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WO1998046650A1 - Preparations catalysantes pour la fabrication de (co) polymeres olefiniques - Google Patents

Preparations catalysantes pour la fabrication de (co) polymeres olefiniques Download PDF

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Publication number
WO1998046650A1
WO1998046650A1 PCT/EP1998/001787 EP9801787W WO9846650A1 WO 1998046650 A1 WO1998046650 A1 WO 1998046650A1 EP 9801787 W EP9801787 W EP 9801787W WO 9846650 A1 WO9846650 A1 WO 9846650A1
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Prior art keywords
alkyl
aryl
independently
another
cis
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PCT/EP1998/001787
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German (de)
English (en)
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Michael GEPRÄGS
Walter Heitz
Uwe Peucker
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Basf Aktiengesellschaft
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Priority to EP98917089A priority Critical patent/EP0973810A1/fr
Priority to JP54341098A priority patent/JP2001518968A/ja
Priority to AU70420/98A priority patent/AU7042098A/en
Publication of WO1998046650A1 publication Critical patent/WO1998046650A1/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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—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
    • 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
    • C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
    • C08F4/63912—Component covered by group C08F4/62 containing a transition metal-carbon bond in combination with an organoaluminium compound

Definitions

  • the present invention relates to a catalyst preparation suitable for the (co) polymerisation of olefins, obtainable by mixing a metal complex of the general formula (A)
  • M independently of one another chromium, molybdenum or tungsten
  • R 1 to R 5 independently of one another are hydrogen, Ci- to Cio-alkyl, unsubstituted or substituted by Ci- to Cio-alkyl C- 3 - to C 7 -cycloalkyl, C 6 - to cis-aryl, substituted C 6 - to Ci ⁇ Aryl, where 2 adjacent radicals can together represent 4 to 18 carbon atoms having saturated or unsaturated cyclic groups, or Si (R 6 ) 3 with
  • R6 independently of one another Ci - to Cio-alkyl, C 3 - to Cio - cycloalkyl or C 6 - Cis-aryl,
  • Ci to C 0 alkyl independently of one another Ci to C 0 alkyl, C 3 to Cio-cycloalkyl, C 6 to Cis aryl or aralkyl having 1 to 10 C atoms in the alkyl radical and 6 to 18 C atoms in the aryl radical, and a compound (B) forming metallocenium ions in an inert liquid reaction medium.
  • the present invention further relates to the use of the catalyst preparation mentioned for the (co) polymerization of olefins and to a process for the preparation of olefin (co) polymers from cycloolefinic and / or ⁇ -olefinic monomer units.
  • Heterogeneous catalyst systems based on chromium as transition metal which are suitable for the polymerization of olefins have been known for some time (see also A. Clark, Catal. Rev. 1969, 3, 145 and FJ Karol, GL Brown, JM Davison, J. Polym. , Polym. Chem. Ed. 1973, 11, 413).
  • Binuclear chromium complexes such as [Cp * Cr (CH 3 ) ( ⁇ -Cl)] 2 or
  • 1,2-linked norbornene is characterized by high temperature and chemical resistance.
  • this is eg by means of palladium catalysis according to Risse et al. (J. Mol. Catal. 1992, 76, 219) or Sen et al. (J. Organomet. Chem. 1988, 358, 567) available homopolynorbornene is usually amorphous and has a very high glass transition temperature (T g value) at which decomposition already occurs, which precludes practical further processing from the outset.
  • T g value glass transition temperature
  • the present invention was therefore based on the object of providing catalyst systems based on metals from group VIB of the periodic table of the elements which are suitable for the homo- and copolymerization of cycloolefinic and / or ⁇ -olefinic monomer units.
  • the invention was also based on the object of finding a process for the preparation of (co) polymers from cycloolefinic and / or ⁇ -olefinic monomer units.
  • Z independently of one another chlorine, bromine, iodine, hydrogen or C 1 -C 6 -alkyl
  • R 1 to R 5 independently of one another hydrogen, Ci to C 6 alkyl, unsubstituted or substituted by Ci to C 6 alkyl substituted C 5 to C cycloalkyl, C 6 to C 5 aryl, substituted C 6 to Cis-aryl, where 2 adjacent radicals together can represent saturated or unsaturated cyclic groups having 4 to 15 carbon atoms, or Si (R 6 ) 3 with
  • R 6 independently of one another are C 1 to C 6 alkyl, C 3 to C 6 cycloalkyl or C 6 to Cio aryl, and
