WO2012133936A1 - Catalyst for producing ethylene-based polymer and method for producing the same - Google Patents

Catalyst for producing ethylene-based polymer and method for producing the same Download PDF

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WO2012133936A1
WO2012133936A1 PCT/JP2012/059295 JP2012059295W WO2012133936A1 WO 2012133936 A1 WO2012133936 A1 WO 2012133936A1 JP 2012059295 W JP2012059295 W JP 2012059295W WO 2012133936 A1 WO2012133936 A1 WO 2012133936A1
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titanium trichloride
titanium
tert
silyl
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Takayuki Hishiya
Takahiro Hino
Taichi Senda
Masaya Tanimoto
Yasutoyo Kawashima
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • 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
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • 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
    • 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
    • C08F4/65927—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 bridged

Definitions

  • the present invention relates to a catalyst for producing an ethylenic polymer and a method for producing an ethylenic polymer using the catalyst.
  • Linear low density polyethylene, linear ultra low density polyethylene, and the like, are known as ethylenic polymers having short chain branches.
  • the physical properties of ethylenic polymers vary depending on the- structures of the short chain branches. For example, the strength of an ethylenic polymer having a butyl branch is known to be higher than the strength of an ethylenic polymer having an ethyl branch. Furthermore, it is known that the melting point of an ethylenic polymer having a larger amount of butyl branches is lower than the melting point of an ethylenic polymer having a smaller amount of butyl branches.
  • Ethylenic polymers having short chain branches have been conventionally produced by using ethylene and a-oleftn as raw material monomers in the presence of a catalyst obtained by bringing a complex for olefin polymerization into contact with an activating co- catalyst component.
  • ethylenic polymers having an ethyl branch have been produced by copolymerizing ethylene with 1-butene
  • ethylenic polymers having a butyl branch have been produced by copolymerizing ethylene with 1-hexene.
  • Non Patent Literatures 1 and 2 a method for producing an ethylenic polymer having a butyl branch by using only ethylene as a raw material monomer in the presence of a catalyst obtained by simultaneously bringing dimethylsilylene(tert- butylamido)(tetramethylcyclopentadienyl)titanium dichloride (hereinafter, referred to as a "titanium complex 1”) as a titanium complex for olefin polymerization and [ 1-(1 -methyl- 1- phenylethyl)-cyclopentadienyl]titanium trichloride (hereinafter, referred to as a "titanium complex 2”) as a titanium complex for tnmerization of ethylene into contact with MMAO as an activating co-catalyst component in a reactor has been reported.
  • a catalyst obtained by simultaneously bringing dimethylsilylene(tert- butylamido)(tetramethylcyclopentadien
  • the Non Patent Literature 1 reports that when the reaction temperature is 45 to 50°C, the rate of a repeat unit derived from 1- hexene in an ethylenic polymer is extremely low as compared with the case where the reaction temperature is 25 to 30°C, and that when the reaction temperature is 70°C, no repeat unit derived from 1 -hexene is observed in an ethylenic polymer.
  • the Non Patent Literature 2 reports a method for producing an ethylenic polymer by using only ethylene as a raw material monomer in the presence of a catalyst obtained by simultaneously bringing rac-dimethylsilylene bis(2-methylbenz[e]indenyl)zirconium dichloride (hereinafter, referred to as a "zirconium complex 1 ”) as a zirconium complex for olefin polymerization and titanium complex 2 as the titanium complex for tnmerization of ethylene into contact with MMAO in a reactor.
  • zirconium complex 1 rac-dimethylsilylene bis(2-methylbenz[e]indenyl)zirconium dichloride
  • the problem to be solved by the present invention is to provide a catalyst capable of efficiently producing an ethylenic polymer having short chain branches even though only ethylene is used as a raw material monomer and to provide a method for producing an ethylenic polymer by the catalyst.
  • a first aspect of the present invention relates to a catalyst for producing an ethylenic polymer, which is prepared from a complex (I) represented by formula (1), (2-1) or (2-2), a complex for olefin polymerization, an activating co-catalyst component, and a carrier, wherein the complex (I) and the complex for olefin polymerization are supported by a carrier:
  • M 1 represents a transition metal atom of Group 4 of the periodic table of the elements
  • Cp represents a group having a cyclopentadiene-type anionic skeleton
  • J 1 represents an atom selected from Groups 13 to 16 of the periodic table of the elements
  • 1 and m each represent 1 or 0, and 1 + m is an integer equal to (the valence of J 1 - 2);
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , X 1 , X 2 and X 3 each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, or a disubstituted amino group, of R 1 , R 2 , R 3 , R 4 and R 5 , two groups bonded to the two adjoining carbon atoms may be bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded, R 6 and R 7 may be bonded to each other to form a ring together with J 1 to which they are bonded, and two roups of X 1 , X 2 and X 3 may be bonded to each other to form a ring together with M 1 ;
  • M 2 represents a transition metal atom of Group 4 of the periodic table of the elements
  • a 21 represents an oxygen atom, a nitrogen atom, a phosphorus atom or a sulfur atom
  • Z 1 is a group linking A 21 to N, in which the number of the shortest bonds linking A 21 to N is 4 to
  • a bond linking A 21 to Z 1 may be a double bond
  • R 21 , R 22 , R 23 , R 24 , R 25 and X 4 each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, or a disubstituted amino group, two or more groups of R 21 , R 22 , R 23 , R 24 and R 25 may be bonded to each other, the three X 4 groups each may be the same or different from each other, and two or more X 4 groups may be bonded to each other to form a ring together with M 2 ;
  • R 26 represents a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbylidene group, or a substituted hydrocarbylidene group, a bond linking R 26 to A 21 may be a double bond, and R 26 may be bonded to Z 1 ;
  • M 2 represents a transition metal atom of Group 4 of the periodic table of the elements
  • a 22 represents a nitrogen atom or a phosphorus atom
  • Z 2 is a group linking A 22 to N, and the number of the shortest bonds linking A 22 to N is 4 to 6;
  • R 21 , R 22 , R 23 , R 24 , R 25 and X 4 each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, or a disubstituted amino group, two or more groups of R 21 , R 22 , R 23 , R 2 and R 25 may be bonded to each other, the three X 4 groups may be the same or different from each other, and two or more X 4 groups may be bonded to each other to form a ring together with M 2 ; and
  • R 27 and R 28 represent a hydrogen atom, a halogen atom, a hydrocarbyl group, or a substituted hydrocarbyl group, and R 28 may be bonded to Z 2 .
  • a second aspect of the present invention relates to a method for producing an ethylenic polymer in which olefin including ethylene is polymerized by the catalyst for producing an ethylenic polymer.
  • the present invention can provide a catalyst capable of efficiently producing an ethylenic polymer having short chain branches even though only ethylene is used as a raw material monomer and a method for producing an ethylenic polymer by the catalyst.
  • polymerization includes not only homopolymerization but also copolymerization.
  • ethylenic polymer includes a homopolymer of ethylene and a copolymer of ethylene and another monomer.
  • the complex (I) can oligomerize ethylene by the complex (I) and the activating co-catalyst component to synthesize a-olefin. Oligomerization of ethylene means changing of ethylene into 2 to 20-mer compound, and the number of the carbon atoms of the a-olefin is 4 to 40.
  • the suitable complex is a complex capable of synthesizing at least one ⁇ -olefin selected from the group consisting of 1-butene, 1-hexene and 1-octene from ethylene, and more suitable complex is a complex capable of synthesizing 1-hexene from ethylene.
  • the complex (I) is a compound represented by any of formula (1), formula (2-1) mentioned later, and formula (2-1) mentioned later:
  • M 1 represents a transition metal atom of Group 4 of the periodic table of the elements
  • Cp represents a group having a cyclopentadiene-type anionic skeleton
  • J 1 represents an atom selected from Groups 13 to 16 of the periodic table of the elements
  • 1 and m each represent 1 or 0, and 1 + m is an integer equal to (the valence of J 1 - 2);
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , X 1 , X 2 and X 3 each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, or a disubstituted amino group, of R 1 , R 2 , R 3 , R 4 and R 5 , two groups bonded to the two adjoining carbon atoms may be bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded, R 6 and R 7 may be bonded to each other to form a ring together with J 1 to which they are bonded, and two groups of X 1 , X 2 and X 3 may be bonded to each other to form a ring together with M 1 .
  • Cp in formula (1) represents a group having a cyclopentadiene-type anionic skeleton, and examples thereof include a r
  • J 1 in formula (1) represents an atom selected from Groups 13 to 16 of the periodic table of the elements, and examples thereof include a boron atom, a carbon atom, a silicon atom, a nitrogen atom, a phosphorus atom, and an oxygen atom and a sulfur atom.
  • a carbon atom or a silicon atom Preferable example is a carbon atom or a silicon atom, and more preferable example is silicon atom.
  • 1 and m each represent 1 or 0, and 1 + m is an integer equal to (the valence of J 1 - 2).
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • a chlorine atom is preferable.
  • hydrocarbyl group examples include an alkyl group, an aryl group, and an aralkyl group. Furthermore, the number of the carbon atoms of the hydrocarbyl group is preferably 1 to 20, and more preferable 1 to 10.
  • alkyl group examples include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, a neopentyl group, an amyl group, a n-hexyl group, a heptyl group, a n-octyl group, a n- nonyl group, a n-decyl group, a n-dodecyl group, a n-tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group and a n-eicosyl group.
  • alkyl group examples include an alkyl group having 1 to 20 carbon atoms, more preferable examples include an alkyl group having 1 to 10 carbon atoms, and further preferable examples include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group and an amyl group.
  • aryl group examples include a phenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, a 2,3-xylyl group, a 2,4-xylyl group, a 2,5-xylyl group, a 2,6-xylyl group, a 3,4-xylyl group, a 3,5-xylyl group, a 2,3,4-trimethylphenyl group, a 2,3,5-trimethylphenyl group, a 2,3,6-trimethylphenyl group, a 2,4,6-trimethylphenyl group, a 3,4,5-trimethylphenyl group, a 2,3,4,5-tetramethylphenyl group, a 2,3,4,6-tetramethylphenyl group, a 2,3,5,6- tetramethylphenyl group, a pentamethylphenyl group, an ethylphenyl group, a diethylphenyl group, a n-(
  • aryl group examples include an aryl group having 6 to 20 carbon atoms, more preferable examples include an aryl group having 6 to 10 carbon atoms, further preferable examples include a phenyl group, a methylphenyl group, a dimethylphenyl group, a tnmethylphenyl group, a diethylphenyl group, particularly preferable examples include a phenyl group, a dimethylphenyl group, and a diethylphenyl group.
  • Examples of the aralkyl group include a benzyl group, a (2-methylphenyl)methyl group, a (3-methylphenyl)methyl group, a (4-methylphenyl)methyl group, a (2,3- dimethylphenyl)methyl group, a (2,4-dimethylphenyl)methyl group, a (2,5- dimethylphenyl)methyl group, a (2,6-dimethylphenyl)methyl group, a (3,4- dimethylphenyl)methyl group, a (3,5-dimethylphenyl)methyl group, a (2,3,4- trimethylphenyl)methyl group, a (2,3,5-trimethylphenyl)methyl group, a (2,3,6- trimethylphenyl)methyl group, a (3,4,5-trimethylphenyl)methyl group, a (2,4,6- trimethylphenyl)methyl group, a (2,3,4,5-trimethylphenyl)methyl group, a (2,4,6- trimethylphenyl
  • aralkyl group examples include an aralkyl group having 7 to 20 carbon atoms, more preferable examples of the aralkyl group include an aralkyl group having 7 to 10 carbon atoms, and further preferable example of the aralkyl group is a benzyl group.
  • halogenated alkyl group examples include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, a dibromomethyl group, a tribromomethyl group, a fluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, and a perfluorohexyl group.
  • the halogenated alkyl group is preferably a halogenated alkyl group having 1 to 20 carbon atoms, and more preferably a halogenated alkyl group having 1 to 10 carbon atoms.
  • halogenated aryl group examples include a fluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group, a pentafluorophenyl group, a chlorophenyl group, a bromophenyl group, and an iodophenyl group.
  • the halogenated aryl group is preferably a halogenated aryl group having 6 to 20 carbon atoms, and more preferably a halogenated aryl group having 6 to 10 carbon atoms.
  • halogenated aralkyl group examples include a group in which a part or all of the hydrogen atoms present in the above-mentioned aralkyl group are substituted with a halogen atom.
  • the halogenated aralkyl group is preferably a halogenated aralkyl group having 7 to 20 carbon atoms and more preferably a halogenated aralkyl group having 7 to 10 carbon atoms.
  • hydrocarbyloxy group examples include an alkoxy group, an aryloxy group, and an aralkyloxy group.
  • the number of carbon atoms of the hydrocarbyloxy group is preferably 1 to 20, and more preferably 1 to 10.
  • alkoxy group examples include a methoxy group, an ethoxy group, a n- propoxy group, an isopropoxy group, n-butoxy group, a sec-butoxy group, a tert-butoxy group, a n-pentyloxy group, a neopentyloxy group, a n-hexyloxy group, a n-octyloxy group, a n-nonyloxy group, a n-decyloxy group, a n-undecyloxy group, a n-dodecyloxy group, a tridecyloxy group, a tetradecyloxy group, a n-pentadecyloxy group, a hexadecyloxy group, a heptadecyloxy group, an octadecyloxy group, a nonadecyloxy group, and a n
  • the alkoxy group is preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 10 carbon atoms, and further preferably a methoxy group, an ethoxy group, and a tert-butoxy group.
  • aryloxy group examples include a phendxy group, a 2-methylphenoxy group, a 3-methylphenoxy group, a 4-methylphenoxy group, a 2,3-dimethylphenoxy group, a 2,4-dimethylphenoxy group, a 2,5-dimethylphenoxy group, a 2,6-dimethylphenoxy group, a 3,4- dimethylphenoxy group, a 3,5-dimethylphenoxy group, a 2,3,4-trimethylphenoxy group, a 2,3,5- trimethylphenoxy group, a 2,3,6-trimethylphenoxy group, a 2,4,5-trimethylphenoxy group, a 2,4,6-trimethylphenoxy group, a 3,4,5-trimethylphenoxy group, a 2,3,4,5-tetramethylphenoxy group, a 2,3,4,6-tetramethylphenoxy group, a 2,3,5,6-tetramethylphenoxy group, a
  • a preferable example of the aryloxy group is an aryloxy group having 6 to 20 carbon atoms, a more preferable example is an aryloxy group having 6 to 10 carbon atoms, and further preferable examples are a phenoxy group, a 2-niethylphenoxy group, a 3-methylphenoxy group, and a 4- methylphenoxy group.
  • aralkyloxy group examples include a benzyloxy group, a (2- methylphenyl)methoxy group, a (3-methylphenyl)methoxy group, a (4-methylphenyl)methoxy group, a (2,3-dimethylphenyl)methoxy group, a (2,4-dimethylphenyl)methoxy group, a (2,5- dimethylphenyl)methoxy group, a (2,6-dimethylphenyl)methoxy group, a (3,4- dimethylphenyl)methoxy group, a (3,5-dimethylphenyl)methoxy group, a (2,3,4- trimethylphenyl)methoxy group, a (2,3,5-trimethylphenyl)methoxy group, a (2,3,6- trimethylphenyl)methoxy group, a (2,4,5-trimethylphenyl)methoxy group, a (2,4,6- trimethylphenyl)methoxy
  • a preferable example of the aralkyloxy group is an aralkyloxy group having 7 to 20 carbon atoms, a more preferable example is an aralkyloxy group having 7 to 10 carbon atoms, and a further preferable example is a benzyloxy group.
  • the substituted hydrocarbyloxy group is a group in which one or more hydrogen atoms in the hydrocarbyloxy group are substituted with groups other than the hydrocarbyl group and/or a halogen atom.
  • examples thereof include halogenated hydrocarbyl groups such as a halogenated alkoxy group, a halogenated aryloxy group, and a halogenated aralkyloxy group.
  • the number of carbon atoms of the substituted hydrocarbyloxy group is preferably 1 to 20, and more preferably 1 to 10.
  • halogenated alkoxy group examples include a group in which a part or all of the hydrogen atoms present in the above-mentioned alkoxy group is substituted with a halogen atom.
  • halogenated alkoxy group examples include a halogenated alkoxy group having 1 to 20 carbon atoms and more preferable examples include a halogenated alkoxy group having 1 to 10 carbon atoms.
  • halogenated aryloxy group examples include a group in which a part or all of the hydrogen atoms present in the above-mentioned aryloxy group are substituted with a halogen atom.
  • halogenated aryloxy group examples include a halogenated aryloxy group having 6 to 20 carbon atoms and more preferable examples include a halogenated aryloxy group having 6 to 10 carbon atoms.
  • halogenated aralkyloxy group examples include a group in which a part or all of the hydrogen atoms present in the above-mentioned aralkyloxy group are substituted with a halogen atom.
  • halogenated aralkyloxy group examples include a halogenated aralkyloxy group having 7 to 20 carbon atoms and more preferable examples include a halogenated aralkyloxy group having 7 to 10 carbon atoms.
  • Examples of the substituted silyl group include a group represented by -Si(R 1 ) 3 , wherein the three R 12 groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and at least one of R 12 is a hydrocarbyl group or a halogenated hydrocarbyl group.
  • Examples of the hydrocarbyl group of R 12 include alkyl groups such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a n-pentyl group, a n-hexyl group, a cyclohexyl group, a n- heptyl group, a n-octyl group, a n-nonyl group, and a n-decyl group; and an aryl group such as a phenyl group.
  • halogenated hydrocarbyl group examples include a group in which a part or all of the hydrogen atoms present in these hydrocarbyl groups are substituted with a halogen atom.
  • the number of the carbon atoms of the hydrocarbyl group and the halogenated hydrocarbyl group is preferably 1 to 10. Furthermore, the total number of the carbon atoms of three R 12 is preferably 1 to 20, and more preferably 3 to 18.
  • Examples of the substituted silyl group include a monosubstituted silyl group having one hydrocarbyl group or halogenated hydrocarbyl group such as a methylsilyl group, an ethylsilyl group, and a phenylsilyl group, and groups in which a part or all of the hydrogen atoms in the hydrocarbyl group bonded to a silicon atom in the above-mentioned groups are substituted with a halogen atom; a disubstituted silyl group having two of hydrocarbyl groups and/or halogenated hydrocarbyl groups such as a dimethylsilyl group, a diethylsilyl group, and a diphenylsilyl group, and groups in which a part or all of the hydrogen atoms in the hydrocarbyl group bonded to a silicon atom in the above-mentioned groups are substituted with a halogen atom; and a trisubstituted silyl group
  • the substituted silyl group include a trisubstituted silyl group, and more preferable examples thereof include a trimethylsilyl group, a tert-butyldimethylsilyl group, a triphenylsilyl group, and groups in which a part or all of the hydrogen atoms in these groups are substituted with a halogen atom.
  • Examples of the disubstituted amino group include a group represented by - N(R 13 ) 2 , wherein the two R 13 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the two R 13 groups are bonded to each other to form a ring together with nitrogen atoms to which the two groups are bonded.
  • Examples of the hydrocarbyl group in R 13 include alkyl groups such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a n-pentyl group, a n-hexyl group, a cyclohexyl group, a n- heptyl group, a n-octyl group, a n-nonyl group, and a n-decyl group; and aryl groups such as a phenyl group.
  • halogenated hydrocarbyl group examples include a group in which a part or all of the hydrogen atoms present in these hydrocarbyl groups are substituted with a halogen atom.
  • the number of the carbon atoms of the hydrocarbyl group and the halogenated hydrocarbyl group is preferably 1 to 10 and more preferably 1 to 5. Furthermore, the total number of the carbon atoms of the two R 13 groups is preferably 2 to 20, and more preferably 2 to 10.
  • disubstituted amino group examples include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, a di-sec-butylamino group, a di-tert-butylamino group, a di-isobutylamino group, a tert- butyl isopropylamino group, a di-n-hexylamino group, a di-n-octylamino group, a di-n- decylamino group, a diphenylamino group, a bistrimethylsilylamino group, a bis-tert- butyldimethylsilylamino group, a pyrrolyl group, a pyrrolidinyl group, a piperidinyl group, a carbazolyl group, a dihydroin
  • disubstituted amino group examples include a dimethylamino group, a diethylamino group, a pyrrolidinyl group, a piperidinyl group, and groups in which a part or all of the hydrogen atoms are substituted with a halogen atom.
  • two groups bonded to the two adjoining carbon atoms may be bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded.
  • the ring examples include a cyclopropane ring, a cyclopropene ring, a cyclobutane ring, a cyclobutene ring, a cyclopentane ring, a cyclopentene ring, a cyclohexane ring, a cyclohexene ring, a cycloheptane ring, a cycloheptene ring, a cyclooctane ring, a cyclooctene ring, a benzene ring, a naphthalene ring, an anthracene ring, and saturated or unsaturated hydrocarbyl rings such as rings in which a hydrogen atom in these rings are substituted with a hydrocarbyl group having 1 to 20 carbon atoms.
  • R 6 and R 7 may be bonded to each other to form a ring together with J 1 to which they are bonded.
  • J 1 is a silicon atom
  • examples of the ring include a silacyclopropane ring, a silacyclobutane ring, a silacyclopentane ring, a silacyclohexane ring and saturated or unsaturated silahydrocarbyl rings in which a hydrogen atom in these rings is substituted with a hydrocarbyl group having 1 to 20 carbon atoms.
  • examples of the ring include a cyclopropane ring, a cyclopropene ring, a cyclobutane ring, a cyclobutene ring, a cyclopentane ring, a cyclopentene ring, a cyclohexane ring, a cyclohexene ring, a cycloheptane ring, a cycloheptene ring, a cyclooctane ring, a cyclooctene ring, a benzene ring, a naphthalene ring, an anthracene ring, and saturated or Unsaturated hydrocarbyl rings such as a ring in which a hydrogen atom in these rings is substituted with a hydrocarbyl group having 1 to 20 carbon atoms.
  • R l , R 2 , R 3 , R 4 , and R 5 are each preferably a hydrogen atom, a halogen atom, or a hydrocarbyl group having 1 to 20 carbon atoms, and more preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.
  • R 1 , R 2 , R 3 , R 4 and R 5 examples include the below-mentioned substructures for the substructural formula (3) in formula (1):
  • R 1 , R 2 , R 3 , R 4 and R 5 have the same meanings as in R 1 , R 2 , R 3 , R 4 and R 5 , respectively, in formula (1).
  • the examples include phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, tetramethylphenyl, pentamethylphenyl, ethylphenyl, diethylphenyl, tert-butylphenyl, di-tert- butylphenyl, tert-butylmethylphenyl, di(tert-butyl)methylphenyl, naphthyl, anthracenyl, chlorophenyl, dichlorophenyl, fluorophenyl, pentafluorophenyl, bis(tri£luoromethyl)phenyl, and methoxyphenyl.
  • preferable substructures are phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, and diethylphenyl.
  • R 6 and R 7 are each preferably a hydrogen atom, or a hydrocarbyl group having 1 to 20 carbon atoms, and more preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.
  • Examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, a phenyl group, a 4- methylphenyl group, a 3-methylphenyl group, a 2-methylphenyl group, a 3,5-dimethylphenyl group, a 3,5-diethylphenyl group, a 3,5-di-tert-butylphenyl group, a naphthyl group, and a benzyl group.
  • R 6 and R 7 have the same meanings as in R 6 and R 7 , respectively, in formula (1).
  • the examples include dimethylsilylene, diethylsilylene, ethylmethylsilylene, di(n- propyl)silylene, methyl(n-propyl)silylene, di(n-butyl)silylene, n-butylmethylsilylene, n- hexylmethylsilylene, methyl(n-octyl)silylene, n-decylmethylsilylene, methyl(n- octadecyl)silylene, cyclohexylmethylsilylene, cyclotetramethylenesilylene, diphenylsilylene, di(3,5-dimethylphenyl)silylene, di(3,5-diethylphenyl)silylene, and methylphenylsilylene.
  • Preferable examples of the substructure formula (4) include a substructure formula in which R 6 is a methyl group, R 7 is an alkyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a halogenated alkyl group having 2 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms; a substructure formula in which R 6 and R 7 are the same alkyl group having 2 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, halogenated alkyl group having 2 to 20 carbon atoms or aryl group having 6 to 20 carbon atoms; and a substructure formula in which R 6 and R 7 are different alkyl group having 2 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, halogenated alkyl group having 2 to 20 carbon atoms or aryl group having 6 to 20 carbon atoms.
  • substructures represented by these substructure formulae include dimethylsilylene, diethylsilylene, ethylmethylsilylene, n- butylmethylsilylene, cyclohexylmethylsilylene, cyclotetramethylenesilylene, diphenylsilylene, methylphenylsilylene, di(3,5-dimethylphenyl)silylene, di(3,5-diethylphenyl)silylene, and (3,5- dimethylphenyl)(3,5-di-tert-butylphenyl)silylene.
  • R 6 and R 7 have the same meanings as in R 6 and R 7 , respectively, in formula (1).
  • the examples include isopropylidene, 1-ethylpropylene, 1-methylpropylene, 1-n- propylbutylene, 1-methylbutylene, 1-n-butylpentylene, 1-methylpentylene, 1-methylheptylene, 1-methylnonylene, 1-methyldodecylene, 1-methylnonadecylene, 1-cyclohexylethylene, cyclotetramethylenemethylene, diphenylmethylene, 1-phenylethylene, di(3,5- dimethylphenyl)methylene, di(3,5-diethylphenyl)methylene, (3,5-dimethylphenyl)(3,5-di-tert- butylphenyl)methylene, di(3,5-diphenylphenyl)methylene, and di(3,5- dibenzylphenyl)methylene. [0055]
  • Preferable examples of the substructure formula (5) include a substructure formula in which R 6 is a methyl group, R 7 is an alkyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a halogenated alkyl group having 2 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms; a substructure formula in which R 6 and R 7 are the same alkyl group having 2 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, halogenated alkyl group having 2 to 20 carbon atoms or aryl group having 6 to 20 carbon atoms; and a substructure formula in which R 6 and R 7 are different alkyl group having 2 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, halogenated alkyl group having 2 to 20 carbon atoms or aryl group having 6 to 20 carbon atoms.
  • substructures represented by these substructure formulas include isopropylidene, 1-ethylpropylene, 1-methylpropylene, 1- methylpentylene, 1-cyclohexyl ethylene, cyclotetramethylenemethylene, diphenylmethylene, 1- phenylethylene, di(3,5-dimethylphenyl)methylene, di(3,5-diethylphenyl)methylene, and (3,5- dimethylphenyl)(3 , 5 -di-tert-butylphenyl)methylene.
  • X 1 , X 2 and X 3 are each preferably a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, or a substituted hydrocarbyloxy group, and more preferably a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a halogenated alkoxy group having 1 to 20 carbon atoms, a halogenated aryloxy group having 6 to 20 carbon atoms, and a halogenated aralkyloxy group having 7 to 20 carbon atoms.
  • the compound represented by formula (1) can be preferably a compound re resented by formula (1-2):
  • M 1 represents a transition metal atom of Group 4 of the periodic table of the elements
  • R ⁇ R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , X 1 , X 2 and X 3 each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, or disubstituted amino group, of R 1 , R 2 , R 3 , R 4 and R 5 , two groups bonded to the two adjoining carbon atoms may be bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded, R 6 and R 7 may be bonded to each other to form a ring together with a silicon atom to which they are bonded, of R 8 , R 9 , R 10 and R n , two groups bonded to the two adjoining carbon atoms may be
  • M 1 in formula (1-2) represents a transition metal atom of Group 4 of the periodic table of the elements; and examples thereof include a titanium atom, a zirconium atom and a hafnium atom. Among them, a titanium atom is preferable.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , X 1 , X 2 and X 3 have the same meanings as in R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , X 1 , X 2 and X 3 , respectively, in formula (1), and the meanings of a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a
  • hydrocarbyloxy group a substituted hydrocarbyloxy group, a substituted silyl group, and a disubstituted amino group
  • examples thereof and preferable embodiments thereof preferable atoms, preferable groups, the number of the carbon atoms of the preferable groups, and the like) are the same as the meanings thereof, the examples thereof, and preferable embodiments thereof described in formula (1).
  • R 8 , R 9 , R 10 , and R 11 each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, or a disubstituted amino group.
  • halogen atom a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group or a disubstituted amino group
  • examples thereof and preferable embodiments thereof are the same as the meanings thereof, the examples thereof, and preferable embodiments thereof described in formula (1).
  • the ring examples include a cyclopropane ring, a cyclopropene ring, a cyclobutane ring, a cyclobutene ring, a cyclopentane ring, a cyclopentene ring, a cyclohexane ring, a cyclohexene ring, a cycloheptane ring, a cycloheptene ring, a cyclooctane ring, a cyclooctene ring, a benzene ring, a naphthalene ring, an anthracene ring, and a saturated or unsaturated hydrocarbyl ring such as rings in which a hydrogen atom in these rings is substituted with a hydrocarbyl group having 1 to 20 carbon atoms.
  • R 1 , R 2 , R 3 , R 4 , and R 5 are preferably a hydrogen atom, a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms, and more preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms.
  • examples of preferable combination of R 1 , R 2 , R 3 , R 4 , and R 5 include substructures represented by the substructure formula (3) in formula (1).
  • preferable substructures are phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, and diethylphenyl.
  • R 6 and R 7 are preferably a hydrogen atom, and a hydrocarbyl group having 1 to 20 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms.
  • Examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, a phenyl group, a 4- methylphenyl group, a 3-methylphenyl group, a 2-methylphenyl group, a 3, 5 -dimethylphenyl group, a 3,5-diethylphenyl group, a 3,5-di-tert-butylphenyl group, a naphthyl group, and a benzyl group.
  • examples of preferable combination of R 6 and R 7 include substructures represented by the substructure formula (4) in formula (1).
  • Preferable examples of the substructure formula (4) include a substructure formula in which R 6 is a methyl group, R 7 is an alkyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a halogenated alkyl group having 2 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms; a substructure formula in which R 6 and R 7 are the same alkyl group having 2 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, halogenated alkyl group having 2 to 20 carbon atoms or aryl group having 6 to 20 carbon atoms; and a substructure formula in which R 6 and R 7 are the different alkyl group having 2 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, halogenated alkyl group having 2 to 20 carbon atoms or
  • cyclohexylmethylsilylene cyclotetramethylenesilylene, diphenylsilylene, methylphenylsilylene, di(3,5-dimethylphenyl)silylene, di(3,5-diethylphenyl)silylene, and (3,5-dimethylphenyl)(3,5-di- tert-butylphenyl)silylene.
  • R 8 , R 9 , R 10 and R 11 are preferably a hydrogen atom, a halogen atom, and a hydrocarbyl group having 1 to 20 carbon atoms, and more preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. Furthermore, at least one of R 8 , R 9 , R 10 and R 11 is preferably a halogen atom or a substituent other than a hydrogen atom.
  • R 8 , R 9 , R 10 and R 11 in formula (1-2) include the below- mentioned substructures for the substructural formula (6) in formula (1):
  • R 8 , R 9 , R 10 and R u have the same meanings as in R 8 , R 9 , R 10 and R 11 , respectively, in formula (1-2), in which at least one of them is a cyclopentadienyl substructure having a substituent other than a hydrogen atom or having a halogen atom. Examples thereof include the following substructures.
  • the examples include methylcyclopentadienyl, ethylcyclopentadienyl, n- propylcyclopentadienyl, isopropylcyclopentadienyl, n-butylcyclopentadienyl, sec- butylcyclopentadienyl, tert-butylcyclopentadienyl, dimethylcyclopentadienyl,
  • a preferable cyclopentadienyl substructure is tetramethylcyclopentadienyl.
  • Examples of the compound represented by formula (1) include a compound re resented by formula (1-3):
  • M 1 represents a transition metal atom of Group 4 of the periodic table of the elements
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , X 1 , X 2 and X 3 each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, or a disubstituted amino group, of R 1 , R 2 , R 3 , R 4 and R 5 , two groups bonded to the two adjoining carbon atoms may be bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded, R 6 and R 7 may be bonded to each other to form a ring together with carbon atoms to which they are bonded, of R 8 , R 9
  • M 1 in formula (1-3) represents a transition metal atom of Group 4 of the periodic table of the elements, and examples thereof include a titanium atom, a zirconium atom and a hafnium atom. Among them, a titanium atom is preferable.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 X 1 , X 2 and X 3 have the same meanings as in R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , X 1 , X 2 and X 3 , respectively, in formula (1), and the meanings of a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a
  • hydrocarbyloxy group a substituted hydrocarbyloxy group, a substituted silyl group, and a disubstituted amino group
  • examples thereof, and preferable embodiments thereof preferable atoms, preferable groups, the number of the carbon atoms of the preferable groups, and the like) are the same as the meanings thereof, the examples thereof, and preferable embodiments thereof described in formula (1).
  • R 8 , R 9 , R 10 , and R u each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, or a disubstituted amino group.
  • halogen atom a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, and a disubstituted amino group
  • examples thereof and preferable embodiments thereof are the same as the meanings thereof, the examples thereof, and preferable embodiments thereof described in formula (1).
  • two groups bonded to the two adjoining carbon atoms may be bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded.
  • the ring examples include a cyclopropane ring, a cyclopropene ring, a cyclobutane ring, a cyclobutene ring, a cyclopentane ring, a cyclopentene ring, a cyclohexane ring, a cyclohexene ring, a cycloheptane ring, a cycloheptene ring, a cyclooctane ring, a cyclooctene ring, a benzene ring, a naphthalene ring, an anthracene ring, and a saturated or unsaturated hydrocarbyl ring such as rings in which a hydrogen atom in these rings is substituted with a hydrocarbyl group having 1 to 20 carbon atoms.
  • R 1 , R 2 , R 3 , R 4 , and R 5 are preferably a hydrogen atom, a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms, and more preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms.
  • examples of preferable combination of R 1 , R 2 , R 3 , R 4 , and R 5 include substructures represented by the substructure formula (3) in formula (1).
  • preferable substructures are phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, and diethylphenyl.
  • R 6 and R 7 are each preferably a hydrogen atom, and a hydrocarbyl group having 1 to 20 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms.
  • Examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, a phenyl group, a 4-methylphenyl group, a 3-methylpheny group, a 2-methylphenyl group, a 3,5- dimethylphenyl group, a 3,5-a diethylphenyl group, a 3,5-di-tert-butylphenyl group, a naphthyl group, and a benzyl group.
  • examples of preferable combination of R 6 and R 7 include substructures represented by the substructure formula (5) in formula (1).
  • Preferable examples of the substructure formula (5) include a substructure formula in which R 6 is a methyl group, R 7 is an alkyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a halogenated alkyl group having 2 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms; a substructure formula in which R 6 and R 7 are the same alkyl group having 2 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, halogenated alkyl group having 2 to 20 carbon atoms or aryl group having 6 to 20 carbon atoms; and a substructure formula in which R 6 and R 7 are the different alkyl group having 2 to 20 carbo atoms, aryl group having 6 to 20 carbon atoms, halogenated alkyl group having 2 to 20 carbon atoms or
  • substructures represented by these substructure formulae include isopropylidene, 1-ethylpropylene, 1-methylpropylene, 1-methylpentylene, 1-cyclohexylethylene, cyclotetramethylenemethylene, diphenylmethylene, 1-phenylethylene, di(3,5- dimethylphenyl)methylene, di(3,5-diethylphenyl)methylene, and (3,5-dimethylphenyl)(3,5-di- tert-butylphenyl)methylene.
  • R 8 , R 9 , R 10 and R 11 are preferably a hydrogen atom, a halogen atom, or a hydrocarbyl group having 1 to 20 carbon atoms, and more preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. Furthermore, at least one of R 8 , R 9 , R 10 and R u is preferably a halogen atom or a substituent other than a hydrogen atom.
  • R 8 , R 9 , R 10 and R 11 in formula (1-3) include the substructural formula (6) in formula (1):
  • R 8 , R 9 , R 10 and R n have the same meanings as in R 8 , R 9 , R 10 and R 11 , respectively, in formula (1-3), in which at least one is a cyclopentadienyl substructure having a substituent other than a hydrogen atom or having a halogen atom. Examples thereof include the following substructures.
  • the examples include methylcyclopentadienyl, ethylcyclopentadienyl, n- propylcyclopentadienyl, isopropylcyclopentadienyl, n-butylcyclopentadienyl, sec- butylcyclopentadienyl, tert-butylcyclopentadienyl, dimethylcyclopentadienyl,
  • preferable cyclopentadienyl substructure is tetramethylcyclopentadienyl.
  • Examples of the compound represented by formula (1) include the following compounds:
  • examples of the compounds represented by formula (1) also include compounds in which a silicon atom is substituted with a carbon atom in any one of the above- mentioned compounds.
  • Preferable examples of the compounds represented by formula (1) include [1- dimethylphenylsilyl-3-trimethylsilylcyclopentadienyl]titanium trichloride, [ 1 -tris(3 ,5-dimethylphenyl)silyl-3-trim
  • Examples of method for producing the compound represented by formula (1) include a method described in Organometallics 2002, 21, 5122-5135.
  • examples of a method for producing the compound represented by formula (1) include a method for producing a compound, which includes a first step of reacting a substituted cyclopentadiene compound represented by formula (7) (hereinafter, referred to as a "substituted cyclopentadiene compound (7)”) with a base in the presence of an amine compound, and a second step of reacting a transition metal compound represented by formula (8)
  • reaction metal compound (8) (hereinafter, referred to as a "transition metal compound (8)") with the reaction product of the substituted cyclopentadiene compound (7) and the base:
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 have the same meanings as in R 1 , R 2 , R 3 , R 4 , R 5 , R 6 and R 7 , respectively, in formula (1), and R 8 , R 9 , R 10 and R 11 have the same meanings as in R 8 , R 9 , R 10 and R u res ectivel in formula (1-2);
  • M 1 , X 1 , X 2 and X 3 have the same meanings as in M 1 , X 1 , X 2 and X 3 , respectively, in formula (1), and X 11 represents a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, or a disubstituted amino group, and n represents 0 or 1.
  • X 11 in formula (8) is a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, or a disubstituted amino group, and the meanings and the examples of these groups are the same as the meanings and the examples of the groups described in formula
  • the substituted cyclopentadiene compound (7) include isomers in which positions of double bonds of the cyclopentadiene ring thereof are different from each other are the following constitutional isomers.
  • the compound represented by formula (7) includes isomers whose positions of the double bonds of each cyclopentadienyl ring are different from each other.
  • formula (7) represents any one of them or a mixture of them.
  • transition metal compound (8) examples include halogenated titanium such as titanium tetrachloride, titanium trichloride, titanium tetrabromide, and titanium tetraiodide; titanium amide such as tetrakis(dimethylamino)titanium, dichlorobis(dimethylamino)titanium, trichloro(dimethylamino)titanium, and tetrakis(diethylamino)titanium; alkoxytitanium such as tetraisopropoxytitanium, tetra-n-butoxytitanium, dichlorodiisopropoxytitanium, and
  • the preferable transition metal compound (8) is titanium tetrachloride.
  • examples of the base to be reacted with the substituted cyclopentadiene compound (7) include an organic alkaline metal compound.
  • examples of the organic alkaline metal compound include organic lithium compounds such as methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, lithium trimethylsilyl acetylide, lithium acetylide, (trimethylsilyl)methyllithium, vinyllithium, phenyllithium, and allyllithium.
  • the amount of the base to be used is in the range from 0.5 mol to 5 mol with respect to 1 mol of the substituted cyclopentadienyl compound (7).
  • an amine compound is used in the reaction between the substituted cyclopentadiene compound (7) and the base in the first reaction step.
  • an amine compound examples include a primary amine compound such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, tert-butylamine, n-octylamine, n-decylamine, aniline, and ethylenediamine; a secondary amine compound such as dimethylamine, diethylamine, di-n- propylamine, diisopropylamine, di-n-butylamine, di-tert-butylamine, di-n-octylamine, di-n- decylamine, pyrroline, hexamethyldisilazane, and diphenylamine; a tertiary amine compound such as trimethylamine, triethylamine, tri-n-propylamine, tri-n
  • the amount of such an amine compound to be used is preferably 10 mol or less, more preferably in the range from 0.5 mol to 10 mol, and further preferably, 1 mol to 5 mol with respect to 1 mol of base.
  • the reaction between the substituted cyclopentadiene compound (7) and the base is preferably carried out in a solvent. Furthermore, when a solvent is used, the substituted cyclopentadiene compound (7) and the base are reacted in the solvent, the transition metal compound (8) is then added to the reaction mixture, and thereby the transition metal compound (8) can be further reacted with the reaction product of the substituted cyclopentadiene compound (7) and the base. A solid may be precipitated in a reaction solution obtained by allowing the substituted cyclopentadiene compound (7) and the base to be reacted with each other.
  • a solvent may be added, or the precipitated solid may be once separated by filtration, and the solvent may be added to the separated solid so that the precipitated solid can be dissolved or suspended, and then the transition metal compound (8) may be added thereto.
  • the substituted cyclopentadiene compound (7), the base and the transition metal compound (8) are added to the solvent simultaneously, and thereby the first reaction step and the second reaction step can be carried out substantially at the same time.
  • an inactive solvent which does not remarkably prevent the progress of the reactions in these steps.
  • a solvent to be used include aprotic compounds including an aromatic hydrocarbon such as benzene and toluene; an aliphatic hydrocarbon such as hexane and heptane; ether compounds such as diethyl ether, tetrahydrofuran and 1,4-dioxane; an amide compound such as hexamethylphosphoric amide and
  • the amount of the solvent to be used is preferably 1 part by weight to 200 parts by weight and more preferably 3 parts by weight to 50 parts by weight with respect to 1 part by weight of the substituted cyclopentadiene compound (7).
  • the amount of the transition metal compound (8) to be used is preferably 0.5 mol to 3 mol and more preferably 0.7 mol to 1.5 mol with respect to 1 mol of the substituted cyclopentadiene compound (7).
  • reaction temperatures in the first reaction step and the second reaction step may be -100°C or higher and not higher than the boiling point of the solvent
  • temperatures are preferably -80°C to 100°C.
  • the compound represented by formula (1) can be taken out from the reaction product, which has been obtained through the first reaction step and the second reaction step, by various known purification methods. Examples of the methods include a method of carrying out the first reaction step and the second reaction step, then filtering off precipitates in the reaction solution, then concentrating the filtrate to precipitate a transition metal compound, and collecting the precipitated transition metal compound by filtration.
