CN101641308A - Alkylaromatic lubricant fluids - Google Patents

Alkylaromatic lubricant fluids Download PDF

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Publication number
CN101641308A
CN101641308A CN200880009098A CN200880009098A CN101641308A CN 101641308 A CN101641308 A CN 101641308A CN 200880009098 A CN200880009098 A CN 200880009098A CN 200880009098 A CN200880009098 A CN 200880009098A CN 101641308 A CN101641308 A CN 101641308A
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replace
unsubstituted
composition
naphthalene
alkyl aromatic
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贝丝·A·永恩
玛格丽特·M·吴
克里斯汀·N·埃利娅
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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

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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)

Abstract

The alkylaromatic compositions include an aromatic moiety other than unsubstituted naphthalene; and an alkyl moiety having a carbon atom number in the range between 12 to 40, wherein said alkyl moietyis attached to said aromatic moiety such that at least 25 mol % of the benzylic carbons are quaternary. The process for producing the alkylaromatic compositions include contacting at least one an aromatic compound and a mono-olefin having a carbon atom number in the range between 12 to 40 in the presence of an acidic alkylation catalyst under alkylation conditions, wherein at least 50 mol % of the mono-olefin structure comprises a vinylidenyl structure, and thereby producing said alkylaromatic compound having at least 25 mol % of benzylic carbons that are quaternary. The alkylaromatic compositions disclosed herein are liquids that have improved thermo- and oxidative stability and pour point.

Description

Alkylaromatic lubricant fluids
Technical field
The present invention relates to novel alkyl aromatic composition as lubricant base and additive.More particularly, disclosed by the invention is to have the temperature stability of improvement and the season of oxidative stability replace (quaternary-substituted) alkyl aromatic composition, and it is obtained via the alkene alkanisation that contains the vinylidene structure by aromatics.The invention still further relates to and utilize the tart Alkanizing catalyst to produce the alkylated aromatic method for compositions.
Background technology
Lubricating oil is that a kind of can being introduced between two solid surface as film also can be reduced friction the material of heat and wearing and tearing.Past is over 50 years, and the performance of how to make great efforts to improve based on the lubricating oil of mineral oil is the emphasis of the development activities of petrochemical industry always.How to keep the performance that it is reduced friction, how in thermostability and oxidative stability with prevent that aspects such as wearing and tearing from prolonging its work-ing life, and how to improve its viscous index and pour point and it is equivalent to or is better than mineral oil, these all are related fields of existing development activities.Therefore these effort have caused many synthetic fluidic inventions, comprise the main synthetic fluid of poly-alpha olefins (polyalpha-olefin (PAO)) that is formed by the low dimerization of alpha-olefin or 1-alkene.Synthetic fluid is the term that can be used for being described below the various uses material, such as especially being used as lubricating oil, thermal conduction agent, corrosion inhibitor etc.The synthetic fluidic composition of PAO is saturated hydrocarbon polymer, thus with compare based on mineral oil and composition with polar group (comprising aromatic hydrocarbon), its polarity a little less than.In order to improve PAO this class fluidic solubility and dispersibility, can in said composition, add the common base oil of polar with polar additive in the help dissolved composition and the sludge in the use.The common base oil of this polar, for example, the consumption of ester or alkyl aromatics be base oil composition about 3 weight % to about 50 weight %.The common base oil of polar might be introduced bad side effect; Such as, if add the common base oil of ester class, may cause hydrolytic instability, and add the common base oil of typical alkyl aromatic, may cause that then cold property worsens and degree of cleaning reduce.The ucon oil of finishing is mixed with additive to improve their qualities in special applications by prescription usually.Usually the additive of usefulness comprises oxidation retarder, dispersion agent, washing agent, rust-preventive agent, anti-wear agent, extreme-pressure additive, metal passivator, pour point depressant, viscous index rising agent, and other similar additive.Like this, institute's formulated fluids is such composition, and it includes numerous components, and wherein the maximum component of amount is a lubricant base.Lubricating oil is except the complexity of its prescription, and its oily standard of performance also has the trend that improves constantly, and this trend is determined by the equipment that upgrades and the ever-increasing complicacy of engine.Therefore, there is such demand always,, thereby makes the field that needs at all, comprise thermostability and oxidative stability aspect, provide lubricating oil that improved performance is all arranged by formulated promptly to how improving the individual features of lubricant base.
Alkyl aromatic compound has been understood a lot of years.For instance, United States Patent (USP) the 6th, 491, No. 809 (Briot etc.) described how to use alkylating agent (such as alkene, alcohol, halogenide etc.) to come alkylated aromatic compound (such as benzene, toluene, isopropyl benzene etc.) with the manufacture order alkyl aromatic compound, its grafted aliphatic chain contains the carbon number that is selected from 2-20 carbon.United States Patent (USP) the 6th, 429, No. 345 (Joly etc.) have described under the katalysis of the catalyzer that contains at least a EUO type structural zeolite, at least contain the alkene of 9 carbon atoms with at least a per molecule, generate at least a 2-that is selected from, 3-, 4-, the method of the compound of 5-and 6-alkylbenzene is at least in part with its sour form and at least a matrix.U.S. Patent number 5,254,274 (Ho etc.) have then described how to use C 20-C 1300Olefin oligomer alkylated aromatic compound under the effect of tart Alkanizing catalyst, thereby make alkyl aromatic product, normally alkyl aromatic hydrocarbon polymer.More about the visible L.R.Rudnick of discussion of alkyl aromatic compound and other relevant ucon oil and Synthetic Lubricantsand High-Performance Functional Fluids (the Marcel Dekker company of R.L.Shubkin collaboration, New York, 1999).
PAOs can have catalyzer (such as AlCl 3, BF 3, or improved BF 3) existence create down by reaction (reacting an olefin feed) with the alkene charging.The method of making PAOs is disclosed, such as, following patent: United States Patent (USP) the 3rd, 149, No. 178, the 3rd, 382, No. 291, the 3rd, 742, No. 082, the 3rd, 769, No. 363, the 3rd, 780, No. 128, the 4th, 172, No. 855, and the manufacture method of all having described PAOs for the 4th, 956, No. 122.Novel PAO lubricating oil component because of its a spot of double-bond isomerism that contains, has formed different types of PAO (HVI-PAO) with high viscosity coefficient.Wherein, a kind of HVI-PAO is arranged by the reaction of reduction chrome catalysts and 'alpha '-olefin monomers and obtain.Such PAOs is at United States Patent (USP) the 4th, 827, No. 073, the 4th, 827, No. 064, the 4th, 967, No. 032, description all arranged in the 4th, 926, No. 004 and the 4th, 914, No. 254.