  • a metallocenium ion-forming compound (B) which, for example, is an open-chain and / or cyclic alumoxane compound of the general formula (BI) or (B-II)
  • R 7 independently of one another denotes a C 1 -C 4 -alkyl group
  • n an integer from 5 to 30,
  • Suitable metals M in complexes (A) are the metals from group VIB of the Periodic Table of the Elements, that is, in addition to molybdenum and tungsten, especially chromium. Those binuclear complexes (A) which exclusively have chromium as metal M are preferred. The metals mentioned are generally present in the metal complexes (A) with a triple positive charge.
  • the bridging igand Z of the binuclear complex (A) is, in particular, independently of one another, in particular fluorine, chlorine, bromine, iodine, hydrogen or C 1 -C 20 -alkyl, preferably C 1 -C 6 -alkyl, such as methyl, ethyl, n-propyl, n-butyl or n-hexyl, in question. Chlorine, bromine, iodine and C 1 -C 6 -alkyl, such as methyl or n-butyl, are particularly suitable, chlorine, iodine or bromine being preferably used.
  • Z is usually present in (A) as a ⁇ -ligand.
  • the two bridge ligands Z can be the same or different, but in general these ligands are identical.
  • the negatively charged 5-membered carbocycles which can be mono- or polysubstituted, for example linear, with halogen, such as fluorine, chlorine or bromine, are suitable as the monoanionic cyclic ligand or branched Ci- to Cio-alkyl, preferably Ci to C6 alkyl such as methyl, ethyl, n-propyl, i-propyl, n-butyl or t-butyl, C 3 - to C cycloalkyl, preferably C 5 - to C 7 -cycloalkyl, such as cyclopropyl or cyclohexyl, or C 6 - to cis-aryl, preferably C 6 - to cis-aryl, such as phenyl or naphthyl.
  • Ci to Cio-alkyl preferably Ci to C6 alkyl such as methyl, ethyl, n-propyl, i-propyl, n-but
  • aryl substituents also fall, for example, with Ci to C6 alkyl such as methyl or 1-propyl, or with halogen, such as fluorine, chlorine or bromine-substituted C 6 - to C-aryl, preferably C 6 to -aryl.
  • halogen such as fluorine, chlorine or bromine-substituted C 6 - to C-aryl, preferably C 6 to -aryl.
  • Two adjacent radicals for example R 1 and R 2 or R 3 and R 4 , can also together form a saturated or unsaturated cyclic group containing 4 to 18, preferably 4 to 15 carbon atoms. This also includes fused-on unsaturated or aromatic rings or ortho-fused aryl units, which gives, for example, indenyl, fluorenyl or benzindenyl systems.
  • radicals R 1 to R 5 are silyl substituents Si (R 6 ) 3 , in which the radicals R 6 , independently of one another, C 1 to C 10 alkyl, preferably C 1 to C 6 alkyl, for example methyl, ethyl or i-Propyl, C 3 - to Cio-cycloalkyl, preferably C 3 - to C 6 -cycloalkyl, for example cyclopropyl or cyclohexyl, or C 6 - to cis-aryl, preferably C 6 - to Cio-aryl, for example phenyl.
  • C 1 to C 10 alkyl preferably C 1 to C 6 alkyl, for example methyl, ethyl or i-Propyl
  • C 3 - to Cio-cycloalkyl preferably C 3 - to C 6 -cycloalkyl, for example cyclopropyl or cyclohexyl
  • metal M complexing ligands are particularly suitable among the aforementioned compounds cyclopentadienyl, penta-Ci to C ⁇ -alkylcyclopentadienyl, indenyl, fluorenyl or benz - indenyl, the last three ligands mentioned one or more times with Ci to C 6 - Alkyl groups can be substituted. Cyclopentadienyl, Penta-Ci- are preferred to C 4 -alkylcyclopenta- dienyl, indenyl, and 1- to 3 -fold Ci- to C-alkylated indenyl. Cyclopentadienyl or pentamethylcyclopentadienyl are particularly preferred. Binuclear complexes (A) are usually used which have two identical complexing cyclic monoanionic ligands. However, these ligands can also differ from one another in their ring system and / or substitution pattern.
  • the formally monovalent ligand Y preferably represents linear or branched C 1 -C 20 -alkyl, in particular C 1 -C 10 -alkyl, for example methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t- Butyl, C 3 - to Cio-cycloalkyl, preferably C 3 - to C 6 -cycloalkyl, such as cyclopropyl or cyclohexyl, C 6 - to cis-aryl, preferably C 6 - to cis-aryl, such as phenyl or naphthyl, or aralkyl 1 to 10, in particular with 1 to 6 carbon atoms in the alkyl radical and 6 to 18, in particular 6 to 15 carbon atoms in the aryl radical, for example benzyl.
  • ligand Y are n-propyl, i-propyl or naphthyl and in particular methyl, ethyl, n-butyl, i-butyl, t-butyl, phenyl or benzyl.
  • the radicals Y can be either the same or different, but are preferably present as identical ligands.