  • X 1 , X 2 and X 3 are each a halogen atom with an alkaline metal compound having a hydrogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group or a substituted hydrocarbyloxy group; a method of reacting the compound represented by formula (1) in which X 1 , X 2 and X 3 are each a halogen atom with an alkaline earth metal compound having a hydrogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group or a substituted hydrocarbyloxy group.
  • the above-mentioned substituted cyclopentadiene compound (7) can be produced by the steps of: reacting a substituted cyclopentadiene compound represented by formula (9) (hereinafter, referred to as a "substituted cyclopentadiene compound (9)") with a base in the presence of an amine compound; and reacting the reaction product of the substituted
  • halogenated silicon compound (10) a halogenated silicon compound represented by formula (10) (hereinafter, referred to as a "halogenated silicon compound (10)"):
  • R 8 , R 9 , R 10 and R 11 have the same meanings as in R 8 , R 9 , R 10 and R u , respectively, in formula (1-2), and the compound represented by the formula:
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 have the same meanings as in R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and
  • R 7 respectively, in formula (1), and X 12 represents a halogen atom.
  • the meanings of the groups to be used in R 8 , R 9 , R 10 , and R 11 , the examples of the groups, and the preferable groups are the same as the meanings of the groups, the examples of the groups, and the preferable groups described in formula (1-2).
  • the meanings of the groups to be used in R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , and R 7 , the examples of the groups, and the preferable groups are the same as the meanings of the groups, examples of the groups, and the preferable groups described in formula (1).
  • X 12 represents a halogen atom.
  • Examples of the substituted cyclopentadiene compound (9) include methylcyclopentadiene, 1,2-dimethyl cyclopentadiene, 1,3-dimethylcyclopentadiene, 1,2,3- trimethylcyclopentadiene, 1 ,2,4-trimethylcyclopentadiene, 1 ,2,3 ,4-tetramethyl cyclopentadiene, ethylcyclopentadiene, 1,2-diethylcyclopentadiene, 1,3-diethylcyclopentadiene, 1,2,3- triethylcyclopentadiene, 1,2,4-triethylcyclopentadiene, 1,2,3,4-tetraethylcyclopentadiene, n- propylcyclopentadiene, isopropy Icy clop entadiene, n-butylcyclopentadiene, sec- butylcyclopentadiene, tert-butylcyclopent
  • neopentylcyclopentadiene n-hexylcyclopentadiene, n-octylcyclopentadiene,
  • Examples of the base to be reacted with the substituted cyclopentadiene compound (9) include alkaline metal hydrides such as lithium hydride, sodium hydride, and potassium hydride; and alkaline earth metal hydride such as calcium hydride.
  • the amount of the base to be used is usually 0.5 mol to 3 mol and more preferably 0.9 mol to 2 mol with respect to 1 mol of the substituted cyclopentadiene compound
  • an amine compound is used together with the base.
  • examples of such an amine compound include primary anilines such as aniline, chloroaniline, bromoaniline, fluoroaniline, dichloroaniline, dibromoaniline, difiuoroaniline, trichloroaniline, tribromoaniline,
  • Examples also include naphthylamine, naphthylmethylamine, benzylamine, propylamine, butylamine, pentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, 2-aminopyridine, 3-aminopyridine, and 4- aminopyridine.
  • the amount of the amine compound to be used is usually 0.001 mol to 2 mol and preferably 0.01 mol to 0.5 mol with respect to 1 mol of the base.
  • the reaction between the substituted cyclopentadiene compound (9) and the base is carried out in a solvent that is inactive with respect to the reaction.
  • a solvent include aprotic compounds including aromatic hydrocarbon such as benzene, toluene and xylene; aliphatic hydrocarbon such as pentane, hexane, heptane, octane, and cyclohexane; ether compounds such as diethyl ether, methyl t-butyl ether, tetrahydrofuran, and 1,4-dioxane; amide compounds such as hexamethylphosphoric amide, dimethylformamide, dimethylacetamide, and N-methyl-pyrrolidone; halogenated hydrocarbon such as chlorobenzene and dichlorobenzene.
  • the amount of the solvent to be used is preferably 1 part by weight to 200 parts by weight and more preferably 3 parts by weight to 30 parts by weight with respect to 1 part by weight of the substituted cyclopentadiene compound (9).
  • the substituted cyclopentadiene compound (9), the base, and the amine compound may be mixed simultaneously in the solvent, or the base and the amine compound may be previously mixed and then the substituted cyclopentadiene compound (9) may be mixed therewith.
  • the reaction temperature is preferably 0°C to 70°C, and more preferably 10°C to 60°C.
  • halogenated silicon compound (10) examples include
  • the amount of the halogenated silicon compound (10) to be used is usually 0.2 mol to 2 mol and more preferably 0.33 mol to 1.25 mol with respect to 1 part by weight of the substituted cyclopentadiene compound (9) used in preparation of the reaction product of the substituted cyclopentadiene compound (9) and the base.
  • a solvent inactive to the reaction.
  • a solvent include aprotic compounds including an aromatic hydrocarbon such as benzene, toluene and xylene; an aliphatic hydrocarbon such as pentane, hexane, heptane, octane, and cyclohexane; an ether, compound such as diethyl ether, methyl t-butyl ether, tetrahydrofuran, and 1,4-dioxane; an amide compound such as
  • the amount of the solvent to be used is preferably 1 part by weight to 200 parts by weight and more preferably 3 parts by weight to 30 parts by weight with respect to 1 part by weight of the substituted cyclopentadiene compound (9) which has been used for preparation of the reaction product of the substituted cyclopentadiene compound (9) and the base.
  • the reaction of the reaction product of the substituted cyclopentadiene compound (9) and the base with the halogenated silicon compound (10) is usually carried out by mixing the base, the amine compound and the substituted cyclopentadiene compound (9) in a solvent, then mixing the halogenated silicon compound (10) therewith.
  • the reaction may be carried out by employing a method of mixing the base, the amine compound, the substituted cyclopentadiene compound (9) and the halogenated silicon compound (10) in a solvent once simultaneously.
  • the reaction temperature is preferably 0°C to 70°C, and more preferably 10°C to 60°C.
  • Examples of the complex (I) include compounds represented by formula (2-1) or f rmula (2-2):
  • M 2 represents a transition metal atom of Group 4 of the periodic table of the elements
  • a 21 represents an oxygen atom, a nitrogen atom, a phosphorus atom or a sulfur atom
  • Z 1 is a group linking A 21 to N, in which the number of the shortest bonds linking A 21 to N is 4 to
  • a bond linking A 21 to Z 1 may be a double bond
  • R 21 , R 22 , R 23 , R 24 , R 25 and X 4 each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, or a disubstituted amino group, two or more groups of R 21 , R 22 , R 23 , R 24 and R 25 may be bonded to each other, the three X 4 groups each may be the same or different from each other, and two or more X 4 groups may be bonded to each other to form a ring together with M 2 ;
  • R 26 represents a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbylidene group, and a substituted hydrocarbylidene group, a bond linking R 26 to A 21 may be a double bond, and R 26 may be bonded to Z 1 ;
  • M 2 represents a transition metal atom of Group 4 of the periodic table of the elements
  • a 22 represents a nitrogen atom or a phosphorus atom
  • Z 2 is a group linking A 22 to N, and the number of the shortest bonds linking A 22 to N is 4 to 6;
  • R 21 , R 22 , R 23 , R 24 , R 25 and X 4 each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, or a disubstituted amino group, two or more groups of R 21 , R 22 , R 23 , R 24 and R 25 may be bonded to each other, the three X 4 groups may be the same or different from each other, and two or more X 4 groups may be bonded to each other to form a ring together with M 2 ; and
  • R and R represent a hydrogen atom, a halogen atom, a hydrocarbyl group, and a substituted hydrocarbyl group, and R 28 may be bonded to Z 2 .
  • M 2 in formula (2-1) and formula (2-2) each represents a transition metal atom of Group 4 of the periodic table of the elements, and examples thereof include a titanium atom, a zirconium atom and a hafnium atom. Among them, a titanium atom is preferable.
  • R 21 , R 22 , R 23 , R 24 , R 25 and X 4 in formula (2-1) and formula (2-2) each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, or a disubstituted amino group, and the meanings and the examples of these groups are the same as the meanings and the examples described in formula (1).
  • R 21 , R 22 , R 23 , R 24 , R 25 and X 4 the number of the carbon atoms of a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group and a substituted
  • hydrocarbyloxy group is preferably 1 to 20, and more preferably 1 to 10.
  • Preferable examples of the hydrocarbyl group include an alkyl group, an aryl group, and an aralkyl group.
  • the substituted hydrocarbyl group is preferably a halogenated hydrocarbyl group, and more preferably a halogenated alkyl group, a halogenated aryl group, and a halogenated aralkyl group.
  • the hydrocarbyloxy group is preferably an alkoxy group, an aryloxy group, and an aralkyloxy group.
  • the substituted hydrocarbyloxy group is preferably a halogenated aralkyloxy group, and preferably a halogenated alkoxy group, and a halogenated aryloxy group.
  • the substituted silyl group in R 21 , R 22 , R 23 , R 24 , R 25 and X 4 is preferably a trisubstituted silyl group.
  • the number of the carbon atoms of the hydrocarbyl group and the halogenated hydrocarbyl group, which are bonded to a silicon atom is preferably 1 to 10.
  • the total number of the carbon atoms of the hydrocarbyl group and the halogenated hydrocarbyl group, which are bonded to a silicon atom is preferably 1 to 20, and more preferably 3 to 18.
  • Preferable examples thereof include a trimethylsilyl group, a tnethylsilyl group, a tnphenylsilyl group, a dimethylphenylsilyl group, and groups in which a part or all of hydrogen atoms are substituted with a halogen atom in these groups are preferable.
  • the number of the carbon atoms of the hydrocarbyl group and the halogenated hydrocarbyl group bonded to a nitrogen atom is preferably 1 to 10, and more preferably 1 to 5.
  • the total number of the carbon atoms of the hydrocarbyl group and a halogenated hydrocarbyl group bonded to a nitrogen atom is 2 to 20, and more preferably 2 to 10.
  • Two or more groups of R , R , R , R , and R may be bonded to each other to form a ring together with carbon atoms on a benzene ring to which R 21 to R 24 are bonded, or the carbon atom may form a ring together with a carbon atom to which R 25 is bonded.
  • the ring examples include a cyclopropane ring, a cyclopropene ring, a cyclobutane ring, a cyclobutene ring, a cyclopentane ring, a cyclopentene ring, a cyclohexane ring, a cyclohexene ring, a cycloheptane ring, a cycloheptene ring, a cyclooctane ring, a cyclooctene ring, a benzene ring, a naphthalene ring, an anthracene ring, and saturated or unsaturated hydrocarbyl ring such as rings in which a hydrogen atom in these rings are substituted with a hydrocarbyl group having 1 to 20 carbon atoms.
  • R 21 is more preferably a phenyl group, an a-cumyl group, a tert-butyl group, or a 1-adamanthyl group, and further preferably a 1-adamanthyl group.
  • R 23 is more preferably a methyl group, a cyclohexyl group, a tert-butyl group, or a 1-adamanthyl group, and further preferably a methyl group.
  • R 22 , R 24 , and R 25 are more preferably a hydrogen atom.
  • X 4 is more preferably a halogen atom or an alkyl group, and further preferably a chlorine atom, a bromine atom, and a methyl group.
  • a 21 represents an oxygen atom, a nitrogen atom, a phosphorus atom or a sulfur atom
  • a 22 represents a nitrogen atom or a phosphorus atom.
  • R 26 represents a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbylidene group, or a substituted hydrocarbylidene group, and a bond linking R 26 to A 21 may be a double bond, and the meanings and the examples of the hydrocarbyl group and the substituted hydrocarbyl group are the same as the meanings and the examples of described in formula (1).
  • hydrocarbylidene group examples include a methylidyne group, an ethylidyne group, a benzylidene group, and a cyclohexylidene group.
  • the substituted hydrocarbylidene group is a group in which one or more hydrogen atoms in the
  • hydrocarbylidene group are substituted with a group other than a hydrocarbyl group and/or a halogen atom. Examples thereof include a halogenated hydrocarbylidene group.
  • the number of the carbon atoms of a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbylidene group and a substituted hydrocarbylidene group is preferably 1 to 10, and more preferably 1 to 5.
  • R 26 and Z 1 may be bonded to each other to form a ring together with A 21 .
  • the ring may be an aliphatic ring or an aromatic ring, or a heterocycle.
  • R 26 is preferably a hydrocarbyl group having 1 to 10 carbon atoms, more preferably a methyl group, an ethyl group, and an isopropyl group, and further preferably a methyl group.
  • R 27 and R 28 each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, and a substituted hydrocarbyl group, and the meanings and the examples of the hydrocarbyl group and the substituted hydrocarbyl group are the same as the meanings and the examples thereof described in formula (1).
  • the number of the carbon atoms of a hydrocarbyl group and a substituted hydrocarbyl group is preferably 1 to 10, and more preferably 1 to 5.
  • R 27 is preferably a hydrocarbyl group having 1 to 10 carbon atoms, more preferably a methyl group, an ethyl group, or an isopropyl group, and further preferably a methyl group.
  • R 28 and Z 2 may be bonded to each other to form a ring together with A 22 .
  • the ring may be an aliphatic ring or an aromatic ring, or a heterocycle.
  • R 28 is preferably a hydrocarbyl group having 1 to 10 carbon atoms, more preferably a methyl group, an ethyl group, or an isopropyl group, and further preferably a methyl group.
  • Z 1 is a group linking A 21 to N, and the number of the shortest bonds linking A 21 to N is 4 to 6; and a bond linking A to Z may be a double bond.
  • Z is a group linking A to N, and the number of the shortest bonds linking A to N is 4 to 6.
  • Z 1 and Z 2 include a group for forming a structure represented by the substructure formula (2-3) by combining the following A 21 and N, or a group for forming a structure represented by the substructure formula (2-4) by combining the following A 22 and N:
  • R 31 , R 32 , R 33 , and R 34 each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, or a substituted hydrocarbyloxy group
  • R 31 and R 32 may be bonded to each other to form a ring together with a carbon atom to which R 31 is bonded and a carbon atom to which R 32 is bonded
  • R 33 and R 34 be bonded to each other to form a ring together with a carbon atom to which R 33 is bonded and a carbon atom to which R 34 is bonded
  • R 34 and R 26 bonded to A 1 may be bonded to each other
  • R and R bonded to A may be bonded to each other to form a ring together with A 22 .
  • R 31 , R 32 , R 33 , and R 34 the meanings and examples of a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group and a substituted hydrocarbyloxy group are the same as the meanings and the examples described in formula (1).
  • the number of the carbon atoms of a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group and a substituted hydrocarbyloxy group is preferably 1 to 20, and more preferably 1 to 10.
  • the hydrocarbyl group include an alkyl group, an aryl group, and an aralkyl group.
  • the substituted hydrocarbyl group include a halogenated hydrocarbyl group, and more preferable examples include a halogenated alkyl group, a halogenated aryl group, and a halogenated aralkyl group.
  • hydrocarbyloxy group examples include an alkoxy group, an aryloxy group, and an aralkyloxy group.
  • substituted hydrocarbyloxy group examples include a halogenated aralkyloxy group, and more preferable examples include a halogenated alkoxy group, and a halogenated aryloxy group.

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Abstract

The present invention is aimed at providing a catalyst capable of efficiently producing an ethylenic polymer having a short chain branch even when only ethylene is used as a raw material monomer, and a method for producing an ethylenic polymer by the catalyst. Is disclosed a catalyst for producing an ethylenic polymer, which is prepared from a complex (I) represented by formula (1), (2-1) or (2-2), a complex for olefin polymerization, an activating co-catalyst component and a carrier, wherein the complex (I) and the complex for olefin polymerization are supported by the carrier:

Description

DESCRIPTION
CATALYST FOR PRODUCING ETHYLENE-BASED POLYMER AND
METHOD FOR PRODUCING THE SAME
[Technical Field]
[0001]
The present invention relates to a catalyst for producing an ethylenic polymer and a method for producing an ethylenic polymer using the catalyst. [Background Art]
[0002]
Linear low density polyethylene, linear ultra low density polyethylene, and the like, are known as ethylenic polymers having short chain branches. The physical properties of ethylenic polymers vary depending on the- structures of the short chain branches. For example, the strength of an ethylenic polymer having a butyl branch is known to be higher than the strength of an ethylenic polymer having an ethyl branch. Furthermore, it is known that the melting point of an ethylenic polymer having a larger amount of butyl branches is lower than the melting point of an ethylenic polymer having a smaller amount of butyl branches.
[0003]
Ethylenic polymers having short chain branches have been conventionally produced by using ethylene and a-oleftn as raw material monomers in the presence of a catalyst obtained by bringing a complex for olefin polymerization into contact with an activating co- catalyst component. For example, ethylenic polymers having an ethyl branch have been produced by copolymerizing ethylene with 1-butene, and ethylenic polymers having a butyl branch have been produced by copolymerizing ethylene with 1-hexene.
[0004]
Recently, a method for producing an ethylenic polymer having short chain branches by using only ethylene as a raw material monomer have been studied. For example, a method for producing an ethylenic polymer by using only ethylene as a raw material monomer by a catalyst obtained by bringing a complex for oligomerization of ethylene and a complex for olefin polymerization into contact with an activating co-catalyst component in one reactor have been reported.
[0005] For example, in Non Patent Literatures 1 and 2, a method for producing an ethylenic polymer having a butyl branch by using only ethylene as a raw material monomer in the presence of a catalyst obtained by simultaneously bringing dimethylsilylene(tert- butylamido)(tetramethylcyclopentadienyl)titanium dichloride (hereinafter, referred to as a "titanium complex 1") as a titanium complex for olefin polymerization and [ 1-(1 -methyl- 1- phenylethyl)-cyclopentadienyl]titanium trichloride (hereinafter, referred to as a "titanium complex 2") as a titanium complex for tnmerization of ethylene into contact with MMAO as an activating co-catalyst component in a reactor has been reported. The Non Patent Literature 1 reports that when the reaction temperature is 45 to 50°C, the rate of a repeat unit derived from 1- hexene in an ethylenic polymer is extremely low as compared with the case where the reaction temperature is 25 to 30°C, and that when the reaction temperature is 70°C, no repeat unit derived from 1 -hexene is observed in an ethylenic polymer.
[0006]
The Non Patent Literature 2 reports a method for producing an ethylenic polymer by using only ethylene as a raw material monomer in the presence of a catalyst obtained by simultaneously bringing rac-dimethylsilylene bis(2-methylbenz[e]indenyl)zirconium dichloride (hereinafter, referred to as a "zirconium complex 1 ") as a zirconium complex for olefin polymerization and titanium complex 2 as the titanium complex for tnmerization of ethylene into contact with MMAO in a reactor. In the Non Patent Literature, as the amount to be used of titanium complex 2 is increased with respect to the amount to be used of zirconium complex 1, the melting point of the ethylenic polymer to be manufactured can be lowered, but the productivity is reported to be reduced.
[Citation List]
[Non Patent Literature]
[0007]
[Non Patent Literature 1] Macromolecular Rapid Communications 2004, 25, 647-652.
[Non Patent Literature 2] Journal of Polymer Science: Part A: Polymer Chemistry 2004, 42, 4327-4336.
[Summary of Invention]
[Technical Problem]
[0008]
In such circumstances, the problem to be solved by the present invention is to provide a catalyst capable of efficiently producing an ethylenic polymer having short chain branches even though only ethylene is used as a raw material monomer and to provide a method for producing an ethylenic polymer by the catalyst.
[Solution to Problem]
[0009]
That is to say, a first aspect of the present invention relates to a catalyst for producing an ethylenic polymer, which is prepared from a complex (I) represented by formula (1), (2-1) or (2-2), a complex for olefin polymerization, an activating co-catalyst component, and a carrier, wherein the complex (I) and the complex for olefin polymerization are supported by a carrier:
Figure imgf000005_0001
wherein M1 represents a transition metal atom of Group 4 of the periodic table of the elements; Cp represents a group having a cyclopentadiene-type anionic skeleton;
J1 represents an atom selected from Groups 13 to 16 of the periodic table of the elements;
1 and m each represent 1 or 0, and 1 + m is an integer equal to (the valence of J1 - 2); and
R1, R2, R3, R4, R5, R6, R7, X1, X2 and X3 each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, or a disubstituted amino group, of R1, R2, R3, R4 and R5, two groups bonded to the two adjoining carbon atoms may be bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded, R6 and R7 may be bonded to each other to form a ring together with J1 to which they are bonded, and two roups of X1, X2 and X3 may be bonded to each other to form a ring together with M1;
Figure imgf000005_0002
wherein M2 represents a transition metal atom of Group 4 of the periodic table of the elements; A21 represents an oxygen atom, a nitrogen atom, a phosphorus atom or a sulfur atom; Z1 is a group linking A21 to N, in which the number of the shortest bonds linking A21 to N is 4 to
6;
a bond linking A21 to Z1 may be a double bond;
R21, R22, R23, R24, R25 and X4 each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, or a disubstituted amino group, two or more groups of R21, R22, R23, R24 and R25 may be bonded to each other, the three X4 groups each may be the same or different from each other, and two or more X4 groups may be bonded to each other to form a ring together with M2;
R26 represents a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbylidene group, or a substituted hydrocarbylidene group, a bond linking R26 to A21 may be a double bond, and R26 may be bonded to Z1;
Figure imgf000006_0001
wherein M2 represents a transition metal atom of Group 4 of the periodic table of the elements; A22 represents a nitrogen atom or a phosphorus atom;
Z2 is a group linking A22 to N, and the number of the shortest bonds linking A22 to N is 4 to 6; R21, R22, R23, R24, R25 and X4 each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, or a disubstituted amino group, two or more groups of R21, R22, R23, R2 and R25 may be bonded to each other, the three X4 groups may be the same or different from each other, and two or more X4 groups may be bonded to each other to form a ring together with M2; and
R27 and R28 represent a hydrogen atom, a halogen atom, a hydrocarbyl group, or a substituted hydrocarbyl group, and R28 may be bonded to Z2.
[0010]
A second aspect of the present invention relates to a method for producing an ethylenic polymer in which olefin including ethylene is polymerized by the catalyst for producing an ethylenic polymer. [Advantageous Effects of Invention]
[0011]
The present invention can provide a catalyst capable of efficiently producing an ethylenic polymer having short chain branches even though only ethylene is used as a raw material monomer and a method for producing an ethylenic polymer by the catalyst.
[0012]
In the present invention, the term "polymerization" includes not only homopolymerization but also copolymerization. Furthermore, the term "ethylenic polymer" includes a homopolymer of ethylene and a copolymer of ethylene and another monomer.
[0013]
[Complex (I)]
The complex (I) can oligomerize ethylene by the complex (I) and the activating co-catalyst component to synthesize a-olefin. Oligomerization of ethylene means changing of ethylene into 2 to 20-mer compound, and the number of the carbon atoms of the a-olefin is 4 to 40. The suitable complex is a complex capable of synthesizing at least one α-olefin selected from the group consisting of 1-butene, 1-hexene and 1-octene from ethylene, and more suitable complex is a complex capable of synthesizing 1-hexene from ethylene.
[0014]
The complex (I) is a compound represented by any of formula (1), formula (2-1) mentioned later, and formula (2-1) mentioned later:
Figure imgf000007_0001
wherein M1 represents a transition metal atom of Group 4 of the periodic table of the elements; Cp represents a group having a cyclopentadiene-type anionic skeleton;
J1 represents an atom selected from Groups 13 to 16 of the periodic table of the elements;
1 and m each represent 1 or 0, and 1 + m is an integer equal to (the valence of J1 - 2); and
R1, R2, R3, R4, R5, R6, R7, X1, X2 and X3 each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, or a disubstituted amino group, of R1, R2, R3, R4 and R5, two groups bonded to the two adjoining carbon atoms may be bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded, R6 and R7 may be bonded to each other to form a ring together with J1 to which they are bonded, and two groups of X1, X2 and X3 may be bonded to each other to form a ring together with M1.
[0015]
M1 in formula (1) represents a transition metal atom of Group 4 of the periodic table of the elements, and examples thereof include a titanium atom, a zirconium atom and a hafnium atom. Among them, a titanium atom is preferable.
[0016]
Cp in formula (1) represents a group having a cyclopentadiene-type anionic skeleton, and examples thereof include a r|5-cyclopentadienyl group, a η5- methylcyclopentadienyl group, a r|5-ethylcyclopentadienyl group, a r|5-n-propylcyclopentadienyl group, Ti5-isopropylcyclopentadienyl group, a r|5-n-butylcyclopentadienyl group, a r|5-sec- butylcyclopentadienyl group, a T]5-tert-butylcyclopentadienyl group, a η5- dimethylcyclopentadienyl group, a ri5-trimethylcyclopentadienyl group, a η5- tetramethylcyclopentadienyl group, a r|5-phenylcyclopentadienyl group, a η5- benzylcyclopentadienyl group, a r|5-indenyl group, a r|5-fluorenyl group, a r|5-tetrahydroindenyl group, a ^-methyltetrahydroindenyl group, a r|5-dimethyltetrahydroindenyl group, and a η5- octahydrofluorenyl group. A substituted cyclopentadienyl group is preferable.
[0017]
J1 in formula (1) represents an atom selected from Groups 13 to 16 of the periodic table of the elements, and examples thereof include a boron atom, a carbon atom, a silicon atom, a nitrogen atom, a phosphorus atom, and an oxygen atom and a sulfur atom. Preferable example is a carbon atom or a silicon atom, and more preferable example is silicon atom.
[0018]
1 and m each represent 1 or 0, and 1 + m is an integer equal to (the valence of J1 - 2).
[0019]
R1, R2, R3, R4, R5, R6, R7, X1, X2 and X3 each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, or a disubstituted amino group.
[0020]
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. A chlorine atom is preferable.
[0021] Examples of the hydrocarbyl group include an alkyl group, an aryl group, and an aralkyl group. Furthermore, the number of the carbon atoms of the hydrocarbyl group is preferably 1 to 20, and more preferable 1 to 10.
[0022]
Examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, a neopentyl group, an amyl group, a n-hexyl group, a heptyl group, a n-octyl group, a n- nonyl group, a n-decyl group, a n-dodecyl group, a n-tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group and a n-eicosyl group. Preferable examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms, more preferable examples include an alkyl group having 1 to 10 carbon atoms, and further preferable examples include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group and an amyl group.
[0023]
Examples of the aryl group include a phenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, a 2,3-xylyl group, a 2,4-xylyl group, a 2,5-xylyl group, a 2,6-xylyl group, a 3,4-xylyl group, a 3,5-xylyl group, a 2,3,4-trimethylphenyl group, a 2,3,5-trimethylphenyl group, a 2,3,6-trimethylphenyl group, a 2,4,6-trimethylphenyl group, a 3,4,5-trimethylphenyl group, a 2,3,4,5-tetramethylphenyl group, a 2,3,4,6-tetramethylphenyl group, a 2,3,5,6- tetramethylphenyl group, a pentamethylphenyl group, an ethylphenyl group, a diethylphenyl group, a n-propylphenyl group, an isopropylphenyl group, a n-butylphenyl group, a sec- butylphenyl group, a tert-butylphenyl group, a n-pentylphenyl group, a neopentylphenyl group, a n-hexylphenyl group, a n-octylphenyl group, a n-decylphenyl group, a n-dodecylphenyl group, a n-tetradecylphenyl group, a naphthyl group, and an anthracenyl group. Preferable examples of the aryl group include an aryl group having 6 to 20 carbon atoms, more preferable examples include an aryl group having 6 to 10 carbon atoms, further preferable examples include a phenyl group, a methylphenyl group, a dimethylphenyl group, a tnmethylphenyl group, a diethylphenyl group, particularly preferable examples include a phenyl group, a dimethylphenyl group, and a diethylphenyl group.
[0024]
Examples of the aralkyl group include a benzyl group, a (2-methylphenyl)methyl group, a (3-methylphenyl)methyl group, a (4-methylphenyl)methyl group, a (2,3- dimethylphenyl)methyl group, a (2,4-dimethylphenyl)methyl group, a (2,5- dimethylphenyl)methyl group, a (2,6-dimethylphenyl)methyl group, a (3,4- dimethylphenyl)methyl group, a (3,5-dimethylphenyl)methyl group, a (2,3,4- trimethylphenyl)methyl group, a (2,3,5-trimethylphenyl)methyl group, a (2,3,6- trimethylphenyl)methyl group, a (3,4,5-trimethylphenyl)methyl group, a (2,4,6- trimethylphenyl)methyl group, a (2,3,4,5-tetramethylphenyl)methyl group, a (2,3,4,6- tetramethylphenyl)methyl group, a (2,3,5,6-tetramethylphenyl)methyl group, a
(pentamethylphenyl)methyl group, an (ethylphenyl)methyl group, a (n-propylphenyl)methyl group, an (isopropylphenyl)methyl group, a (n-butylphenyl)methyl group, a (sec- butylphenyl)methyl group, a (tert-butylphenyl)methyl group, a (n-pentylphenyl)methyl group, a (neopentylphenyl)methyl group, a (n-hexylphenyl)methyl group, a (n-octylphenyl)methyl group, a (n-decylphenyl)methyl group, a (n-dodecylphenyl)methyl group, a (n-tetradecylphenyl)methyl group, a naphthylmethyl group, and an anthracenylmethyl group. Preferable examples of the aralkyl group include an aralkyl group having 7 to 20 carbon atoms, more preferable examples of the aralkyl group include an aralkyl group having 7 to 10 carbon atoms, and further preferable example of the aralkyl group is a benzyl group.
[0025]
The substituted hydrocarbyl group is a group in which one or more hydrogen atoms in the hydrocarbyl group are substituted with groups other than the hydrocarbyl group and/or a halogen atom. Examples thereof include halogenated hydrocarbyl groups such as a halogenated alkyl group, a halogenated aryl group, and a halogenated aralkyl group. The number of carbon atoms of the substituted hydrocarbyl group is preferably 1 to 20, and more preferably 1 to 10.
[0026]
Examples of the halogenated alkyl group include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, a dibromomethyl group, a tribromomethyl group, a fluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, and a perfluorohexyl group. The halogenated alkyl group is preferably a halogenated alkyl group having 1 to 20 carbon atoms, and more preferably a halogenated alkyl group having 1 to 10 carbon atoms.
[0027]
Examples of the halogenated aryl group include a fluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group, a pentafluorophenyl group, a chlorophenyl group, a bromophenyl group, and an iodophenyl group. The halogenated aryl group is preferably a halogenated aryl group having 6 to 20 carbon atoms, and more preferably a halogenated aryl group having 6 to 10 carbon atoms.
[0028]
Examples of the halogenated aralkyl group include a group in which a part or all of the hydrogen atoms present in the above-mentioned aralkyl group are substituted with a halogen atom. The halogenated aralkyl group is preferably a halogenated aralkyl group having 7 to 20 carbon atoms and more preferably a halogenated aralkyl group having 7 to 10 carbon atoms.
[0029]
Examples of the hydrocarbyloxy group include an alkoxy group, an aryloxy group, and an aralkyloxy group. The number of carbon atoms of the hydrocarbyloxy group is preferably 1 to 20, and more preferably 1 to 10.
[0030]
Examples of the alkoxy group include a methoxy group, an ethoxy group, a n- propoxy group, an isopropoxy group, n-butoxy group, a sec-butoxy group, a tert-butoxy group, a n-pentyloxy group, a neopentyloxy group, a n-hexyloxy group, a n-octyloxy group, a n-nonyloxy group, a n-decyloxy group, a n-undecyloxy group, a n-dodecyloxy group, a tridecyloxy group, a tetradecyloxy group, a n-pentadecyloxy group, a hexadecyloxy group, a heptadecyloxy group, an octadecyloxy group, a nonadecyloxy group, and a n-eicosyloxy group. The alkoxy group is preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 10 carbon atoms, and further preferably a methoxy group, an ethoxy group, and a tert-butoxy group.
[0031]
Examples of the aryloxy group include a phendxy group, a 2-methylphenoxy group, a 3-methylphenoxy group, a 4-methylphenoxy group, a 2,3-dimethylphenoxy group, a 2,4-dimethylphenoxy group, a 2,5-dimethylphenoxy group, a 2,6-dimethylphenoxy group, a 3,4- dimethylphenoxy group, a 3,5-dimethylphenoxy group, a 2,3,4-trimethylphenoxy group, a 2,3,5- trimethylphenoxy group, a 2,3,6-trimethylphenoxy group, a 2,4,5-trimethylphenoxy group, a 2,4,6-trimethylphenoxy group, a 3,4,5-trimethylphenoxy group, a 2,3,4,5-tetramethylphenoxy group, a 2,3,4,6-tetramethylphenoxy group, a 2,3,5,6-tetramethylphenoxy group, a
pentamethylphenoxy group, an ethylphenoxy group, a n-propylphenoxy group, an
isopropylphenoxy group, a n-butylphenoxy group, a sec-butylphenoxy group, a tert- butylphenoxy group, a n-hexylphenoxy group, a n-octylphenoxy group, a n-decylphenoxy group, a n-tetradecylphenoxy group, a naphthoxy group, and an anthracenoxy group. A preferable example of the aryloxy group is an aryloxy group having 6 to 20 carbon atoms, a more preferable example is an aryloxy group having 6 to 10 carbon atoms, and further preferable examples are a phenoxy group, a 2-niethylphenoxy group, a 3-methylphenoxy group, and a 4- methylphenoxy group.
[0032]
Examples of the aralkyloxy group include a benzyloxy group, a (2- methylphenyl)methoxy group, a (3-methylphenyl)methoxy group, a (4-methylphenyl)methoxy group, a (2,3-dimethylphenyl)methoxy group, a (2,4-dimethylphenyl)methoxy group, a (2,5- dimethylphenyl)methoxy group, a (2,6-dimethylphenyl)methoxy group, a (3,4- dimethylphenyl)methoxy group, a (3,5-dimethylphenyl)methoxy group, a (2,3,4- trimethylphenyl)methoxy group, a (2,3,5-trimethylphenyl)methoxy group, a (2,3,6- trimethylphenyl)methoxy group, a (2,4,5-trimethylphenyl)methoxy group, a (2,4,6- trimethylphenyl)methoxy group, a (3,4,5-trimethylphenyl)methoxy group, a (2,3,4,5- tetramethylphenyl)methoxy group, a (2,3,4,6-tetramethylphenyl)methoxy group, a (2,3,5,6- tetramethylphenyl)methoxy group, a (pentamethylphenyl)methoxy group, an
(ethylphenyl)methoxy group, a (n-propylphenyl)methoxy group, an (isopropylphenyl)methoxy group, a (n-butylphenyl)methoxy group, a (sec-butylphenyl)methoxy group, a (tert- butylphenyl)methoxy group, a (n-hexylphenyl)methoxy group, a (n-octylphenyl)methoxy group, a (n-decylphenyl)methoxy group, a naphthyl methoxy group, and an anthracenyl methoxy group. A preferable example of the aralkyloxy group is an aralkyloxy group having 7 to 20 carbon atoms, a more preferable example is an aralkyloxy group having 7 to 10 carbon atoms, and a further preferable example is a benzyloxy group.
[0033]
The substituted hydrocarbyloxy group is a group in which one or more hydrogen atoms in the hydrocarbyloxy group are substituted with groups other than the hydrocarbyl group and/or a halogen atom. Examples thereof include halogenated hydrocarbyl groups such as a halogenated alkoxy group, a halogenated aryloxy group, and a halogenated aralkyloxy group. The number of carbon atoms of the substituted hydrocarbyloxy group is preferably 1 to 20, and more preferably 1 to 10.
[0034]
Examples of the halogenated alkoxy group include a group in which a part or all of the hydrogen atoms present in the above-mentioned alkoxy group is substituted with a halogen atom. Preferable examples of the halogenated alkoxy group include a halogenated alkoxy group having 1 to 20 carbon atoms and more preferable examples include a halogenated alkoxy group having 1 to 10 carbon atoms. [0035]
Examples of the halogenated aryloxy group include a group in which a part or all of the hydrogen atoms present in the above-mentioned aryloxy group are substituted with a halogen atom. Preferable examples of the halogenated aryloxy group include a halogenated aryloxy group having 6 to 20 carbon atoms and more preferable examples include a halogenated aryloxy group having 6 to 10 carbon atoms.
[0036]
Examples of the halogenated aralkyloxy group include a group in which a part or all of the hydrogen atoms present in the above-mentioned aralkyloxy group are substituted with a halogen atom. Preferable examples of the halogenated aralkyloxy group include a halogenated aralkyloxy group having 7 to 20 carbon atoms and more preferable examples include a halogenated aralkyloxy group having 7 to 10 carbon atoms.
[0037]
Examples of the substituted silyl group include a group represented by -Si(R1 )3, wherein the three R12 groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and at least one of R12 is a hydrocarbyl group or a halogenated hydrocarbyl group.
[0038]
Examples of the hydrocarbyl group of R12 include alkyl groups such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a n-pentyl group, a n-hexyl group, a cyclohexyl group, a n- heptyl group, a n-octyl group, a n-nonyl group, and a n-decyl group; and an aryl group such as a phenyl group. Examples of the halogenated hydrocarbyl group include a group in which a part or all of the hydrogen atoms present in these hydrocarbyl groups are substituted with a halogen atom. The number of the carbon atoms of the hydrocarbyl group and the halogenated hydrocarbyl group is preferably 1 to 10. Furthermore, the total number of the carbon atoms of three R12 is preferably 1 to 20, and more preferably 3 to 18.
[0039]
Examples of the substituted silyl group include a monosubstituted silyl group having one hydrocarbyl group or halogenated hydrocarbyl group such as a methylsilyl group, an ethylsilyl group, and a phenylsilyl group, and groups in which a part or all of the hydrogen atoms in the hydrocarbyl group bonded to a silicon atom in the above-mentioned groups are substituted with a halogen atom; a disubstituted silyl group having two of hydrocarbyl groups and/or halogenated hydrocarbyl groups such as a dimethylsilyl group, a diethylsilyl group, and a diphenylsilyl group, and groups in which a part or all of the hydrogen atoms in the hydrocarbyl group bonded to a silicon atom in the above-mentioned groups are substituted with a halogen atom; and a trisubstituted silyl group having three of hydrocarbyl groups and/or halogenated hydrocarbyl groups such as a trimethylsilyl group, a triethylsilyl group, a tri-n-propylsilyl group, a triisopropylsilyl group, a tri-n-butylsilyl group, a tri-sec-butylsilyl group, a tri-tert-butyl silyl group, atriisobutylsilyl group, a tert-butyl-dimethylsilyl group, a tri-n-pentylsilyl group, a tri-n- hexylsilyl group, a tncyclohexylsilyl group, a tnphenylsilyl group, and groups in which a part or all of the hydrogen atoms in the hydrocarbyl group bonded to a silicon atom in the above- mentioned groups are substituted with a halogen atom. Preferable examples of the substituted silyl group include a trisubstituted silyl group, and more preferable examples thereof include a trimethylsilyl group, a tert-butyldimethylsilyl group, a triphenylsilyl group, and groups in which a part or all of the hydrogen atoms in these groups are substituted with a halogen atom.
[0040]
Examples of the disubstituted amino group include a group represented by - N(R13)2, wherein the two R13 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the two R13 groups are bonded to each other to form a ring together with nitrogen atoms to which the two groups are bonded.
[0041]
Examples of the hydrocarbyl group in R13 include alkyl groups such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a n-pentyl group, a n-hexyl group, a cyclohexyl group, a n- heptyl group, a n-octyl group, a n-nonyl group, and a n-decyl group; and aryl groups such as a phenyl group. Examples of the halogenated hydrocarbyl group include a group in which a part or all of the hydrogen atoms present in these hydrocarbyl groups are substituted with a halogen atom. The number of the carbon atoms of the hydrocarbyl group and the halogenated hydrocarbyl group is preferably 1 to 10 and more preferably 1 to 5. Furthermore, the total number of the carbon atoms of the two R13 groups is preferably 2 to 20, and more preferably 2 to 10.
[0042]
Examples of the disubstituted amino group include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, a di-sec-butylamino group, a di-tert-butylamino group, a di-isobutylamino group, a tert- butyl isopropylamino group, a di-n-hexylamino group, a di-n-octylamino group, a di-n- decylamino group, a diphenylamino group, a bistrimethylsilylamino group, a bis-tert- butyldimethylsilylamino group, a pyrrolyl group, a pyrrolidinyl group, a piperidinyl group, a carbazolyl group, a dihydroindolyl group, a dihydroisoindolyl group, and groups in which a part or all of the hydrogen atoms in these groups are substituted with a halogen atom. Preferable examples of the disubstituted amino group include a dimethylamino group, a diethylamino group, a pyrrolidinyl group, a piperidinyl group, and groups in which a part or all of the hydrogen atoms are substituted with a halogen atom.
[0043]
Of Rl, R2, R3, R4 and R5, two groups bonded to the two adjoining carbon atoms may be bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded. Examples of the ring include a cyclopropane ring, a cyclopropene ring, a cyclobutane ring, a cyclobutene ring, a cyclopentane ring, a cyclopentene ring, a cyclohexane ring, a cyclohexene ring, a cycloheptane ring, a cycloheptene ring, a cyclooctane ring, a cyclooctene ring, a benzene ring, a naphthalene ring, an anthracene ring, and saturated or unsaturated hydrocarbyl rings such as rings in which a hydrogen atom in these rings are substituted with a hydrocarbyl group having 1 to 20 carbon atoms.
[0044]
R6 and R7 may be bonded to each other to form a ring together with J1 to which they are bonded. When J1 is a silicon atom, examples of the ring include a silacyclopropane ring, a silacyclobutane ring, a silacyclopentane ring, a silacyclohexane ring and saturated or unsaturated silahydrocarbyl rings in which a hydrogen atom in these rings is substituted with a hydrocarbyl group having 1 to 20 carbon atoms. Furthermore, when J1 is a carbon atom, examples of the ring include a cyclopropane ring, a cyclopropene ring, a cyclobutane ring, a cyclobutene ring, a cyclopentane ring, a cyclopentene ring, a cyclohexane ring, a cyclohexene ring, a cycloheptane ring, a cycloheptene ring, a cyclooctane ring, a cyclooctene ring, a benzene ring, a naphthalene ring, an anthracene ring, and saturated or Unsaturated hydrocarbyl rings such as a ring in which a hydrogen atom in these rings is substituted with a hydrocarbyl group having 1 to 20 carbon atoms.
[0045]
Rl, R2, R3, R4, and R5 are each preferably a hydrogen atom, a halogen atom, or a hydrocarbyl group having 1 to 20 carbon atoms, and more preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.