Having patent to describe 'alpha '-olefin monomers by one or more 3-24 of containing carbon atom recently contacts with transistion metal compound, anion active agent and alkylaluminium cpd and prepares the HVI-PAOs composition.New composition meets the unique property of HVA-PAOs oligomerization, wherein has a small amount of double-bond isomerism to take place.Such HVI-PAOs announces in WO2007011462A1 number and WO2007011832A1 number that at pct international patent description is arranged.
Resemble United States Patent (USP) the 5th, 688, No. 887 and the 6th, 043, No. 401, and pct international patent announces the same described in WO2007011973A1 number, new low viscous PAOs composition can also be made with metallocene catalyst.The material of the material of separate low molecular amount, the non-lubricated scope molecular weight of representative is very necessary to the volatility and the viscosity of control product.Less to make molecular-weight average when changing oligomeric condition, during low viscous product, the dimer of non-lubricated scope or lighting end meeting increase.Being increased in of the output of dimer by product become in the technology make useful than the heavy economical load in the whole process of low-viscosity oil.
Correspondingly, people are exploring always and are better making the alkyl aromatic fluid composition and have the heat of improvement and the method for the alkyl aromatic fluid composition of oxidative stability.Similarly, people are also exploring the novel method that can utilize the byproduct that produces in the catalytic process of metallocene catalyst to make the new synthetic lubricating fluid of production.
Summary of the invention
The present invention relates to the alkyl aromatic composition, it contains the aromatic portion except that the naphthalene of unsaturation, and the moieties of carbonatoms between 12-40; Described moieties links to each other with aromatic portion, makes that having the benzylic carbon atoms of 25 moles of % at least in the described composition is quaternary carbon atom.
The present invention relates to a kind of method for preparing alkyl aromatic compound simultaneously, this method comprises: under alkylating condition, at least a aromatics and the monoolefine that contains 12-40 carbon atom are contacted in the presence of acid Alkanizing catalyst, wherein the monoolefine structure of at least 50 moles of % contains the vinylidene structure, and therefore having the benzylic carbon atoms of 25 moles of % at least in the alkyl aromatic compound that is produced is quaternary carbon atom.
The present invention provides the byproduct that produces in the catalytic process of utilizing metallocene catalyst to make the method for new synthetic lubricating fluid simultaneously.
Correspondingly, the invention provides useful alkyl aromatic fluid composition with thermostability and oxidative stability.
In addition, the present invention also provides useful lubricating oil additive, and this additive is to obtain as the alkylating agent alkylated aromatic compound by the low-molecular-weight alkene that utilization contains vinylidene.
All are about these and further feature and attribute of alkyl aromatic composition described in the invention, that be suitable for liquid lubricating oil composition or additive, and prepare alkyl aromatic method for compositions of the present invention and their advantageous application and purposes, will be conspicuous all by detailed description hereinafter.
Describe in detail
In the circumstantial letter and claims of this paper, all numerical value is " approximately " or " being similar to " value of described numerical value, and they have also comprised experimental error and variation that those of ordinary skills can predict.Have been found that with alkene that contains the vinylidene structure and aromatics reaction, can obtain a kind of new synthetic base oil with lubrication qualities of obvious improvement.This new lubricant base can create by this way: promptly, make that a sizable part is the alkylating aromatic compound that replaces in season in all alkylating aromatic compounds that it comprised.
In some embodiments, monoolefine can obtain in the resulting non-lubricant from the alpha-olefin poly process of metallocene catalysis.The monoolefine that otherwise obtains, if it is wherein contain a considerable amount of vinylidene structures, very useful too.
What be equally applicable to be used in the disclosed method of the present invention is the charging or the discharging of refinery.The alkene that is suitable for preparing the mixture of dimer or dimer, tripolymer etc. comprises about 3-20 carbon atom, for example, the 1-polypropylene, 1-butylene, the 1-hexene, the 1-octene, 1-decene, 1-laurylene, 1-tetradecylene, and the 1-hexadecylene, or branched-chain alkene, such as, 4-methyl-1-pentene, or their mixture.Aforementioned monoolefine is that carbonatoms is less than 30 the alkene that contains the vinylidene structure, also may be the mixture of alkene, wherein contains a considerable amount of alkene or three substituted olefines that contain the vinylidene structure.As a rule, at least 50 moles of %, or at least 55 moles of %, or at least 60 moles of %, or the above-mentioned monoolefine structure of at least 65 moles of % contains the vinylidene structure.
Described aromatics can be benzene, naphthalene, furans, thiophene, anthracene, phenanthrene, pyrroles, indoles, thionaphthene, dibenzothiophene, cumarone, diphenylene-oxide, phenoxazine thiophene (phenoxathiin), thianthrene, biphenyl, pyrene, with and composition thereof, wherein each class all may optionally be substituent.
In further preferred embodiment, this aromatics can also be toluene, neighbour or p-Xylol, hydroxybenzene, alkoxy benzene, such as anisole or phenetole, thioanisole, phenyl ether, ditan, dihydroxyphenyl propane, sulfuration bis-phenol (bisphenol sulfide), diphenyl sulfide, naphthalene, methylnaphthalene, methoxy naphthalene, ethoxy naphthalene, sulfuration methylnaphthalene (methylnaphthalsulfide), sulfuration ethyl naphthalene (ethylnaphthylsulfide), or its mixture.In preferred embodiment, this aromatics can also or replace naphthalene for substituted benzene.
Method and product
Method in common is as follows among the present invention:
Figure A20088000909800111
In the present invention, aromatic hydrocarbons, the aromatic hydrocarbons that comprises replacement, by olefin alkylation, wherein, quite a few alkene is that the vinylidene substituent is (common, at least 50 moles of %, perhaps at least 55 moles of %, perhaps at least 60 moles of %, perhaps the monoolefine structure of at least 65 moles of % comprises the vinylidene structure).These alkene can be derived from the oligomer of the non-lubricated scope that produces in metallocene-low viscosity alpha-olefin poly process (reaction A).These are used for alkylating alkene and wherein contain a considerable amount of isomer that contain the vinylidene structure.Other the method that can make the alkene that contains the vinylidene structure is also contained within the scope of the present invention.Solid acid catalyst such as zeolite or Knut Fridell-Krafft (Friedel Crafts) alkylation catalyst such as AlCl 3Or BF 3Also can be used to catalytic alkylation, the novel composition that this reaction obtained includes the benzylic carbon atoms that a considerable amount of seasons replace.These compositions table reveal excellent stack solvability (additive solubilizing properties).