  • Particularly preferred metal complexes (A) are bis [ ⁇ -chloro (methyl) penta ethylcyclopentadienyl chromium (III)], bis [ ⁇ -bromo (methyl) pentamethylcyclopentadienyl chromium (III)], bis [ ⁇ -chlorocyclopentadienyl (methyl) chromium (III)], Bis t ⁇ -chloro (ethyl) pentamethylcyclopentadienylchrom (III)], bis t ⁇ -chloro (phenyl) pentamethylcyclopentadienylchrom (III)], bis [ ⁇ -chloro (benzyl) pentamethylcyclopentadienylchrom (III)], bis [ ⁇ -chloropentamethylcyclopentilienyl (trim) chromium (III)] and bis [ ⁇ -chlorocyclopentadienyl (trimethylsilylmethyl) chromium (III)
  • Very particularly preferred metal catalysts A) are bis [ ⁇ -chloro (methyl) pentamethylcyclopentadienyl chromium (III)], bis [ ⁇ -chloro (ethyl) pentamethylcyclopentadienyl chromium (III)], bis [ ⁇ -chloro (phenyl) pentamethylcyclopentadienyl chromium (III)] and bis [ ⁇ -chloro (benzyl) pentamethylcyclopentadienyl chromium (III)].
  • the catalyst preparation according to the invention can contain only a defined metal complex of the formula (A) and can also comprise any mixture of compounds covered by the general formula (A).
  • the cyclopentadienyl ligand is generally introduced by treating complex salts, such as tris (tetrahydrofuran) chromium (III) chloride, with organometallic compounds, such as pentamethylcyclopentadienyllithium.
  • complex salts such as tris (tetrahydrofuran) chromium (III) chloride
  • organometallic compounds such as pentamethylcyclopentadienyllithium.
  • the complex obtained is then alkylated with Grignard organic compounds, such as benzyl magnesium chloride or lithium organic compounds, such as methyl lithium, to form a binuclear complex.
  • Grignard organic compounds such as benzyl magnesium chloride or lithium organic compounds, such as methyl lithium
  • the catalyst preparation according to the invention contains a compound (B) which forms metallocenium ions.
  • a compound (B) which forms metallocenium ions are strong, neutral Lewis acids and ionic compounds with Lewis acid cations.
  • G represents an element of main group I or II of the Periodic Table of the Elements, such as lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, strontium or barium, in particular lithium or sodium,
  • Main group of the periodic table of the elements means, in particular boron, aluminum or galium, preferably boron,
  • Ci to Ci alkyl independently of one another for hydrogen, linear or branched Ci to Co alkyl, preferably Ci to Ci alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t -Butyl or n-hexyl, mono- or polysubstituted Ci to C 2 o alkyl, preferably Ci to Cio alkyl, for example with halogen atoms such as fluorine, chlorine, bromine or iodine, C 6 to Cis aryl, preferably C 6 - to Cis-aryl, for example phenyl, which can also be substituted one or more times, for example with halogen atoms such as fluorine, chlorine, bromine or iodine, for example pentafluorophenyl, aralkyl with 1 to 10 C atoms, preferably 1 to 6 carbon atoms in the alkyl radical and 6 to
  • C o-alkoxy such as methoxy, ethoxy or i-propoxy, or C 6 - to cis-aryloxy, preferably C 6 - to cis-aryloxy, for example phenoxy, and
  • the anion in a compound of the general formula (B-III) is preferably a non-coordinating counterion.
  • Main group of the periodic table of the elements means, in particular boron, aluminum or galium, preferably boron,
  • X 5 to X 7 independently of one another for hydrogen, linear or branched Ci to Co alkyl, preferably Ci to C 0 alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl or n-hexyl, mono- or polysubstituted ci- to co-alkyl, preferably ci- to cio-alkyl, for example with halogen atoms such as fluorine, chlorine,
  • Bromine or iodine C 6 - to cis-aryl, preferably C 6 - to cis-aryl, for example phenyl, which can also be substituted one or more times, for example with halogen atoms such as fluorine, chlorine, bromine or iodine, for example pentafluorophenyl, aralkyl with 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms in the alkyl radical and 6 to 18 carbon atoms, preferably 6 to 15 carbon atoms in the aryl radical, for example benzyl or fluorine, chlorine, bromine or iodine.
  • halogen atoms such as fluorine, chlorine, bromine or iodine, for example pentafluorophenyl
  • aralkyl with 1 to 10 carbon atoms preferably 1 to 6 carbon atoms in the alkyl radical and 6 to 18 carbon atoms, preferably 6 to 15 carbon atoms in the ary
  • radicals X 5 to X 7 are those which have halogen substituents. Pentafluorophenyl should preferably be mentioned. Particularly preferred are compounds of the general formula (B-IV) in which X 5 , X 6 and X 7 are the same, preferably tris (pentafluorophenyl) bora.
  • those compounds which have an Al — C bond are suitable as alumoxane compounds.
  • R 7 independently of one another denotes a C 1 -C 4 -alkyl group, preferably a methyl or ethyl group, and m represents an integer from 5 to 30, preferably 10 to 25.
