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WO1999054368A1 - Procede de production de polypropylene dote de metallocenes speciaux - Google Patents

Procede de production de polypropylene dote de metallocenes speciaux Download PDF

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Publication number
WO1999054368A1
WO1999054368A1 PCT/EP1999/002563 EP9902563W WO9954368A1 WO 1999054368 A1 WO1999054368 A1 WO 1999054368A1 EP 9902563 W EP9902563 W EP 9902563W WO 9954368 A1 WO9954368 A1 WO 9954368A1
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WO
WIPO (PCT)
Prior art keywords
group
cyclopentadienyl
indenyl
dimethylsilanediylbis
mixture
Prior art date
Application number
PCT/EP1999/002563
Other languages
German (de)
English (en)
Inventor
Cornelia Fritze
Gerhard Erker
Johannes Ruwwe
Original Assignee
Targor Gmbh
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
Priority claimed from DE1998117724 external-priority patent/DE19817724A1/de
Priority claimed from DE19817723A external-priority patent/DE19817723A1/de
Application filed by Targor Gmbh filed Critical Targor Gmbh
Priority to EP99922097A priority Critical patent/EP1084160A1/fr
Priority to JP2000544706A priority patent/JP2002512276A/ja
Publication of WO1999054368A1 publication Critical patent/WO1999054368A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+

Definitions

  • the present invention relates to a new process for the production of
  • supported catalyst systems have been proposed in which the metallocene and / or the aluminum compound serving as cocatalyst are fixed on an inorganic support material.
  • the object of the present invention is to provide a process for the preparation of polyolefins with specially substituted metallocenes.
  • the object on which the present invention is based is achieved by a polymerization process which is based on the polymerization with specially substituted metallocenes in a special solvent mixture.
  • the present invention relates to a process for the preparation of polyolefins by polymerization of one or more olefins, characterized in that the polymerization in the presence of a compound of the formula
  • R 1 are the same or different and are a hydrogen atom, a C-1-C30-fluorine-containing group, preferably C-
  • SiR ⁇ in which R, identical or different, represents a hydrogen atom or a C1-C40-carbon-containing group, preferably C 1 -C 20 -alkyl, C1-C-10-
  • Fluoroalkyl C-
  • Residues R1 can be connected to one another in such a way that the residues R ⁇ and the atoms of the cyclopentadienyl ring connecting them form a C4-C24 ring system, which in turn can be substituted, with the proviso that at least one of the residues R1 carries at least one fluorine atom or with is substituted by a fluorine atom.
  • L are the same or different and a hydrogen atom, a -C-C ⁇ o-alkyl group, a C ⁇ -C ⁇ -alkoxy group, a C6-C20-aryl group, a Cß-C-io-aryloxy group, a C2-C- ⁇ o-alkenyl group, an OH group, an NR 2 group, where R is a C-
  • Z denotes a bridging structural element between the two cyclopentadienyl rings, and v is 0 or 1 4 and containing in the presence of a mixture
  • the compound of the formula (I) is preferably in the form of a catalyst system comprising at least one specially substituted metallocene, at least one cocatalyst and, if appropriate, at least one further additive component.
  • At least one is used as the metallocene component of the catalyst system
  • Z is preferably a group M 2 R 4 R 5 , in which M 2 is carbon, silicon, germanium or tin and R 4 and R ⁇ are identical or different and are a C1-C20 hydrocarbon group, preferably C-
  • Z is CH2, CH2CH2, CH (CH3) CH2, CH (C 4 Hg) C (CH 3) 2, C (CH3) 2, (CH 3) 2 Si, (CH 3 CH 2) 2 Si , (CH 3 ) ((CH3) 3C) Si, (CH 3 ) 2Ge, (CH 3 ) 2 Sn, (C 6 H 5 ) 2 Si, (C 6 H 5 ) (CH 3 ) Si, (C 6 H 5 ) 2 Ge, (C 6 H 5 ) 2 Sn, (CH 2 ) 4 Si, CH 2 Si (CH 3 ) 2 , oC 6 H 4 or 2,2 ' - (C 6 H 4 ) 2 .