[0046]
Examples of the preferable combination of R1, R2, R3, R4 and R5 include the below-mentioned substructures for the substructural formula (3) in formula (1):
Figure imgf000016_0001
wherein R1, R2, R3, R4 and R5 have the same meanings as in R1, R2, R3, R4 and R5, respectively, in formula (1).
[0047]
The examples include phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, tetramethylphenyl, pentamethylphenyl, ethylphenyl, diethylphenyl, tert-butylphenyl, di-tert- butylphenyl, tert-butylmethylphenyl, di(tert-butyl)methylphenyl, naphthyl, anthracenyl, chlorophenyl, dichlorophenyl, fluorophenyl, pentafluorophenyl, bis(tri£luoromethyl)phenyl, and methoxyphenyl.
[0048]
Among the substructures listed herein as examples, preferable substructures are phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, and diethylphenyl.
[0049]
R6 and R7 are each preferably a hydrogen atom, or a hydrocarbyl group having 1 to 20 carbon atoms, and more preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. Examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, a phenyl group, a 4- methylphenyl group, a 3-methylphenyl group, a 2-methylphenyl group, a 3,5-dimethylphenyl group, a 3,5-diethylphenyl group, a 3,5-di-tert-butylphenyl group, a naphthyl group, and a benzyl group.
[0050]
Examples of the preferable combination of R6, R7 and J1 include the below- mentioned substructures for the substructural formula (4) in formula (1) in which 1 = 1 and m = 1 are satisfied, and J1 is a silicon atom:
Figure imgf000016_0002
wherein R6 and R7 have the same meanings as in R6 and R7, respectively, in formula (1).
[0051] The examples include dimethylsilylene, diethylsilylene, ethylmethylsilylene, di(n- propyl)silylene, methyl(n-propyl)silylene, di(n-butyl)silylene, n-butylmethylsilylene, n- hexylmethylsilylene, methyl(n-octyl)silylene, n-decylmethylsilylene, methyl(n- octadecyl)silylene, cyclohexylmethylsilylene, cyclotetramethylenesilylene, diphenylsilylene, di(3,5-dimethylphenyl)silylene, di(3,5-diethylphenyl)silylene, and methylphenylsilylene.
[0052]
Preferable examples of the substructure formula (4) include a substructure formula in which R6 is a methyl group, R7 is an alkyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a halogenated alkyl group having 2 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms; a substructure formula in which R6 and R7 are the same alkyl group having 2 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, halogenated alkyl group having 2 to 20 carbon atoms or aryl group having 6 to 20 carbon atoms; and a substructure formula in which R6 and R7 are different alkyl group having 2 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, halogenated alkyl group having 2 to 20 carbon atoms or aryl group having 6 to 20 carbon atoms. Examples of the substructures represented by these substructure formulae include dimethylsilylene, diethylsilylene, ethylmethylsilylene, n- butylmethylsilylene, cyclohexylmethylsilylene, cyclotetramethylenesilylene, diphenylsilylene, methylphenylsilylene, di(3,5-dimethylphenyl)silylene, di(3,5-diethylphenyl)silylene, and (3,5- dimethylphenyl)(3,5-di-tert-butylphenyl)silylene.
[0053]
Furthermore, examples of the preferable combination of R6, R7and J1 include the below- mentioned substructures for the substructural formula (5) in formula (1) in which 1 = 1 and m = 1 are satisfied and J1 is a carbon atom:
Figure imgf000017_0001
wherein R6 and R7 have the same meanings as in R6 and R7, respectively, in formula (1).
[0054]
The examples include isopropylidene, 1-ethylpropylene, 1-methylpropylene, 1-n- propylbutylene, 1-methylbutylene, 1-n-butylpentylene, 1-methylpentylene, 1-methylheptylene, 1-methylnonylene, 1-methyldodecylene, 1-methylnonadecylene, 1-cyclohexylethylene, cyclotetramethylenemethylene, diphenylmethylene, 1-phenylethylene, di(3,5- dimethylphenyl)methylene, di(3,5-diethylphenyl)methylene, (3,5-dimethylphenyl)(3,5-di-tert- butylphenyl)methylene, di(3,5-diphenylphenyl)methylene, and di(3,5- dibenzylphenyl)methylene. [0055]
Preferable examples of the substructure formula (5) include a substructure formula in which R6 is a methyl group, R7 is an alkyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a halogenated alkyl group having 2 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms; a substructure formula in which R6 and R7 are the same alkyl group having 2 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, halogenated alkyl group having 2 to 20 carbon atoms or aryl group having 6 to 20 carbon atoms; and a substructure formula in which R6 and R7 are different alkyl group having 2 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, halogenated alkyl group having 2 to 20 carbon atoms or aryl group having 6 to 20 carbon atoms. Examples of the substructures represented by these substructure formulas include isopropylidene, 1-ethylpropylene, 1-methylpropylene, 1- methylpentylene, 1-cyclohexyl ethylene, cyclotetramethylenemethylene, diphenylmethylene, 1- phenylethylene, di(3,5-dimethylphenyl)methylene, di(3,5-diethylphenyl)methylene, and (3,5- dimethylphenyl)(3 , 5 -di-tert-butylphenyl)methylene.
[0056]
X1, X2 and X3 are each preferably a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, or a substituted hydrocarbyloxy group, and more preferably a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, a halogenated alkoxy group having 1 to 20 carbon atoms, a halogenated aryloxy group having 6 to 20 carbon atoms, and a halogenated aralkyloxy group having 7 to 20 carbon atoms.
[0057]
The compound represented by formula (1) can be preferably a compound re resented by formula (1-2):
Figure imgf000018_0001
wherein M1 represents a transition metal atom of Group 4 of the periodic table of the elements; and
R\ R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, X1, X2 and X3 each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, or disubstituted amino group, of R1, R2, R3, R4 and R5, two groups bonded to the two adjoining carbon atoms may be bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded, R6 and R7 may be bonded to each other to form a ring together with a silicon atom to which they are bonded, of R8, R9, R10 and Rn, two groups bonded to the two adjoining carbon atoms may be bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded, and two groups of X1, X2 and X3 may be bonded to each other to form a ring together with M1.
[0058]
M1 in formula (1-2) represents a transition metal atom of Group 4 of the periodic table of the elements; and examples thereof include a titanium atom, a zirconium atom and a hafnium atom. Among them, a titanium atom is preferable.
[0059]
In formula (1-2), R1, R2, R3, R4, R5, R6, R7, X1, X2 and X3 have the same meanings as in R1, R2, R3, R4, R5, R6, R7, X1, X2 and X3, respectively, in formula (1), and the meanings of a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a
hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, and a disubstituted amino group, a ring in which of R1, R2, R3, R4 and R5, two groups bonded to the two adjoining carbon atoms are bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded and a ring in which R6 and R7 are bonded to each other to form a ring together with a silicon atom to which they are bonded, examples thereof and preferable embodiments thereof (preferable atoms, preferable groups, the number of the carbon atoms of the preferable groups, and the like) are the same as the meanings thereof, the examples thereof, and preferable embodiments thereof described in formula (1).
[0060]
In formula (1-2), R8, R9, R10, and R11 each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, or a disubstituted amino group. The meanings of a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group or a disubstituted amino group, and examples thereof and preferable embodiments thereof (preferable atoms, preferable groups, the number of the carbon atoms of the preferable groups, and the like) are the same as the meanings thereof, the examples thereof, and preferable embodiments thereof described in formula (1).
[0061] In formula (1-2), of R8, R9, R10 and R11, two groups bonded to the two adjoining carbon atoms may be bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded. Examples of the ring include a cyclopropane ring, a cyclopropene ring, a cyclobutane ring, a cyclobutene ring, a cyclopentane ring, a cyclopentene ring, a cyclohexane ring, a cyclohexene ring, a cycloheptane ring, a cycloheptene ring, a cyclooctane ring, a cyclooctene ring, a benzene ring, a naphthalene ring, an anthracene ring, and a saturated or unsaturated hydrocarbyl ring such as rings in which a hydrogen atom in these rings is substituted with a hydrocarbyl group having 1 to 20 carbon atoms.
[0062]
In formula (1-2), R1, R2, R3, R4, and R5 are preferably a hydrogen atom, a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms, and more preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms.
[0063]
In formula (1-2), examples of preferable combination of R1, R2, R3, R4, and R5 include substructures represented by the substructure formula (3) in formula (1). Among them, preferable substructures are phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, and diethylphenyl.
[0064]
In formula (1-2), R6 and R7 are preferably a hydrogen atom, and a hydrocarbyl group having 1 to 20 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. Examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, a phenyl group, a 4- methylphenyl group, a 3-methylphenyl group, a 2-methylphenyl group, a 3, 5 -dimethylphenyl group, a 3,5-diethylphenyl group, a 3,5-di-tert-butylphenyl group, a naphthyl group, and a benzyl group.
[0065]
In formula (1-2), examples of preferable combination of R6 and R7 include substructures represented by the substructure formula (4) in formula (1). Preferable examples of the substructure formula (4) include a substructure formula in which R6 is a methyl group, R7 is an alkyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a halogenated alkyl group having 2 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms; a substructure formula in which R6 and R7 are the same alkyl group having 2 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, halogenated alkyl group having 2 to 20 carbon atoms or aryl group having 6 to 20 carbon atoms; and a substructure formula in which R6 and R7 are the different alkyl group having 2 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, halogenated alkyl group having 2 to 20 carbon atoms or aryl group having 6 to 20 carbon atoms. Examples of the substructures represented by these substructure formulae include dimethylsilylene, diethylsilylene, ethylmethylsilylene, n-butylmethylsilylene,
cyclohexylmethylsilylene, cyclotetramethylenesilylene, diphenylsilylene, methylphenylsilylene, di(3,5-dimethylphenyl)silylene, di(3,5-diethylphenyl)silylene, and (3,5-dimethylphenyl)(3,5-di- tert-butylphenyl)silylene.
[0066]
In formula (1-2), R8, R9, R10 and R11 are preferably a hydrogen atom, a halogen atom, and a hydrocarbyl group having 1 to 20 carbon atoms, and more preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. Furthermore, at least one of R8, R9, R10 and R11 is preferably a halogen atom or a substituent other than a hydrogen atom.
[0067]
Examples of R8, R9, R10 and R11 in formula (1-2) include the below- mentioned substructures for the substructural formula (6) in formula (1):
Figure imgf000021_0001
wherein R8, R9, R10 and Ru have the same meanings as in R8, R9, R10 and R11, respectively, in formula (1-2), in which at least one of them is a cyclopentadienyl substructure having a substituent other than a hydrogen atom or having a halogen atom. Examples thereof include the following substructures.
[0068]
The examples include methylcyclopentadienyl, ethylcyclopentadienyl, n- propylcyclopentadienyl, isopropylcyclopentadienyl, n-butylcyclopentadienyl, sec- butylcyclopentadienyl, tert-butylcyclopentadienyl, dimethylcyclopentadienyl,
trimethylcyclopentadienyl, tetramethylcyclopentadienyl phenylcyclopentadienyl,
benzylcyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, methyltetrahydroindenyl, dimethyltetrahydroindenyl, and octahydrofluorenyl.
[0069] Among the cyclopentadienyl substructures shown as examples herein, a preferable cyclopentadienyl substructure is tetramethylcyclopentadienyl.
[0070]
Examples of the compound represented by formula (1) include a compound re resented by formula (1-3):
Figure imgf000022_0001
wherein M1 represents a transition metal atom of Group 4 of the periodic table of the elements; R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, X1, X2 and X3 each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, or a disubstituted amino group, of R1, R2, R3, R4 and R5, two groups bonded to the two adjoining carbon atoms may be bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded, R6 and R7 may be bonded to each other to form a ring together with carbon atoms to which they are bonded, of R8, R9, R10 and R11, two groups bonded to the two adjoining carbon atoms may be bonded to each other to form a ring together with the two carbon atoms to which they are bonded, and two groups of X1, X2 and X3 may be bonded to each other to form a ring together with M1.
[0071]
M1 in formula (1-3) represents a transition metal atom of Group 4 of the periodic table of the elements, and examples thereof include a titanium atom, a zirconium atom and a hafnium atom. Among them, a titanium atom is preferable.
[0072]
In formula (1-3), R1, R2, R3, R4, R5, R6, R7 X1, X2 and X3 have the same meanings as in R1, R2, R3, R4, R5, R6, R7, X1, X2 and X3, respectively, in formula (1), and the meanings of a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a
hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, and a disubstituted amino group, a ring in which of R1, R2, R3, R4 and R5, two groups bonded to the two adjoining carbon atoms are bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded and a ring in which R6 and R7 are bonded to each other to form a ring together with a carbon atom to which they are bonded, examples thereof, and preferable embodiments thereof (preferable atoms, preferable groups, the number of the carbon atoms of the preferable groups, and the like) are the same as the meanings thereof, the examples thereof, and preferable embodiments thereof described in formula (1).
[0073]
In formula (1-3), R8, R9, R10, and Ru each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, or a disubstituted amino group. The meanings of a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, and a disubstituted amino group, and examples thereof and preferable embodiments thereof (preferable atoms, preferable groups, the number of carbon atoms of the preferable groups, and the like) are the same as the meanings thereof, the examples thereof, and preferable embodiments thereof described in formula (1).
[0074]
In formula (1-3), of R8, R9, R10 and R11, two groups bonded to the two adjoining carbon atoms may be bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded. Examples of the ring include a cyclopropane ring, a cyclopropene ring, a cyclobutane ring, a cyclobutene ring, a cyclopentane ring, a cyclopentene ring, a cyclohexane ring, a cyclohexene ring, a cycloheptane ring, a cycloheptene ring, a cyclooctane ring, a cyclooctene ring, a benzene ring, a naphthalene ring, an anthracene ring, and a saturated or unsaturated hydrocarbyl ring such as rings in which a hydrogen atom in these rings is substituted with a hydrocarbyl group having 1 to 20 carbon atoms.
[0075]
In formula (1-3), R1, R2, R3, R4, and R5 are preferably a hydrogen atom, a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms, and more preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms.
[0076]
In formula (1-3), examples of preferable combination of R1, R2, R3, R4, and R5 include substructures represented by the substructure formula (3) in formula (1). Among them, preferable substructures are phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, and diethylphenyl.
[0077]
In formula (1-3), R6 and R7 are each preferably a hydrogen atom, and a hydrocarbyl group having 1 to 20 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. Examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, a phenyl group, a 4-methylphenyl group, a 3-methylpheny group, a 2-methylphenyl group, a 3,5- dimethylphenyl group, a 3,5-a diethylphenyl group, a 3,5-di-tert-butylphenyl group, a naphthyl group, and a benzyl group.
[0078]
In formula (1-3), examples of preferable combination of R6 and R7 include substructures represented by the substructure formula (5) in formula (1). Preferable examples of the substructure formula (5) include a substructure formula in which R6 is a methyl group, R7 is an alkyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a halogenated alkyl group having 2 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms; a substructure formula in which R6 and R7 are the same alkyl group having 2 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, halogenated alkyl group having 2 to 20 carbon atoms or aryl group having 6 to 20 carbon atoms; and a substructure formula in which R6 and R7 are the different alkyl group having 2 to 20 carbo atoms, aryl group having 6 to 20 carbon atoms, halogenated alkyl group having 2 to 20 carbon atoms or aryl group having 6 to 20 carbon atoms. Examples of the substructures represented by these substructure formulae include isopropylidene, 1-ethylpropylene, 1-methylpropylene, 1-methylpentylene, 1-cyclohexylethylene, cyclotetramethylenemethylene, diphenylmethylene, 1-phenylethylene, di(3,5- dimethylphenyl)methylene, di(3,5-diethylphenyl)methylene, and (3,5-dimethylphenyl)(3,5-di- tert-butylphenyl)methylene.
[0079]
In formula (1-3), R8, R9, R10 and R11 are preferably a hydrogen atom, a halogen atom, or a hydrocarbyl group having 1 to 20 carbon atoms, and more preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. Furthermore, at least one of R8, R9, R10 and Ru is preferably a halogen atom or a substituent other than a hydrogen atom.
[0080]
Examples of R8, R9, R10 and R11 in formula (1-3) include the substructural formula (6) in formula (1):
Figure imgf000025_0001
wherein R8, R9, R10 and Rn have the same meanings as in R8, R9, R10 and R11, respectively, in formula (1-3), in which at least one is a cyclopentadienyl substructure having a substituent other than a hydrogen atom or having a halogen atom. Examples thereof include the following substructures.
[0081]
The examples include methylcyclopentadienyl, ethylcyclopentadienyl, n- propylcyclopentadienyl, isopropylcyclopentadienyl, n-butylcyclopentadienyl, sec- butylcyclopentadienyl, tert-butylcyclopentadienyl, dimethylcyclopentadienyl,
trimethylcyclopentadienyl, tetramethylcyclopentadienyl, phenylcyclopentadienyl,
benzylcyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, methyltetrahydroindenyl, dimethyltetrahydroindenyl, and octahydrofluorenyl.
[0082]
Among the cyclopentadienyl substructures shown as examples herein, preferable cyclopentadienyl substructure is tetramethylcyclopentadienyl.
[0083]
Examples of the compound represented by formula (1) include the following compounds:
[ 1 -dimethylphenyls ilyl-cyclopentadienyl]titanium trichloride,
[ 1 -dimethylphenylsiilyl-2-methylcyclopentadienyl]titanium trichloride,
[ 1 -dimethylphenyl siilyl-3-methylcyclopentadienyl]titanium trichloride,
[ 1 -dimethylphenyls ilyl-2,3-dimethylcyclopentadienyl]titanium trichloride,
[ 1 -dimethylphenylsiilyl-2,4-dimethylcyclopentadienyl]titaniutn trichloride,
[ 1 -dimethylphenylsiilyl-2,5-dimethylcyclopentadienyl]titanium trichloride,
[ 1 -dimethylphenylsi ily 1-2, 3 , 5 -trimethy Icy clopentadieny l]titanium trichloride,
[ 1 -dimethylphenyls; ilyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride,
[ 1 -dimethylphenylsiilyl-2-ethylcyclopentadienyl]titanium trichloride,
[ 1 -dimethylphenylsiily 1-3 -ethylcyclopentadieny l]titanium trichloride,
[ 1 -dimethylphenylsiilyl-2-n-propylcyclopentadienyl]titanium trichloride,
[ 1 -dimethylphenyls iilyl-3 -n-propylcyclopentadienyl]titanium trichloride,
[ 1 -dimethylphenylsiilyl-2-isopropylcyclopentadienyl]titanium trichloride, -dimethylphenylsi yl-2-n-butylcyclopentadienyl]titanium trichloride, -dimethylphenylsi yl-3 -n-butylcyclopentadienyl]titanium trichloride, -dimethylphenylsi yl-2-sec-butylcyclopentadienyl]titanium trichloride, -dimethylphenylsi yl-3 -sec-butyl cyclopentadienyljtitanium trichloride, -dimethylphenylsi yl-2-tert-butylcyclopentadienyl]titanium trichloride, -dimethylphenylsi yl-3-tert-butylcyclopentadienyl]titanium trichloride, -dimethylphenylsi yl-2-phenylcyclopentadienyl]titanium trichloride, -dimethylphenyl si yl-3-phenylcyclopentadienyl]titanium trichloride, -dimethylphenylsi yl-2-benzylcyclopentadienyl]titanium trichloride, -dimethylphenylsi yl-3 -benzylcyclopentadienyljtitanium trichloride, -dimethylphenylsi yl-indenyl]titanium trichloride,
-dimethylphenylsi yl-2-methylindenyl]titanium trichloride,
-dimethylphenylsi yl-fluorenyl]titanium trichloride,
-dimethylphenylsi yl-tetrahydroindenyl]titanium trichloride,
-dimethylphenylsi yl-2-methyltetrahydroindenyl]titanium trichloride,-dimethylphenylsi yl-octahydrofluorenyl]titanium trichloride,
084]
-diethylphenylsily -cyclopentadienyljtitanium trichloride,
-diethylphenylsily -2-methylcyclopentadienyl]titanium trichloride,
-diethylphenylsily -3 -methylcyclopentadienyl]titanium trichloride,
-diethylphenylsily -2,3-dimethylcyclopentadienyl]titanium trichloride, -diethylphenylsily -2,4-dimethylcyclopentadienyl]titanium trichloride, -diethylphenylsily -2, 5-dimethylcyclopentadienyl]titanium trichloride, -diethylphenylsily -2, 3 , 5-trimethylcyclopentadienyl]titanium trichloride, -diethylphenylsily -2,3,4,5-tetramethylcyclopentadienylJtitanium trichloride, -diethylphenylsily -2-ethylcyclopentadienyl]titanium trichloride,
-diethylphenylsily -3 -ethy lcyclopentadieny l]titanium trichloride,
-diethylphenylsily -2-n-propylcyclopentadienyl]titanium trichloride, -diethylphenylsily! -3 -n-propylcyclopentadienyl]titanium trichloride, -diethylphenylsily -2-isopropylcyclopentadienyl]titanium trichloride, -diethylphenylsily -3-isopropylcyclopentadienyl]titanium trichloride, -diethylphenylsily -2-n-butylcyclopentadienyl]titanium trichloride,
-diethylphenylsily -3 -n-butylcyclopentadienyl]titanium trichloride,
-diethylphenylsily -2-sec-butylcyclopentadienyl]titanium trichloride, 1-diethylphenylsiilyl-3 -sec-butylcyclopentadienyl]titanium trichloride,
1-diethylphenylsiilyl-2-tert-butylcyclopentadienyl]titanium trichloride,
1-diethylphenylsiilyl-3-tert-butylcyclopentadienyl]titanium trichloride,
'1-diethylphenyls ilyl-2-phenylcyclopentadienyl]titanium trichloride,
1-diethylphenylsii!lyl-3 -phenylcyclopentadienyl]titanium trichloride,
1-diethylphenylsiillyl-2-benzylcyclopentadienyl]titanium trichloride,
1-diethylphenylsiilyl-3 -benzylcyclopentadienyl]titanium trichloride,
1-diethylphenylsiilyl-indenyl]titanium trichloride,
1-diethylphenylsiilyl-2-methyl indenyljtitanium trichloride,
9-diethylphenyls ilyl-fluorenyl]titanium trichloride,
1-diethylphenyls ilyl-tetrahydroindenyl]titanium trichloride,
1-diethylphenylsiilyl-2-methyltetrahydroindenyl]titanium trichloride,
9-diethylphenylsiilyl-octahydrofluorenyl]titanium trichloride,
0085]
1 -cyclotetramethylene(phenyl)si yl-cyclopentadienyl]titanium trichloride,
1 -cyclotetramethy lene(pheny l)si yl-2-methylcyclopentadienyl]titanium trichloride,
1 -cyclotetramethylene(phenyl)si yl-3-methylcyclopentadienyl]titanium trichloride,
1 -cyclotetramethylene(phenyl)si yl-2,3-dimethylcyclopentadienyl]titanium trichloride, 1 -cyclotetramethylene(phenyl)si yl-2,4-dimethylcyclopentadienyl]titanium trichloride, 1 -cyclotetramethylene(phenyl)si yl-2, 5-dimethylcyclopentadienyl]titanium trichloride, 1 -cyclotetramethylene(phenyl)si yl-2, 3 , 5-trimethylcyclopentadienyl]titanium trichloride, 1 -cyclotetramethylene(phenyl)si yl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride, 1 -cyclotetramethylene(phenyl)si yl-2- ethylcyclopentadienyljtitanium trichloride,
1 -cyclotetramethylene(phenyl)si yl-3- ethylcyclopentadienyljtitanium trichloride,
1 -cyclotetramethylene(phenyl)si yl-2-n-propylcyclopentadienyl]titanium trichloride, 1 -cyclotetramethylene(phenyl)si yl-3 -n-propylcyclopentadienyl]titanium trichloride, 1 -cyclotetramethylene(phenyl)si yl-2-isopropylcyclopentadienyl]titanium trichloride, 1 -cyclotetramethylene(phenyl)si yl-3-isopropylcyclopentadienyl]titanium trichloride, 1 -cyclotetramethylene(phenyl)si yl-2-n-butylcyclopentadienyl]titanium trichloride,
1 -cyclotetramethylene(phenyl)si yl-3 -n-butylcyclopentadienyl]titanium trichloride,
1 -cyclotetramethylene(pheny l)si yl-2-sec-butylcyclopentadienyl]titanium trichloride, 1 -cyclotetramethy lene(phenyl)si yl-3 -sec-butylcyclopentadienyl]titanium trichloride, 1 -cyclotetramethylene(phenyl)si yl-2-tert-butylcyclopentadienyl]titanium trichloride, 1 -cyclotetramethylene(phenyl)si yl-3 -tert-butylcyclopentadienyl]titanium trichloride, [ 1 -cyclotetramethylene(phenyl)silyl-2-phenylcyclopentadienyl]titanium trichloride,
[ 1 -cyclotetramethylene(phenyl)silyl-3 -phenylcyclopentadienyljtitanium trichloride,
[ 1 -cyclotetramethylene(phenyl)silyl-2-benzylcyclopentadienyl]titanium trichloride,
[l-cyclotetramethylene(phenyl)silyl-3-benzylcyclopentadienyl]titanium trichloride,
[ 1 -cyclotetramethylene(phenyl)silyl-indenyl]titanium trichloride,
[ 1 -cyclotetramethylene(phenyl)silyl-2-methylindenyl]titanium trichloride,
[9-cyclotetramethylene(phenyl)silyl-fluorenyl]titanium trichloride,
[ 1 -cyclotetramethylene(phenyl)silyl-tetrahydroindenyl]titanium trichloride,
[ 1 -cyclotetramethylene(phenyl)silyl-2-methyltetrahydroindenyl]titanium trichloride,
[9-cyclotetramethylene(phenyl)silyl-octahydrofluorenyl]titanium trichloride,
[0086]
[ 1 -ethylmethylphenylsilyl-cyclopentadienyl]titanium trichloride,
[ 1 -ethylmethylphenylsilyl-2-methylcyclopentadienyl]titanium trichloride,
[l-ethylmethylphenylsilyl-3 -methyl cyclopentadienyl]titanium trichloride,
[l-ethylmethylphenylsilyl-2,3-dimethylcyclopentadienyl]titanium trichloride,
[l-ethylmethylphenylsilyl-2,4-dimethylcyclopentadienyl]titanium trichloride,
[l-ethylmethylphenylsilyl-2,5-dimethylcyclopentadienyl]titanium trichloride,
[l-ethylmethylphenylsilyl-2,3,5-trimethylcyclopentadienyl]titanium trichloride,
[l-ethylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride,
[ 1 -ethylmethylphenylsilyl-2-ethylcyclopentadienyl]titanium trichloride,
[ 1 -ethylmethylphenylsilyl-3 -ethylcyclopentadienyljtitanium trichloride,
[ 1 -ethylmethylphenylsilyl-2-n-propylcyclopentadienyl]titanium trichloride,
[1 -ethylmethylphenylsilyl-3 -n-propylcyclopentadienyl]titanium trichloride,
[ 1 -ethylmethylphenylsilyl-2-isopropylcyclopentadienyl]titanium trichloride,
[ 1 -ethylmethylphenylsilyl-3 -isopropylcyclopentadienyl]titanium trichloride,
[ 1 -ethylmethylphenylsilyl-2-n-butylcyclopentadienyl]titanium trichloride,
[ 1 -ethylmethylphenylsilyl-3-n-butylcyclopentadienyl]titanium trichloride,
[ 1 -ethylmethylphenylsilyl-2-sec-butylcyclopentadienyl]titanium trichloride,
[ 1 -ethylmethylphenylsilyl-3 -sec-butyl cyclopentadienyljtitanium trichloride,
[ 1 -ethylmethylphenylsilyl-2-tert-butyl cyclopentadienyljtitanium trichloride,
[ 1 -ethylmethylphenylsilyl-3 -tert-butylcyclopentadienyl]titanium trichloride,
[ 1 -ethylmethylphenylsilyl-2-phenyl cyclopentadienyljtitanium trichloride,
[ 1 -ethylmethylphenylsilyl-3 -phenylcyclopentadienyljtitanium trichloride,
[ 1 -ethylmethylpheny lsilyl-2-benzylcyclopentadienyl]t anium trichloride, ' 1 -ethylmethylphenylsily 3 -benzylcyclopentadienyljtitanium trichloride,
[ 1 -ethylmethylphenylsily indenyl]titanium trichloride,
' 1 -ethylmethylphenylsily 2-methyl indenyl]titanium trichloride,
9-ethylmethylphenylsily fluorenyl]titanium trichloride,
" 1 -ethylmethylphenylsily -tetrahydroindenyljtitanium trichloride,
" 1 -ethylmethylphenylsily -2-methyltetrahydroindenyl]titanium trichloride,
^-ethylmethylphenylsily -octahydrofluorenyljtitanium trichloride,
;0087]
[ 1 -n-butylmethylphenylsi yl-cyclopentadienyl]titanium trichloride,
1 -n-butylmethylphenylsi yl-2-methylcyclopentadienyl]titanium trichloride,
1 -n-butylmethylphenylsi yl-3-methylcyclopentadienyl]titanium trichloride,
1 -n-butylmethylphenylsi yl-2,3-dimethylcyclopentadienyl]titanium trichloride, 1 -n-butylmethylphenylsi yl-2,4-dimethylcyclopentadienyl]titanium trichloride, 1 -n-butylmethylphenylsi yl-2, 5-dimethylcyclopentadienyl]titanium trichloride, 1 -n-butylmethylphenylsi y 1-2, 3 , 5 -trimethylcyclopentadieny 1] titanium trichloride, 1 -n-butylmethylphenylsi yl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride, 1 -n-butylmethylphenylsi yl-2-ethylcyclopentadienyl]titanium trichloride,
1 -n-butylmethylphenylsi yl-3 -ethylcyclopentadienyl]titanium trichloride,
1 -n-butylmethylphenylsi yl-2-n-propylcyclopentadienyl]titanium trichloride, 1 -n-butylmethylphenylsi yl-3 -n-propylcyclopentadieny ljtitanium trichloride, 1 -n-butylmethylphenylsi yl-2-isopropylcyclopentadienyl]titanium trichloride, 1 -n-butylmethylphenylsi yl-3 -isopropylcyclopentadienyl]titanium trichloride, 1 -n-butylmethylphenylsi yl-2-n-butylcyclopentadienyl]titanium trichloride,
1 -n-butylmethylphenylsi yl-3 -n-butylcyclopentadienyl]titanium trichloride,
1 -n-butylmethylphenylsi y 1-2-sec-butyl cy clopentadieny ljtitanium trichloride, 1 -n-butylmethylphenylsi yl-3 -sec-butylcyclopentadienyl]titanium trichloride, 1 -n-butylmethylphenylsi yl-2-tert-butylcyclopentadienyl]titanium trichloride, 1 -n-butylmethylphenylsi yl-3 -tert-butylcyclopentadienyl]titanium trichloride, 1 -n-butylmethylphenylsi yl-2-phenylcyclopentadienyl]titanium trichloride,
1 -n-butylmethylphenylsi yl-3-phenylcyclopentadienyl]titanium trichloride,
1 -n-butylmethylphenylsi yl-2-benzylcyclopentadienyl]titanium trichloride,
1 -n-butylmethylphenylsi yl-3 -benzylcyclopentadienyl]titanium trichloride,
1 -n-butylmethylphenylsi yl-indenyl]titanium trichloride,
1 -n-butylmethylphenylsi yl-2-methylindenyl]titanium trichloride, 9-n-butylmethylphenylsilyl-fluorenyl]titanium trichloride,
1 -n-butylmethylphenylsilyl-tetrahydroindenyl]titanium trichloride,
1 -n-butylmethylphenylsilyl-2-methyltetrahydroindenyl]titanium trichloride,
9-n-butylmethylphenylsilyl-octahydrofluorenyl]titanium trichloride,
0088]
~ 1 -methyldiphenyls ilyl -cyclopentadienyljtitanium trichloride,
11 -methyldiphenyls .lyl -2-methylcy clopentadieny 1] titanium trichloride,
"1 -methyldiphenyls Llyl -3 -methylcyclopentadienyl]titanium trichloride,
] 1 -methyldiphenyls Llyl -2,3-dimethylcyclopentadienyl]titanium trichloride,
^ 1 -methyldiphenyls ilyl -2,4-dimethylcyclopentadienyl]titanium trichloride,
" 1 -methyldiphenyls ilyl -2, 5-dimethylcyclopentadienyl]titanium trichloride,
' 1 -methyldiphenyls ilyl -2,3,5-trimethylcyclopentadienyl]titanium trichloride,
~ 1 -methyldiphenyls ilyl -2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride,
" 1 -methyldiphenyls ilyl -2-ethylcyclopentadienyl ]titanium trichloride,
1 -methyldiphenyls ilyl -3-ethylcyclopentadienyl]titanium trichloride,
1 -methyldiphenyls ilyl -2-n-propylcyclopentadienyl]titanium trichloride,
1 -methyldiphenyls ilyl -3 -n-propylcyclopentadienyl]titanium trichloride,
' 1 -methyldiphenyls ilyl -2-isopropylcyclopentadienyl]titanium trichloride,
~ 1 -methyldiphenyls ilyl -2-n-butylcyclopentadienyl]titanium trichloride,
1 -methyldiphenyls lyl -3-n-butylcyclopentadienyl]titanium trichloride,
1 -methyldiphenyls lyl -2-sec-butylcyclopentadienyl]titanium trichloride,
1 -methyldiphenylsi lyl -3 -sec-butylcyclopentadienyl]titanium trichloride,
1 -methyldiphenyls lyl -2-tert-butylcyclopentadienyl]titanium trichloride,
1 -methyldiphenyls lyl -3 -tert-butylcyclopentadienyl]titanium trichloride,
1 -methyldiphenylsi lyl -2-phenylcyclopentadienyl]titanium trichloride,
1 -methyldiphenylsi lyl -3 -phenyl cyclopentadienyljtitanium trichloride,
1 -methyldiphenylsi lyl -2-benzylcyclopentadienyl]titanium trichloride,
1 -methyldiphenylsi lyl -3 -benzylcyclopentadienyl]titanium trichloride,
1 -methyldiphenyl si lyl -indenyl]titanium trichloride,
1 -methyldiphenyl si lyl -2-methylindenyl]titanium trichloride,
9-methyldiphenylsi lyl -fluorenyl]titanium trichloride,
1 -methyldiphenylsi lyl -tetrahydroindenyl]titanium trichloride,
1 -methyldiphenylsi lyl -2-methyltetrahydroindenyl]titanium trichloride,
9-methyldiphenylsi lyl -octahydrofluorenyl]titanium trichloride, 0089]
-cyclopentadienyljtitanium trichloride,
-2-methylcyclopentadienyl]titanium trichloride,
-3 -methylcyclopentadienyl]titanium trichloride,
-2,3-dimethylcyclopentadienyl]titanium trichloride, -2,4-dimethylcyclopentadienyl]titanium trichloride, -2, 5-dimethylcyclopentadienyl]titanium trichloride, -2, 3 , 5-trimethylcyclopentadienyl]titanium trichloride, -2,3,4,5 -tetramethy lcyclopentadienyl]titanium trichloride, -2-ethylcyclopentadienyl]titanium trichloride,
-3-ethylcyclopentadienyl]titanium trichloride,
-2-n-propylcyclopentadienyl]titanium trichloride, -3 -n-propylcyclopentadienyl]titanium trichloride, -2-isopropylcyclopentadienylJtitanium trichloride, -2-n-butylcyclopentadienyl]titanium trichloride,
-3 -n-butylcy clopentadienyl]titanium trichloride,
-2-sec-butylcyclopentadienyl]titanium trichloride, -3-sec-butylcyclopentadienyl]titanium trichloride, -2-tert-butylcyclopentadienyl]titanium trichloride, -3 -tert-butylcyclopentadienyl]titanium trichloride, -2-phenylcyclopentadienyl]titanium trichloride,
-3 -phenylcyclopentadienyljtitanium trichloride,
-2-benzylcyclopentadienyl]titanium trichloride,
-3 -benzylcyclopentadienyl]titanium trichloride,
-indenyljtitanium trichloride,
-2-methyl indenyl]titanium trichloride,
-fluorenyl]titanium trichloride,
-tetrahydroindenyljtitanium trichloride,
-2-methyltetrahydroindenyl]titanium trichloride,
Figure imgf000031_0001
-octahydrofluorenyljtitanium trichloride,
0090]
l-cyclohexylmethylphenylsilyl-cyclopentadienyl]titanium trichloride,
l-cyclohexylmethylphenylsilyl-2-methylcyclopentadienyl]titanium trichloride,
1 -cyclohexylmethylphenylsilyl-3 -methylcyclopentadienyl]titanium trichloride, -cyclohexylmethylphenyls 2, 3 -dimethy lcyclopentadienyl]titanium trichloride, -cyclohexylmethylphenyls 2.4- dimethylcyclopentadienyl]titanium trichloride, -cyclohexylmethylphenyls 2.5- dimethylcyclopentadienyl]titanium trichloride, -cyclohexylmethylphenyls 2,3 , 5-trimethylcyclopentadienyl]titanium trichloride, -cyclohexylmethylphenyls 2,3 ,4,5-tetramethylcyclopentadienyl]titanium trichloride, -cyclohexylmethylphenyls -2-ethylcyclopentadienyl]titanium trichloride,
-cyclohexylmethylphenyls -3 -ethylcyclopentadienyljtitanium trichloride,
-cyclohexylmethylphenyls -2-n-propylcyclopentadienyl]titanium trichloride, .