  • oligomeric alumoxane compounds are usually prepared by reacting a solution of trialkylaluminum with water and include in EP-A 0 284 708 and US-A 4,794,096.
  • the oligomeric alumoxane compounds obtained are mixtures of both linear and cyclic chain molecules of different lengths, so that m is to be regarded as the mean.
  • the alumoxane compounds can also be present in a mixture with other metal alkyls, preferably with aluminum alkyls, such as triisobutyl aluminum or triethyl aluminum.
  • Prefers methylalumoxane is used, the production of which is described in detail, for example, in EP-A 284 708.
  • metallocenium ion-forming compounds (B) aryloxyalumoxanes, as described in US Pat. No. 5,391,793, amidoaluminoxanes, as described in US Pat , as described in EP-A 0 621 279, or mixtures thereof are used.
  • alumoxanes described are used either as such or in the form of a solution or suspension, for example in aliphatic or aromatic hydrocarbons, such as toluene or xylene, or mixtures thereof.
  • Z in general formula (A) is halogen, i.e. Fluorine, chlorine, bromine or iodine and especially chlorine, bromine or iodine means, in a particularly preferred embodiment of the catalyst preparation according to the invention, the listed alumoxane compounds (B-I) and / or (B-II) are used as component (B). Alternatively or in a mixture with the alumoxanes, ionic compounds with Lewis acid cations of the general formula (B-IV) can also be used. If, on the other hand, the ligand Z in (A) represents hydrogen or a Ci to Co alkyl radical, the above-mentioned strong, neutral Lewis acids (B-III) preferred.
  • Components (A) and (B) of the catalyst preparation according to the invention can be mixed together in an inert liquid reaction medium.
  • a reaction medium is considered inert if it is essentially free of water, compounds containing hydroxyl groups and oxygen.
  • Suitable inert liquid reaction media are those in which components (A) and (B) are partially or completely soluble.
  • Preferred are liquids which are at least slightly polar, for example aromatic hydrocarbons with 6 to 20 carbon atoms, such as benzene, toluene or xylene. Toluene and xylene and mixtures thereof are particularly preferred.
  • aliphatic hydrocarbons or halogenated aliphatic hydrocarbons can also be used, such as pentane, hexane, octane, perfluoromethylcyclohexane, perfluorohexane, perfluorooctane, perfluorodecalin or mixtures thereof. It is also possible to use mixtures consisting of aromatic and / or aliphatic hydrocarbons.
  • the preferred inert reaction medium is toluene.
  • Components (A) and (B) can be added to the reaction medium at the same time or in succession, the sequence of addition generally not being important.
  • the metal complex (A) is usually initially introduced and then component (B) is added with stirring.
  • components (A) and (B) are allowed to act in the reaction medium for a period in the range from 0.1 sec to 60 min, preferably from 0.1 sec to 30 min, before the catalyst preparation with the starting mixture to be polymerized Is brought into contact.
  • the process steps described are advantageously carried out under a protective gas atmosphere in order to avoid contamination with moisture or oxygen.
  • the catalyst preparation according to the invention is generally produced at temperatures in the range from -50 to 50 ° C., preferably in the range from -10 to 40 ° C.
  • Catalyst preparations in which the molar ratio of the amount of alumoxane compound (B) to the amount of component (A) used are in the range from 10: 1 to 10 6 : 1 and in particular in the range from 10: 1 to 10: 1 are particularly suitable .
  • the metallocenium ion-forming compound (B) is based on a component containing boron, it has proven particularly suitable if the molar ratio of boron from the metallocenium ion-forming compound (B) to transition metal from the metal complex (A) is in the range from 0.1 : 1 to 10: 1, in particular from 1: 1 to 5: 1.
  • the catalyst preparations according to the invention can be used for the production of olefin (co) polymers.
  • cycloolefinic and / or ⁇ -olefinic monomer units are produced at a temperature in the range from -50 to 150 ° C., preferably in the range from -15 to 60 ° C. and particularly preferably in the range polymerized from -5 to 40 ° C in the presence of the inventive catalyst systems described above.
  • all monomers of these classes of compounds come as cyclo- or ⁇ -olefinic monomer units, e.g. bridged or non-bridged cycloolefins and mono- or diolefins.
  • strained ring systems are advantageously used which have one or more olefinic bonds in the cycle.
