WO1997007141A1 - Catalyst constituents and catalyst system with a high degree of polymerisation activity for the production of polymers - Google Patents

Catalyst constituents and catalyst system with a high degree of polymerisation activity for the production of polymers Download PDF

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Publication number
WO1997007141A1
WO1997007141A1 PCT/EP1996/003563 EP9603563W WO9707141A1 WO 1997007141 A1 WO1997007141 A1 WO 1997007141A1 EP 9603563 W EP9603563 W EP 9603563W WO 9707141 A1 WO9707141 A1 WO 9707141A1
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group
polymerization
catalyst system
catalyst
arylalkyl
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PCT/EP1996/003563
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German (de)
French (fr)
Inventor
Walter Kaminsky
Stephan Lenk
Volker Scholz
Herbert Roesky
Axel Herzog
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Targor Gmbh
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Priority to EP96928453A priority Critical patent/EP0857179A1/en
Publication of WO1997007141A1 publication Critical patent/WO1997007141A1/en

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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
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • 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
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65925—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually non-bridged
    • 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
    • C08F2420/04—Cp or analog not bridged to a non-Cp X ancillary anionic donor
    • 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 catalyst components and catalyst systems with high polymerization activity for the production of polymers, the polymers having a high melting point.
  • the present invention further relates to an economical and environmentally friendly process for producing polymers with a high melting point.
  • Organometallic fluorides containing ⁇ system are obtained by reacting a fluorine-free organometallic halide with a tin fluoride of the general formula R 3 SnF, in which R are the same or different and are C -, - C 10 - alkyl, C 6 -C 14 aryl, C 2 -C 10 alkenyl, C 7 -C 20 arylalkyl or C 7 -C 1 5 alkylaryl.
  • EP-A-210 615 discloses catalysts for the polymerization of styrene and processes for the polymerization of monostyrene to syndiotactic polystyrene.
  • a catalyst component for the polymerization of olefins which comprises at least one compound of the general formula (I):
  • M 1 Ti, Zr or Hf
  • Ra c 5 (R 1 , R 2 , R 3 , R, 4 R 5 ) or C 6 (R 1 , R 2 , R 3 , R 4 , R 5 , R 6 ), where R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are the same or different and a hydrogen atom, a C 1 -C 20 alkyl group, a 0, -0.0 alkoxy group, a C
  • -C ⁇ o-Fiuoralkyl a C 6 -C 20 aryl group, a C 6 -C 10 aryloxy group, a C 2 -C 10 alkenyl group, a C 6 -C 10 fluoroaryl group, a C 7 -C 40 arylalkyl group , a C 7 -C 40 alkylaryl group, or a C 8 -C 40 arylalkenyl group an OH group, an NR 7 2 or SR 8 1 group, where R 7 and R 8 are a C j -C ⁇ alkyl group , a C ⁇ CT Q alkoxy group, a C ⁇ C ⁇ fuoralkyl group, a C 6 -C 20 aryl group, a C 6 -C 10 aryloxy group, a C 2 -C 10 - Alkenyl group, a C 6 -C 10 fluoroaryl group, a C 7 -C 40 arylal
  • the present invention has the advantage that catalyst systems with a high polymerization activity are obtained with these catalyst components.
  • the polymerization activity of the catalysts according to the invention is calculated in the mass of the polymer produced, based on the amount of compound of the 4th group of the periodic table and based on the polymerization time.
  • the particular advantage of the present invention is that with catalyst systems with high polymerization activity, polymers with high melting points are obtained.
  • the increase in the polymerization activity in previously known catalyst systems has hitherto had the disadvantage that the melting points of the polymers obtained always decrease. Due to the high polymerization activity of the catalyst systems, polymerization with smaller amounts of catalyst systems can be carried out with very good results. This makes the polymerization process very economical and environmentally friendly.
  • Catalysts according to the invention which have a cyclopentadienyl ring as ligand and 3 fluorine atoms bonded directly to the metal atom M 1 are preferred. Catalyst systems with these catalyst components show good polymerization activity.
  • Catalysts according to the invention which have a five-fold methylated cyclopentadienyl ring as ligand and 3 fluorine atoms on the metal atom M 1 are particularly preferred. Catalyst systems with these catalyst components show very good polymerization activity.
  • Titanium is particularly preferred as the transition metal atom. Good polymerization activities are predominantly achieved with titanium as the transition metal.
  • a catalyst component is provided, containing at least one bridging R 9 between at least two radicals R a .
  • R 9 is preferred
  • R 10 and R 1 1 are the same or different and is a hydrogen atom, a halogen atom or a C. - C 40 carbon-containing group, such as a Alkyl, a C ⁇ C ⁇ fluoroalkyl, a C ⁇ C ⁇ alkoxy, a C 6 -C 14 aryl, a C 6 -C 10 fluoroaryl, a C 6 -C ⁇ 0 aryloxy- , a C 2 -C 10 alkenyl, a C 7 -C 40 arylalkyl, a C 7 -C 40 alkylaryl, or a C 8 -C 40 arylalkenyl group or R 10 and R 1 1 each with the they form one or more rings connecting atoms and x is an integer from zero to 18, M 2 is silicon, germanium or tin.
  • R 9 can also link two units of the formula (I) to one another.
  • the organometallic halides required as the starting compound are commercially available or can be prepared by processes known from the literature.
  • the tin fluorides required as starting material can be methods known from the literature are produced (Ber. Dtsch. Chem. Ges. (1918), Vol. 51, 1447).
  • a catalyst system comprising at least one catalyst component and at least one organic boron and / or at least one organic aluminum and / or at least one organic tin compound as cocatalyst.
  • the catalyst system can be obtained by contacting at least one catalyst component with at least one organic boron and / or at least one organic aluminum and / or at least one organic tin compound. It arises in particular as a reaction product of at least one catalyst component and at least one organic boron and / or organic aluminum and / or organic tin compounds as well as reaction products of these compounds with condensing agents such as water. Very good polymerization activities are obtained with these catalyst systems.
  • the cocatalyst component which can be contained in the catalyst system according to the invention contains at least one compound of the type of an aluminoxane or a Lewis acid or an ionic compound which is converted into a cationic compound by reaction with a catalyst component.
  • a compound of the general formula II is preferred as the aluminoxane
  • Aluminoxanes can e.g. cyclic as in formula
  • radicals R in the formulas (II), (III), (IV) and (V) can be the same or different and a C, -C 20 hydrocarbon group such as a C, -C 6 alkyl group, a C 6 - C 18 aryl group, benzyl or hydrogen, and p is an integer from 2 to 50, preferably 10 to 35.
  • the organic radicals are preferably the same and are methyl, isobutyl, n-butyl, phenyl or benzyl, and methyl is particularly preferred. If the organic radicals are different, they are preferably methyl and hydrogen, methyl and isobutyl or methyl and n-butyl, hydrogen or isobutyl or n-butyl being present.
  • the Lewis acid used is preferably at least one organoboron or organoaluminum compound which contains C, -C 20 -carbon-containing groups, such as branched or unbranched alkyl or haloalkyl groups. According to the invention, a catalyst system is provided which can additionally contain a support.
  • the carrier component of the catalyst system according to the invention is preferably at least one inorganic oxide, such as SiO 2 , Al 2 O 3 , MgO, ZrO 2 , TiO 2 , B 2 O 3 , CaO, ZnO, ThO 2 , carbonates, such as Na 2 CO 3 , K 2 CO 3 , CaCO 3 , MgCO 3 , sulfates such as Na 2 SO 4 , Al 2 (SO 4 ) 3 , BaSO 4 , nitrates such as KNO 3 , Mg (NO 3 ) 2 , Al (NO 3 ) 3 and oxides , such as Na 2 O, K 2 O, and Li 2 O.
  • inorganic oxide such as SiO 2 , Al 2 O 3 , MgO, ZrO 2 , TiO 2 , B 2 O 3 , CaO, ZnO, ThO 2
  • carbonates such as Na 2 CO 3 , K 2 CO 3 , CaCO 3 , MgCO 3
  • silica and / or alumina and / or polymer supports are provided as supports.
  • polymers and / or copolymers obtainable by polymerization with a catalyst system according to the invention are provided.
  • Polymers and / or copolymers of 1-alkenes and vinyl aromatics, obtainable by polymerization with a catalyst system according to the invention are particularly provided.
  • Syndiotactic polymers obtainable by polymerization with a catalyst system according to the invention are very particularly provided.
  • Syndiotactic polystyrene obtainable by polymerization with a catalyst system according to the invention is most preferred.
  • fluorine-containing transition metal compounds are used as catalyst components, organic boron and / or organic aluminum and / or organic tin compounds and reaction products thereof with condensing agents, such as water, as cocatalyst component and vinyl aromatic monomer in any order.
  • One or more carriers can be used.
  • One or more solvents can be added in any order.
  • the components are entered and the reaction takes place without pressure or under reduced or elevated pressure in the atmosphere of an inert gas, such as, for. B. nitrogen, argon or a mixture of these.
  • the reaction is preferably carried out in the temperature range from 10 to 70.degree.
  • the components of the catalyst system are used in any molar ratio to one another.
  • a ratio of aluminum to titanium of 100 to 1000 is preferred.
  • the use of a catalyst system for the production of a polymer and / or copolymer, in particular for the polymerization and / or copolymerization of 1-alkenes and vinylaromatics, very particularly for the polymerization of styrene, is provided.
  • a 100 ml glass reactor heated to 50 ° C. was stirred with 14.1 ml of toluene, 5 ml of a toluene solution of methylaluminoxane (7.5 '10 "4 mol / 5 ml), 20 ml of styrene and 0.9 ml of a toluene solution in succession with argon counterflow Solution of cyclopentadienyltitanium trifluoride (2.5 '10 "6 mol / 0.9 ml) charged.
  • the addition of the titanium compound was taken as the starting point for the polymerization.
  • about 50 ml of a mixture of hydrochloric acid and ethanol was added. The mixture was stirred for a further 12 hours.
  • the solid product was filtered off and washed neutral with ethanol.
  • the polymer was dried in vacuo at room temperature.
  • Comparative example 1 was carried out in accordance with example 1, CpTiCl 3 being used as catalyst.
  • Example 2 was carried out in accordance with Example 1, Cp * TiF 3 being used as the catalyst. Comparative Example 2
  • Comparative example 2 was carried out in accordance with example 1, Cp * TiCl 3 being used as the catalyst.
  • Table 1 shows the polymerization activities of the catalysts used in Example 1 and Comparative Example 1 and the characteristic data of the polymers obtained in Example 1 and Comparative Example 1.
