
  • Alkylaromatic compounds have been known for many years.
  • US Patent No. 6,491,809 (Briot et al. ) discloses the alkylation of aromatic compounds (e.g., benzene, toluene, cumene) by alkylating agents (e.g., olefins, alcohol, halides) for producing aromatic monoalkyls whose grafted aliphatic chain comprises a carbon number that is selected from 2 to 20 carbons.
  • alkylating agents e.g., olefins, alcohol, halides
  • PAOs can be produced by reacting an olefin feed in the presence of a catalyst such as AlCl 3 , BF 3 , or promoted BF 3 .
  • a catalyst such as AlCl 3 , BF 3 , or promoted BF 3 .
  • Processes for the production of PAOs are disclosed, for example, in the following patents: U.S, Pat. Nos. 3,149,178 ; 3,382,291 ; 3,742,082 ; 3,769,363 ; 3,780,128 ; 4,172,855 ; and 4,956,122 .
  • Novel PAO lubricant compositions in which little double bond isomerization is found has resulted in different classes of high viscosity index PAO (HVI-PAO).
  • reduced chromium catalyst is reacted with an alpha-olefin monomer.
  • Such PAOs are described in U.S. Pat Nos. 4,827,073 ; 4,827,064 ; 4,967,032 ; 4,926,004 ; and 4,914,254 .
  • HVI-PAOs compositions prepared by contacting one or more alpha-olefins monomers having 3 to 24 carbons atoms with a transition metal compound, an anion activator and an alkyl aluminum compound.
  • the novel compositions conform to the unique specificity of the HVI-PAO oligomerization reaction in that little double bond isomerization occurs.
  • Such HVI-PAOs are described in PCT Patent Publication Nos. W02007011462 A1 and W02007011832 A1 .
  • Novel compositions of low viscosity PAOs can also be prepared from metallocene catalysts as taught in U.S. Patents 5,688,887 and 6,043,401 and PCT Patent Publication No. WO2007011973 A1 . Separation of the low molecular weight material, representing non-lube range molecular weight material, is necessitated to control product volatility and viscosity. As oligomerization conditions are changed to produce the lower viscosity products of lower average molecular weight, the non-lube range dimer or light end fraction increases. The increase in dimer by-product yield represents a substantial economic burden on the overall process to produce useful lower viscosity lubricant in the process.
  • the present disclosure relates to an alkylaromatic compositions comprising an aromatic moiety other than unsubstituted naphthalene; and an alkyl moiety having a carbon atom number in the range between 16 to 40, wherein said alkyl moiety is attached to said aromatic moiety such that at least 25 mol% of the benzylic carbons are quaternary.
  • the present disclosure also includes a process for the preparation of an alkylaromatic compound comprising: contacting at least one an aromatic compound and a mono-olefin having a carbon atom number in the range between 16 to 40 in the presence of an acidic alkylation catalyst under alkylation conditions, wherein at least 50 mol% of the mono-olefin comprises a vinylidenyl structure and thereby producing said alkylaromatic compound having at least 25 mol% of benzylic carbons that are quaternary.
  • the present disclosure also provides a process for the utilization of the by-product from the metallocene process to produce a novel synthetic lubricant fluid.
  • the present disclosure provides useful alkylaromatic fluid compositions that have thermal and oxidative stability.
  • the present disclosure provides useful lubricant additives from aromatics alkylation by using vinylidene containing low molecular weight olefins as the alkylating agent.
  • the mono-olefin may be derived from the non-lubricant of metallocene-catalyzed alpha olefin polymerization process.
  • Monoolefins derived in other manners with a significant amount of vinylidene may also be advantageous.
  • Olefins suitable for the preparation of the dimers or mixtures of dimers, trimers and the like contain from about 3 to 20 carbons, such as 1-propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, and 1-hexadecene or branched olefins such as 4-methyl-1-pentene or mixtures thereof.
  • the mono-olefin is a vinylidene with a carbon atom number less than 30 and may be a mixture of olefins with a significant amount of vinylidenes or trisubstituted olefins. Generally, at least 50 mol% , or at least 55 mol%, or at least 60 mol%, or at least 65 mol%, of the mono-olefin comprises a vinylidenyl structure.
