EP0807096A1 - Procede de preparation d'oligomeres d'olefine - Google Patents

Procede de preparation d'oligomeres d'olefine

Info

Publication number
EP0807096A1
EP0807096A1 EP96900602A EP96900602A EP0807096A1 EP 0807096 A1 EP0807096 A1 EP 0807096A1 EP 96900602 A EP96900602 A EP 96900602A EP 96900602 A EP96900602 A EP 96900602A EP 0807096 A1 EP0807096 A1 EP 0807096A1
Authority
EP
European Patent Office
Prior art keywords
olefin oligomers
alkyl
catalyst systems
substituents
range
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP96900602A
Other languages
German (de)
English (en)
Inventor
Joachim Rösch
Hans-Joachim Müller
Günther SCHWEIER
Peter Tanzmeier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0807096A1 publication Critical patent/EP0807096A1/fr
Ceased legal-status Critical Current

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Classifications

    • 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.

Abstract

Un procédé permet des préparer des oligomères d'oléfine ayant une distribution du poids moléculaire Mw/Mn dans une plage comprise entre 1,0 et 2,4 par oligomérisation d'oléfines en présence de systèmes catalyseurs en alliages organométalliques. L'indice de turbidité du mélange de réaction contenant des catalyseurs est compris entre 1 et 10. Ces oligomères d'oléfine sont utiles comme matières de base pour la préparation de lubrifiants, d'additifs de carburants et d'huiles, et comme macromonomères.
EP96900602A 1995-02-01 1996-01-20 Procede de preparation d'oligomeres d'olefine Ceased EP0807096A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19503089 1995-02-01
DE19503089 1995-02-01
PCT/EP1996/000235 WO1996023751A1 (fr) 1995-02-01 1996-01-20 Procede de preparation d'oligomeres d'olefine

Publications (1)

Publication Number Publication Date
EP0807096A1 true EP0807096A1 (fr) 1997-11-19

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EP96900602A Ceased EP0807096A1 (fr) 1995-02-01 1996-01-20 Procede de preparation d'oligomeres d'olefine

Country Status (2)

Country Link
EP (1) EP0807096A1 (fr)
WO (1) WO1996023751A1 (fr)

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US6706828B2 (en) 2002-06-04 2004-03-16 Crompton Corporation Process for the oligomerization of α-olefins having low unsaturation
US7524910B2 (en) 2002-10-15 2009-04-28 Exxonmobil Chemical Patents Inc. Polyolefin adhesive compositions and articles made therefrom
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US8227392B2 (en) 2008-01-25 2012-07-24 Exxonmobil Research And Engineering Company Base stocks and lubricant blends containing poly-alpha olefins
US9469704B2 (en) 2008-01-31 2016-10-18 Exxonmobil Chemical Patents Inc. Utilization of linear alpha olefins in the production of metallocene catalyzed poly-alpha olefins
US8865959B2 (en) 2008-03-18 2014-10-21 Exxonmobil Chemical Patents Inc. Process for synthetic lubricant production
CA2718894C (fr) 2008-03-31 2013-01-15 Exxonmobil Chemical Patents Inc. Fabrication d'une pao haute viscosite stable au cisaillement
WO2009135876A1 (fr) 2008-05-07 2009-11-12 Basf Se COPOLYMÈRES BISÉQUENCÉS α-OLÉFINE/ISOBUTÈNE
CN107586353A (zh) 2009-12-24 2018-01-16 埃克森美孚化学专利公司 用于生产新型合成基础油料的方法
WO2012027139A2 (fr) 2010-08-25 2012-03-01 Exxonmobil Chemical Patents Inc. Hydrocarbures synthétiques fluides pouvant être fonctionnalisés et leur procédé intégré de production
US9815915B2 (en) 2010-09-03 2017-11-14 Exxonmobil Chemical Patents Inc. Production of liquid polyolefins
WO2012134688A1 (fr) 2011-03-30 2012-10-04 Exxonmobil Chemical Patents Inc. Polyalpha-oléfines par oligomérisation et isomérisation
US8623796B2 (en) 2011-05-27 2014-01-07 Exxonmobil Research And Engineering Company Oil-in-oil compositions and methods of making
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US8569216B2 (en) 2011-06-16 2013-10-29 Exxonmobil Research And Engineering Company Lubricant formulation with high oxidation performance
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Also Published As

Publication number Publication date
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