Alkene
Be applicable to the purpose of the alkyl aromatic composition of liquid lubricating oil composition described in the invention or additive from preparation, obtain to have the composition of thermostability and oxidative stability, need such alkyl aromatic composition, it contains the benzylic carbon atoms that a considerable amount of seasons replace, and its total branched carbon atomicity is between 12-40.For instance, selected composition can be by the aromatic substrate of highly active zeolite catalyst, monocycle or dicyclo, and metallocene contain the vinylidene structure in the by product of catalytic alpha-olefin polymerization this triangular reaction of alkene prepare.The PAO reaction of metallocene catalysis is made of the oligomerization with the contacted 1-alkene of the catalyzer of metallocenes type.One of feature of this oligomerization is for analyzing to determine its produced dialkyl group ethene (dialkylvinylidenic) and 1 by infrared and NMR, the mixture of 2 dialkyl group or trialkyl-single olefin oligomerization body, above-mentioned oligomerization produces the by product that comprises the alkene with vinylidene structure.Method of the present invention can obtain the 1-alkene of dimerization attitude of the unhydrogenation of significant proportion, or the alpha-olefin with following vinylidene structure:
CH 2＝CR 1R 2
R wherein 1And R 2Be alkyl group.Other compositions of olefines that contains 12-40 carbon atom also can be with in the method for the invention, and this comprises the resulting olefin oligomer of olefin oligomerization reaction by acid or metallocene catalysis, and these alkene comprise, such as, propylene and/or butylene and/or amylene.The tripolymer or the polymeric existence that contain the vinylidene structure are also very favourable.Other the method that can form the alkene precursor that is rich in the vinylidene structure also can be used.In the presence of Z-type catalyst (such as triisobutyl aluminium), the reaction of alpha-olefin can form the dimer (with reference to Canadian Patent the 1st, 034, No. 967) that contains the vinylidene structure.Come two poly-alpha olefinss with cyclopentadienyl zirconium dichloride or hafnium metallocene, aikyiaiurnirsoxan beta and optional trialkylaluminium coenzyme, cause optionally forming the dimer that contains the vinylidene structure and (see United States Patent (USP) the 4th, 658, No. 078 and the 5th, 087, No. 788, be incorporated herein by reference).
Other monoolefine with following replacement mode also can be used for obtaining to have the alkyl aromatic compound that season replaces, wherein R 1, R 2, and R 3Be alkyl group, R 4Be the hydrogen or alkyl group, and total carbon atom number is between 12-40:
R 1R 2C＝CR 3R 4
In general, in method of the present invention, at least 50 moles of %, or at least 55 moles of %, or at least 60 moles of %, or the monoolefine structure of at least 65 moles of % contains the vinylidene structure.
Alkylation
An acidic catalyst that can influence the olefin alkylation aromatics comprises acid halide (Lewis acid), protonic acid (acid of Bu Langsi Taide), and Zeo-karb, Knut Fridell-Krafft catalyzer, and solid acid comprises zeolite.
Though have a lot of an acidic catalysts to promote the alkylation of alkene to aromatics, the present invention shows, is used to prepare the purpose that is suitable for as the alkyl aromatic composition of liquid lubricating oil composition or additive, highly active zeolite may be effectively.Can be used to prepare the non-limitative example that is suitable for as the highly active zeolite alkyl aromatic composition, that have surface acidity of liquid lubricating oil composition and additive includes, but is not limited to: MCM-22, MCM-36, MCM-49, MCM-56, ITQ-1, ITQ-3 and their any combination.United States Patent (USP) the 4th, 954, No. 325, the 5th, 229, No. 341, the 5th, 236, No. 575, the 5th, 362, No. 697, the 6th, 077, No. 498, and the 6th, 500, No. 404 (all introducing for your guidance in full) disclosed MCM-22 respectively, MCM-36, MCM-49, MCM-56, ITQ-1, ITQ-3.
Lewis acidic non-limitative example comprises aluminum chloride, aluminum bromide, iron(ic) chloride (III), zinc chloride, boron trifluoride etc.The non-limitative example of cloth Lanace Taide acid comprises sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, phosphoric acid etc.
Aromatics of the present invention be can be used for and replacement and unsubstituted monocycle or dinuclear aromatics and composition thereof comprised.Favourable situation is that the aromatic series part of these aromatics is selected from one of following group at least: benzene, toluene, dimethylbenzene, ethylbenzene and naphthalene.Suitable aromatics includes, but not limited to replace or unsubstituted benzene, replace or unsubstituted naphthalene, replace or unsubstituted furans, replace or unsubstituted thiophene, replace or unsubstituted anthracene, replace or unsubstituted phenanthrene, replace or unsubstituted pyrroles, replace or unsubstituted indoles, replace or unsubstituted thionaphthene, replace or unsubstituted dibenzothiophene, replace or unsubstituted cumarone, replace or unsubstituted diphenylene-oxide, replace or unsubstituted phenoxazine (phenoxanthiin), replace or unsubstituted thianthrene, replace or unsubstituted biphenyl, replace or unsubstituted pyrene, dihydroxyphenyl propane, sulfuration bis-phenol, anisole, thioanisole, diphenyloxide, diphenyl sulfide, ditan, above-mentioned replacement analogue, and their mixture.Replacing naphthalene is the particularly preferred aromatics that is used for The compounds of this invention and method disclosed herein.Another slightly inferior preferred aromatics that is used for the present composition disclosed herein and method then is unsubstituted naphthalene compound.
In a preferred embodiment, aromatics is a benzene, toluene, adjacent-, between-or p-Xylol, hydroxybenzene, alkoxy benzene such as anisole or phenetole, thioanisole, phenyl ether, ditan, diphenyl sulfide, naphthalene, methylnaphthalene, methoxynaphthalene, the oxyethyl group naphthalene, sulfuration methylnaphthalene (methylnaphthal sulfide), sulfuration ethyl naphthalene (ethylnaphthylsulfide), dihydroxyphenyl propane, sulfuration bis-phenol, and their mixture.
These aromatics can be substituted.Suitable replacement group comprises alkyl, hydroxyl, and alkoxyl group such as methoxy or ethoxy, aryloxy such as phenoxy group, alkylthio such as methylthio group, arylthio such as thiophenyl, and aralkyl is such as benzyl.So, described in some preferred embodiments aromatics is mono-substituted benzene, such as toluene perhaps is disubstituted benzene, such as p-Xylol, m-xylene or o-Xylol.
The amount of catalyzer of reactor of packing into is the 0.1%-20% of the amount of olefinic material, is preferably 0.5%-5%.Aromatics, such as benzene, naphthalene, 1,2, the 4-Three methyl Benzene, and the mol ratio of alkene initial reactant is usually between 1: 3 to 20: 1, preferably 1: 2 to 10: 1, but according to the alkylation degree of needed aromatics, this ratio can correspondingly be adjusted.