  • Example 2 The polymerization activities of those in Example 2 and Comparative Example 2 are shown in Table 2 below used catalysts and the characteristic data of the polymers obtained in Example 2 and Comparative Example 2.
  • a 200 ml glass reactor heated to 30 ° C. was stirred in succession with argon counterflow with 49 ml of toluene, 0.58 g (0.01 mol) of methylaluminoxane, 50 ml of styrene and 1 ml of a toluene solution of methylcyclopentadienyltitanium trifluoride (10 -5 mol / ml ) loaded.
  • the addition of the titanium compound was taken as the starting point for the polymerization. After 4 minutes, about 50 ml of a mixture of hydrochloric acid and ethanol was added. The mixture was stirred for a further 12 hours. The solid product was filtered off and washed neutral with ethanol. The polymer was dried in vacuo at room temperature.
  • Comparative example 3 was carried out in the same way as in example 3, methylcyclopentadienyltitanium trichloride being used as the catalyst.
  • Table 3 shows the polymerization activities of the catalysts used in Example 3 and Comparative Example 3 and the characteristic data of the polymers obtained in Example 3 and Comparative Example 3.
  • Example 4 was carried out according to Example 3, using EtMe 4 CpTiF 3 as catalyst. Comparative example 4 was carried out in accordance with example 3, EtMe 4 CpTiCl 3 being used as catalyst.
  • Table 4 below shows the polymerization activities of the catalysts used in Example 4 and Comparative Example 4 and the characteristic data of the polymers obtained in Example 4 and Comparative Example 4.
  • Example 5 was carried out in accordance with Example 3, PrMe 4 CpTiF 3 being used as the catalyst. Comparative example 5 was carried out in the same way as in example 3, using PrMe 4 CpTiCI 3 as catalyst.
  • Table 5 below shows the polymerization activities of the catalysts used in Example 5 and Comparative Example 5 and the characteristic data of the polymers obtained in Example 5 and Comparative Example 5.
  • Example 6 was carried out in accordance with Example 3, BuMe 4 CpTiF 3 being used as catalyst. Comparative example 6 was carried out in accordance with example 3, using BuMe 4 CpTiCI 3 as catalyst.
  • Table 6 below shows the polymerization activities of the catalysts used in Example 6 and Comparative Example 6 and the characteristic data of the polymers obtained in Example 6 and Comparative Example 6.
  • Examples 7, 8 and 9 were carried out in accordance with Example 3, the catalysts used being Cp * 2 TiF, Cp * TiF 2 (OCOC 6 F 5 ) and Cp * TiF 2 (OCOCF 3 ).
  • Table 7 below shows the polymerization activities of the catalysts used in Examples 7, 8 and 9 and the characteristic data of the polymers obtained.
  • Titanium compound in mol and based on the polymerization time in h is titanium compound in mol and based on the polymerization time in h:

Abstract

In the present invention, catalyst systems with a high degree of polymerisation are described which contain at least one catalyst constituent of general formula (I): RnMXm, in which M1 is Ti, Zr or Hf, Ra is C5 (R?1, R2, R3, R4, R5¿) or C¿6? (R?1, R2, R3, R4, R5, R6¿) wherein R?1, R2, R3, R4, R5 and R6¿ are identical or different, and a hydrogen atom, a C¿1?-C20 alkyl group, a C1-C10 alkoxy group, a C1-C10 fluoroalkyl group, a C6-C20 aryl group, a C6-C10 aryloxy group, a C2-C10 alkenyl group, a C6-C10 fluoroaryl group, a C7-C40 arylalkyl group, a C7-C40 alkylaryl group, a C8-C40 arylalkenyl group, a silyl group, a germyl group, or adjacent groups R?1, R2, R3, R4, R5 and R6¿ which form with the connecting atoms thereof a ring system; Rb is one fluorine atom when m = 1, at least one fluorine atom when m > 1 and can be identical or different, and be at least one hydrogen atom, a C¿1?-C20 alkyl group, a C1-C10 alkyoxy group, a C1-C10 fluoroalkyl group, a C6-C20 aryl group, a C6-C10 aryloxy group, a C2-C10 alkenyl group, a C6-C10 fluoroaryl group, a C7-C40 arylalkyl group, a C7-C40 alkylaryl group, or a C8-C40 arylalkenyl group, an OH group, a NR?7¿2 group or SR81 group, wherein R?7 and R8¿ are a C¿1?-C20 alkyl group, a C1-C10 alkoxy group, a C1-C10 fluoroalkyl group, a C6-C20 aryl group, a C6-C10 aryloxy group, a C2-C10 alkenyl group, a C6-C10 fluoroalryl group, a C7-C40 arylalkyl group, a C7-C40 alkylaryl group, a C8-C40 arylalkenyl group, a silyl group, a germyl group or a halogen atom, m and n are integers, m + n = 2 to 4, and m is at least 1.

Description

Katalysatorkomponente und Katalysatorsystem mit hoher Polymerisationsaktivität zur Herstellung von PolymerenCatalyst component and catalyst system with high polymerization activity for the production of polymers
Die vorliegende Erfindung betrifft Katalysatorkomponenten und Katalysatorsysteme mit hoher Polymerisationsaktivität zur Herstellung von Polymeren, wobei die Polymere einen hohen Schmelzpunkt aufweisen. Die vorliegende Erfindung betrifft weiter ein wirtschaftliches und umweltschonendes Verfahren zur Herstellung von Polymeren mit einem hohen Schmelzpunkt.The present invention relates to catalyst components and catalyst systems with high polymerization activity for the production of polymers, the polymers having a high melting point. The present invention further relates to an economical and environmentally friendly process for producing polymers with a high melting point.
Aus DE-A-4332009 ist ein Verfahren zur Herstellung von Organometallfluoriden bekannt. Dabei werden π-System-haltige Organometallfluoride durch Umsetzung eines fluorfreien Organometalihalogenids mit einem Zinnfluorid der allgemeinen Formel R3SnF erhalten, worin R gleich oder verschieden sind und C-,-C10- Alkyl-, C6-C14-Aryl-, C2-C10-Alkenyl-, C7-C20-Arylalkyl- oder C7-C1 5-Alkylaryl bedeuten.DE-A-4332009 discloses a process for the production of organometallic fluorides. Organometallic fluorides containing π system are obtained by reacting a fluorine-free organometallic halide with a tin fluoride of the general formula R 3 SnF, in which R are the same or different and are C -, - C 10 - alkyl, C 6 -C 14 aryl, C 2 -C 10 alkenyl, C 7 -C 20 arylalkyl or C 7 -C 1 5 alkylaryl.
Aus EP-A-210 615 sind Katalysatoren für die Polymerisation von Styrol und Verfahren zur Polymerisation von Monostyrol zu syndiotaktischem Polystyrol bekannt.EP-A-210 615 discloses catalysts for the polymerization of styrene and processes for the polymerization of monostyrene to syndiotactic polystyrene.
Aus Macromolecules 21 (1988), 3356 ist bekannt, daß Titanverbindungen mit einem Cyclopentadienylring besonders hohe Polymerisationsaktivität aufweisen. Die mit diesen Verbindungen als Katalysatoren erhaltenen Styrolpolymere weisen vergleichsweise niedrige Schmelzpunkte auf.From Macromolecules 21 (1988), 3356 it is known that titanium compounds with a cyclopentadienyl ring have particularly high polymerization activity. The styrene polymers obtained as catalysts with these compounds have comparatively low melting points.
Die Aufgabe der vorliegenden Erfindung liegt darin, eine Katalysatorkomponente und ein Katalysatorsystem mit hoher Polymerisationsaktivität bereitzustellen, wobei Polymere mit hohen Schmelzpunkten erhalten werden. Eine weitere Aufgabe der vorliegenden Erfindung liegt darin, ein wirtschaftliches und umweltschonendes Polymerisationsverfahren bereitzustellen.The object of the present invention is to provide a catalyst component and a catalyst system with high polymerization activity, polymers with high melting points being obtained. Another object of the present invention is to provide an economical and to provide environmentally friendly polymerization processes.
