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WO1998006759A9 - Catalyseurs zwitterion ansa metallocene du groupe iv pour la polymerisation d'alpha-olefines - Google Patents

Catalyseurs zwitterion ansa metallocene du groupe iv pour la polymerisation d'alpha-olefines

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Publication number
WO1998006759A9
WO1998006759A9 PCT/US1997/013793 US9713793W WO9806759A9 WO 1998006759 A9 WO1998006759 A9 WO 1998006759A9 US 9713793 W US9713793 W US 9713793W WO 9806759 A9 WO9806759 A9 WO 9806759A9
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group
substituted
unsubstituted
alkyl
aryl
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PCT/US1997/013793
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WO1998006759A1 (fr
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Priority to EP97938137A priority Critical patent/EP0920455B1/fr
Priority to AU40532/97A priority patent/AU4053297A/en
Priority to DE69723084T priority patent/DE69723084T2/de
Publication of WO1998006759A1 publication Critical patent/WO1998006759A1/fr
Publication of WO1998006759A9 publication Critical patent/WO1998006759A9/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Definitions

  • ZAM Group IV Zwitterion Ansa Metallocene (ZAM) Catalysts For Alpha-Olefin Polymerization
  • the present invention generally relates to olefin polymerization catalysts, and more specifically to single component metallocene catalysts for ⁇ -olefin polymerization.
  • catalysts require an anionic co-catalyst (or a catalyst activator) , typically perfluorophenylborates or methyl aluminoxane (MAO) , to generate the catalytically active cationic fourteen electron d° species .
  • anionic co-catalyst typically perfluorophenylborates or methyl aluminoxane (MAO)
  • MAO-based systems predominate in industrial applications.
  • MAO must be present in large molar excess (200-2000 times that of the metallocene catalyst) , its presence accounts for over 50% of the cost of the catalytic system. In addition to the increased expense, little is known about MAO's structure or role in the polymerization reaction. Moreover, because MAO may also provide an additional route for chain termination (via chain transfer to the trimethyl aluminum) , this complicates the design of more selective catalysts.
  • Another approach is to incorporate a counter anion for a Group IV catalyst directly into the ligand.
  • Jordan, et al . (Crowther, et al . , J. Am . Chem. Soc . 113:1455 (1991)) prepared catalyst in which one cyclopentadienyl (Cp) ligand is replaced by a dianionic dicarbolide ligand.
  • Cp cyclopentadienyl
  • the resulting complex was expected to be capable of ⁇ -olefin polymerization.
  • these complexes readily undergo ⁇ - elimination, have low activity, and only oligomerize polypropylene.
  • Figure 1 illustrates the result of energy calculations comparing a zwitterion ansa metallocene (ZAM) catalyst with a standard Ziegler-Natta catalyst for each step of olefin polymerization.
  • ZAM zwitterion ansa metallocene
  • Figure 2 illustrates transition state enthalpies for two ZAM catalysts and a standard Ziegler-Natta catalyst .
  • ZAM zwitterion ansa metallocene
  • M is selected from a group consisting of Group III, Group IV, Group V, and Group VI elements
  • E is boron or aluminum
  • R x and R 2 are each independently selected from a group consisting of hydrogen, fluorine, substituted or unsubstituted C x to C 10 alkyl, substituted or unsubstituted to C 6 to C 15 aryl, and substituted and unsubstituted C x to C 10 alkoxy;
  • R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , and R l ⁇ are each independently selected from a group consisting of hydrogen, substituted or unsubstituted C x to C 10 alkyl, substituted or unsubstituted C to C 10 alkoxy, substituted or unsubstituted C 6 to C 15 aryl, substituted or unsubstituted C 3 to C 10 cycloalkyl, and Si(R 12 ) 3 where R 12 is selected from the group consisting of C- L to C 10 alkyl, C 6 to C 15 aryl, or C 3 to C 10 cycloalkyl; and,
  • R 7 is selected from a group consisting of hydrogen, methyl, tert-butyl, benzyl, phenyl, hydride, and Si(R 13 ) 3 where R 13 is selected from a group consisting of C ⁇ to C 10 alkyl, C 6 to C 15 aryl, and C 3 to C 10 cyclolalkyl .
  • each pair of adjacent radicals on the cyclopentadienyl rings (e.g., R 4 and R 5 or R 10 and R 1X ) together may also form a cyclic group having 4 to 15 carbon atoms which in turn may be further substituted.
  • M is a Group IV metal
  • R and R 2 are each an electron withdrawing group
  • R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , and R l are each selected from a group consisting of hydrogen, methyl, isopropyl, tert-butyl and trimethylsilyl .
  • M is zirconium.
  • the invention further includes a method for polymerizing olefins comprising the step of contacting an olefin with a catalyst of the type described above.
  • the olefin may be a C 3 -C 10 ⁇ -olefin, and the olefin may be contacted with the catalyst in the presence of a solvent .
  • the catalysts of the present invention are zwitterion ansa metallocenes that are referred to as ZAM catalysts.
  • the inventive catalysts eliminates the need for a counterion like MAO while retaining or improving most of the various kinetic steps in olefin polymerization over prior art Ziegler-Natta catalysts .
  • ZAM catalysts are of the general formula:
  • M is selected from a group consisting of Group III, Group IV, Group V, and Group VI elements;
  • E is boron or aluminum;
  • R ⁇ and R 2 are each independently selected from a group consisting of hydrogen, fluorine, substituted or unsubstituted C ⁇ to C 10 alkyl, substituted or unsubstituted to C 6 to C 15 aryl, and substituted and unsubstituted C to C 10 alkoxy;
  • R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , and R ⁇ are each independently selected from a group consisting of hydrogen, substituted or unsubstituted C-_ to C 10 alkyl, substituted or unsubstituted C-_ to C 10 alkoxy, substituted or unsubstituted C 6 to C 15 aryl, substituted or unsubstituted C 3 to C 10 cycloalkyl, and Si(R 12 ) 3 where R 12 is selected from the group consisting of C to C 10 alkyl, C 6 to C 15 aryl, or C 3 to C 10 cycloalkyl; and, R 7 is selected from a group consisting of hydrogen, methyl, tert-butyl, benzyl, phenyl, hydride, and Si(R 13 ) 3 where R 13 is selected from a group consisting of C to C 10 alkyl, C 6 to C 15 aryl, and C 3 to C 10
  • each pair of adjacent radicals on the cyclopentadienyl rings may also form a cyclic group having 4 to 15 carbon atoms which in turn may be further substituted.
  • Examples of compounds wherein one or more pairs of adjacent radicals form cyclic ring include but are not limited to:
  • R-_ and R 2 are each a group which increases the electrophilicity of the metal center.
  • suitable groups include but are not limited to F, C 6 F 5 , and CF 3 .
  • M is a Group IV metal
  • R 3 3,' R 4 ,' R5e,' R ⁇ 6 6,' R ⁇ a 8#' R ⁇ 9' R 10' and R ⁇ l are each selected from a group consisting of hydrogen, methyl, isopropyl, tert-butyl and trimethylsilyl .
  • M is zirconium.
  • E is boron or aluminum
  • R r and R 2 are each independently selected from a group consisting of hydrogen, fluorine, substituted or unsubstituted C ⁇ to C 10 alkyl, substituted or unsubstituted to C 6 to C 15 aryl, and substituted and unsubstituted C to C 10 alkoxy;
  • R 3 , R 4 , R 5 , and R 6 are each independently selected from a group consisting of hydrogen, substituted or unsubstituted C to C 10 alkyl, substituted or unsubstituted C-, ⁇ to C 10 alkoxy, substituted or unsubstituted C 6 to C 15 aryl, substituted or unsubstituted C 3 to C 10 cycloalkyl, and Si(R 9 ) 3 where R 9 is selected from the group consisting of C to C 10 alkyl, C 6 to C 15 aryl, or C 3 to C 10 cycloalkyl, wherein each pair of adjacent radicals together also may form a substituted or unsubstituted cyclic group having 4 to 15 carbons;
  • R 7 is selected from a group consisting of hydrogen, substituted or unsubstituted C to C 10 alkyl, substituted or unsubstituted C x to C 10 alkoxy, substituted or unsubstituted C 6 to C 15 aryl, substituted or unsubstituted C 3 to C 10 cycloalkyl, and Si(R 10 ) 3 where R 10 is selected from the group consisting of C x to C 10 alkyl, C 6 to C 15 aryl, or C 3 to C 10 cycloalkyl; and,
  • R 8 is selected from a group consisting of hydrogen, methyl, tert-butyl, benzyl, phenyl, hydride, and Si(R 11 ) 3 where R x is selected from a group consisting of C to C 10 alkyl, C 6 to C 15 aryl, and C 3 to C 10 cyclolalkyl .
  • R 7 is tert-butyl or trimethyl-silyl .
  • These compounds are variations of traditional metallocene catalysts and are generally referred to as mono-Cp "constrained- geometry catalysts" (or CGC) .
  • CGC constrained- geometry catalysts
  • the invention further includes a method for polymerizing olefins comprising the step of contacting an olefin with a catalyst of the types described above.
  • the olefin may be a C 3 -C 10 ⁇ -olefin, and the olefin may be contacted with the catalyst in the presence of a solvent .
  • the constrained-geometry embodiment of the present invention may be synthesized by known methods in the art, including but not limited to the protocol described by Organometallics, 9 : 866-869 (1990) which is incorporated herein by reference.
  • the metallocene catalysts of the present invention may also be prepared by a variety of methods known in the art including the protocol described below. Although the protocol is for the preparation of (C 6 F 5 ) 2 B (C 5 H 4 ) 2 ZrCH 3 , persons skilled in the art would readily know how to adapt the protocol for the various inventive embodiments.
  • DFT Density Functional Theory
  • the Zr was described with the LACVP Hay Wadt effective core potential (ECP) to replace the core electrons [leaving the (4s) 2 (4p) 6 [ (4d) (5s) (5p)] 4 electrons to be described explicitly] and using the standard double zeta contraction.
  • ECP effective core potential
  • the results of the insertion reaction are summarized in Figure 1 which displays the energies along the reaction coordinates for ZAM I and control II.
  • Figure 1 illustrates, the standard cationic metallocene binds ethylene exothermically by approximately 23 kcal/mol while the corresponding ZAM binds exothermically by about 16 kcal/mol.
  • the insertion barrier for the cationic metallocene ranges from about 6-10 kcal/mol while ZAM has an insertion barrier of just less than 3 kcal/mol.
  • the remaining energies of the ZAM catalyst were consistent with the energies of the cationic catalyst at the same level of theory.
  • the energetics for the insertion reaction for ZAM I, ZAM III and control II are summarized in figure 2.
  • the results for ZAM I and control II were calculated using DLDA-B3LYP and are consistent with the results using NLDA-GGAII.