Usually, when the zeolite catalysis method is used, catalyzer is placed in the slurry reactor.And reaction can be carried out in the mode of fixed bed operate continuously, and wherein catalyzer is loaded in the tubular reactor with the shape of ball shape or stretching shape and is heated to required temperature.Reactant is introduced reactor with specific weight hourly space velocity (WHSV), its scope is between about 0.1-about 20, and it is about 5 to be preferably about 0.5-, with the purpose of the conversion that reaches realization high level.The effecting reaction temperature of preparation alkyl aromatic composition, for instance, can be between room temperature to 350 ℃, preferably between 75 ℃ to 350 ℃.When temperature was higher than 200 ℃, catalyzer may influence isomerization, and therefore preferred temperature is for being lower than 200 ℃.Preferred reaction conditions comprises: about 1 to 30 atmospheric pressure, in slurry reactor, preferred catalyzer Intake Quantity is extremely about 5 weight % of about 1 weight %, and perhaps in the fixed bed operate continuously, the value of preferred sample introduction speed WHSV is between about 0.2 to about 4.Reactant can be gas phase or liquid phase.They can be purified, are not also promptly mixed or dilution with any other material wittingly; Perhaps, they also can contact with catalyst composition under the help of carrier gas or thinner (for example hydrogen or nitrogen).Alkylation reaction can adopt the reaction formation of batch processing, utilizes the pressure stirred reactor of sealing usually, and adopts the protection of inert gas system; Perhaps, alkylation reaction also can adopt fixing or the moving-bed catalysis system carries out with semicontinuous or operate continuously mode.
Usually, if utilize Knut Fridell-Krafft catalyzer to influence alkylation reaction (seeing United States Patent (USP) the 6th, 071, No. 864), such as, adopt AlCl 3Or the BF of improvement 3Make catalyzer, then Fan Ying condition can be located between-30 ℃ to 350 ℃, and typical temperature is that the pressure of following is typically 700 to 7000kPa between 30 ℃ to 90 ℃.When condition became harsh more, Knut Fridell-Krafft catalyzer may cause the isomerization of the alkene that contains the vinylidene structure, caused the season substituted alkyl aromatic compound that comprises in the alkyl aromatic product quantity is reduced.Alkylated reaction can adopt the reaction formation of batch processing, utilizes the pressure stirred reactor of the sealing that has the protection of inert gas system usually, and perhaps it also can adopt semicontinuous or operate continuously mode.
In the present invention, any separation method that provides the liquid alkyl aromatic composition of usefulness all may be utilized.An example of the useful separated scheme after the alkanisation of aromatics is to adopt excessive lighter ebullient hydrocarbon polymer (lighter boilinghydrocarbon), aromatics for example, and carry out alkylation experiment and all be consumed up to all alkene (contain vinylidene structure or other C12-C40 alkene).The fluid composition of reactant can be by common method then, such as gravity separation or filtration separate with acid zeolite, and unreacted aromatics can be separated from fluid composition by vacuum distilling and recirculation.Usually adopted under the situation of Knut Fridell-Krafft catalyzer in reaction, reaction mixture can come deactivation with the acid or the alkaline solution of dilution, washing again, and drying, as United States Patent (USP) the 5th, 254, No. 274 and the 6th, 071, No. 864 are described the same.Though alkylating product has the bromine number of minimizing compared to initial alkene, moderately giving remaining alkene and dimer by product hydrogenation also is optional means.
The alkylated aromatic that can be used as liquid lubricating oil and additive composition so just is provided.
Composition
Alkyl aromatic compound of the present invention has following nonrestrictive structure:
Figure A20088000909800161
Wherein, have a R group at least, this group of significant proportion is R 2R 3CCH 3Group, wherein R has about 6-40 carbon atom, perhaps 12-40 carbon atom, perhaps 16-24 carbon atom, and R 2And R 3Be alkyl group.For example:
Figure A20088000909800162
The amount of the aromatics that season replaces is to estimate by the ownership of NMR DEPT being tested resulting signal.Especially, what be connected with aromatic portion is such moieties, it makes that the benzylic carbon atoms of at least 25 moles of % is a quaternary carbon atom, or make that at least 30% benzylic carbon atoms is a quaternary carbon atom, or make that at least 35% benzylic carbon atoms is a quaternary carbon atom, or make that at least 40% benzylic carbon atoms is a quaternary carbon atom, or make that at least 50% benzylic carbon atoms is a quaternary carbon atom, or make that at least 70% benzylic carbon atoms is a quaternary carbon atom.
Can obtain other aromatic structure with other alkene, the season that the aromatics of these different structures may cause having following formula replaces:
Figure A20088000909800163
R wherein 1, R 2And R 3Be alkyl group R 4Be hydrogen or alkyl group.
The primary product that the present invention describes is the monoalkyl aromatic compounds of group, but the present invention also can form polysubstituted aromatic composition and alkene-olefin product.Having the olefin isomerization phenomenon or do not containing under the situation of olefin reactant of vinylidene structure, the alkylated aromatic hydrocarbon that non-season replaces also is present in the product.
Under the situation that has enough strong an acidic catalyst, alkene may experience skeleton and reset and formation tertiary carbon positive ion (R3C +, R=alkyl wherein), thus this tertiary carbon positive ion can the alkanisation aromatic substrate generate the composition that contains the benzyl quaternary carbon atom that adjoins aromatic nucleus.To be that the ratio of the benzyl quaternary carbon atom in the alkyl aromatic composition is enough high (be defined as and make that the benzylic carbon atoms of at least 25 moles of % is a quaternary carbon atom one of advantage of the present invention, or make that at least 30% benzylic carbon atoms is a quaternary carbon atom, or make that at least 35% benzylic carbon atoms is a quaternary carbon atom, or make that at least 40% benzylic carbon atoms is a quaternary carbon atom, or make that at least 50% benzylic carbon atoms is a quaternary carbon atom, or make that at least 70% benzylic carbon atoms is a quaternary carbon atom), thus improved thermal stability and oxidative stability provided for said composition.As an illustration, in the present invention, alkyl aromatic composition with heat and oxidative stability is such composition, it is wherein a considerable amount of that (benzylic carbon atoms that is defined as feasible at least 25 moles of % is a quaternary carbon atom, or make that at least 30% benzylic carbon atoms is a quaternary carbon atom, or make that at least 35% benzylic carbon atoms is a quaternary carbon atom, or make that at least 40% benzylic carbon atoms is a quaternary carbon atom, or make that at least 50% benzylic carbon atoms is a quaternary carbon atom, or making that at least 70% benzylic carbon atoms is a quaternary carbon atom) benzylic carbon atoms is quaternary carbon atom.The heat and the oxidative stability that have when the liquid lubrication oil compositions that is made of alkyl aromatic compound are high more, and they are just low more to the demand of the additive of keeping required heat and oxidative stability.