-cyclohexylmethylphenyls -3 -n-propylcyclopentadienyl]titanium trichloride, -cyclohexylmethylphenyls] -2-isopropylcyclopentadienyl]titanium trichloride, -cyclohexylmethylphenyls -3-isopropylcyclopentadienyl]titanium trichloride, -cyclohexylmethylphenyls -2-n-butylcyclopentadienyl]titanium trichloride,
-cyclohexylmethylphenyls 3 -n-butylcyclopentadienyl]titanium trichloride,
-cyclohexylmethylphenyls 2- sec-butylcyclopentadienyl]titanium trichloride, -cyclohexylmethylphenyls; 3- sec-butylcyclopentadienyl]titanium trichloride, -cyclohexylmethylphenyls: ■2-tert-butylcyclopentadienyl]titanium trichloride, -cyclohexylmethylphenyls: 3 -tert-butylcyclopentadienyl]titanium trichloride, -cyclohexylmethylphenyls: 2-phenylcyclopentadienyl]titanium trichloride,
-cyclohexylmethylphenyls: 3 -phenylcyclopentadieny l]titanium trichloride,
-cyclohexylmethylphenyls; 2- benzylcyclopentadienyl]titanium trichloride,
-cyclohexylmethylphenyls; 3- benzylcyclopentadienyl]titanium trichloride,
-cyclohexylmethylphenyls; indenyl]titanium trichloride,
-cyclohexylmethylphenyls; 2-methylindenyl]titanium trichloride,
-cyclohexylmethylphenyls; fluorenyljtitanium trichloride,
-cyclohexylmethylphenyl s: tetrahydroindenyl]titanium trichloride,
-cyclohexy methylphenyls: -2-methyltetrahydroindenyl]titanium trichloride,
-cyclohexylmethylphenyls: octahydrofluorenyl]titanium trichloride,
091]
-methyl(n-octadecyl)pheny yl-cyclopentadienyl]titanium trichloride,
-methyl(n-octadecyl)pheny yl-2-methylcyclopentadienyl]titanium trichloride, -methyl(n-octadecyl)pheny yl-3 -methyl cyclopentadienyl]titanium trichloride, -methyl(n-octadecyl)pheny yl-2,3 -dimethylcyclopentadienyljtitanium trichloride, -methyl(n-octadecyl)pheny yl-2,4-dimethylcyclopentadienyl]titanium trichloride, -methyl(n-octadecyl)pheny yl-2, 5 -dimethylcy clopentadienyl]titanium trichloride, 1 -methy l(n-octadecyl)pheny Is y 1-2, 3 , 5 -trimethylcyclopentadienyljtitanium trichloride, 1 -methyl(n-octadecyl)phenyls yl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride, 1 -methyl(n-octadecyl)phenyls yl-2-ethylcyclopentadienyl]titanium trichloride,
1 -methyl(n-octadecyl)phenyls yl-3-ethylcyclopentadienyl]titanium trichloride,
1 -methyl(n-octadecyl)phenyls yl-2-n-propylcyclopentadienyl]titanium trichloride, 1 -methyl(n-octadecyl)phenyls yl-3-n-propylcyclopentadienyl]titanium trichloride, 1 -methyl(n-octadecyl)phenyls: yl-2-isopropylcyclopentadienyl]titanium trichloride, 1 -methyl(n-octadecyl)phenyls yl-3 -isopropylcyclopentadienyl]titanium trichloride, 1 -methyl(n-octadecyl)phenylsi yl-2-n-butylcyclopentadienyl]titanium trichloride,
1 -methy l(n-octadecyl)pheny lsi yl-3 -n-butylcyclopentadienyl]titanium trichloride,
1 -methyl(n-octadecyl)phenyls yl-2-sec-butylcyclopentadienyl]titanium trichloride, 1 -methyl(n-octadecyl)phenylsi yl-3-sec-butylcyclopentadienyl]titanium trichloride, 1 -methyl(n-octadecyl)phenylsi yl-2-tert-butylcyclopentadienyl]titanium trichloride, 1 -methyl(n-octadecyl)phenyls yl-3 -tert-butylcyclopentadienyl]titanium trichloride, 1 -methyl(n-octadecyl)phenyls yl-2-phenylcyclopentadienyl]titanium trichloride,
1 -methyl(n-octadecyl)phenyls yl-3 -phenylcyclopentadienyljtitanium trichloride,
1 -methyl(n-octadecyl)phenyls yl-2-benzylcyclopentadienyl]titanium trichloride,
1 -methyl(n-octadecyl)phenyls yl-3 -benzylcyclopentadienyl]titanium trichloride,
1 -methyl(n-octadecyl)phenyls yl-indenyl]titanium trichloride,
1 -methyl(n-octadecyl)phenyls yl-2-methylindenyl]titanium trichloride,
9-methyl(n-octadecyl)phenyls: yl-fluorenyl]titanium trichloride,
1 -methyl(n-octadecyl)phenyls! yl-tetrahydroindenyl]titanium trichloride,
1 -methyl(n-octadecyl)phenylsi yl-2-methyltetrahydroindenyl]titanium trichloride,
9-methyl(n-octadecyl)phenylsi yl-octahydrofluorenyl]titanium trichloride,
0092]
l-triphenylsilyl- cyclopentadienyljtitanium trichloride,
l-triphenylsilyl- 2- methylcyclopentadienyl]titanium trichloride,
l-triphenylsilyl- 3 - methyl cyclopentadienyl]titanium trichloride,
l-triphenylsilyl- 2.3- dimethylcyclopentadienyl]titanium trichloride,
l-triphenylsilyl- 2.4- dimethylcyclopentadienyl]titanium trichloride,
1-triphenylsilyl- 2.5- dimethylcyclopentadienyl]titanium trichloride,
1-triphenylsilyl- 2,3,5-trimethylcyclopentadienyl]titanium trichloride,
l-triphenylsilyl- 2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride,
l-triphenylsilyl- 2-ethylcyclopentadienyl]titanium trichloride, [ 1 -triphenylsilyl-3 -ethyl cyclopentadienyl]titanium trichloride,
[ 1 -triphenylsilyl-2-n-propylcyclopentadienyl]titanium trichloride,
[l-triphenylsilyl-3-n-propylcyclopentadienyl]titanium trichloride,
[ 1 -triphenylsilyl-2-isopropylcyclopentadienyl]titanium trichloride,
[ 1 -triphenylsilyl-3 -isopropylcyclopentadienyljtitanium trichloride,
[ 1 -triphenylsilyl-2-n-butylcyclopentadienyl]titanium trichloride,
[ 1 -triphenylsilyl-3 -n-butylcyclopentadienyl]titanium trichloride,
[ 1 -triphenylsilyl-2-sec-butylcyclopentadienyl]titanium trichloride,
[ 1 -triphenylsilyl-3 -sec-butyl cyclopentadienyl]titanium trichloride,
[ 1 -triphenylsilyl-2-tert-butylcyclopentadienyl]titanium trichloride,
[ 1 -triphenylsilyl-3-tert-butylcyclopentadienyl]titanium trichloride,
[ 1 -triphenylsilyl-2-phenylcyclopentadienyl]titanium trichloride,
[ 1 -triphenylsilyl-3 -phenylcyclopentadienyljtitanium trichloride,
[ 1 -trip henylsilyl-2-benzylcyclopentadienyl]titanium trichloride,
[ 1 -triphenylsilyl-3-benzylcyclopentadienyl]titanium trichloride,
[ 1 -tripheny lsily -indeny l]titanium trichloride,
[ 1 -triphenylsilyl-2-methylindenyl]titanium trichloride,
[9-triphenylsilyl-fluorenyl]titanium trichloride,
[l-triphenylsilyl-tetrahydroindenyl]titanium trichloride,
[l-triphenylsilyl-2-methyltetrahydroindenyl]titanium trichloride,
[9-triphenylsilyl-octahydrofluorenyl]titanium trichloride,
[0093]
[ 1 -tri(4-n-butylphenyl)silyl-cyclopentadienyl]titanium trichloride,
[ 1 -tri(4-n-butylphenyl)silyl-2-methylcyclopentadienyl]titanium trichloride,
[ 1 -tri(4-n-butylphenyl)silyl-3 -methyl cyclopentadienyl]titanium trichloride,
[l-tri(4-n-butylphenyl)silyl-2,3-dimethylcyclopentadienyl]titanium trichloride,
[ 1 -tri(4-n-butylphenyl)silyl-2,4-dimethylcyclopentadienyl]titanium trichloride,
[l-tri(4-n-butylphenyl)silyl-2,5-dimethylcyclopentadienyl]titanium trichloride,
[l-tri(4-n-butylphenyl)silyl-2,3,5-trimethylcyclopentadienyl]titanium trichloride, [l-tri(4-n-butylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride, [ 1 -tri(4-n-butylphenyl)silyl-2-ethylcyclopentadienyl]titanium trichloride,
[l-tri(4-n-butylphenyl)silyl-3-ethylcyclopentadienylJtitanium trichloride,
[ 1 -tri(4-n-butylphenyl)silyl-2-n-propylcyclopentadienyl]titanium trichloride,
[ 1 -tri(4-n-butylphenyl)silyl-3-n-propylcyclopentadienyl]titanium trichloride, l-tri(4-n-butylphenyl)silyl-2-isopropylcyclopentadienyl]titanium trichloride, l-tri(4-n-butylphenyl)silyl-3-isopropylcyclopentadienyl]titanium trichloride, l-tri(4-n-butylphenyl)silyl-2-n-butylcyclopentadienyl]titanium trichloride,
1 -tri(4-n-butylphenyl)silyl-3 -n-butylcyclopentadienyl]titanium trichloride, l-tri(4-n-butylphenyl)silyl-2-sec-butylcyclopentadienyl]titanium trichloride, 1 -tri(4-n-butylphenyl)silyl-3 -sec-butylcyclopentadienyl]titanium trichloride, l-tri(4-n-butylphenyl)silyl-2-tert-butylcyclopentadienyl]titanium trichloride, l-tri(4-n-butylphenyl)silyl-3-tert-butylcyclopentadienyl]titanium trichloride, l-tri(4-n-butylphenyl)silyl-2-phenylcyclopentadienyl]titanium trichloride, l-tri(4-n-butylphenyl)silyl-3-phenylcyclopentadienyl]titanium trichloride,
1 -tri(4-n-butylphenyl)silyl-2-benzylcyclopentadienyl]titanium trichloride,
1 -tri(4-n-butylphenyl)silyl-3-benzylcyclopentadienyl]titanium trichloride,
1 -tri(4-n-butylphenyl)silyl-indenyl]titanium trichloride,
l-tri(4-n-butylphenyl)silyl-2-methyl indenyl]titanium trichloride,
9-tri(4-n- butylphenyl)silyl-fluorenyl]titanium trichloride,
l-tri(4-n-butylphenyl)silyl-tetrahydroindenyl]titanium trichloride,
l-tri(4-n-butyIphenyl)silyl-2-methyltetrahydroindenyl]titanium trichloride,
9-tri(4-n-butylphenyl)silyl-octahydrofluorenyl]titanium trichloride,
0094]
1 -tri(3 -methylphenyl)silyl-cyclopentadienyl]titanium trichloride,
1 -tri(3 -methylphenyl)silyl-2-methylcyclopentadienyl]titanium trichloride,
1 -tri(3 -methylphenyl)silyl-3 -methylcyclopentadienyl]titanium trichloride, l-tri(3-methylphenyl)silyl-2,3-dimethylcyclopentadienyl]titanium trichloride, 1 -tri(3 -methylphenyl)silyl-2,4-dimethylcyclopentadienyl]titanium trichloride, 1 -tri(3-methylphenyl)silyl-2,5-dimethylcyclopentadienyl]titanium trichloride, l-tri(3-methylphenyl)silyl-2,3,5-trimethylcyclopentadienyl]titanium trichloride, l-tri(3-methylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride, l-tri(3-methylphenyl)silyl-2-ethylcyclopentadienyl]titanium trichloride,
1 -tri(3 -methylphenyl)silyl-3 -ethylcyclopentadienyl]titanium trichloride,
l-tri(3-methylphenyl)silyl-2-n-propylcyclopentadienyl]titanium trichloride, l-tri(3-methylphenyl)silyl-3-n-propylcyclopentadienyl]titanium trichloride, 1 -tri(3 -methylphenyl)silyl-2-isopropylcyclopentadienyl]titanium trichloride, l-tri(3-methylphenyl)silyl-3-isopropylcyclopentadienyl]titanium trichloride, l-tri(3-methylphenyl)silyl-2-n-butylcyclopentadienyl]titanium trichloride, [ 1 -tri(3-methylphenyl)silyl-3-n-butylcyclopentadienyl]titanium trichloride,
[l-tri(3-methylphenyl)silyl-2-sec-butylcyclopentadienyl]titanium trichloride,
[ 1 -tri(3 -methylphenyl)silyl-3 -sec-butyl cyclopentadienyljtitanium trichloride,
[ 1 -tri(3-methylphenyl)silyl-2-tert-butylcyclopentadienyl]titanium trichloride,
[l-tri(3-methylphenyl)silyl-3-tert-butylcyclopentadienyl]titanium trichloride,
[ 1 -tri(3 -methylphenyl)silyl-2-phenyl cyclopentadienyljtitanium trichloride,
[l-tri(3-methylphenyl)silyl-3-phenylcyclopentadienyl]titanium trichloride,
[ 1 -tri(3 -methylphenyl)silyl-2 -benzyl cyclopentadienyljtitanium trichloride,
[l-tri(3-methylphenyl)silyl-3-benzylcyclopentadienyl]titanium trichloride,
[ 1 -tri(3-methylphenyl)silyl-indenyl]titanium trichloride,
[ 1 -tri(3 -methylphenyl)silyl-2-methyl indenyl]titanium trichloride,
[9-tri(3-methylphenyl)silyl-fluorenyl]titanium trichloride,
[ 1 -tri(3-methylphenyl)silyl-tetrahydroindenyl]titanium trichloride,
[ 1 -tri(3 -methylphenyl)sily l-2-methyltetrahydroindenyl]titanium trichloride,
[9-tri(3-methylphenyl)silyl-octahydrofluorenyl]titanium trichloride,
[0095]
[ 1 -tri(3 -isopropylphenyl)silyl-cyclopentadienyl]titanium trichloride,
[ 1 -tri(3 -isopropylphenyl)silyl-2-methy lcyclopentadienyljtitanium trichloride,
[ 1 -tri(3 -isopropylphenyl)silyl-3 -methylcyclopentadienyljtitanium trichloride,
[ 1 -tri(3-isopropylphenyl)silyl-2,3 -dimethylcyclopentadienyl]titanium trichloride,
[ 1 -tri(3-isopropylphenyl)silyl-2,4-dimethylcyclopentadienyl]titanium trichloride,
[l-tri(3-isopropylphenyl)silyl-2,5-dimethylcyclopentadienyl]titanium trichloride,
[l-tri(3-isopropylphenyl)silyl-2,3,5-trimethylcyclopentadienyl]titanium trichloride,
[ 1 -tri(3 -isopropylpheny l)si lyl-2, 3,4,5 -tetramethy lcyclopentadienyljtitanium trichloride,
[ 1 -tri(3-isopropylphenyl)silyl-2-ethylcyclopentadienyl]titanium trichloride,
[ 1 -tri(3 -isopropylphenyl)silyl-3 -ethylcyclopentadienyl Jtitanium trichloride,
[ 1 -tri(3-isopropylphenyl)silyl-2-n-propyl cyclopentadienyljtitanium trichloride,
[l-tri(3-isopropylphenyl)silyl-3-n-propylcyclopentadienyljtitanium trichloride,
[ 1 -tri(3-isopropylphenyl)silyl-2-isopropylcyclopentadienyl]titanium trichloride,
[l-tri(3-isopropylphenyl)silyl-3-isopropylcyclopentadienyl]titanium trichloride,
[ 1 -tri(3 -isopropylphenyl)silyl-2-n-butylcyclopentadienyl]titanium trichloride,
[ 1 -tri(3 -isopropylpheny l)silyl-3 -n-butylcyclopentadienyl]titanium trichloride,
[ 1 -tri(3 -isopropylphenyl)silyl-2-sec-butylcyclopentadienyl]titanium trichloride,
[ 1 -tri(3 -isopropylphenyl)silyl-3 -sec-butylcyclopentadienyl]titanium trichloride, 1 -tri(3 -isopropylphenyl)s lyl-2-tert-butylcyclopentadienyl]titanium trichloride, 1 -tri(3-isopropylphenyl)s lyl-3 -tert-butylcyclopentadienyl]titanium trichloride,
1 -tri(3-isopropylphenyl)s lyl-2-phenylcyclopentadienyl]titanium trichloride,
l-tri(3-isopropylphenyl)s lyl-3 -phenylcyclopentadienyl]titanium trichloride,
l-tri(3-isopropylphenyl)si lyl-2-benzylcyclopentadienyl]titanium trichloride,
1 -tri(3-isopropylphenyl)s lyl-3 -benzylcyclopentadienyljtitanium trichloride,
1 -tri(3 -isopropylphenyl)s lyl-indenyl]titanium trichloride,
1 -tri(3 -isopropylpheny l)s lyl-2-methylindenyl]titanium trichloride,
9-tri(3 -isopropylphenyl)s lyl-fluorenyl]titanium trichloride,
1 -tri(3 -isopropylpheny l)s lyl-tetrahydroindenyl]titanium trichloride,
1 -tri(3-isopropylphenyl)s lyl-2-methyltetrahydroindenyl]titanium trichloride,
-tri(3 -isopropylphenyl)s: lyl-octahydrofluorenyl]titanium trichloride,
096]
-dimethyli 5-d; methylphenyl)si yl-cyclopentadienyl]titanium trichloride,
-dimethyli 5-d: methylphenyl)si yl-2-methylcyclopentadienyl]titanium trichloride,
-dimethyli 5-d: methylphenyl)si yl-3-methylcyclopentadienyl]titanium trichloride,
-dimethyl 5-d methylphenyl)si yl-2, 3 -dimethyl cyclopentadienyl]titanium trichloride, -dimethyli 5-d methylphenyl)si yl-2,4-dimethylcyclopentadienyl]titanium trichloride, -dimethyli 5-d methylphenyl)si yl-2,5-dimethylcyclopentadienyl]titanium trichloride, -dimethyli 5-d; methylphenyl)si yl-2,3,5-trimethylcyclopentadienyl]titanium trichloride, -dimethyli 5-d methylphenyl)si yl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride, -dimethyli 5-d methylphenyl)si yl-2-ethylcyclopentadienyl]titanium trichloride,
-dimethyli 5-d methylphenyl)si yl-3-ethylcyclopentadienyl]titanium trichloride,
-dimethyli 5-d methylphenyl)si yl-2-n-propylcyclopentadienyl]titanium trichloride, -dimethyli 5-d methylphenyl)si yl-3 -n-propylcyclopentadienyl]titanium trichloride, -dimethyli 5-d methylphenyl)si yl-2-isopropylcyclopentadienyl]titanium trichloride, -dimethyli 5-d methylphenyl)si yl-3 -isopropylcyclopentadienyljtitanium trichloride, -dimethyli 5-d methylphenyl)si yl-2-n-butylcyclopentadienyl]titanium trichloride,
-dimethyli 5-d methylphenyl)si yl-3 -n-butylcyclopentadienyl]titanium trichloride,
-dimethyli 5-d methylphenyl)si yl-2-sec-butylcyclopentadienyl]titanium trichloride, -dimethyl) 5-d methylphenyl)si yl-3 -sec-butylcyclopentadienyl]titanium trichloride, -dimethyli 5-d methylphenyl)si yl-2-tert-butylcyclopentadienyl]titanium trichloride, -dimethyl! 5-d; methylphenyl)si yl-3-tert-butylcyclopentadienyl]titanium trichloride, -dimethyl! 5-d; methylphenyl)si yl-2-phenylcyclopentadienyl]titanium trichloride, [1-dimethyi 3,5-d methylphenyl)silyl-3-phenylcyclopentadienyl]titanium trichloride,
[1 -dimethyl 5-d methylphenyl)silyl-2-benzylcyclopentadienyl]titanium trichloride,
[1 -dimethyl 5-d methylphenyl)silyl-3-benzylcyclopentadienyl]titanium trichloride,
[1 -dimethyl 5-d methylphenyl)silyl-indenyl]titanium trichloride,
[1-dimethyi 5-d methylphenyl)silyl-2-methyl indenyl]titanium trichloride,
[9-dimethy] 5-d methylphenyl)silyl-fluorenyl]titanium trichloride,
[1 -dimethyl 5-d methylphenyl)silyl-tetrahydroindenyl]titanium trichloride,
[1 -dimethyl 5-d methylphenyl)silyl-2-methyltetrahydroindenyl]titanium trichloride,
[9-dimethyl 5-d methylphenyl)silyl-octahydrofluorenyl]titanium trichloride,
[0097]
[1 -dimethyl 5-d: -n-hexylpheny l-cyclopentadienyl]titanium trichloride,
[1 -dimethyl 5-d -n-hexylpheny l-2-methylcyclopentadienyl]titanium trichloride,
[1 -dimethyl 5-d: -n-hexylpheny 1-3 -methylcyclopentadienyljtitanium trichloride,
[1 -dimethyl 5-d: -n-hexylpheny l-2,3-dimethylcyclopentadienyl]titanium trichloride,
[1 -dimethyl 5-d: -n-hexylpheny l-2,4-dimethylcyclopentadienyl]titanium trichloride,
[1 -dimethyl 5-d -n-hexylphenyi 1-2, 5-dimethylcyclopentadieny IJtitanium trichloride,
[1 -dimethyl 5-d -n-hexylpheny 1-2,3, 5-trimethylcyclopentadienyl]titanium trichloride, [1 -dimethyl 5-d n-hexylpheny l-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride, [1 -dimethyl 5-d n-hexylpheny l-2-ethylcyclopentadienyl]titanium trichloride,
[1 -dimethyl 5-d -n-hexylpheny l-3-ethylcyclopentadienyl]titanium trichloride,
[1 -dimethyl 5-d n-hexylphenyl l-2-n-propylcyclopentadienyl]titanium trichloride,
[1 -dimethyl 5-d -n-hexylpheny l-3-n-propylcyclopentadienyl]titanium trichloride,
[1 -dimethyl 5-d n-hexylpheny l-2-isopropylcyclopentadienyl]titanium trichloride,
[1 -dimethyl 5-d n-hexylpheny 1-3 -isopropylcyclopentadieny ljtitanium trichloride,
[1 -dimethyl 5-d -n-hexylpheny! l-2-n-butylcyclopentadienyl]titanium trichloride,
[1 -dimethyl 5-d n-hexylpheny 1-3 -n-butylcyclopentadienyl]titanium trichloride,
[1 -dimethyl 5-d n-hexylphenyl l-2-sec-butylcyclopentadienyl]titanium trichloride,
[1 -dimethyl 5-d -n-hexylpheny l-3-sec-butylcyclopentadienyl]titanium trichloride,
[1 -dimethyl 5-d n-hexylpheny l-2-tert-butylcyclopentadienyI]titanium trichloride,
[1 -dimethyl 5-d n-hexylpheny! l-3-tert-butylcyclopentadienyl]titanium trichloride,
[1 -dimethyl 5-d n-hexylphenyl l-2-phenylcyclopentadienyl]titanium trichloride,
[1 -dimethyl 5-d n-hexylpheny l-3-phenylcyclopentadienyl]titanium trichloride,
[1 -dimethyl 5-d n-hexylpheny l-2-benzylcyclopentadienyl]titanium trichloride,
[1 -dimethyl 5-d n-hexylpheny l-3-benzylcyclopentadienyl]titanium trichloride, [l-dimethyl(3,5-di-n-hexylphenyl)silyl-indenyl]titanium trichloride,
[l-dimethyl(3,5-di-n-hexylphenyl)silyl-2-methyl indenyl]titanium trichloride,
[9-dimethyl(3,5-di-n-hexylphenyl)silyl-fluorenyl]titanium trichloride,
[l-dimethyl(3,5-di-n-hexylphenyl)silyl-tetrahydroindenyl]titanium trichloride,
[l-dimethyl(3,5-di-n-hexylphenyl)silyl-2-methyltetrahydroindenyl]titanium trichloride,
[9-dimethyl(3 , 5-di-n-hexylphenyl)silyl-octahydrofluorenyl]titanium trichloride,
[0098]
[l-n-butylmethyl(3,5-dimethylphenyl)silyl-cyclopentadienyl]titanium trichloride,
[l-n-butylmethyl(3,5-dimethylphenyl)silyl-2-methylcyclopentadienyl]titanium trichloride,
[ 1 -n-butylmethyl(3 , 5-dimethylphenyl)silyl-3 -methylcyclopentadienyl]titanium trichloride,
[l-n-butylmethyl(3,5-dimethylphenyl)silyl-2,3-dimethylcyclopentadienyl]titanium trichloride, [l-n-butylmethyl(3,5-dimethylphenyl)silyl-2,4-dimethylcyclopentadienyl]titanium trichloride, [ 1 -n-butylmethyl(3 , 5 -dimethylphenyl)silyl-2, 5-dimethylcyclopentadienyl]titanium trichloride, [ 1 -n-buty Imethy 1(3 , 5 -dimethy lphenyl)sily 1-2, 3 , 5 -trimethylcyclopentadienyl]titanium trichloride, [l-n-butylmethyl(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride,
[l-n-butylmethyl(3,5-dimethylphenyl)silyl-2-ethylcyclopentadienyl]titanium trichloride,
[l-n-butylmethyl(3,5-dimethylphenyl)silyl-3-ethylcyclopentadienyl]titanium trichloride,
[l-n-butylmethyl(3,5-dimethylphenyl)silyl-2-n-propylcyclopentadienyl]titanium trichloride, [ 1 -n-butylmethyl(3 , 5-dimethylphenyl)silyl-3 -n-propylcyclopentadienyl]titanium trichloride, [ 1 -n-butylmethyl(3 ,5-dimethylphenyl)silyl-2-isopropylcyclopentadienyl]titanium trichloride, [l-n-butylmethyl(3,5-dimethylphenyl)silyl-3-isopropylcyclopentadienyl]titanium trichloride, [l-n-butylmethyl(3,5-dimethylphenyl)silyl-2-n-butylcyclopentadienyl]titanium trichloride, [ 1 -n-butylmethyl(3, 5-dimethylphenyl)silyl-3 -n-butylcyclopentadienyl]titanium trichloride, [l-n-butylmethyl(3,5-dimethylphenyl)silyl-2-sec-butylcyclopentadienyl]titanium trichloride, [l-n-butylmethyl(3,5-dimethylphenyl)silyl-3-sec-butylcyclopentadienyl]titanium trichloride, [ 1 -n-butylmethyl(3 , 5-dimethylphenyl)silyl-2-tert-butylcyclopentadienyl]titanium trichloride, [l-n-butylmethyl(3,5-dimethylphenyl)silyl-3-tert-butylcyclopentadienyl]titanium trichloride, [ 1 -n-butylmethyl(3, 5-dimethylphenyl)silyl-2-phenylcyclopentadienyl]titanium trichloride,
[ 1 -n-butylmethyl(3, 5-dimethylphenyl)silyl-3-phenylcyclopentadienyl]titanium trichloride,
[ 1 -n-butylmethyl(3, 5-dimethylphenyl)silyl-2-benzylcyclopentadienyl]titanium trichloride,
[l-n-butylmethyl(3,5-dimethylphenyl)silyl-3-benzylcyclopentadienyl]titanium trichloride,
[l-n-butylmethyl(3,5-dimethylphenyl)silyl-indenyl]titanium trichloride,
[ 1 -n-butylmethyl(3,5-dimethylphenyl)silyl-2-methylindenyl]titanium trichloride, 9-n-butylmethyl(3,5-dimethylphenyl)silyl-fluorenyl]titanium trichloride, l-n-butylmethyl(3,5-dimethylphenyl)silyl-tetrahydroindenyl]titanium trichloride, l-n-butylmethyl(3,5-dimethylphenyl)silyl-2-methyltetrahydroindenyl]titanium trichloride, 9-n-butylmethyl(3,5-dimethylphenyl)silyl-octahydrofluorenyl]titanium trichloride, 099]
-tris(3 , 5 -dimethylphenyl) sily l-cyclopentadienyl]titanium trichloride,
-tris(3 , 5-dimethylphenyl)sily l-2-methylcyclopentadienyl]titanium trichloride,
-tris(3,5-dimethylphenyl)sily [-3 -methylcyclopentadienyl]titanium trichloride,
-tris(3,5-dimethylphenyl)sily l-2,3-dimethylcyclopentadienyl]titanium trichloride, -tris(3 , 5-dimethylphenyl)sily l-2,4-dimethylcyclopentadienyl]titanium trichloride, -tris(3 , 5 -dimethylphenyl) sily [-2,5-dimethylcyclopentadienyl]titanium trichloride, -tris(3 , 5 -dimethylphenyl) sily l-2,3,5-trimethylcyclopentadienyl]titanium trichloride, -tris(3,5-dimethylphenyl)sily l-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride, -tris(3 , 5 -dimethylphenyl) sily l-2-ethylcyclopentadienyl]titanium trichloride,
-tris(3 , 5 -dimethylphenyl) sily 1-3 -ethylcyclopentadienyljtitanium trichloride,
-tris(3,5-dimethylphenyl)silyi l-2-n-propylcyclopentadienyl]titanium trichloride,
-tris(3 , 5-dimethylphenyl)sily [-3 -n-propylcyclopentadieny l]titanium trichloride,
-tris(3, 5-dimethylphenyl)sily [-2-isopropylcyclopentadienyl]titanium trichloride,
-tris(3,5-dimethylphenyl)sily [-3 -isopropylcyclopentadienyljtitanium trichloride,
-tris(3,5-dimethylphenyl)sily i-2-n-butylcyclopentadienyl]titanium trichloride,
-tris(3 , 5 -dimethylphenyl) sily 1-3 -n-butylcyclopentadienyl]titanium trichloride,
-tris(3 ,5-dimethylphenyl)sily l-2-sec-butylcyclopentadienyl]titanium trichloride,
-tris(3,5-dimethylphenyl)sily 1-3 -sec-butylcyclopentadienyl]titanium trichloride,
-tris(3 , 5 -dimethylphenyl) sily i-2-tert-butylcyclopentadienyl]titanium trichloride,
-tris(3 , 5 -dimethylphenyl) sily [-3 -tert-butylcyclopentadienyl]titanium trichloride,
-tris(3 , 5-dimethylphenyl)sily l-2-phenylcyclopentadienyl]titanium trichloride,
-tris(3, 5-dimethylphenyl)sily 1-3 -phenylcyclopentadienyl]titanium trichloride,
-tris(3,5-dimethylphenyl)sily i-2-benzylcyclopentadienyl]titanium trichloride,
-tris(3 , 5 -dimethylphenyl) sily l-3-benzylcyclopentadienyl]titanium trichloride,
-tris(3 , 5-dimethylphenyl)sily l-indenyl]titanium trichloride,
-tris(3 , 5-dimethylphenyl)sily [-2-methylindenyl]titanium trichloride,
'-tris(3,5-dimethylphenyl)silyi 1-fluorenylJtitanium trichloride,
-tris(3,5-dimethylphenyl)sily l-tetrahydroindenyl] titanium trichloride,
-tris(3,5-dimethylphenyl)sily [-2-methyltetrahydroindenyl]titanium trichloride, 9-tris(3 , 5 -dimethy lpheny 1) sily 1-oct ahydrofluorenyljtitanium trichloride, 0100]
[ 1 -tris(3, 5-diethylphenyl )silyl -cyclopentadienyl]titanium trichloride,
[ 1 -tris(3 , 5 -diethy lpheny 1 )silyl -2-methylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3, 5-diethylphenyl )silyl -3 -methylcyclopentadienyljtitanium trichloride,
[ 1 -tris(3 , 5 -diethylphenyl )silyl -2,3-dimethylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3 , 5-diethylphenyl )silyl -2,4-dimethylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3 , 5 -diethylphenyl )silyl -2,5-dimethylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3 , 5-diethylphenyl )silyl -2,3,5-trimethylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3 , 5-diethylphenyl )silyl -2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3 , 5 -diethylphenyl )silyl -2-ethylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3 , 5 -diethylphenyl )silyl -3 -ethylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3 , 5 -diethylphenyl )silyl -2-n-propylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3 , 5 -diethylphenyl )silyl -3-n-propylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3 , 5 -diethylphenyl )silyl -2-isopropylcyclopentadienyl]titanium trichloride,
[l-tris(3, 5-diethylphenyl )silyl -3 -isopropylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3 , 5 -diethylphenyl )silyl -2-n-butylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3 , 5 -diethylphenyl )silyl -3 -n-butylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3 , 5 -diethylphenyl )silyl -2-sec-butylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3 , 5 -diethylphenyl )silyl -3 -sec-butylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3 , 5 -diethylphenyl )silyl -2-tert-butylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3 , 5 -diethylphenyl )silyl -3 -tert-butylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3 , 5 -diethylphenyl )silyl -2-phenylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3 , 5 -diethylphenyl )silyl -3 -phenylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3 , 5-diethylphenyl )silyl -2-benzylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3 , 5 -diethylphenyl )silyl -3 -benzylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3 , 5 -diethy phenyl )silyl -indenyl]titanium trichloride,
[ 1 -tris(3 , 5 -diethylphenyl )silyl -2-methylindenyl]titanium trichloride,
[9-tris(3 , 5-diethylphenyl )silyl -fluorenyl]titanium trichloride,
[ 1 -tris(3 , 5-diethylphenyl )silyl -tetrahydroindenyl]titanium trichloride,
[ 1 -tris(3 , 5 -diethylphenyl )silyl -2-methyltetrahydroindenyl]titanium trichloride,
[9-tris(3 , 5 -diethylphenyl )silyl -octahydrofluorenyl]titanium trichloride,
[0101]
l-tris(3,5-diisopropylphenyl)silyl-cyclopentadienyl]titanium trichloride, ■ 1 -tris(3 ,5-diisopropylphenyl)silyl-2-methylcyclopentadienyl]titanium trichloride,
-tris(3,5-diisopropylphenyl)silyl-3-methylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3,5-diisopropylphenyl)silyl-2,3-dimethylcyclopentadienyl]titanium trichloride,
-tris(3,5-diisopropylphenyl)silyl-2,4-dimethylcyclopentadienyl]titanium trichloride, -tris(3,5-diisopropylphenyl)silyl-2,5-dimethylcyclopentadienyl]titanium trichloride, -tris(3,5-diisopropylphenyl)silyl-2,3,5-trimethylcyclopentadienyl]titanium trichloride, -tris(3,5-diisopropylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride, 1 -tris(3,5-diisopropylphenyl)silyl-2-ethylcyclopentadienyl]titanium trichloride,
l-tris(3,5-diisopropylphenyl)silyl-3-ethylcyclopentadienyl]titanium trichloride,
-tris(3,5-diisopropylphenyl)silyl-2-n-propylcyclopentadienyl]titanium trichloride, l-tris(3,5-diisopropylphenyl)silyl-3-n-propylcyclopentadienyl]titanium trichloride, l-tris(3,5-diisopropylphenyl)silyl-2-isopropylcyclopentadienyl]titanium trichloride, l-tris(3,5-diisopropylphenyl)silyl-3-isopropylcyclopentadienyl]titanium trichloride, 1 -tris(3 , 5 -diisopropylphenyl)silyl-2-n-butylcyclopentadienyl]titanium trichloride,
; 1 -tris(3 , 5-diisopropylphenyl)silyl-3 -n-butylcyclopentadienyl]titanium trichloride,
-tris(3,5-diisopropylphenyl)silyl-2-sec-butylcyclopentadienyl]titanium trichloride, ; 1 -tris(3 , 5-diisopropylphenyl)silyl-3 -sec-butylcyclopentadienyl]titanium trichloride, l-tris(3,5-diisopropylphenyl)silyl-2-tert-butylcyclopentadienyl]titanium trichloride, 1 -tris(3 , 5-diisopropylphenyl)silyl-3 -tert-butyIcyclopentadienyl]titanium trichloride, ;i-tris(3,5-diisopropylphenyl)silyl-2-phenylcyclopentadienyl]titanium trichloride,
; 1 -tris(3 ,5-diisopropylphenyl)silyl-3 -phenylcyclopentadienyl]titanium trichloride,
1 -tris(3,5-diisopropylphenyl)silyl-2-benzylcyclopentadienyl]titanium trichloride,
' 1 -tris(3,5-diisopropylphenyl)silyl-3-benzylcyclopentadienyl]titanium trichloride,
\ 1 -tris(3,5-diisopropylphenyl)silyl-indenyl]titanium trichloride,
' 1 -tris(3 , 5 -dii sopropylphenyl) silyl-2-methyl indenyl]titanium trichloride,
9-tris(3,5-diisopropylphenyl)silyl-fluorenyl]titanium trichloride,
l-tris(3,5-diisopropylphenyl)silyl-tetrahydroindenyl]titanium trichloride,
l-tris(3,5-diisopropylphenyl)silyl-2-methyltetrahydroindenyl]titanium trichloride,
9-tris(3,5-diisopropylphenyl)silyl-octahydrofluorenyl]titanium trichloride,
0102]
l-tris(3,5-di-tert-butylphenyl)silyl-cyclopentadienyl]titanium trichloride,
l-tris(3,5-di-tert-butylphenyl)silyl-2-methylcyclopentadienyl]titanium trichloride, l-tris(3,5-di-tert-butylphenyl)silyl-3-methylcyclopentadienyl]titanium trichloride, l-tris(3,5-di-tert-butylphenyl)silyl-2,3-dimethylcyclopentadienyl]titanium trichloride, [l-tris(3,5-di-tert-butylphenyl)silyl-2,4-dimethylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-di-tert-butylphenyl)silyl-2,5-dimethylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3 , 5-di-tert-butylphenyl)silyl-2, 3 , 5-trimethylcyclopentadienyl]titanium trichloride, [l-tris(3,5-di-tert-butylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride, [l-tris(3,5-di-tert-butylphenyl)silyl-2-ethylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-di-tert-butylphenyl)silyl-3-ethylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-di-tert-butylphenyl)silyl-2-n-propylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3 , 5 -di-tert-butylphenyl) silyl-3 -n-propylcycl opentadienyl Jtitanium trichloride,
[l-tris(3,5-di-tert-butylphenyl)silyl-2-isopropylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-di-tert-butylphenyl)silyl-3-isopropylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-di-tert-butylphenyl)silyl-2-n-butylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-di-tert-butylphenyl)silyl-3-n-butylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-di-tert-butylphenyl)silyl-2-sec-butylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-di-tert-butylphenyl)silyl-3-sec-butylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-di-tert-butylphenyl)silyl-2-tert-butylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3 , 5-di-tert-butylphenyl)silyl-3 -tert-butylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-di-tert-butylphenyl)silyl-2-phenylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3 , 5 -di-tert-butylphenyl) silyl-3 -pheny lcyclopentadieny l]titanium trichloride,
[l-tris(3,5-di-tert-butylphenyl)silyl-2-benzylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-di-tert-butylphenyl)silyl-3-benzylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3 , 5 -di-tert-butylphenyl) silyl-indeny 1] titanium trichloride,
[l-tris(3,5-di-tert-butylphenyl)silyl-2-methyl indenyl]titanium trichloride,
[9-tris(3,5-di-tert-butylphenyl)silyl-fluorenyl]titanium trichloride,
[ 1 -tris(3, 5-di-tert-butylphenyl)silyl-tetrahydroindenyl]titanium trichloride,
[l-tris(3,5-di-tert-butylphenyl)silyl-2-methyltetrahydroindenyl]titanium trichloride,
[9-tris(3,5-di-tert-butylphenyl)silyl-octahydrofluorenyl]titanium trichloride,
[0103]
[l-tris(3,5-di-n-hexylphenyl)silyl-cyclopentadienyl]titanium trichloride,
[l-tris(3,5-di-n-hexylphenyl)silyl-2-methylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-di-n-hexylphenyl)silyl-3-methylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-di-n-hexylphenyl)silyl-2,3-dimethylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-di-n-hexylphenyl)silyl-2,4-dimethylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3,5-di-n-hexylphenyl)silyl-2,5-dimethylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-di-n-hexylphenyl)silyl-2,3,5-trimethylcyclopentadienyl]titanium trichloride, -tris(3,5-di-■n-hexylphenyl)si lyl-2,3 ,4, 5-tetramethylcyclopentadienyl]titanium trichloride,
-tris(3 5-di-•n-hexylphenyl)si lyl-2-ethylcyclopentadienyl]titanium trichloride,
-tris(3 5-di-•n-hexylphenyl)si lyl-3 -ethylcyclopentadienyl]titanium trichloride,
-tris(3 5-di- n-hexylphenyl)si lyl-2-n-propylcyclopentadienyl]titanium trichloride,
-tris(3 5-di- n-hexylphenyl)si lyl-3 -n-propylcyclopentadienyl]titanium trichloride,
-tris(3 5-di-■n-hexylphenyl)si lyl-2-isopropylcyclopentadienyl]titanium trichloride,
-tris(3 5-di- n-hexylphenyl)si lyl-3 -isopropylcyclopentadienyl]titanium trichloride,
-tris(3 5-di- n-hexylphenyl)si lyl-2-n-butylcyclopentadienyl]titanium trichloride,
-tris(3 5-di- n-hexylphenyl)si lyl-3 -n-butylcyclopentadienyl]titanium trichloride,
-tris(3 5-di- n-hexylphenyl)si lyl-2-sec-butylcyclopentadienyl]titanium trichloride,
-tris(3 5-di- n-hexylphenyl)si lyl-3 -sec-butylcyclopentadienyl]titanium trichloride,
-tris(3 5-di- n-hexylphenyl)si lyl-2-tert-butylcyclopentadienyl]titanium trichloride,
-tris(3 5-di- n-hexylphenyl)si lyl-3 -tert-butylcyclopentadienyl]titanium trichloride,
-tris(3 5-di- n-hexylphenyl)si lyl-2-phenylcyclopentadienyl]titanium trichloride,
-tris(3 5-di- n-hexylphenyl)si lyl-3 -phenylcyclopentadienyljtitanium trichloride,
-tris(3 5-di- n-hexylphenyl)si lyl-2-benzylcyclopentadienyl]titanium trichloride,
-tris(3 5-di- n-hexylphenyl)si lyl-3 -benzylcyclopentadienyljtitanium trichloride,
-tris(3 5-di- n-hexylphenyl)si lyl-indenyl]titanium trichloride,
-tris(3 5-di- n-hexylphenyl)si lyl-2-methyl indenyljtitanium trichloride,
-tris(3 5-di- n-hexylphenyl)si lyl-fluorenyl]titanium trichloride,
-tris(3 5-di- n-hexylphenyl)si lyl-tetrahydroindenyl]titanium trichloride,
-tris(3 5-di- n-hexylphenyl)si lyl-2-methyltetrahydroindenyl]titanium trichloride,
9-tris(3 5-di-n-hexylphenyl)si lyl-octahydrofluorenyl]titanium trichloride,
0104]
l-n-butylmethyl(2,4,6-trimethylphenyl)silyl-cyclopentadienyl]titanium trichloride,
l-n-butylmethyl(2,4,6-trimethylphenyl)silyl-2-methylcyclopentadienyl]titanium trichloride, l-n-butylmethyl(2,4,6-trimethylphenyl)silyl-3-methylcyclopentadienyl]titanium trichloride, l-n-butylmethyl(2,4,6-trimethylphenyl)silyl-2,3-dimethylcyclopentadienyl]titanium trichloride, l-n-butylmethyl(2,4,6-trimethylphenyl)silyl)-2,4-dimethylcyclopentadienyl]titanium trichloride, l-n-butylmethyl(2,4,6-trimethylphenyl)silyl-2,5-dimethylcyclopentadienyl]titanium trichloride, l-n-butylmethyl(2,4,6-trimethylphenyl)silyl-2,3,5-trimethylcyclopentadienyl]titanium trichloride,
[l-n-butylmethyl(2,4,6-trimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride, l-n-butylmethyl(2,4,6-trimethylphenyl)s lyl-2-ethylcyclopentadienyl]titanium trichloride, l-n-butylmethyl(2,4,6-trimethylphenyl)s lyl-3 -ethylcyclopentadienyl]titanium trichloride, l-n-butylmethyl(2,4,6-trimethylphenyl)s lyl-2-n-propylcyclopentadienyl]titanium trichloride, l-n-butylmethyl(2,4,6-trimethylphenyl)s! lyl-3 -n-propylcyclopentadienyl]titanium trichloride, l-n-butylmethyl(2,4,6-trimethylphenyl)s lyl-2-isopropylcyclopentadienyl]titanium trichloride, l-n-butylmethyl(2,4,6-trimethylphenyl)si lyl-3 -isopropylcyclopentadienyl]titanium trichloride, l-n-butylmethyl(2,4,6-trimethylphenyl)s lyl-2-n-butylcyclopentadienyl]titanium trichloride, l-n-butylmethyl(2,4,6-trimethylphenyl)s lyl-3 -n-butylcyclopentadienyl]titanium trichloride, l-n-butylmethyl(2,4,6-trimethylphenyl)s lyl-2-sec-butylcyclopentadienyl]titanium trichloride, l-n-butylmethyl(2,4,6-trimethylphenyl)s lyl-3-sec-butylcyclopentadienyl]titanium trichloride, 1 -n-butylmethyl(2,4, 6-trimethylphenyl)s lyl-2-tert-butylcyclopentadienyl]titanium trichloride, l-n-butylmethyl(2,4,6-trimethylphenyl)s lyl-3 -tert-butylcyclopentadienyl]titanium trichloride, l-n-butylmethyl(2,4,6-trimethylphenyl)s lyl-2-phenylcyclopentadienyl]titanium trichloride, l-n-butylmethyl(2,4,6-trimethylphenyl)s lyl-3-phenylcyclopentadienyl]titanium trichloride, l-n-butylmethyl(2,4,6-trimethylphenyl)s lyl-2-benzylcyclopentadienyl]titanium trichloride, l-n-butylmethyl(2,4,6-trimethylphenyl)s lyl-3-benzylcyclopentadienyl]titanium trichloride, l-n-butylmethyl(2,4,6-trimethylphenyl)s lyl-indenyl]titanium trichloride,
l-n-butylmethyl(2,4,6-trimethylphenyl)s lyl-2-methyl indenyl]titanium trichloride,
9-n-butylmethyl(2,4,6-trimethylphenyl)s lyl-fluorenyl]titanium trichloride,
1 -n-butylmethyl(2,4,6-trimethylphenyl )s lyl-tetrahydroindenyl]titanium trichloride, l-n-butylmethyl(2,4,6-trimethylphenyl)s: lyl-2-methyltetrahydroindenyl]titanium trichloride, 9-n-butylmethyl(2,4,6-trimethylphenyl lyl-octahydrofluorenyl]titanium trichloride,
0105]
l-n-butylmethyl(pentamethylphenyl)si cyclopentadienyl]titanium trichloride,
l-n-butylmethyl(pentamethylphenyl)si 2-methylcyclopentadienyl]titanium trichloride, l-n-butylmethyl(pentamethylphenyl)si 3 -methylcyclopentadienyl]titanium trichloride, l-n-butylmethyl(pentamethylphenyl)si 2,3 -dimethylcyclopentadienyl]titanium trichloride, l-n-butylmethyl(pentamethylphenyl)si 2.4- dimethylcyclopentadienyl]titanium trichloride, l-n-butylmethyl(pentamethylphenyl)si 2.5- dimethylcyclopentadienyl]titanium trichloride, l-n-butylmethyl(pentamethylphenyl)si 2,3,5 -trimethy lcyclopentadieny l]titanium trichloride, l-n-butylmethyl(pentamethylphenyl)si 2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride,
l-n-butylmethyl(pentamethylphenyl)si 2-ethylcyclopentadienyl]titanium trichloride, l-n-butylmethyl(pentamethylphenyl)si 3 -ethylcyclopentadienyljtitanium trichloride, [ 1 -n-butylmethyl(pentamethylphenyl)silyl-2-n-propylcyclopentadienyl]titanium trichloride, [ 1 -n-butylmethyl(pentamethylphenyl)silyl-3-n-propylcyclopentadienyl]titanium trichloride, [ 1 -n-butylmethyl(pentamethylphenyl)silyl-2-isopropylcyclopentadienyl]titanium trichloride, [ 1 -n-butylmethyl(pentamethylphenyl)silyl-3-isopropylcyclopentadienyl]titanium trichloride, [ 1 -n-butylmethyl(pentamethylphenyl)silyl-2-n-butylcyclopentadienyl]titanium trichloride, [ 1 -n-butylmethyl(pentamethylphenyl)silyl-3-n-butylcyclopentadienyl]titanium trichloride, [ 1 -n-butylmethyl(pentamethylphenyl)silyl-2-sec-butylcyclopentadienyl]titanium trichloride, [l-n-butylmethyl(pentamethylphenyl)silyl-3-sec-butylcyclopentadienyl]titanium trichloride, [ 1 -n-butylmethyl(pentamethylphenyl)silyl-2-tert-butylcyclopentadienyl]titanium trichloride, [ 1 -n-butylmethyl(pentamethylphenyl)silyl-3-tert-butylcyclopentadienyl]titanium trichloride, [ 1 -n-butylmethyl(pentamethylphenyl)silyl-2-phenylcyclopentadienyl]titanium trichloride, [ 1 -n-butylmethyl(pentamethylphenyl)silyl-3 -phenyl cyclopentadienyljtitanium trichloride, [ 1 -n-butylmethyl(pentamethylphenyl)silyl-2-benzylcyclopentadienyl]titanium trichloride, [ 1 -n-butylmethyl(pentamethylphenyl)silyl-3 -benzylcyclopentadienyl]titanium trichloride, [ 1 -n-butylmethyl(pentamethylphenyl)silyl-indenyl]titanium trichloride,
[ 1 -n-butylmethyl(pentamethylphenyl)sily 1-2-methyl indeny l]titanium trichloride,
[9-n-butylmethyl(pentamethylphenyl)silyl-fluorenyl]titaniuni trichloride,
[ 1 -n-butylmethyl(pentamethylpheny l)sily 1-tetrahy droindenyl]titanium trichloride,