Die der vorliegenden Erfindung zugrundeliegende Aufgabe wird durch eine Katalysatorkomponente für die Polymerisation von Olefinen gelöst, die mindestens eine Verbindung der allgemeinen Formel (I) enthält:The object on which the present invention is based is achieved by a catalyst component for the polymerization of olefins which comprises at least one compound of the general formula (I):
R^MVJD,R ^ MVJD,
worinwherein
M1 = Ti, Zr oder Hf ist,M 1 = Ti, Zr or Hf,
Ra = c5 (R1 , R2, R3, R,4 R5) oder C6 (R1 , R2, R3, R4, R5, R6) ist, wobei R1 , R2, R3, R4, R5 und R6 gleich oder verschieden und ein Wasserstoffatom, eine C1-C20-Alkylgruppe, eine 0,-0,0- Alkoxygruppe, eine C|-C10-Fluoralkylgruppe, eine C6-C20- Arylgruppe, eine C6-C10-Aryloxygruppe, eine C2-C10- Alkenylgruppe, eine C6-C10-Fluorarylgruppe, eine C7-C40- Arylalkylgruppe, eine C7-C40-Alkylarylgruppe, eine C8-C40- Arylalkenylgruppe, eine Silyl-, eine Germylgruppe bedeuten oder benachbarte Reste R1 , R2, R3, R4, R5 und R6 mit den sie verbindenden Atomen ein Ringsystem bilden,Ra = c 5 (R 1 , R 2 , R 3 , R, 4 R 5 ) or C 6 (R 1 , R 2 , R 3 , R 4 , R 5 , R 6 ), where R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are the same or different and a hydrogen atom, a C 1 -C 20 alkyl group, a 0, -0.0 alkoxy group, a C | -C 10 fluoroalkyl group, a C 6 -C 20 aryl group, a C 6 -C 10 aryloxy group, a C 2 -C 10 alkenyl group, a C 6 -C 10 fluoroaryl group, a C 7 -C 40 arylalkyl group , a C 7 -C 40 alkylaryl group, a C 8 -C 40 arylalkenyl group, a silyl or a germyl group or adjacent radicals R 1 , R 2 , R 3 , R 4 , R 5 and R 6 with those connecting them Atoms form a ring system,
Rb = ein Fluoratom wenn m = 1 ist, mindestens ein Fluoratom wenn m > 1 ist und sein kann gleich oder verschieden mindestens ein Wasserstoffatom, eine C,-C20-Alkylgruppe, eine C,-C10- Alkoxygruppe, eine 0.,-Cτo-Fiuoralkylgruppe, eine C6-C20- Arylgruppe, eine C6-C10-Aryloxygruppe, eine C2-C10- Alkenylgruppe, eine C6-C10-Fluorarylgruppe, eine C7-C40- Arylalkylgruppe, eine C7-C40-Alkylarylgruppe, oder eine C8-C40- Arylalkenylgruppe eine OH-Gruppe, eine NR7 2- oder SR8 1-Gruppe, wobei R7 und R8 eine Cj-C^-Alkylgruppe, eine C^CT Q- Alkoxygruppe, eine C^C^-Fiuoralkylgruppe, eine C6-C20- Arylgruppe, eine C6-C10-Aryloxygruppe, eine C2-C10- Alkenylgruppe, eine C6-C10-Fluorarylgruppe, eine C7-C40- Arylalkylgruppe, eine C7-C40-Alkylarylgruppe, oder eine C8-C40- Arylalkenylgruppe bedeuten, eine Silylgruppe, eine Germylgruppe, ein Halogenatom bedeuten, eine -OC(O)F, eine -OC(O)CRc 3, eine -OC(O)C5Rd 4 oder eine -OC(O)C6Re 5 Gruppe ist wobei Rc, Rd und Re mindestens ein Fluoratom bedeuten und Rc, Rd und Re sein können gleich oder verschieden mindestens ein Wasserstoffatom, eine C,-C20-Alkylgruppe, eine C^C^-Alkoxygruppe, eine C.,-C10- Fiuoralkylgruppe, eine C6-C20-Arylgruppe, eine C6-C10- Aryloxygruppe, eine C2-C10-Alkenylgruppe, eine C6-C10- Fluorarylgruppe, eine C7-C40-Arylalkylgruppe, eine C7-C40- Alkylarylgruppe, eine C8-C40-Arylalkenylgruppe eine OH-Gruppe, eine NR7 2- oder SR8-Gruppe, eine Silylgruppe, eine Germylgruppe oder ein Halogenatom, m und n ganze Zahlen sind, m + n = 2 bis 4 ist und m mindestens 1 ist.R b = a fluorine atom when m = 1, at least one fluorine atom when m> 1 and can be identical or different at least one hydrogen atom, a C, -C 20 alkyl group, a C, -C 10 alkoxy group, a 0. , -Cτo-Fiuoralkylgruppe, a C 6 -C 20 aryl group, a C 6 -C 10 aryloxy group, a C 2 -C 10 alkenyl group, a C 6 -C 10 fluoroaryl group, a C 7 -C 40 arylalkyl group , a C 7 -C 40 alkylaryl group, or a C 8 -C 40 arylalkenyl group an OH group, an NR 7 2 or SR 8 1 group, where R 7 and R 8 are a C j -C ^ alkyl group , a C ^ CT Q alkoxy group, a C ^ C ^ fuoralkyl group, a C 6 -C 20 aryl group, a C 6 -C 10 aryloxy group, a C 2 -C 10 - Alkenyl group, a C 6 -C 10 fluoroaryl group, a C 7 -C 40 arylalkyl group, a C 7 -C 40 alkylaryl group, or a C 8 -C 40 arylalkenyl group mean a silyl group, a germyl group, a halogen atom, is an -OC (O) F, an -OC (O) CR c 3 , an -OC (O) C 5 R d 4 or a -OC (O) C 6 R e 5 group where R c , R d and R e denotes at least one fluorine atom and R c , R d and R e may be the same or different at least one hydrogen atom, a C 1 -C 20 -alkyl group, a C 1 -C 4 -alkoxy group, a C 1 -C 10 -fluoroalkyl group , a C 6 -C 20 aryl group, a C 6 -C 10 aryloxy group, a C 2 -C 10 alkenyl group, a C 6 -C 10 fluoroaryl group, a C 7 -C 40 arylalkyl group, a C 7 - C 40 - alkylaryl group, a C 8 -C 40 arylalkenyl group, an OH group, an NR 7 2 or SR 8 group, a silyl group, a germyl group or a halogen atom, m and n are integers, m + n = 2 is 4 and m is at least 1.
Die vorliegende Erfindung hat den Vorteil, daß mit diesen Katalysatorkomponenten, Katalysatorsysteme mit einer hohen Polymerisationsaktivität erhalten werden. Die Polymerisationsaktivität der erfindungsgemäßen Katalysatoren wird in Masse des produzierten Polymers, bezogen auf die Stoffmenge der Verbindung der 4. Gruppe des Periodensystems und bezogen auf die Polymerisationszeit berechnet. Der besondere Vorteil der vorliegenden Erfindung liegt darin, daß mit Katalysatorsystemen mit hoher Polymerisationsaktivität, Polymere mit hohen Schmelzpunkten erhalten werden. Die Erhöhung der Polymerisationsaktivität bei bisher bekannten Katalysatorsystemen, war bisher mit dem Nachteil behaftet, daß die Schmelzpunkte der erhaltenen Polymere stets abnahmen. Durch die hohe Polymerisationsaktivität der Katalysatorsysteme, kann eine Polymerisation mit geringeren Mengen an Katalysatorsystemen mit sehr guten Ergebnissen durchgeführt werden. Dadurch wird das Polymerisationsverfahren sehr wirtschaftlich und umweltfreundlich. Bevorzugt sind erfindungsgemäße Katalysatoren, die einen Cyclopentadienylring als Ligand und 3 Fluoratome direkt am Metallatom M1 gebunden aufweisen. Katalysatorsysteme mit diesen Katalysatorkomponenten zeigen eine gute Polymerisationsaktivität.The present invention has the advantage that catalyst systems with a high polymerization activity are obtained with these catalyst components. The polymerization activity of the catalysts according to the invention is calculated in the mass of the polymer produced, based on the amount of compound of the 4th group of the periodic table and based on the polymerization time. The particular advantage of the present invention is that with catalyst systems with high polymerization activity, polymers with high melting points are obtained. The increase in the polymerization activity in previously known catalyst systems has hitherto had the disadvantage that the melting points of the polymers obtained always decrease. Due to the high polymerization activity of the catalyst systems, polymerization with smaller amounts of catalyst systems can be carried out with very good results. This makes the polymerization process very economical and environmentally friendly. Catalysts according to the invention which have a cyclopentadienyl ring as ligand and 3 fluorine atoms bonded directly to the metal atom M 1 are preferred. Catalyst systems with these catalyst components show good polymerization activity.
Besonders bevorzugt sind erfindungsgemäße Katalysatoren, die einen fünffach methylierten Cyclopentadienylring als Ligand und 3 Fluoratome am Metallatom M1 aufweisen. Katalysatorsysteme mit diesen Katalysatorkomponenten zeigen eine sehr gute Polymerisationsaktivität.Catalysts according to the invention which have a five-fold methylated cyclopentadienyl ring as ligand and 3 fluorine atoms on the metal atom M 1 are particularly preferred. Catalyst systems with these catalyst components show very good polymerization activity.
Besonders bevorzugt ist Titan als Übergangsmetallatom. Mit Titan ais Ubergangsmetall werden überwiegend gute Polymerisationsaktivitäten erreicht.Titanium is particularly preferred as the transition metal atom. Good polymerization activities are predominantly achieved with titanium as the transition metal.
Erfindungsgemäß ist eine Katalysatorkomponente vorgesehen, enthaltend mindestens eine Verbrückung R9 zwischen mindestens zwei Resten Ra.According to the invention, a catalyst component is provided, containing at least one bridging R 9 between at least two radicals R a .
R9 ist bevorzugtR 9 is preferred
1 0 1 0 1 0 1 0 1 01 0 1 0 1 0 1 0 1 0
RR
II.
0 — U — 0 — — c M ' - c — kr —0 - U - 0 - - c M '- c - kr -
1 1 1 1 1 t 1 1 1 11 1 1 1 1 t 1 1 1 1
I 0 1 0 1 0 1 0 I 0 I 0 1 0 1 0 2 _I 0 1 0 1 0 1 0 I 0 I 0 1 0 1 0 2 _
M M z - — c — c 2MM z - - c - c 2
M 2 -M 2 -
1 t 1 1 1 1 1 1 1 1 1 1 1 1 1 11 t 1 1 1 1 1 1 1 1 1 1 1 1 1 1
1 0 1 0 1 01 0 1 0 1 0
R , υ RR , υ R
I I I c — c - cI I I c - c - c
1 1 1 1 1 1 >«1 0. /A . « 1 0 . -6»- -S - S O . >o2 , N R ' CO . r ^> ( 0 ) * ' °1 1 1 1 1 1 > « 1 0 . / A. « 1 0 . -6 »- -S - SO. > o 2 , NR 'CO. r ^> (0) * '°
> >R ' ° O d «>> R '° O d «
wobei R10 und R1 1 gleich oder verschieden sind und ein Wasserstoffatom, ein Halogenatom oder eine C.,-C40-kohlenstoff haltige Gruppe ist, wie eine
Figure imgf000007_0001
Alkyl-, eine C^C^-Fluoralkyl-, eine C^C^-Alkoxy-, eine C6-C14-Aryl-, eine C6-C10-Fluoraryl-, eine C6-Cι0-Aryloxy-, eine C2-C10-Alkenyl-, eine C7-C40- Arylalkyl-, eine C7-C40-Alkylaryl-, oder eine C8-C40-Arylalkenylgruppe oder R10 und R1 1 jeweils mit den sie verbindenden Atomen einen oder mehrere Ringe bilden und x eine ganze Zahl von Null bis 18 ist, M2 Silizium, Germanium oder Zinn ist. R9 kann auch zwei Einheiten der Formel (I) miteinander verknüpfen.wherein R 10 and R 1 1 are the same or different and is a hydrogen atom, a halogen atom or a C. - C 40 carbon-containing group, such as a
Figure imgf000007_0001
Alkyl, a C ^ C ^ fluoroalkyl, a C ^ C ^ alkoxy, a C 6 -C 14 aryl, a C 6 -C 10 fluoroaryl, a C 6 -Cι 0 aryloxy- , a C 2 -C 10 alkenyl, a C 7 -C 40 arylalkyl, a C 7 -C 40 alkylaryl, or a C 8 -C 40 arylalkenyl group or R 10 and R 1 1 each with the they form one or more rings connecting atoms and x is an integer from zero to 18, M 2 is silicon, germanium or tin. R 9 can also link two units of the formula (I) to one another.