  • the aromatic compound may be benzene, furan, thiophene, anthracene, phenanthrene, pyrole, indole, benzothiophene, dibenzothiophene, benzofuran, dibenzofuran, phenoxathiin, thianthrene, biphenyl, pyrene, and mixtures thereof, each of which can be optionally substituted.
  • the aromatic compound may be toluene, o-, or p-xylene, hydroxyl benzene, alkoxybenzene such as methoxy or ethoxybenzene, thioanisole, diphenylether, diphenylmethane, bisphenol-A, bisphenol sulfide, diphenyl sulfide, methylnaphthalene, methoxynaphthalene, ethoxynaphthalene, methylnaphthal sulfide, ethyl naphthylsulfide, or mixtures thereof.
  • the aromatic compound may be substituted benzene or substituted naphthalene.
  • aromatic hydrocarbons including substituted aromatic hydrocarbons
  • olefins containing a significant amount of vinylidene substitution (generally, at least 50 mol% , or at least 55 mol%, or at least 60 mol%, or at least 65 mol%, of the mono-olefin includes vinylidene).
  • olefins can be from the non-lube range oligomers made during the metallocene-low viscosity alpha olefin polymerization process (reaction A).
  • the olefins used in the alkylation have a significant amount of vinylidene isomers.
  • the solid state acid catalysts such as zeolites or Friedel Crafts alkylation catalysts such as AlCl 3 or BF 3 are used to catalyze the alkylation.
  • the resulting novel compositions contain a significant amount of quaternary substitution at the benzylic carbon.
  • the compositions exhibit excellent additive solubilizing properties.
  • selected compositions can be prepared by a high activity zeolite catalyst, a one or two ring aromatic substrate, and a vinylidene olefin that is a by-product from the metallocene-catalyzed alpha-olefin polymerization process.
  • the metallocene-catalyzed PAO process consists of the oligomerization of 1-alkenes in contact with a metallocene type catalyst.
  • a characteristic of the oligomerization reaction from which these vinylidene olefin by-products are produced is the production of mixtures of dialkyl vinylidenic and 1,2 dialkyl or trialkyl mono-olefin oligomers as determined by infrared and NMR analysis.
  • olefinic compositions having 16 to 40 carbon atoms may be used in the processes of the present disclosure, including olefin oligomers from the acid or metallocene catalyzed oligomerization of alkenes including, for example, propylene and/or butenes and/or pentenes.
  • alkenes including, for example, propylene and/or butenes and/or pentenes.
  • vinylidene-containing trimers or higher order are also advantageous.
  • Other processes that form olefinic precursors enriched in vinylidenes can also be used.
  • Acidic catalysts capable of affecting alkylation of aromatics with olefins include acidic halides (Lewis acids), protonic acids (Bronsted acids), cation exchange resins, Friedel Crafts catalysts, and solid acids including zeolites.
  • high activity zeolites may be effective.
  • Non-limiting exemplary high activity zeolites with surface acidity useful for preparing alkylaromatic compositions that are useful as liquid lubricant compositions and additives include, but are not limited to, MCM-22, MCM-36, MCM-49, MCM-56, ITQ-1, ITQ-3 and any combination thereof.
  • Non-limiting exemplary Lewis acids include aluminum chloride, aluminum bromide, iron (III) chloride, zinc chloride, boron trifluoride and others.
  • Non-limiting exemplary Bronsted acids include sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, phosphoric acid and others.
  • Aromatic compounds which may be used in the present disclosure include substituted and unsubstituted one and two ring aromatics and mixtures thereof.
  • the aromatic moiety is at least one chosen from: benzene, toluene, xylenes, and ethylbenzene.
  • Suitable aromatic compounds include, but are not limited to, substituted or unsubstituted benzene, substituted naphthalene, substituted or unsubstituted furan, substituted or unsubstituted thiophene, substituted or unsubstituted anthracene, substituted or unsubstituted phenanthrene, substituted or unsubstituted pyrole, substituted or unsubstituted indole, substituted or unsubstituted benzothiophene, substituted or unsubstituted dibenzothiophene, substituted or unsubstituted benzofuran, substituted or unsubstituted dibenzofuran, substituted or unsubstituted phenoxanthiin, substituted or unsubstituted thianthrene, substituted or unsubstituted biphenyl, substituted or unsubstituted pyrene, bisphenol A, bisphenol sulfide,
  • the aromatic compound is benzene, toluene, o-, m- or p-xylene, hydroxybenzene, alkoxybenzene such as methoxy or ethoxybenzene, thioanisole, diphenylether, diphenylmethane, diphenyl sulfide, methylnaphthalene, methoxynaphthalene, ethoxynaphthalene, methylnaphthyl sulfide, ethyl naphthylsulfide, bisphenol-A, bisphenol sulfide or a mixture thereof.