  • Z can also be mono- or polycyclic with one or more Rl radicals
  • Chiral bridged metallocenes of the formula (I) are preferred, in particular those in which v is 1 and one or both cyclopentadienyl rings are substituted such that they represent an indenyl ring.
  • the indenyl ring is preferably substituted, in particular in the 2-, 4-, 2,4,5-, 2,4,6-, 2,4,7 or 2,4,5,6-position, with C1-C20 carbon-containing Groups which can be halogenated, linear, cyclic or branched and / or substituted with C-
  • Hydrocarbon radicals in particular CF3 or C2F5 radicals, mean that two or more substituents of the indenyl ring can together form a ring system.
  • M ⁇ is titanium, zirconium or hafnium
  • R1 are the same or different and are a hydrogen atom, a C-1-C30 fluorine-containing group, preferably C-
  • R ⁇ is a hydrogen atom or a C ⁇ -C4o-carbon-containing group, preferably C ⁇
  • Alkyl especially methyl, ethyl, tert-butyl, cyclohexyl or octyl, C2-C25-alkenyl, C3-Ci5-alkylalkenyl or C6-C24-aryl, where two or more
  • R is a C-
  • Z particularly preferably denotes a group M 2 R4R5, in which M 2 is carbon, silicon or germanium and R 4 and R5, identical or different, denote a C1-C20 hydrocarbon group such as C 1 -C 4 -alkyl or Cg-C 1 -aryl .
  • Z is particularly preferably equal to CH2, CH2CH2, CH (CH3) CH2, CH (C 4 H 9 ) C (CH3) 2, C (CH 3 ) 2 , (CH 3 ) 2 Si, (CH 3 CH 2 ) 2 Si , (CH 3 ) ((CH 3 ) 3 C) Si,
  • Z can also form a mono- or polycyclic ring system with one or more R1 radicals.
  • Chiral bridged metallocenes of the formula (I) are particularly preferred, especially those in which v is 1 and one or both cyclopentadienyl rings are substituted such that they represent an indenyl ring.
  • the indenyl ring is preferably substituted, in particular in the 2-, 4-, 2,4,5-, 2,4,6-, 2,4,7 or 2,4,5,6-position, with -C-C20 carbon-containing groups, the halogenated, linear, cyclic or branched and / or C "
  • Arylalkenyl group a CQ to C20 aryl group, especially a phenyl,
  • Naphthyl, phenanthryl or anthracenyl group which is fluorinated and / or perfluorinated C-
  • Pentatrifluoromethylphenyl 4-Pentafluorethylphenyl, 3-PentafIuorethylphenyI, 2-PentafluorethylphenyI, 3,5-Dipentafluorethylphenyl, 2,6-Dipentafluorethylphenyl, Mono-, Di-, Tri- and Tetrafluoronaphthyl, Penta (Pentatfluorethyl) phenyl mean, also two of the indenyl ring can together form a ring system.
  • organometallic compound according to formula (I) examples but not limiting examples are:
  • 1,2-ethanediyl ( ⁇ 5 -3- (2 ' , 2 ' , 2 ' , -trifluoroethyl) cyclopentadienyl) ( ⁇ 5 -3-butylcyclopentadienyl) zirconium dichloride
  • 1,2-ethanediyl ( ⁇ 5-3- (1 ⁇ , 1 ⁇ , 2 ⁇ , 2 ⁇ -perfluorooctyl) cyclopentadienyl) ( ⁇ 5-3-butyIcyclopentadienyl) zirconium dichloride
