WO1998057997A1 - PROCEDE DE PREPARATION DE POLYOLEFINES A UNE TEMPERATURE ELEVEE A L'AIDE DE Zr METALLOCENE - Google Patents

PROCEDE DE PREPARATION DE POLYOLEFINES A UNE TEMPERATURE ELEVEE A L'AIDE DE Zr METALLOCENE Download PDF

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Publication number
WO1998057997A1
WO1998057997A1 PCT/NL1998/000350 NL9800350W WO9857997A1 WO 1998057997 A1 WO1998057997 A1 WO 1998057997A1 NL 9800350 W NL9800350 W NL 9800350W WO 9857997 A1 WO9857997 A1 WO 9857997A1
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group
atoms
process according
metallocene
polymerisation
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PCT/NL1998/000350
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English (en)
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Jacob Renkema
Peter Jozef Hubert Windmuller
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Dsm N.V.
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Publication of WO1998057997A1 publication Critical patent/WO1998057997A1/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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene

Definitions

  • the invention relates to a process for the polymerisation of one or more ⁇ -olefins and optionally a diene to form a polyolefin at a temperature above 100°C with the aid of a catalyst system comprising a zirconium (Zr) -based metallocene.
  • a catalyst system comprising a zirconium (Zr) -based metallocene.
  • a drawback of polymers with a narrow MWD is their poor processability and poor flow behaviour.
  • the aim of the present invention is to eliminate the poor processability of such polyolefins through synthesis of polymers with a bimodal MWD.
  • a bimodal MWD is a molecular weight distribution with two or more peaks as can be seen via Size Exclusion Chromatography in combination with Differential Viscosimetry (SEC-DV) .
  • a broadened MWD, which contains a primary or main peak and one or more small secondary peaks, is also considered as a bimodal MWD.
  • the invention provides a process for the polymerisation of one or more ⁇ -olefins at a temperature above 100°C with the aid of a catalyst system comprising a Zr metallocene, the process being characterised in that the Zr metallocene is a compound having the formula:
  • R 1 is, independently of one another, H, an alkyl group with 1-10 C atoms, an alkylaryl group with 7-20 C atoms or an aromatic group with 6-20 C atoms,
  • R 1 groups are H, methyl, tertiary butyl, neopentyl, phenyl or benzyl. H or a methyl (Me) group are preferably used as the R 1 group .
  • the Zr metallocene (Formula 1) to be used in the process according to the invention consists of two ringsystems .
  • Each ringsystem contains a 5-membered and a 6-membered ring.
  • the two 5-membered rings are bound to the Zr atom.
  • the ringsystems are indenyl groups .
  • the ringsystems are tetrahydroindenyl groups.
  • R 3 groups may themselves, too, form part of a ringsystem, so that fluorenyl groups can also be present in the Zr metallocenes of the present invention.
  • the two ringsystems which may or may not be substituted, are bridged by an ethylene bridge.
  • An ethylene bridge consists of two C-atoms that bind the two ringsystems to one another.
  • the bridge may be bound to the 5-ring at two positions: at a 1 position or at the 2 position.
  • the ethylene bridge is substituted with R 2 groups.
  • An R 2 group can be H, an alkyl group with 1-10 C atoms, an alkylaryl group with 7-20 C atoms, an aromatic group with 6-20 C atoms and a silanylene group with 3-30 C atoms.
  • R 2 is preferably independently H, methyl, phenyl or tri ethylsilyl.
  • the ringsystems of Formula I are independently of one another substituted at different positions with R 3 groups.
  • An R 3 group can be H, an alkyl group with 1-10 C atoms, an alkylaryl group with 7-20 C atoms, an aromatic group with 6-20 C atoms or a silanylene group with 3-30 C atoms.
  • R 3 is preferably independently H, methyl, ethyl, isopropyl, tertiary butyl, trimethylsilyl or phenyl.
  • a silanylene group is a silicon-containing group, -SiR 4 3 , which is bound via the Si atom.
  • the silanylene group itself also contains three R 4 groups, which may be H, alkyl groups with 1-10 C atoms, alkylaryl groups with 7-20 C atoms, aromatic groups with 6-20 C atoms, halogenides, alkoxides with 1-10 C atoms and amido groups with 1-10 C atoms.
  • R 4 is an alkyl group with 1-10 C atoms.
  • the alkyl group of R 1 , R 2 , R 3 , R 4 or the silanylene group may be linear, branched and/or substituted and may or may not contain one or more atoms from any one of Groups 14, 15, 16 or 17 of the Periodic System as published in the Handbook of Chemistry and Physics, 67 th edition, 1986-1987, inner front page, CRC-Press, Florida.
  • Bridged ringsystems can form different stereoisomers. Both racemic and meso stereoisomers may occur. It is preferable to use a racemic Zr metallocene.
  • the bimodality of the polymer obtained can be made visible with the aid of SEC-DV.
  • the chromatogram from a polymer made according to the present invention clearly shows two or more peaks in the case of a bimodal polymer.
  • the bimodality can also be described by determining the MWD. For example, an MWD ⁇ 3 is indicative of a unimodal distribution, while an MWD > 3 for polymers prepared with Zr metallocenes, as used in the process according to the invention, characterises a bimodal distribution.