  • the aromatic compound can be substituted. Suitable substituent groups include alkyl, hydroxy, alkoxy such as methoxy or ethoxy, aroxy such as phenoxy, alkylthio such as methanethio, arylthio such as phenylthio, and aralkyl such as benzyl.
  • the aromatic compound is a mono-substituted benzene, for example toluene, or a disubstituted benzene, for example para-, meta- or ortho-xylene.
  • the amount of catalyst charged to a reactor relative to the olefinic material is 0.1% to 20%, preferably 0.5% to 5%.
  • the mole ratio of aromatic compound e.g., benzene, naphthalene, 1,2,4-trimethylbenzene to olefin starting material is typically between 1:3 and 20:1, preferably 1:2 to 10:1, but depending on the degree of alkylation of the aromatic which is desired, the ratio may be altered accordingly.
  • the catalyst is charged in a slurry reactor.
  • the reaction may be carried out in a fixed-bed continuous operation wherein the catalyst is in pellet or extruded form and packed in a tubular reactor heated to a desirable temperature.
  • the feed is introduced at a specific weight hourly space velocity (WHSV) ranging from about 0.1 to about 20, preferably from about 0.5 to about 5, to achieve a high conversion.
  • WHSV weight hourly space velocity
  • An effective reaction temperature for the preparation of the alkylaromatic compositions is, for example, between room temperature and 350 °C, advantageously between 75 °C and 350 °C. Above 200 °C, the catalyst may affect isomerization, therefore a more advantageous temperature is below 200°C.
  • Preferred reaction conditions include a pressure of from about 1 to about 30 atmospheres, a preferred catalyst charge from about 1 wt% to about 5 wt% in a slurry reactor or a WHSV of about 0.2 to about 4 in a fixed bed continuous operation.
  • the reactants can be in either the vapor phase or the liquid phase and can be neat, i.e., free from intentional admixture or dilution with other material, or they can be brought into contact with the catalyst composition with the aid of carrier gases or diluents such as , for example, hydrogen or nitrogen.
  • the alkylation can be carried out as a batch-type reaction typically employing a closed, pressurized, stirred reactor with an inert gas blanketing system or in a semi-continuous or continuous operation utilizing a fixed or moving bed catalyst system.
  • a Friedel Crafts catalyst when used to affect the alkylation ( US Patent 6,071,864 ), e.g., AlCl 3 or promoted BF 3 , process conditions may be carried out a temperature between -30 and 350 °C, typically at a temperature between 30 °C and 90 °C with a pressure typically between 700 and 7000 kPA. As conditions become more severe the Friedel Crafts catalysts causes isomerization of the vinylidene olefin so that the alkylaromatic product will contain a decreased amount of quaternary substituted alkylated aromatic.
  • the alkylation can be carried out as a batch-type reaction typically employing a closed, pressurized, stirred reactor with an inert gas blanketing system or in a semi-continuous or continuous operation.
  • any means of separation that will provide a useful liquid alkylaromatic composition may be utilized.
  • a useful separation scheme following the alkylation of an aromatic is to use an excess of the lighter boiling hydrocarbon, for example, an aromatic and run the alkylation experiment until all of the olefin (vinylidene or other C16-C40 olefin) has been consumed. Then the liquid composition can be separated from the acidic zeolite by ordinary means such as gravity separation or filtration and the unreacted aromatic can be separated from the liquid composition by vacuum distillation and recycled.
  • the reaction mixture can be quenched with a dilute acid or base solution, washed with water and dried as described in US Patents 5,254,274 and 6,071,864 .
  • the product of the alkylation has reduced bromine number compared to the starting olefin, mild hydrotreating of residual olefin or dimer co-product is an option.
