WO2002079272A1 - Procede de preparation d'un polyethylene de poids moleculaire eleve - Google Patents

Procede de preparation d'un polyethylene de poids moleculaire eleve Download PDF

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Publication number
WO2002079272A1
WO2002079272A1 PCT/NL2002/000194 NL0200194W WO02079272A1 WO 2002079272 A1 WO2002079272 A1 WO 2002079272A1 NL 0200194 W NL0200194 W NL 0200194W WO 02079272 A1 WO02079272 A1 WO 02079272A1
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group
carbon atoms
ethylene
process according
containing group
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PCT/NL2002/000194
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English (en)
Inventor
Gerardus Johannes Maria Gruter
Bing Wang
Adrianus Hendricus Joseph Franciscus De Keijzer
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Dsm N.V.
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Publication of WO2002079272A1 publication Critical patent/WO2002079272A1/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
    • C08F10/00—Homopolymers and copolymers 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
    • 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
    • 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
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound

Definitions

  • the invention relates to a process for the preparation of a high- molecular-weight homo- or copolymeric polyethylene having a weight-average molecular weight (as determined via Size Exclusion Chromatography combined with a viscosity detector (SEC-DV)) of between 500,000 and 10,000,000 g/mol, in the presence of a metallocene catalyst composition.
  • a weight-average molecular weight as determined via Size Exclusion Chromatography combined with a viscosity detector (SEC-DV) of between 500,000 and 10,000,000 g/mol
  • Metallocene catalysts for the production of polyethylene with a relatively high molecular weight have recently been developed, as described in for instance WO-A-99/02.540.
  • the metallocene catalysts used therein contain highly complex cyclopentadienyl ligands with at least four fused rings.
  • a drawback of the known process is that it only rarely results in a polyethylene having a weight-average molecular weight of more than 500,000 g/mol. Most of the polyethylenes obtained have a weight-average molecular weight of less than 300,000 g/mol. It has now been found that a high-molecular-weight homo- or copolymeric polyethylene having a weight-average molecular weight of between 500,000 and 10,000,000 g/mol (as determined via SEC-DV) can be obtained when ethylene and optionally a minor amount of another ⁇ -olefin is polymerized in the presence of a metallocene catalyst composition comprising a double-bridged bisindenyl metal complex of Formula 1 :
  • Ri to R 10 are substituents which are equal or different and are each independently chosen from the group comprising a hydrogen atom, a halogen atom, a hydrocarbon group with 1-20 carbon atoms, and a hydrocarbon group with 1-20 carbon atoms in which one or more hydrogen and/or carbon atoms have been replaced by hetero atoms;
  • Bi and B 2 are bridging groups which are equal or different; in the case of a homopolymerization of ethylene, B ⁇ and B 2 each independently represent a group chosen from the group comprising a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, a tin-containing group, -O-, -CO-, -S-, -SO 2 -, -Se-, -NR-, -PR-, -P(O)R-, -BR-, and -AIR-, wherein, for each group independently, R is chosen from the group comprising a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and a halogen- containing hydrocarbon group having 1 to 20 carbon atoms; in the case of a copolymehzation of ethylene with a minor amount of another ⁇ -o
  • M is a transition metal of the lanthanides and/or of Group 3, 4, 5 or 6 of the Periodic Table of the Elements;
  • Q is an anionic ligand and k is the number of Q groups.
  • Double-bridged bisindenyl metal complexes according to Formula 1 are known from JP-A-00095820 for the polymerization of propylene. Said publication does not teach, however, that such double-bridged bisindenyl metal complexes are suitable as catalysts for the polymerization of ethylene to a high-molecular-weight polyethylene.
  • the substituents R ⁇ to R 10 on the indenyl rings can be equal or different and are chosen form the group comprising a hydrogen atom, a halogen atom, a hydrocarbon group with 1-20 carbon atoms, and a hydrocarbon group with 1-20 carbon atoms in which one or more hydrogen atoms have been replaced by hetero atoms.
  • the hydrocarbon group with 1-20 carbon atoms can be linear, branched, cyclic or aromatic.ln the hydrocarbon groups in which one or more hydrogen atoms have been replaced by hetero atoms, the hydrogen atoms have preferably been replaced by halogen atoms or organic silyl substituents.
  • two adjacent substituents of the indenyl compound can be bonded with each other to form a ring system.
  • hydrocarbon substituents forming a ring This may for instance result in the formation of benzoindenyl.
  • the substituents on the indenyl ring are for instance alkyl, aryl, aralkyl, trialkylsilyl, dialkylaminoalkyl, alkoxyalkyl and haloalkyl, such as for instance methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, 2-ethylhexyl, decyl, phenyl, benzyl, trimethylsilyl, triethylsilyl, phenyldimethylsilyl, diphenylmethylsilyl, triphenylsilyl, dimethylaminoethyl, methoxyethyl, (dimethyl)(dimethylamino)silyl and 2-chloroethyl.
  • ⁇ -olefins preferably each independently represent a silicon-containing group, a germanium-containing group or a tin-containing group.
  • B T and B 2 are of the following structure:
  • R' and R" groups each independentlly represent hydrogen, a hydrocarbon group with 1-20 carbon atoms, or a hydrocarbon group with 1-20 carbon atoms in which one or more hydrogen atoms have been replaced by hetero atoms.
  • the hydrocarbon group with 1 -20 carbon atoms can be linear, branched, cyclic or aromatic.
  • the hydrogen atoms have preferably been replaced by halogen atoms or organic Si, Ge or Sn substituents.
  • Examples of hydrocarbon groups are a methylene group, an ethylene group, a propylene group, and a butylene group.
  • E is preferably a Si atom.
  • Suitable bridging groups B ⁇ and B 2 are dialkyl silylene, dialkyl germylene, tetraalkyl disilylene, dialkyl silaethylene (-SiR' 2 -CH 2 -), and tetraalkyl silaethylene (-SiR' 2 -CR" 2 ).
  • the R' and R" groups in such bridging groups preferably each independently represent hydrogen, an alkyl group containing 1-4 carbon atoms or an aryl group, for example a phenyl group.
  • the R' and R" groups preferably each independently represent a methyl group or an ethyl group.
  • Bj and B 2 each are of the following formula:
  • R'" is an alkyl group with 1-4 C atoms.
  • Catalysts with two dialkylsilylene bridges exhibit a higher activity. Polymerization of ethylene by means of such catalysts results in a polyethylene having a higher molecular weight.
  • M is a transition metal chosen from the lanthanides or from Groups 3,
  • M is by preference a transition metal from Group 4, in particular Ti, Zr or Hf.
  • Q is an anionic ligand which is sigma-bonded to the transition metal M.
  • ligands which can be identical or different, are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an arylalkyl group, an alkoxy group, an aryloxy group, and a group with a hetero atom chosen from Groups 14, 15 or 16 of the
  • Periodic System of the Elements such as:
  • - an amine group or an amide group, - a sulphur-containing group, such as a sulphide, - a phosphorus-containing group, such as a phosphine.
  • the ligand Q can also be an anionic ligand which is bonded to the transition metal M via a covalent metal-carbon bond and additionally shows a non-covalent interaction with M via one or more functional groups.
