WO1996023751A1 - Process for preparing olefin oligomers - Google Patents

Process for preparing olefin oligomers Download PDF

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Publication number
WO1996023751A1
WO1996023751A1 PCT/EP1996/000235 EP9600235W WO9623751A1 WO 1996023751 A1 WO1996023751 A1 WO 1996023751A1 EP 9600235 W EP9600235 W EP 9600235W WO 9623751 A1 WO9623751 A1 WO 9623751A1
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WIPO (PCT)
Prior art keywords
olefin oligomers
alkyl
catalyst systems
substituents
range
Prior art date
Application number
PCT/EP1996/000235
Other languages
German (de)
French (fr)
Inventor
Joachim Rösch
Hans-Joachim Müller
Günther SCHWEIER
Peter Tanzmeier
Original Assignee
Basf Aktiengesellschaft
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Priority to EP96900602A priority Critical patent/EP0807096A1/en
Publication of WO1996023751A1 publication Critical patent/WO1996023751A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
    • C07C2/34—Metal-hydrocarbon complexes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/22—Organic complexes

Definitions

  • the present invention relates to an improved process for the preparation of olefin oligomers with a molecular weight distribution Mw / Mn in the range from 1.0 to 2.4 by oligomerization of olefins in the presence of metallocene catalyst systems.
  • the invention further relates to olefin oligomers obtainable by a process according to claims 1 to 4, and to the use of the olefin oligomers for the production of lubricants or fuel additives.
  • Olefin oligomers are valuable starting products for the production of fuel and oil additives, lubricants and plasticizers. They can also be used as macromonomers.
  • the modified products obtainable from the olefin oligomers such as, for example, lubricants or fuel additives, have a narrow, monomodal molecular weight distribution. If, on the other hand, the molecular weight distribution is relatively broad, the relatively high molecular weight oligomer fractions can have an adverse effect on the shear stability or valve cleaning characteristics.
  • EP-A 0 268 214 describes the oligomerization of propylene with five-fold alkyl-substituted cyclopentadienyl complexes (metallocene complexes) without the molecular weight distribution Mw / Mn of the propylene oligomers being disclosed.
  • EP-A 0 596 553 describes olefin oligomerizations with metallocene catalysts, the cyclopentadienyl ligands of which are substituted by different alkyls.
  • Mw / Mn of the oligomers is not mentioned.
  • EP-A 0 540 108 describes the preparation of olefin oligomers having a molecular weight distribution of 1.1 to 5.0. However, very special preparative, complex metallocene complexes are also used as catalyst components, the productivity and solubility of which leave something to be desired.
  • the olefins are linear and ring-shaped with 2 to 12 carbon atoms, for example ⁇ -olefins such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 4-methylpentene-1 or vinylcyclohexane are suitable, and also olefins with an internal double bond such as E- and Z-2-butene, E- and Z-2-pentene, E- and Z- 3-witches.
  • ⁇ -olefins such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 4-methylpentene-1 or vinylcyclohexane are suitable, and also ole
  • Cyclopropanes, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclonones, cyclodecene and norbornene are suitable as cycloolefins.
  • C 2 - to C - ⁇ -01efins, such as ethylene, propene, 1-butene and in particular propene, are preferably used.
  • oligomerize mixtures of different olefins having 2 to 12 carbon atoms In addition to the pure olefins, it is of course also possible to oligomerize mixtures of different olefins having 2 to 12 carbon atoms.
  • the molar ratio of the individual olefin components to one another is generally not critical if one observes that the amount of ethylene units in the cooligomers is generally 0.01 to 5 mol%, preferably 0.01 to 3 mol%, in total is particularly 0.01 to 2 mol%.
  • the reaction mixture is the mixture which is present in the time after all reaction components have been combined until the catalyst system has been destroyed after the oligomerization reaction has taken place.
  • the solubility of the catalyst system in the reaction mixture is determined by measuring the turbidity of the reaction mixture analogously to DIN 38404.
  • the catalyst system is largely soluble in the sense of the invention if the turbidity number is in the range from 1 to 10, preferably in the range from 1 to 3.
  • the metallocene component of the catalyst system is a so-called titanocene-zirconocene and hafnocene derivative, hence complexes of titanium, zirconium and hafnium, in which the metal atom M is bonded between two optionally substituted cyclopentadienyl groups, the remaining valences of Central atom M are saturated by easily exchangeable leaving atoms or leaving groups X 1 , X 2 .
  • Suitable metallocene complexes are those with the general formula Cp 2 MX x X 2 in which M is titanium, zirconium or hafnium, preferably zirconium.
  • Cp represent a pair of optionally substituted cyclopentadienyl ligands.
  • the cyclopentadienyl rings are substituted symmetrically.
  • the type, number and also the position of the alkyl substituents of the one Cp ring is identical to the type, number and also position of the alkyl substituents of the second Cp ring.
  • the number of alkyl groups per cyclopentadienyl ring is 1 to 4.
  • Suitable C5 to C3c alkyl radicals for the purposes of the invention are the aliphatic pentyl, hexyl, heptyl, octyl, nonyl, decyl,
  • N-Octadecyl is particularly suitable.
  • C 5 - to C 3 o-alkyl-substituted cyclopentadienyl units can also be substituted by 1 to 2 C - to Cio-alkylene units, which together with the cyclopen- tadienyl unit form a fused ring system, such as the tetrahydroindenyl system.
  • substituted cyclopentadienyl ligands are also possible in pairs in which at least one cyclopentadienyl unit is substituted with at least one organosilyl group -Si (R 1 ) 3 .
  • R 1 then denotes a Ci to C 3 o-carbon organic group such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec.-butyl, tert.-butyl, n -Pentyl, i-pentyl, neo-pentyl, hexyl, heptyl, octyl, nonyl, cyclohexyl, phenyl, p-tolyl.
  • Preferred organosilyl radicals are trimethylsilyl and tert-butyldimethylsilyl, in particular trimethylsilyl.
  • the symmetrical substitution pattern is not absolutely necessary, but is also not excluded.
  • X 1 , X 2 of the metallocene complexes of the general formula I are: hydrogen, halogen such as fluorine, bromine, iodine and preferably chlorine.
  • alcoholates such as methanolate, ethanolate, n- and i-propanolate, phenolate, trifluoromethylphenolate, naphtholate, silanolate may be mentioned.
  • Cio-alkyl radicals in particular methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neo -Pentyl, hexyl, preferably methyl, tert-butyl and neo-pentyl.
  • alicyclic C 3 to C 2 hydrocarbon radicals such as cyclopropyl, cyclobutyl, cyclopentyl and in particular cyclohexyl or C 5 to C 2 o-bicycloalkyl, such as bicyclopentyl, and in particular bicycloheptyl and bicyclooctyl.
  • substituents X 1 , X 2 with aromatic structural units are C ⁇ - to cis-aryl, preferably phenyl, or naphthyl, alkyl aryl or arylalkyl, each having 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical such as tolyl, benzyl.
  • metallocene complexes I are: bis (n-oetadecylcyclopentadienyl) zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride, bis (tetrahydroindenyl) zirconium dichloride, bis [(tert.-butyldimethylsilydichlorodichlorodichloride) dichloride -butylcyclopentadienyl) zirconium dichloride.
  • the metallocene complexes of the general formula I can be synthesized in a simple manner by known processes, for example Brauer (ed.): Handbuch der preparative inorganic chemistry, volume 2, 3rd editions, pages 1395 to 1397, Enke, Stuttgart 1978.