  • the alkylaromatic products may have the following non-limiting structures: wherein a significant portion of at least one R group is the radical R 2 R 3 CCH 3 and wherein R has from 16 to 40 carbons, or 16 to 24 carbons and R 2 and R 3 are alkyl groups.
  • R group is the radical R 2 R 3 CCH 3 and wherein R has from 16 to 40 carbons, or 16 to 24 carbons and R 2 and R 3 are alkyl groups.
  • R 2 and R 3 are alkyl groups.
  • the amount of quaternary substituted aromatic was estimated from assignments determined by NMR DEPT experiments.
  • the alkyl moiety attached to the aromatic moiety may be such that at least 25 mol% of the benzylic carbons are quaternary or such that at least 30 mol% of the benzylic carbons are quaternary, or such that at least 35 mol% of the benzylic carbons are quaternary, or such that at least 40 mol% of the benzylic carbons are quaternary, or such that at least 50 mol% of the benzylic carbons are quaternary, or such that at least 70 mol% of the benzylic carbons are quaternary
  • Other aromatic structures that may be obtained using alternative olefins could result in quaternary substitution such as the general structure: where R 1 , R 2 , and R 3 are alkyl groups and R 4 is a hydrogen or alkyl group.
  • Monoalkylated aromatics are the primary product disclosed herein, although multi-substituted aromatic compositions and olefin-olefin products may also be formed.
  • the presence of non-quaternary alkylated aromatics are also present under the condition of isomerization of the olefin or the presence of non-vinylidene olefin reactants.
  • alkylaromatic compositions having quaternary benzylic carbon at sufficiently high levels (defined as at least 25 mol% of the benzylic carbons are quaternary, or such that at least 30 mol% of the benzylic carbons are quaternary, or such that at least 35 mol% of the benzylic carbons are quaternary, or such that at least 40 mol% of the benzylic carbons are quaternary, or such that at least 50 mol% of the benzylic carbons are quaternary, or such that at least 70 mol% of the benzylic carbons are quaternary), such as to provide improved thermal and oxidative stability to the composition.
  • An illustrative example of an alkylaromatic composition from the present disclosure having thermal and oxidative stability is a composition where a significant amount (defined as at least 25 mol% of the benzylic carbons are quaternary. or such that at least 30 mol% of the benzylic carbons are quaternary, or such that at least 35 mol% of the benzylic carbons are quaternary, or such that at least 40 mol% of the benzylic carbons are quaternary, or such that at least 50 mol% of the benzylic carbons are quaternary, or such that at least 70 mol%) of the benzylic carbons are quaternary.
  • alkylaromatic compositions made from an aromatic moiety of unsubstituted naphthalene exhibit an oxidative stability as measured by RBOT of greater than 150, or greater than 155, or greater than 160, or greater than 165 minutes.
  • Alkylaromatic compositions made from an aromatic moiety of toluene exhibit an oxidative stability as measured by RBOT of greater than 30, or greater than 35, or greater than 40, or greater than 45 minutes.
  • alkylaromatic compositions made from an aromatic moiety of benzene exhibit an oxidative stability as measured by RBOT of greater than 20, or greater than 25, or greater than 30, or greater than 35 minutes.
  • the greater the degree of branching and greater the chain length of the alkyl moiety yields a lower RBOT (poorer oxidative stability).
  • compositions including alkylaromatic compositions useful as liquid lubricant compositions must be liquid over a wide temperature range.
  • the pour point is the lowest temperature at which a fluid will flow.
  • the lower the pour point of a liquid lubricant composition the lower the requirement for pour point depressant additives, which is advantageous.
  • the disclosed alkylaromatic compositions have pour points that are less than or equal to -30°C, or less than or equal to -35°C, or less than or equal to -40°C, or less than or equal to -45°C , or less than or equal to -50°C.
  • the lower the degree of branching and the greater the chain length of the alkyl moiety yields a higher (less advantageous) pour point.
  • Example 2 The procedure was similar to Example 1 except that 250 g 2-octyl-1-dodecene was used. Yield: 268 g clear, bright yellow fluid (74% based on olefin).
  • Comparative Example 1 is a commercial alkylated naphthalene made from 1-hexadecene, naphthalene, and USY catalyst. The majority of isomers are mono-alkylated with a mixture of alpha and beta naphthalene substitution.