Die folgenden Beispiele sollen die in der allgemeinen Formel I beschriebenen Organometallfluoride näher erläutern, erheben aber keinen Anspruch auf Vollständigkeit:The following examples are intended to explain the organometallic fluorides described in general formula I, but do not claim to be complete:
Ethylenbis(indenyl)zirkoniumdif luorid Ethylenbis(4,5, 6, 7-tetrahydroindenyl)zirkoniumdif luorid Ethylenbis(2-methylindenyi)zirkoniumdif luorid Ethylenbis(2,4-dimethylindenyl)zirkoniumdif luorid Dimethylsilandiylbis(2-methyl-4,5-benzoindenyl)zirkoniumdif luorid Dimethylsilandiylbis(2-methyl-4,6-diisopropylindenyl)zirkoniumdif luorid Dimethylsilandiylbis(2-methyl-4-phenyiindenyl)zirkoniumdif luorid Dimethylsilandiylbis(2-ethyl-4-phenylindenyl)zirkoniumdif luorid Dimethylsilandiylbis(2-methyl-4-(1 -naphthyl)indenyl)zirkoniumdif luorid Dimethylsilandiylbis(indenyl)zirkoniumdif luorid Dimethylsilandiylbis(2-methyl-4-ethylindenyl)zirkoniumdif luorid Dimethylsilandiylbis(2-methyl-4-isopropylindenyl)zirkoniumdif luorid Dimethylsilandiylbis(2-methyl-4-methylindenyl)zirkoniumdif luorid Dimethylsilandiylbis(2-ethyl-4-methylindenyl)zirkoniumdif luorid Dimethylsilandiylbis(2-methyl-α-acenaphth-1 -indenyl)zirkoπiumdif luoridEthylene bis (indenyl) zirconium difluoride ethylene bis (4,5, 6, 7-tetrahydroindenyl) zirconium difluoride ethylene bis (2-methylindenyi) zirconium difluoride ethylene bis (2,4-dimethylindenyl) zirconium difluoride dimethylsilanedylylbis (2-methyl) -benzid zirconium difluorid dimethylsilanediylbis (2-methyl-4,6-diisopropylindenyl) zirconium difluorid dimethylsilanediylbis (2-methyl-4-phenyiindenyl) zirconium difluorid dimethylsilanediylbis (2-ethyl-4-phenylindenyldifluidyl-1-dimethylsilidyl-1-diuridium) -naphthyl) indenyl) zirconium difluorid dimethylsilanediylbis (indenyl) zirconiumdif luorid dimethylsilanediylbis (2-methyl-4-ethylindenyl) zirconiumdif luorid dimethylsilanediylbisyl (2-methyl-4-isopropylindenyldimidyldilidyldimidyldisilidyldimidium) (2-ethyl-4-methylindenyl) zirconium difluoride Dimethylsilanediylbis (2-methyl-α-acenaphth-1 -indenyl) zirconium difluoride
Phenylmethylsilandiylbis(2-methyl-4-phenylindenyl)zirkoniumdifluoridPhenylmethylsilanediylbis (2-methyl-4-phenylindenyl) zirconium difluoride
Phenylmethylsilandiylbis(2-methyl-indenyl)zirkoniumdifluoridPhenylmethylsilanediylbis (2-methyl-indenyl) zirconium difluoride
Ethylenbis(2-methyl-4,5-benzoindenyl)zirkoniumdifluoridEthylene bis (2-methyl-4,5-benzoindenyl) zirconium difluoride
Ethylenbis(2-methyl-4,6-diisopropylindenyl)zirkoniumdifluoridEthylene bis (2-methyl-4,6-diisopropylindenyl) zirconium difluoride
Ethylenbis(2-methyl-4-phenylindenyl)zirkoniumdifluoridEthylene bis (2-methyl-4-phenylindenyl) zirconium difluoride
Ethylenbis(2-ethyl-4-phenylindenyl)zirkoniumdifluoridEthylene bis (2-ethyl-4-phenylindenyl) zirconium difluoride
Ethylenbis(2-methyl-4-(1 -naphthyl)indenyl)zirkoniumdifluoridEthylenebis (2-methyl-4- (1-naphthyl) indenyl) zirconium difluoride
Ethylenbis(indenyl)zirkoniumdifluoridEthylene bis (indenyl) zirconium difluoride
Ethylenbis(2-methyl-4-ethylindenyl)zirkoniumdifluoridEthylene bis (2-methyl-4-ethylindenyl) zirconium difluoride
Ethylenbis(2-methyl-4-isopropylindenyl)zirkoniumdifluoridEthylene bis (2-methyl-4-isopropylindenyl) zirconium difluoride
Ethylenbis(2-methyl-4-methylindenyl)zirkoniumdif luoridEthylene bis (2-methyl-4-methylindenyl) zirconium difluoride
Ethylenbis(2-ethyl-4-methylindenyl)zirkoniumdifluoridEthylene bis (2-ethyl-4-methylindenyl) zirconium difluoride
Ethylenbis(2-methyl-α-acenaphth-1 -indenyl)zirkoniumdifluoridEthylene bis (2-methyl-α-acenaphth-1 -indenyl) zirconium difluoride
Bis(2-methyl-4,5-benzoindenyl)zirkoniumdifluoridBis (2-methyl-4,5-benzoindenyl) zirconium difluoride
Bis{2-methyl-4,6-diisopropylindenyl)zirkoniumdif luoridBis {2-methyl-4,6-diisopropylindenyl) zirconium difluoride
Bis(2-methyl-4-phenylindenyl)zirkoniumdif luoridBis (2-methyl-4-phenylindenyl) zirconium difluoride
Bis(2-ethyl-4-phenylindenyl)zirkoniumdif luoridBis (2-ethyl-4-phenylindenyl) zirconium difluoride
Bis(2-methyl-4-(1-naphthyl)indenyl)zirkoniumdif luoridBis (2-methyl-4- (1-naphthyl) indenyl) zirconium difluoride
Bis(indenyl)zirkoniumdif luoridBis (indenyl) zirconium difluoride
Bis(2-methyl)-4-ethylindenyl)zirkoniumdifluoridBis (2-methyl) -4-ethylindenyl) zirconium difluoride
Bis(2-methyl-4-isopropylindenyl)zirkoniumdifluoridBis (2-methyl-4-isopropylindenyl) zirconium difluoride
Bis(2-methyl-4-methylindenyl)zirkoniumdif luoridBis (2-methyl-4-methylindenyl) zirconium difluoride
Bis(2-ethyl-4-methylindenyl)zirkoniumdif luoridBis (2-ethyl-4-methylindenyl) zirconium difluoride
Bis(2-methyl-α-acenaphth-1 -indenyl)zirkoniumdif luoridBis (2-methyl-α-acenaphth-1 -indenyl) zirconium difluoride
Bis(n-Butyl-cyciopentadienyl)zirkoniumdifluoridBis (n-butyl-cyciopentadienyl) zirconium difluoride
Bis(cyclopentadienyl)zirkoniumdif luoridBis (cyclopentadienyl) zirconium difluoride
Bis(pentamethylcyclopentadienyl)zirkoniumdifluoridBis (pentamethylcyclopentadienyl) zirconium difluoride
CyclopentadienylzirkoniumtrifluoridCyclopentadienyl zirconium trifluoride
Pentamethylcyclopentadienylzirkoniumtrif luoridPentamethylcyclopentadienyl zirconium trifluoride
(2-Methyl-4,5-benzoindenyl)zirkoniumtrifluorid (2-Methyl-4,6-diisopropylindenyl)zirkoniumtrif luorid (2-Methyi-4-phenylindenyl)zirkoniumtrif luorid . (2-Ethyl-4-phenylindenyl)zirkoniumtrif luorid (2-Methyl-4-(1-naphthyl)indenyl)zirkoniumtrif luorid Indenγlzirkoniumtrif luorid (2-Methyl-4-ethylindenyl)zirkoniumtrif luorid (2-Methyl-4-isopropylindenyl)zirkoniumtrif luorid (2-Methyl-4-methylindenyl)zirkoniumtrif luorid (2-Ethyl-4-methylindenyl)zirkoniumtrif luorid (2-Methyl-α-acenaphth-1-indenyl)zirkoniumtrif luorid (n-Butyl-cyclopentadienyl)zirkoniumtrifluorid lsopropyliden(9-fluorenyl)cyclopentadienylzirkoniumdif luorid Diphenylmethylen.9-f luorenyl)cyclopentadienylzirkoniumdif luorid Phenylmethylmethylen(9-fluorenyl)cyclopentadienylzirkoniumdif luorid Dimethylsiiandiyl(9-fluorenyl)cyclopentadienylzirkoniumdif luorid lsopropyliden(9-fluorenyl)(3-methyi-cyciopentadienyl)zirkoniumdifluorid Diphenylmethylen(9-fluorenyl)(3-methγl-cyclopentadienyl)zirkoniumdif luorid Phenylmethylmethylen(9-fluorenyl)(3-methyl-cyclopentadienyl)zirkoniumdifluorid Dimethylsilandiyl(9-fluorenyl)(3-methyl-cyclopentadienyl)zirkoniumdif luorid lsopropyiiden(9-fluorenyl)(3-isopropyl-cyclopentadienyl)zirkoniumdif luorid Diphenylmethylen(9-fluorenyl)(3-isopropyl-cyclopentadienyl)zirkoniumdifluorid Phenylmethylmethylen(9-fluorenyl)(3-isopropyl- cyclopentadienyDzirkoniumdif luorid(2-methyl-4,5-benzoindenyl) zirconium trifluoride (2-Methyl-4,6-diisopropylindenyl) zirconium trif luoride (2-methyl-4-phenylindenyl) zirconium trif luoride. (2-Ethyl-4-phenylindenyl) zirconium trif luoride (2-methyl-4- (1-naphthyl) indenyl) zirconium trif luorid indenγl zirconium trif luorid (2-methyl-4-ethylindenyl) zirconium trif luorid (2-methyl-4-zirconium trifluoride) luoride (2-methyl-4-methylindenyl) zirconium trif luorid (2-ethyl-4-methylindenyl) zirconium trif luorid (2-methyl-α-acenaphth-1-indenyl) zirconium trif luorid (n-butyl-cyclopentadienyl) zirconium trifluoride fluorenyl) cyclopentadienylzirkoniumdif tetrafluoride Diphenylmethylen.9-f luorenyl) cyclopentadienylzirkoniumdif Phenylmethylmethylen tetrafluoride (9-fluorenyl) cyclopentadienylzirkoniumdif Dimethylsiiandiyl tetrafluoride (9-fluorenyl) cyclopentadienylzirkoniumdif tetrafluoride isopropylidene (9-fluorenyl) (3-methyl-cyciopentadienyl) zirkoniumdifluorid diphenylmethylene (9-fluorenyl) ( 3-methγl-cyclopentadienyl) zirconium difluoride phenylmethylmethylene (9-fluorenyl) (3-methyl-cyclopentadienyl) zirconium difluoride dimethylsilanediyl (9-fluorenyl) (3-methyl-cyclopentadienyl) zirconium difluoride (9-propylene) -fluorenyl) (3-isopropyl-cyclopentadienyl) zirconium difluoride diphenylmethylene (9-fluorenyl) (3-isopropyl-cyclopentadienyl) zirconium difluoride phenylmethylmethylene (9-fluorenyl) (3-isopropyl-cyclopentadienylduoridium difluoride)
