WO2002006356A1 - Procede de production de polyolefines a repartition bimodale etroite de poids moleculaire - Google Patents

Procede de production de polyolefines a repartition bimodale etroite de poids moleculaire Download PDF

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Publication number
WO2002006356A1
WO2002006356A1 PCT/EP2001/008235 EP0108235W WO0206356A1 WO 2002006356 A1 WO2002006356 A1 WO 2002006356A1 EP 0108235 W EP0108235 W EP 0108235W WO 0206356 A1 WO0206356 A1 WO 0206356A1
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WIPO (PCT)
Prior art keywords
alkyl
aryl
cio
radical
group
Prior art date
Application number
PCT/EP2001/008235
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German (de)
English (en)
Inventor
Marc Oliver Kristen
Dieter Lilge
Peter Jutzi
Christian Mueller
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Basell Polyolefine Gmbh
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Publication of WO2002006356A1 publication Critical patent/WO2002006356A1/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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—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
    • 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
    • C08F2420/00—Metallocene catalysts
    • C08F2420/06—Cp analog where at least one of the carbon atoms of the non-coordinating part of the condensed ring is replaced by a heteroatom
    • 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 present invention relates to a process for the preparation of polyolefins at pressures from 5 to 4,000 bar and temperatures from 20 to 350 ° C. in the presence of a catalyst system which is an organometallic compound from the group of the metallocenes or the catalytically active iron or cobalt -, Nickel or palladium complexes, which organometallic compound has a Lewis base functionality which is arranged so that it can coordinate intramolecularly to the central metal atom of the organometallic compound.
  • a catalyst system which is an organometallic compound from the group of the metallocenes or the catalytically active iron or cobalt -, Nickel or palladium complexes, which organometallic compound has a Lewis base functionality which is arranged so that it can coordinate intramolecularly to the central metal atom of the organometallic compound.
  • Monomodal based on the molecular weight distribution M w / M n , means in the present application that the molar mass distribution has a single maximum.
  • bimodal based on the molecular weight distribution M w / M n , means that the course of the molar mass distribution curve has two turning points on one flank.
  • Catalyst systems with a uniformly defined active center so-called single-site catalysts, are becoming increasingly important in the polymerization of olefins.
  • These catalyst systems lead to polymers with monomodal, narrow molecular weight distributions, which results in particularly favorable mechanical properties.
  • the monomodal molecular weight distribution often makes it difficult to process polymers produced in this way.
  • Such a polymer mixture or, more generally, polymers with a broadened and often bimodal molecular weight distribution can be obtained in various ways.
  • two or more polymer granules or polymer granules can be homogeneously mixed with one another, for example in an extruder.
  • the disadvantage of this method is the additional processing costs due to the additional processing step.
  • a third possibility for producing bimodal or multimodal polymers is to premix several catalysts with different polymerization properties.
  • Such polymerization processes using several catalysts are e.g. known from EP-A 128 045, EP-A 0 619 325 or EP-A 0 516 018.
  • metallocene catalysts More and more chemical variations of the metallocene catalysts, the best-known group of single-site catalysts, are known. For example, also describes metallocene compounds with substituents that carry a Lewis base group. The Lewis base groups are primarily oxygen or nitrogen functionalities. Unbridged metallocene complexes or metallocene catalysts with Lewis base functionalities are e.g. in WO 97/27227, US-A 5 563 284 and DE-A 43 03 647. Bridged metallocene catalysts with Lewis base substituents are described in EP-A 0 608 054.
  • the method according to the invention had the object, using only a catalyst complex and to get Polyolefinpolymerisate with fewer machines, which have good processing properties and a narrow bimodal molecular '''weight distribution.
  • the present invention is based on the observation that when using special single-site catalyst systems, namely those which have a Lewis base functionality which is able to coordinate to the central metal atom of the complex, a bimodal one at certain temperatures Molecular weight distribution occurs with a molecular weight distribution M w / M n of ⁇ 5, so that a bimodal adjustment of the molecular weight distribution in the direction of the desired polymer properties is possible by suitable temperature control using only one catalyst complex.
  • the method according to the invention is suitable in principle for the production of very different polyolefins.
  • the invention e.g. Polymerize or copolymerize ethylene, propylene or higher olefins alone or as a mixture of these monomers.
  • polar comonomers such as vinyl acetate, acrylic or methacrylic acid esters or these acids themselves with ethylene or olefins.
  • the process is also suitable for the production of vinyl aromatic polymers.