  • a preferred process is based on the lithium salts of the appropriately substituted cyclopentadienyls, which are reacted with the transition metal halides.
  • the catalyst systems according to the invention also contain activators B) which are known per se and are also called cocatalysts in the literature. In general, they alkylate the transition metal component A) of the catalyst system and / or abstract a ligand X from the transition metal component, so that a catalyst system for the oligomerization of olefinically unsaturated hydrocarbons can ultimately result.
  • activators B which are known per se and are also called cocatalysts in the literature. In general, they alkylate the transition metal component A) of the catalyst system and / or abstract a ligand X from the transition metal component, so that a catalyst system for the oligomerization of olefinically unsaturated hydrocarbons can ultimately result.
  • Organometallic compounds of the 1st to 3rd main group or the 2nd subgroup of the periodic table are generally suitable for this task, but other acceptor compounds such as, for example, carbocation salts can also be used.
  • activator compounds are aluminum organyl, boron organyle and carbocation salts.
  • Open-chain or cyclic alumoxane compounds of the general formula II or III are preferred, which can be obtained according to US Pat. No. 4,794,096 by reacting aluminum trialkyls with water.
  • R represents a Ci to C ß alkyl group, preferably Methyl ⁇ or ethyl group, and m is an integer from 5 to 30, preferably 10 to 25th
  • the oligomeric alumoxane compounds are present as mixtures of both linear and cyclic chain molecules of different lengths, so that m is to be regarded as the mean.
  • R 2 is hydrogen, C 1 - to C 10 -alkyl, preferably C 1 to C 4 -alkyl, in particular methyl, ethyl, butyl.
  • R 2 can also represent arylalkyl or alkylaryl, each having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical.
  • aluminum alkyls A1 (R 2 ) 3 are furthermore suitable in which R 2 can mean fluorine, chlorine, bromine or iodine in addition to the radicals defined above, with the proviso that at least one radical R 2 is a C-organic radical or is a hydrogen atom.
  • Particularly preferred compounds are trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, di-isobutyl aluminum hydride, diethyl aluminum chloride.
  • organic boron compounds are also very suitable as activators, for example tris-arylboron compounds, preferably tris (pentafluorophenyl) boron, furthermore salts of carbonium ions, preferably triphenylmethyl tetraaryl borate, in particular triphenylmethyl tetra (pentafluoropheny dborate).
  • tris-arylboron compounds preferably tris (pentafluorophenyl) boron
  • furthermore salts of carbonium ions preferably triphenylmethyl tetraaryl borate, in particular triphenylmethyl tetra (pentafluoropheny dborate).
  • Al, B or C compounds mentioned are known or can be obtained in a manner known per se.
  • the activators can be used alone or as mixtures in the catalyst system.
  • the activator component B) is preferably used in a molar excess with respect to the metal complex A).
  • the molar ratio of activator B) to metal complex A) is generally 100: 1 to 10000: 1, preferably 100: 1 to 1000: 1.
  • the constituents of the catalyst systems according to the invention can be introduced into the oligomerization reactor individually or as a mixture in any order; the metallocene complex is preferably mixed with at least one activator component before it enters the reactor, that is to say preactivated.
  • a particular advantage of the catalyst systems of the process according to the invention is their substantial solubility in the reaction mixture.
  • the oligomers according to the invention can be prepared in the conventional reactors used for the oligomerization of olefins, either batchwise or preferably continuously.
  • Suitable reactors include Konuierlich operated stirred kettle, where it is also possible to use a number of several stirred kettles connected in series.
  • the oligomerization can be carried out in the gas phase, in a suspension, in liquid monomers and in inert solvents.
  • solvents in particular liquid hydrocarbons such as benzene, ethylbenzene or toluene are used.
  • the oligomerizations are preferably carried out in a reaction mixture in which the liquid monomer is present in excess, preferably more than 60% by volume absolute and in particular more than 80% by volume absolute.
  • the oligomeric aluminoxane compound preferably as a solution in toluene
  • the olefin with 2 to 12 carbon atoms is added and the temperature is increased.
  • oligomerization is carried out for 20 to 800 minutes, preferably 50 to 200 minutes.
  • the temperatures here are from 0 to 250 ° C., preferably from 20 to 200 ° C., and the work is carried out at pressures from 100 to 300,000 kPa, preferably in the range from 100 to 10,000 kPa and in particular in the range from 100 to 4000 kPa.
  • the oligomerization can therefore be carried out using the low-pressure, medium-pressure and high-pressure processes.
  • the amount of catalyst used is not critical.
  • oligomers with molecular weights Mw (weight average) of preferably 100 to 20,000, particularly preferably 100 to 10,000, in particular 100 to 5,000, which have a high content of terminal vinylidene double bonds.
  • the degree of polymerization of the olefin oligomers is generally in the range from 2 to 200, preferably in the range from 2 to 100.
  • the molecular weight distribution Mw / Mn (weight average / number average), measured with the method of gel permeation chromatography (GPC) at 35 ° C. with polystyrene as column material and THF as solvent against a polystyrene standard, the 5 olefin oligomers thus obtained is 1. 0 to 2.4, preferably 1.8 to 2.2 and in particular 1.8 to 2.0.
  • the GPC diagram advantageously shows only a relative maximum for the molecular weight distribution, i.e. there is a monomodal molecular weight distribution.
  • the olefin oligomers obtained in this way can be further processed with the customary chemical reactions, such as hydoformylation or hydroamination or a combination of both methods, to functionalized oligo-olefins which are suitable, for example, as lubricants or fuel or oil additives are. Because of their double bond content, the olefin oligomers obtained can also be used as macromonomers.

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  • Organic Chemistry (AREA)
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Abstract

A process is disclosed for preparing olefin oligomers with a molecular weight distribution Mw/Mn in a range from 1.0 to 2.4 by oligomerisation of olefins in the presence of metallocene catalyst systems. The turbidity index of the catalyst-containing reaction mixture lies in a range from 1 to 10. The olefin oligomers are useful as starting materials for preparing lubricants, fuel and oil additives, and as macromonomers.

Description

Verfahren zur Herstellung von Olefin-OligomerenProcess for the preparation of olefin oligomers
Beschreibungdescription
Die vorliegende Erfindung betrifft ein verbessertes Verfahren zur Herstellung von Olefin-Oligomeren mit einer Molekulargewichtsver¬ teilung Mw/Mn im Bereich von 1,0 bis 2,4 durch Oligomerisierung von Olefinen in Gegenwart von Metallocenkatalysatorsystemen.The present invention relates to an improved process for the preparation of olefin oligomers with a molecular weight distribution Mw / Mn in the range from 1.0 to 2.4 by oligomerization of olefins in the presence of metallocene catalyst systems.
Weiterhin betrifft die Erfindung Olefin-Oligomeren erhältlich nach einem Verfahren gemäß den Ansprüchen 1 bis 4, sowie die Ver¬ wendung der Olefin-Oligomeren zur Herstellung von Schmierstoffen oder Kraftstoffadditiven.The invention further relates to olefin oligomers obtainable by a process according to claims 1 to 4, and to the use of the olefin oligomers for the production of lubricants or fuel additives.
Olefin-Oligomere sind wertvolle Ausgangsprodukte für die Herstel¬ lung von Kraftstoff- und öladditiven, Schmierstoffen und Weichma¬ chern. Weiterhin können sie als Makromonomere eingesetzt werden.Olefin oligomers are valuable starting products for the production of fuel and oil additives, lubricants and plasticizers. They can also be used as macromonomers.