Abstract

Des catalyseurs métallocènes à un seul composant pour la polymérisation d'α-oléfine sont décrits. Les catalyseurs métallocènes cationiques de l'art antérieur requièrent un co-catalyseur anionique séparé tel que l'aluminoxane de méthyl (MAO). Cependant, en raison de leur fonctionnalité 'intégrée' co-catalyseur anionique, les catalyseurs zwittérion ansa métallocène (ZAM) n'ont pas besoin d'un co-catalyseur anionique séparé.
PCT/US1997/013793 1996-08-09 1997-08-08 Catalyseurs zwitterion ansa metallocene du groupe iv pour la polymerisation d'alpha-olefines Ceased WO1998006759A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP97938137A EP0920455B1 (fr) 1996-08-09 1997-08-08 Catalyseurs zwitterion ansa metallocene du groupe iv pour la polymerisation d'alpha-olefines
AU40532/97A AU4053297A (en) 1996-08-09 1997-08-08 Group iv zwitterion ansa metallocene (zam) catalysts for alpha-olefin polymerization
DE69723084T DE69723084T2 (de) 1996-08-09 1997-08-08 Katalysator auf basis eines zwitterionischen ansa metallocens der gruppe iv für die polymerisation von alpha-olefinen

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US2439596P 1996-08-09 1996-08-09
US60/024,395 1996-08-09
US08/907,395 1997-08-07
US90739598A 1998-01-01 1998-01-01

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WO1998006759A1 WO1998006759A1 (fr) 1998-02-19
WO1998006759A9 true WO1998006759A9 (fr) 1998-06-25

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US6891004B2 (en) 2000-03-14 2005-05-10 Denki Kagaku Kogyo Kabushiki Kaisha Transition metal catalyst component for polymerization, and method for producing a polymer by means thereof
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US8148481B2 (en) 2008-12-18 2012-04-03 Univation Technologies, Llc Method for seed bed treatment for a polymerization reaction
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US9650453B2 (en) 2012-12-28 2017-05-16 Univation Technologies, Llc Methods of integrating aluminoxane production into catalyst production
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JP6621845B2 (ja) 2015-05-08 2019-12-18 エクソンモービル ケミカル パテンツ インコーポレイテッド 重合方法
WO2018063764A1 (fr) 2016-09-27 2018-04-05 Exxonmobil Chemical Patents Inc. Procédé de polymérisation
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WO2018118155A1 (fr) 2016-12-20 2018-06-28 Exxonmobil Chemical Patents Inc. Procédé de polymérisation
US11591417B2 (en) 2017-12-13 2023-02-28 Exxonmobil Chemical Patents Inc. Deactivation methods for active components from gas phase polyolefin polymerization processes
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