  • Propylene is preferably homopolymerized or copolymerized with higher ⁇ -olefins and / or vinyl aromatic compounds.
  • Highly suitable higher ⁇ -olefins are C - bis
  • C ⁇ o-Alk-1-enes such as ethylene, 1-butene, 1-hexene, 1-octene; well-suited vinyl aromatic compounds are styrene and styrene derivatives.
  • Preferred bimodal propylene copolymers with Mw / Mn ⁇ 5 are those which contain at least 50 mol% of propylene. Copolymers of this type which have isotactic and / or hemisotactic propylene sequences are particularly preferred.
  • Preferred bimodal propylene homopolymers with M w / M n ⁇ 5 are isotactic and hemiisotactic propylene homopolymers.
  • the process according to the invention can be carried out in a pressure range from 5 to 4,000 bar.
  • the process can be carried out in the customary polymerization plants known to those skilled in the art and by the customary polymerization processes. Examples include polymerization processes in gas phase reactors, in particular in gas phase fluidized bed reactors, polymerizations in solution or suspension polymerization processes. The methods mentioned are usually operated at pressures between 1 and 50 bar, in particular between 5 and 40 bar.
  • the process according to the invention is carried out at a reaction temperature which results in a molecular weight distribution of ⁇ 5.0, preferably ⁇ 4.0.
  • Reaction temperatures which are very suitable are from 20 to 120 ° C., particularly preferably 60 to 100 oC -
  • the process according to the invention can also be carried out in high-pressure polymerization processes, for example in a stirred autoclave or in tubular reactors, pressures of 500 to 4000 bar, preferably 1000 to 3000 bar and Temperatures of 160 ° C to 350 ° C, preferably 200 ° C to 240 ° C are used.
  • the reaction temperature of the process according to the invention depends on the one hand on the catalytically active organometallic compound used and on the other hand on the desired molecular weight distribution and the bimodal curve shape of the GPC chromatogram of the polymer.
  • the suitable polymerization temperature can easily be determined by a few preliminary tests.
  • organometallic compounds which are part of the catalyst system have a Lewis base functionality which is arranged in such a way that it can coordinate intramolecularly to the central metal atom of the organometallic compound.
  • This feature can be achieved through a variety of possible chemical structures and arrangements, as well as through a variety of substitution patterns.
  • the type of substitution or the chemical nature of the Lewis base ligands is therefore less critical than the possibility of the above-mentioned coordination ability.
  • the catalyst systems used in the process according to the invention can contain various organometallic compounds as the catalytically active compound.
  • a preferred embodiment of the process is characterized in that a metallocene complex of the general formula I is used as the organometallic compound
  • R 1 to R 5 are hydrogen, C] _- to Cio-alkyl, 5- to 7-membered cycloalkyl, which in turn can carry a Ci- to Cio-aryl as a substituent, C 6 - to C 5 -aryl or arylalkyl , where appropriate also two adjacent radicals together can stand for cyclic groups having 4 to 15 carbon atoms, Si (R 6 ), a group with Lewis base functionality or together with a radical X ⁇ to X 4 a bridge member to Metal atom M,
  • R 5 Ci to Cio-alkyl, C 6 to C 15 aryl or C 3 to Cio-cycloalkyl,
  • X 1 to X 4 fluorine, chlorine, bromine, iodine, hydrogen, C] _- to Cio-alkyl, C ⁇ - to Ci 5 ⁇ aryl, alkylaryl with 1 to 10 C-atoms in the alkyl radical and 6 to 20 C- Aryl atoms, -OR 12 , -NR 1 R 13 or
  • Rl2 and R 13 Ci- C ⁇ 0 alkyl, C 6 - to C 15 -aryl, alkylaryl, arylene lalkyl, fluoroalkyl or fluoroaryl each having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical,
  • R 7 to R 11 are hydrogen, C ⁇ to Cio-alkyl, 5 to 7-membered
  • Cycloalkyl which in turn can carry a C 1 -C 8 -alkyl as a substituent, C 6 ⁇ to C ⁇ 5 aryl or arylalkyl, where optionally two adjacent radicals together can also represent cyclic groups having 4 to 15 C atoms, Si (R 14 ) 3 , a group with Lewis base functionality or, together with a radical R 1 to R 5, a bridge member between the cyclopentadienyl systems,
  • Rl 4 Ci to C 10 alkyl, C 6 to C 5 aryl or C 3 to
  • Preferred metals M are titanium and zirconium, in particular zirconium.
  • R 1 to R 5 are methyl, ethyl, propyl, n-butyl, isobutyl and tert-butyl.
  • the cyclopentadienyl nucleus can be substituted one or more times, preferably once or twice, with such alkyl groups.
  • cyclopentadienyl systems are particularly suitable in which two adjacent radicals R 1 to R 5 are linked to form cyclic groups which in turn can carry substituents. Examples include substituted and unsubstituted indenyl, tetrahydroindenyl, benzindenyl and fluorenyl residues.
  • a substituent with a Lewis base group can additionally be present.
  • one of the ligands X 1 to X 4 is also a cyclopentadienyl system, so that a biscyclopentadienyl complex is therefore present.
  • one of the radicals X 1 to X 4 can also represent a bridge member which is connected to the cyclopentadienyl nucleus depicted in formula I, so that a monocyclopentadienyl complex is present.
  • the further radicals X 1 to X 4 are preferably halogen, in particular chlorine, or C 1 -C 4 -alkyl, chlorine being particularly advantageous as a ligand, in particular for precursors of the catalytically active complex.
  • radicals R 7 to R 11 the same radicals are preferred as were mentioned for the radicals R 1 to R 5 .