Es ist im allgemeinen vorteilhaft, wenn die aus den Olefin-Oligo¬ meren erhältlichen modifizierten Produkte, wie zum Beispiel Schmierstoffe oder Kraftstoffadditive eine enge, monomodale Molekulargewichtsverteilung haben. Ist die Molekulargewichtsver¬ teilung andererseits relativ breit, dann können die relativ hoch- molekularen Oligomerfraktionen einen nachteiligen Effekt auf die Scherstabilität oder Ventilreinigungscharakteristik haben.It is generally advantageous if the modified products obtainable from the olefin oligomers, such as, for example, lubricants or fuel additives, have a narrow, monomodal molecular weight distribution. If, on the other hand, the molecular weight distribution is relatively broad, the relatively high molecular weight oligomer fractions can have an adverse effect on the shear stability or valve cleaning characteristics.
Daher ist es im allgemeinen vorteilhaft, wenn die AusgangsStoffe selbst, also die Olefin-Oligomeren, bereits eine enge Molekular- gewichtsVerteilung Mw/Mn aufweisen.It is therefore generally advantageous if the starting materials themselves, ie the olefin oligomers, already have a narrow molecular weight distribution Mw / Mn.
In der EP-A 0 268 214 wird die Oligomerisierung von Propylen mit fünffach alkylsubstituierten Cyclopentadienylkomplexen (Metallocenkomplexe) beschrieben, ohne daß die Molekulargewichts- Verteilung Mw/Mn der Propylenoligomeren offenbart wird.EP-A 0 268 214 describes the oligomerization of propylene with five-fold alkyl-substituted cyclopentadienyl complexes (metallocene complexes) without the molecular weight distribution Mw / Mn of the propylene oligomers being disclosed.
Die EP-A 0 596 553 beschreibt Olefin-Oligomerisierungen mit Metallocenkatalysatoren, deren Cyclopentadienyl-Liganden unter¬ schiedlich Alkyl-substituiert sind. Auch hier wird die Molekular- gewichtsVerteilung Mw/Mn der Oligomeren nicht erwähnt.EP-A 0 596 553 describes olefin oligomerizations with metallocene catalysts, the cyclopentadienyl ligands of which are substituted by different alkyls. Here, too, the molecular weight distribution Mw / Mn of the oligomers is not mentioned.
Die beschriebenen Metallocenkomplexe sind aufwendig herzustellen, ihre Produktivität sowie ihre Löslichkeit im Monomeren läßt zu wünschen übrig. Die EP-A 0 540 108 beschreibt die Herstellung von Olefin-Oligome¬ ren der Molekulargewichtsverteilung von 1,1 bis 5,0. Allerdings werden auch hier sehr spezielle präparativ aufwendige Metallocen¬ komplexe als Katalysatorbestandteile verwendet deren Produktivi- tat und Löslichkeit zu wünschen übrig läßt.The metallocene complexes described are difficult to prepare, their productivity and their solubility in the monomer leave something to be desired. EP-A 0 540 108 describes the preparation of olefin oligomers having a molecular weight distribution of 1.1 to 5.0. However, very special preparative, complex metallocene complexes are also used as catalyst components, the productivity and solubility of which leave something to be desired.
Aufgabe der vorliegenden Erfindung war es daher, ein verbessertes Verfahren zur Herstellung von Olefin-Oligomeren aus Olefinen be¬ reitzustellen, deren Molekulargewichtsverteilung im Bereich von 1,0 bis 2,4 liegt, und die mit hoher Produktivität unter Verwen¬ dung leicht zugänglicher, gut löslicher Katalysatorsysteme herge¬ stellt werden können.It was therefore an object of the present invention to provide an improved process for the preparation of olefin oligomers from olefins whose molecular weight distribution is in the range from 1.0 to 2.4 and which is easily accessible with high productivity using soluble catalyst systems can be manufactured.
Demgemäß wurde ein Verfahren zur Herstellung von Olefin-Oligome- ren mit einer MolekulargewichtsVerteilung Mw/Mn im Bereich von 1,0 bis 2,4 durch Oligomerisierung von Olefinen in Gegenwart von Metallocenkatalysatorsystemen gefunden, wobei die Trübungszahl des katalysatorhaltigen Reaktionsgemisches im Bereich von 1 bis 10 liegt.Accordingly, a process for the preparation of olefin oligomers with a molecular weight distribution Mw / Mn in the range from 1.0 to 2.4 by oligomerization of olefins in the presence of metallocene catalyst systems was found, the turbidity number of the catalyst-containing reaction mixture in the range from 1 to 10 lies.
Außerdem wurden die Olefin-Oligomerenmischungen erhältlich mit dem Verfahren gemäß der Ansprüche 1 bis 4 gefunden, sowie die Verwendung der Olefin-Oligomeren zur Herstellung von Schmier¬ stoffen oder Kraftstoffadditiven.In addition, the olefin-oligomer mixtures obtainable by the process according to claims 1 to 4 were found, and the use of the olefin-oligomers for the production of lubricants or fuel additives.
Von den Olefinen sind lineare und ringförmige mit 2 bis 12 C-Ato- men, also beispielsweise α-Olefine wie Ethylen, Propen, 1-Buten, 1-Penten, 1-Hexen, 1-Hepten, 1-Octen 1-Nonen, 1-Decen, 1-Undecen, 1-Dodecen, 4-Methylpenten-l oder Vinylcyclohexan geeignet, sowie Olefine mit interner Doppelbindung wie E- und Z-2-Buten, E- und Z-2-Penten, E-und Z-3-Hexen. Als Cycloolefine eignen sich gut Cy- clopropen, Cyclobuten, Cyclopenten, Cyclohexen, Cyclohepten, Cycloocten, Cyclononen, Cyclodecen und Norbornen. Vorzugsweise verwendet man C2- bis C -α-01efine, wie Ethylen, Propen, 1-Buten und insbesondere Propen.The olefins are linear and ring-shaped with 2 to 12 carbon atoms, for example α-olefins such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 4-methylpentene-1 or vinylcyclohexane are suitable, and also olefins with an internal double bond such as E- and Z-2-butene, E- and Z-2-pentene, E- and Z- 3-witches. Cyclopropanes, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclonones, cyclodecene and norbornene are suitable as cycloolefins. C 2 - to C -α-01efins, such as ethylene, propene, 1-butene and in particular propene, are preferably used.
Neben den reinen Olefinen können selbstverständlich auch Gemische unterschiedlicher Olefine mit 2 bis 12 Kohlenstoffatomen oligo- merisiert werden. Das molare Verhältnis der einzelnen Olefinkom- ponenten zueinander ist im allgemeinen nicht kritisch, wenn man beachtet, daß die Menge an Ethyleneinheiten in den Cooligomeren im allgemeinen 0,01 bis 5 mol-%, bevorzugt 0,01 bis 3 mol-%, ins¬ besondere 0,01 bis 2 mol-% beträgt.In addition to the pure olefins, it is of course also possible to oligomerize mixtures of different olefins having 2 to 12 carbon atoms. The molar ratio of the individual olefin components to one another is generally not critical if one observes that the amount of ethylene units in the cooligomers is generally 0.01 to 5 mol%, preferably 0.01 to 3 mol%, in total is particularly 0.01 to 2 mol%.