  • Comparative Example 2 is an alkylated toluene made from C20 internal olefins, toluene, and a Friedel Crafts catalyst. The majority of isomers are mono-alkylated with little quaternary substitution. Table 1.
  • Examples 1-5 have a single branch at the vinylidene carbon and should be identical in structure to vinylidenes made via the metallocene processes.
  • Examples 1, 2, 4, and 5 have 70, 68, and 72 %, respectively, of an isomer with a quaternary carbon alpha to the naphthalene or toluene ring.
  • Example 3 provides an example of an alkylated naphthalene made from a vinylidene which does not have a significant amount of quaternary substitution.
  • the process of using high activity zeolites with acidity on the surface results in higher concentrations of quaternary substitution for bulky vinylidenes.
  • Use of other acidic catalysts such as BF 3 etherate should result in high amounts of quaternary substitution.
  • Example 4 demonstrates that the BF 3 -etherate catalyst has similar selectivity with respect to quaternary substitution: Table 2.
  • Sample Example 4 Example 5
  • Example 6 Comparative Example 2
  • Examples 1 - 4 have much improved pour points (D5985 method) compared to Comparative Example 1, demonstrating that the branching improves pour points.
  • Example 1 can be directly compared to Comparative Example 1 since both lubricants have the same molecular weight.
  • the RBOT Rotary Bomb Oxidation Test, D2272 method
  • the RBOT is 334 and 196 minutes, respectively, proving that the quaternary carbon causes an improvement in the oxidation stability of the lubricant.
  • the B10 oxidation test (M334 method) demonstrates improvement of the acid number (0.32 vs. 2.26 mg/gKOH, D664-1 method), viscosity increase (2 vs. 13 wt%, D445-5 method) and Pb loss (0.6 vs. 14.3 wt%, D2272 method) during catalytic oxidation of Example 1 vs. Example 3.
  • Example 2 which is higher in molecular weight and viscosity than Example 1 and Comparative Example 1, also shows improved or equal B10 oxidation properties relative to Comparative Example 1, but not exceeding those of Example 1.
  • Example 3 demonstrates the loss of resistance to oxidation when there is little quaternary substitution due to isomerization of the vinylidene during the reaction.
  • the USY catalyst was a poor alkylation catalyst for the alkylation of naphthalene with vinylidenes due to the bulk of the olefin.
  • USY catalyst is an excellent alkylation catalyst for conventional alkylated naphthalenes for which linear alpha olefins are used.
  • the result of this isomerization was poorer RBOT results compared to Comparative Examples 1, although their B10 oxidation results were similar.
  • Example 5 can be directly compared to Comparative Example 2 since both lubricants have the same molecular weight.
  • the RBOT Rotary Bomb Oxidation Test, D2272 method
  • the RBOT is 45 and 20 minutes, respectively, proving that the quaternary carbon causes an improvement in the oxidation stability of the lubricant.
  • Oxidation stability was analyzed under the Rotating Bomb Oxidation Test (RBOT) and the B-10 oxidation test.
  • RBOT test protocol is described in ASTM D2272.
  • the B-10 oxidation test is used to evaluate mineral oil and synthetic lubricants either with or without additives. The evaluation is based on the resistance of the lubricant to oxidation by air under specified conditions as measured by the formation of sludge, the corrosion of a lead specimen, and changes in neutralization number and viscosity. In this method, the sample is placed in a glass oxidation cell together with iron, copper and aluminum catalysts and a weighed lead corrosion specimen.
  • the cell and its contents are placed in a bath maintained at a specified temperature and a measured volume of dried air is bubbled through the sample for the duration of the test.
  • the cell is removed from the bath and the catalyst assembly is removed from the cell.
  • the oil is examined for the presence of sludge, the total acid number (TAN) (ASTM 664), and Kinematic Viscosity (kV) increase at 100° C (ASTM D445).
  • the lead specimen is cleaned and weighed to determine the loss in weight.
  • Example 1 The products described in Examples 1 - 6 were made with a monoolefin with a >95 mol% vinylidene content.
  • the procedure for Example 1 resulted in 70 mol% quaternary isomer for alkylated aromatics.
  • the procedure for Example 5 resulted in 54 mol % quaternary isomer.