  • a functional group can be an atom, but also a group of atoms which are bonded to each other.
  • the functional group preferably is an atom from Group 17 of the Periodic System of the Elements or a group which contains one or more elements of Group 15, 16 or 17 of the Periodic System of the Elements. Examples of functional groups are F, CI, Br, a dialkylamino ' group, and an alkoxy group.
  • Q can for instance be a phenyl group with one of the ortho positions substituted with a functional group which is capable of donating electron density to the transition metal M.
  • Q can also be a methyl group with one or more of the positions on the ⁇ -carbon atom being substituted with a functional group which is capable of donating electron density to the transition metal M.
  • methyl groups which are substituted at one or more ⁇ -positions are benzyl, diphenylmethyl, ethyl, propyl and butyl substituted with a functional group which is capable of donating electron density to the transition metal M.
  • Preferably at least one of the ortho positions of the benzyl group is substituted with a functional group which is capable of donating electron density to the transition metal M.
  • Q groups examples include: 2,6-difluorophenyl, 2,4,6-trifluorophenyl, pentafluorophenyl, 2-alkoxyphenyl, 2,6-dialkoxyphenyl, 2,4,6-tri(trifluoromethyl)phenyl,
  • Q is a monoanionic ligand which is sigma-bonded to the transition metal M.
  • Q is CI or a methyl group.
  • k is the number of Q groups in the indenyl compound, and depends on the valency of the transition metal M and the valency of the Q groups themselves. In the double-bridged bisindenyl compound according to Formula 1 , k is equal to the valency of M minus 2, divided by the valency of Q.
  • the cocatalyst can be an organometal compound with a metal chosen from Group 1 , 2, 12 or 13 of the Periodic System of the Elements.
  • suitable compounds without being restricted thereto, are organoaluminium compounds, amyl sodium, butyl lithium, diethyl zinc, butyl magnesium chloride and dibutyl magnesium.
  • organoaluminium compounds such as for instance thalkylaluminium compounds (for example triethylaluminium and triisobutylaluminium); alkylaluminium hydrides (for example diisobutyl aluminium hydride); alkylalkoxy organoaluminium compounds; halogen-containing organoaluminium compounds (for example diethyl aluminium chloride, diisobutyl aluminium chloride, and ethyl aluminium sesquichloride); and aluminoxanes.
  • aluminoxanes are used as organoaluminium compound. These aluminoxanes can contain a minor amount of thalkylaluminium, preferably 0.5 - 15 mol% trialkylaluminium.
  • the catalyst composition according to the invention can contain an ion complex.
  • This ion complex consists of a cation and a compatible non-coordinating anion which is relatively big and which can stabilize the active catalyst particle that is formed when the ion complex and the double-bridged bisindenyl metal complex are combined.
  • the bond between such a compatible non-coordinating anion and the transition metal is sufficiently labile to enable the compatible non-coordinating anion to be replaced by an unsaturated monomer during the olefin polymerization.
  • Such ion complexes have already been described for instance in EP-A-426,637, and are also known from EP-A-277,003 and EP-A-277,004.
  • such a complex contains a triaryl borate, a tetraaryl borate, or an aluminium or silicon equivalent thereof.
  • suitable ion complexes are: - dimethylanilinium tetrakis (pentafluorophenyl) borate; dimethylanilinium bis(7,8-dicarbaundecaborate)-cobaltate (III); tri(n-butyl)ammonium tetraphenyl borate; triphenylcarbenium tetrakis (pentafluorophenyl) borate; dimethylanilinium tetraphenyl borate; and - tris(pentafluorophenyl) borane.
  • reaction mixture can also contain a minor amount of scavenger.
  • a scavenger is an organometal compound which reacts with impurities in the reaction mixture. Organoaluminium compounds are commonly used as scavenger. Examples of scavengers are trioctylaluminium, triethylaluminium and triisobutylaluminium.
  • the metallocene catalyst composition on the basis of the double- bridged bisindenyl metal complex and optionally a cocatalyst can be applied on a carrier as well as without a carrier.
  • suitable carrier materials are silica, alumina and MgCI 2 .
  • silica is used as the carrier material.
  • the weight-average molecular weight of the high-molecular-weight polyethylene according to the invention is preferably between 750,000 and 10,000,000 g/mol, more preferably between 750,000 and 5,000,000 g/mol, as determined by SEC- DV.
  • the high-molecular-weight polyethylene is obtained by the homopolymerization of ethylene or by the copolymerization of ethylene with a minor amount of another ⁇ -olefin as the comonomer to yield an ethylene copolymer.
  • the amount of comonomer in the ethylene copolymer generally varies from 0.25 to at most 45 wt.%.
  • the other ⁇ -olefin is preferably an ⁇ -olefin with 3-12 carbon atoms, more preferably an ⁇ -olefin chosen from the group comprising propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, and 1-octene, or a mixture of two or more of these ⁇ -olefins; most preferably an ⁇ -olefin chosen from the group comprising propene, 1-butene, 1-hexene, and 1-octene.
  • the polymerization can be carried out in the known manner, in the gas phase as well as in a liquid medium. In a liquid medium both solution and suspension polymerization are possible.
  • the amount of catalyst used in a liquid medium normally is such that the catalyst concentration during the polymerization is between 10 "8 and 10 ⁇ 2 mol/l of the reaction mixture.
  • the polymerization can be carried out at atmospheric pressure, but also at elevated pressure, up to 500 MPa, continuously or discontinuously.
  • the polymerization is preferably carried out at a pressure of between 0.1 and 25 MPa. High pressures of 100 MPa and more can be used if the polymerization is carried out in a so-called high-pressure reactor. If the polymerization is carried out at elevated temperature the polymerization rate is usually higher.
  • the polymerization is therefore preferably carried out at a temperature of 95 to 300°C, more preferably at a temperature of 100 to 200°C, in particular at a temperature between 100 and 180°C.
  • the polymerization can be carried out in several steps, in series as well as parallel. If required the metallocene catalyst composition, the temperature, the hydrogen concentration, the pressure, the residence time, etc. can be varied from step to step. In this way it is possible to obtain products with a controllable, for example broad, molecular weight distribution.
  • High-molecular-weight polyethylenes i.e. with a weight average molecular weight higher than 500,000 g/mol, are commercially produced using a Ziegler catalyst. In such a process, however, relatively large amounts of catalyst are required, which remain in the product or need to be removed. The resulting polyethylenes usually feature a relatively broad molecular weight distribution.
  • the polyethylenes (PE) produced according to Examples l-V were analysed by * SEC-DV using a Waters M150C GPC (including a DRI detector) connected via a heated transfer line with a Viscotek H502B viscosimeter.
  • a Waters M150C GPC including a DRI detector
  • Viscotek H502B viscosimeter
  • Four TSK GMHxL-HT columns were applied. 1 ,2,4-trichlorobenzene was used as the eluent.
  • Universal and conventional calibration was done using polyethylene standards.
  • the flow was 1.0 ml/min, the injection volume 300 ⁇ l, the column temperature 140°C and the injection temperature 150°C.
  • the data were processed using Viscotek TriSEC 2.7 software.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