  • bimodal polyolefins can be obtained by carrying out a polymerisation of ⁇ -olefins with mixed catalysts. The mixing of different polyolefins that have first been separately prepared results in well-processable polyolefins, as described in US 3, 884,993.
  • bimodal polymers are_ obtained at temperatures of > 100°C by using in the polymerisation a single Zr metallocene.
  • the Zr metallocene needs to be activated with a cocatalyst.
  • Activation means transforming the neutral Zr-metallocene to a cationic catalyst species that is active in the polymerisation of an ⁇ -olefin. This activation may be the replacement of an R 1 group in the metallocene by a different substituent, or the removal of an R 1 group, so that a cationic Zr metallocene is formed.
  • Suitable cocatalysts are for example aluminoxanes .
  • Aluminoxanes may occur as cyclic or as linear structures, as described in EP 646 604 A and WO 92 21685 A.
  • Aluminoxanes can be prepared in the manner known from these patent publications; they are also commercially available. Methyl aluminoxanes produced by
  • Witco, Ethyl and Akzo can be mentioned as examples of commercially available aluminoxanes.
  • Use can also be made of organoaluminium oxides having the formula R 2 A1- 0-AlR 2 , where R is an alkyl group or an alkoxy group as described in WO 93 25591 A.
  • cocatalysts for the conversion into cationic compounds are mentioned for example in WO 91 09882 A.
  • These cocatalysts are compounds that contain a non-coordinating or poorly coordinating anion or form such anion in the reaction with the Zr metallocene.
  • These catalyst systems have the advantage that smaller amounts of cocatalyst can be used, which can result in a considerable cost saving.
  • Examples of such cocatalysts are tris-pentafluorophenylborate and dimethylanilinium tetrakis-pentafluorophenylborate .
  • Particularly suitable cocatalysts for the Zr metallocene are aluminoxanes and pentafluorophenyl borates.
  • the Zr metallocene and the cocatalyst can be etered into the reactor separately or they can first be premixed for a certain period of time.
  • one or more metal alkyl compounds can also be added to the reaction medium.
  • the metal alkyl compounds serve as scavengers: they capture polar contaminations in the polymerisation medium.
  • metal alkyl compounds examples include trialkyl aluminium compounds, dialkyl aluminium alkyoxy compounds, dialkylaluminium halogenide compounds, alkyl lithium compounds and dialkyl magnesium compounds, etc.
  • the components of the catalyst system can be used (entirely or partly) on a carrier or without a carrier.
  • An advantage of a catalyst system deposited on a carrier is that a lower ratio of the cocatalyst relative to the active component can be used at the same catalyst activity. Catalyst systems deposited on carriers are used predominantly in gas-phase and suspension processes.
  • the carrier to be used is any carrier known as a carrier for metallocene catalysts, for example Si0 2 or A1 2 0 3 .
  • the invention relates to a process for the polymerisation of one or more ⁇ -olefins and optionally a diene.
  • suitable ⁇ -olefins are ethylene, propylene, 1-butene, 1-hexene, 1-octene, l-decene and mixtures hereof. It is also possible to carry out a copolymerisation with different ⁇ -olefins and optionally with a diene.
  • copolymers are rubbery polymers containing ethylene and a different ⁇ - olefin and a diene (EADM) .
  • Propylene, 1-butene, 1- pentene, 1-hexene, 1-octene and 1-decene can be mentioned as suitable ⁇ -olefins that, besides ethylene, can be used as a monomer in the preparation of an EADM polymer. Mixtures of these alkenes can also be used, in which case propylene and/or butene-1 are/is preferable.
  • dienes examples include: 1,3- butadiene, isoprene, 2, 3-dimethylbutadiene, 1,3,2- ethylbutadiene, piperylene, mycrene, allene, 1,2- butadiene, 1, 4, 9-decatrienes, 1, 4-hexadiene, 1,5- hexadiene and 4-methylhexadiene-l,4.
  • Alicyclic polyunsaturated compounds which may or may not contain a bridge group, may be mono- or polycyclic.
  • Examples of such compounds are norbornadiene and its alkyl derivatives; the alkylidene norbornenes, in particular the 5-alkylidene norbornenes-2, in which the alkylidene group contains from 1 to 20, preferably from 1 to 8 carbon atoms; the alkenylnorbornenes , in particular the 5-alkenylnorbornenes-2 , in which the alkenyl group contains from 2 to 20 and preferably from 2 to 10 carbon atoms, for example 5- (2 ' -methyl- 2 'butenyl) norbornene-2 and 5- (3 ' -methyl- 2 ' butenyl) norbornene-2 ; vinyl norbornene , dicyclopentadiene and the polyunsaturated compounds of bicyclo- (2,2,1) -heptane, bicyclo- (2,2,2) -octane, bicyclo- (3 , 2, 1) -octane and bicyclo- (3 , 2 , 2) -nonane,
  • the temperature of the polymerisation lies above 100°C. At temperatures lower than 100°C products with a narrow, unimodal MWD are obtained. Polymerisation can be carried out at a temperature above 250°C. The polymerisation above 250 °C will yield very low molecular weight polymers or oligomers . To obtain a polyolefin with a molecular weight (Mw) above about 10 kg/mol, polymerisation is preferably carried out at a temperature of up to 200°C.