More particularly, be that the oxidative stability that alkyl aromatic composition that substrate generates shows is weighed with RBOT with the aromatic group of unsubstituted naphthalene, it was worth greater than 150 minutes, or greater than 155 minutes, or greater than 160 minutes, or greater than 165 minutes.With the aromatic group of toluene is that the oxidative stability that alkylated aromatic composition that substrate generates shows is weighed with RBOT, and it was worth greater than 30 minutes, or greater than 35 minutes, or greater than 40 minutes, or greater than 45 minutes.In addition, be that the oxidative stability that alkylated aromatic composition that substrate generates shows is weighed with RBOT with the aromatic group of benzene, it was worth greater than 20 minutes, or greater than 25 minutes, or greater than 30 minutes, or greater than 35 minutes.In general, the branch of moieties is many more, and chain length is long more, then RBOT value low more (oxidative stability is low more).
Another advantage of alkyl aromatic composition among the present invention is that the pour point of the composition that forms of the present invention is of great use.Comprise the composition of alkanisation aromatic composition if, must in than wide temperature range, be in liquid state as liquid lubricating oil composition.Pour point is that liquid can the mobile minimum temperature.The pour point of liquid lubricating oil composition is low more, and then its requirement to pour point depressant is just low more, and this is very favourable.Especially, the pour point of the alkylated aromatic composition that the present invention is disclosed all is less than or equal to-30 ℃, perhaps is less than or equal to-35 ℃, perhaps is less than or equal to-40 ℃, perhaps is less than or equal to-45 ℃, perhaps is less than or equal to-50 ℃.As a rule, the branch degree of moieties is low more, and chain length is long more, and then pour point is with regard to high more (unfavorable more).
Following nonrestrictive example only is used to illustrate various embodiments of the present invention and its advantage that is had.Those of ordinary skill in the art can make various changes according to prior art to following proposal not exceeding within the scope of the present invention.Correspondingly, following embodiment only is used to further specify rather than limit the present invention.
Embodiment
Embodiment 1
Prepare alkylnaphthalene from 2-hexyl-1-decene and naphthalene
Contain 200 gram 2-hexyl-1-decene, 228 gram naphthalenes, 200 gram decane (choose), and 10 solution that restrain highly active zeolite catalysts (MCM-22) are heated to 125 ℃ and be maintained at this temperature 48 hours under nitrogen.This solution is cooled and filters.Removing any by distillation is that boiling point is lower than 160 ℃ component under the 1 millitorr condition in vacuum tightness, and the material in the lube range is then separated from mixture.Product: 231 grams are transparent, are close to colourless liquid (yield based on alkene is 74%).
Embodiment 2
Prepare alkylnaphthalene from 2-octyl group-1-laurylene and naphthalene
Process is similar with embodiment 1, except used be 250 gram 2-octyl group-1-laurylenes.Product: 268 grams are transparent, jonquilleous liquid (yield based on alkene is 74%).
Embodiment 3
Prepare alkylnaphthalene from 2-octyl group-1-laurylene and naphthalene
Contain 250 gram 2-octyl group-1-laurylenes, 114 gram naphthalenes, 200 gram decane, and the solution of 15 gram USY catalyzer are heated to 175 ℃ and be maintained at this temperature 8 days under nitrogen.This solution is cooled and filters.Removing any by distillation is that boiling point is lower than 160 ℃ component under the 1 millitorr condition in vacuum tightness, and the material in the lube range is then separated from mixture.Product: 254 grams are transparent, are close to colourless liquid (yield based on alkene is 62%).
Embodiment 4
Prepare alkylnaphthalene from 2-hexyl-1-decene and naphthalene
17.1 the naphthalene of gram and 50 milliliters hexane are heated to 45 ℃ under nitrogen, to the mixture dropping BF of this naphthalene 3.OEt 2(0.5 milliliter), and 20.0 gram 2-hexyl-1-decene.Reaction product is carried out GC subsequently and is analyzed.(several days) reaction mixture is washed to neutrality and uses dried over sodium sulfate with 5% NaOH deactivation after finishing.Removing any by distillation is that boiling point is lower than 160 ℃ component under the 1 millitorr condition in vacuum tightness, and the material in the lubricant scope is then separated from mixture.Product: 21 gram transparent liquids are 67% based on the yield of alkene.
Embodiment 5
Prepare alkyl toluene from 2-octyl group-1-laurylene and toluene
The toluene of 460 grams, the 2-octyl group-1-laurylene of 140 grams, and the MCM-49 that pulverizes (4.0 gram) is heated to backflow under nitrogen.Reaction product is carried out GC subsequently and is analyzed.Several days reaction mixtures are cooled and filter after finishing.Removing any by distillation is that boiling point is lower than 160 ℃ component under the 1 millitorr condition in vacuum tightness, and the material in the lubricant scope is then separated from mixture.Product: 155 grams are 67% based on the yield of alkene.
Embodiment 6
Prepare alkylbenzene from 2-decyl-1-tetradecylene and benzene
The benzene of 175 grams, the 2-decyl-1-tetradecylene of 140 grams, and the MCM-49 that pulverizes (4.0 gram) is heated to backflow under nitrogen.Reaction product is carried out GC subsequently and is analyzed.Several days reaction mixtures are cooled and filter after finishing.Removing any by distillation is that boiling point is lower than 160 ℃ component under the 1 millitorr condition in vacuum tightness, and the material of lubricant scope is then separated from mixture.Product: 158 gram clear, colorless liquid are 91% based on the yield of alkene.
Comparative Examples 1
Comparative Examples 1 is by the 1-hexadecylene, the commercially available alkylnaphthalene that naphthalene and USY catalyzer make.Its isomer is mainly the mixture of single substituted alkyl naphthalene of replacement of α position and the replacement of β position.
Comparative Examples 2
Comparative Examples 2 is by internal olefin (C20), the alkyl toluene that toluene and friedel-crafts catalysts make.Its isomer is mainly single substituted alkyl toluene, and a spot of season substituent that is is wherein arranged.