La présente invention concerne un procédé de préparation d'un polyéthylène homopolymère ou copolymère de poids moléculaire élevé possédant un poids moléculaire moyen (tel que déterminé par chromatographie d'exclusion diffusion combinée à un détecteur de viscosité) compris entre 500 000 et 10 000 000, le polyéthylène homopolymère ou copolymère étant préparé par polymérisation d'éthylène et éventuellement d'une petite quantité d'une autre oléfine α avec une composition de catalyseur de métallocène contenant un complexe métallique de bisindényle à double liaison de formule (1).
PCT/NL2002/000194 2001-03-29 2002-03-27 Procede de preparation d'un polyethylene de poids moleculaire eleve WO2002079272A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6906155B1 (en) * 1998-06-25 2005-06-14 Idemitsu Petrochemical Co., Ltd. Propylene polymer and composition containing the same, molded object and laminate comprising these, and processes for producing propylene polymer and composition containing the same
EP2050767A1 (fr) 2007-10-19 2009-04-22 Braskem S.A. Procédé pour la production d'un support catalytique et catalyseurs métallocènes supportés pour la production de polymères d'éthylène avec des alpha-oléfines, de poids moléculaire élevé et très élevé et de large distribution de poids moléculaires et produits résultants dudit procédé
JPWO2010117028A1 (ja) * 2009-04-10 2012-10-18 出光興産株式会社 αオレフィンオリゴマーおよびその製造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0721954A1 (fr) * 1993-09-30 1996-07-17 Idemitsu Kosan Co., Ltd. Compose d'un metal de transition, catalyseur de polymerisation d'olefine, et procede de production d'un polymere olefinique a l'aide du catalyseur
EP0818458A1 (fr) * 1995-03-30 1998-01-14 Idemitsu Kosan Company Limited Compose de metaux de transition, catalyseur de polymerisation pour olefines et procede d'elaboration de polymeres d'olefines
WO1999067303A1 (fr) * 1998-06-25 1999-12-29 Idemitsu Petrochemical Co., Ltd. Polymere de propylene et composition contenant ce polymere, objet moule et stratifie contenant ce polymere et cette composition, et procedes pour produire ce polymere de propylene et la composition contenant ce polymere
EP0970974A1 (fr) * 1997-03-21 2000-01-12 Idemitsu Petrochemical Co., Ltd. Procede de production de polymeres d'olefines