  • 1,2-ethanediyl ( ⁇ 5 -3- (2 ' , 2 ' , 2 ' , -trifluoroethyl) cyclopentadienyl) ( ⁇ 5 -3-butylcyclopentadienyl) hafnium dichloride
  • 1,2-ethanediyI ( ⁇ 5 -3- (2 ' , 2 ' , 2 ' , -trifluoroethyl) cyclopentadienyl) ( ⁇ 5 -cyclopentadienyl) - zirconium dichloride
  • 1,2-ethanediyl ( ⁇ 5 -3- (1 1, 1 ⁇ , 2 ' H, 2 ⁇ -perfluorooctyl) cyclopentadienyl) ( ⁇ 5 -cyclopentadienyl) zirconium dichloride
  • 1,2-ethanediyl ( ⁇ 5 -3- (2 ' , 2 ' , 2 ' , -trifluoroethyl) cyclopentadienyl) ( ⁇ 5 -cyclopentadienyl) hafnium dichloride
  • 1,2-ethanediyl ( ⁇ 5-3- (1 ⁇ , 1 ' H, 2 ⁇ , 2 ⁇ -perfluorooctyl) cyclopentadienyl) ( ⁇ 5 -cyclopentadienyl) hafnium dichloride
  • 1,2-ethanediyl ( ⁇ 5-3- (1 ⁇ , 1 ⁇ , 2 ' H, 2 ⁇ -perfluorooctyl) cyclopentadienyl) ( ⁇ 5-3-butylcyclopentadienyl) zirconium dichloride
  • 1,2-ethanediyl ( ⁇ 5 -3- (1 ⁇ , 1 ' H, 2 ⁇ , 2 ⁇ -perfluorooctyl) cyclopentadienyl) ( ⁇ 5 -3-butylcyclopentadienyl) hafnium dichloride
  • Dimethylsilanediylbis ( ⁇ 5 -3- (1 ' H, 1 ' H, 2 ⁇ , 2 ⁇ -perfluorooctyl) cyclopentadienyl) zirconium dichloride
  • Dimethylsilanediylbis ( ⁇ 5 -3- (2 ' , 2 ' , 2 ' , -trifluoroethyl) cyclopentadienyl) hafnium dichloride
  • Dimethylsilanediylbis ( ⁇ 5 -2- (2 ' , 2 ' , 2 ' , -trifluoroethyl) indenyl) zirconium dichloride
  • Dimethylsilanediylbis ( ⁇ 5-2- (2 ' , 2 ' , 2 ' , -trifluoroethyl) -4- (1-naphthyl) -indenyl) - zirconium dichloride
  • Dimethylsilandiybis ( ⁇ 5 -2- (2 ' , 2 ' , 2 ' , -trifluoroethyl) -4,5-benzo-indenyl) - zirconium dichloride
  • DimethylsiIandiylbis ( ⁇ 5 -2- (2 ' , 2 ' , 2 ' , -trifluoroethyl ) -4- (4 '-tert-butyl-phenyl) indenyl) - zirconium dichloride
  • Dimethylsilanediylbis ( ⁇ 5 -2- (1 ' H, 1 ⁇ , 2 ' H, 2 ⁇ -perfluorooctyl) -4-phenyl-indenyl) - zirconium dichloride
  • Dimethylsilandiybis ( ⁇ 5 -2- (1 ⁇ , 1 ⁇ , 2 ⁇ , 2 ⁇ - perfluorooctyl) -4,5-benzo-indenyl) zirconium dichloride
  • Dimethylsilanediylbis (2-n-butyl-4- (pentafluorophenyl) -indenyl) ZrCl2 Dimethylsilanediylbis (2-sec.-butyl-4- (3,5-difluorophenyl) -indenyl) ZrCl2 DimethyIsilanediylbis (2-sec.-butyl-4- (4-trifluoromethylphenyI) -indenyl) ZrCl2 dimethylsilanediylbis (2-sec.-butyl-4- (3,5-ditrifluoromethylphenyl) -indenyl) ZrCl2 dimethylsilanediylbis (2-sec.-butyl-4- (4-pentafluoroethylphenyl) -indenyl) ZrCl2
  • Dimethylsilanediylbis (2-ethyl-4- (3,5-ditrifluoromethylphenyl) -indenyl) ZrCl2 Dimethylsilanediylbis (2-ethyl-4- (4-pentafluoroethylphenyl) -indenyl) ZrCl2 16 DimethyIsilandiyIbis (2-ethyl-4- (3,5-dipentafluoroethylphenyl) -indenyl) ZrCl2 Dimethylsilanediylbis (2-ethyl-4- (pentafluorophenyl) -indenyl) ZrCl2
  • the dimethyl compounds are also important.
  • the compounds of the formula (I) used in the process according to the invention are preferably used together with at least one cocatalyst or one cocatalyst component.