An die Katalysatorsysteme des erfindungsgemäßen Verfahrens werden keine besonderen Anforderungen gestellt, außer daß sie in dem Re- aktionsgemisch weitgehend löslich sind. Das Reaktionsgemisch ist die Mischung, welche in der Zeit nach dem Zusammengeben aller Re¬ aktionskomponenten bis spätestens zum Zerstören des Katalysator¬ systems nach erfolgter Oligomerisierungsreaktion vorliegt. Die Löslichkeit des Katalysatorsystems im Reaktionsgemisch wird durch die Messung der Trübung des Reaktionsgemisches analog DIN 38404 bestimmt. Eine weitgehende Löslichkeit des Katalysator¬ systems im Sinne der Erfindung liegt vor, wenn die Trübungszahl im Bereich von 1 bis 10, vorzugsweise im Bereich von 1 bis 3 liegt.No particular requirements are imposed on the catalyst systems of the process according to the invention, except that they are largely soluble in the reaction mixture. The reaction mixture is the mixture which is present in the time after all reaction components have been combined until the catalyst system has been destroyed after the oligomerization reaction has taken place. The solubility of the catalyst system in the reaction mixture is determined by measuring the turbidity of the reaction mixture analogously to DIN 38404. The catalyst system is largely soluble in the sense of the invention if the turbidity number is in the range from 1 to 10, preferably in the range from 1 to 3.
Bei der Metallocenkomponente des Katalysatorsystems handelt es sich um sogenannte Titanocen- Zirkonocen- und Hafnocenderivate, mithin um Komplexe des Titans, Zirkoniums und Hafniums, bei denen das Metallatom M sandwichartig zwischen zwei gegebenenfalls sub- stituierten Cyclopentadienyl-Gruppen gebunden ist, wobei die restlichen Valenzen des Zentralatoms M durch leicht austauschbare Abgangsatome oder Abgangsgruppen X1, X2 abgesattigt sind.The metallocene component of the catalyst system is a so-called titanocene-zirconocene and hafnocene derivative, hence complexes of titanium, zirconium and hafnium, in which the metal atom M is bonded between two optionally substituted cyclopentadienyl groups, the remaining valences of Central atom M are saturated by easily exchangeable leaving atoms or leaving groups X 1 , X 2 .
Geeignete Metallocenkomplexe sind solche mit der allgemeinen For- mel Cp2MXxX2 in welchen M Titan, Zirconium oder Hafnium, vorzugs¬ weise Zirconium, bedeuten.Suitable metallocene complexes are those with the general formula Cp 2 MX x X 2 in which M is titanium, zirconium or hafnium, preferably zirconium.
Cp stehen für ein Paar von, gegebenenfalls, substituierten Cyclo- pentadienyl-Liganden.Cp represent a pair of optionally substituted cyclopentadienyl ligands.
Für den Fall, daß die Substituenten C5- bis C3o-Alkylgruppen be¬ deuten sind die Cyclopentadienylringe symmetrisch substituiert. Dies bedeutet, daß sowohl Art, Anzahl, als auch die Position der Alkyl- Substituenten des einen Cp-Ringes identisch ist mit Art, Anzahl und auch Position der Alkyl-Substituenten des zweiten Cp- Ringes. Die Anzahl der Alkylgruppen pro Cyclopentadienylring be¬ trägt 1 bis 4.In the event that the substituents are C 5 to C 3 o-alkyl groups, the cyclopentadienyl rings are substituted symmetrically. This means that the type, number and also the position of the alkyl substituents of the one Cp ring is identical to the type, number and also position of the alkyl substituents of the second Cp ring. The number of alkyl groups per cyclopentadienyl ring is 1 to 4.
Geeignete C5- bis C3c-Alkylreste im Sinne der Erfindung sind die aliphatischen Pentyl, Hexyl, Heptyl, Octyl, Nonyl, Decyl,Suitable C5 to C3c alkyl radicals for the purposes of the invention are the aliphatic pentyl, hexyl, heptyl, octyl, nonyl, decyl,
Undecyl, Dodecyl, Tridecyl, Tetradecyl, Pentadecyl, Hexadecyl, Heptadecyl, Octadecyl, Nonadecyl und Eicosyl und ihre Isomere, wie beispielsweise neo-Pentyl, iso-Octyl, sowie die cycloali- phatischen Cyclopentyl, Cyclohexyl.Undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl and their isomers, such as neo-pentyl, iso-octyl, and the cycloaliphatic cyclopentyl, cyclohexyl.
Besonders gut geeignet ist n-Octadecyl.N-Octadecyl is particularly suitable.
Die, gegebenenfalls C5- bis C3o-Alkylsubstituierten, Cyclopenta- dienyleinheiten können aber auch mit je 1 bis 2 C - bis Cio-Al- kyleneinheiten substituiert sein, die zusammen mit der Cyclopen- tadienyleinheit ein anneliertes Ringsystem, wie beispielsweise das Tetrahydroindenylsystem, bilden.The optionally C 5 - to C 3 o-alkyl-substituted cyclopentadienyl units can also be substituted by 1 to 2 C - to Cio-alkylene units, which together with the cyclopen- tadienyl unit form a fused ring system, such as the tetrahydroindenyl system.
Als substituierte Cyclopentadienyl-Liganden kommen aber auch sol- ehe Paare in Frage in welchen mindestens eine Cyclopentadieny- leinheit mit mindestens einer Organosilylgruppe -Si(R1)3 substi¬ tuiert ist. R1 bedeutet dann eine Ci- bis C3o-Kohlenstoff-organi- sche Gruppe wie Methyl, Ethyl, n-Propyl, i-Propyl, n-Butyl, i-Butyl, sec.-Butyl, tert.-Butyl, n-Pentyl, i-Pentyl, neo-Pentyl, Hexyl, Heptyl, Octyl, Nonyl, Cyclohexyl, Phenyl, p-Tolyl. Bevor¬ zugte Organosilylreste sind Trimethylsilyl und ter .-Butyldi- methylsilyl, insbesondere Trimethylsilyl.However, substituted cyclopentadienyl ligands are also possible in pairs in which at least one cyclopentadienyl unit is substituted with at least one organosilyl group -Si (R 1 ) 3 . R 1 then denotes a Ci to C 3 o-carbon organic group such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec.-butyl, tert.-butyl, n -Pentyl, i-pentyl, neo-pentyl, hexyl, heptyl, octyl, nonyl, cyclohexyl, phenyl, p-tolyl. Preferred organosilyl radicals are trimethylsilyl and tert-butyldimethylsilyl, in particular trimethylsilyl.
Für den Fall der Organosilylsubstitution an den Cyclopentadieny- leinheiten ist das symmetrische Substitutionsmuster nicht zwin¬ gend notwendig, aber auch nicht ausgeschlossen.In the case of organosilyl substitution on the cyclopentadienyl units, the symmetrical substitution pattern is not absolutely necessary, but is also not excluded.
Als leicht austauschbare, formal negativ geladene Abgangsatome oder Abgangsgruppen X1, X2 der Metallocenkomplexe der allgemeinen Formel I seien genannt: Wasserstoff, Halogen wie Fluor, Brom, lod und vorzugsweise Chlor.Easily exchangeable, formally negatively charged leaving atoms or leaving groups X 1 , X 2 of the metallocene complexes of the general formula I are: hydrogen, halogen such as fluorine, bromine, iodine and preferably chlorine.
Darüber hinaus seien genannt Alkoholate, wie Methanolat, Ethano- lat, n- und i-Propanolat, Phenolat, Trifluormethylphenolat, Naph- tholat, Silanolat.In addition, alcoholates such as methanolate, ethanolate, n- and i-propanolate, phenolate, trifluoromethylphenolate, naphtholate, silanolate may be mentioned.