  • Tensioned ring systems are to be understood in particular as those at which the bond geometry of the double bond units shows deviations from corresponding free, untensioned systems. The deviations can either be that the bond angles in the sp 2 plane do not allow an optimal overlap of the orbitals involved, or that a bond from the sp 2 plane is forced.
  • cyclopropene, cyclopentene, dicyclopentadiene, bicyclo [2.2.1] hept-2-ene or bicyclo [2.2.2] oct-2-ene come as cycloolefinic monomer units, in each case also in substituted form, for example with alkyl, aryl or functional groups based on elements from groups IVA, VA, VIA or VIIA of the Periodic Table of the Elements.
  • norbornene derivatives are, for example, compounds in which the carbon valences that are not at the Ring formation are involved, by alkyl radicals, such as methyl, ethyl, i-, n-propyl, i-, n-, s-, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl or their structure analogues
  • Cycloalkyl radicals such as cyclopropyl, cyclopentyl, cyclohexyl, are substituted by aryl radicals, such as phenyl or naphthyl, or by alkylaryl radicals, such as benzyl
  • Periodic table of the elements such as silyl, carboxy
  • Both single and multiple substituted norbornene derivatives can be used.
  • the ⁇ -olefinic compounds used in the process according to the invention are, for example, ethylene or C 3 -C 1 -alkenes, in particular C 3 -C 1 -alk-1-enes.
  • Ethylene, propylene, but-1-ene, isobutene, 4-methyl-pent-1-ene, hex-1-ene, oct-1-ene and mixtures thereof are preferred, and ethylene is particularly preferred.
  • mixtures of cycloolefinic or ⁇ -olefinic monomers or mixtures of cycloolefinic and ⁇ -olefinic monomers can also be used.
  • the cyclo- and / or ⁇ -olefinic monomer units are polymerized in the presence of a catalyst system which comprises a metal complex (A) in which the substituents have the following meaning:
  • Z independently of one another chlorine, bromine, iodine, hydrogen or C - to C 6 -alkyl
  • R 1 to R 5 independently of one another are hydrogen, Ci to C 6 alkyl, unsubstituted or substituted by C 1 to C 10 alkyl, C 3 to C 7 cycloalkyl, C 6 to Cis aryl, substituted C ⁇ to Cis Aryl, where 2 adjacent radicals together can represent saturated or unsaturated cyclic groups having 4 to 15 carbon atoms, or Si (R 6 ) 3 with
  • R 6 independently of one another are C 1 to C 6 alkyl, C 3 to C 6 cycloalkyl or C 6 to Cio aryl, and
  • Ci to Cio alkyl C 3 to C 6 cycloalkyl, C 6 to Cis aryl or aralkyl with 1 to 10 C atoms in the alkyl radical and 6 to 15 C atoms in the aryl radical,
  • R 7 independently of one another denotes a C 1 -C 4 -alkyl group
  • n an integer from 5 to 30,
  • the process according to the invention comprises both bulk polymerization, i.e. in a monomer which is already in liquid form at atmospheric pressure or which liquefies only under the selected reaction pressures, such as ethylene, propylene, norbornene, tetracyclododecene, cyclopentene or cyclooctene, and also the polymerization in solution.
  • aliphatic or aromatic hydrocarbons having 4 to 20 carbon atoms or mixtures thereof, for example butane, pentane, hexane, cyclohexane, toluene, xylene or ethylbenzene, can be used as suitable solvents.
  • the polymerization is preferably carried out at temperatures in the range from -50 to 150 ° C., in particular in the range from -5 to 40 ° C., and at a pressure from 0.1 to 100 bar, particularly preferably from 0.1 to 50 bar and in particular from 0.5 to 20 bar.
  • the usual polymerization times are in the range from 0.5 to 100 hours, but satisfactory polymerization results can also be achieved with reaction times in the range from 0.5 to 10 hours.
  • the starting monomer concentration is usually set to a value in the range from 0.1 to 8.5 mol / 1.
  • the components (A) and (B) of the catalyst system can be added to the reaction mixture in different ways.
  • the metal complex (A) is usually initially introduced, then the monomer (s) are added and the compound (B) which forms metallocenium ions is then added either as a solid or in dissolved or suspended form.
  • the monomer can be introduced and then components (A) and (B) of the catalyst system can be added, regardless of the order of addition.
  • the catalyst preparation according to the invention described above ie the mixture of components (A) and (B) prepared beforehand in an inert reaction medium, is used.
  • the catalyst preparation according to the invention can either be added to the starting monomer or, if appropriate, placed in a polymerization medium.
  • the polymerization can be terminated, for example, by adding protic compounds, for example alcohols, such as methanol, dilute mineral acids, such as hydrochloric acid (HC1), or carboxylic acids, such as acetic acid, or mixtures thereof.