  • the cocatalyst component contains at least one compound of the type one
  • Aluminoxane or a Lewis acid or an ionic compound which converts this into a cationic compound by reaction with a metallocene is aluminoxane or a Lewis acid or an ionic compound which converts this into a cationic compound by reaction with a metallocene.
  • a compound of the general formula (II) is preferred as the aluminoxane
  • Aluminoxanes can be cyclic as in formula (III)
  • the radicals R in the formulas (II), (III), (IV) and (V) can be the same or different and a C ⁇
  • the radicals R are preferably the same and are methyl, isobutyl, n-butyl, phenyl or benzyl, particularly preferably methyl.
  • R radicals are preferably methyl and hydrogen, methyl and isobutyl or methyl and n-butyl, with hydrogen or isobutyl or n-butyl being preferably present in an amount of 0.01 to 40% (number of R radicals).
  • the aluminoxane can be prepared in various ways by known methods. According to a known method, an aluminum hydrocarbon compound and / or a hydridoaluminum hydrocarbon compound is reacted with water (gaseous, solid, liquid or bound - for example as water of crystallization) in an inert solvent, such as toluene. To produce an aluminoxane with different alkyl groups R, two different aluminum trialkyls (AIR3 + AIR'3) are reacted with water according to the desired composition and reactivity, cf. S. Pasynkiewicz,
  • At least one organoboron or organoaluminum is preferred as Lewis acid
  • Compound used that contain -C-C20 carbon-containing groups such as branched or unbranched alkyl or haloalkyl, such as methyl, propyl, isopropyl, isobutyl, trifluoromethyl, unsaturated groups, such as aryl or haloaryl such as phenyl, tolyl, benzyl groups, p-fluorophenyl , 3,5-difluorophenyl, pentachlorophenyl, pentafluorophenyl, 3,4,5 trifluorophenyl and 3,5
  • -C-C20 carbon-containing groups such as branched or unbranched alkyl or haloalkyl, such as methyl, propyl, isopropyl, isobutyl, trifluoromethyl, unsaturated groups, such as aryl or haloaryl such as phenyl, tolyl, benzyl groups, p-fluorophenyl , 3,5-di
  • Organoboron compounds are particularly preferred.
  • Lewis acids are trifluoroborane, triphenylborane, tris (4-fluorophenyl) borane, tris (3,5-difluorophenyl) borane, tris (4-fluoromethylphenyl) borane,
  • Tris (pentafluoropheny!) Borane, di (bis (pentafluorophenyl) boroxy) methylalane, di (bisphenylboroxy) methylalane, di (bis (pentafluorophenyl) boroxy) isopropylalane are particularly preferred.
  • Compounds which contain a non-coordinating anion, such as tetrakis (pentafluorophenyl) borates, are preferably used as ionic cocatalysts,
  • Tetraphenylborate SbFß-, CF3SO3- or CIO4-.
  • a cationic counterion As a cationic counterion
  • Lewis bases such as methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p- Nitro-N, N-dimethylaniline, triethylphosphine, triphenylphosphine, diphenylphosphine, tetrahydrothiophene and triphenylcarbenium are used.
  • Ferrocenium tetrakis (pentafluorophenyl) borate and / or ferrocenium tetrakis (pentafluorophenyl) aluminate are ferrocenium tetrakis (pentafluorophenyl) aluminate.
  • Triphenylcarbenium tetrakis (pentafluorophenyl) borate and / or N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate are preferred.
  • Mixtures of at least one Lewis acid and at least one ionic compound can also be used.
  • At least one of the above-described metallocene components (compound of the formula I) is brought into contact with at least one of the above-described cocatalyst components in a suitable solvent in order to obtain a soluble reaction product.
  • Preferred solvents for the production of the metallocene-cocatalyst mixture are hydrocarbons and hydrocarbon mixtures which are liquid at the selected reaction temperature and in which the individual components preferably dissolve.
  • the solubility of the individual components is not a requirement if it is ensured that the reaction product of the metallocene and cocatalyst component is soluble in the chosen solvent.