Weiterhin empfehlen sich für X1, X2 besonders aliphatische Ci- bis Cio-Alkyl-Reste, insbesondere Methyl, Ethyl, Propyl, iso-Propyl, Butyl, iso-Butyl, sec.-Butyl, tert.-Butyl, Pentyl, neo-Pentyl, Hexyl, vorzugsweise Methyl, tert.-Butyl und neo-Pentyl. Desweite- ren alicyclische C3 bis Cι2-Kohlenwasserstoffreste, wie Cyclo- propyl, Cyclobutyl, Cyclopentyl und insbesondere Cyclohexyl oder C5- bis C2o-Bicycloalkyl, wie Bicyclopentyl, und insbesondere Bi- cycloheptyl und Bicyclooctyl.Furthermore, particularly recommended for X 1 , X 2 are aliphatic Ci to Cio-alkyl radicals, in particular methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neo -Pentyl, hexyl, preferably methyl, tert-butyl and neo-pentyl. Furthermore, alicyclic C 3 to C 2 hydrocarbon radicals, such as cyclopropyl, cyclobutyl, cyclopentyl and in particular cyclohexyl or C 5 to C 2 o-bicycloalkyl, such as bicyclopentyl, and in particular bicycloheptyl and bicyclooctyl.
Als Substituenten X1, X2 mit aromatischen Struktureinheiten seien genannt Cβ- bis Cis-Aryl, bevorzugt Phenyl, oder Naphthyl, Alkyl- aryl oder Arylalkyl, mit jeweils 1 bis 10 C-Atomen im Alkylrest und 6 bis 20 C-Atomen im Arylrest, wie beispielsweise Tolyl, Benzyl.Examples of substituents X 1 , X 2 with aromatic structural units are Cβ- to cis-aryl, preferably phenyl, or naphthyl, alkyl aryl or arylalkyl, each having 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical such as tolyl, benzyl.
Beispiele für geeignete Metallocenkomplexe I sind: Bis (n-oetade- cylcyclopentadienyl) zirconiumdichlorid, Bis (trimethylsilylcyclo- pentadienyl) zirconiumdichlorid, Bis (tetrahydroindenyl) zirconium¬ dichlorid, Bis[ (tert.-ButyldimethylsilyDcyclopentadienyl]zirco- niumdichlorid, Bis(Di-tert-butylcyclopentadienyl) zirconium¬ dichlorid. Die Metallocenkomplexe der allgemeinen Formel I können auf einfa¬ che Weise nach bekannten Verfahren, z.B. Brauer (Hrsg.): Handbuch der Präparativen Anorganischen Chemie, Band 2, 3.Aufläge, Seite 1395 bis 1397, Enke, Stuttgart 1978 synthetisiert werden. Ein be- vorzugtes Verfahren geht von den Lithiumsalzen der entsprechend substituierten Cyclopentadienylen aus, welche mit den Übergangs- metallhalogeniden umgesetzt werden.Examples of suitable metallocene complexes I are: bis (n-oetadecylcyclopentadienyl) zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride, bis (tetrahydroindenyl) zirconium dichloride, bis [(tert.-butyldimethylsilydichlorodichlorodichloride) dichloride -butylcyclopentadienyl) zirconium dichloride. The metallocene complexes of the general formula I can be synthesized in a simple manner by known processes, for example Brauer (ed.): Handbuch der preparative inorganic chemistry, volume 2, 3rd editions, pages 1395 to 1397, Enke, Stuttgart 1978. A preferred process is based on the lithium salts of the appropriately substituted cyclopentadienyls, which are reacted with the transition metal halides.
Zweckmäßigerweise wird nur ein Metallocenkomplex in der Oligome- risierungsreaktion eingesetzt, es ist aber auch möglich, Mischungen verschiedener Metallocenkomplexe zu verwenden.Only one metallocene complex is expediently used in the oligomerization reaction, but it is also possible to use mixtures of different metallocene complexes.
Neben den Metallocenkomplexen A) enthalten die erfindungsgemäßen Katalysatorsysteme noch Aktivatoren B) die an sich bekannt sind und im Schrifttum auch Cokatalysatoren genannt werden. Im allge¬ meinen alkylieren sie die Übergangsmetallkomponente A) des Katalysatorsystems und/oder abstrahieren einen Liganden X von der Übergangsmetall-Komponente, so daß letztendlich ein Katalysator¬ system für die Oligomerisierung von olefinisch ungesättigten Koh- lenwasserstoffen entstehen kann. Für diese Aufgabe sind im allge¬ meinen metallorganische Verbindungen der 1. bis 3. Hauptgruppe oder der 2. Nebengruppe des Periodensystems geeignet, jedoch kön¬ nen auch andere Akzeptorverbindungen wie beispielsweise Carboka- tionen-Salze eingesetzt werden.In addition to the metallocene complexes A), the catalyst systems according to the invention also contain activators B) which are known per se and are also called cocatalysts in the literature. In general, they alkylate the transition metal component A) of the catalyst system and / or abstract a ligand X from the transition metal component, so that a catalyst system for the oligomerization of olefinically unsaturated hydrocarbons can ultimately result. Organometallic compounds of the 1st to 3rd main group or the 2nd subgroup of the periodic table are generally suitable for this task, but other acceptor compounds such as, for example, carbocation salts can also be used.
Besonders gut geeignete Aktivatorverbindungen sind Aluminiu -Or- ganyle, Bor-Organyle und Carbokationen-Salze. Bevorzugt sind offenkettige oder cyclische Alumoxanverbindungen der allgemeinen Formel II oder III, die nach US-A 4,794,096 durch Umsetzung von Aluminiumtrialkylen mit Wasser erhalten werden können.Particularly suitable activator compounds are aluminum organyl, boron organyle and carbocation salts. Open-chain or cyclic alumoxane compounds of the general formula II or III are preferred, which can be obtained according to US Pat. No. 4,794,096 by reacting aluminum trialkyls with water.
RR
AI- 4-0 —AI -4- m IIAI- 4-0 —AI -4- m II
-f- O AI - III m-f- O AI - III m
Hierin steht R für eine Ci- bis Cß-Alkylgruppe, bevorzugt Methyl¬ oder Ethylgruppe, und m für eine ganze Zahl von 5 bis 30, bevor- zugt 10 bis 25. In der Regel liegen die oligomeren Alumoxanverbindungen als Gemi¬ sche unterschiedlich langer, sowohl linearer als auch cyclischer Kettenmoleküle vor, so daß m als Mittelwert anzusehen ist.Herein, R represents a Ci to C ß alkyl group, preferably Methyl¬ or ethyl group, and m is an integer from 5 to 30, preferably 10 to 25th As a rule, the oligomeric alumoxane compounds are present as mixtures of both linear and cyclic chain molecules of different lengths, so that m is to be regarded as the mean.