  • Bridged metallocene complexes are understood to mean those which either have a bridge between a cyclopentadienyl radical and the central metal atom, or those in which the bridge member connects two cyclopentadienyl radicals to one another.
  • a particularly advantageous embodiment of the process according to the invention is characterized in that the metallocene complex of the formula I has a bridge member between two cyclopentadienyl systems.
  • R 15 and R 16 are a C 1 -C 2 -hydrocarbyl radical with at least one oxygen, sulfur, nitrogen or phos ⁇ i- ' phosphorus-containing substituent means.
  • R 15 and R 16 are chemically very different C 1 -C 8 -hydrocarbyl groups.
  • Examples include alkoxyphenyl radicals which are connected to the silicon atom via an alkylene group.
  • Alkylamino or alkoxy groups which are bonded to the silicon via alkylene radicals having a length of 1 to 10 carbon atoms are also suitable.
  • residues in which the Lewis base functionality is based in a thioether or ester group examples include C 1 -C 4 -alkyl esters of carboxylic acid groups, the carboxylic acid in turn being able to be bonded to the silicon atom via an alkylene radical.
  • cyclic ethers such as tetrahydrofuranyl groups, which are likewise bonded to the silicon atom via a suitable alkylene radical, are also suitable.
  • silyl bridges of the general formula II analog bridge members with germanium atoms or C 1 -C 3 -alkylene groups, which can be substituted in an analogous manner to the silicon atom, are also suitable.
  • a further preferred embodiment of the process is characterized in that at least one of the radicals R 1 to R 5 or R 7 to R 11 denotes a radical of the general formula lilac or Illb
  • R 17 and R 18 are hydrogen, C 1 to C 10 alkyl, C 5 to C 5 aryl or C 3 to C 10 cycloalkyl,
  • R 19 and R 20 are Ci to C ⁇ 0 alkyl, C 6 - to C ⁇ 5 aryl or C 3 - to Cio-cycloalkyl,
  • n is an integer in the range from 0 to 10
  • the radicals R 17 and R 18 are preferably hydrogen or lower alkyl such as methyl or ethyl, the radicals R 19 and R 20 are preferably short alkyl groups such as methyl, ethyl, propyl or butyl.
  • n is preferably a number between 2 and 6, in particular 2 or 4.
  • y is preferably nitrogen, z is preferably oxygen.
  • Metallocene complexes in which one of the cyclopentadienyl systems is a substituted or unsubstituted fluorenyl system have proven to be particularly advantageous for use in the process according to the invention.
  • organometallic compounds can also be used in the process according to the invention.
  • a further embodiment of the process according to the invention is therefore characterized in that a compound of the general formula IV is used as the organometallic compound
  • R 21 to R 32 are hydrogen, Ci- to Cio-alkyl, 5- to 7-membered cycloalkyl, which in turn is a C ⁇ ⁇ to Cio-alkyl
  • C ⁇ - to Cis-aryl or arylalkyl can also represent cyclic groups having 4 to 15 C atoms, Si (R 6 ) 3 or a group with Lewis Base functionality, at least one radical R 21 to R 32 must be such a group with Lewis base functionality, R 33 and R 34 fluorine, chlorine, bromine, iodine, hydrogen, C ⁇ ⁇ bis
  • M 'a metal from the Villa group of the Periodic Table.
  • radicals R 21 to R 32 are in particular lower alkyl groups such as methyl, ethyl, propyl or butyl, the aromatic ring systems preferably being substituted one to three times with such alkyl groups. For the structure of the group with Lewis base functionality, this already applies to the corresponding metallocene complexes. At least one of the radicals R 21 to R 32 preferably denotes a radical of the general formula lilac or Illb.
  • an organometallic compound as described above, for the production of polyolefins with a molecular weight distribution iy ⁇ , / M n , measured by gel permeation chromatography, of ⁇ 5.0, preferably ⁇ 4.
  • the catalyst complexes can be prepared by customary methods known to those skilled in the art. Information on the production of metallocene complexes can be obtained, for example, from WO 97/27227.
  • the above-mentioned organometallic complexes In order to develop catalytic polymerization activity, the above-mentioned organometallic complexes generally have to be activated by a cocatalyst.
  • the methods for activating the catalyst complexes are generally known and do not constitute a special feature of this invention.
  • the metallocene complexes can be activated in a known manner with alumoxanes, in particular with methylalumoxane, or with ionizing compounds which are capable of complexing a metallocenium cation in a non-coordinating manner.
  • Solvent toluene and part of the MAO solution filled (see respective test instructions).
  • the total volume during the polymerization was 200 ml.
  • the contents were brought to the desired temperature and 5 bar of propylene were injected;
  • the propylene pressure was kept constant over the entire polymerization period.
  • the preactivated catalyst solution was introduced into the autoclave using a pressure burette.
  • the polymerization was stopped by adding 20 ml of isopropanol.
  • the polymerization of propylene with (1) / MA0 resulted in a propylene polymer that is soluble in toluene.
  • the polymer-containing solution was therefore concentrated after the polymerization process in a solution of 200 ml of methanol, 200 ml of water and 50 ml. HCl solution added and stirred for 18 h. The organic phase was then separated off and concentrated to about 5 ml. Acetone (approx. 20 ml) was then added, the polypropylene being obtained as a colorless, stretchable and elastic solid.