  • suitable solvents include alkanes such as pentane, isopentane, hexane, heptane, octane and nonane, cycloalkanes such as cyclopentane and cyclohexane, and aromatics such as benzene, toluene. Ethylbenzene and diethylbenzene. Toluene is very particularly preferred.
  • alkanes such as pentane, isopentane, hexane, heptane, octane and nonane
  • cycloalkanes such as cyclopentane and cyclohexane
  • aromatics such as benzene, toluene. Ethylbenzene and diethylbenzene. Toluene is very particularly preferred.
  • Cocatalyst and metallocene can be varied over a wide range.
  • a molar ratio of cocatalyst to transition metal in the metallocene of 1: 1 to 1000: 1 is preferably set, very particularly preferably a ratio of 1: 1 to 500: 1.
  • 30% toluene solutions are preferably used, the use 10% solutions are also possible. 21
  • the preactivation time is 1 minute to 200 hours.
  • the preactivation can take place at room temperature (25 ° C).
  • room temperature 25 ° C.
  • the use of higher temperatures can shorten the time required for preactivation and cause an additional increase in activity.
  • a higher temperature means a range between 50 ° C and 100 ° C.
  • an ⁇ -olefin such as styrene
  • an antistatic as described in US Serial No. during or after the preparation of the metallocene-cocatalyst mixture. 08/365280 described, are added.
  • the present process for the production of polyolefins by polymerizing one or more olefins can also be carried out with the aid of a supported catalyst system.
  • the preparation of such systems is described, for example, in EP-A-0,576,970.
  • polymerisation is understood to mean homopolymerization and also copolymerization, but preferably homopolymerization
  • olefins examples include 1-olefins such as ethene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene or 1-octene, styrene, dienes such as 1, 3-butadiene, 1, 4 - Hexadiene, vinyl norbornene, norbomadiene, ethyl norbornadiene and cyclic olefins such as norbornene, tetracyclododecene or methylnorbornene. 22
  • 1-olefins such as ethene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene or 1-octene, styrene, dienes such as 1, 3-butadiene, 1, 4 - Hexadiene, vinyl norbornene, norbomadiene, ethyl norbornadiene and cyclic olefin
  • mixtures of the above olefins can also be copolymerized.
  • the polymerization is carried out at a temperature of -60 ° C to 300 ° C, preferably 50 ° C to 200 ° C, most preferably 50 ° C to 80 ° C.
  • the pressure is 0.5 bar to 2000 bar, preferably 5 bar to 64 bar.
  • the polymerization can be carried out continuously or batchwise, in one or more stages, the process according to the invention always being carried out in the presence of a mixture of at least two hydrocarbons, a non-halogenated and a halogenated hydrocarbon.
  • the two hydrocarbons are advantageously not miscible with one another and form a two-phase system, the lower phase being the halogenated hydrocarbon.
  • non-halogenated hydrocarbons examples include straight-chain and branched alkanes, in particular those with 3 to 20
  • Carbon atoms especially pentane, isopentane, hexane, heptane, octane, and nonane, cycloalkanes such as cyclopentane and cyclohexane, and substituted and unsubstituted aromatics such as benzene, toluene.
  • cycloalkanes such as cyclopentane and cyclohexane
  • substituted and unsubstituted aromatics such as benzene, toluene.
  • Suitable halogenated hydrocarbons include one or more fluorinated alkanes, such as perfluoroheptane and perfluoroisohexane, one or more fluorinated cycloalkanes, such as perfluoro (methylcyclohexane).
  • a mixture of toluene with perfluoro (methylcyclohexane) is very particularly preferably used.
  • the mixing ratio of the two hydrocarbons is 1: 1 to 100: 1, particularly preferably 1: 1 to 10: 1, particularly preferably 1: 1. 23
  • the above mixture is mixed at a stirring speed of 1 to 10,000 revolutions per minute.
  • a prepolymerization can be carried out with the aid of the polymerization process according to the invention.
  • prepolymerization this is preferred in the
  • Polymerization used propylene.
  • Catalyst systems which contain two or more different metallocenes of the formula I are preferably used to produce polypropylene with a broad molecular weight distribution.
  • hydrogen is added as a molecular weight regulator and / or to increase the activity.