[ 1 -n-butylmethyl(pentamethylphenyl)silyl-2-methy ltetrahydroindenyljtitanium trichloride, [9-n-butylmethyl(pentamethylphenyl)silyl-octahydrofluorenyl]titanium trichloride,
[0106]
[l-(3,5-di-tert-butylphenyl)bis(3,5-dimethylphenyl)silyl-cyclopentadienyl]titanium trichloride,
[l-(3,5-di-tert-butylphenyl)bis(3,5-dimethylphenyl)silyl-2-methylcyclopentadienyl]titanium trichloride,
v
[l-(3,5-di-tert-butylphenyl)bis(3,5-dimethylphenyl)silyl-3-methylcyclopentadienyl]titanium trichloride,
[l-(3,5-di-tert-butylphenyl)bis(3,5-dimethylphenyl)silyl-2,3-dimethylcyclopentadienyl]titanm trichloride,
[l-(3,5-di-tert-butyiphenyl)bis(3,5-dimethylphenyl)silyl-2,4-dimethylcyclopentadienyl]titanium trichloride,
[l-(3,5-di-tert-butylphenyl)bis(3,5-dimethylphenyl)silyl-2,5-dimethylcyclopentadienyl]titaniurn trichloride,
[ 1 -(3 , 5 -di-tert-butylphenyl)bis(3 , 5 -dimethylphenyl)silyl-2, 3,5- trimethylcyclopentadienyljtitanium trichloride, [ 1 -(3, 5-di-tert-butylphenyl)bis(3 , 5-dimethy lphenyl)si ■2,3,4,5- tetramethylcydopentadienyl]titanium trichloride,
[ 1 -(3, 5-di-tert-butylphenyl)bis(3 , 5-dimethylphenyl )si ■2-ethylcyclopentadienyl]titanium trichloride,
[l-(3,5-di-tert-butylphenyl)bis(3,5-dimethylphenyl)si •3-ethylcyclopentadienyl]titanium trichloride,
[ 1 -(3, 5 -di-tert-butylphenyl)bis(3, 5-dimethylphenyl )si ■2-n-propylcyclopentadienyl]titanium trichloride,
[ 1 -(3 , 5 -di-tert-butylpheny l)bi s(3 , 5 -dimethylphenyl )si ■3-n-propylcyclopentadienyl]titanium trichloride,
[l-(3,5-di-tert-butylphenyl)bis(3, 5-dimethylphenyl )si ■2-isopropylcyclopentadienyl]titanium trichloride,
[ 1 -(3 , 5 -di-tert-butylpheny l)bis(3 , 5 -dimethylphenyl )si ■3-isopropylcyclopentadienyl]titanium trichloride,
[ 1 -(3, 5-di-tert-butylphenyl)bis(3, 5-dimethylphenyl )si ■2-n-butylcyclopentadienyl]titanium trichloride,
[ 1 -(3, 5-di-tert-butylphenyl)bis(3 , 5-dimethylphenyl )si -3-n-butylcyclopentadienyl]titanium trichloride,
[ 1 -(3, 5-di-tert-butylphenyl)bis(3 , 5-dimethylphenyl )si -butylcyclopentadienyljtitanium trichloride,
[ 1 -(3 , 5 -di-tert-butylphenyl)bis(3 , 5 -dimethylphenyl )si -butylcyclopentadienyljtitanium trichloride,
[ 1 -(3 , 5 -di-tert-butylpheny l)bi s(3 , 5 -dimethylphenyl )si; 2-tert-butylcyclopentadienyl]titanium trichloride,
[l-(3,5-di-tert-butylphenyl)bis(3, 5-dimethylphenyl )si 3-tert-butylcyclopentadienyl]titanium trichloride,
[l-(3,5-di-tert-butylphenyl)bis(3, 5-dimethylphenyl )si ■2-phenylcyclopentadienyl]titanium trichloride,
[ 1 -(3 , 5 -di-tert-butylpheny l)bis(3 , 5 -dimethylphenyl )si iylcyclopentadienyl]titanium trichloride,
[ 1 -(3, 5-di-tert-butylphenyl)bis(3,5-dimethylphenyl )si •2-benzylcyclopentadienyl]titanium trichloride,
[ 1 -(3, 5-di-tert-butylphenyl)bis(3 , 5-dimethylphenyl )si ■3-benzylcyclopentadienyl]titanium trichloride, [ 1 -(3 , 5 -di-tert-butylpheny i)bis(3 , 5 -dimethy lpheny l)sily 1-indeny l]titanium trichloride,
[l-(3,5-di-tert-butylphenyl)bis(3,5-dimethylphenyl)silyl-2-methyl indenyl]titanium trichloride, [9-(3,5-di-tert-butylphenyl)bis(3,5-dimethylphenyl)silyl-fluorenyl]titanium trichloride,
[l-(3,5-di-tert-butylphenyl)bis(3,5-dimethylphenyl)silyl-tetrahydroindenyl]titanium trichloride, [l-(3,5-di-tert-butylphenyl)bis(3,5-dimethylphenyl)silyl-2-methyltetrahydroindenyl]titanium trichloride,
[9-(3,5-di-tert-butylphenyl)bis(3,5-dimethylphenyl)silyl-octahydrofluorenyl]titanium trichloride, [0107]
[ 1 -(3 , 5 -di-tert-butylpheny 1)(3 , 5 -diethylphenyl)(3 , 5 -dimethylphenyl)sily 1- cyclopentadienyl]titanium trichloride,
[l-(3,5-di-tert-butylphenyl)(3,5-diethylphenyl)(3,5-dimethylphenyl)silyl-2- methylcyclopentadienyljtitanium trichloride,
[ 1 -(3 ,5-di-tert-butylphenyl)(3 , 5-diethy lphenyl)(3 , 5-dimethylphenyl)silyl-3 - methylcyclopentadienyljtitanium trichloride,
[ 1 -(3, 5-di-tert-butylphenyl)(3, 5-diethy lphenyl)(3 , 5-dimethylphenyl)silyl-2, 3 - dimethylcyclopentadienyl]titanium trichloride,
[l-(3,5-di-tert-butylphenyl)(3,5-diethylphenyl)(3,5-dimethylphenyl)silyl-2,4- dimethylcyclopentadienyl]titanium trichloride,
[ 1 -(3,5-di-tert-butylphenyl)(3 , 5-diethylphenyl)(3 , 5-dimethylphenyl)silyl-2,5- dimethylcyclopentadienyljtitanium trichloride,
[l-(3,5-di-tert-butylphenyl)(3,5-diethylphenyl)(3,5-dimethylphenyl)silyl-2,3,5- trimethylcyclopentadienyl]titanium trichloride,
[l-(3,5-di-tert-butylphenyl)(3,5-diethylphenyl)(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride,
[l-(3,5-di-tert-butylphenyl)(3,5-diethylphenyl)(3,5-dimethylphenyl)silyl-2- ethylcyclopentadienyljtitanium trichloride,
[ 1 -(3 , 5 -di-tert-butylpheny 1)(3 , 5 -diethy lpheny 1)(3 , 5 -dimethylphenyl) silyl-3 - ethylcyclopentadienyl]titanium trichloride,
[ 1 -(3 , 5 -di-tert-butylpheny 1)(3 , 5 -diethylphenyl)(3 , 5 -dimethylphenyl) silyl-2-n- propylcyclopentadienyl]titanium trichloride,
[ 1 -(3 , 5 -di-tert-butylphenyl)(3 , 5 -diethy lphenyl)(3 , 5 -dimethylphenyl) sily 1-3 -n- propylcyclopentadienyljtitanium trichloride,
[l-(3,5-di-tert-butylphenyl)(3,5-diethylphenyl)(3,5-dimethylphenyl)silyl-2- isopropylcyclopentadienyl]titanium trichloride, [ 1 -(3, 5-di-tert-butylphenyl)(3 , 5-diethylphenyl)(3 , 5-dimethylphenyl)silyl-3 - isopropylcyclopentadienyl]titanium trichloride,
[ 1 -(3 , 5 -di-tert-butylpheny 1)(3 , 5 -diethylpheny 1)(3 , 5 -dimethylphenyl) sily 1-2-n- butylcyclopentadienyl]titanium trichloride,
[ 1 -(3 , 5 -di-tert-butylpheny 1)(3 , 5-diethy lpheny 1)(3 , 5 -dimethylphenyl)sily 1-3 -n- butylcyclopentadienyl]titanium trichloride,
[l-(3,5-di-tert-butylphenyl)(3,5-diethylphenyl)(3,5-dimethylphenyl)silyl-2-sec- butylcyclopentadienyl]titanium trichloride,
[ 1 -(3, 5 -di-tert-butylphenyl)(3, 5 -diethylpheny 1)(3 , 5-dimethylphenyl)silyl-3 -sec- butylcyclopentadienyljtitanium trichloride,
[ 1 -(3 , 5 -di-tert-butylpheny 1)(3 , 5 -diethylpheny 1)(3 , 5 -dimethylphenyl) sily 1-2-tert- butylcyclopentadienyl]titanium trichloride,
[l-(3,5-di-tert-butylphenyl)(3,5-diethylphenyl)(3,5-dimethylphenyl)silyl-3-tert- butylcyclopentadienyl]titanium trichloride,
[ 1 -(3 , 5 -di-tert-butylpheny 1)(3 , 5 -diethy lphenyl)(3 , 5 -dimethylphenyl) sily 1-2- phenylcyclopentadienyl]titanium trichloride,
[l-((3,5-di-tert-butylphenyl)(3,5-diethylphenyl)(3,5-dimethylphenyl)silyl-3- phenylcyclopentadienyljtitanium trichloride,
[l-(3,5-di-tert-butylphenyl)(3,5-diethylphenyl)(3,5-dimethylphenyl)silyl-2- benzylcyclopentadienyljtitanium trichloride,
[ 1 -(3 , 5 -di-tert-butylpheny 1)(3 , 5 -diethylpheny 1)(3 , 5 -dimethylphenyl) silyl-3 - benzylcyclopentadienyl]titanium trichloride,
[ 1 -(3 , 5 -di-tert-butylpheny 1)(3 , 5 -diethylpheny 1)(3 , 5 -dimethylphenyl) sily 1-indeny 1] titanium trichloride,
[ 1 -(3 , 5 -di-tert-butylpheny 1)(3 , 5 -diethy lpheny 1)(3 , 5 -dimethylphenyl) silyl-2-methyl indenyl]titanium trichloride,
[9-(3,5-di-tert-butylphenyl)(3,5-diethylphenyl)(3,5-dimethylphenyl)silyl-fluorenyl]titanium trichloride,
[ 1 -(3 , 5 -di-tert-butylpheny l)(3 , 5 -diethy lpheny 1)(3 , 5-dimethylphenyl) silyl- tetrahydroindenyljtitanium trichloride,
[l-(3,5-di-tert-butylphenyl)(3,5-diethylphenyl)(3,5-dimethylphenyl)silyl-2- methyltetrahydroindenyl]titanium trichloride,
[9-(3 , 5-di-tert-butylphenyl)(3 , 5-diethylphenyl)(3 , 5-dimethylphenyl)sily 1- octahydrofluorenyl]titanium trichloride, 108]
l-tris(3,5-diphenylphenyl)silyl-cyclopentadienyl]titanium trichloride,
l-tris(3,5-diphenylphenyl)silyl-2-methylcyclopentadienyl]titanium trichloride,
1 -tris(3,5-dtphenylphenyl)silyl-3-methylcyclopentadienyl]titanium trichloride,
1 -tris(3,5-diphenylphenyl)silyl-2,3-dimethylcyclopentadienyl]titanium trichloride, l-tris(3,5-diphenylphenyl)silyl-2,4-dimethylcyclopentadienyl]titanium trichloride,
1 -tris(3,5-diphenylphenyl)silyl-2,5-dimethylcyclopentadienyl]titanium trichloride,
1 -tris(3,5-diphenylphenyl)silyl-2,3,5-trimethylcyclopentadienyl]titanium trichloride, l-tris(3,5-diphenylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride, l-tris(3,5-diphenylphenyl)silyl-2-ethylcyclopentadienyl]titanium trichloride,
1 -tris(3 , 5-diphenylphenyl)silyl-3 -ethylcyclopentadienyl]titanium trichloride,
l-tris(3,5-diphenylphenyl)silyl-2-n-propylcyclopentadienyl]titanium trichloride,
1 -tris(3 , 5-diphenylphenyl)silyl-3 -n-propylcyclopentadienyl]titanium trichloride, l-tris(3,5-diphenylphenyl)silyl-2-isopropylcyclopentadienyl]titanium trichloride, l-tris(3,5-diphenylphenyl)silyl-3-isopropylcyclopentadienyl]titanium trichloride,
1 -tris(3 , 5-diphenylphenyl)silyl-2-n-butylcyclopentadienyl]titanium trichloride,
1 -tris(3 , 5-diphenylphenyl)silyl-3 -n-butylcyclopentadienyl]titanium trichloride, l-tris(3,5-diphenylphenyl)silyl-2-sec-butylcyclopentadienyl]titanium trichloride, l-tris(3,5-diphenylphenyl)silyl-3-sec-butylcyclopentadienyl]titanium trichloride, l-tris(3,5-diphenylphenyl)silyl-2-tert-butylcyclopentadienyl]titanium trichloride, 1 -tris(3 , 5-diphenylphenyl)silyl-3 -tert-butylcyclopentadienyl]titanium trichloride,
1 -tris(3,5-diphenylphenyl)silyl-2-phenylcyclopentadienyl]titanium trichloride,
1 -tris(3,5-diphenylphenyl)silyl-3-phenylcyclopentadienyl]titanium trichloride, l-tris(3,5-diphenylphenyl)silyl-2-benzylcyclopentadienyl]titanium trichloride,
1 -tris(3,5-diphenylphenyl)silyl-3-benzylcyclopentadienyl]titanium trichloride,
1 -tris(3 , 5-diphenylphenyl)siIyl-indenyl]titanium trichloride,
1 -tris(3 , 5-diphenylphenyl)silyl-2-methylindenyl]titanium trichloride,
9-tris(3,5-diphenylphenyl)silyl-fluorenyl]titanium trichloride,
l-tris(3,5-diphenylphenyl)silyl-tetrahydroindenyl]titanium trichloride,
l-tris(3,5-diphenylphenyl)silyl-2-methyltetrahydroindenyl]titanium trichloride,
-tris(3,5-diphenylphenyl)silyl-octahydrofluorenyl]titanium trichloride,
0109]
1 -tris(3 , 5-dibenzylphenyl)silyl-cyclopentadienyl]titanium trichloride,
l-tris(3,5-dibenzylphenyl)silyl-2-methylcyclopentadienyl]titanium trichloride, [l-tris(3,5-dibenzylphenyl)silyl-3-methylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-dibenzylphenyl)silyl-2,3-dimethylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-dibenzylphenyl)silyl-2,4-dimethylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-dibenzylphenyl)silyl-2,5-dimethylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-dibenzylphenyl)silyl-2,3,5-trimethylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-dibenzylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-dibenzylphenyl)silyl-2-ethylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-dibenzylphenyl)silyl-3-ethylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-dibenzylphenyl)silyl-2-n-propylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3 , 5-dibenzylphenyl)silyl-3 -n-propylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3 , 5-dibenzylphenyl)silyl-2-isopropylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-dibenzylphenyl)silyl-3-isopropylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-dibenzylphenyl)silyl-2-n-butylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-dibenzylphenyl)silyl-3-n-butylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-dibenzylphenyl)silyl-2-sec-butylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-dibenzylphenyl)silyl-3-sec-butylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-dibenzylphenyl)silyl-2-tert-butylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-dibenzylphenyl)silyl-3-tert-butylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-dibenzylphenyl)silyl-2-phenylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-dibenzylphenyl)silyl-3-phenylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-dibenzylphenyl)silyl-2-benzylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-dibenzylphenyl)silyl-3-benzylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-dibenzylphenyl)silyl-indenyl]titanium trichloride,
[l-tris(3,5-dibenzylphenyl)silyl-2-methyl indenyljtitanium trichloride,
[9-tris(3,5-dibenzylphenyl)silyl-fluorenyl]titanium trichloride,
[l-tris(3,5-dibenzylphenyl)silyl-tetrahydroindenyl]titanium trichloride,
[l-tris(3,5-dibenzylphenyl)silyl-2-methyltetrahydroindenyl]titaniura trichloride,
[9-tris(3,5-dibenzylphenyl)silyl-octahydrofluorenyl]titanium trichloride;
[0110]
a chlorinated zirconium compound in which "titanium" is substituted with "zirconium" in any one of the above-mentioned compounds;
a chlorinated hafnium compound in which "titanium" is substituted with
"hafnium" in any one of the above-mentioned compounds;
a fluorinated titanium compound in which "chloride" is substituted with "fluoride" in any one of the above-mentioned compounds;
a brominated titanium compound in which "chloride" is substituted with
"bromide" in any one of the above-mentioned compounds;
an iodinated titanium compound in which "chloride" is substituted with "iodide" in any one of the above-mentioned compounds;
a hydrogenated titanium compound in which "chloride" is substituted with "hydride" in any one of the above-mentioned compounds;
a methylated titanium compound in which "chloride" is substituted with "methyl" in any one of the above-mentioned compounds;
a phenylated titanium compound in which "chloride" is substituted with "phenyl" in any one of the above-mentioned compounds;
a benzylated titanium compound in which "chloride" is substituted with "benzyl" in any one of the above-mentioned compounds;
a methoxidated titanium compound in which "chloride" is substituted with "methoxide" in any one of the above-mentioned compounds;
a n-butoxylated titanium compound in which "chloride" is substituted with "n- butoxide" in any one of the above-mentioned compounds;
an isopropoxylated titanium compound in which "chloride" is substituted with "isopropoxide" in any one of the above-mentioned compounds;
a phenoxylated titanium compound in which "chloride" is substituted with
"phenoxide" in any one of the above-mentioned compounds;
a benziloxidated titanium compound in which "chloride" is substituted with "benziloxide" in any one of the above-mentioned compounds;
a dimethylamidated titanium compound in which "chloride" is substituted with "dimethylamide" in any one of the above-mentioned compounds; and
a diethylamidated titanium compound in which "chloride" is substituted with "diethylamide" in any one of the above-mentioned compounds.
[0111]
Furthermore, examples of the compounds represented by formula (1) also include compounds in which a silicon atom is substituted with a carbon atom in any one of the above- mentioned compounds.
[0112]
Preferable examples of the compounds represented by formula (1) include [1- dimethylphenylsilyl-3-trimethylsilylcyclopentadienyl]titanium trichloride, [ 1 -tris(3 ,5-dimethylphenyl)silyl-3-trim
[l-dimethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride,
[l-diethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride,
[l-cyclotetramethylene(phenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride, [l-ethylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride,
[l-n-butylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride,
[l-methyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride,
[l-cyclohexylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride,
[ 1 -methyl(n-octadecyl)phenylsilyl-2,3 ,4, 5 -tetramethylcyclopentadienyljtitanium trichloride, [l-triphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride,
[l-tri(4-n-butylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride,
[l-dimethyl(3,5-dimethylphenyl)silyl-2,3,4,5-tetr^
[l-n-butylmethyl(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride,
[l-methyldi(4-methylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride, [l-tris(3,5-diethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride,
[l-(3,5-di-tert-butylphenyl)bis(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride.
[0113]
Examples of method for producing the compound represented by formula (1) include a method described in Organometallics 2002, 21, 5122-5135.
[0114]
Furthermore, examples of a method for producing the compound represented by formula (1) include a method for producing a compound, which includes a first step of reacting a substituted cyclopentadiene compound represented by formula (7) (hereinafter, referred to as a "substituted cyclopentadiene compound (7)") with a base in the presence of an amine compound, and a second step of reacting a transition metal compound represented by formula (8)
(hereinafter, referred to as a "transition metal compound (8)") with the reaction product of the substituted cyclopentadiene compound (7) and the base:
[0115]
Figure imgf000054_0001
wherein R1, R2, R3, R4, R5, R6 and R7 have the same meanings as in R1, R2, R3, R4, R5, R6 and R7, respectively, in formula (1), and R8, R9, R10 and R11 have the same meanings as in R8, R9, R10 and Ru res ectivel in formula (1-2);
Figure imgf000054_0002
wherein M1, X1, X2 and X3 have the same meanings as in M1, X1, X2 and X3, respectively, in formula (1), and X11 represents a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, or a disubstituted amino group, and n represents 0 or 1.
[0116]
In formula (7), the meanings of the groups to be used as R1, R2, R3, R4, R5, R6, R7 R8, R9, R10, and R11, the examples of the groups, and the preferable groups are the same as in the meanings of the groups, the examples of the groups, and the preferable groups described in formula (1).
[0117]
In formula (8), the meanings of the groups to be used as M1, X1, X2 and X3, the examples of the groups, and the preferable groups are the same as in the meanings of the groups, the examples of the groups, and the preferable groups described in formula (1).
[0118]
X11 in formula (8) is a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, or a disubstituted amino group, and the meanings and the examples of these groups are the same as the meanings and the examples of the groups described in formula
(1).
[0119]
The substituted cyclopentadiene compound (7) include isomers in which positions of double bonds of the cyclopentadiene ring thereof are different from each other are the following constitutional isomers.
Figure imgf000055_0001
The compound represented by formula (7) includes isomers whose positions of the double bonds of each cyclopentadienyl ring are different from each other. In the present invention, formula (7) represents any one of them or a mixture of them.
[0120]
Examples of the transition metal compound (8) include halogenated titanium such as titanium tetrachloride, titanium trichloride, titanium tetrabromide, and titanium tetraiodide; titanium amide such as tetrakis(dimethylamino)titanium, dichlorobis(dimethylamino)titanium, trichloro(dimethylamino)titanium, and tetrakis(diethylamino)titanium; alkoxytitanium such as tetraisopropoxytitanium, tetra-n-butoxytitanium, dichlorodiisopropoxytitanium, and
trichloroisopropoxytitanium. Among them, the preferable transition metal compound (8) is titanium tetrachloride.
[0121]
In the first reaction step, examples of the base to be reacted with the substituted cyclopentadiene compound (7) include an organic alkaline metal compound. Examples of the organic alkaline metal compound include organic lithium compounds such as methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, lithium trimethylsilyl acetylide, lithium acetylide, (trimethylsilyl)methyllithium, vinyllithium, phenyllithium, and allyllithium.
[0122]
The amount of the base to be used is in the range from 0.5 mol to 5 mol with respect to 1 mol of the substituted cyclopentadienyl compound (7).
[0123]
In the reaction between the substituted cyclopentadiene compound (7) and the base in the first reaction step, an amine compound is used. Examples of such an amine compound include a primary amine compound such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, tert-butylamine, n-octylamine, n-decylamine, aniline, and ethylenediamine; a secondary amine compound such as dimethylamine, diethylamine, di-n- propylamine, diisopropylamine, di-n-butylamine, di-tert-butylamine, di-n-octylamine, di-n- decylamine, pyrroline, hexamethyldisilazane, and diphenylamine; a tertiary amine compound such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine,
diisopropylethylamine, tri-n-octylamine, tri-n-decylamine, triphenylamine, Ν,Ν,Ν',Ν'- tetramethylethylenediamine, N-methylpyrroline, and 4-dimethylaminopyridine. The amount of such an amine compound to be used is preferably 10 mol or less, more preferably in the range from 0.5 mol to 10 mol, and further preferably, 1 mol to 5 mol with respect to 1 mol of base.
[0124]
The reaction between the substituted cyclopentadiene compound (7) and the base is preferably carried out in a solvent. Furthermore, when a solvent is used, the substituted cyclopentadiene compound (7) and the base are reacted in the solvent, the transition metal compound (8) is then added to the reaction mixture, and thereby the transition metal compound (8) can be further reacted with the reaction product of the substituted cyclopentadiene compound (7) and the base. A solid may be precipitated in a reaction solution obtained by allowing the substituted cyclopentadiene compound (7) and the base to be reacted with each other. In this case, until the precipitated solid is dissolved, a solvent may be added, or the precipitated solid may be once separated by filtration, and the solvent may be added to the separated solid so that the precipitated solid can be dissolved or suspended, and then the transition metal compound (8) may be added thereto. Furthermore, in the case where a solvent is used, the substituted cyclopentadiene compound (7), the base and the transition metal compound (8) are added to the solvent simultaneously, and thereby the first reaction step and the second reaction step can be carried out substantially at the same time.
[0125]
As the solvent to be used in the first reaction step and the solvent to be used in the second reaction step, an inactive solvent, which does not remarkably prevent the progress of the reactions in these steps, is used. Examples of such a solvent to be used include aprotic compounds including an aromatic hydrocarbon such as benzene and toluene; an aliphatic hydrocarbon such as hexane and heptane; ether compounds such as diethyl ether, tetrahydrofuran and 1,4-dioxane; an amide compound such as hexamethylphosphoric amide and
dimethylformamide; a polar compound such as acetonitrile, propionitrile, acetone, diethyl ketone, methyl isobutyl ketone, and cyclohexanone; a halogenated hydrocarbon such as dichloromethane, dichloroethane, chlorobenzene, and dichlorobenzene. One or more of these compounds can be used. The amount of the solvent to be used is preferably 1 part by weight to 200 parts by weight and more preferably 3 parts by weight to 50 parts by weight with respect to 1 part by weight of the substituted cyclopentadiene compound (7).
[0126]
The amount of the transition metal compound (8) to be used is preferably 0.5 mol to 3 mol and more preferably 0.7 mol to 1.5 mol with respect to 1 mol of the substituted cyclopentadiene compound (7).
[0127]
The reaction temperatures in the first reaction step and the second reaction step may be -100°C or higher and not higher than the boiling point of the solvent, and the
temperatures are preferably -80°C to 100°C.
[0128]
The compound represented by formula (1) can be taken out from the reaction product, which has been obtained through the first reaction step and the second reaction step, by various known purification methods. Examples of the methods include a method of carrying out the first reaction step and the second reaction step, then filtering off precipitates in the reaction solution, then concentrating the filtrate to precipitate a transition metal compound, and collecting the precipitated transition metal compound by filtration.
[0129]
Furthermore, for the compound represented by formula (1) in which a part or all of X1, X2 and X3 is (are) a hydrogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, or a substituted hydrocarbyloxy group, there are a method of reacting the compound represented by formula (1) in which X1, X2 and X3 are each a halogen atom with an alkaline metal compound having a hydrogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group or a substituted hydrocarbyloxy group; a method of reacting the compound represented by formula (1) in which X1, X2 and X3 are each a halogen atom with an alkaline earth metal compound having a hydrogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group or a substituted hydrocarbyloxy group. Examples of the alkaline metal in the alkaline metal compound include lithium and sodium. Furthermore, examples of the alkaline earth metal in the alkaline earth metal compound include magnesium and calcium.
[0130]
The above-mentioned substituted cyclopentadiene compound (7) can be produced by the steps of: reacting a substituted cyclopentadiene compound represented by formula (9) (hereinafter, referred to as a "substituted cyclopentadiene compound (9)") with a base in the presence of an amine compound; and reacting the reaction product of the substituted
cyclopentadiene compound (9) and the base with a halogenated silicon compound represented by formula (10) (hereinafter, referred to as a "halogenated silicon compound (10)"):
[0131]
Figure imgf000058_0001
wherein R8, R9, R10 and R11 have the same meanings as in R8, R9, R10 and Ru, respectively, in formula (1-2), and the compound represented by the formula:
Figure imgf000058_0002
is an of the followin five compounds or a mixture thereof
Figure imgf000058_0003
Figure imgf000058_0004
wherein R1, R2, R3, R4, R5, R6, and R7 have the same meanings as in R1, R2, R3, R4, R5, R6, and
R7, respectively, in formula (1), and X12 represents a halogen atom.
[0132]
In formula (9), the meanings of the groups to be used in R8, R9, R10, and R11, the examples of the groups, and the preferable groups are the same as the meanings of the groups, the examples of the groups, and the preferable groups described in formula (1-2). In formula (10), the meanings of the groups to be used in R1, R2, R3, R4, R5, R6, and R7, the examples of the groups, and the preferable groups are the same as the meanings of the groups, examples of the groups, and the preferable groups described in formula (1). X12 represents a halogen atom.
[0133]
Examples of the substituted cyclopentadiene compound (9) include methylcyclopentadiene, 1,2-dimethyl cyclopentadiene, 1,3-dimethylcyclopentadiene, 1,2,3- trimethylcyclopentadiene, 1 ,2,4-trimethylcyclopentadiene, 1 ,2,3 ,4-tetramethyl cyclopentadiene, ethylcyclopentadiene, 1,2-diethylcyclopentadiene, 1,3-diethylcyclopentadiene, 1,2,3- triethylcyclopentadiene, 1,2,4-triethylcyclopentadiene, 1,2,3,4-tetraethylcyclopentadiene, n- propylcyclopentadiene, isopropy Icy clop entadiene, n-butylcyclopentadiene, sec- butylcyclopentadiene, tert-butylcyclopentadiene, n-pentylcyclopentadiene,
neopentylcyclopentadiene, n-hexylcyclopentadiene, n-octylcyclopentadiene,
phenylcyclopentadiene, naphthylcyclopentadiene, trimethylsilylcyclopentadiene,
triethylsilylcyclopentadiene, and tert-butyldimethylsilylcyclopentadiene.
[0134]
Examples of the base to be reacted with the substituted cyclopentadiene compound (9) include alkaline metal hydrides such as lithium hydride, sodium hydride, and potassium hydride; and alkaline earth metal hydride such as calcium hydride.
[0135]
The amount of the base to be used is usually 0.5 mol to 3 mol and more preferably 0.9 mol to 2 mol with respect to 1 mol of the substituted cyclopentadiene compound
(9).
[0136]
In the reaction between the substituted cyclopentadiene compound (9) and the base, an amine compound is used together with the base. Examples of such an amine compound include primary anilines such as aniline, chloroaniline, bromoaniline, fluoroaniline, dichloroaniline, dibromoaniline, difiuoroaniline, trichloroaniline, tribromoaniline,
trifluoroaniline, tetrachloroaniline, tetrabromoaniline, tetrafluoroaniline, pentachloroaniline, pentafluoroaniline, nitroaniline, dinitroaniline, hydroxyaniline, phenylenediamine, anisidine, dimethoxyaniline, trimethoxyaniline, ethoxyaniline, diethoxyaniline, triethoxyaniline, n- propoxyaniline, isopropoxyaniline, n-butoxyaniline, sec-butoxyaniline, isobutoxyaniline, t- butoxyaniline, phenoxyaniline, methylaniline, ethylaniline, n-propylaniline, isopropylaniline, n- butylaniline, sec-butylaniline, isobutyla iline, t-butylaniline, dimethylanihne, diethylaniline, di- n-propylaniline, diisopropylaniline, di-n-butylaniline, di-sec-butylaniline, diisobutylaniline, di-t- butylaniline, trimethylaniline, triethylaniline, diisopropylaniline, phenylaniline, benzylaniline, aminobenzoic acid, methyl aminobenzoate, ethyl aminobenzoate, n-propyl aminobenzoate, isopropyl aminobenzoate, n-butyl aminobenzoate, isobutyl aminobenzoate, sec-butyl aminobenzoate, and t-butyl aminobenzoate. Examples also include naphthylamine, naphthylmethylamine, benzylamine, propylamine, butylamine, pentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, 2-aminopyridine, 3-aminopyridine, and 4- aminopyridine.
[0137]
The amount of the amine compound to be used is usually 0.001 mol to 2 mol and preferably 0.01 mol to 0.5 mol with respect to 1 mol of the base.
[0138]
The reaction between the substituted cyclopentadiene compound (9) and the base is carried out in a solvent that is inactive with respect to the reaction. Examples of such a solvent include aprotic compounds including aromatic hydrocarbon such as benzene, toluene and xylene; aliphatic hydrocarbon such as pentane, hexane, heptane, octane, and cyclohexane; ether compounds such as diethyl ether, methyl t-butyl ether, tetrahydrofuran, and 1,4-dioxane; amide compounds such as hexamethylphosphoric amide, dimethylformamide, dimethylacetamide, and N-methyl-pyrrolidone; halogenated hydrocarbon such as chlorobenzene and dichlorobenzene. One or more of these compounds can be used. The amount of the solvent to be used is preferably 1 part by weight to 200 parts by weight and more preferably 3 parts by weight to 30 parts by weight with respect to 1 part by weight of the substituted cyclopentadiene compound (9).
[0139]
In the reaction between the substituted cyclopentadiene compound (9) and the base, the substituted cyclopentadiene compound (9), the base, and the amine compound may be mixed simultaneously in the solvent, or the base and the amine compound may be previously mixed and then the substituted cyclopentadiene compound (9) may be mixed therewith. The reaction temperature is preferably 0°C to 70°C, and more preferably 10°C to 60°C.
[0140]
Examples of the halogenated silicon compound (10) include
chloroethylmethylphenylsilane, chlorodiethylphenylsilane, chloromethyl(n-propyl)phenylsilane, chloromethyl(isopropyl)phenylsilane, chloro(n-butyl)methylphenylsilane, chloro(sec- butyl)methylphenylsilane, chloro(tert-butyl)methylphenylsilane, chloromethyl(n- pentyl)phenylsilane, chloromethyl(neopentyl)phenylsilane, amylchloromethylphenylsilane, chloro(n-hexyl)methylphenylsilane, chlorocyclohexylmethylphenylsilane, chloromethyl(n- octyl)phenylsilane, chloro(n-decyl)methylphenylsilane, chloro(n-dodecyl)methylphenylsilane, chloromethyl(n-octadecyl)phenylsilane, chlorobenzyldiphenylsilane, chloro(n-butyl)methyl(3- methylphenyl)silane, chloro(n-butyl)methyl(4-methylphenyl)silane, chloro(n-butyl)methyl(3,5- dimethylphenyl)silane, chloro(n-butyl)methyl(4-n-butylphenyl)silane, chloro(n-butyl)methyl(4- phenylphenyl)silane, chloro(n-butyl)methyl(4-methoxyphenyl)silane, chloro(n-butyl)methyl(4- phenoxyphenyl)silane, chloro(n-butyl)methyl(4-trimethylsilylphenyl)silane, chloro(n- butyl)methyl(4-dimethylaminophenyl)silane, and chloro(n-butyl)methyl(4- benzyloxyphenyl)silane.
[0141]
The amount of the halogenated silicon compound (10) to be used is usually 0.2 mol to 2 mol and more preferably 0.33 mol to 1.25 mol with respect to 1 part by weight of the substituted cyclopentadiene compound (9) used in preparation of the reaction product of the substituted cyclopentadiene compound (9) and the base.
[0142]
The reaction of the reaction product of the substituted cyclopentadiene compound
(9) and the base with the halogenated silicon compound (10) is usually carried out in a solvent inactive to the reaction. Examples of such a solvent include aprotic compounds including an aromatic hydrocarbon such as benzene, toluene and xylene; an aliphatic hydrocarbon such as pentane, hexane, heptane, octane, and cyclohexane; an ether, compound such as diethyl ether, methyl t-butyl ether, tetrahydrofuran, and 1,4-dioxane; an amide compound such as
hexamethylphosphoric amide, dimethylformamide, dimethyl acetamide, and N-methyl- pyrrolidone; a halogenated hydrocarbon such as chlorobenzene and dichlorobenzene. One or more of these compounds can be used. The amount of the solvent to be used is preferably 1 part by weight to 200 parts by weight and more preferably 3 parts by weight to 30 parts by weight with respect to 1 part by weight of the substituted cyclopentadiene compound (9) which has been used for preparation of the reaction product of the substituted cyclopentadiene compound (9) and the base.
[0143]
The reaction of the reaction product of the substituted cyclopentadiene compound (9) and the base with the halogenated silicon compound (10) is usually carried out by mixing the base, the amine compound and the substituted cyclopentadiene compound (9) in a solvent, then mixing the halogenated silicon compound (10) therewith. The reaction may be carried out by employing a method of mixing the base, the amine compound, the substituted cyclopentadiene compound (9) and the halogenated silicon compound (10) in a solvent once simultaneously. The reaction temperature is preferably 0°C to 70°C, and more preferably 10°C to 60°C.
[0144]
After the reaction is finished, water, a sodium hydrogen carbonate aqueous solution, a sodium carbonate aqueous solution, an ammonium chloride aqueous solution, an aqueous solution of, for example, hydrochloric acid, or the like, is added to the obtained reaction solution, the solution is then separated between an organic layer and an aqueous layer, and a solution containing the substituted cyclopentadiene compound (7) is obtained as the organic phase. When the solvent is removed from the organic phase by a known method, the substituted cyclopentadiene compound (7) can be obtained.
[0145]
Examples of the complex (I) include compounds represented by formula (2-1) or f rmula (2-2):
Figure imgf000062_0001
wherein M2 represents a transition metal atom of Group 4 of the periodic table of the elements; A21 represents an oxygen atom, a nitrogen atom, a phosphorus atom or a sulfur atom;
Z1 is a group linking A21 to N, in which the number of the shortest bonds linking A21 to N is 4 to
6;
a bond linking A21 to Z1 may be a double bond;
R21, R22, R23, R24, R25 and X4 each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, or a disubstituted amino group, two or more groups of R21, R22, R23, R24 and R25 may be bonded to each other, the three X4 groups each may be the same or different from each other, and two or more X4 groups may be bonded to each other to form a ring together with M2;
R26 represents a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbylidene group, and a substituted hydrocarbylidene group, a bond linking R26 to A21 may be a double bond, and R26 may be bonded to Z1;
[0146]
Figure imgf000063_0001
wherein M2 represents a transition metal atom of Group 4 of the periodic table of the elements; A22 represents a nitrogen atom or a phosphorus atom;
Z2 is a group linking A22 to N, and the number of the shortest bonds linking A22 to N is 4 to 6; R21, R22, R23, R24, R25 and X4 each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, or a disubstituted amino group, two or more groups of R21, R22, R23, R24 and R25 may be bonded to each other, the three X4 groups may be the same or different from each other, and two or more X4 groups may be bonded to each other to form a ring together with M2; and
27 28
R and R represent a hydrogen atom, a halogen atom, a hydrocarbyl group, and a substituted hydrocarbyl group, and R28 may be bonded to Z2.
[0147]
M2 in formula (2-1) and formula (2-2) each represents a transition metal atom of Group 4 of the periodic table of the elements, and examples thereof include a titanium atom, a zirconium atom and a hafnium atom. Among them, a titanium atom is preferable.
■ [0148]
R21, R22, R23, R24, R25 and X4 in formula (2-1) and formula (2-2) each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, or a disubstituted amino group, and the meanings and the examples of these groups are the same as the meanings and the examples described in formula (1).
[0149]
In R21, R22, R23, R24, R25 and X4, the number of the carbon atoms of a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group and a substituted
hydrocarbyloxy group is preferably 1 to 20, and more preferably 1 to 10. Preferable examples of the hydrocarbyl group include an alkyl group, an aryl group, and an aralkyl group. The substituted hydrocarbyl group is preferably a halogenated hydrocarbyl group, and more preferably a halogenated alkyl group, a halogenated aryl group, and a halogenated aralkyl group. The hydrocarbyloxy group is preferably an alkoxy group, an aryloxy group, and an aralkyloxy group. The substituted hydrocarbyloxy group is preferably a halogenated aralkyloxy group, and preferably a halogenated alkoxy group, and a halogenated aryloxy group.
[0150]
The substituted silyl group in R21, R22, R23, R24, R25 and X4 is preferably a trisubstituted silyl group. In the substituted silyl group, the number of the carbon atoms of the hydrocarbyl group and the halogenated hydrocarbyl group, which are bonded to a silicon atom, is preferably 1 to 10. Furthermore, in the substituted silyl group, the total number of the carbon atoms of the hydrocarbyl group and the halogenated hydrocarbyl group, which are bonded to a silicon atom, is preferably 1 to 20, and more preferably 3 to 18. Preferable examples thereof include a trimethylsilyl group, a tnethylsilyl group, a tnphenylsilyl group, a dimethylphenylsilyl group, and groups in which a part or all of hydrogen atoms are substituted with a halogen atom in these groups are preferable.