Dimethylsilandiyl(9-fluorenyl)(3-isopropyl-cyclopentadienyl)zirkoniumdif luorid lsopropyliden(2,7-ditert.-butyl-9-fluorenyl)cyclopentadienylzirkoniumdif luorid Diphenylmethylen(2,7-ditert.-butyl-9- fluorenyDcyclopentadienylzirkoniumdif luorid Phenylmethylmethylen(2,7-ditert.-butyl-9-fluorenyl)cyclopenta- dienylzirkoniumdif luoridDimethylsilanediyl (9-fluorenyl) (3-isopropyl-cyclopentadienyl) zirconium difluoride isopropylidene (2,7-ditert.-butyl-9-fluorenyl) cyclopentadienylzirconium difluoride diphenylmethylene (2,7-ditert.-butyl-9-fluoridylmethyl (phenyldiryldiryldimidyldiryldiryldidylmethyl) (phenyldidyldiryldimidyldiryldiryldidylmethyl (phenyldidyldiryldiryldidyldiryldidyldiryldihydroxyl) , 7-di-tert-butyl-9-fluorenyl) cyclopentadienylzirconium difluoride
Dimethylsilandiyl(2,7-ditert.-butyl-9-fluorenyl)cyclopentadienylzirkoniumdif luorid Ethylenbis(indenyl)titandif luorid Ethylenbis(4,5,6,7-tetrahydroindenyl)titandifluoridDimethylsilanediyl (2,7-ditert.-butyl-9-fluorenyl) cyclopentadienylzirconium difluoride ethylene bis (indenyl) titanium difluoride Ethylene bis (4,5,6,7-tetrahydroindenyl) titanium difluoride
Ethylenbis(2-methylindenyl)titandifluoridEthylene bis (2-methylindenyl) titanium difluoride
Dimethylsilandiylbis(indenyl)titandifluoridDimethylsilanediylbis (indenyl) titanium difluoride
Bis(indenyl)titandifluoridBis (indenyl) titanium difluoride
Bis(cyclopentadienyl)titandifluoridBis (cyclopentadienyl) titanium difluoride
Bis(pentamethylcyclopentadienyl)titandifluoridBis (pentamethylcyclopentadienyl) titanium difluoride
CyclopentadienyltitantrifluoridCyclopentadienyltitanium trifluoride
PentamethylcyclopentadienyltitantrifluoridPentamethylcyclopentadienyltitanium trifluoride
IndenyltitantrifluoridIndenyltitanium trifluoride
(n-Butyl-cyclopentadienyl)titantrifluorid lsopropyliden(9-fluorenyl)cyclopentadienyltitandif luorid(n-Butyl-cyclopentadienyl) titanium trifluoride isopropylidene (9-fluorenyl) cyclopentadienyltitanium difluoride
Ethylenbis(indenyl)hafniumdifluoridEthylene bis (indenyl) hafnium difluoride
Ethylenbis(4,5,6,7-tetrahydroindenyl)hafniumdif luoridEthylene bis (4,5,6,7-tetrahydroindenyl) hafnium difluoride
Ethylenbis(2-methylindenyl)hafniumdif luoridEthylene bis (2-methylindenyl) hafnium difluoride
Dimethylsilandiylbis(indenyl)hafniumdif luoridDimethylsilanediylbis (indenyl) hafnium difluoride
Bis(indenγl)hafniumdifluoridBis (indenγl) hafnium difluoride
Bis(cyclopentadienyl)hafniumdif luoridBis (cyclopentadienyl) hafnium difluoride
Bis(pentamethylcyclopentadienyl)hafniumdifluoridBis (pentamethylcyclopentadienyl) hafnium difluoride
Cyclopentadienylhafniumtrif luoridCyclopentadienylhafniumtrif luorid
Pentamethylcyclopentadienylhafniumtrif luoridPentamethylcyclopentadienylhafniumtrif luorid
Indenylhafniumtrif luoridIndenylhafniumtrif luorid
(n-Butyl-cyclopentadienyl)hafniumtrifluorid lsopropyliden(9-fluorenyl)cyclopentadienylhafniumdifluorid(n-Butyl-cyclopentadienyl) hafnium trifluoride isopropylidene (9-fluorenyl) cyclopentadienyl hafnium difluoride
Bis(cyciopentadienyl)titanf luorid)Bis (cyciopentadienyl) titanf luorid)
Bis(Methylcyclopentadienyl-titanf luorid)Bis (methylcyclopentadienyl-titanium fluoride)
Bis(pentamethylcyclopentadienyl)titanf luoridBis (pentamethylcyclopentadienyl) titanium fluoride
[(Me3SiC5H4)Ti(F)Nt-Bu]2 [(Me 3 SiC 5 H 4 ) Ti (F) Nt-Bu] 2
Die als Ausgangsverbindung benötigten Organometallhalogenide sind kommerziell erhältlich oder können nach literaturbekannten Verfahren hergestellt werden. Die als Ausgangsstoff benötigten Zinnfluoride können nach literaturbekannten Methoden hergestellt werden (Ber. Dtsch. Chem. Ges. (1918), Bd. 51 , 1447).The organometallic halides required as the starting compound are commercially available or can be prepared by processes known from the literature. The tin fluorides required as starting material can be methods known from the literature are produced (Ber. Dtsch. Chem. Ges. (1918), Vol. 51, 1447).
Erfindungsgemäß ist ein Katalysatorsystem vorgesehen, enthaltend mindestens eine Katalysatorkomponente und mindestens eine organische Bor- und/oder mindestens eine organische Aluminium- und/oder mindestens eine organische Zinnverbindung als Cokatalysator. Das Katalysatorsystem ist erhältlich durch Inkontaktbringen mindestens einer Katalysatorkomponente mit mindestens einer organischen Bor- und/oder mindestens einer organischen Aluminium- und/oder mindestens einer organischen Zinnverbindung. Es entsteht insbesondere als Reaktionsprodukt mindestens einer Katalysatorkomponente und mindestens einer organischen Bor- und/oder organischen Aluminium- und/oder organischen Zinnverbindungen sowie Reaktionsprodukten dieser Verbindungen mit Kondensationsmitteln, wie Wasser. Mit diesen Katalysatorsystemen werden sehr gute Polymerisationsaktivitäten erhalten. Die Cokatalysatorkomponente, die erfindungsgemäß im Katalysatorsystem enthalten sein kann, enthält mindestens eine Verbindung vom Typ eines Aluminoxans oder einer Lewis- Säure oder einer ionischen Verbindung, die durch Reaktion mit einer Kataiysatorkomponente in eine kationische Verbindung überführt wird.According to the invention, a catalyst system is provided, comprising at least one catalyst component and at least one organic boron and / or at least one organic aluminum and / or at least one organic tin compound as cocatalyst. The catalyst system can be obtained by contacting at least one catalyst component with at least one organic boron and / or at least one organic aluminum and / or at least one organic tin compound. It arises in particular as a reaction product of at least one catalyst component and at least one organic boron and / or organic aluminum and / or organic tin compounds as well as reaction products of these compounds with condensing agents such as water. Very good polymerization activities are obtained with these catalyst systems. The cocatalyst component which can be contained in the catalyst system according to the invention contains at least one compound of the type of an aluminoxane or a Lewis acid or an ionic compound which is converted into a cationic compound by reaction with a catalyst component.
Als Aluminoxan wird bevorzugt eine Verbindung der allgemeinen Formel IIA compound of the general formula II is preferred as the aluminoxane
(R AIOL (II)(R AIOL (II)
verwendet. Aluminoxane können z.B. cyclisch wie in Formelused. Aluminoxanes can e.g. cyclic as in formula
Figure imgf000011_0001
Figure imgf000011_0001
oder linear wie in Formel IV
Figure imgf000012_0001
or linear as in Formula IV
Figure imgf000012_0001
oder vom Cluster-Typ wie in Formel V sein, wie sie in neuerer Literatur beschrieben werden; vgl. JACS 1 17 (1995), 6465-74, Organometallics 13 (1994), 2957-2969.or be of the cluster type as in Formula V as described in more recent literature; see. JACS 1 17 (1995), 6465-74, Organometallics 13 (1994), 2957-2969.
Figure imgf000012_0002
Figure imgf000012_0002
Die Reste R in den Formeln (II), (lll), (IV) und (V) können gleich oder verschieden sein und eine C,-C20-Kohlenwasserstoff gruppe wie eine C,-C6- Alkylgruppe, eine C6-C18-Arylgruppe, Benzyl oder Wasserstoff bedeuten, und p eine ganze Zahl von 2 bis 50, bevorzugt 10 bis 35 bedeuten.The radicals R in the formulas (II), (III), (IV) and (V) can be the same or different and a C, -C 20 hydrocarbon group such as a C, -C 6 alkyl group, a C 6 - C 18 aryl group, benzyl or hydrogen, and p is an integer from 2 to 50, preferably 10 to 35.