  • the polymerisation temperature influences the degree of bimodality. A higher polymerisation temperature has been found to result in a more bimodal polymer: the peaks observable in the chromatogram are further separated from one another, as a result of which the MWD also becomes larger. Those skilled in the art can readily determine through experiment what degree of bimodality should be set to obtain good processability.
  • the pressure of the polymerisation is usually between 0.05 and 400 MPa. Preferably the pressure is between 0.05 and 10 MPa, so that the technical feasibility is relatively simple.
  • the polymerisation time may vary between a few seconds and several hours. The polymerisation time is generally between a few minutes and 3 hours .
  • the ⁇ -olefins can be polymerised in a known manner, in the gas phase and also in a liquid reaction medium. Both solution and suspension polymerisation are suitable in the latter case.
  • Solvents known for a solution polymerisation can be used.
  • aliphatic hydrocarbons such as hexane and heptane, or of mixtures of aliphatic hydrocarbons.
  • the solvent may nevertheless contain small amounts of an aromatic hydrocarbon, for example toluene.
  • MAO methyl aluminoxane
  • toluene may serve as a solvent so as to be able to meter the MAO in solution into the polymerisation reactor.
  • the polymer can be processed further in different ways. Both evaporation of the solvent and steam coagulation are suitable in the case of liquid-phase processes.
  • the polymer's molecular weight can be set via techniques known to those skilled in the art, for example, as already mentioned, by choosing the polymerisation temperature.
  • the molecular weight can also be varied by using chain length regulators, such as diethyl zinc and preferably hydrogen. Very small amounts of hydrogen already influence the molecular weight sufficiently.
  • the process of the invention is suitable for producing polyethylene, polypropylene and also copolymers of various ⁇ -olefins, for example copolymers of propylene and butene-1, copolymers of ethylene and " propylene, copolymers of ethylene and butene-1, copolymers of ethylene and hexene-1 or copolymers of ethylene and octene-1.
  • the bimodal copolymers generally contain between 20 and 90 wt.% ethylene.
  • the copolymers may be semi-crystalline or even entirely amorphous.
  • Amorphous polymers are polymers that contain no crystallinity above 25°C, measured with the aid of differential scanning calorimetry (DSC) . Products with an ethylene content of between 25 and 80 wt.% are preferred.
  • An example of an amorphous copolymer is a polymer that consists of ethylene, propylene and a diene (EPDM) and has an ethylene content of between 40 and 70 wt.%.
  • EPDM diene
  • Such copolymers are suitable for many different applications, for example for manufacturing hoses, conveyor belts, sealing profiles. They can optionally be vulcanised by the usual methods (for example with the aid of substances yielding free radicals such as peroxides, or with the aid of sulphur) .
  • the invention will be elucidated with reference to some examples.
  • the catalyst employed, racemic C 2 H 4 ⁇ Indenyl) 2 ZrMe 2 was synthesised according to EP 485 820 A.
  • the cocatalyst (dimethylanilinium tetrakis- pentafluorophenylborate) was obtained from a commercial supplier. Trioctylaluminium (TOA) was used as a scavenger.
  • TOA Trioctylaluminium
  • the polymers ⁇ compositions were analysed with the aid of Fourier Transform Infra Red Spectroscopy (FT-IR) and their molecular weights and molecular weight distributions with the aid of SEC-DV.
  • FT-IR Fourier Transform Infra Red Spectroscopy
  • the FT-IR measurements give the compositions of the different monomers in weight percentages relative to the overall composition.
  • Apparatus - Waters M150c Gel Permeation Chromatograph (GPC) with a DRI detector
  • Viscotel Differential Viscometer (DV) Viscotel Differential Viscometer (DV) , model 100-
  • Detectors in a parallel configuration with a heated line interface Detectors in a parallel configuration with a heated line interface (HLI) .
  • LiChroma III pump pulse dampener (Viscotek) and high-sensitivity accessory (Waters)
  • Boiling point spirit, ethylene, propylene, Zr metallocene, TOA (0.4 mmol/hour) and cocatalyst (0.4 mmol/hour) were continuously fed to a 1-litre steel reactor.
  • the monomers and the dispersing agent had been freed of oxygen and dried beforehand, by successively passing them through a Cu-deoxo column and a column filled with 4A and 13X molecular sieves.
  • a polyolefin based on ethylene and propylene was prepared in the reactor.
  • the solution was continuously removed from the reactor and flashed, the catalyst system was killed with the aid of isopropanol and the polyolefin was stabilised with approx. 1000 ppm
  • Irganox 1076 R The polymer was worked up and analysed.
  • Examples I and II copolymers of ethylene and propylene were prepared at polymerisation temperatures above 100°C. Polymers with a bimodal MWD were obtained, with an MWD > 3.
  • Comparative Experiment A a polymer with a comparable composition was prepared using the same catalyst system at a temperature of 60°C. A unimodal polymer with an MWD ⁇ 3 was obtained.
  • Table 1 shows the polymerisation conditions of the Examples and the Comparative Experiment.
  • Table 2 lists the polymer properties of the polyolefins obtained.
  • Appendix A shows the SEC-DV chromatograms of