Als Cokatalysatoren sind im allgemeinen auch Aluminiumorganyle der allgemeinen Formel Al(R2)3 geeignet, wobei R2 Wasserstoff, Cj-- bis Cio-Alkyl, vorzugsweise Ci- bis C4- Alkyl, insbesondere Methyl, Ethyl, Butyl bedeutet. Darüber hinaus kann R2 auch für Arylalkyl oder Alkylaryl mit jeweils 1 bis 10 C-Atomen im Alkyl- rest und 6 bis 20 C-Atomen im Arylrest stehen.Also suitable as cocatalysts are generally aluminum organyls of the general formula Al (R 2 ) 3 , where R 2 is hydrogen, C 1 - to C 10 -alkyl, preferably C 1 to C 4 -alkyl, in particular methyl, ethyl, butyl. In addition, R 2 can also represent arylalkyl or alkylaryl, each having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical.
weiterhin sind Aluminiumalkyle A1(R2)3 geeignet in denen R2 außer den oben definierten Resten noch Fluor, Chlor, Brom oder lod be¬ deuten kann, mit der Maßgabe, daß mindestens ein Rest R2 ein C-or- ganischer Rest oder ein Wasserstoffatom ist. Besonders bevorzugte Verbindungen sind Trimethylaluminium, Triethylaluminium, Triiso- butylaluminium, Di-isobutylaluminiumhydrid, Diethylaluminium- chlorid.aluminum alkyls A1 (R 2 ) 3 are furthermore suitable in which R 2 can mean fluorine, chlorine, bromine or iodine in addition to the radicals defined above, with the proviso that at least one radical R 2 is a C-organic radical or is a hydrogen atom. Particularly preferred compounds are trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, di-isobutyl aluminum hydride, diethyl aluminum chloride.
Außerdem sind als Aktivatoren noch Bor-organische Verbindungen gut geeignet, beispielsweise Tris-arylborverbindungen, bevorzugt Tris (pentafluorophenyl)bor, weiterhin Salze von Carboniumionen, bevorzugt Triphenylmethyltetraarylborat, insbesondere Triphenyl- methyltetra(pentafluorophenyDborat.In addition, organic boron compounds are also very suitable as activators, for example tris-arylboron compounds, preferably tris (pentafluorophenyl) boron, furthermore salts of carbonium ions, preferably triphenylmethyl tetraaryl borate, in particular triphenylmethyl tetra (pentafluoropheny dborate).
Die genannten AI-, B- oder C-Verbindungen sind bekannt oder in an sich bekannter Weise erhältlich.The Al, B or C compounds mentioned are known or can be obtained in a manner known per se.
Die Aktivatoren können für sich allein oder als Mischungen im Katalysatorsystem eingesetzt werden.The activators can be used alone or as mixtures in the catalyst system.
Vorzugsweise setzt man die Aktivatorkomponente B) im molaren Überschuß bezüglich des Metallkomplexes A) ein.The activator component B) is preferably used in a molar excess with respect to the metal complex A).
Das Molverhältnis von Aktivator B) zu Metallkomplex A) beträgt im allgemeinen 100 : 1 bis 10000 : 1, vorzugsweise 100 : 1 bis 1000 : 1.The molar ratio of activator B) to metal complex A) is generally 100: 1 to 10000: 1, preferably 100: 1 to 1000: 1.
Die Bestandteile der erfindungsgemäßen Katalysatorsysteme können in beliebiger Reihenfolge einzeln oder als Gemisch in den Oligo- merisierungsreaktor eingebracht werden, vorzugsweise wird der Metallocenkomplex mit mindestens einer Aktivatorkomponente vor dem Eintritt in den Reaktor gemischt, das bedeutet voraktiviert. Ein besonderer Vorteil der Katalysatorsysteme des erfindungs¬ gemäßen Verfahrens ist ihre weitgehende Löslichkeit im Reaktions¬ gemisch.The constituents of the catalyst systems according to the invention can be introduced into the oligomerization reactor individually or as a mixture in any order; the metallocene complex is preferably mixed with at least one activator component before it enters the reactor, that is to say preactivated. A particular advantage of the catalyst systems of the process according to the invention is their substantial solubility in the reaction mixture.
Die Herstellung der erfindungsgemäßen Oligomeren kann in den üb¬ lichen, für die Oligomerisation von Olefinen verwendeten Reak¬ toren entweder diskontinuierlich oder bevorzugt kontinuierlich durchgeführt werden. Geeignete Reaktoren sind u.a. kon inuierlich betriebene Rührkessel, wobei man gegebenenfalls auch eine Reihe von mehreren hintereinander geschalteten Rührkesseln verwenden kann.The oligomers according to the invention can be prepared in the conventional reactors used for the oligomerization of olefins, either batchwise or preferably continuously. Suitable reactors include Konuierlich operated stirred kettle, where it is also possible to use a number of several stirred kettles connected in series.
Die Oligomerisation kann in der Gasphase, in einer Suspension, in flüssigen Monomeren und in inerten Lösungsmitteln durchgeführt werden. Bei der Oligomerisation in Lösungsmitteln werden ins¬ besondere flüssige Kohlenwasserstoffe wie Benzol, Ethylbenzol oder Toluol verwendet. Vorzugsweise werden die Oligomerisierungen in einem Reaktionsgemisch durchgeführt in welchem das flüssige Monomere im Überschuß vorliegt, vorzugsweise zu mehr als 60 Vol.-% absolut und insbesondere zu mehr als 80 Vol.-% absolut.The oligomerization can be carried out in the gas phase, in a suspension, in liquid monomers and in inert solvents. In the case of oligomerization in solvents, in particular liquid hydrocarbons such as benzene, ethylbenzene or toluene are used. The oligomerizations are preferably carried out in a reaction mixture in which the liquid monomer is present in excess, preferably more than 60% by volume absolute and in particular more than 80% by volume absolute.
Bei einem bevorzugten erfindungsgemäßen Verfahren zur Herstellung der Olefin-Oligomeren wird zunächst die oligomere Aluminoxanver- bindung, bevorzugt als Lösung in Toluol, vorgelegt. Hierzu wird beispielsweise das Olefin mit 2 bis 12 C-Atomen zugegeben und die Temperatur wird erhöht. Nach Zugabe des Metallocenkomplexes wird 20 bis 800 Minuten, bevorzugt 50 bis 200 Minuten oligomerisiert. Die Temperaturen betragen hierbei 0 bis 250°C, bevorzugt 20 bis 200°C und man arbeitet bei Drücken von 100 bis 300000 kPa, vor- zugsweise im Bereich von 100 bis 10000 kPa und insbesondere im Bereich von 100 bis 4000 kPa.In a preferred process according to the invention for the preparation of the olefin oligomers, the oligomeric aluminoxane compound, preferably as a solution in toluene, is initially introduced. For this purpose, for example, the olefin with 2 to 12 carbon atoms is added and the temperature is increased. After addition of the metallocene complex, oligomerization is carried out for 20 to 800 minutes, preferably 50 to 200 minutes. The temperatures here are from 0 to 250 ° C., preferably from 20 to 200 ° C., and the work is carried out at pressures from 100 to 300,000 kPa, preferably in the range from 100 to 10,000 kPa and in particular in the range from 100 to 4000 kPa.
Man kann die Oligomerisation also im Niederdruck-, Mitteldruck- und Hochdruckverfahren durchführen. Die Menge an eingesetztem Ka- talysator ist nicht kritisch.The oligomerization can therefore be carried out using the low-pressure, medium-pressure and high-pressure processes. The amount of catalyst used is not critical.
Man erhält somit Oligomere mit Molekulargewichten Mw (Gewichts¬ mittelwert) von vorzugsweise 100 bis 20000, besonders bevorzugt 100 bis 10000, insbesondere 100 bis 5000, die einen hohen Gehalt an endständigen Vinyliden-Doppelbindungen aufweisen.This gives oligomers with molecular weights Mw (weight average) of preferably 100 to 20,000, particularly preferably 100 to 10,000, in particular 100 to 5,000, which have a high content of terminal vinylidene double bonds.