  • protic compounds for example alcohols, such as methanol, dilute mineral acids, such as hydrochloric acid (HC1), or carboxylic acids, such as acetic acid, or mixtures thereof.
  • the volume ratio of termination reagent to reaction mixture is generally in the range from 1: 1 to 1:10.
  • the polymer product is isolated in a customary manner, for example by precipitation in an excess alcohol such as methanol.
  • both homopolymers and copolymers can be obtained from the olefinic monomer units described above.
  • the polymers mentioned are also summarized here under the name olefin (co) polymers.
  • the term (co) polymerization also includes the homo- and copolymerization of the olefinic monomer units listed.
  • homopolymers which are obtainable from cycloolefinic monomers are polymers of norbornene, cyclopentadiene and cyclopentene.
  • olefin (co) polymers can be obtained in high molecular weight.
  • Olefin (co) polymers with average molecular weights M n up to 2 million g / mol can be produced.
  • the molecular weight distributions M w / M n obtained generally range from 1.03 to 3.5 and preferably assume values in the range from 1.05 to 2.0.
  • the molecular weights M n and the molecular weight distributions M w / M n can be determined by gel permeation chromatography (GPC), based on a polystyrene standard.
  • copolymers of cycloolefinic and ⁇ -olefinic monomer units accessible via the process according to the invention can consist of up to 99% by weight, based on the total copolymer, of a copolymerized component which is based on a cycloolefinic monomer unit. Accordingly, copolymers of at least one cycloolefinic component, such as norbornene, and at least one ⁇ -olefinic component, such as ethylene, which contain 5 to 95% by weight and in particular 20 to 70% by weight of a component based on a cycloolefinic monomer unit, are accessible .
  • olefin (co) polymers with cycloolefinic monomer units have a T g value which is considerably reduced in comparison with homopolymers made from these cycloolefins.
  • the ⁇ g value of a norbornene / ethene copolymer obtained by the process according to the invention with a molar fraction of 60% of ethene is 40.1 ° C. (determined by means of DSC) (the T g value of polynorbornene is above 300 ° C).
  • copolymers with a proportion of cycloolefinic monomer units whose glass transition temperature value can be set over a wide range are accessible via the processes according to the invention.
  • copolymers are available with Tg values in the range from 100 ° C. to -60 ° C. and in particular from 60 ° C. to -40 ° C.
  • These copolymers containing cycloolefin units are usually crystalline only from a proportion of 80 mol% of ⁇ -olefin component, for example ethylene (determined on the basis of X-ray powder spectra with the aid of a wide-angle goniometer (Cu-K f radiation, 1.54
  • cycloolefinic monomer units are linked by a 1, 2 linkage, i.e. while maintaining the ring system, incorporated into homo- or copolymers.
  • Catalyst system a high comonomer incorporation of cyclolefinic monomers, as a result of which polymer products which are readily soluble in organic solvents and have an adjustable glass transition temperature are obtained. Furthermore, good results can be achieved even with a low ratio of component (B) to metal complex (A) forming metallocenium ions and with a relatively low polymerization temperature. Another advantage is that the metal complex (A) is easily accessible preparatively. The process according to the invention thus permits a process — technically simple preparation of olefin (co) polymers.
  • Cycloolefin monomers can be polymerized with ring retention is also avoided that the polymers obtained have (additional) double bond units, which ultimately has an advantageous effect on the mechanical and rheological properties of the polymer molding compositions.
  • the DSC data were determined using the Mettler DSC 30 at a heating rate of 10 K / min.
  • the metal complex (1) (25.3 mg; 0.05 mmol) was dissolved in 10 ml of toluene and 2 g (21.2 mmol) of norbornene was added.
  • the polymerization of norbornene was carried out by dissolving the metal complex (1) in 10 ml of toluene and adding the appropriate amount of norbornene according to Table 1. To this mixture was added methylalumoxane solution (1.53 M in toluene), so that the molar ratio to that used
  • Amount of metal complex was 100: 1.
  • the polymerization temperature was 25 ° C. After 2 hours, the polymerization was stopped by adding methanol. The polymer was filtered off, washed with methanol and dried in vacuo at 60 ° C. Further information can be found in Table 1: Table 1