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Abstract

L'invention concerne un procédé de polymérisation d'une ou plusieurs α-oléfines permettant de former une polyoléfine à une température dépassant 100 °C à l'aide d'un système catalyseur comprenant un Zr métallocène, le Zr métallocène étant un composé représenté par la formule (I), dans laquelle R1 désigne, indépendamment, H, un groupe alkyle contenant de 1 à 10 atomes de carbone, un groupe alkylaryle contenant de 7 à 20 atomes de carbone ou un groupe aromatique contenant de 6 à 20 atomes de carbone R2 et R3 désignent, indépendamment l'un de l'autre, H, un groupe alkyle contenant de 1 à 10 atomes de carbone, un groupe alkylaryle contenant de 7 à 20 atomes de carbone ou un groupe aromatique contenant de 6 à 20 atomes de carbone ou un groupe sinalylène contenant de 3 à 30 atomes de carbone, n valant 4 ou 8.
PCT/NL1998/000350 1997-06-18 1998-06-17 PROCEDE DE PREPARATION DE POLYOLEFINES A UNE TEMPERATURE ELEVEE A L'AIDE DE Zr METALLOCENE WO1998057997A1 (fr)

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NL1006346 1997-06-18
NL1006346A NL1006346C2 (nl) 1997-06-18 1997-06-18 Werkwijze voor de bereiding van polyolefines bij hoge temperatuur met behulp van Zr-metallocenen.