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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

L'invention concerne un procédé de production de polyoléfines sous des pressions de 1 à 4 000 bars et à des températures de 20 à 350 DEG C, en présence d'un système catalytique contenant un composé métallorganique du groupe des métallocènes ou des complexes catalytiquement actifs fer, cobalt, nickel ou palladium. Ce composé métallorganique présente une fonctionnalité de base de Lewis agencée de sorte qu'elle peut former de façon intramoléculaire une liaison de coordination avec l'atome métallique central du composé métallorganique. La température de réaction est réglée de manière que la polyoléfine obtenue présente une répartition bimodale du poids moléculaire MW/MN, mesurée par chromatographie de perméation sur gel, inférieure à 5.
PCT/EP2001/008235 2000-07-18 2001-07-17 Procede de production de polyolefines a repartition bimodale etroite de poids moleculaire WO2002006356A1 (fr)

Applications Claiming Priority (2)

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DE10035308.8 2000-07-18
DE2000135308 DE10035308A1 (de) 2000-07-18 2000-07-18 Verfahren zur Herstellung von Plyolefinen mit enger, birnodaler Molekurargewichtsverteilung

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1026179A1 (fr) * 1999-02-01 2000-08-09 Elenac GmbH Procédé de préparation de polyoléfines présentant une large distribution de poids moléculaire

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1026179A1 (fr) * 1999-02-01 2000-08-09 Elenac GmbH Procédé de préparation de polyoléfines présentant une large distribution de poids moléculaire

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