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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne une préparation catalysante s'obtenant par mélange d'un complexe (A), dans laquelle les substituants ont la signification suivante: M désigne chrome, molybdène ou tungstène, Z désigne fluor, chlore, brome, iode, hydrogène ou alkyle C1-C20, R1 à R5 sont, indépendamment les uns des autres, hydrogène, alkyle C¿1?-C10, cycloalkyle C3-C7 non substitué ou bien substitué par alkyle C1-C10, aryle C6-C18, aryle C6-C18 substitué, 2 restes voisins pouvant également représenter conjointement des groupes cycliques saturés ou insaturés présentant 4 à 18 atomes de C, ou bien Si(R?6)¿3 où R6 désigne indépendamment alkyle C¿1?-C10, cycloalkyle C3-C10 ou aryle C6-C18, Y désigne indépendamment alkyle C1-C20, cycloalkyle C3-C10, aryle C6-C18 ou bien aralkyle avec 1 à 10 atomes de C dans le reste alkyle et 6 à 18 atomes de C dans le reste aryle, et d'un composé formant des ions de métallocène (B) dans un milieu de réaction liquide inerte.
PCT/EP1998/001787 1997-04-11 1998-03-26 Preparations catalysantes pour la fabrication de (co) polymeres olefiniques WO1998046650A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP98917089A EP0973810A1 (fr) 1997-04-11 1998-03-26 Preparations catalysantes pour la fabrication de (co) polymeres olefiniques
JP54341098A JP2001518968A (ja) 1997-04-11 1998-03-26 オレフィン（共）重合体を製造するための触媒調剤
AU70420/98A AU7042098A (en) 1997-04-11 1998-03-26 Catalyst preparations for producing olefin (co)polymers