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0260999A1 (fr) * 1986-09-19 1988-03-23 Exxon Chemical Patents Inc. Polymérisation d'éthylène à haute température et haute pression
EP0347128A1 (fr) * 1988-06-16 1989-12-20 Exxon Chemical Patents Inc. Procédé de préparation d'élastomères éthylène-alpha-oléfine à haut poids moléculaire en utilisant un catalyseur métalocène-alumoxane
EP0485822A2 (fr) * 1990-11-12 1992-05-20 Hoechst Aktiengesellschaft Procédé de préparation d'un polymère oléfinique à haut poids moléculaire
WO1994011406A1 (fr) * 1992-11-11 1994-05-26 Dsm N.V. Composes d'indenyle et constituants catalytiques destines a la polymerisation des olefines
EP0643078A2 (fr) * 1993-09-13 1995-03-15 Montell Technology Company bv Procédé de préparation de polymères d'éthylène et produits ainsi obtenus
EP0659773A1 (fr) * 1993-12-21 1995-06-28 Union Carbide Chemicals & Plastics Technology Corporation Préparation de polyoléfines possédant des ramifications à chaîne longue par un procédé en phase gazeuse
WO1995030698A1 (fr) * 1994-05-06 1995-11-16 Dsm N.V. Procede de preparation d'un polymere elastomere a partir d'ethylene, d'une alpha-olefine et eventuellement d'un diene
EP0702030A1 (fr) * 1991-05-27 1996-03-20 Hoechst Aktiengesellschaft Procédé de préparation de polyoléfines à large répartition de poids moléculaire
EP0709405A1 (fr) * 1994-10-25 1996-05-01 Tosoh Corporation Procédé de préparation de polymères d'oléfines
EP0745615A1 (fr) * 1994-12-20 1996-12-04 Mitsui Petrochemical Industries, Ltd. Procede de production de polymere d'ethylene et polymere d'ethylene obtenu

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0260999A1 (fr) * 1986-09-19 1988-03-23 Exxon Chemical Patents Inc. Polymérisation d'éthylène à haute température et haute pression
EP0347128A1 (fr) * 1988-06-16 1989-12-20 Exxon Chemical Patents Inc. Procédé de préparation d'élastomères éthylène-alpha-oléfine à haut poids moléculaire en utilisant un catalyseur métalocène-alumoxane
EP0485822A2 (fr) * 1990-11-12 1992-05-20 Hoechst Aktiengesellschaft Procédé de préparation d'un polymère oléfinique à haut poids moléculaire
EP0702030A1 (fr) * 1991-05-27 1996-03-20 Hoechst Aktiengesellschaft Procédé de préparation de polyoléfines à large répartition de poids moléculaire
WO1994011406A1 (fr) * 1992-11-11 1994-05-26 Dsm N.V. Composes d'indenyle et constituants catalytiques destines a la polymerisation des olefines
EP0643078A2 (fr) * 1993-09-13 1995-03-15 Montell Technology Company bv Procédé de préparation de polymères d'éthylène et produits ainsi obtenus
EP0659773A1 (fr) * 1993-12-21 1995-06-28 Union Carbide Chemicals & Plastics Technology Corporation Préparation de polyoléfines possédant des ramifications à chaîne longue par un procédé en phase gazeuse
WO1995030698A1 (fr) * 1994-05-06 1995-11-16 Dsm N.V. Procede de preparation d'un polymere elastomere a partir d'ethylene, d'une alpha-olefine et eventuellement d'un diene
EP0709405A1 (fr) * 1994-10-25 1996-05-01 Tosoh Corporation Procédé de préparation de polymères d'oléfines
EP0745615A1 (fr) * 1994-12-20 1996-12-04 Mitsui Petrochemical Industries, Ltd. Procede de production de polymere d'ethylene et polymere d'ethylene obtenu

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