Der Polymerisationsgrad der Olefin-Oligomeren liegt im allgemei¬ nen im Bereich von 2 bis 200, vorzugsweise im Bereich von 2 bis 100. Die Molekulargewichtsverteilung Mw/Mn (Gewichtsmittelwert/Zahlen¬ mittelwert), gemessen mit der Methode der Gelpermeationschromato- graphie (GPC) bei 35°C mit Polystyrol als Säulenmaterial und THF als Lösungsmittel gegen einen Polystyrolstandard, der so 5 erhaltenen Olefin-Oligomeren beträgt 1,0 bis 2,4, vorzugsweise 1,8 bis 2,2 und insbesondere 1,8 bis 2,0.The degree of polymerization of the olefin oligomers is generally in the range from 2 to 200, preferably in the range from 2 to 100. The molecular weight distribution Mw / Mn (weight average / number average), measured with the method of gel permeation chromatography (GPC) at 35 ° C. with polystyrene as column material and THF as solvent against a polystyrene standard, the 5 olefin oligomers thus obtained is 1. 0 to 2.4, preferably 1.8 to 2.2 and in particular 1.8 to 2.0.
Das GPC-Diagra m zeigt vorteilhaft nur ein relatives Maximum für die Molekulargewichtsverteilung, d.h.es liegt eine monomodale 0 Molekulargewichtsverteilung vor.The GPC diagram advantageously shows only a relative maximum for the molecular weight distribution, i.e. there is a monomodal molecular weight distribution.
Die so erhaltenen Olefin-Oligomere lassen sich mit den üblichen chemischen Reaktionen, wie zum Beispiel Hydoformylierung oder Hy- droaminierung oder einer Kombination beider Methoden, zu funktio- 5 nalisierten Oligo-Olefinen weiterverarbeiten, welche zum Beispiel als Schmierstoffe oder Kraftstoff- bzw. Öladditive geeignet sind. Aufgrund ihres Doppelbindungsanteils sind die erhaltenen Olefin- Oligomere außerdem als Makromonomere verwendbar.The olefin oligomers obtained in this way can be further processed with the customary chemical reactions, such as hydoformylation or hydroamination or a combination of both methods, to functionalized oligo-olefins which are suitable, for example, as lubricants or fuel or oil additives are. Because of their double bond content, the olefin oligomers obtained can also be used as macromonomers.
0 Beispiele0 examples
Herstellung von Olefin-OligomerenManufacture of olefin oligomers
Beispiel 1 5Example 1 5
In einem 1 1-Rührautoklaven wurden 16 ml einer 1,7 molaren Methy- lalumoxan-Lösung in Toluol vorgelegt, 500 g (11,9 mol) flüssiges Propen auf ondensiert und auf 50°C erwärmt. Dabei stellte sich ein Druck von 2200 kPa ein. Anschließend wurden 79,6 mg (0,1 mmol)16 ml of a 1.7 molar methylalumoxane solution in toluene were placed in a 1 l stirred autoclave, 500 g (11.9 mol) of liquid propene were condensed and heated to 50.degree. A pressure of 2200 kPa was set. Then 79.6 mg (0.1 mmol)
30 Bis(n-Octadecylcyclopentadienyl)zirconiumdichlorid, gelöst in 9,4 ml 1,7 molarer toluolischer Methylaluminoxanlösung (AI : Zr = 432 : 1) zugegeben. Dann wurde 120 Minuten lang oligomerisiert, der Reaktor entspannt und die Trübungszahl bestimmt. Sie betrug 1,8. Es wurden 450 g flüssiges Propenoligomerengemisch isoliert: Mw =30 bis (n-octadecylcyclopentadienyl) zirconium dichloride, dissolved in 9.4 ml of 1.7 molar toluene methylaluminoxane solution (AI: Zr = 432: 1), were added. The mixture was then oligomerized for 120 minutes, the reactor was depressurized and the turbidity number was determined. It was 1.8. 450 g of liquid propene oligomer mixture were isolated: Mw =
35 990, Mn = 520, Mw/Mn = 1,9.35,990, Mn = 520, Mw / Mn = 1.9.
Beispiel 2Example 2
Es wurde wie in Beispiel 1 gearbeitet, jedoch wurde anstatt 40 Bis (n-Octadecylcyclopentadienyl) zirconiumdichlorid 25,0 mg ( 0,05 mmol) Bist (tert-Butyldimethylsilyl)cyclopentadienyl] zirconium¬ dichlorid gelöst in 14,7 ml 1,7 molarer toluolischer Methyl¬ aluminoxanlösung (AI : Zr = 1040 : 1) als Metallocenkomplex ein¬ gesetzt. Man erhielt 450 g flüssiges Propylenoligomerengemisch. 45 Mw = 3600, Mn = 1800, Mw/Mn = 2,0. Trübungszahl des Reaktionsge¬ misches 2,1. Beispiel 3The procedure was as in Example 1, but instead of 40 bis (n-octadecylcyclopentadienyl) zirconium dichloride 25.0 mg (0.05 mmol) of bis (tert-butyldimethylsilyl) cyclopentadienyl] zirconium dichloride was dissolved in 14.7 ml 1.7 molar toluene methyl aluminoxane solution (Al: Zr = 1040: 1) used as a metallocene complex. 450 g of liquid propylene oligomer mixture were obtained. 45 Mw = 3600, Mn = 1800, Mw / Mn = 2.0. Turbidity number of the reaction mixture 2.1. Example 3
Zu 204 g Cyclopenten gab man 90 ml einer 1,7 m toluolischen Methylaluminoxanlösung (153 mmol) und anschließend 240 mg (0,3 mmol) Bis (n-Octadecylcyclopentadienyl) zirconium-dichlorid (AI : Zr = 510 : 1), oligomerisierte 10 h bei 30°C und bestimmte die Trübungszahl. Man erhielt 30 g Cyclopentenoligomere, Mw = 700, Mn = 350; Mw/Mn = 2,0. Trübungszahl des Reaktionsgemisches 1,8.90 ml of a 1.7 m toluene methylaluminoxane solution (153 mmol) and then 240 mg (0.3 mmol) of bis (n-octadecylcyclopentadienyl) zirconium dichloride (Al: Zr = 510: 1), oligomerized 10, were added to 204 g of cyclopentene h at 30 ° C and determined the turbidity number. 30 g of cyclopentene oligomers were obtained, Mw = 700, Mn = 350; Mw / Mn = 2.0. Turbidity number of the reaction mixture 1.8.
Beispiel 4Example 4
Es wurde wie in Beispiel 1 gearbeitet, jedoch wurden 40 mg ( 0,1 mmol) Bis(tetrahydroindenyl)zirconiumdichlorid in 4,5 ml 1,7 m toluolischer Methylaluminoxanlösung gelöst (AI : Zr = 348 : 1) eingesetzt. Man erhielt 450 g flüssiges Propylenoligomer, Mw = 3600, Mn = 1800, Mw/Mn = 2,0. Trübungszahl des Reaktionsgemisches 2,7.The procedure was as in Example 1, but 40 mg (0.1 mmol) of bis (tetrahydroindenyl) zirconium dichloride were dissolved in 4.5 ml of 1.7 M toluene methylaluminoxane solution (Al: Zr = 348: 1). 450 g of liquid propylene oligomer were obtained, Mw = 3600, Mn = 1800, Mw / Mn = 2.0. Turbidity number of the reaction mixture 2.7.