Bevorzugt sind die organischen Reste gleich und bedeuten Methyl, Isobutyl, n- Butyl, Phenyl oder Benzyl, besonders bevorzugt ist Methyl. Sind die organischen Reste unterschiedlich, so sind sie bevorzugt Methyl und Wasserstoff, Methyl und Isobutyl oder Methyl und n-Butyl, wobei Wasserstoff bzw. Isobutyl oder n-Butyl enthalten sind. Als Lewis-Säure werden bevorzugt mindestens eine bor- oder aluminiumorganische Verbindung eingesetzt, die C,- C20-kohlenstoffhaltige Gruppen enthalten, wie verzweigte oder unverzweigte Alkyl- oder Halogenalkylgruppen. Erfindungsgemäß ist ein Katalysatorsystem vorgesehen, das zusätzlich einen Träger enthalten kann. Die Trägerkomponente des erfindungsgemäßen Katalysatorsystems ist bevorzugt mindestens ein anorganisches Oxid, wie SiO2, AI2O3, MgO, ZrO2, TiO2, B2O3, CaO, ZnO, ThO2, Carbonate, wie Na2CO3, K2CO3, CaCO3, MgCO3, Sulfate, wie Na2SO4, AI2(SO4)3, BaSO4, Nitrate, wie KNO3, Mg(NO3)2, AI(NO3)3 sowie Oxide, wie Na2O, K2O ,und Li2O. Als Träger sind insbesondere Silica und/oder Alumina und/oder Polymerträger vorgesehen. Erfindungsgemäß sind Polymere und/oder Copolymere, erhältlich durch Polymerisation mit einem erfindungsgemäßen Katalysatorsystem vorgesehen. Polymere und/oder Copolymere von 1 -Alkenen und Vinylaromaten, erhältlich durch Polymerisation mit einem erfindungsgemäßen Katalysatorsystem sind besonders vorgesehen. Syndiotaktische Polymere, erhältlich durch Polymerisation mit einem erfindungsgemäßen Katalysatorsystem sind ganz besonders vorgesehen. Syndiotaktisches Polystyrol, erhältlich durch Polymerisation mit einem erfindungsgemäßen Katalysatorsystem ist am meisten bevorzugt.The organic radicals are preferably the same and are methyl, isobutyl, n-butyl, phenyl or benzyl, and methyl is particularly preferred. If the organic radicals are different, they are preferably methyl and hydrogen, methyl and isobutyl or methyl and n-butyl, hydrogen or isobutyl or n-butyl being present. The Lewis acid used is preferably at least one organoboron or organoaluminum compound which contains C, -C 20 -carbon-containing groups, such as branched or unbranched alkyl or haloalkyl groups. According to the invention, a catalyst system is provided which can additionally contain a support. The carrier component of the catalyst system according to the invention is preferably at least one inorganic oxide, such as SiO 2 , Al 2 O 3 , MgO, ZrO 2 , TiO 2 , B 2 O 3 , CaO, ZnO, ThO 2 , carbonates, such as Na 2 CO 3 , K 2 CO 3 , CaCO 3 , MgCO 3 , sulfates such as Na 2 SO 4 , Al 2 (SO 4 ) 3 , BaSO 4 , nitrates such as KNO 3 , Mg (NO 3 ) 2 , Al (NO 3 ) 3 and oxides , such as Na 2 O, K 2 O, and Li 2 O. In particular, silica and / or alumina and / or polymer supports are provided as supports. According to the invention, polymers and / or copolymers obtainable by polymerization with a catalyst system according to the invention are provided. Polymers and / or copolymers of 1-alkenes and vinyl aromatics, obtainable by polymerization with a catalyst system according to the invention, are particularly provided. Syndiotactic polymers obtainable by polymerization with a catalyst system according to the invention are very particularly provided. Syndiotactic polystyrene, obtainable by polymerization with a catalyst system according to the invention is most preferred.
Zur Polymerisation von bevorzugt vinylaromatischen Monomeren werden erfindungsgemäß fluorhaltige Übergangsmetallverbindungen als Katalysatorkomponente, organische Bor- und/oder organische Aluminium und/oder organische Zinnverbindungen und Reaktionsprodukte derselben mit Kondensationsmitteln, wie Wasser, als Cokatalysatorkomponente sowie vinylaromatisches Monomer in beliebiger Reihenfolge eingesetzt. Es können ein oder mehrere Träger verwendet werden. Es können eines oder mehrere Lösungsmittel in beliebiger Reihenfolge dazu gegeben werden. Das Eingeben der Komponenten und die Reaktion erfolgt drucklos oder unter vermindertem oder erhöhten Druck in der Atmosphäre eines Inertgases, wie z. B. Stickstoff, Argon oder einem Gemisch dieser. Die Reaktion wird bevorzugt im Temperaturbereich von 10 bis 70 °C durchgeführt. Die Bestandteile des Katalysatorsystems werden in beliebigem molaren Verhältnis zueinander eingesetzt. Bevorzugt ist ein Verhältnis von Aluminium zu Titan von 100 bis 1000. Erfindungsgemäß ist die Verwendung eines Katalysatorsystems zur Herstellung eines Polymers und/oder Copolymers, besonders zur Polymerisation und/oder Copolymerisation von 1-Alkenen und Vinylaromaten, ganz besonders zur Polymerisation von Styrol vorgesehen.To polymerize vinyl aromatic monomers, according to the invention, fluorine-containing transition metal compounds are used as catalyst components, organic boron and / or organic aluminum and / or organic tin compounds and reaction products thereof with condensing agents, such as water, as cocatalyst component and vinyl aromatic monomer in any order. One or more carriers can be used. One or more solvents can be added in any order. The components are entered and the reaction takes place without pressure or under reduced or elevated pressure in the atmosphere of an inert gas, such as, for. B. nitrogen, argon or a mixture of these. The reaction is preferably carried out in the temperature range from 10 to 70.degree. The components of the catalyst system are used in any molar ratio to one another. A ratio of aluminum to titanium of 100 to 1000 is preferred. According to the invention, the use of a catalyst system for the production of a polymer and / or copolymer, in particular for the polymerization and / or copolymerization of 1-alkenes and vinylaromatics, very particularly for the polymerization of styrene, is provided.
Die Erfindung wird anhand von Beispielen näher erläutert.The invention is explained in more detail by means of examples.
BeispieleExamples
Beispiel 1example 1
Ein auf 50 °C temperierter 100 ml Glasreaktor wurde unter Rühren im Argongegenstrom nacheinander mit 14,1 ml Toluol, 5 ml einer toluolischen Methylaluminoxanlösung (7,5 ' 10"4 mol/5ml), 20 ml Styrol und 0,9 ml einer toluolischen Lösung von Cyclopentadienyltitantrif luorid (2,5 ' 10"6 mol/0,9 ml) beschickt. Die Zugabe der Titanverbindung wurde als Startpunkt der Polymerisation genommen. Nach 10 Minuten wurden etwa 50 ml eines Gemisches von Salzsäure und Ethanol hinzugegeben. Es wurde weitere 12 Stunden gerührt. Das feste Produkt wurde abfiltriert und mit Ethanol neutral gewaschen. Das Polymer wurde im Vakuum bei Raumtemperatur getrocknet.A 100 ml glass reactor heated to 50 ° C. was stirred with 14.1 ml of toluene, 5 ml of a toluene solution of methylaluminoxane (7.5 '10 "4 mol / 5 ml), 20 ml of styrene and 0.9 ml of a toluene solution in succession with argon counterflow Solution of cyclopentadienyltitanium trifluoride (2.5 '10 "6 mol / 0.9 ml) charged. The addition of the titanium compound was taken as the starting point for the polymerization. After 10 minutes, about 50 ml of a mixture of hydrochloric acid and ethanol was added. The mixture was stirred for a further 12 hours. The solid product was filtered off and washed neutral with ethanol. The polymer was dried in vacuo at room temperature.
Vergleichsbeispiel 1Comparative Example 1
Das Vergleichsbeispiel 1 wurde entsprechend dem Beispiel 1 durchgeführt, wobei als Katalysator CpTiCI3 verwendet wurde.Comparative example 1 was carried out in accordance with example 1, CpTiCl 3 being used as catalyst.
Beispiel 2Example 2
Beispiel 2 wurde entsprechend dem Beispiel 1 durchgeführt, wobei als Katalysator Cp*TiF3 verwendet wurde. Vergleichsbeispiel 2Example 2 was carried out in accordance with Example 1, Cp * TiF 3 being used as the catalyst. Comparative Example 2
Das Vergleichsbeispiel 2 wurde entsprechend dem Beispiel 1 durchgeführt, wobei als Katalysator Cp*TiCI3 verwendet wurde.Comparative example 2 was carried out in accordance with example 1, Cp * TiCl 3 being used as the catalyst.
Aus der nachstehend aufgeführten Tabelle 1 gehen die Polymerisationsaktivitäten der im Beispiel 1 und im Vergleichsbeispiel 1 eingesetzten Katalysatoren und die charakteristischen Daten der im Beispiel 1 und im Vergleichsbeispiel 1 erhaltenen Polymere hervor.Table 1 below shows the polymerization activities of the catalysts used in Example 1 and Comparative Example 1 and the characteristic data of the polymers obtained in Example 1 and Comparative Example 1.
Tabelle 1Table 1
Figure imgf000015_0001
Figure imgf000015_0001
Aus der nachstehenden aufgeführten Tabelle 2 gehen die Polymerisationsaktivitäten der im Beispiel 2 und Vergleichsbeispiel 2 eingesetzten Katalysatoren und die charakteristischen Daten der im Beispiel 2 und Vergleichsbeispiel 2 erhaltenen Polymere hervor.The polymerization activities of those in Example 2 and Comparative Example 2 are shown in Table 2 below used catalysts and the characteristic data of the polymers obtained in Example 2 and Comparative Example 2.
Tabelle 2Table 2
Figure imgf000016_0001
Figure imgf000016_0001
Beispiel 3Example 3
Ein auf 30 °C temperierter 200 ml Glasreaktor wurde unter Rühren im Argongegenstrom nacheinander mit 49 ml Toluol, 0,58 g (0,01 mol) Methylaluminoxan, 50 ml Styrol und 1 ml einer toluolischen Lösung von Methylcyclopentadienyltitantrifluorid (10-5 mol/ml) beschickt. Die Zugabe der Titanverbindung wurde als Startpunkt der Polymerisation genommen. Nach 4 Minuten wurden etwa 50 ml eines Gemisches von Salzsäure und Ethanol hinzugegeben. Es wurde weitere 12 Stunden gerührt. Das feste Produkt wurde abfiltriert und mit Ethanol neutral gewaschen. Das Polymer wurde im Vakuum bei Raumtemperatur getrocknet.A 200 ml glass reactor heated to 30 ° C. was stirred in succession with argon counterflow with 49 ml of toluene, 0.58 g (0.01 mol) of methylaluminoxane, 50 ml of styrene and 1 ml of a toluene solution of methylcyclopentadienyltitanium trifluoride (10 -5 mol / ml ) loaded. The addition of the titanium compound was taken as the starting point for the polymerization. After 4 minutes, about 50 ml of a mixture of hydrochloric acid and ethanol was added. The mixture was stirred for a further 12 hours. The solid product was filtered off and washed neutral with ethanol. The polymer was dried in vacuo at room temperature.
Vergleichsbeispiel 3Comparative Example 3
Das Vergleichsbeispiel 3 wurde entsprechend dem Beispiel 3 durchgeführt, wobei als Katalysator Methylcyclopentadienyltitantrichlorid verwendet wurde.Comparative example 3 was carried out in the same way as in example 3, methylcyclopentadienyltitanium trichloride being used as the catalyst.