The lubricating quality of table 1. vinylidene alkylated aromatic compound
The sample aromatic group Embodiment 1 naphthalene Embodiment 2 naphthalenes Embodiment 3 naphthalenes Reference examples 1 naphthalene
Alkene C16 contains the alkene of vinylidene structure C20 contains the alkene of vinylidene structure C20 contains the alkene of vinylidene structure ??C16LAO
Catalyzer ??MCM-22 ??MCM-22 ??USY ??USY
??kV100℃，cSt ??5.4 ??6.7 ??5.8 ??4.7
??kV40℃，cSt ??40.5 ??49.9 ??38.7 ??29
??VI ??26 ??67 ??69 ??65
Pour point, ℃ ??＜-52.7 ??＜-52.3 ??＜-54.2 ??-39
Aniline point, ℃ ??37 ??54 ??49 ??34
B10 oxidation (40h@325F)
Sludge Do not have Do not have Tracer level Do not have
??D664-1，mg/gKOH ??0.32 ??0.90 ??2.40 ??2.26
% viscosity increases ??2 ??15 ??17 ??13
Plumbous minimizing, weight % ??0.6 ??4.66 ??13.9 ??14.3
RBOT, minute ??334 ??167 ??86 ??196
The Noack volatility, % reduces ??13.8 ??5.2 ??8.2 ??12.7
Season replaces isomer mole % (NMR) ??70 ??68 ??＜10 ??N/A
The alkene that is used for synthetic embodiment 1-5 has independent branch on the carbon atom of vinylidene structure, and structurally should be identical with the alkene that contains the vinylidene structure that obtains by metallocene-catalyzed process.Embodiment 1,2,4 and 5 has 70,68 respectively, and 72% isomer, and the α position carbon atom that it is connected with naphthalene nucleus or toluene ring is the carbon atom that replaces in season.Embodiment 3 provides the example of the alkylnaphthalene that obtains from the alkene that contains the vinylidene structure, wherein season the quantity of substituent and little.Adopt highly active method with zeolite of acidic surface, even adopt the bigger alkene that contains the vinylidene structure of volume ratio, the season that also can obtain high density replaces.Adopt other an acidic catalyst, such as boron trifluoride-ether (BF 3-etherate), also can cause a large amount of seasons to replace.
Embodiment 4 has showed that boron trifluoride-ether catalyzer also has similar selectivity for catalysis generation season substituent:
Table 2.
Sample Embodiment 4 Embodiment 5 embodiment 6 reference examples 2
Aromatic group Naphthalene The toluene benzene toluene
Alkene C16 contains vinylidene structure alkene C20 contains inferior ethene C24 and contains vinylidene C20 alkylene structure alkene structures alkene
Catalyzer Boron trifluoride-ether MCM-49M CM-49 Knut Fridell-Krafft catalyzer
??kV100℃，cSt ??5.2 4.0?????????4.4????????5.2
??kV40℃，cSt ??34.8 20.0????????19.9???????32.1
??VI ??55 72??????????115????????86
Pour point, ℃ ??-54 -51?????????-30????????-51
RBOT, minute 45??????????31?????????20
Season replaces isomer, mole % ??72 54??????????72?????????＜5％
Embodiment 1-4 has greatly improved pour point (D5985 method) compared to reference examples 1, shows that branch can improve pour point.
Direct and reference examples 1 comparison of embodiment 1 energy is because two kinds of lubricating oil have identical molecular weight.Their RBOT (Rotary Bomb Oxidation Test, D2272 method) value was respectively 334 and 196 minutes, proved that quaternary carbon atom can improve oxidation of lubricating oil stability.In addition, B 10 oxidation tests (M334 method) show, embodiment 1 and embodiment 3 compare, in the process of catalyzed oxidation, acid number (0.32vs.2.26 milligram/gram KOH, D664-1 method), viscosity increases (2vs.13 weight %, the D445-5 method), and lead loss (0.6vs.14.3 weight %, D2272 method) improvement is all arranged.
Embodiment 2, though its molecular weight and viscosity, have equally also shown B-10 oxidisability identical with reference examples 1 or improvement greater than embodiment 1 and reference examples 1, the degree of its improvement is no more than embodiment 1.
Embodiment 3 is presented at the isomerization of working as the alkene that contains the vinylidene structure in the reaction process and causes having only in the reaction product under the situation of a spot of season substituent existence the oxidation resistant ability drop of product.Contain the olefin alkylation naphthalene of vinylidene structure for catalysis, because the bulky of this class alkene, the catalytic effect of USY catalyzer is very poor.But for traditional alkylnaphthalene, because its used alkyl is linear alpha-olefin, the USY catalyzer then is outstanding Alkanizing catalyst.Therefore, above-mentioned isomerisation of olefin has caused embodiment 3 and embodiment 1 by comparison, and the RBOT value is lower, although their B-10 oxidation test result is close.
Embodiment 5 can be directly and reference examples 2 do contrast because these two kinds of lubricating oil have identical molecular weight.Their RBOT (rotary oxygen bomb oxidation test, D2272 method) value was respectively 45 and 20 minutes, proved that the carbon atom that replaces in season can improve oxidation of lubricating oil stability.
The product that obtains is analyzed and is summarized as follows.The oxidative stability of product is analyzed with rotary oxygen bomb oxidation test (RBOT) and B-10 oxidation test.Wherein, the testing program of RBOT has description at ASTM D2272; The B-10 oxidation test then is used for weighing mineral oil and ucon oil, and no matter it has or does not have additive.Evaluation to oxidation of lubricating oil stability is based on its ability of anti-atmospheric oxidation under given conditions, and this atmospheric oxidation then is to weigh with sludge formation, the corrosion of plumbous sample preparation product and the change of viscosity and neutral value.In this method, the lead corrosion sample of lubricating oil sample and iron, copper, Al catalysts and known weight is placed in the glass oxidizing chamber together.Oxidizing chamber and its content are placed in the bath in the lump and maintain specific temperature, and in entire test, the dry air of measured quantity is fed sample by the form with bubble.From bath, take out oxidizing chamber then, take catalyst mixture again away.Check lubricating oil sample sees whether there is sludge, its total acid value (TAN) (ASTM664), with and the increase (ASTM D445) of kinematic viscosity (kV) 100 ℃ the time.Plumbous sample preparation product are cleaned and weigh with the loss that ascertains its weight.
Embodiment 7
The product of describing in embodiment 1-6 is that the monoolefine with vinylidene structural content＞95 mole % prepares.The season that the method for employing embodiment 1 can generate the alkyl aromatic compound of 70 moles of % replaces isomer.The season that the method for employing embodiment 5 can generate 54 moles of % replaces isomer.The content that these results are used to calculate the vinylidene structure is the theoretical yield of the monoolefine of 50-65 mole %, is listed in following table 3.
Table 3.
The applicant makes great efforts to disclose in this manual the embodiment and the application of the relevant disclosed theme that all can rational expectation.Yet the present invention exists certainly and can not estimate, unsubstantiality, but still can be considered as the variation of equivalent way of the present invention.Although this specification sheets has adopted above-mentioned concrete exemplary embodiment explanation the present invention, but to one skilled in the art, aforementioned description according to this specification sheets, do not exceeding in the spirit and scope of the present invention, many substitute modes, modification and the variant of the foregoing description are conspicuous.Correspondingly, this specification sheets should be understood that to have a mind to comprise these all based in this specification sheets about substitute mode, the modifications and variations of detailed description of the present invention.