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0721954A1 (fr) * 1993-09-30 1996-07-17 Idemitsu Kosan Co., Ltd. Compose d'un metal de transition, catalyseur de polymerisation d'olefine, et procede de production d'un polymere olefinique a l'aide du catalyseur
EP0818458A1 (fr) * 1995-03-30 1998-01-14 Idemitsu Kosan Company Limited Compose de metaux de transition, catalyseur de polymerisation pour olefines et procede d'elaboration de polymeres d'olefines
EP0970974A1 (fr) * 1997-03-21 2000-01-12 Idemitsu Petrochemical Co., Ltd. Procede de production de polymeres d'olefines
WO1999067303A1 (fr) * 1998-06-25 1999-12-29 Idemitsu Petrochemical Co., Ltd. Polymere de propylene et composition contenant ce polymere, objet moule et stratifie contenant ce polymere et cette composition, et procedes pour produire ce polymere de propylene et la composition contenant ce polymere
EP1095951A1 (fr) * 1998-06-25 2001-05-02 Idemitsu Petrochemical Co., Ltd. Polymere de propylene et composition contenant ce polymere, objet moule et stratifie contenant ce polymere et cette composition, et procedes pour produire ce polymere de propylene et la composition contenant ce polymere

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6906155B1 (en) * 1998-06-25 2005-06-14 Idemitsu Petrochemical Co., Ltd. Propylene polymer and composition containing the same, molded object and laminate comprising these, and processes for producing propylene polymer and composition containing the same
US7544758B2 (en) 1998-06-25 2009-06-09 Idemitsu Kosan Co., Ltd. Propylene polymer and composition containing the same, molded object and laminate comprising these, and processes for producing propylene polymer and composition containing the same
EP2050767A1 (fr) 2007-10-19 2009-04-22 Braskem S.A. Procédé pour la production d'un support catalytique et catalyseurs métallocènes supportés pour la production de polymères d'éthylène avec des alpha-oléfines, de poids moléculaire élevé et très élevé et de large distribution de poids moléculaires et produits résultants dudit procédé
JPWO2010117028A1 (ja) * 2009-04-10 2012-10-18 出光興産株式会社 αオレフィンオリゴマーおよびその製造方法

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