Aus der nachstehenden aufgeführten Tabelle 3 gehen die Polymerisationsaktivitäten der im Beispiel 3 und Vergleichsbeispiel 3 eingesetzten Katalysatoren und die charakteristischen Daten der im Beispiel 3 und Vergleichsbeispiel 3 erhaltenen Polymere hervor.Table 3 below shows the polymerization activities of the catalysts used in Example 3 and Comparative Example 3 and the characteristic data of the polymers obtained in Example 3 and Comparative Example 3.
Tabelle 3Table 3
Figure imgf000017_0001
Beispiel 4 und Vergleichsbeispiel 4
Figure imgf000017_0001
Example 4 and Comparative Example 4
Beispiel 4 wurde entsprechend dem Beispiel 3 durchgeführt, wobei als Katalysator EtMe4CpTiF3 verwendet wurde. Das Vergleichsbeispiel 4 wurde entsprechend dem Beispiel 3 durchgeführt, wobei als Katalysator EtMe4CpTiCI3 verwendet wurde.Example 4 was carried out according to Example 3, using EtMe 4 CpTiF 3 as catalyst. Comparative example 4 was carried out in accordance with example 3, EtMe 4 CpTiCl 3 being used as catalyst.
Aus der nachstehenden aufgeführten Tabelle 4 gehen die Polymerisationsaktivitäten der im Beispiel 4 und Vergleichsbeispiel 4 eingesetzten Katalysatoren und die charakteristischen Daten der im Beispiel 4 und Vergleichsbeispiel 4 erhaltenen Polymere hervor.Table 4 below shows the polymerization activities of the catalysts used in Example 4 and Comparative Example 4 and the characteristic data of the polymers obtained in Example 4 and Comparative Example 4.
Tabelle 4Table 4
Figure imgf000018_0001
Beispiel 5 und Vergleichsbeispiel 5
Figure imgf000018_0001
Example 5 and Comparative Example 5
Beispiel 5 wurde entsprechend dem Beispiel 3 durchgeführt, wobei als Katalysator PrMe4CpTiF3 verwendet wurde. Das Vergleichsbeispiel 5 wurde entsprechend dem Beispiel 3 durchgeführt, wobei als Katalysator PrMe4CpTiCI3 verwendet wurde.Example 5 was carried out in accordance with Example 3, PrMe 4 CpTiF 3 being used as the catalyst. Comparative example 5 was carried out in the same way as in example 3, using PrMe 4 CpTiCI 3 as catalyst.
Aus der nachstehenden aufgeführten Tabelle 5 gehen die Polymerisationsaktivitäten der im Beispiel 5 und Vergleichsbeispiel 5 eingesetzten Katalysatoren und die charakteristischen Daten der im Beispiel 5 und Vergleichsbeispiel 5 erhaltenen Polymere hervor.Table 5 below shows the polymerization activities of the catalysts used in Example 5 and Comparative Example 5 and the characteristic data of the polymers obtained in Example 5 and Comparative Example 5.
Tabelle 5Table 5
Figure imgf000019_0001
Beispiel 6 und Vergleichsbeispiel 6
Figure imgf000019_0001
Example 6 and Comparative Example 6
Beispiel 6 wurde entsprechend dem Beispiel 3 durchgeführt, wobei als Katalysator BuMe4CpTiF3 verwendet wurde. Das Vergleichsbeispiel 6 wurde entsprechend dem Beispiel 3 durchgeführt, wobei ais Katalysator BuMe4CpTiCI3 verwendet wurde.Example 6 was carried out in accordance with Example 3, BuMe 4 CpTiF 3 being used as catalyst. Comparative example 6 was carried out in accordance with example 3, using BuMe 4 CpTiCI 3 as catalyst.
Aus der nachstehenden aufgeführten Tabelle 6 gehen die Polymerisationsaktivitäten der im Beispiel 6 und Vergleichsbeispiel 6 eingesetzten Katalysatoren und die charakteristischen Daten der im Beispiel 6 und Vergleichsbeispiel 6 erhaltenen Polymere hervor.Table 6 below shows the polymerization activities of the catalysts used in Example 6 and Comparative Example 6 and the characteristic data of the polymers obtained in Example 6 and Comparative Example 6.
Tabelle 6Table 6
Figure imgf000020_0001
Beispiele 7, 8 und 9
Figure imgf000020_0001
Examples 7, 8 and 9
Beispiele 7, 8 und 9 wurden entsprechend dem Beispiel 3 durchgeführt, wobei als Katalysatoren Cp*2TiF, Cp*TiF2(OCOC6F5) und Cp*TiF2(OCOCF3) verwendet wurden.Examples 7, 8 and 9 were carried out in accordance with Example 3, the catalysts used being Cp * 2 TiF, Cp * TiF 2 (OCOC 6 F 5 ) and Cp * TiF 2 (OCOCF 3 ).
Aus der nachstehenden aufgeführten Tabelle 7 gehen die Polymerisationsaktivitäten der in Beispielen 7, 8 und 9 eingesetzten Katalysatoren und die charakteristischen Daten der erhaltenen Polymere hervor.Table 7 below shows the polymerization activities of the catalysts used in Examples 7, 8 and 9 and the characteristic data of the polymers obtained.
Tabelle 7Table 7
Figure imgf000021_0001
Figure imgf000021_0001
a) Cp = Cyclopentadienyl, Cp* = Pentamethylcyclopentadienyl, Me = methyl, Et = ethyl, Pr = propyl und Bu = butyl b) Polymerisationstemperatur c) Polymerisationszeit d) Ausbeute an syndiotaktischem Polystyrol βl Polymerisationsaktivität des Katalysatorsystems in Ausbeute syndiotaktischen Polystyrols (sPS) in kg bezogen auf die Stoffmenge der a) Cp = cyclopentadienyl, Cp * = pentamethylcyclopentadienyl, Me = methyl, Et = ethyl, Pr = propyl and Bu = butyl b) polymerization temperature c) polymerization time d) yield of syndiotactic polystyrene βl polymerization activity of the catalyst system in yield syndiotactic polystyrene (sPS) in kg based on the amount of substance
Titanverbindung in mol und bezogen auf die Polymerisationszeit in h:Titanium compound in mol and based on the polymerization time in h:
(kg sPS/mol Ti • h) f) Schmelzpunkt(e) des Polystyrols aus der 2. Aufheizkurve des DSC(kg sPS / mol Ti • h) f) Melting point (s) of the polystyrene from the 2nd heating curve of the DSC
(differential scanning calorimetry) gl Massenmittel der Molekularmasse des Polystyrols, dividiert durch 1000, bestimmt durch GPC (gel permeation chromatography) h) Zahlenmittel der Molekularmasse des Polystyrols, dividiert durch 1000, bestimmt durch GPC (gel permeation chromatography) '' Polydispersität des Polystyrols, bestimmt durch GPC (gel permeation chromatography) '' Konzentration der Titanverbindung in mol/l k) Konzentration an Methylaluminoxan in mol/l (differential scanning calorimetry) gl mass average molecular weight of the polystyrene divided by 1000, determined by GPC (gel permeation chromatography) h) number average molecular weight of the polystyrene divided by 1000, determined by GPC (gel permeation chromatography) '' polydispersity of the polystyrene, determined by GPC (gel permeation chromatography) '' concentration of the titanium compound in mol / l k) concentration of methylaluminoxane in mol / l

Claims

Patentansprüche claims
1. Katalysatorkomponente für die Polymerisation von Olefinen, enthaltend mindestens eine Verbindung der allgemeinen Formel (I):1. Catalyst component for the polymerization of olefins, comprising at least one compound of the general formula (I):
Ra„M1 Rb m (I),R a „M 1 R b m (I),
worinwherein
M1 = Ti, Zr oder Hf ist,M 1 = Ti, Zr or Hf,
Ra = C5 (R1 , R2, R3, R,4 R5) oder C6 (R1 , R2, R3, R4, R5, R6) ist, wobei R1 , R2, R3, R4, R5 und R6 gleich oder verschieden und ein Wasserstoffatom, eine C^C^-Alkylgruppe, eine CpCTQ-Alkoxygruppe, eine C.,-C10-Fluoralkylgruppe, eine C6-C20-Arylgruppe, eine C6-C10-Aryloxygruppe, eine C2- C10-Alkenylgruppe, eine C6-C10-Fluorarylgruppe, eine C7- C40-Arylalkylgruppe, eine C7-C40-Alkylarylgruppe, eine C8- C40-Arylalkenylgruppe, eine Silyl-, eine Germylgruppe bedeuten oder benachbarte Reste R1 , R2, R3, R4, R5 und R6 mit den sie verbindenden Atomen ein Ringsystem bilden,R a = C 5 (R 1 , R 2 , R 3 , R, 4 R 5 ) or C 6 (R 1 , R 2 , R 3 , R 4 , R 5 , R 6 ), where R 1 , R 2 , R 3 , R 4 , R 5 and R 6 the same or different and a hydrogen atom, a C ^ C ^ alkyl group, a CpCT Q alkoxy group, a C., - C 10 fluoroalkyl group, a C 6 -C 20 Aryl group, a C 6 -C 10 aryloxy group, a C 2 - C 10 alkenyl group, a C 6 -C 10 fluoroaryl group, a C 7 - C 40 arylalkyl group, a C 7 -C 40 alkylaryl group, a C 8 - C 40 arylalkenyl group, a silyl or a germyl group or neighboring radicals R 1 , R 2 , R 3 , R 4 , R 5 and R 6 form a ring system with the atoms connecting them,
Rb = ein Fluoratom wenn m = 1 ist, mindestens ein Fluoratom wenn m > 1 ist und sein kann gleich oder verschieden mindestens ein Wasserstoffatom, eine C,-C20- Alkylgruppe, eine C.,-C10-Alkoxygruppe, eine
Figure imgf000023_0001
Fluoralkylgruppe, eine C6-C20-Arylgruppe, eine C6-C10- Aryloxygruppe, eine C2-C10-Alkenylgruppe, eine C6-C10- Fluorarylgruppe, eine C7-C40-Arylalkylgruppe, eine C7-C40- Aikylarylgruppe, oder eine C8-C40-Arylalkenylgruppe eine OH-Gruppe, eine NR7 2- oder SR8-Gruppe, wobei R7 und R8 eine C1-C20-Alkylgruppe, eine C^C^- Alkoxygruppe, eine C.,-C10-Fluoralkylgruppe, eine C6-C20- Arylgruppe, eine C6-C10-Aryloxygruppe, eine C2-C10- Alkenylgruppe, eine C6-C10-Fluorarylgruppe, eine C7-C40- Arylalkylgruppe, eine C7-C40-Alkylarylgruppe, eine C8-C40- Arylalkenylgruppe, eine Silylgruppe, eine Germylgruppe oder ein Halogenatom bedeuten, eine -OC(O)F, eine -OC(O)CRc 3, eine -OC(O)C5Rd 4 oder eine -OC(O)C6Re 5 Gruppe ist wobei Rc, Rd und Re mindestens ein Fluoratom bedeuten und Rc, Rd und Re sein können gleich oder verschieden mindestens ein Wasserstoffatom, eine Cλ-C2Q- Alkylgruppe, eine
Figure imgf000024_0001
Fluoralkylgruppe, eine C6-C20-Arylgruppe, eine C6-C10- Aryloxygruppe, eine C2-C10-Alkenylgruppe, eine C6-C10- Fluorarylgruppe, eine C7-C40-Arylalkylgruppe, eine C7-C40- Alkylarylgruppe, eine C8-C40-Arylalkenylgruppe eine OH- Gruppe, eine NR7 2- oder SR8-Gruppe, eine Silylgruppe, eine Germylgruppe oder ein Halogenatom, m und n ganze Zahlen sind, m + n = 2 bis 4 ist und m mindestens 1 ist.R b = a fluorine atom if m = 1, at least one fluorine atom if m> 1 and can be the same or different at least one hydrogen atom, a C, -C 20 alkyl group, a C., - C 10 alkoxy group, a
Figure imgf000023_0001
Fluoroalkyl group, a C 6 -C 20 aryl group, a C 6 -C 10 aryloxy group, a C 2 -C 10 alkenyl group, a C 6 -C 10 fluoroaryl group, a C 7 -C 40 arylalkyl group, a C 7 -C 40 - aikylaryl group, or a C 8 -C 40 arylalkenyl group an OH group, an NR 7 2 or SR 8 group, where R 7 and R 8 are a C 1 -C 20 alkyl group, a C ^ C ^ - alkoxy group, a C, -C 10 fluoroalkyl group, a C 6 -C 20 - Aryl group, a C 6 -C 10 aryloxy group, a C 2 -C 10 alkenyl group, a C 6 -C 10 fluoroaryl group, a C 7 -C 40 arylalkyl group, a C 7 -C 40 alkylaryl group, a C 8 -C 40 - arylalkenyl group, a silyl group, a germyl group or a halogen atom, an -OC (O) F, an -OC (O) CR c 3 , an -OC (O) C 5 R d 4 or an -OC ( O) C 6 R e 5 group where R c , R d and R e represent at least one fluorine atom and R c , R d and R e may be the same or different at least one hydrogen atom, a C λ -C 2Q alkyl group, a
Figure imgf000024_0001
Fluoroalkyl group, a C 6 -C 20 aryl group, a C 6 -C 10 aryloxy group, a C 2 -C 10 alkenyl group, a C 6 -C 10 fluoroaryl group, a C 7 -C 40 arylalkyl group, a C 7 -C 40 - alkylaryl group, a C 8 -C 40 arylalkenyl group, an OH group, an NR 7 2 or SR 8 group, a silyl group, a germyl group or a halogen atom, m and n are integers, m + n = Is 2 to 4 and m is at least 1.