The patent of all references, testing program and alternative document comprise priority document in this specification sheets, and be inconsistent and be suitable under the situation that law allowed on ground in discord the present invention, all introduced for your guidance in full.When listing the upper and lower bound of numerical value in the specification sheets, in all scopes between this bound also all should be included in.
Claims (according to the modification of the 19th of treaty)
1. alkyl aromatic composition comprises:
Aromatic series part except that unsubstituted naphthalene; And
The moieties of carbonatoms between 12-40, wherein said moieties partly link to each other with described aromatic series and make that the benzylic carbon atoms of at least 25 moles of % is a quaternary carbon atom.
2. the described alkyl aromatic composition of claim 1, wherein the benzylic carbon atoms of at least 35 moles of % is a quaternary carbon atom.
3. the described alkyl aromatic composition of claim 1, wherein the benzylic carbon atoms of at least 70 moles of % is a quaternary carbon atom.
4. the described alkyl aromatic composition of claim 1, wherein said aromatic series partly is selected from: benzene, toluene, dimethylbenzene, ethylbenzene, naphthalene, diphenyl sulfide, diphenyloxide, and composition thereof.
5. the described alkyl aromatic composition of claim 1, wherein said aromatic series partly is selected from: replace or unsubstituted benzene, replace naphthalene, replace or unsubstituted furans, replace or unsubstituted thiophene, replace or unsubstituted anthracene, replace or unsubstituted phenanthrene, replace or unsubstituted pyrroles, replace or unsubstituted indoles, replace or unsubstituted thionaphthene, replace or unsubstituted dibenzothiophene, replace or unsubstituted cumarone, replace or unsubstituted diphenylene-oxide, replace or unsubstituted phenoxazine thiophene, replace or unsubstituted thianthrene, replace or unsubstituted biphenyl, replace or unsubstituted pyrene dihydroxyphenyl propane, sulfuration bis-phenol, anisole, thioanisole, diphenyloxide, diphenyl sulfide, ditan, and composition thereof.
6. the described alkyl aromatic composition of claim 1, wherein said aromatic series partly is selected from: toluene, adjacent-, between-or right-dimethylbenzene, hydroxybenzene, anisole or phenetole, thioanisole, phenyl ether, ditan, diphenyl sulfide, methylnaphthalene, methoxynaphthalene, the oxyethyl group naphthalene, sulfuration methylnaphthalene, sulfuration ethyl naphthalene, dihydroxyphenyl propane, the sulfuration bis-phenol, with and composition thereof.
7. the described alkyl aromatic composition of claim 1, the carbonatoms of wherein said moieties is between 16-24.
8. the described alkyl aromatic composition of claim 4, wherein said aromatic series partly is toluene.
9. the described alkyl aromatic composition of claim 8, the RBOT value of the oxidative stability of wherein said composition is more than 30 minutes.
10. the described alkyl aromatic composition of claim 4, wherein said aromatic series partly is benzene.
11. the described alkyl aromatic composition of claim 10, the RBOT value of the oxidative stability of wherein said composition is more than 20 minutes.
12. the described alkyl aromatic composition of claim 1, the pour point of wherein said composition are less than or equal to-35 ℃.
13. the described alkyl aromatic composition of claim 12, the pour point of wherein said composition are less than or equal to-50 ℃.
14. prepare the method for alkyl aromatic compound, comprise: under alkylating condition, at least a aromatic series part is contacted in the presence of acid Alkanizing catalyst at the monoolefine between the 12-40 with carbonatoms, wherein the monoolefine structure of at least 50 moles of % includes the vinylidene structure, and therefore having the benzylic carbon atoms of 25 moles of % at least in the described alkyl aromatic compound that obtains is quaternary carbon atom.
15. the described method of claim 14 further comprises: separate and reclaim described alkyl aromatic compound.
16. it is quaternary carbon atom that the described method of claim 14, wherein said alkyl aromatic compound have the benzylic carbon atoms of at least 65 moles of %.
17. the described method of claim 14, wherein said acid Alkanizing catalyst is selected from: zeolite catalyst, MCM-22, MCM-57, MCM-36, MCM-49, MCM-56, ITQ-1, and ITQ-3.
18. the described method of claim 14, wherein said acid Alkanizing catalyst is a friedel-crafts catalysts, and it is selected from: BF 3, improvement BF 3, AlCl 3, SnCl 4, FeCl 3, and ZnCl 2
19. the described method of claim 14, wherein said aromatic series partly is selected from: benzene, and toluene, dimethylbenzene, ethylbenzene, naphthalene, diphenyl sulfide, diphenyloxide, with and composition thereof.
20. the described method of claim 14, wherein said aromatic series partly is selected from: replace or unsubstituted benzene, replace or unsubstituted naphthalene, replace or unsubstituted furans, replace or unsubstituted thiophene, replace or unsubstituted anthracene, replace or unsubstituted phenanthrene, replace or unsubstituted pyrroles, replace or unsubstituted indoles, replace or unsubstituted thionaphthene, replace or unsubstituted dibenzothiophene, replace or unsubstituted cumarone, replace or unsubstituted diphenylene-oxide, replace or unsubstituted phenoxazine thiophene, replace or unsubstituted thianthrene, replace or unsubstituted biphenyl, replace or unsubstituted pyrene dihydroxyphenyl propane, sulfuration bis-phenol, anisole, thioanisole, diphenyloxide, diphenyl sulfide, ditan, with and composition thereof.
21. the described method of claim 14, wherein said aromatic series partly is selected from: toluene, adjacent-,-or right-dimethylbenzene, hydroxybenzene, anisole or phenetole, thioanisole, phenyl ether, ditan, diphenyl sulfide, naphthalene, methylnaphthalene, methoxynaphthalene, the oxyethyl group naphthalene, sulfuration methylnaphthalene, sulfuration ethyl naphthalene, dihydroxyphenyl propane, the sulfuration bis-phenol, with and composition thereof.
22. the described method of claim 14, the carbonatoms of wherein said monoolefine is between 16-24.
23. the described method of claim 14, wherein said monoolefine rise and are derived from aluminum alkyl catalyst.
24. the described method of claim 23, wherein said aluminum alkyl catalyst are triisobutyl aluminium.
25. the described method of claim 14, wherein said monoolefine works the alpha-olefin polymerization that is derived from metallocene catalysis.
26. the described method of claim 14, wherein said monoolefine rise and are derived from carbonatoms and are less than 40 the alkene that contains the vinylidene structure.
27. the described method of claim 26, the wherein said alkene that contains the vinylidene structure is selected from: 2-hexyl-1-decene, 2-octyl group-1-dodecylene or 2-decyl-tetradecene, with and composition thereof.
28. the described method of claim 14, wherein the described monoolefine structure of at least 65 moles of % contains the vinylidene structure.