[0151]
In the disubstituted amino group of R21, R22, R23, R24, R25 and X4, the number of the carbon atoms of the hydrocarbyl group and the halogenated hydrocarbyl group bonded to a nitrogen atom is preferably 1 to 10, and more preferably 1 to 5. The total number of the carbon atoms of the hydrocarbyl group and a halogenated hydrocarbyl group bonded to a nitrogen atom is 2 to 20, and more preferably 2 to 10.
[0152]
Two or more groups of R , R , R , R , and R may be bonded to each other to form a ring together with carbon atoms on a benzene ring to which R21 to R24 are bonded, or the carbon atom may form a ring together with a carbon atom to which R25 is bonded. Examples of the ring include a cyclopropane ring, a cyclopropene ring, a cyclobutane ring, a cyclobutene ring, a cyclopentane ring, a cyclopentene ring, a cyclohexane ring, a cyclohexene ring, a cycloheptane ring, a cycloheptene ring, a cyclooctane ring, a cyclooctene ring, a benzene ring, a naphthalene ring, an anthracene ring, and saturated or unsaturated hydrocarbyl ring such as rings in which a hydrogen atom in these rings are substituted with a hydrocarbyl group having 1 to 20 carbon atoms.
[0153]
R21 is more preferably a phenyl group, an a-cumyl group, a tert-butyl group, or a 1-adamanthyl group, and further preferably a 1-adamanthyl group.
[0154]
R23 is more preferably a methyl group, a cyclohexyl group, a tert-butyl group, or a 1-adamanthyl group, and further preferably a methyl group.
[0155]
R22, R24, and R25 are more preferably a hydrogen atom.
[0156]
X4 is more preferably a halogen atom or an alkyl group, and further preferably a chlorine atom, a bromine atom, and a methyl group.
[0157]
A21 represents an oxygen atom, a nitrogen atom, a phosphorus atom or a sulfur atom, and A22 represents a nitrogen atom or a phosphorus atom.
[0158]
R26 represents a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbylidene group, or a substituted hydrocarbylidene group, and a bond linking R26 to A21 may be a double bond, and the meanings and the examples of the hydrocarbyl group and the substituted hydrocarbyl group are the same as the meanings and the examples of described in formula (1).
[0159]
Examples of the hydrocarbylidene group include a methylidyne group, an ethylidyne group, a benzylidene group, and a cyclohexylidene group. The substituted hydrocarbylidene group is a group in which one or more hydrogen atoms in the
hydrocarbylidene group are substituted with a group other than a hydrocarbyl group and/or a halogen atom. Examples thereof include a halogenated hydrocarbylidene group.
[0160]
In R26, the number of the carbon atoms of a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbylidene group and a substituted hydrocarbylidene group is preferably 1 to 10, and more preferably 1 to 5.
[0161]
R26 and Z1 may be bonded to each other to form a ring together with A21. The ring may be an aliphatic ring or an aromatic ring, or a heterocycle.
[0162]
R26 is preferably a hydrocarbyl group having 1 to 10 carbon atoms, more preferably a methyl group, an ethyl group, and an isopropyl group, and further preferably a methyl group.
[0163]
R27 and R28 each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, and a substituted hydrocarbyl group, and the meanings and the examples of the hydrocarbyl group and the substituted hydrocarbyl group are the same as the meanings and the examples thereof described in formula (1).
[0164]
In R27 and R28, the number of the carbon atoms of a hydrocarbyl group and a substituted hydrocarbyl group is preferably 1 to 10, and more preferably 1 to 5.
[0165]
R27 is preferably a hydrocarbyl group having 1 to 10 carbon atoms, more preferably a methyl group, an ethyl group, or an isopropyl group, and further preferably a methyl group.
[0166]
R28 and Z2 may be bonded to each other to form a ring together with A22. The ring may be an aliphatic ring or an aromatic ring, or a heterocycle.
[0167]
R28 is preferably a hydrocarbyl group having 1 to 10 carbon atoms, more preferably a methyl group, an ethyl group, or an isopropyl group, and further preferably a methyl group.
[0168]
Z1 is a group linking A21 to N, and the number of the shortest bonds linking A21 to N is 4 to 6; and a bond linking A to Z may be a double bond. Z is a group linking A to N, and the number of the shortest bonds linking A to N is 4 to 6.
[0169]
Examples of Z1 and Z2 include a group for forming a structure represented by the substructure formula (2-3) by combining the following A21 and N, or a group for forming a structure represented by the substructure formula (2-4) by combining the following A22 and N:
Figure imgf000066_0001
wherein A21 and A22 have the same meanings as in AZ1 and A"", respectively, in formula (2-1) and formula (2-2); R31, R32, R33, and R34 each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, or a substituted hydrocarbyloxy group, R31 and R32 may be bonded to each other to form a ring together with a carbon atom to which R31 is bonded and a carbon atom to which R32 is bonded, and R33 and R34 be bonded to each other to form a ring together with a carbon atom to which R33 is bonded and a carbon atom to which R34 is bonded, and R34 and R26 bonded to A 1 may be bonded to each other
1 1A H 00
to form a ring together with A , and R and R bonded to A may be bonded to each other to form a ring together with A22.
[0170]
In R31, R32, R33, and R34, the meanings and examples of a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group and a substituted hydrocarbyloxy group are the same as the meanings and the examples described in formula (1).
[0171]
In R , R , R , and R , the number of the carbon atoms of a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group and a substituted hydrocarbyloxy group is preferably 1 to 20, and more preferably 1 to 10. Preferable examples of the hydrocarbyl group include an alkyl group, an aryl group, and an aralkyl group. Preferable examples of the substituted hydrocarbyl group include a halogenated hydrocarbyl group, and more preferable examples include a halogenated alkyl group, a halogenated aryl group, and a halogenated aralkyl group. Preferable examples of the hydrocarbyloxy group include an alkoxy group, an aryloxy group, and an aralkyloxy group. Preferable examples of the substituted hydrocarbyloxy group include a halogenated aralkyloxy group, and more preferable examples include a halogenated alkoxy group, and a halogenated aryloxy group.
[0172]
A ring formed by bonding R to R , a ring formed by bonding R to R , a ring formed by bonding R34 to R26, and a ring formed by bonding R34 to R28 may be an aliphatic ring, or an aromatic ring, or a heterocycle.
[0173]
Examples of a method for producing the compound represented by formula (2-1) or formula (2-2) include a method described in WO2009/005003.
[0174]
Examples of the compound represented by formula (2-1) or formula (2-2) include the following compounds.
Figure imgf000068_0001
Figure imgf000069_0001
Figure imgf000070_0001
Figure imgf000070_0002
wherein M2 represents a transition metal atom of Group 4 of the periodic table of the elements; A21 represents an oxygen atom, a nitrogen atom, a phosphorus atom or a sulfur atom;
R , R , R , R , R and each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, or a disubstituted amino group, two or more groups of R21, R22, R23, R24 and R25 may be bond to each other, the three X4 groups each may be the same or different from each other, and two or more X4 groupsmay be bonded to each other to form a ring together with M2;
R26 represents a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbylidene group, or a substituted hydrocarbylidene group, and a bond linking R26 to A21 may be a double bond; and
R , R , R , R , R , R , R and R each represent a hydrogen atom or a hydrocarbyl group; 0176]
Figure imgf000071_0001
wherein M2 represents a transition metal atom of Group 4 of the periodic table of the elements; A22 represents a nitrogen atom or a phosphorus atom;
R , R , R , R , R and Λ each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, or a disubstituted amino group, two or more groups of R21, R22, R23, R24 and R25 may be bonded to each other, the three X4 groups each may be the same or different from each other, and two or more X4 groupsmay be bonded to each other to form a ring together with M2;
R and R represent a hydrogen atom, a halogen atom, a hydrocarbyl group, or a substituted hydrocarbyl group;
R41, R42, R43, R44, R45, R46, R47 and R48 each represent a hydrogen atom or a hydrocarbyl group.
[0177]
The definition, the examples, and the preferable atoms of M2 in formula (2-a) and formula (2-b) are the same as the definition, the examples and the preferable atoms of M2 in formula (2-1) and formula (2-2).
[0178]
The definition and the examples of A21 and A22 in formula (2-a) and formula (2-b) are the same as the definition and the examples of A21 and A22 in formula (2-1) and formula (2- 2).
[0179]
The definition, the examples and the preferable atoms and groups of R , R , R , R24, R25 and X4 in formula (2-a) and formula (2-b) are the same as the definition, the examples and the preferable atoms and groups of R21, R22, R23, R24, R25 and X4 in formula (2-1) and formula (2-2).
[0180]
The definitions, examples and preferable groups of R26, R27 and R28 in formula (2- a) and formula (2-b) are the same as the definitions, the examples and the preferable groups of R26, R27 and R28 in formula (2-1) and formula (2-2).
[0181]
R41, R42, R43, R44, R45, R46, R47 and R48 in formula (2-a) and formula (2-b) each represent a hydrogen atom, or a hydrocarbyl group. The hydrocarbyl group is preferably an alkyl group. The number of the carbon atoms of the hydrocarbyl group is preferably 1 to 10 and more preferably 1 to 5.
[0182]
[Complex for olefin polymerization]
Examples of a complex for olefin polymerization include a compound represented by formula (11) or (12). Olefin polymerization herein means the changing of olefin into a polymer, and more specifically, production of a polymer by polymerizing an olefin monomer. The molecular weight of the polymer is larger than the molecular weight of an oligomer (2- to 20-mer) and generally has 10000 or more.
[0183]
The formulae (11) and (12) are as follows:
Figure imgf000072_0001
wherein M3 represents a transition metal atom of Group 4 of the periodic table of the elements; Cp1 represents a group having a cyclopentadiene-type anionic skeleton;
J2 represents a group linking Cp1 to A2 by one or two atoms of Group 14 of the periodic table of the elements;
A2 represents a group linking J2 to M3, the linking group being a group bonded to M3 at its an atom of Group 15 of the periodic table of the elements or atom of Group 16 of the periodic table of the elements, or a group having a cyclopentadiene-type anionic skeleton; and
X5 and X6 each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, or a disubstituted amino group;
0184]
Figure imgf000073_0001
wherein M4 represents a transition metal atom of Group 4 of the periodic table of the elements; Cp2 and Cp3 represent a group having a cyclopentadiene-type anionic skeleton; and
X7 and X8 each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, or a disubstituted amino group.
[0185]
M3 and M4 each represent a transition metal atom of Group 4 of the periodic table of the elements, and the examples thereof include a titanium atom, a zirconium atom and a hafnium atom.
[0186]
Examples of the group having a cyclopentadiene-type anionic skeleton of Cp1, Cp2 and Cp3 and A2 include a r|5-cyclopentadienyl group, a Ti5-methylcyclopentadienyl group, a rj5-tert-butylcyclopentadienyl group, a r|5-tetramethylcyclopentadienyl group, a rj5-indenyl group, a rj5-fiuorenyl group, and a r|5-azulenyl group.
[0187]
Examples of J2 include -SiR2-, -CR2-, -SiR2SiR2-, -CR2CR2-, -CR=CR-, - CR_SiR2-, or -GeR -. R herein represents a hydrogen atom, a hydrocarbyl group having not greater than 20 carbon atoms, a halogenated hydrocarbyl group having not greater than 20 carbon atoms, or a group represented by -Si(R)3 having not greater than 20 carbon atoms, wherein the three R' groups each represent a hydrogen atom, a halogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and at least one R is a hydrocarbyl group or a halogenated hydrocarbyl group. A plurality of R may be the same or different from each other.
[0188] Examples of the hydrocarbyl group having not greater than 20 carbon atoms of R in J2 include alkyl groups such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, a neopentyl group, an amyl group, a n-hexyl group, a n-octyl group, a n-decyl group, and a n-dodecyl group; aralkyl groups such as a benzyl group, a (2-methylphenyl)methyl group, a (3- methylphenyl)methyl group, a (4-methylphenyl)methyl group, a (2,3-dimethylphenyl)methyl group, a (2,4-dimethylphenyl)methyl group, a (2,5-dimethylphenyl)methyl group, a (2,6- dimethylphenyl)methyl group, a (3,4-dimethylphenyl)methyl group, a (3,5- dimethylphenyl)methyl group, a (2,3,4-trimethylphenyl)methyl group, a (2,3,5- trimethylphenyl)methyl group, a (2,3,6-trimethylphenyl)methyl group, a (3,4,5- trimethylphenyl)methyl group, a (2,4,6-trimethylphenyl)methyl group, a (2,3,4,5- tetramethylphenyl)methyl group, a (2,3,4,6-tetramethylphenyl)methyl group, a (2,3,5,6- tetramethylphenyl)methyl group, a (pentamethylphenyl)methyl group, an (ethylphenyl)methyl group, a (n-propylphenyl)methyl group, an (isopropylphenyl)methyl group, a (n- butylphenyl)methyl group, a (sec-butylphenyl)methyl group, and a (tert-butylphenyl)methyl group; and aryl groups such as a phenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, a 2,3-xylyl group, a 2,4-xylyl group, a 2,5-xylyl group, a 2,6-xylyl group, a 3,4-xylyl group, a 3,5- xylyl group, a 2,3,4-trimethylpheny group, a 2,3,5-trimethylphenyl group, a 2,3,6- trimethylphenyl group, a 2,4,6-trimethylphenyl group, a 3,4,5-trimethylphenyl group, a 2,3,4,5- tetramethylphenyl group, a 2,3,4,6-tetramethylphenyl group, a 2,3,5,6-tetramethylphenyl group, a pentamethylphenyl group, an ethylphenyl group, a n-propylphenyl group, an isopropylphenyl group, a n-butylphenyl group, a sec-butylphenyl group, and a tert-butylphenyl group.
Examples of the halogenated hydrocarbyl group having not greater than 20 carbon atoms include groups in which a part or all of hydrogen atoms are substituted with a halogen atom in the above- mentioned hydrocarbyl groups. Examples of the group represented by -Si(R')3 having not greater than 20 carbon atoms include a methylsilyl group, an ethylsilyl group, a phenylsilyl group, a dimethylsilyl group, a diethylsilyl group, a diphenylsilyl group, a trimethylsilyl group, a triethylsilyl group, a tri-n-propylsilyl group, a triisopropylsilyl group, a tri-n-butylsilyl group, a tri-sec-butylsilyl group, a tri-tert-butylsilyl group, a triisobutylsilyl group, a tert-butyl- dimethylsilyl group, a tri-n-pentylsilyl group, a tri-n-hexylsilyl group, a tricyclohexylsilyl group, a triphenylsilyl group, groups in which a part or all of the hydrogen atoms are substituted with a halogen atom in the above-mentioned groups.
[0189]
Preferable examples of J2 include -SiR2-, -CR2-, or -CR2CR2-. Furthermore, preferable examples of R include a hydrogen atom and a methyl group.
[0190]
In A2, examples of a group linking J2 to M3, the linking group being a group bonded to M3 by an atom of Group 15 of the periodic table of the elements or atom of Group 16 of the periodic table of the elements include -0-, -S-, -NR-, -PR-, and groups represented by the following formulae (i) to (iv). R herein represents a hydrogen atom, a hydrocarbyl group having not greater than 20 carbon atoms, a halogenated hydrocarbyl group having not greater than 20 carbon atoms, or a group represented by -Si(R")3 having not greater than 20 carbon atoms, wherein the three R" groups each represent a hydrogen atom, a halogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and at least one R" is a hydrocarbyl group or a halogenated hydrocarbyl group. Furthermore, a hydrogen atom on a benzene ring of the group represented by the following formulae (i) to (iv) may be substituted with a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, or a disubstituted amino group. When the hydrogen atoms bonded to the two adjoining carbon atoms on the benzene ring are substituted with these groups, the substituents bonded to the two carbon atoms may form a ring together with the two carbon atoms to which the substituents are bonded.
0191]
Figure imgf000075_0001
[0192]
Examples of the hydrocarbyl group having not greater than 20 carbon atoms of R in A2 include alkyl groups such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, a neopentyl group, an amyl group, a n-hexyl group, a n-octyl group, a n-decyl group, and a n-dodecyl group; aralkyl groups such as a benzyl group, a (2-methylphenyl)methyl group, a (3- methylphenyl)methyl group, a (4-methylphenyl)methyl group, a (2,3-dimethylphenyl)methyl group, a (2,4-dimethylphenyl)methyl group, a (2,5-dimethylphenyl)methyl group, a (2,6- dimethylphenyl)methyl group, a (3,4-dimethylphenyl)methyl group, a (3,5- dimethylphenyl)methyl group, a (2,3,4-trimethylphenyl)methyl group, a (2,3,5- trimethylphenyl)methyl group, a (2,3,6-trimethylphenyl)methyl group, a (3,4,5- trimethylphenyl)methyl group, a (2,4,6-trimethylphenyl)methyl group, a (2,3,4,5- tetramethylphenyl)methyl group, a (2,3,4,6-tetramethylphenyl)methyl group, a (2,3,5,6- tetramethylphenyl)methyl group, a (pentamethylphenyl)methyl group, an (ethylphenyl)methyl group, a (n-propylphenyl)methyl group, an (isopropylphenyl)methyl group, a (n- butylphenyl)methyl group, a (sec-butylphenyl)methyl group, and a (tert-butylphenyl)methyl group; and aryl groups such as a phenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, a 2,3-xylyl group, a 2,4-xylyl group, a 2,5-xylyl group, a 2,6-xylyl group, a 3,4-xylyl group, a 3,5- xylyl group, a 2,3,4-trimethylphenyl group, a 2,3,5-trimethylphenyl group, a 2,3,6- trimethylphenyl group, a 2,4,6-trimethylphenyl group, a 3,4,5-trimethylphenyl group, a 2,3,4,5- tetramethylphenyl group, a 2,3,4,6-tetramethylphenyl group, a 2,3,5,6-tetramethylphenyl group, a pentamethylphenyl group, an ethylphenyl group, a n-propylphenyl group, an isopropylphenyl group, a n-butylphenyl group, a sec-butylphenyl group, and a tert-butylphenyl group.
Examples of the halogenated hydrocarbyl group having not greater than 20 carbon atoms include groups in which a part or all of hydrogen atoms are substituted with a halogen atom in the above- mentioned hydrocarbyl groups. Examples of the group represented by -Si(R")3 having not greater than 20 carbon atoms include a methylsilyl group, an ethylsilyl group, a phenylsilyl group, a dimethylsilyl group, a diethylsilyl group, a diphenylsilyl group, a trimethylsilyl group, a triethylsilyl group, a tri-n-propylsilyl group, a triisopropylsilyl group, a tri-n-butylsilyl group, a tri-sec-butylsilyl group, a tri-tert-butylsilyl group, a triisobutylsilyl group, a tert-butyl- dimethylsilyl group, a tri-n-pentylsilyl group, a tri-n-hexylsilyl group, a tricyclohexylsilyl group, a triphenylsilyl group, groups in which a part or all of the hydrogen atoms are substituted with a halogen atom in the above-mentioned groups.
[0193]
In A2, examples of a group linking J2 to M3, the linking group being a group bonded to M3 by its atom of Group 15 of the periodic table of the elements or atom of Group 16 of the periodic table of the elements, include -NR- and a group represented by the above- mentioned formula (i) (as mentioned above, a hydrogen atom on the benzene ring may be substituted). Furthermore, R is preferably a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a norbornyl group, a benzyl group, or a phenyl group.
[0194]
Examples of X5, X6, X7, X8, and a halogen atom of the substituent on the benzene ring of the groups represented by formulae (i) to (iv) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. A preferable example is a chlorine atom.
[0195]
Examples of X5, X6, X7, X8, and a hydrocarbyl group of the substituent on the benzene ring of the groups represented by formulae (i) to (iv) include an alkyl group, an aryl group, and an aralkyl group. The number of the carbon atoms of the hydrocarbyl group is preferably 1 to 20.
[0196]
Examples of the alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, a neopentyl group, an amyl group, a n-hexyl group, a heptyl group, a n-octy group, a n- nonyl group, a n-decyl group, a n-dodecyl group, a n-tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group and a n-eicosyl group. Preferable examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms, more preferable examples include a methyl group, an ethyl group, an isopropyl group, a tert-butyl group and an amyl group.
[0197]
Examples of the aryl group include a phenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, a 2,3-xylyl group, a 2,4-xylyl group, a 2,5-xylyl group, a 2,6-xylyl group, a 3,4-xylyl group, a 3,5-xylyl group, a 2,3,4-trimethylphenyl group, a 2,3,5-trimethylphenyl group, a 2,3,6-trimethylphenyl group, a 2,4,6-trimethylphenyl group, a 3,4,5-trimethylphenyl group, a 2,3,4,5-tetramethylphenyl group, a 2,3,4,6-tetramethylphenyl group, a 2,3,5,6- tetramethylphenyl group, a pentamethylphenyl group, an ethylphenyl group, a n-propylphenyl group, an isopropylphenyl group, a n-butylphenyl group, a sec-butylphenyl group, a tert- butylphenyl group, a n-pentylphenyl group, a neopentylphenyl group, a n-hexylphenyl group, a n-octylphenyl group, a n-decylphenyl group, a n-dodecylphenyl group, a n-tetradecylpheny group, a naphthyl group, an anthracenyl group. Preferable examples of the aryl group include an aryl group having 6 to 20 carbon atoms, and a more preferable example is a phenyl group.
[0198]
Examples of the aralkyl group include a benzyl group, a (2-methylphenyl)methyl group, a (3-methylphenyl)methyl group, a (4-methylphenyl)methyl group, a (2,3- dimethylphenyl)methyl group, a (2,4-dimethylphenyl)methyl group, a (2,5- dimethylphenyl)methyl group, a (2,6-dimethylphenyl)methyl group, a (3,4- dimethylphenyl)methyl group, a (3,5-dimethylphenyl)methyl group, a (2,3,4- trimethylphenyl)methyl group, a (2,3,5-trimethylphenyl)methyl group, a (2,3,6- trimethylphenyl)methyl group, a (3,4,5-trimethylphenyl)methyl group, a (2,4,6- trimethylphenyl)methyl group, a (2,3,4,5-tetramethylphenyl)methyl group, a (2,3,4,6- tetramethylphenyl)methyl group, a (2,3,5,6-tetramethylphenyl)methyl group, a
(pentamethylphenyl)methyl group, an (ethylphenyl)methyl group, a (n-propylphenyl)methyl group, an (isopropylphenyl)methyl group, a (n-butylphenyl)methyl group, a (sec- butylphenyl)methyl group, a (tert-butylphenyl)methyl group, a (n-pentylphenyl)methyl group, a (neopentylphenyl)methyl group, a (n-hexylphenyl)methyl group, a (n-octylphenyl)methyl group, a (n-decylphenyl)methyl group, a (n-dodecylphenyl)methyl group, a (n-tetradecylphenyl)methyl group, a naphthylmethyl group, and an anthracenylmethyl group. Preferable examples of the aralkyl group include an aralkyl group having 7 to 20 carbon atoms, and a more preferable example is a benzyl group.
[0199]
Examples of X5, X6, X7, X8, and a substituted hydrocarbyl group of the substituent on the benzene ring of the groups represented by formulae (i) to (iv) include halogenated hydrocarbyl groups such as a halogenated alkyl group, a halogenated aryl group, and a halogenated aralkyl group. The number of the carbon atoms in the substituted
hydrocarbyl group is 1 to 20.
[0200]
Examples of the halogenated alkyl group include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a tnchloromethyl group, a bromomethyl group, a dibromomethyl group, a tribromomethyl group, an iodomethyl group, a diiodomethyl group, a triiodomethyl group, a fiuoroethyl group, a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, a pentafluoroethyl group, a chloroethyl group, a dichloroethyl group, a trichloroethyl group, a tetrachloroethyl group, a pentachloroethyl group, a bromoethyl group, a dibromoethyl group, a tribromoethyl group, a tetrabromoethyl group, a pentabromoethyl group, a perfiuoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluorooctyl group, a
perfluorododecyl group, a perfluoropentadecyl group, a perfluoroeicosyl group, a
perchloropropyl group, a perchlorobutyl group, a perchloropentyl group, a perchlorohexyl group, a perchlorooctyl group, a perchlorododecyl group, a perchloropentadecyl group, a
perchloroeicosyl group, a perbromopropyl group, a perbromobutyl group, a perbromopentyl group, a perbromohexyl group, a perbromooctyl group, a perbromododecyl group, a
perbromopentadecyl group, and a perbromoeicosyl group. The halogenated alkyl group is preferably a halogenated alkyl group having 1 to 20 carbon atoms.
[0201]
Examples of the halogenated aryl group include a fluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group, a pentafluorophenyl group, a chlorophenyl group, a bromophenyl group, and an iodophenyl group. The halogenated aryl group is preferably a halogenated aryl group having 6 to 20 carbon atoms.
[0202]
Examples of the halogenated aralkyl group include a group in which a part or all of the hydrogen atoms present in the above-mentioned aralkyl group are substituted with a halogen atom. The halogenated aralkyl group is preferably a halogenated aralkyl group having 7 to 20 carbon atoms.
[0203]
Examples of Xs, X6, X7, X8, and a hydrocarbyloxy group of the substituent on the benzene ring of the groups represented by formulae (i) to (iv) include an alkoxy group, an aryloxy group, and an aralkyloxy group. The number of the carbon atoms of the
hydrocarbyloxy group is preferably 1 to 20.
[0204]
Examples of the alkoxy group include a methoxy group, an ethoxy group, a n- propoxy group, an isopropoxy group, n-butoxy group, a sec-butoxy group, a tert-butoxy group, a n-pentoxy group, a neopentoxy group, a n-hexoxy group, a n-octoxy group, a n-dodesoxy group, a n-pentadesoxy group, and a n-icosoxy group. Preferable examples of the alkoxy group include an alkoxy group having 1 to 20 carbon atoms, and more preferable examples include a methoxy group, an ethoxy group, and a tert-butoxy group.
[0205]
Examples of the aryloxy group include a phenoxy group, a 2-methylphenoxy group, a 3-methylphenoxy group, a 4-methylphenoxy group, a 2, 3 -dimethylphenoxy group, a 2,4-dimethylphenoxy group, a 2,5-dimethylphenoxy group, a 2,6-dimethylphenoxy group, a 3,4- dimethylphenoxy group, a 3,5-dimethylphenoxy group, a 2,3,4-trimethylphenoxy group, a 2,3,5- trimethylphenoxy group, a 2,3,6-trimethylphenoxy group, a 2,4,5-trimethylphenoxy group, a 2,4,6-trimethylphenoxy group, a 3,4,5-trimethylphenoxy group, a 2,3,4,5-tetramethylphenoxy group, a 2,3,4,6-tetramethylphenoxy group, a 2,3,5,6-tetramethylphenoxy group, a
pentamethylphenoxy group, an ethylphenoxy group, a n-propylphenoxy group, an
isopropylphenoxy group, a n-butylphenoxy group, a sec-butylphenoxy group, a tert- butylphenoxy group, a n-hexylphenoxy group, a n-octylphenoxy group, a n-decyl phenoxy group, a n-tetradecy phenoxy group, a naphthoxy group, and an anthracenoxy group. A preferable example of the aryloxy group is an aryloxy group having 6 to 20 carbon atoms, and more preferable example is a phenoxy group.
[0206]
Examples of the aralkyloxy group include a benzyloxy group, a (2- methylphenyl)methoxy group, a (3-methylphenyl)methoxy group, a (4-methylphenyl)methoxy group, a (2,3-dimethylphenyl)methoxy group, a (2,4-dimethylphenyl)methoxy group, a (2,5- dimethylphenyl)methoxy group, a (2,6-dimethylphenyl)methoxy group, a (3,4- dimethylphenyl)methoxy group, a (3,5-dimethylphenyl)methoxy group, a (2,3,4- trimethylphenyl)methoxy group, a (2,3,5-trimethylphenyl)methoxy group, a (2,3,6- trimethylphenyl)methoxy group, a (2,4,5-trimethylphenyl)methoxy group, a (2,4,6- trimethylphenyl)methoxy group, a (3,4,5-trimethylphenyl)methoxy group, a (2,3,4,5- tetramethylphenyl)methoxy group, a (2,3,4,6-tetramethylphenyl)methoxy group, a (2,3,5,6- tetramethylphenyl)methoxy group, a (pentamethylphenyl)methoxy group, an
(ethylphenyl)methoxy group, a (n-propylphenyl)methoxy group, an (isopropylphenyl)methoxy group, a (n-butylphenyl)methoxy group, a (sec-butylphenyl)methoxy group, a (tert- butylphenyl)methoxy group, a (n-hexylphenyl)methoxy group, a (n-octylphenyl)methoxy group, a (n-decylphenyl)methoxy group, a (n-tetradecylphenyl)methoxy group, a naphthyl methoxy group, and an anthracenyl methoxy group. A preferable example of the aralkyloxy group is an aralkyloxy group having 7 to 20 carbon atoms, and a more preferable example is a benzyloxy group.
[0207]
Examples of X5, X6, X7, X8, and a substituted hydrocarbyloxy group of the substituent on the benzene ring of the groups represented by formulae (i) to (iv) include a halogenated hydrocarbyl group such as a halogenated alkoxy group, a halogenated aryloxy group, and a halogenated aralkyloxy group. The number of the carbon atoms of the substituted hydrocarbyloxy group is preferably 1 to 20.
[0208]
Examples of the halogenated alkoxy group include a group in which a part or all of the hydrogen atoms present in the above-mentioned alkoxy group are substituted with a halogen atom. A preferable example of the halogenated alkoxy group is a halogenated alkoxy group having 1 to 20 carbon atoms.
[0209]
Examples of the halogenated aryloxy group include a group in which a part or all of the hydrogen atoms present in the above-mentioned aryloxy group are substituted with a halogen atom. Preferable examples of the halogenated aryloxy group include a halogenated aryloxy group having 6 to 20 carbon atoms.
[0210]
Examples of the halogenated aralkyloxy group include a group in which a part or all of the hydrogen atoms present in the above-mentioned aralkyloxy group are substituted with a halogen atom. Preferable examples of the halogenated aralkyloxy group include a halogenated aralkyloxy group having 7 to 20 carbon atoms.
[0211]
Examples of X5, X6, X7, X8, and a substituted silyl group of the substituent on the benzene ring of the groups represented by formulae (i) to (iv) include a group represented by - Si(R14)3, wherein the three R14 groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and at least one R14 is a hydrocarbyl group or a halogenated hydrocarbyl group.
[0212]
Examples of the hydrocarbyl group in R14 include alkyl groups such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a n-pentyl group, a n-hexyl group, a cyclohexyl group, a n- heptyl group, a n-octyl group, a n-nonyl group, and a n-decyl group; and aryl groups such as a phenyl group. Examples of the halogenated hydrocarbyl group include a group in which a part or all of the hydrogen atoms present in these hydrocarbyl groups are substituted with a halogen atom. The number of the carbon atoms of the hydrocarbyl group and the halogenated hydrocarbyl group is preferably 1 to 10. Furthermore, the total number of the carbon atoms of the three R14 groups is preferably 1 to 20, and more preferably 3 to 18.
[0213]
Examples of the substituted silyl group include a monosubstituted silyl group having one hydrocarbyl group or halogenated hydrocarbyl group such as a methylsilyl group, an ethylsilyl group, and a phenylsilyl group, and groups in which a part or all of the hydrogen atoms in the hydrocarbyl group bonded to a silicon atom in the above-mentioned groups are substituted with a halogen atom; a disubstituted silyl group having two of hydrocarbyl groups and/or halogenated hydrocarbyl groups such as a dimethylsilyl group, a diethylsilyl group, and a diphenylsilyl group, and groups in which a part or all of the hydrogen atoms in the hydrocarbyl group bonded to a silicon atom in the above-mentioned groups are substituted with a halogen atom; and a trisubstituted silyl group having three of hydrocarbyl groups and/or halogenated hydrocarbyl groups such as a trimethylsilyl group, a triethylsilyl group, a tri-n-propyl silyl group, a triisopropylsilyl group, a tri-n-butylsilyl group, a tri-sec-butylsilyl group, a tri-tert-butylsilyl group, a triisobutylsilyl group, a tert-butyl-dimethylsilyl group, a tri-n-pentylsilyl group, a tri-n- hexylsilyl group, a tricyclohexylsilyl group, a triphenylsilyl group, and groups in which a part or all of the hydrogen atoms in the hydrocarbyl group bonded to a silicon atom in the above- mentioned groups are substituted with a halogen atom. Preferable examples of the substituted silyl group include a trisubstituted silyl group, and more preferable examples thereof include a trimethylsilyl group, a tert-butyldimethylsilyl group, a tnphenylsilyl group, and groups in which a part or all of the hydrogen atoms in these groups are substituted with a halogen atom.
[0214]
Examples of X5, X6, X7, X8, and the disubstituted amino group of the substituent on the benzene ring of the groups represented by formulae (i) to (iv) include a group represented by -N(R15)2, wherein the two R15 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the two R15 groups are bonded to each other to form a ring together with nitrogen atoms to which the two R15 groups are bonded.
[0215]
Examples of the hydrocarbyl group in R15 include alkyl groups such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a n-pentyl group, a n-hexyl group, a cyclohexyl group, a n- heptyl group, a n-octyl group, a n-nonyl group, and a n-decyl group; and aryl groups such as a phenyl group. Examples of the halogenated hydrocarbyl group include a group in which a part or all of the hydrogen atoms present in these hydrocarbyl groups are substituted with a halogen atom. The number of the carbon atoms of the hydrocarbyl group and the halogenated hydrocarbyl group is preferably 1 to 10 and more preferably 1 to 5. Furthermore, the total number of the carbon atoms of the two R15 is preferably 2 to 20, and more preferably 2 to 10.
[0216]
Examples of the disubstituted amino group include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, a di-sec-butylamino group, a di-tert-butylamino group, a di-isobutylamino group, a tert- butylisopropylamino group, a di-n-hexylamino group, a di-n-octylamino group, a di-n- decylamino group, a diphenylamino group, a bistrimethylsilylamino group, a bis-tert- butyldimethylsilylamino group, a pyrrolyl group, a pyrrolidinyl group, a piperidinyl group, a carbazolyl group, a dihydroindolyl group, a dihydroisoindolyl group, and groups in which a part or all of the hydrogen atoms in these groups are substituted with a halogen atom. Preferable examples of the disubstituted amino group include a dimethylamino group, a diethylamino group, a pyrrolidinyl group, a piperidinyl group, and groups in which a part or all of the hydrogen atoms in these groups are substituted with a halogen atom.
[0217]
When hydrogen atoms bonded to the two adjoining carbon atoms on the benzene ring of the above-mentioned formulae (i) to (iv) are substituted with these groups, the substituents bonded to the two carbon atoms may form a ring together with two carbon atoms to which the substituents are bonded. Examples of the ring include a cyclopropane ring, a cyclopropene ring, a cyclobutane ring, a cyclobutene ring, a cyclopentane ring, a cyclopentene ring, a cyclohexane ring, a cyclohexene ring, a cycloheptane ring, a cycloheptene ring, a cyclooctane ring, a cyclooctene ring, a benzene ring, a naphthalene ring, an anthracene ring, and saturated or unsaturated hydrocarbyl ring such as rings in which a hydrogen atom in these rings are substituted with a hydrocarbyl group having 1 to 20 carbon atoms. The examples also include rings in which a carbon atom on the ring in these rings is substituted with silicon, for example, a silacyclopropane ring, silacyclobutane ring, a silacyclopentane ring, and a silacyclohexane ring.
[0218]
Preferable examples of the substituents on the benzene ring of the group represented by the above-mentioned formulae (i) to (iv) include a hydrocarbyl group having 1 to 20 carbon atoms.
[0219]
Preferable examples of X5, X6, X7, and X8 include a halogen atom and a hydrocarbyloxy group having 1 to 20 carbon atoms.
[0220]
Examples of methods for producing the compounds represented by the above- mentioned formula (11) or (12) include methods described in JP-A-3-163088, JP-A-3- 188092, JP-A-4-268307, JP-A-6-206890, and JP-A-9-87313.