  • Another alkyl aluminum compound such as trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trioctyl aluminum or isoprenyl aluminum, can additionally be added to the reactor to render the polymerization system inert (for example to separate off existing catalyst poisons in the olefin). This is added to the polymerization system in a concentration of 100 to 0.01 mmol AI per kg reactor content. Triisobutyl aluminum and triethyl aluminum are preferably used in a concentration of 10 to 01 mmol Al per kg reactor content.
  • the polypropylene produced by the process according to the invention has a uniform grain morphology and has no fine grain proportions. No deposits or caking occur during the polymerization.
  • the polyolefin produced by the process according to the invention is particularly suitable for producing tear-resistant, hard and rigid molded articles such as fibers, 24
  • Filaments, injection molded parts, foils, plates or large hollow bodies, such as pipes, are suitable.
  • organometallic compounds were produced and handled with the exclusion of air and moisture under an argon protective gas, such as Schlenk technology or glove box. All required solvents were flushed with argon before use and absoluteized using a molecular sieve. The metallocenes used were
  • No metallocene can be detected in the toluene phase.
  • the fluorine phase gives 12 mg from 0.9 ml.
  • Precipitation 72 mg of 99 mg from 2 ml of perfluoromethyicyclohexane
  • Soluble 28 mg of 99 mg in 2 ml of perfluoromethyicyclohexane
  • Partition coefficient from 28 mg metallocene in 2 ml solvent mixture: toluene: 0 mg from 0.9 ml perfluoromethyicyclohexane: 12 mg from 0.9 ml 25th
  • ⁇ > 20
  • Example 1 In a Schlenk flask, 21 mg of bis (2 ' , 2 ' , 2 ' -trifluoroethyl) cyclopentadienyl) -
  • the precipitated polymer is located between the lower fluorous phase and the upper toluene phase.
  • the polymerization is stopped by adding 2 ml of methanol / 2N hydrochloric acid (1: 1).
  • the polyethylene obtained is filtered off and dried in an oil pump vacuum.
  • Example 4 21 mg of bis (2 ' , 2 ' , 2 ' - trifluoroethyl) cyclopentadienyl) (cyclopentadienyl) zirconium dimethyl are mixed with 21 mg of trityltetrakis (pentafluorophenyl) borate in a Schlenk flask. A mixture of 8 ml of perfluoro (methylcyclohexane), 2 ml of toluene and 0.5 ml of triisobutyl aluminum solution is added.
  • the emulsion obtained is evacuated once with vigorous stirring and then with

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Abstract

L'invention concerne un nouveau procédé de production de polyoléfines à l'aide de métallocènes spécialement substitués et en présence d'un mélange contenant au moins un hydrocarbure non halogéné et au moins un hydrocarbure halogéné.
PCT/EP1999/002563 1998-04-21 1999-04-16 Procede de production de polypropylene dote de metallocenes speciaux WO1999054368A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP99922097A EP1084160A1 (fr) 1998-04-21 1999-04-16 Procede de production de polypropylene dote de metallocenes speciaux
JP2000544706A JP2002512276A (ja) 1998-04-21 1999-04-16 特定のメタロセンを使用するポリプロピレンの製造方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE1998117724 DE19817724A1 (de) 1998-04-21 1998-04-21 Verfahren zur Herstellung von Polypropylen mit speziellen Metallocenen
DE19817724.0 1998-04-21
DE19817723.2 1998-04-21
DE19817723A DE19817723A1 (de) 1998-04-21 1998-04-21 Verfahren zur Herstellung von Polyolefinen mit speziellen Metallocenen

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4426122A1 (de) * 1993-07-22 1995-02-23 Nippon Oil Co Ltd Katalysatorkomponente für die Polymerisation von Olefinen
EP0722955A1 (fr) * 1995-01-18 1996-07-24 BP Chemicals Limited Procédé de polymérisation d'oléfines
WO1997008216A1 (fr) * 1995-08-28 1997-03-06 Exxon Chemical Patents Inc. Procede de production de polypropylene modifie par dienes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4426122A1 (de) * 1993-07-22 1995-02-23 Nippon Oil Co Ltd Katalysatorkomponente für die Polymerisation von Olefinen
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