Claims (30)

1. alkyl aromatic composition comprises:
Aromatic series part except that unsubstituted naphthalene; And
The moieties of carbonatoms between 12-40, wherein said moieties partly links to each other with described aromatic series, makes that the benzylic carbon atoms of at least 25 moles of % is a quaternary carbon atom.
2. the described alkyl aromatic composition of claim 1, wherein the benzylic carbon atoms of at least 35 moles of % is a quaternary carbon atom.
3. the described alkyl aromatic composition of claim 1, wherein the benzylic carbon atoms of at least 70 moles of % is a quaternary carbon atom.
4. the described alkyl aromatic composition of claim 1, wherein said aromatic series partly is selected from: benzene, toluene, dimethylbenzene, ethylbenzene, naphthalene, diphenyl sulfide, diphenyloxide, and composition thereof.
5. the described alkyl aromatic composition of claim 1, wherein said aromatic series partly is selected from: replace or unsubstituted benzene, replace naphthalene, replace or unsubstituted furans, replace or unsubstituted thiophene, replace or unsubstituted anthracene, replace or unsubstituted phenanthrene, replace or unsubstituted pyrroles, replace or unsubstituted indoles, replace or unsubstituted thionaphthene, replace or unsubstituted dibenzothiophene, replace or unsubstituted cumarone, replace or unsubstituted diphenylene-oxide, replace or unsubstituted phenoxazine thiophene, replace or unsubstituted thianthrene, replace or unsubstituted biphenyl, replace or unsubstituted pyrene dihydroxyphenyl propane, sulfuration bis-phenol, anisole, thioanisole, diphenyloxide, diphenyl sulfide, ditan, with and composition thereof.
6. the described alkyl aromatic composition of claim 1, wherein said aromatic series partly is selected from: toluene, adjacent-, between-or right-dimethylbenzene, hydroxybenzene, anisole or phenetole, thioanisole, phenyl ether, ditan, diphenyl sulfide, methylnaphthalene, methoxynaphthalene, the oxyethyl group naphthalene, sulfuration methylnaphthalene, sulfuration ethyl naphthalene, dihydroxyphenyl propane, the sulfuration bis-phenol, with and composition thereof.
7. the described alkyl aromatic composition of claim 1, the carbonatoms of wherein said moieties is between 16-24.
8. the described alkyl aromatic composition of claim 4, wherein said aromatic series partly is toluene.
9. the described alkyl aromatic composition of claim 8, the RBOT value of the oxidative stability of wherein said composition is more than 30 minutes.
10. the described alkyl aromatic composition of claim 4, wherein said aromatic series partly is benzene.
11. the described alkyl aromatic composition of claim 10, the RBOT value of the oxidative stability of wherein said composition is more than 20 minutes.
12. the described alkyl aromatic composition of claim 1, the pour point of wherein said composition are less than or equal to-35 ℃.
13. the described alkyl aromatic composition of claim 12, the pour point of wherein said composition are less than or equal to-50 ℃.
14. prepare the method for alkyl aromatic compound, comprise: under alkylating condition, at least a aromatics is contacted in the presence of acid Alkanizing catalyst at the monoolefine between the 12-40 with carbonatoms, wherein the monoolefine structure of at least 50 moles of % includes the vinylidene structure, is quaternary carbon atom thereby have the benzylic carbon atoms of 25 moles of % in the described alkyl aromatic compound that obtains at least.
15. the described method of claim 14 further comprises: separate and reclaim described alkyl aromatic compound.
16. it is quaternary carbon atom that the described method of claim 14, wherein said alkyl aromatic compound have the benzylic carbon atoms of at least 65 moles of %.
17. the described method of claim 14, wherein said acid Alkanizing catalyst is selected from: zeolite catalyst, MCM-22, MCM-57, MCM-36, MCM-49, MCM-56, ITQ-1, and ITQ-3.
18. the described method of claim 14, wherein said acid Alkanizing catalyst is a friedel-crafts catalysts, and it is selected from: BF 3, improvement BF 3, AlCl 3, SnCl 4, FeCl 3, and ZnCl 2
20. the described method of claim 14, wherein said aromatic series partly is selected from: benzene, and toluene, dimethylbenzene, ethylbenzene, naphthalene, diphenyl sulfide, diphenyloxide, and composition thereof.
21. the described method of claim 14, wherein said aromatic series partly is selected from: replace or unsubstituted benzene, replace or unsubstituted naphthalene, replace or unsubstituted furans, replace or unsubstituted thiophene, replace or unsubstituted anthracene, replace or unsubstituted phenanthrene, replace or unsubstituted pyrroles, replace or unsubstituted indoles, replace or unsubstituted thionaphthene, replace or unsubstituted dibenzothiophene, replace or unsubstituted cumarone, replace or unsubstituted diphenylene-oxide, replace or unsubstituted phenoxazine thiophene, replace or unsubstituted thianthrene, replace or unsubstituted biphenyl, replace or unsubstituted pyrene dihydroxyphenyl propane, sulfuration bis-phenol, anisole, thioanisole, diphenyloxide, diphenyl sulfide, ditan, with and composition thereof.
22. the described method of claim 14, wherein said aromatic series partly is selected from: toluene, adjacent-,-or right-dimethylbenzene, hydroxybenzene, anisole or phenetole, thioanisole, phenyl ether, ditan, diphenyl sulfide, naphthalene, methylnaphthalene, methoxy naphthalene, the ethoxy naphthalene, sulfuration methylnaphthalene, sulfuration ethyl naphthalene, dihydroxyphenyl propane, the sulfuration bis-phenol, with and composition thereof.
23. the described method of claim 14, the carbonatoms of wherein said monoolefine is between 16-24.
24. the described method of claim 14, wherein said moieties rise and are derived from aluminum alkyl catalyst.
25. the described method of claim 24, wherein said aluminum alkyl catalyst are triisobutyl aluminium.
26. the described method of claim 14, wherein said moieties works the alpha-olefin polymerization that is derived from metallocene catalysis.
The alkene of self-contained vinylidene structure 27. the described method of claim 24, wherein said moieties originate from, the carbonatoms of this alkene is less than 40.
The alkene of self-contained vinylidene structure 28. the described method of claim 26, wherein said moieties originate from, the carbonatoms of this alkene is less than 40.
29. the described method of claim 27, the wherein said alkene that contains the vinylidene structure is selected from 2-hexyl-1-decene, 2-octyl group-1-dodecylene or 2-decyl-tetradecene, with and composition thereof.
30. the described method of claim 28, the wherein said alkene that contains the vinylidene structure is selected from: 2-hexyl-1-decene, 2-octyl group-1-dodecylene or 2-decyl-tetradecene, with and composition thereof.
31. the method in the claim 14, wherein the described monoolefine structure of at least 65 moles of % contains the vinylidene structure.
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