[0221]
Examples of the compounds represented by the above-mentioned formula (11) or (12) include the following compounds:
[0222]
a compound represented by formula (11) in which A2 is a group linking J2 to M3, the linking group being a group bonded to M3 by its atom of Group 15 of the periodic table of the elements or atom of Group 16 of the periodic table of the elements:
methylene(tert-butylamido)(cyclopentadienyl)titanium dichloride, methylene(cyclohexylamido)(cyclopentadienyl)titanium dichloride,
methylene(phenylamido)(cyclopentadienyl)titanium dichloride,
methylene(benzylamido)(cyclopentadienyl)titanium dichloride, methylene(tert- butylphosphido)(cyclopentadienyl)titanium dichloride, methylene(cyclohexylphosphido)(cyclopentadienyl)titanium dichloride,
methylene(phenylphosphido)(cyclopentadienyl)titanium dichloride,
methylene(benzylphosphido)(cyclopentadienyl)titanium dichloride,
[0223]
isopropylidene(tert-butylamido)(cyclopentadienyl)titanium dichloride,
isopropylidene(cyclohexylamido)(cyclopentadienyl)titanium dichloride,
isopropylidene(phenylamido)(cyclopentadienyl)titanium dichloride,
isopropylidene(benzylamido)(cyclopentadienyl)titanium dichloride, isopropylidene(tert- butylphosphido)(cyclopentadienyl)titanium dichloride,
isopropylidene(cyclohexylphosphido)(cyclopentadienyl)titanium dichloride,
isopropylidene(phenylphosphido)(cyclopentadienyl)titanium dichloride,
isopropylidene(benzylphosphido)(cyclopentadienyl)titanium dichloride,
[0224]
diphenylmethylene(tert-butylamido)(cyclopentadienyl)titanium dichloride,
diphenylmethylene(cyclohexylamido)(cyclopentadienyl)titanium dichloride,
diphenylmethylene(phenylamido)(cyclopentadienyl)titanium dichloride,
diphenylmethylene(benzylamido)(cyclopentadienyl)titanium dichloride, diphenylmethylenei butylphosphido)(cyclopentadienyl)titanium dichloride,
diphenylmethylene(cyclohexylphosphido)(cyclopentadienyl)titanium dichloride,
diphenylmethylene(phenylphosphido)(cyclopentadienyl)titanium dichloride,
diphenylmethylene(benzylphosphido)(cyclopentadienyl)titanium dichloride,
[0225]
1,2- ethylene(tert-butylamido)(cyclopentadienyl)titanium dichloride, 1,2- ethylene(cyclohexylamido)(cyclopentadienyl)titanium dichloride, 1 ,2- ethylene(phenylamido)(cyclopentadienyl)titanium dichloride, 1,2- ethylene(benzylamido)(cyclopentadienyl)titanium dichloride, 1 ,2-ethylene(tert- butylphosphido)(cyclopentadienyl)titanium dichloride, 1,2- ethylene(cyclohexylphosphido)(cyclopentadienyl)titanium dichloride, 1 ,2- ethylene(phenylphosphido)(cyclopentadienyl)titanium dichloride, 1,2- ethylene(benzylphosphido)(cyclopentadienyl)titanium dichloride,
[0226]
dimethylsilylene(tert-butylamido)(cyclopentadienyl)titanium dichloride, dimethylsilylene (cyclohexylamido)(cyclopentadienyi)titanium dichloride,
dimethylsilylene(phenylamido)(cyclopentadienyl)titanium dichloride, dimethylsilylene(benzylamido)(cyclopentadienyl)titanium dichloride, dimethylsilylene(tert- butylphosphido)(cyclopentadienyl)titanium dichloride,
dimethylsilylene(cyclohexylphosphido)(cyclopentadienyl)titanium dichloride,
dimethylsilylene(phenylphosphido)(cyclopentadienyl)titanium dichloride,
dimethylsilylene(benzylphosphido)(cyclopentadienyl)titanium dichloride,
[0227]
diphenylsilylene(tert-butylamido)(cyclopentadienyl)titanium dichloride,
diphenylsilylene(cyclohexylamido)(cyclopentadienyl)titanium dichloride,
diphenylsilylene(phenylamido)(cyclopentadienyl)titanium dichloride,
diphenylsilylene(benzylamido)(cyclopentadienyl)titanium dichloride, diphenylsilylene(tert- butylphosphido)(cyclopentadienyl)titanium dichloride,
diphenylsilylene(cyclohexylphosphido)(cyclopentadienyl)titanium dichloride,
diphenylsilylene(phenylphosphido)(cyclopentadienyl)titanium dichloride,
diphenylsilylene(benzylphosphido)(cyclopentadienyl)titanium dichloride,
[0228]
1 ,2-tetramethyldisilylene(tert-butylamido)(cyclopentadienyl)titanium dichloride, 1 ,2- tetramethyldisilylene(cyclohexylamido)(cyclopentadienyl)titanium dichloride, 1 ,2- tetramethyldisilylene(phenylamido)(cyclopentadienyl)titanium dichloride, 1,2- tetramethyldisilylene(benzylamido)(cyclopentadienyl)titanium dichloride, 1,2- tetramethyldisilylene(tert-butylphosphido)(cyclopentadienyl)titanium dichloride, 1 ,2- tetramethyldisilylene(cyclohexylphosphido)(cyclopentadienyl)titanium dichloride, 1,2- tetramethyldisilylene(phenylphosphido)(cyclopentadienyl)titanium dichloride, 1,2- tetramethyldisilylene(benzylphosphido)(cyclopentadienyl)titanium dichloride;
[0229]
a compound in which titanium is replaced with zirconium or hafnium in any one of the above-mentioned compounds; a compound in which cyclopentadienyl is replaced with methylcyclopentadienyl, n-butylcyclopentadienyl, t-butylcyclopentadienyl,
tetramethylcyclopentadienyl, indenyl or fluorenyl in any one of the above-mentioned compounds; a compound in which t-butylamide is replaced with an oxygen atom or a sulfur atom in any one of the above-mentioned compounds; and a compound in which chloride is replaced with bromide, iodide, hydride, methy, phenyl, benzyl, methoxide, n-butoxide, isopropoxide, phenoxide, benzyloxide, dimethyl amide or diethyl amide in any one of the above-mentioned compounds;
[0230] methylene(cyclopentadienyl)(3 , 5-dimethyl-2-phenoxy)titanium dichloride, methylene(cyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride,
methylene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride,
methylene(cyclopentadienyl)(3-phenyl-2-phenoxy)titanium dichloride,
methylene(cyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, methylene(cyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, methylene(cyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, methylene(cyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride,
[0231]
methylene(methylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride,
methylene(methylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride,
methyl ene(methylcyclopentadienyl)(3 -tert-butyl-5 -methyl -2-phenoxy)titanium dichloride, methylene(methylcyclopentadienyl)(3-phenyl-2-phenoxy)titanium dichloride,
methylene(methylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, methylene(methylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, methylene(methylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, methylene(methylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride,
[0232]
methylene(tert-butylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride,
methylene(tert-butylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride,
methylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, methyl ene(tert-butylcyclopentadienyl)(3 -phenyl -2-phenoxy)titanium dichloride, methyl ene(tert- butylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, methylene(tert-butylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, methylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, methylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride, [0233]
methylene(tetramethylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, methylene(tetramethylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride,
methylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, methylene(tetramethylcyclopentadienyl)(3 -phenyl-2-phenoxy)titanium dichloride,
methylene(tetramethylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, methylene(tetramethylcyclopentadienyl)(3 -trimethylsilyl-5 -methyl-2- phenoxy)titanium dichloride, methylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methoxy-2- phenoxy)titanium dichloride, methylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-chloro-2- phenoxy)titanium dichloride,
[0234]
methylene(trimethylsilylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, methylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, methylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, methylene(trimethylsilylcyclopentadienyl)(3-phenyl-2-phenoxy)titanium dichloride,
methylene(trimethylsilylcyclopentadienyl)(3-tert-butyldimethylsiiyl-5-methyl-2- phenoxy)titanium dichloride, methylene(trimethylsilylcyclopentadienyl)(3 -trimethylsilyl-5- methyl-2-phenoxy)titanium dichloride, methyl ene(trimethylsilylcyclopentadienyl)(3 -tert-butyl-5- methoxy-2-phenoxy)titanium dichloride, methylene(trimethy lsilylcyclopentadienyl)(3 -tert-butyl- 5 -chloro-2-phenoxy)titanium dichloride,
[0235]
methylene(fluorenyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, methylene(fluorenyl)(3-tert- butyl-2-phenoxy)titanium dichloride, methylene(fluorenyl)(3-tert-butyl-5-methyl-2- phenoxy)titanium dichloride, methylene(fluorenyl)(3-phenyl-2-phenoxy)titanium dichloride, methylene(fluorenyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, methylene(fluorenyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride,
methylene(fluorenyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride,
methylene(fluorenyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride,
[0236]
isopropylidene(cyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride,
isopropylidene(cyclopentadienyl)(3 -tert-butyl-2-phenoxy)titanium dichloride, isopropylidene (cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride,
isopropylidene(cyclopentadienyl)(3-phenyl-2-phenoxy)titanium dichloride,
isopropylidene(cyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(cyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, isopropylidene(cyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride,
[0237]
isopropylidene(methylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, isopropylidene(methylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, isopropylidene(methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(methylcyclopentadienyl)(3-phenyl-2-phenoxy)titanium dichloride,
isopropylidene(methylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(methylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2- phenoxy)titanium dichloride, isopropylidene(methylcyclopentadienyl)(3-tert-butyl-5-methoxy-2- phenoxy)titanium dichloride, isopropylidene(methylcyclopentadienyl)(3-tert-butyl-5-chloro-2- phenoxy)titanium dichloride,
[0238]
isopropylidene(tert-butylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, isopropylidene(tert-butylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, isopropylidene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(tert-butylcyclopentadienyl)(3-phenyl-2-phenoxy)titanium dichloride,
isopropylidene(tert-butylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2- phenoxy)titanium dichloride, isopropylidene(tert-butylcyclopentadienyl)(3-trimethylsilyl-5- methyl-2-phenoxy)titanium dichloride, isopropylidene(tert-butylcyclopentadienyl)(3 -tert-butyl- 5-methoxy-2-phenoxy)titanium dichloride, isopropylidene(tert-butylcyclopentadienyl)(3-tert- butyl-5-chloro-2-phenoxy)titanium dichloride,
[0239]
isopropylidene(tetramethylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, isopropylidene(tetramethylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, isopropylidene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(tetramethylcyclopentadienyl)(3-phenyl-2-phenoxy)titanium dichloride, isopropylidene(tetramethylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2- phenoxy)titanium dichloride, isopropylidene(tetramethylcyclopentadienyl)(3-trimethylsilyl-5- methyl-2-phenoxy)titanium dichloride, isopropylidene(tetramethylcyclopentadienyl)(3 -tert- butyl-5-methoxy-2-phenoxy)titanium dichloride, isopropylidene(tetramethylcyclopentadienyl)(3- tert-butyl-5-chloro-2-phenoxy)titanium dichloride,
[0240]
isopropylidene(trimethylsilylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, isopropylidene(trimethylsilylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, isopropylidene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(trimethylsilylcyclopentadienyl)(3-phenyl-2-phenoxy)titanium dichloride, isopropylidene(tritnethylsilylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2- phenoxy)titanium dichloride, isopropylidene(trimethylsilylcyclopentadienyl)(3-trimethylsilyl-5- methyl-2-phenoxy)titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl)(3-tert- butyl-5-methoxy-2-phenoxy)titanium dichloride,
isopropylidene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride,
[0241]
isopropyl idene(fluoreny 1)(3 , 5 -dimethy 1-2-phenoxy )titanium dichloride,
isopropylidene(fluorenyl)(3 -tert-butyl-2-phenoxy)titanium dichloride,
isopropylidene(fluorenyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride,
isopropylidene(fluorenyl)(3 -phenyl-2-phenoxy)titanium dichloride, isopropylidene(fluorenyl)(3 - tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene (fluorenyl)(3- trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(fluorenyl)(3 -tert-butyl-5- methoxy-2-phenoxy)titanium dichloride, isopropylidene(fluorenyl)(3-tert-butyl-5-chloro-2- phenoxy)titanium dichloride,
[0242]
diphenylmethy lene(cyclopentadienyl)(3 , 5 -dimethy l-2-phenoxy)titanium dichloride,
diphenylmethylene(cyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride,
diphenylmethylene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, diphenylmethylene(cyclopentadienyl)(3-phenyl-2-phenoxy)titanium dichloride,
diphenylmethylene(cyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, diphenylmethylene(cyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, diphenylmethylene(cyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, diphenylmethylene(cyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride,
[0243]
diphenylmethylene(methylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, diphenylmethylene(methylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, diphenylmethylene(methylcyclopentadienyI)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, diphenylmethylene(methylcyclopentadienyl)(3-phenyl-2-phenoxy)titanium dichloride, diphenylmethylene(methylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2- phenoxy)titanium dichloride, diphenylmethylene(methylcyclopentadienyl)(3-trimethylsilyl-5- methy l-2-phenoxy)titanium dichloride, dipheny lmethylene(methylcyclopentadieny 1)(3 -tert- butyl-5-methoxy-2-phenoxy)titanium dichloride, diphenylmethylene(methylcyclopentadienyl)(3 - tert-butyl-5-chloro-2-phenoxy)titanium dichloride,
[0244] diphenylmethylene(tert-butylcyclopentadienyl)(3,5-dirnethyl-2-phenoxy)titanium dichloride, diphenylmethylene(tert-butylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, diphenylmethylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, diphenylmethylene(tert-butylcyclopentadienyl)(3-phenyl-2-phenoxy)titanium dichloride, diphenylmethylene(tert-butylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2- phenoxy)titanium dichloride, diphenylmethylene(tert-butylcyclopentadienyl)(3-trimethylsilyl-5- methyl-2-phenoxy)titanium dichloride, diphenylmethylene(tert-butylcyclopentadienyl)(3 -tert- butyl-5-methoxy-2-phenoxy)titanium dichloride, diphenylmethylene(tert- butylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride,
[0245]
diphenylmethylene(tetramethylcyclopentadienyl)(3 , 5-dimethyl-2-phenoxy)titanium dichloride, diphenylmethylene(tetramethylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, diphenylmethy lene(tetramethylcyclopentadieny 1)(3 -tert-butyl- 5 -methy l-2-phenoxy)titanium dichloride, diphenylmethylene(tetramethylcyclopentadienyl)(3-phenyl-2-phenoxy)titanium dichloride, diphenylmethylene(tetramethylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl- 2-phenoxy)titanium dichloride, diphenylmethylene(tetramethylcyclopentadienyl)(3 - trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride,
diphenylmethylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, diphenylmethylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-chloro-2- phenoxy)titanium dichloride,
[0246]
diphenylmethylene(trimethylsilylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, diphenylmethylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, diphenylmethylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, diphenylmethylene(trimethylsilylcyclopentadienyl)(3-phenyl-2-phenoxy)titanium dichloride, diphenylmethylene(trimethylsilylcyclopentadienyl)(3-tert-butyldimethylsilyl-5- methyl-2-phenoxy)titanium dichloride, diphenylmethylene(trimethylsilylcyclopentadienyl)(3 - trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride,
diphenylmethylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniurn dichloride, diphenylmethylene(trimethylsilylcyclopentadienyl)(3-tert-butyl -5-chloro-2- phenoxy)titanium dichloride,
[0247]
diphenylmethylene(fluorenyl)(3,5-dimethyl-2-phenoxy)titanium dichloride,
diphenylmethylene(fluorenyl)(3-tert-butyl-2-phenoxy)titanium dichloride, diphenylmethylene(fluorenyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, diphenylmethylene(fluorenyl)(3-phenyl-2-phenoxy)titanium dichloride,
diphenylmethylene(fluorenyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, diphenylmethylene(fluorenyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, diphenylmethylene(fluorenyl)(3 -tert-butyl- 5-methoxy-2-phenoxy)titanium dichloride, diphenylmethylene(fluorenyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride;
[0248]
a compound in which titanium is replaced with zirconium or hafnium in any one of the above-mentioned compounds; a compound in which chloride is replaced with bromide, iodide, hydride, methyl, phenyl, benzyl, methoxide, n-butoxide, isopropoxide, phenoxide, benzyloxide, dimethyl amide or diethyl amide in any one of the above-mentioned compounds; a compound in which (cyclopentadienyl) is replaced with (dimethylcyclopentadienyl),
(trimethylcyclopentadienyl), (n-butylcyclopentadienyl), (tert- butyldimethylsilylcyclopentadienyl) or (indenyl) in any one of the above-mentioned compounds; a compound in which 3,5-dimethyl-2-phenoxy is replaced with 2-phenoxy, 3-methyl-2-phenoxy, 3,5-di-tert-butyl-2-phenoxy, 3-phenyl-5-methyl-2-phenoxy, 3-tert-butyldimethylsilyl-2-phenoxy or 3-trimethylsilyl-2-phenoxy in any one of the above-mentioned compounds; and a compound in which methylene is replaced with diethyl methylene in any one of the above-mentioned compounds;
[0249]
dimethylsilylene(cyclopentadienyl)(2-phenoxy)titanium dichloride, dimethylsilylene (cyclopentadienyl)(3-methyl-2-phenoxy)titanium dichloride,
dimethylsilylene(cyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride,
dimethylsilylene(cyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride,
dimethylsilylene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(cyclopentadienyl)(3,5-di-tert-butyl-2-phenoxy)titanium dichloride,
dimethylsilylene (cyclopentadienyl)(5-methyl-3-phenyl-2-phenoxy)titanium dichloride, dimethylsilylene(cyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(cyclopentadienyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titanium dichloride, dimethylsilylene (cyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, dimethylsilylene(cyclopentadienyl)(3-tert-butyl -5-chloro-2-phenoxy)titanium dichloride, dimethylsilylene(cyclopentadienyl)(3,5-diamyl-2-phenoxy)titanium dichloride,
[0250]
dimethylsilylene(methylcyclopentadienyl)(2-phenoxy)titanium dichloride, dimethylsilylene(methylcyclopentadienyl)(3-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(methylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, dimethylsilylene(methylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, dimethylsilylene(methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, dimethylsilyiene(methylcyclopentadienyl)(3,5-di-tert-butyl-2-phenoxy)titanium dichloride, dimethylsilylene(methylcyclopentadienyl)(5-methyl-3-phenyl-2-phenoxy)titanium dichloride, dimethylsilylene(methylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2- phenoxy)titanium dichloride, dimethylsilylene(methylcyclopentadienyl)(5-methyl-3- trimethylsilyl-2-phenoxy)titanium dichloride, dimethylsilylene(methylcyclopentadienyl)(3 -tert- butyl-5-methoxy-2-phenoxy)titanium dichloride, dimethylsilylene(methylcyclopentadienyl)(3- tert-butyl-5-chloro-2-phenoxy)titanium dichloride,
dimethylsilylene(methylcyclopentadienyl)(3 , 5-diamyl-2-phenoxy)titanium dichloride,
[0251]
dimethylsilylene(n-butylcyclopentadienyl)(2-phenoxy)titanium dichloride, dimethylsilylene (n- butylcyclopentadienyl)(3-methyl-2-phenoxy)titanium dichloride, dimethylsilylene (n- butylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, dimethylsilylene(n- butylcyclopentadienyl)(3 -tert-butyl-2-phenoxy)titanium dichloride, dimethylsilylene(n- butylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(n- butylcyclopentadienyl)(3,5-di-tert-butyl-2-phenoxy)titanium dichloride, dimethylsilylene (n- butylcyclopentadienyl)(5-methyl-3-phenyl-2-phenoxy)titanium dichloride, dimethylsilylene(n- butylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(n-butylcyclopentadienyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titanium dichloride, dimethylsilylene(n-butylcyclopentadienyl)(3-tert-butyl-5-methoxy-2- phenoxy)titanium dichloride, dimethylsilylene(n-butylcyclopentadienyl)(3-tert-butyl-5-chloro-2- phenoxy)titanium dichloride, dimethylsilylene(n-butylcyclopentadienyl)(3,5-diamyl-2- phenoxy)titanium dichloride,
[0252]
dimethylsilylene(tert-butylcyclopentadienyl)(2-phenoxy)titanium dichloride,
dimethylsilylene(tert-butylcyclopentadienyl)(3-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(tert-butylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, dimethyl silylene(tert-butylcyclopentadieny 1)(3 -tert-butyl-2-phenoxy)titanium dichloride, dimethylsilylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(tert-butylcyclopentadienyl)(3,5-di-tert-butyl-2-phenoxy)titanium dichloride, dimethylsilylene(tert-butylcyclopentadienyl)(5-methyl-3-phenyl-2-phenoxy)titanium dichloride, dimethylsilylene(tert-butylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2- phenoxy)titanium dichloride, dimethylsilylene(tert-butylcyclopentadienyl)(5-methyl-3- trimethylsilyl-2-phenoxy)titaniurn dichloride, dimethylsilylene(tert-butylcyclopentadienyl)(3- tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, dimethylsilylene(tert- butylcyclopentadieny 1)(3 -tert-butyl- 5 -chloro-2-phenoxy)titanium dichloride,
dimethylsilylene(tert-butylcyclopentadienyl)(3,5-diamyl-2-phenoxy)titanium dichloride,
[0253]
dimethylsilylene(tetramethylcyclopentadienyl)(2-phenoxy)titanium dichloride,
dimethylsilylene(tetramethylcyclopentadienyl)(3-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(tetramethylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(tetramethylcyclopentadienyl)(3,5-di-tert-butyl-2-phenoxy)titanium dichloride, dimethylsilylene(tetramethylcyclopentadienyl)(5-methyl-3-phenyl-2- phenoxy)titanium dichloride, dimethylsilylene(tetramethylcyclopentadienyl)(3 -tert- butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride,
dimethylsilylene(tetramethylcyclopentadienyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titanium dichloride, dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methoxy-2- phenoxy)titanium dichloride, dimethylsilylene(tetramethylcyclopentadienyl)(3 -tert-butyl-5- chloro-2-phenoxy)titanium dichloride, dimethylsilylene(tetramethylcyclopentadienyl)(3,5- diamyl-2-phenoxy)titanium dichloride,
[0254]
dimethylsilylene(trimethylsilylcyclopentadienyl)(2-phenoxy)titanium dichloride,
dimethylsilylene(trimethylsilylcyclopentadienyl)(3-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(trimethylsilylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, dimethylsilylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, dimethylsilylene(trirnethylsilylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(trimethylsilylcyclopentadienyl)(3,5-di-tert-butyl-2- phenoxy)titanium dichloride, dimethylsilylene(trimethylsilylcyclopentadienyl)(5-methyl-3- phenyl-2-phenoxy)titanium dichloride, dimethylsilylene(trimethylsilylcyclopentadienyl)(3 -tert- butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride,
dimethylsilylene(trimethylsilylcyclopentadienyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titanium dichloride, dimethylsilylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methoxy-2- phenoxy)titanium dichloride, dimethylsilylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5- chloro-2-phenoxy)titanium dichloride, dimethylsilylene(trimethylsilylcyclopentadienyl)(3,5- diamyl-2-phenoxy)titanium dichloride,
[0255]
dimethylsilylene(indenyl)(2-phenoxy)titanium dichloride, dimethylsilylene(indenyl)(3-methyl-2- phenoxy)titanium dichloride, dimethylsilylene(indenyl)(3,5-dimethyl-2-phenoxy)titaniuni dichloride, dimethylsilylene (indenyl)(3-tert-butyl-2-phenoxy)titanium dichloride,
dimethylsilylene(indenyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride,
ditnethylsilylene(indenyl)(3 , 5-di-tert-butyl-2-phenoxy)titanium dichloride,
dimethylsilylene(indenyl)(5-methyl-3-phenyl-2-phenoxy)titanium dichloride,
dimethylsilylene(indenyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(indenyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titanium dichloride,
dimethylsilylene(indenyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride,
dimethylsilylene(indenyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride,
dimethylsilylene(indenyl)(3,5-diamyl-2-phenoxy)titanium dichloride,
[0256]
dimethylsilylene(fluorenyl)(2-phenoxy)titanium dichloride, dimethylsilylene(fluoreny 1)(3 - methyl-2-phenoxy)titanium dichloride, dimethylsilylene(fluorenyl)(3 , 5-dimethyl-2- phenoxy)titanium dichloride, dimethylsilyIene(fluorenyl)(3 -tert-butyl-2-phenoxy)titanium dichloride, dimethylsilylene(fluorenyl)(3 -tert-butyl-5-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(fluorenyl)(3,5-di-tert-butyl-2-phenoxy)titanium dichloride,
dimethylsilylene(fluorenyl)(5-methyl-3-phenyl-2-phenoxy)titanium dichloride,
dimethylsilylene(fluorenyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(fluorenyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titanium dichloride, dimethylsilylene(fluorenyl)(3-tert-butyl-5-methoxy-2-phenoxy)titanium dichloride,
dimethylsilylene(fluorenyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride,
dimethylsilylene(fluorenyl)(3,5-diamyl-2-phenoxy)titanium dichloride,
dimethylsilylene(tetramethylcyclopentadienyl)( 1 -naphthoxy-2-yl)titanium dichloride;
[0257]
a compound in which (cyclopentadienyl) is replaced with
(dimethylcyclopentadienyl), (trimethylcyclopentadienyl), (ethylcyclopentadienyl), (n- propylcyclopentadienyl), (isopropylcyclopentadienyl), (sec-butylcyclopentadienyl),
(isobutylcyclopentadienyl), (tert-butyldimethylsilylcyclopentadienyl), (phenylcyclopentadienyl), (methylindenyl) or (phenylindenyl) in any one of the above-mentioned compounds; a compound in which 2-phenoxy is replaced with 3-phenyl-2-phenoxy, 3-trimethylsilyl-2-phenoxy or 3-tert- butyldimethylsilyl-2-phenoxy in any one of the above-mentioned compounds; a compound in which dimethylsilylene is replaced with diethylsilylene, diphenylsilylene or dimethoxy silylene in any one of the above-mentioned compounds; a compound in which titanium is replaced with zirconium or hafnium in any one of the above-mentioned compounds; and a compound in which chloride is replaced with bromide, iodide, hydride, methyl, phenyl, benzyl, methoxide, n- butoxide, isopropoxide, phenoxide, benzyloxide, dimethylamide or diethylamide in any one of the above-mentioned compounds;
[0258]
a compound represented by formula (11) in which A2 is a group having a cyclopentadiene-type anionic skeleton:
methylenebis(cyclopentadienyl)zirconium dichloride,
isopropylidenebis(cyclopentadienyl)zirconium dichloride,
diphenylmethylenebis(cyclopentadienyl)zirconium dichloride, 1 ,2-ethylene- bis(cycIopentadienyl)zirconium dichloride, dimethylsilylenebis(cyclopentadienyl)zirconium dichloride, diphenylsilylenebis(cyclopentadienyl)zirconium dichloride, 1,2- tetramethyldisilylene-bis(cyclopentadienyl)zirconium dichloride,
[0259]
methylenebis(methylcyclopentadienyl)zirconium dichloride,
isopropylidenebis(methylcyclopentadienyl)zirconium dichloride,
diphenylmethylenebis(methylcyclopentadienyl)zirconium dichloride, 1,2-ethylene- bis(methylcyclopentadienyl)zirconium dichloride,
dimethylsilylenebis(methylcyclopentadienyl)zirconium dichloride,
diphenylsilylenebis(methylcyclopentadienyl)zirconium dichloride, 1 ,2-tetramethyldisilylene- bis(methylcyclopentadienyl)zirconium dichloride,
[0260]
methylenebis(n-butylcyclopentadienyl)zirconium dichloride, isopropylidenebis(n- butylcyclopentadienyl)zirconium dichloride, diphenylmethylenebis(n- butylcyclopentadienyl)zirconium dichloride, l,2-ethylene-bis(n- butylcyclopentadienyl)zirconium dichloride, dimethylsilylenebis(n- butylcyclopentadienyl)zirconium dichloride, diphenylsilylenebis(n- butylcyclopentadieny l)zirconium dichloride, 1 ,2-tetramethyldisilylene-bis(n- butylcyclopentadienyl)zirconium dichloride,
[0261]
methylenebis(tert-butylcyclopentadienyl)zirconium dichloride, isopropylidenebis(tert- butylcyclopentadienyl)zirconium dichloride, diphenylmethylenebis(tert- butylcyclopentadienyl)zirconium dichloride, 1 ,2-ethylene-bis(tert- butylcyclopentadienyl)zirconium dichloride, dimethylsilylenebis(tert- butylcyclopentadienyl)zirconium dichloride, diphenylsilylene bis(tert- butylcyclopentadienyl)zirconium dichloride, l,2-tetramethyldisilylene-bis(tert- butylcyclopentadienyl)zirconium dichloride,
[0262]
methylenebis(tetramethylcyclopentadienyl)zirconium dichloride,
isopropylidenebis(tetramethylcyclopentadienyl)zirconium dichloride,
diphenylmethylenebis(tetramethylcyclopentadienyl)zirconium dichloride, 1,2-ethylene- bis(tetramethylcyclopentadienyl)zirconium dichloride,
dimethylsilylenebis(tetramethylcyclopentadienyl)zirconium dichloride,
diphenylsilylenebis(tetramethylcyclopentadienyl)zirconium dichloride, 1 ,2- tetramethyldisilylene-bis(tetramethylcyclopentadienyl)zirconium dichloride,
[0263]
methylenebis(indenyl)zirconium dichloride, isopropylidenebis(indenyl)zirconium dichloride, diphenylmethylenebis(indenyl)zirconium dichloride, 1 ,2-ethylene-bis(indenyl)zirconium dichloride, dimethylsilylenebis(indenyl)zirconium dichloride,
diphenylsilylenebis(indenyl)zirconium dichloride, 1 ,2-tetramethy disilylene- bis(indenyl)zirconium dichloride,
[0264]
methylenebis(fluorenyl)zirconium dichloride, isopropylidenebis(fluorenyl)zirconium dichloride, diphenylmethylenebis(fluorenyl)zirconium dichloride, 1 ,2-ethylene-bis(fluorenyl)zirconium dichloride, dimethylsilylenebis(fluorenyl)zirconium dichloride,
diphenylsilylenebis(fluorenyl)zirconium dichloride, 1,2-tetramethyldisilylene- bis(fluorenyl)zirconium dichloride,
[0265]
methylenebis(azulenyl)zirconium dichloride, isopropylidenebis(azulenyl)zirconium dichloride, diphenylmethylenebis(azulenyl)zirconium dichloride, 1 ,2-ethylene-bis(azulenyl)zirconium dichloride, dimethylsilylenebis(azulenyl)zirconium dichloride,
diphenylsilylenebis(azulenyl)zirconium dichloride, 1 ,2-tetramethyldisilylene- bis(azulenyl)zirconium dichloride,
[0266]
methylenebis[2-ethyl-4-(2-fluoro-4-biphenylyl)-4H-azulenyl]zirconium dichloride, isopropylidenebis[2-ethyl-4-(2-fluoro-4-biphenylyl)-4H-azulenyl]zirconium dichloride, diphenylmethylenebis[2-ethyl-4-(2-fluoro-4-biphenylyl)-4H-azulenyl]zirconium dichloride, 1,2- ethylenebis[2-ethyl-4-(2-fluoro-4-biphenylyl)-4H-azulenyl]zirconium dichloride,
dimethylsilylenebis[2-ethyl-4-(2-fluoro-4-biphenylyl)-4H-azulenyl]zirconium dichloride, diphenylsilylenebis[2-ethyl-4-(2-fluoro-4-biphenylyl)-4H-azulenyl]zirconium dichloride, 1 ,2- tetramethyldisilylene-bis[2-ethyl-4-(2-fluoro-4-biphenylyl)-4H-azulenyl]zirconium dichloride, [0267]
methylene(cyclopentadienyl)(tetramethylcyclopentadienyl)zirconium dichloride,
isopropylidene(cyclopentadienyl)(tetramethylcyclopentadienyl)zirconium dichloride, diphenylmethylene(cyclopentadienyl)(tetramethylcyclopentadienyl)zirconium dichloride, 1,2- ethylene-(cyclopentadienyl)(tetramethylcyclopentadienyl)zirconium dichloride,
dimethylsilylene(cyclopentadienyl)(tetramethylcyclopentadienyl)zirconium dichloride, diphenylsilylene(cyclopentadienyl)(tetramethylcyclopentadienyl)zirconium dichloride, 1 ,2- tetramethyldisilylene-(cyclopentadienyl)(tetramethylcyclopentadienyl)zirconium dichloride, [0268]
methylene(cyclopentadienyl)(indenyl)zirconium dichloride,
isopropylidene(cyclopentadienyl)(indenyl)zirconium dichloride,
diphenylmethylene(cyclopentadienyl)(indenyl)zirconium dichloride, 1 ,2-ethylene- (cyclopentadienyl)(indenyl)zirconium dichloride,
dimethylsilylene(cyclopentadienyl)(indenyl)zirconium dichloride,
diphenylsilylene(cyclopentadienyl)(indenyl)zirconium dichloride, 1 ,2-tetramethyldisilylene-
(cyclopentadienyl)(indenyl)zirconium dichloride,
[0269]
methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,
isopropylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride,
diphenylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, 1 ,2-ethylene- (cyclopentadienyl)(fluorenyl)zirconium dichloride,
dimethylsilylene(cyclopentadienyi)(fluorenyl)zirconium dichloride,
diphenylsilylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, 1 ,2-tetramethyldisilylene-
(cyclopentadienyl)(fluorenyl)zirconium dichloride,
[0270]
methylene(3-tert-butyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride, isopropylidene(3-tert-butyl-5-methylcyclopentadienyl)(3,6-di-tert- butylfluorenyl)zirconium dichloride, diphenylmethylene(3-tert-butyl-5- methylcyclopentadienyl)(3 ,6-di-tert-butylfluorenyl)zirconium dichloride, 1 ,2-ethylene-(3-tert- butyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconiun dichloride,
dimethylsilylene(3-tert-butyl-5-methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride, diphenylsilylene(3-tert-butyl-5-methylcyclopentadienyl)(3,6-di-tert- butylfluorenyl)zirconium dichloride, l,2-tetramethyldisilylene-(3-tert-butyl-5- methylcyclopentadienyl)(3,6-di-tert-butylfIuorenyl)zirconium dichloride;
[0271]
a compound in which zirconium is replaced with hafnium or titanium in any one of the above-mentioned compounds; a compound in which cyclopentadienyl is replaced with methylcyclopentadienyl, n-butylcyclopentadienyl, t-butylcyclopentadienyl,
tetramethylcyclopentadienyl, indenyl or fluorenyl in any one of the above-mentioned compounds; and a compound in which chloride is replaced with bromide, iodide, hydride, methyl, phenyl, benzyl, methoxide, n-butoxide, isopropoxide, phenoxide, benzyloxide, dimethylamide or diethylamide in any one of the above-mentioned compounds;
[0272]
a compound represented by formula (12):
bis(cyclopentadienyl)zirconium dichloride,
bis(methylcyclopentadienyl)zirconium dichloride, bis(n-butylcyclopentadienyl)zirconium dichloride, bis(t-butylcyclopentadienyl)zirconium dichloride,
bis(pentamethylcyclopentadienyl)zirconium dichloride, bis(indenyl)zirconium dichloride, bis(fluorenyl)zirconium dichloride,
[0273]
(cyclopentadienyl)(methylcyclopentadienyl)zirconium dichloride, (cyclopentadienyl)(n- butylcyclopentadieny l)zirconium dichloride, (cycl opentadienyl)(t- butylcyclopentadienyl)zirconium dichloride,
(cyclopentadienyl)(pentamethylcyclopentadienyl)zirconium dichloride,
(cyclopentadienyl)(indenyl)zirconium dichloride, (cyclopentadienyl)(fluorenyl)zirconium dichloride;
[0274]
a compound in which zirconium is replaced with titanium or hafnium in any one of the above-mentioned compounds; a compound in which cyclopentadienyl is replaced with methylcyclopentadienyl, n-butylcyclopentadienyl, t-butylcyclopentadienyl,
tetramethylcyclopentadienyl, indenyl or fluorenyl in any one of the above-mentioned compounds; a compound in which chloride is replaced with bromide, iodide, hydride, methyl, phenyl, benzyl, methoxide, n-butoxide, isopropoxide, phenoxide, benzyloxide, dimethylamide or diethyl amide in any one of the above-mentioned compounds.
[0275]
[Activating co-catalyst component]
As the activating co-catalyst component, at least one compound selected from the group consisting of an organic aluminum oxy compound, a boron compound, an organic aluminum compound, and a zinc compound may be used.
[0276]
As the organic aluminum oxy compound, the following compound (Al) and/or (A2) can be used:
(Al): a cyclic aluminoxane having a structure represented by formula: (-A1(E1)-
0-}a;
(A2): a linear aluminoxane having a structure represented by formula: E2{-A1(E2)-
Figure imgf000099_0001
wherein "a" represents an integer of 2 or more; E1 represents a hydrocarbyl group having 1 to 8 carbon atoms, a plurality of E1 may be the same or different from each other, and a part of the plurality of E1 may be an alkoxy group or an aryloxy group containing an electron withdrawing group; "b" represents an integer of 1 or more; E2 represents a hydrocarbyl group having 1 to 8 carbon atoms, a plurality of E2 may be the same or different from each other, and a part of the plurality of E2 may be an alkoxy group or an aryloxy group containing an electron withdrawing group.
[0277]
Examples of the hydrocarbyl group of E1 and E2 include alkyl groups such as a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, an isobutyl group, a normal pentyl group, and a neopentyl group. Furthermore, examples of the electron withdrawing group in the alkoxy group or the aryloxy group containing an electron withdrawing group in E1 and E2 include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a carbonyl group, a sulfone group, and a phenyl group. Examples of the alkoxy group or the aryloxy group containing an electron withdrawing group in E and E include an alkoxy group containing an electron withdrawing group such as a trifluoro methoxy group, and a l,l-bis(trifluoromethyl)-2,2,2-trifluoro ethoxy group; an aryloxy group containing an electron withdrawing group such as 4-ftuorophenoxy group, a 3,4,5- trifiuorophenoxy group, and a 2,3,4,5,6-pentafluorophenoxy group. Acyclic aluminoxane in which E1 is a methyl group, an isobutyl group or a 3,4,5-trifluorophenoxy group, and "a" is 2 to 40, and a linear aluminoxane in which E2 is a methyl group, an isobutyl group or a 3,4,5- trifluorophenoxy group, and b is 1 to 40 are preferable.
[0278]
The above-mentioned aluminoxane can be produced by a known method.
Examples thereof include a method for producing by bringing a solution in which
trialkylaluminum (for example, trimethylaluminum) is dissolved in an organic solvent (benzene, aliphatic hydrocarbyl, or the like) into contact with water. Another example is a method for producing by bringing trialkylaluminum (for example, trimethylaluminum) into contact with a metallic salt (for example, copper sulfate hydrate) containing crystallization water.
[0279]
As the boron compound, one or more boron compounds selected from the group consisting of the following compounds (Bl) to (B5) can be used:
(Bl): a boron compound represented by formula: BQW;
(B2): a borate compound represented by formula: T^ ^Q^Q4)-;
(B3): a borate compound represented by formula: (L-H)+(BQ Q4)-;
(B4): a borate compound represented by formula: T+(BQ5Q6Q7Q8)";
(B5): a borate compound represented by formula: (L-H)+(BQ5Q6Q7Q8)\ wherein B represents a trivalent boron atom, Q1, Q2, Q3 and Q4 each represent a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms, a halogenated hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyl silyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or a dihydrocarbyl amino group having 2 to 20 carbon atoms; T+ represents inorganic or organic cation; and (L-H)+ represents a Broensted acid; Q5, Q6, Q7, and Q8 each represent a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms, a halogenated hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyl silyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or a dihydrocarbyl amino group having 2 to 20 carbon atoms; or groups in which a hydrogen atom in these groups is substituted with a group represented by formula: (-Q9-H), wherein Q9 represents O, S, N or PR, R represents a hydrocarbyl group, a trihydrocarbyl silyl group, a trihydrocarbyl germyl group or hydrogen (hereinafter, referred to as "active group."), and at least one of Q5, Q6, Q7, and Q8 is an active group.
[0280]
In the compounds (Bl) to (B3), preferable examples of Q1, Q2, Q3 and Q4 include a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms or a halogenated hydrocarbyl group having 1 to 20 carbon atoms. Examples of the inorganic cation in T+ include a ferrocenium cation, an alkyl-substituted ferrocenium cation, and a silver cation; and examples of the organic cation include a triphenylmethyl cation. Examples of (BQ1Q2Q3Q4)" include tetrakis(pentafluoropheny l)borate, tetrakis(2, 3,5, 6-tetrafluoropheny l)borate, tetraki s(2, 3 ,4, 5 - tetrafluorophenyl)borate, tetrakis(3,4,5-trifluorophenyl)borate, tetrakis(2,3,4- trifluorophenyl)borate, phenyl tris(pentafluorophenyl)borate, and tetrakis(3,5-bis- trifluoromethylphenyl)borate. Examples of (L-H)+ as Broensted acid include trialkyl- substituted ammonium, Ν,Ν-dialkylanilinium, dialkylammonium, and triarylphosphonium.
[0281]
Examples of the boron compound (Bl) represented by formula: BQ[Q2Q3 include tris(pentafluoropheny l)borane, tri s(2, 3 , 5 , 6-tetrafluoropheny l)borane, tris(2, 3 ,4, 5 - tetrafluorophenyl)borane, tris(3,4,5-trifluorophenyl)borane, tris(2,3,4-trifluorophenyl)borane, and phenylbis(pentafluorophenyl)borane.
[0282]
Examples of the borate compound (B2) represented by formula: T+(BQ1Q2Q3Q4)" include ferrocenium tetrakis(pentafluorophenyl)borate, Ι, Γ-bis-trimethylsilylferrocenium tetrakis(pentafluorophenyl)borate, silver tetrakis(pentafluorophenyl)borate, triphenyl
methyltetrakis(pentafluorophenyl)borate, and triphenyl methyltetrakis(3,5-bis- trifluoromethylphenyl)borate.
[0283]
Examples of the borate compound (B3) represented by formula: (L- H)+( BQ1Q2Q3Q4)" include triethyl ammonium tetrakis(pentafluorophenyl)borate,
tripropylammonium tetrakis(pentafluorophenyl)borate, tri(normal butyl)ammonium
tetrakis(pentafluorophenyl)borate, tri(normal butyl)ammonium tetrakis(3,5-bis- trifluoromethylphenyl)borate, N,N-bis-trimethylsilylanilinium tetrakis(pentafluorophenyl)borate, Ν,Ν-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-diethylanilinium
tetrakis(pentafluorophenyl)borate, N,N-2,4,6-pentamethylanilinium
tetrakis(pentafluorophenyl)borate, N,N-bis-trimethylsilylanilinium tetrakis(3,5-bis- trifluoromethylphenyl)borate, diisopropylammonium tetrakis(pentafluorophenyl)borate, dicyclohexylammonium tetrakis(pentafluorophenyl)borate, triphenylphosphonium
tetrakis(pentafluorophenyl)borate, tri(methylphenyl)phosphonium
tetrakis(pentafluorophenyl)borate, and tri(bis-trimethylsilylphenyl)phosphonium
tetrakis(pentafluorophenyl)borate.
[0284]
Examples of Q5, Q6, Q7, and Q8 in the compounds (B4) and (B5) include a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms, a halogenated hydrocarbyl group having 1 to 20 carbon atoms, or an active group. Examples of the inorganic cation in T+ include a ferrocenium cation, an alkyl-substituted ferrocenium cation, and a silver cation; and examples of the organic cation include a triphenylmethyl cation. Examples of (BQ5Q6Q7Q8)' include triphenyl(hydroxyphenyl)borate, diphenyl-di(hydroxyphenyl)borate, triphenyl(2,4- dihydroxyphenyl)borate, tri(p-tolyl)(hydroxyphenyl)borate,
tris(pentafluorophenyl)(hydroxyphenyl)borate, tris(2,4-dimethylphenyl)(hydroxyphenyl)borate, tris(3,5-dimethylphenyl)(hydroxyphenyl)borate, tris(3,5-di-trifluoromethyl- phenyl)(hydroxyphenyl)borate, tris(pentafluorophenyl)(2-hydroxyethyl)borate,
tris(pentafluorophenyl)(4-hydroxybutyl)borate, tris(pentafluorophenyl)(4- hydroxycyclohexyl)borate, tris(pentafluorophenyl)(4-(4'-hydroxyphenyl)phenyl)borate, and tris(pentafluorophenyl)(6-hydroxy-2-naphthyl)borate. A preferable example is
tris(pentafluorophenyl)(4-hydroxyphenyl)borate. Another preferable anion is a borate in which a hydroxy functional group in the above-mentioned borate is substituted with an amino NHR functional group, wherein R is preferably a methyl group, an ethyl group or a tert-butyl group. Examples of (L-H)+ as Broensted acid include trialkyl-substituted ammonium, N,N- dialkylanilinium, dialkylammonium, and triarylphosphonium.
[0285]
Examples of the borate compound (B4) represented by formula: T+(BQ5Q6Q7Q8)" include ferrocenium tris(pentafluorophenyl)(4-hydroxyphenyl)borate, silver
tris(pentafluorophenyl)(4-hydroxyphenyl)borate, and triphenylmethyl tris(pentafluorophenyl)(4- hydroxyphenyl)borate.
[0286]
Examples of the borate compound (B5) represented by formula: (L- H)+(BQ5Q6Q7Q8)" include tnethylammonium tris(pentafluorophenyl)(4-hydroxyphenyl)borate, tripropylammonium tris(pentafluorophenyl)(4-hydroxyphenyl)borate, tri(normal
butyl)ammonium tris(pentafiuorophenyl)(4-hydroxyphenyl)borate, N,N-diethylanilinium tris(pentafluorophenyl)(4-hydroxyphenyl)borate, N,N-2,4,6-pentamethylanilinium
tris(pentafluorophenyl)(4-hydroxyphenyl)borate, diisopropylammonium
tris(pentafluorophenyl)(4-hydroxyphenyl)borate, dicyclohexylammonium
tris(pentafluorophenyl)(4-hydroxyphenyl)borate, triphenylphosphonium
tris(pentafluorophenyl)(4-hydroxyphenyl)borate, and tri(methylphenyl)phosphonium
tris(pentafluorophenyl)(4-hydroxyphenyl)borate.
[0287] The compounds (B4) and (B5) can be synthesized according to a method described in JP-A- 11-503113.
[0288]
Examples of the organic aluminum compound include a compound represented by formula: E3cAlX,3-c, wherein "c" represents a number in the range of 0 < c < 3; E3 represents a hydrocarbyl group having 1 to 8 carbon atoms; X' represents a hydrogen atom or a halogen atom; when more than one E3 exist, the E3 groups may be the same or different from each other; and when more than one X' exist, the X groups may be the same or different from each other. As the organic aluminum compound, one or more of these compounds may be used.
[0289]
Examples of the organic aluminum compound represented by the above- mentioned formula include trialkylaluminum, dialkylaluminum chloride, alkylaluminum dichloride, and dialkylaluminum hydride. Examples of trialkylaluminum include
trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, and
trihexylaluminum; examples of dialkylaluminum chloride include dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, and dihexylaluminum chloride; examples of alkylaluminum dichloride include methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, and hexylaluminum dichloride; and, examples of dialkylaluminum hydride include
dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride,
diisobutylaluminum hydride, and dihexylaluminum hydride. Trialkylaluminum is preferable, and triethylaluminum and triisobutylaluminum are more preferable.
[0290]
Examples of the zinc compound include a compound obtained by bringing dialkylzinc, fluorinated phenol and water into contact with each other. Furthermore, examples of a zinc compound supported on the carrier mentioned below include a compound obtained by bringing dialkylzinc, fluorinated phenol, water and silica into contact with each other.
Examples of methods therefor include methods described, for example, in JP-A-2001-247612 and WO 2002/051878.
[0291]
[Carrier]
As a carrier, porous materials may be used suitably. Among them, an inorganic material or an organic polymer is used more suitably, and an inorganic material is used further suitably. [0292]
Examples of the inorganic material to be used for the carrier include an inorganic oxide, clay, clay mineral, and zeolite. One or more of them may be used.
[0293]
Examples of the inorganic oxide to be used for the carrier include Si02, A1203,
MgO, Zr02, Ti02, B203, CaO, ZnO, BaO, and Th02, and mixtures thereof, for example, Si02- MgO, Si02-Al203, Si02-Ti02, Si02-V205, Si02-Cr203, and Si02-Ti02-MgO. Among these inorganic oxides, Si02 and A1203 are preferable, and Si02 is more preferable. The above- mentioned inorganic oxide may contain a small amount of carbonate, sulfate, nitrate or oxide component such as Na2C03, K2C03, CaC03, MgC03, Na2S04, A12(S04)3, BaS04, KN03, Mg(N03)2, A1(N03)3, Na20, K20, and Li20.