  • These numbers were used to calculate the theoretical yield for monoolefins with vinylidene contents of 50 - 65% as shown in Table 3 below.
  • Table 3 Theoretical Yield of Quaternary Isomer in Product (mol%) Monolefin Vinylidene Content (mol %) 54% 70% 50 % 27 35 60 % 32 42 65 % 35 45

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Lubricants (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Claims (22)

  1. Composition alkylaromatique comprenant :
    un groupement aromatique autre que naphtalène non substitué ; et
    un groupement alkyle comportant un nombre d'atomes de carbone dans la fourchette entre 16 et 40, ledit groupement alkyle étant fixé audit groupement aromatique de telle sorte qu'au moins 25 % en moles des atomes de carbone benzyliques soient quaternaires.
  2. Composition alkylaromatique selon la revendication 1, dans laquelle au moins 35 % en moles, de préférence au moins 70 % en moles, des atomes de carbone benzyliques sont quaternaires.
  3. Composition alkylaromatique selon la revendication 1, dans laquelle ledit groupement aromatique est le toluène et éventuellement ladite composition possède une stabilité à l'oxydation, mesurée par ASTM D2272, de plus de 30 minutes.
  4. Composition alkylaromatique selon la revendication 1, dans laquelle ledit groupement aromatique est le benzène et éventuellement ladite composition possède une stabilité à l'oxydation, mesurée par ASTM D2272, de plus de 20 minutes.
  5. Composition alkylaromatique selon la revendication 1, dans laquelle ladite composition possède un point d'écoulement inférieur ou égal à -35°C, de préférence inférieur ou égal à -50°C.
  6. Procédé de préparation d'un composé alkylaromatique comprenant : la mise en contact d'au moins un groupement aromatique et d'une mono-oléfine comportant un nombre d'atomes de carbone dans la fourchette entre 16 à 40 en présence d'un catalyseur d'alkylation acide dans des conditions d'alkylation, dans lequel au moins 50 % en moles de la mono-oléfine comprennent une structure vinylidényle, et permettant ainsi de produire ledit composé alkylaromatique comportant au moins 25 % en moles d'atomes de carbone benzyliques qui sont quaternaires.
  7. Procédé selon la revendication 6, comprenant en outre : la séparation et la récupération dudit composé alkylaromatique.
  8. Procédé selon la revendication 6, dans lequel ledit composé alkylaromatique possède au moins 65 % en moles d'atomes de carbone benzyliques qui sont quaternaires.
  9. Procédé selon la revendication 6, dans lequel ledit catalyseur d'alkylation acide est choisi parmi les catalyseurs zéolithiques, MCM-22, MCM-57, MCM-36, MCM-49, MCM-56, ITQ-1 et ITQ-3, ou est un catalyseur de Friedel Craft choisi parmi BF3, BF3 activé, AlCl3, SnCl4, FeCl3 et ZnCl2.
  10. Composition alkylaromatique selon la revendication 1 dans laquelle ledit groupement aromatique est choisi parmi le benzène, le toluène, les xylènes, l'éthyl-benzène, le sulfure de diphényle, l'oxyde de diphényle, et des mélanges de ceux-ci.
  11. Composition alkylaromatique selon la revendication 1 dans laquelle ledit groupement aromatique est choisi parmi le benzène substitué ou non substitué, le naphtalène substitué, le furane substitué ou non substitué, le thiophène substitué ou non substitué, l'anthracène substitué ou non substitué, le phénanthrène substitué ou non substitué, le pyrole substitué ou non substitué, l'indole substitué ou non substitué, le benzothiophène substitué ou non substitué, le dibenzothiophène substitué ou non substitué, le benzofurane substitué ou non substitué, le dibenzofurane substitué ou non substitué, la phénoxanthine substituée ou non substituée, le thianthrène substitué ou non substitué, le biphényle substitué ou non substitué, le pyrène substitué ou non substitué, le bisphénol A, le sulfure de bisphénol, l'anisole, le thioanisole, l'oxyde de diphényle, le sulfure de diphényle, le diphénylméthane, et des mélanges de ceux-ci.