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19715155.8 1997-04-11
DE1997115155 DE19715155A1 (de) 1997-04-11 1997-04-11 Katalysatorzubereitungen für die Herstellung von Olefin(co)polymeren

Publications (1)

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WO1998046650A1 true WO1998046650A1 (fr) 1998-10-22

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PCT/EP1998/001787 WO1998046650A1 (fr) 1997-04-11 1998-03-26 Preparations catalysantes pour la fabrication de (co) polymeres olefiniques

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EP (1) EP0973810A1 (fr)
JP (1) JP2001518968A (fr)
AU (1) AU7042098A (fr)
DE (1) DE19715155A1 (fr)
WO (1) WO1998046650A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004046214A2 (fr) 2002-10-15 2004-06-03 Exxonmobil Chemical Patents Inc. Systeme catalyseur multiple pour la polymerisation d'olefines et polymeres ainsi produits
WO2005113622A1 (fr) 2004-04-15 2005-12-01 Exxonmobil Chemical Patents Inc. Systeme a catalyseurs et reacteurs multiples pour la polymerisation d'olefines et polymeres produits au moyen de ce systeme
EP1914252A1 (fr) 1999-12-16 2008-04-23 Univation Technologies, LLC Procédé de polymérisation
US8318872B2 (en) 2007-12-18 2012-11-27 Univation Technologies, Llc Method for controlling bimodal catalyst activity during polymerization
WO2016086039A1 (fr) 2014-11-25 2016-06-02 Univation Technologies, Llc Procédés de commande de l'indice de fluidité de la polyoléfine
WO2022232760A1 (fr) 2021-04-30 2022-11-03 Exxonmobil Chemical Patents Inc. Procédés pour la transition entre différents catalyseurs de polymérisation dans un réacteur de polymérisation

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0509294A2 (fr) * 1991-03-29 1992-10-21 CHEVRON U.S.A. Inc. Catalyseur de polymérisation d'alpha oléfin à base de composé de métal de groupe 6B contenant des groupes cyclopentadiényl et procédé de polymerisation d'alpha oléfins
WO1994011407A1 (fr) * 1992-11-06 1994-05-26 Chevron Research And Technology Company, A Division Of Chevron U.S.A. Inc. CATALYSEURS DE POLYMERISATION D'ALPHA-OLEFINES DE METAL DE GROUPE 6b A BASE DE CYCLOPENTADIENYLE DIMERE ET TETRAMERE ET PROCEDE DE POLYMERISATION DES ALPHA-OLEFINES
WO1996027621A1 (fr) * 1995-03-03 1996-09-12 Chevron Chemical Company Catalyseurs de cyclopentadienyle a plusieurs valences de metaux alcalins du groupe 6b servant a la polymerisation d'alpha-olephines et leur utilisation dans des processus de polymerisation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0509294A2 (fr) * 1991-03-29 1992-10-21 CHEVRON U.S.A. Inc. Catalyseur de polymérisation d'alpha oléfin à base de composé de métal de groupe 6B contenant des groupes cyclopentadiényl et procédé de polymerisation d'alpha oléfins
WO1994011407A1 (fr) * 1992-11-06 1994-05-26 Chevron Research And Technology Company, A Division Of Chevron U.S.A. Inc. CATALYSEURS DE POLYMERISATION D'ALPHA-OLEFINES DE METAL DE GROUPE 6b A BASE DE CYCLOPENTADIENYLE DIMERE ET TETRAMERE ET PROCEDE DE POLYMERISATION DES ALPHA-OLEFINES
WO1996027621A1 (fr) * 1995-03-03 1996-09-12 Chevron Chemical Company Catalyseurs de cyclopentadienyle a plusieurs valences de metaux alcalins du groupe 6b servant a la polymerisation d'alpha-olephines et leur utilisation dans des processus de polymerisation

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1914252A1 (fr) 1999-12-16 2008-04-23 Univation Technologies, LLC Procédé de polymérisation
WO2004046214A2 (fr) 2002-10-15 2004-06-03 Exxonmobil Chemical Patents Inc. Systeme catalyseur multiple pour la polymerisation d'olefines et polymeres ainsi produits
WO2005113622A1 (fr) 2004-04-15 2005-12-01 Exxonmobil Chemical Patents Inc. Systeme a catalyseurs et reacteurs multiples pour la polymerisation d'olefines et polymeres produits au moyen de ce systeme
US8318872B2 (en) 2007-12-18 2012-11-27 Univation Technologies, Llc Method for controlling bimodal catalyst activity during polymerization
WO2016086039A1 (fr) 2014-11-25 2016-06-02 Univation Technologies, Llc Procédés de commande de l'indice de fluidité de la polyoléfine
WO2022232760A1 (fr) 2021-04-30 2022-11-03 Exxonmobil Chemical Patents Inc. Procédés pour la transition entre différents catalyseurs de polymérisation dans un réacteur de polymérisation

Also Published As

Publication number Publication date
JP2001518968A (ja) 2001-10-16
DE19715155A1 (de) 1998-10-15
AU7042098A (en) 1998-11-11
EP0973810A1 (fr) 2000-01-26

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