Vergleichsbeispiel VIComparative Example VI
Es wurde wie in Beispiel 1 gearbeitet, jedoch wurde anstatt Bis (n-Octadecylcyclopentadienyl) zirconiumdichlorid 29,0 mg ( 0,1 mmol) Bis(cyclopentadienyl)zirconiumdichlorid gelöst in 9,4 ml 1,7 molarer toluolischer Methylaluminoxanlösung (AI : Zr = 500 : 1) als Metallocenkomplex eingesetzt. Man erhielt 440 g flüssiges Propylenoligomerengemisch. Mw = 1550, Mn = 420, Mw/Mn = 3,7. Trü¬ bungszahl des Reaktionsgemisches 85. The procedure was as in Example 1, but instead of bis (n-octadecylcyclopentadienyl) zirconium dichloride 29.0 mg (0.1 mmol) of bis (cyclopentadienyl) zirconium dichloride was dissolved in 9.4 ml of 1.7 molar toluene methylaluminoxane solution (AI: Zr = 500: 1) used as a metallocene complex. 440 g of liquid propylene oligomer mixture were obtained. Mw = 1550, Mn = 420, Mw / Mn = 3.7. Turbidity number of the reaction mixture 85.

Claims

PatentansprücheClaims
1. Verfahren zur Herstellung von Olefin-Oligomeren mit einer Molekulargewichtsverteilung Mw/Mn im Bereich von 1,0 bis 2,4 durch Oligomerisierung von Olefinen in Gegenwart von Metallocenkatalysatorsystemen, dadurch gekennzeichnet, daß die Trübungszahl des katalysatorhaltigen Reaktionsgemisches im Bereich von 1 bis 10 liegt.1. A process for the preparation of olefin oligomers with a molecular weight distribution Mw / Mn in the range from 1.0 to 2.4 by oligomerization of olefins in the presence of metallocene catalyst systems, characterized in that the turbidity number of the catalyst-containing reaction mixture is in the range from 1 to 10 .
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man Katalysatorsysteme verwendet, welche als aktive Bestandteile2. The method according to claim 1, characterized in that catalyst systems are used, which as active ingredients
A) Metallocenkomplexe der allgemeinen Formel IA) Metallocene complexes of the general formula I
Cp2Mχ!χ2 ICp 2 Mχ ! χ 2 I
in der die Substituenten und Indizes folgende Bedeutung haben:in which the substituents and indices have the following meaning:
Cp2 Cp 2
Ein Paar von, wie folgt definiert, substituierten Cyclo- pentadienyl-Liganden:A pair of substituted cyclopentadienyl ligands as defined:
(i) symmetrische Substitution mit je 1 bis 4 C5- bis(i) symmetrical substitution with 1 to 4 C 5 - bis each
C30- Alkylresten, oderC 3 0- alkyl radicals, or
(ii) Substitution mit je 1 bis 2 ringbildenden C4- bis C10- Alkylenresten und je 0 bis 3 Ci- bis C3o-Alkylresten, oder(ii) Substitution with 1 to 2 ring-forming C 4 to C 10 alkylene radicals and 0 to 3 Ci to C 3 o-alkyl radicals each, or
(iii) Substitution mindestens eines Teils des Liganden- Paares mit mindestens einem Silicium-organischen Rest und 0 bis 9 Ci- bis C3o-Alkyl-Resten und/oder 0 bis 4 ringbildenden C4- bis Cχo- Alkylenresten.(iii) Substitution of at least a part of the ligand pair with at least one silicon-organic radical and 0 to 9 Ci to C 3 o-alkyl radicals and / or 0 to 4 ring-forming C 4 to Cχo alkylene radicals.
M ein Titan-, Zirconium- oder Hafniumatom X1, X2 ein formal negativ geladenes Abgangsatom oder eine formal negativ geladene AbgangsgruppeM is a titanium, zirconium or hafnium atom X 1 , X 2 is a formally negatively charged leaving atom or a formally negatively charged leaving group
und B) eine Akzeptorverbindung für die Substituenten X1 und X2 der Komponente A) als Aktivatorand B) an acceptor compound for the substituents X 1 and X 2 of component A) as an activator
enthalten.contain.
Verfahren nach den Ansprüchen 1 bis 2, dadurch gekennzeich¬ net, daß die Katalysatorsysteme als Aktivatoren offenkettige oder cyclische Aluminoxanverbindungen der allgemeinen Formel II oder III enthaltenProcess according to Claims 1 to 2, characterized in that the catalyst systems contain open-chain or cyclic aluminoxane compounds of the general formula II or III as activators
AI- 4-o AI R m IIAI- 4-o AI R m II
-o —A1 - III m-o —A1 - III m
RR
wobei R eine Ci- bis Cβ-Alkylgruppe bedeutet und m für eine ganze Zahl von 5 bis 30 steht.where R is a Ci to Cβ alkyl group and m is an integer from 5 to 30.
4. Verfahren nach den Ansprüchen 1 bis 3, dadurch gekennzeich¬ net, daß die Substituenten X1, X2 Halogen, H, Cι~ bis Cio-Alkyl oder Ci- bis Cio-Alkoxy bedeuten.4. The method according to claims 1 to 3, characterized gekennzeich¬ net that the substituents X 1 , X 2 is halogen, H, C ~ ~ to Cio-alkyl or Ci- to Cio-alkoxy.
5. Olefin-Oligomere, erhältlich nach einem Verfahren gemäß der Ansprüche 1 bis 4.5. olefin oligomers obtainable by a process according to claims 1 to 4.
6. Verwendung der Olefin-Oligomeren zur Herstellung von Schmier¬ stoffen oder Kraftstoffadditiven. 6. Use of the olefin oligomers for the production of lubricants or fuel additives.
PCT/EP1996/000235 1995-02-01 1996-01-20 Process for preparing olefin oligomers WO1996023751A1 (en)

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WO1998052888A1 (en) * 1997-05-23 1998-11-26 Sasol Technology (Proprietary) Limited Production of oligomers
WO1999067347A3 (en) * 1998-06-19 2000-02-17 Basf Ag Metallocene-catalyzed oligodecenes, their production and their use as component in lubricants
US6706828B2 (en) 2002-06-04 2004-03-16 Crompton Corporation Process for the oligomerization of α-olefins having low unsaturation
WO2007011973A1 (en) * 2005-07-19 2007-01-25 Exxonmobil Chemical Patents Inc. Process to produce low viscosity poly-alpha-olefins
US7223822B2 (en) 2002-10-15 2007-05-29 Exxonmobil Chemical Patents Inc. Multiple catalyst and reactor system for olefin polymerization and polymers produced therefrom
US7294681B2 (en) 2002-10-15 2007-11-13 Exxonmobil Chemical Patents Inc. Mutliple catalyst system for olefin polymerization and polymers produced therefrom
US7541402B2 (en) 2002-10-15 2009-06-02 Exxonmobil Chemical Patents Inc. Blend functionalized polyolefin adhesive
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US8921291B2 (en) 2005-07-19 2014-12-30 Exxonmobil Chemical Patents Inc. Lubricants from mixed alpha-olefin feeds
US8921290B2 (en) 2006-06-06 2014-12-30 Exxonmobil Research And Engineering Company Gear oil compositions
US9365663B2 (en) 2008-03-31 2016-06-14 Exxonmobil Chemical Patents Inc. Production of shear-stable high viscosity PAO
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