  12. Composition alkylaromatique selon la revendication 1, dans laquelle ledit groupement aromatique est choisi parmi le toluène, l'o-, m- ou p-xylène, l'hydroxybenzène, le méthoxy ou éthoxybenzène, le thioanisole, le diphényléther, le diphénylméthane, le sulfure de diphényle, le méthylnaphtalène, le méthoxynaphtalène, l'éthoxynaphtalène, le sulfure de méthylnaphtyle, le sulfure d'éthylnaphtyle, le bisphénol-A, le sulfure de bisphénol et des mélanges de ceux-ci.
  13. Composition alkylaromatique selon la revendication 1 ou procédé selon la revendication 6, dans lequel ladite mono-oléfine possède un nombre d'atomes de carbone dans la fourchette entre 16 à 24.
  14. Procédé selon la revendication 6, dans lequel ladite mono-oléfine est dérivée de catalyseurs de type alkyl-aluminium.
  15. Procédé selon la revendication 14, dans lequel ledit catalyseur de type alkyl-aluminium est le triisobutyl-aluminium.
  16. Procédé selon la revendication 6, dans lequel ladite mono-oléfine est dérivée d'un procédé de polymérisation d'alpha-oléfine catalysée par un métallocène.
  17. Procédé selon la revendication 6, dans lequel ladite mono-oléfine est dérivée d'un vinylidène ayant un nombre d'atomes de carbone inférieur à 40.
  18. Procédé selon la revendication 17, dans lequel ledit vinylidène est choisi parmi le 2-hexyl-1-décène, le 2-octyl-1-dodécène ou le 2-décyl-1-tétradécène, et des mélanges de ceux-ci.
  19. Procédé selon la revendication 6, dans lequel au moins 65 % en moles de la mono-oléfine comprend une structure vinylidényle.
  20. Procédé selon la revendication 6, dans lequel ledit groupement aromatique est choisi parmi le benzène, le toluène, les xylènes, l'éthylbenzène, le naphtalène, le sulfure de diphényle, l'oxyde de diphényle, et des mélanges de ceux-ci.
  21. Procédé selon la revendication 6, dans lequel ledit groupement aromatique est choisi parmi le benzène substitué ou non substitué, le naphtalène substitué ou non substitué, le furane substitué ou non substitué, le thiophène substitué ou non substitué, l'anthracène substitué ou non substitué, le phénanthrène substitué ou non substitué, le pyrole substitué ou non substitué, l'indole substitué ou non substitué, le benzothiophène substitué ou non substitué, le dibenzothiophène substitué ou non substitué, le benzofurane substitué ou non substitué, le dibenzofurane substitué ou non substitué, la phénoxanthine substituée ou non substituée, le thianthrène substitué ou non substitué, le biphényle substitué ou non substitué, le pyrène substitué ou non substitué, le bisphénol A, le sulfure de bisphénol, l'anisole, le thioanisole, l'oxyde de diphényle, le sulfure de diphényle, le diphénylméthane, et des mélanges de ceux-ci.
  22. Procédé selon la revendication 6, dans lequel ledit groupement aromatique est choisi parmi le toluène, l'o-, m- ou p-xylène, l'hydroxybenzène, le méthoxy ou éthoxybenzène, le thioanisole, le diphényléther, le diphénylméthane, le sulfure de diphényle, le naphtalène, le méthylnaphtalène, le méthoxynaphtalène, l'éthoxynaphtalène, le sulfure de méthylnaphtyle, le sulfure d'éthylnaphtyle, le bisphénol-A, le sulfure de bisphénol et des mélanges de ceux-ci.
EP08726928.8A 2007-03-20 2008-03-18 Liquides lubrifiants alkylaromatiques Active EP2132156B1 (fr)

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US91901807P 2007-03-20 2007-03-20
US12/075,948 US20080234157A1 (en) 2007-03-20 2008-03-14 Alkylaromatic lubricant fluids
PCT/US2008/003518 WO2008127534A1 (fr) 2007-03-20 2008-03-18 Liquides lubrifiants alkylaromatiques

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JP2010522258A (ja) 2010-07-01
CN101641308A (zh) 2010-02-03
WO2008127534A1 (fr) 2008-10-23
EP2132156A4 (fr) 2011-05-18
SG182167A1 (en) 2012-07-30
US20080234157A1 (en) 2008-09-25

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