2. Katalysatorkomponente nach Anspruch 1 , enthaltend mindestens eine2. Catalyst component according to claim 1, containing at least one
Verbrückung R9 zwischen mindestens zwei Resten Ra, R9 ist bevorzugtBridging R 9 between at least two radicals R a , R 9 is preferred
1 0 R ι o R ι o R ι o1 0 R ι o R ι o R ι o
R 1 0 R 1 0
II.
- 0 - KT - 0 c — 0 — M — — C — M 2 —- 0 - KT - 0 c - 0 - M - - C - M 2 -
1 1 t 1 1 1 1 I t 1
Figure imgf000025_0001
1 1 t 1 1 1 1 I t 1
Figure imgf000025_0001
10 10 R 1010 10 R 10
C - C -C - C -
11 11 1111 11 11
-•0- • 0
/» /AI*' -G«-. -0- ■ %-. ^:so. /SO-, / NR' \ /CO. ^PR,D td«r /B(0)R'/ "/ AI * '-G" -. -0- ■ % -. ^: so. / SO-, / NR '\ / CO. ^ PR , D td «r / B (0) R '
wobei R10 und R11 gleich oder verschieden sind und ein Wasserstoffatom, ein Halogenatom oder eine C^C^-kohlenstoff haltige Gruppe ist wie eine CpC^-Alkyl-, eine C.,-C10-Fluoralkyl-, eine C-,- C10-Alkoxy-, eine C6-C14-Aryl-, eine C6-C10-Fluoraryl-, eine C6-C10- Aryloxy-, eine C2-C10-Alkenyl-, eine C7-C40-Arylalkyl-, eine C7-C40- Alkylaryl-, oder eine C8-C40-Arylalkenylgruppe oder R10 und R11 jeweils mit den sie verbindenden Atomen einen oder mehrere Ringe bilden und x eine ganze Zahl von Null bis 18 ist, M2 Silizium, Germanium oder Zinn ist, R9 kann auch zwei Einheiten der Formel (I) miteinander verknüpfen.where R 10 and R 11 are the same or different and is a hydrogen atom, a halogen atom or a C ^ C ^ carbon-containing group such as a CpC ^ alkyl, a C, -C 10 fluoroalkyl, a C, - C 10 alkoxy, a C 6 -C 14 aryl, a C 6 -C 10 fluoroaryl, a C 6 -C 10 aryloxy, a C 2 -C 10 alkenyl, a C 7 -C 40 arylalkyl, a C 7 -C 40 alkylaryl, or a C 8 -C 40 arylalkenyl group or R 10 and R 11 each form one or more rings with the atoms connecting them and x is an integer of zero to 18, M 2 is silicon, germanium or tin, R 9 can also link two units of the formula (I) to one another.
3. Katalysatorsystem enthaltend mindestens eine Katalysatorkomponente und mindestens eine organische Bor- und/oder mindestens eine organische Aluminium- und/oder mindestens eine organische Zinnverbindung. 3. A catalyst system containing at least one catalyst component and at least one organic boron and / or at least one organic aluminum and / or at least one organic tin compound.
4. Katalysatorsystem nach Anspruch 3, erhältlich durch Inkontaktbringen mindestens einer Katalysatorkomponente mit mindestens einer organischen Bor- und/oder mindestens einer organische Aluminium- und/oder mindestens einer organische Zinnverbindung.4. A catalyst system according to claim 3, obtainable by contacting at least one catalyst component with at least one organic boron and / or at least one organic aluminum and / or at least one organic tin compound.
5. Katalysatorsystem nach Anspruch 3 oder 4, enthaltend mindestens einen anorganischen und/oder organischen Träger.5. A catalyst system according to claim 3 or 4, containing at least one inorganic and / or organic support.
6. Polymer und/oder Copolymer, erhältlich durch Polymerisation mit einem Katalysatorsystem nach den Ansprüchen 3 bis 5.6. polymer and / or copolymer, obtainable by polymerization with a catalyst system according to claims 3 to 5.
7. Polymer und/oder Copolymer von 1 -Alkenen und Vinylaromaten, erhältlich durch Polymerisation mit einem Katalysatorsystem nach den Ansprüchen 3 bis 5.7. polymer and / or copolymer of 1-alkenes and vinyl aromatics, obtainable by polymerization with a catalyst system according to claims 3 to 5.
8. Syndiotaktisches Polymer, erhältlich durch Polymerisation mit einem Katalysatorsystem nach den Ansprüchen 3 bis 5.8. syndiotactic polymer obtainable by polymerization with a catalyst system according to claims 3 to 5.
9. Syndiotaktisches Polystyrol, erhältlich durch Polymerisation mit einem Katalysatorsystem nach den Ansprüchen 3 bis 5.9. syndiotactic polystyrene, obtainable by polymerization with a catalyst system according to claims 3 to 5.
10. Verfahren zur Polymerisation und/oder Copolymerisation mit einem Katalysatorsystem nach den Ansprüchen 3 bis 5.10. A method for polymerization and / or copolymerization with a catalyst system according to claims 3 to 5.
1 1 . Verfahren nach Anspruch 10 zur Polymerisation und/oder Copolymerisation von 1 -Alkenen und Vinylaromaten.1 1. A method according to claim 10 for the polymerization and / or copolymerization of 1-alkenes and vinyl aromatics.
12. Verfahren nach Anspruch 10 oder 1 1 zur Polymerisation von Styrol zu syndiotaktischem Polystyrol. 12. The method according to claim 10 or 1 1 for the polymerization of styrene to syndiotactic polystyrene.
13. Verwendung eines Katalysatorsystems zur Herstellung eines Polymers und/oder Copolymers, besonders zur Polymerisation und/oder Copolymerisation von 1-Alkenen und Vinylaromaten, ganz besonders zur Polymerisation von Styrol. 13. Use of a catalyst system for the production of a polymer and / or copolymer, in particular for the polymerization and / or copolymerization of 1-alkenes and vinylaromatics, very particularly for the polymerization of styrene.
PCT/EP1996/003563 1995-08-18 1996-08-13 Catalyst constituents and catalyst system with a high degree of polymerisation activity for the production of polymers WO1997007141A1 (en)

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WO1999029740A1 (en) * 1997-12-09 1999-06-17 Union Carbide Chemicals & Plastics Technology Cor Poration Unbridged monocyclopentadienyl metal complex catalyst and a process for polyolefin production
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WO1998036004A1 (en) * 1997-02-17 1998-08-20 Bayer Aktiengesellschaft Novel catalyst system, the use thereof in the polymerization of dienes in a solution, suspension and vapour phase and the use of diene rubbers produced therewith
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WO1999029740A1 (en) * 1997-12-09 1999-06-17 Union Carbide Chemicals & Plastics Technology Cor Poration Unbridged monocyclopentadienyl metal complex catalyst and a process for polyolefin production
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WO2001002447A2 (en) * 1999-07-02 2001-01-11 Buna Sow Leuna Olefinverbund Gmbh Catalyst composition and method for the production of syndiotactic styrole polymers
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JP2003505543A (en) * 1999-07-14 2003-02-12 バイエル アクチェンゲゼルシャフト Catalyst systems based on fluorine-containing metal complexes
US6303718B1 (en) 1999-09-17 2001-10-16 Bayer Aktiengesellschaft Composition based on fluorine-containing metal complexes
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US6943134B2 (en) 2002-09-04 2005-09-13 Univation Technologies, Llc Bimodal polyolefin production process and films therefrom
US6884748B2 (en) 2002-09-04 2005-04-26 Univation Technologies, Llc Process for producing fluorinated catalysts
US6875828B2 (en) 2002-09-04 2005-04-05 Univation Technologies, Llc Bimodal polyolefin production process and films therefrom
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