[0294]
Furthermore, the inorganic oxide usually has a hydroxyl group on the surface thereof, and as the inorganic oxide, it is preferable to use a modified inorganic oxide in which active hydrogen of the surface hydroxyl group is substituted with different substituents. The modified inorganic oxide can be obtained by bringing an inorganic oxide and a modifier into contact with each other. Examples of the modifier include a trialkylchlorosilane such as trimethylchlorosilane and tert-butyldimethylchlorosilane, a triarylchlorosilane such as triphenylchlorosilane, a dialkyldichlorosilane such as dimethyldichlorosilane, a
diaryldichlorosilane such as diphenyldichlorosilane, an alkyltrichlorosilane such as
methyltnchlorosilane, an aryltrichlorosilane such as phenyltrichlorosilane, a trialkylalkoxysilane such as trimethylmethoxysilane, a triarylalkoxysilane such as triphenylmethoxysilane, a dialkyldialkoxysilane such as dimethyldimethoxysilane, a diaryldialkoxysilane such as diphenyldimethoxysilane, an alkyltrialkoxysilane such as methyltrimethoxysilane, an
aryltrialkoxysilane such as phenyltrimethoxysilane, a tetraalkoxysilane such as
tetramethoxysilane, an alkyldisilazane such as 1,1,1,3,3,3-hexamethyldisilazane and
tetrachlorosilane.
[0295]
Examples of treatment for bringing the inorganic oxide and the modifier into contact with each other include a method of bringing the inorganic oxide and trialkylaluminum into contact with each other, followed by bringing the obtained product into contact with dialkylamine (e.g., diethylamine, diphenylamine, or the like), alcohol (methanol, ethanol, and the like) or phenol.
[0296] Examples of the clay or the clay mineral include, kaolin, bentonite, kibushi clay, gairome clay, allophane, hisingerite, pyrophyllite, talc, mica, smectite, montmorillonite, hectorite, laponite, saponite, vermiculite, chlorite, palygorskite, kaolinite, nacrite, dickite, and halloysite. Among them, smectite, montmorillonite, hectorite, laponite, and saponite are preferable, and montmorillonite and hectorite are more preferable.
[0297]
Examples of the zeolite include zeolite types of CFI, AFI, MAZ, AET, DON, FAU, CLO, VFI, ABW, ACO, AEI, AEL, AEN, AFQ AFN, AFO, AFR, AFS, AFT, AFX, AFY, AHT, ANA, APC, APD, AST, ASV, ATN, ATO, ATS, ATT, ATV, AWO, and AWW.
[0298]
As the inorganic material, an inorganic oxide is suitably used. Preferably, an inorganic material is dried and does not substantially contain water. An inorganic material which has been dried by heat treatment is preferable. The heat treatment may be carried out with respect to an inorganic material whose moisture content cannot be observed visually at temperatures of usually 100°C to 1,500°C, preferably 100°C to 1,000°C, and more preferably 200°C to 800°C. Heating time is preferably 10 minutes to 50 hours, and more preferably one hour to 30 hours. Examples of the heat-drying method include a method of drying by allowing a dry inert gas (for example, nitrogen, argon, or the like) to flow at a constant flow rate while heating an inorganic material, a method of drying by heating under reduced pressure, and the . like.
[0299]
The average particle diameter of the inorganic material is usually 1 μηι to 5000 μπι, preferably 5 μιη to 1000 μπι, more preferably 10 μπι to 500 μπι, and further preferably 10 μπι to 100 μπι. The pore volume is preferably 0.1 ml/g or more, and more preferably 0.3 ml/g to 10 ml/g. The specific surface area is preferably 10 m2/g to 1000 m2/g and more preferably 100 m2/g to 500 m2/g.
[0300]
Examples of the organic polymer used as the carrier include polystyrene, polyolefin, polypeptide, polyethyleneimine, polycarbonate, and other known organic polymer particles. The organic polymer can be obtained by polymerizing a monomer containing one or more polymeric unsaturated groups. Examples of the monomer include ethylene, a-olefin, an aromatic vinyl compound, and a cyclic olefin. Examples of the monomer include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-l-pentene, styrene, divinylbenzene, norbornene, and dicyclopentadiene. Two or more of these monomers may be used. Preferable monomers are ethylene and styrene.
[0301]
The average particle diameter of the organic polymer is usually 1 μιη to 5000 μπι, preferably 5 μιη to 1000 μιη, and more preferably 10 μπι to 500 μιη. The pore volume is preferably 0.1 ml/g or more, and more preferably 0.3 ml/g to 10 ml/g. The specific surface area is preferably 10 m2/g to 1000 m2/g and more preferably 50 m2/g to 500 m2/g.
[0302]
Preferably, the organic polymer is dried and does not substantially contain water. An organic polymer which has been dried by heat treatment is preferable. With respect to an organic polymer whose moisture content cannot be observed visually, the heat treatment temperature is usually 30°C to 400°C, preferably 50°C to 200°C, and more preferably 70°C to 150°C. Heat treatment time is preferably 10 minutes to 50 hours, and more preferably one hour to 30 hours. Examples of the heat-drying method include a method of drying by allowing a dry inert gas (for example, nitrogen, argon, or the like) to flow at a constant flow rate while heating an organic polymer, and a method of drying by heating under reduced pressure.
[0303]
The geometrical standard deviation of particle diameter of the carrier based on the volume is preferably 2.5 or less, more preferably 2 or less, and further preferably 1.7 or less.
[0304]
[Catalyst for Producing Ethylenic Polymer]
The catalyst for producing an ethylenic polymer of the present invention is a catalyst prepared from a complex (I), a complex for olefin polymerization, an activating co- catalyst component and a carrier, in which the complex (I) and the complex for olefin
polymerization are supported by the carrier. Examples of the catalyst include (1) a catalyst containing the following component (X), (2) a catalyst containing the following component (A) and the following component (B), (3) a catalyst containing the following component (X) and the following component (A), (4) a catalyst containing the following component (X) and the following component (B), and (5) a catalyst containing the following component (X), the following component (A) and the following component (B):
component (X): particles obtained by bringing the complex (I), the complex for olefin polymerization, the activating co-catalyst component and the carrier into contact with each other;
component (A): particles obtained by bringing the complex (I), the activating co- catalyst component and the carrier into contact with each other; component (B): particles obtained by bringing the complex for olefin polymerization, the activating co-catalyst component and the carrier.
[0305]
When the catalysts of the above-mentioned (2) to (5) are used, components to be used among component (X), component (A) and component (B) are previously mixed and the obtained mixture may be supplied to a polymerization reactor, or these components may be supplied separately to a polymerization reactor and then they may be mixed therein. A part of the components to be used may be mixed, and the obtained mixture may be supplied to the polymerization reactor and then the rest of the components may be supplied to the reactor.
Furthermore, an activating co-catalyst component, in addition to component (X), component (A) and component (B), may be supplied to the polymerization reactor.
[0306]
<Component (X)>
A complex (I), a complex for olefin polymerization, an activating co-catalyst component and a carrier may be brought into contact with each other in inert atmosphere. For example, they are brought into contact with each other in a solvent, or in an inert gas.
Examples of the solvent include a saturated aliphatic hydrocarbon such as butane, pentane, hexane, heptane, and octane; and an aromatic hydrocarbon such as toluene and xylene.
Examples of the inert gas include nitrogen gas, helium gas, and argon gas. When the complex (I), the complex for olefin polymerization, the activating co-catalyst component and the carrier are brought into contact with each other in a solvent, component (X) can be obtained by removing the solvent after they are brought into contact with each other. Preferable component (X) is particles obtained by bringing the complex (I), the complex for olefin polymerization, the activating co-catalyst component and the carrier into contact with each other in the solvent, followed by removing the solvent therefrom.
[0307]
When the complex (I), the complex for olefin polymerization, the activating co- catalyst component and the carrier may be brought into contact with each other, these components may be brought into contact with each other at the same time, or any two or more of these components may be previously brought into contact with each other, and then the obtained product may be brought into contact with the rest of the components. Furthermore, each component may be brought into contact separately twice or more. In addition, two kinds or more of each component may be brought into contact with others. Examples of the contact method include the following methods: (XI) a method of bringing the complex (I), the complex for olefin polymerization, the activating co-catalyst component and the carrier into contact with each other at the same time;
(X2) a method of bringing the carrier and the activating co-catalyst component into contact with each other, and then bringing the obtained product into contact with the complex for olefin polymerization, and then with the complex (I);
(X3) a method of bringing the carrier and the activating co-catalyst component into contact with each other, and then bringing the obtained product into contact with the complex (I), and then with the complex for olefin polymerization;
(X4) a method of bringing the carrier and the activating co-catalyst component into contact with each other, and then bringing the obtained product into contact with the complex for olefin polymerization and the complex (I) at the same time;
(X5) a method of bringing the carrier and the complex for olefin polymerization into contact with each other, and then bringing the obtained product into contact with the activating co-catalyst component, then with the complex (I);
(X6) a method of bringing the carrier and the complex (I) into contact with each other, and then bringing the obtained product into contact with the activating co-catalyst component, then with the complex for olefin polymerization;
(X7) a method of bringing the carrier and the activating co-catalyst component into contact with each other, and then bringing the obtained product into contact with the complex for olefin polymerization, then with the complex (I), and further with the activating co- catalyst component;
(X8) a method of bringing the carrier and the activating co-catalyst component into contact with each other, and then bringing the obtained product into contact with the complex (I), then with the complex for olefin polymerization, and further with the activating co- catalyst component;
(X9) a method of bringing the carrier and the activating co-catalyst component into contact with each other, and then bringing the obtained product into contact with the complex for olefin polymerization and the complex (I) at the same time, and further with the activating co-catalyst component;
(XI 0) a method of bringing the carrier and the activating co-catalyst component into contact with each other, and then bringing the obtained product into contact with the activating co-catalyst component, then with the complex (I), and further with the activating co- catalyst component; (XI 1) a method of bringing the carrier and the complex (I) into contact with each other, and then bringing the obtained product into contact with the activating co-catalyst component, then with the complex for olefin polymerization, and further with the activating co- catalyst component;
(XI 2) a method of bringing the carrier and the activating co-catalyst component into contact with each other, and then bringing the obtained product into contact with the complex for olefin polymerization, then with the activating co-catalyst component, then with the complex (I), and further with the activating co-catalyst component;
(X13) a method of bringing the carrier and the activating co-catalyst component into contact with each other, and then bringing the obtained product into contact with the complex (I), then with the activating co-catalyst component, then with the complex for olefin polymerization, and further with the activating co-catalyst component.
A method in which the activating co-catalyst component is brought into contact with the carrier before the complex (I) and the complex for olefin polymerization are brought into contact with the carrier is preferable. Examples of such methods include the above- mentioned methods (X2), (X3), (X4), (X7), (X8), (X9), (X12), and (XI 3). Furthermore, in a method of bringing the activating co-catalyst component separately twice or more, the activating co-catalyst compounds to be used in each time may be the same or different from each other.
[0308]
When the complex (I), the complex for olefin polymerization, the activating co- catalyst component and the carrier are brought into contact with each other, the amount of each component to be used with respect to 100 parts by weight of carrier is preferably 0.05 parts by weight to 20 parts by weight of the complex (I), 0.05 parts by weight to 20 parts by weight of the complex for olefin polymerization, 0.1 parts by weight to 300 parts by weight of the activating co-catalyst component; and more preferably 0.1 parts by weight to 10 parts by weight of complex (I), 0.1 parts by weight to 10 parts by weight of the complex for olefin polymerization, and 0.2 parts by weight to 200 parts by weight of the activating co-catalyst component.
[0309]
The temperature at which the complex (I), the complex for olefin polymerization, the activating co-catalyst component and the carrier are brought into contact with each other is preferably -50°C to 150°C, and further preferably 0°C to 100°C.
[0310]
As component (X), two types or more of particles of the complex (I) may be used, two types or more of particles of the complex for olefin polymerization may be used, and two types or more of particles of the activating co-catalyst component may be used. Furthermore, two types or more of particles containing different contents of the complex (I) and the complex for olefin polymerization may be used.
[0311]
<Component (A)>
A complex (I), an activating co-catalyst component and a carrier may be brought into contact with each other in inert atmosphere. For example, they are brought into contact with each other in a solvent, or in an inert gas. Examples of the solvent include a saturated aliphatic hydrocarbon such as butane, pentane, hexane, heptane, and octane; and an aromatic hydrocarbon such as toluene and xylene. Examples of the inert gas include nitrogen gas, helium gas, and argon gas. When a complex for oligomerization of ethylene, the activating co- catalyst component and the carrier are brought into contact with each other in a solvent, component (A) can be obtained by removing the solvent after they are brought into contact with each other. Preferable component (A) is particles obtained by bringing the complex for oligomerization of ethylene containing a transition metal atom of Group 4 of the periodic table of the elements, the activating co-catalyst component and the carrier into contact with each other in the solvent, followed by removing the solvent therefrom.
[0312]
When the complex (I), the activating co-catalyst component and the carrier may be brought into contact with each other, these components may be brought into contact with each other at the same time, or any two or more of these components may be previously brought into contact with each other, and then the obtained product may be brought into contact with the rest of the components. Furthermore, each component may be brought into contact separately twice or more. In addition, two kinds or more of each component may be brought into contact with others. Examples of the contact method include the following methods:
(Al) a method of bringing the complex (I), the activating co-catalyst component and the carrier into contact with each other at the same time;
(A2) a method of bringing the carrier and the activating co-catalyst component into contact with each other, and then bringing the obtained product into contact with the complex (I);
(A3) a method of bringing the carrier and the complex (I) into contact with each other, and then bringing the obtained product into contact with the activating co-catalyst component;
(A4) a method of bringing the complex (I) and the activating co-catalyst component into contact with each other, and then bringing the obtained product into contact with the carrier;
(A5) a method of bringing the carrier and the activating co-catalyst component into contact with each other, and then bringing the obtained product into contact with the complex (I), and then with the activating co-catalyst component.
A method of bringing the activating co-catalyst component into contact with the carrier before bringing the complex (I) into contact with the carrier is preferable. Examples of such preferable methods include the above-mentioned methods (A2) and (A5). Furthermore, in a method of bringing the activating co-catalyst component separately twice or more, the activating co-catalyst compounds to be used in each time may be the same or different from each other.
[0313]
When the complex (I), the activating co-catalyst component and the carrier are brought into contact with each other, the amount of each component to be used with respect to 100 parts by weight of the carrier is preferably 0.01 parts by weight to 20 parts by weight of the complex (I), and 0.1 parts by weight to 300 parts by weight of the activating co-catalyst component; and more preferably 0.05 parts by weight to 10 parts by weight of the complex (I), and 1 part by weight to 200 parts by weight of the activating co-catalyst component.
[0314]
The temperature at which the complex (I), the activating co-catalyst component and the carrier are brought into contact with each other is preferably -50°C to 150°C, and further preferably 0°C to 100°C.
[0315]
As component (A), two types or more of particles of the complex (I) may be used, and two types or more of particles of the activating co-catalyst component may be used.
[0316]
<Component (B)>
A complex for olefin polymerization, an activating co-catalyst component and a carrier may be brought into contact with each other in inert atmosphere. For example, they are brought into contact with each other in a solvent, or in an inert gas. Examples of the solvent include a saturated aliphatic hydrocarbon such as butane, pentane, hexane, heptane, and octane; and an aromatic hydrocarbon such as toluene and xylene. Examples of the inert gas include nitrogen gas, helium gas, and argon gas. When the complex for olefin polymerization, the activating co-catalyst component and the carrier are brought into contact with each other in a solvent, component (B) can be obtained by removing the solvent after they are brought into contact with each other. Preferable component (B) is particles obtained by bringing the complex for olefin polymerization, the activating co-catalyst component and the carrier into contact with each other in the solvent, followed by removing the solvent therefrom.
[0317]
When the complex for olefin polymerization, the activating co-catalyst component and the carrier may be brought into contact with each other, these components may be brought into contact with each other at the same time, or any two or more of these components may be previously brought into contact with each other, and then the obtained product may be brought into contact with the rest of the components. Furthermore, each product may be brought into contact separately twice or more. In addition, two kinds or more of each component may be brought into contact with others. Examples of the contact method include the following methods:
(Bl) a method of bringing the complex for olefin polymerization, the activating co-catalyst component and the carrier into contact with each other at the same time;
(B2) a method of bringing the carrier and the activating co-catalyst component into contact with each other, and then bringing the obtained product into contact with the complex for olefin polymerization;
(B3) a method of bringing the carrier and the complex for olefin polymerization into contact with each other, and then bringing the obtained product into contact with the activating co-catalyst component;
(B4) a method of bringing the complex for olefin polymerization and the activating co-catalyst component into contact with each other, and then bringing the obtained product into contact with the carrier;
(B5) a method of bringing the carrier and the activating co-catalyst component into contact with each other, and then bringing the obtained product into contact with the complex for olefin polymerization, and then with the activating co-catalyst component.
A method of bringing the activating co-catalyst component into contact with the carrier before bringing the complex for olefin polymerization into contact with the carrier is preferable. Examples of such preferable methods include the above-mentioned methods (B2) and (B5). When the activating co-catalyst component and the carrier are brought into contact with each other, the activating co-catalyst component may be in situ prepared in the presence of the carrier. Furthermore, in a method of bringing the activating co-catalyst component separately twice or more, the activating co-catalyst compounds to be used in each time may be the same or different from each other.
[0318]
When the complex for olefin polymerization, the activating co-catalyst component and the carrier are brought into contact with each other, the amount of each component to be used with respect to 100 parts by weight of the carrier is preferably 0.01 parts by weight to 20 parts by weight of the complex for olefin polymerization, and 0.1 parts by weight to 300 parts by weight of the activating co-catalyst component; and more preferably 0.05 parts by weight to 10 parts by weight of the complex for olefin polymerization, and 1 part by weight to 200 parts by weight of the activating co-catalyst component.
[0319]
The temperature at which the complex for olefin polymerization, the activating co-catalyst component and the carrier are brought into contact with each other is preferably - 50°C to 150°C, and further preferably 0°C to 100°C.
[0320]
As component (B), two types or more of particles of the complex for olefin polymerization may be used, and two types or more of particles of the activating co-catalyst component may be used.
[0321]
Component (X) and component (B) may be a product obtained by prepolymerizing olefins. The prepolymerization may be carried out by using a known method.
[0322]
For the catalyst for producing an ethylenic polymer according to the present invention, the ratio of the total mol of transition metal atoms originated from the complex (I) contained in component (X), component (A) and component (B) to the total mol of transition metal atoms originated from the complex for olefin polymerization contained in component (X), component (A) and component (B) (the ratio of the total mol of transition metal atoms derived from the complex (I) / the total mol of transition metal atoms derived from the complex for olefin polymerization) is usually 0.001 to 100, preferably 0.01 to 50, more preferably 0.1 to 10, and further preferably 0.2 to 8.
[0323]
[Method for Producing Ethylenic Polymer]
In a method for producing an ethylenic polymer according to the present invention, polymerization of olefins including ethylene can be carried out by the above- mentioned catalyst for producing an ethylenic polymer. Examples of olefins other than ethylene include olefins having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1- hexene, 1 -heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-l-pentene, and 4- methyl-l-hexene. A suitable method is a production method of carrying out polymerization by supplying only ethylene as a raw material monomer or supplying ethylene and a monomer capable of being copolymerized with ethylene.
[0324]
Examples of the monomer capable of being copolymerized with ethylene include an olefin having 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 1- heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-l-pentene, and 4-methyl-l-hexene; a cyclic olefin such as norbornene; an alkenyl aromatic hydrocarbyl such as styrene; an unsaturated carboxylic acid such as acrylic acid and methacrylic acid; an unsaturated carboxylic acid ester such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, and ethyl methacrylate; and a vinyl ester compound such as vinyl acetate. These may be used singly or in combinations thereof.
[0325]
Examples of the polymerization method include a solvent polymerization method using an aliphatic hydrocarbyl such as butane, pentane, hexane, heptane, or octane; an aromatic hydrocarbyl such as benzene or toluene; a halogenated hydrocarbyl such as methylenedichloride as a solvent, or a slurry polymerization method, or a gas phase polymerization method in which gaseous monomers are polymerized. Furthermore, methods combining these methods may be employed, and examples thereof include a method of carrying out the solution polymerization method, and then carrying out the gas phase polymerization method, and a method of carrying out the slurry polymerization method, and then carrying out the gas phase polymerization method. Furthermore, any of a continuous polymerization method and a batch polymerization method can be employed. In addition, any of a single-stage polymerization method and a multi-stage polymerization method may be carried out. Preferable method is the slurry polymerization method or the gas phase polymerization method, and more preferable method is the gas phase polymerization method.
[0326]
A polymerization pressure is preferably a normal pressure to 5 MPa. Generally, a polymerization time can be appropriately determined depending on types of target polymers and reaction devices, but it is typically 1 minute to 20 hours. Furthermore, a chain transfer agent such as hydrogen can be added to the reaction system for modulating the molecular weight of an ethylenic polymer. [0327]
A polymerization temperature can range from 0°C to 220°C. The polymerization temperature is preferably 20°C or higher for enhancing economical efficiency, more preferably 40°C or higher, further preferably 50°C or higher, and still further preferably 70°C or higher. Furthermore, for increasing the short chain branches, in particular, the number of butyl branches, the polymerization temperature is preferably 130°C or less, and more preferably 100°C or less.
[0328]
When polymerization is carried out by the multi-stage polymerization method, a plurality of polymerization reactors may be linked in series or in parallel, or polymerization may be carried out by using polymerization reactors linked in series and polymerization reactors linked in parallel. Furthermore, when the polymerization reactors are linked in series in the multi-stage polymerization method, the temperature of the polymerization at the upstream side is preferably made to be lower than the temperature of the polymerization at the downstream side.
[0329]
Component (X), component (A), component (B), and a mixture of two or more of these components, and a mixture of a part of these components may each be supplied to a polymerization reactor as a dispersion liquid in which they are dispersed in an organic solvent. Examples of the organic solvent to be used include a saturated aliphatic hydrocarbon such as butane, pentane, hexane, heptane, and octane. The total concentration of transition metal atoms originated from component (X), component (A) and component (B) in each dispersion liquid is preferably 0.1 μπιοΙ/L to 10 mmol/L, and further preferably 0.2 μηιοΙ/L to 1 mmol L.
[0330]
When the above-mentioned dispersion liquid is supplied to a solution polymerization reactor or a slurry polymerization reactor, an organic solvent of the dispersion liquid is preferably a compound having high affinity for the solvent for polymerization, and the solvent is more preferably the same as the compound of the polymerization solvent. When the above-mentioned dispersion liquid is supplied to the gas phase polymerization reactor, the organic solvent of the dispersion liquid is preferably a compound whose boiling point is lower than the polymerization reaction temperature. Examples of the compound include butane, pentane, and hexane. Furthermore, these dispersion liquids are preferably supplied to a gas phase polymerization reactor in the form of mist.
[0331] A method for producing an ethylenic polymer of the present invention is suitable for producing an ethylenic polymer having short chain branches, more suitable for producing an ethylenic polymer having at least one branch selected from the group of branches consisting of an ethyl branch, a butyl branch and a hexyl branch, and particularly suitable for producing ethylenic polymer having a butyl branch.
[0332]
The ethylenic polymer obtained by the production method of the present invention may be formed into various molded products for application (films, sheets, containers (bottles, trays, etc.), and the like) by a known molding processing method, for example an extrusion method such as a blown film process and a flat die process; a hollow molding; an injection molding; a compression molding; or a cross-linking foaming.
[0333]
The ethylenic polymer may be blended with a known resin and then molded. Furthermore, the molded product may be a single-layered molded product containing an ethylenic polymer, and a multi-layered molded product containing an ethylenic polymer.
[0334]
Examples of the molded product include a film for packaging foods, a container for packaging foods, a packaging material for pharmaceutical preparations, a surface protecting film, a packaging material for electronic components to be used for packaging products such as a semiconductor product, a molded product by cross-linking foaming, a molded product by extrusion foaming, a hollow molded product, a blown-molded bottle, a squeezed bottle, and the like.
[EXAMPLES]
[0335]
The present invention will be described with reference to Examples.
Examples were analyzed by the following methods.
[0336]
<Analysis of Transition Metal Complex>
(1) Proton nuclear magnetic resonance spectrum (1H-NMR)
Device: EX270 manufactured by JEOL Ltd.
Sample cell: tube having a diameter of 5 mm
Measurement solvent: CDC13
Sample concentration: 10 mg/0.5 mL (CDC13)
Measurement temperature: room temperature (about 25°C) Measurement parameter, probe having a diameter of 5 mm, EXMOD NON, OBNUC 1H, number of multiplications: 16 or more
Repeating time: ACQTM 6 seconds, PD 1 second
Internal standard: CDC13 (7.26 ppm)
[0337]
(2) Carbon nuclear magnetic resonance spectrum (13C-NMR)
Device: EX270 manufactured by JEOL Ltd.
Sample cell: tube having a diameter of 5 mm
Measurement solvent: CDC13
Sample concentration: 30 mg/0.5 mL (CDCI3)
Measurement temperature: room temperature (about 25°C)
Measurement parameter: probe having a diameter of 5 mm, EXMOD BCM, OBNUC 13C, number of multiplications: 256 or more
Repeating time: ACQTM 1.79 seconds, PD 1.21 seconds
Internal standard: CDC13 (77.0 ppm)
[0338]
(3) Mass spectrum
[Electron ionization mass spectrometry (EI-MS)]
Device: JMS-T 100GC manufactured by JEOL Ltd.
Ionization voltage: 70 eV
Ion source temperature: 230°C
Acceleration voltage: 7 kV
MASS RANGE: m/z 35-800
[0339]
<Analysis of polymer>
(4) Measurement of amount of butyl branches
(Measurement conditions)
Device: AVANCE600 manufactured by Bruker
Measurement probe: 10 mm probe
Measurement solvent: mixture solution of 1,2-dichlorobenzene / l,2-dichlorobenzene-d4 = 75 / 25 (volume ratio)
Measurement temperature: 130°C
Measurement method: proton decoupling method
Pulse width: 45° Pulse repetition time: 4 secconds
Measurement standard: tetramethylsilane
(Calculation method of the number of butyl branches)
When the sum of peak areas of all the peaks having a peak top in 5 to 50 ppm in 13C-NMR spectrum is defined as 1000, the sum of peak areas of the peaks having a peak top in 38.0 to 38.2 ppm is made to be the number of butyl branches per 1000 carbons (branches/ 1000 C).
[0340]
(5) Measurement of molecular weight
A weight average molecular weight and a number average molecular weight in terms of polystyrene were measured by gel permeation chromatography (GPC) under the following conditions (1) to (8). Subsequently, with reference to "Size-Exclusion
Chromatography, High Performance Liquid Chromatography of Polymer," Mori Sadao, Kyoritsu Shuppan Co., Ltd., December 1991, p.63-64," a weight average molecular weight (Mw) and a number average molecular weight (Mn) in terms of polyethylene were calculated. Specifically, they were calculated from the following formulas.
Weight average molecular weight (Mw) in terms of polyethylene = Weight average molecular weight in terms of polystyrene x (l l / 41.3)
Number average molecular weight (Mn) in terms of polyethylene = Number average molecular weight in terms of polystyrene x ( 11 / 41.3)
(1) Device: Watersl50C manufactured by Waters
(2) Separation column: TOSOH TSKgelGMH6-HT, two columns
(3) Measurement temperature: 140°C
(4) Carrier: orthodichloro benzene
(5) Flow rate: 1.0 mL/min
(6) Amount filled: 500 xL
(7) Detector: differential refractometry
(8) Molecular weight standard substance: standard polystyrene
[0341]
Reference Example 1
"Synthesis of [l-tris(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride (hereinafter, referred to as a "complex 1 ")"
[0342]
"Synthesis of l-tris(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene" Sodium hydride dispersed in mineral oil (0.49 g, 20.45 mmol as sodium hydride) and tetrahydrofuran (23 mL) were charged into a reactor under nitrogen atmosphere. After the temperature of this mixture was raised to 50°C, aniline (0.13 g, 1.36 mmol) was added thereto, and the mixture was stirred at 50°C for one hour. A solution of 1,2,3,4-tetramethylcyclopenta- 1,3-diene (1.83 g, 15.00 mmol) dissolved in tetrahydrofuran (6 mL) was added dropwise thereto, and the mixture solution was stirred at 50°C for 3.5 hours. This solution was cooled to 0°C, a solution of chlorotris(3,5-dimethylphenyl)silane (5.17 g, 13.64 mmol) dissolved in toluene (6 mL) was added dropwise to the solution, and the mixture solution was stirred at room
temperature for three hours, followed by stirring at 50°C for 22 hours. The obtained mixture was added dropwise to 10% sodium carbonate aqueous solution (40 mL) at 0°C. Toluene (50 mL) was added thereto and the solution was divided into an organic phase and an aqueous phase, and the organic phase was washed with water (50 mL) twice and further washed with saturated brine solution (50 mL). The organic phase was dried over sodium sulfate, then filtered and the solvent was vaporized under reduced pressure to form a concentrated solid. After purification by silica gel column chromatography, hexane of 50°C was added to the obtained solid and the mixture was filtered to remove insolubles, and the solvent was removed from a filtrate under reduced pressure, thereby forming a concentrated solid. The obtained solid was washed with a small amount of hexane, and then dried under reduced pressure to obtain l-tris(3,5- dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene (1.49 g, yield 23.4%).
1H-NMR (CDC , δ ppm): 1.54 (s, 6H), 1.60 (s, 6H), 2.27 (s, 18H), 3.73 (s, 1H), 6.98 (s, 3H), 7.17 (s, 6H)
Mass spectrum (EI-MS, m/z): 464 (IVf)
[0343]
"Synthesis of complex 1 "
Under nitrogen atmosphere, to a toluene solution (20 mL) of l-tris(3,5- dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene (0.93 g, 2.00 mmol) and triethylamine (1.01 g, 10.00 mmol), 1.67 M hexane solution (1.32 mL, 2.20 mmol) of n-butyllithium was added dropwise at -78°C, the mixture solution was gradually warmed to room temperature, and the mixture solution was stirred at room temperature for 5 hours. The obtained mixture was cooled to -78°C, and a solution of titanium tetrachloride (0.42 g, 2.20 mol) dissolved in toluene (2 mL) at the same temperature was added dropwise thereto. The obtained mixture was gradually warmed to room temperature, and then the mixture was stirred at room temperature over night. After the reaction, the solvent was vaporized under reduced pressure, heptane was added to the residue and the obtained product was filtered to remove insolubles, and the solvent was removed from the filtrate for concentration under reduced pressure. Furthermore, diethyl ether was added to the residue and the obtained mixture was filtered to remove insolubles, and the solvent was vaporized from the filtrate for concentration under reduced pressure. To the mixture, pentane was added and the mixture was cooled to -20°C, and the obtained solid was filtered and washed with a small amount of pentane, followed by being dried under reduced pressure to obtain a complex 1 (0.03 g, yield: 2.7%) as an orange-colored solid.
1H- MR (CDCls, δ ppm): 2.03 (s, 6H), 2.27 (s, 18H), 2.36 (s, 6H), 7.06 (s, 3H), 7.20 (s, 6H) 13C- MR (CDCI3, δ ppm): 14.52, 17.83, 21.41, 131.63, 132.93, 134.60, 137.03, 142.26, 146.34 Mass spectrum (EI-MS, m/z): 616 (M+)
[0344]
Reference Example 2
Under nitrogen atmosphere, 1 g of dry silica (Sylopol948 manufactured by Grace Davison; 50% volume average particle diameter = 55 μηι; pore volume = 1.67 m /g; specific surface area = 325 m2/g) was weighed in a 200 mL-flask, and 15 mL of anhydrous toluene was added thereto. The mixture was cooled to 0°C by ice bath, and 5.0 mL (amount of organic aluminum oxy compound: 17.5 mmol) of a toluene solution of organic aluminum oxy compound having an Al concentration of 3.5 mol/L (TMAO manufactured by Tosoh Corporation) was then added to the cooled mixture by using a dropping funnel slowly over 30 min while it was stirred. Thereafter, the mixture was heated to 95°C and stirred for 4 hours. After the reaction was finished, the obtained product was cooled to room temperature, and the supernatant was removed by decantation. Furthermore, 15 mL of toluene was added thereto and the mixture was stirred, then stood still and the supernatant was removed by decantation again. This washing operation was carried out three times, and finally the product was dried under reduced pressure at 100°C for one hour to obtain a solid (hereinafter referred to as "Si02 / MAO"). Yield: 1.2 g. Element analysis (% by weight) Si: 24%, Al: 19%.
[0345]
Example 1
Under nitrogen atmosphere, 5 mL of anhydrous toluene was charged into a 100 mL-flask at room temperature. Into the flask, 182 mg of Si02 / MAO, 2.9 mL of a toluene solution of the complex 1 with a concentration of 1 mmol/L, and 0.4 μιηοΐ of racemic ethylene- bis(l-indenyl)zirconium diphenoxide were added, and the solution in the flask was stirred for 5 minutes. After stirring was stopped, the solvent was removed from the solution by evaporation under reduced pressure, and the product was dried under reduced pressure for one hour to obtain a solid (hereinafter, referred to as "solid component A").
[0346]
The inside of a 0.4 L autoclave was dried, 90 mL of toluene was charged into the autoclave, 2 mmol of triisobutylaluminum was added thereto, and ethylene was supplied to the autoclave so that the ethylene pressure might become 2 MPa, and the temperature in the autoclave was adjusted to 40°C. Into the autoclave, 99 mg of solid component A was added, and ethylene was polymerized at 40°C for 30 minutes while the ethylene pressure was made to be constant. Into the autoclave, 2 mL of ethanol was added to stop the reaction. The autoclave was cooled, and a polymerization product was taken out. The obtained
polymerization product was decalcified with hydrochloric acid - ethanol, the polymerization product was taken out by filtration operation, and the polymerization product was dried under reduced pressure to obtain 7.8 g of a polymer. The number of butyl branches of the polymer was 15.5 (branches/1000 C). Furthermore, Mw of the polymer was 104,000, and Mn thereof was 38,000.
[0347]
Example 2
Example 2 was carried out in the same manner as in Example 1 except that the temperature in the autoclave was adjusted to 70°C, and reaction was carried out at 70°C. As a result, 11.2 g of a polymer was obtained. The number of butyl branches of the polymer was 5.6 (branches/ 1000 C) Furthermore, Mw of the polymer was 103,000 and Mn thereof was 43,000.
[0348]
Example 3
Into a 5 L autoclave, 50 g of dried NaCl was placed, and the inside of the autoclave was substituted with argon. The inside temperature of the autoclave was adjusted to 40°C, and ethylene was supplied to the autoclave so that the ethylene pressure might become 2 MPa. Subsequently, 1 mmol of triisobutylaluminum was added into the autoclave, and 105.2 mg of solid component A prepared in Example 1 was added thereto, and ethylene was polymerized by gas phase polymerization at 40°C for 30 minutes. After the reaction, 2mL of ethanol was added into the autoclave to stop the reaction. The autoclave was cooled, and 200 mL of toluene was supplied thereto and the mixture was stirred. Toluene slurry in the autoclave was recovered and filtered, and then the obtained solid was added to 1 L of water. NaCl was dissolved in the mixture while the mixture was stirred for 30 minutes. Residual solid component was recovered by suction filtration, and further washed with ethanol and dried to obtain 5.6 g of a polymer. The number of butyl branches of the polymer was 18.3
(branches/ 1000 C). Furthermore, Mw of the polymer was 75,000, and Mn thereof was 32,000.
[0349]
Example 4
Under nitrogen atmosphere, 5 mL of anhydrous toluene was charged into a 100 mL-flask at room temperature. Into the flask, 1 6 mg of Si02 / MAO, 2.0 mL of a toluene solution of the complex 1 having a concentration of 1 mmol/L, and 0.39 μπιοΐ of racemic ethylene-bis(l-indenyl)zirconium diphenoxide were added, and the solution in the flask was stirred for 5 minutes. After the stirring was stopped, the solvent was removed from the solution by evaporation under reduced pressure, and the product was dried under reduced pressure for one hour to obtain a solid (hereinafter, referred to as "solid component I").
[0350]
Into a 5 L autoclave, 50 g of dried NaCl was placed, and the inside of the autoclave was substituted with argon. The inside temperature of the autoclave was adjusted to 60°C, and ethylene was supplied to the autoclave so that the ethylene pressure might become 2 MPa. Subsequently, 1 mmol of triisobutylaluminum was added into the autoclave, and 115 mg of solid component I was added thereto, and ethylene was polymerized by gas phase
polymerization at 60°C for 30 minutes. After the reaction, 2 mL of ethanol was added into the autoclave to stop the reaction. The autoclave was cooled, and 200 mL of toluene was supplied thereto and the mixture was stirred. Toluene slurry in the autoclave was recovered and filtered, and then the obtained solid was added to 1 L of water. NaCl was dissolved in the mixture while the mixture was stirred for 30 minutes. Residual solid component was recovered by suction filtration, and further washed with ethanol and dried to obtain 10.5 g of a polymer. The number of butyl branches of the polymer was 5.7 (branches/ 1000 C). Furthermore, Mw of the polymer was 77,000, and Mn thereof was 29,000.
[0351]
Example 5
Under nitrogen atmosphere, 5 mL of toluene was charged into a flask, and 2.5 μπιοΐ of the complex l and 274 mg of Si02 / MAO were added thereto, and the mixture was stirred for 5 minutes. The solvent was removed from the solution by evaporation under reduced pressure to obtain a solid (hereinafter, referred to as "solid component B").
Under nitrogen atmosphere, 5 mL of toluene was charged into a flask, and 0.53 μπιοΐ of racemic ethylene-bis(l-indenyl)zirconium diphenoxide and 264 mg of Si02 / MAO were added thereto, and the mixture was stirred for 5 minutes. The solvent was removed from the solution by evaporation under reduced pressure to obtain a solid (hereinafter, referred to as
"solid component C").
[0352]
The inside of a 0.4 L autoclave was dried, 90 mL of toluene was charged into the autoclave, 2 mmol of triisobutylaluminum was added thereto, and ethylene was supplied to the autoclave so that the ethylene pressure might become 2 MPa, and the temperature in the autoclave was adjusted to 40°C. Into the autoclave, 103 mg of solid component B was added, and then 114 mg of solid component C was added, and ethylene was polymerized at 40°C for 60 minutes while the ethylene pressure was kept at 2 MPa. Into the autoclave, 2 mL of ethanol was added to stop the reaction. The autoclave was cooled, and a polymerization product was taken out. The obtained polymerization product was decalcified with hydrochloric acid - ethanol, the polymerization product was taken out by a filtration operation, and the
polymerization product was dried under reduced pressure to obtain 3.5 g of a polymer. The number of butyl branches of the polymer was 16.7 (branches/ 1000 C). Furthermore, Mw of the polymer was 115,000, and Mn thereof was 39,000.
[0353]
Example 6
Example 6 was carried out in the same manner as in Example 5 except that the polymerization solvent was changed from toluene to heptane. As a result, 2.1 g of a polymer was obtained. The number of butyl branches of the polymer was 13.6 (branches/ 1000 C). Furthermore, Mw of the polymer was 113,000, and Mn thereof was 37,000.
[0354]
Example 7
Into a 5 L autoclave, 50 g of dried NaCl was placed, and the inside of the autoclave was substituted with argon. The inside temperature of the autoclave was adjusted to 40°C, and ethylene was supplied to the autoclave so that the ethylene pressure might become 2 MPa. Subsequently, 1 mmol of triisobutylaluminum was added into the autoclave, and 119 mg of solid component B prepared in Example 5 was added thereto, then 23 mg of solid component C was added thereto, and ethylene was polymerized in gas phase at 40°C for 30 minutes. After the reaction, 2 mL of ethanol was added into the autoclave to stop the reaction. The autoclave was cooled, 200 mL of toluene was supplied thereto and the mixture was stirred. Toluene slurry in the autoclave was recovered and filtered, and then the obtained solid was added to 1 L of water. NaCl was dissolved in the mixture while the mixture was stirred for 30 minutes. Residual solid component was recovered by suction filtration, and further washed with ethanol and dried to obtain 2.65 g of a polymer. The number of butyl branches of the polymer was 28.7 (branches/1000 C). Furthermore, Mw of the polymer was 58,000, and Mn thereof was 31,000.
[0355]
Example 8
Under nitrogen atmosphere, 5 mL of toluene was charged into a flask, and 1.92 μπιοΐ of the complex 1 and 192 mg of Si02 / MAO were added thereto, and the mixture was stirred for 5 minutes. The solvent was removed from the mixture by evaporation under reduced pressure to obtain a solid (hereinafter, referred to as "solid component II").
Under nitrogen atmosphere, 5 mL of toluene was charged into a flask, and 0.4 μηιοΐ of racemic ethylene-bis(l-indenyl)zirconium diphenoxide and 264 mg of Si02 / MAO were added thereto, and the mixture was stirred for 5 minutes. The solvent was removed from the mixture by evaporation under reduced pressure to obtain a solid (hereinafter, referred to as "solid component III").
[0356]
Into a 5 L autoclave, 50 g of dried NaCl was placed, and the inside of the autoclave was substituted with argon. The inside temperature of the autoclave was adjusted to 40°C, and ethylene was supplied to the autoclave so that the ethylene pressure might become 2 MPa. Subsequently, 1 mmol of triisobutylaluminum was added into the autoclave, 107 mg of solid component II was added thereto, then 108 mg of solid component ΠΙ was added thereto, and ethylene was polymerized by gas phase polymerization at 60°C for 30 minutes. After the reaction, 2 mL of ethanol was added into the autoclave to stop the reaction. The autoclave was cooled, and 200 mL of toluene was supplied thereto and the mixture was stirred; Toluene slurry in the autoclave was recovered and filtered, and then the obtained solid was added to 1 L of water. NaCl was dissolved in the mixture while the mixture was stirred for 30 minutes.
Residual solid component was recovered by suction filtration, and further washed with ethanol and dried to obtain 10.7 g of a polymer. The number of butyl branches of the polymer was 4.7 (branches/ 1000 C). Furthermore, Mw of the polymer was 103,000, and Mn thereof was 37,000.
[0357]
Example 9
Into a reactor equipped with a stirrer in which nitrogen purge had been carried out, butane and racemic ethylene-bis(l-indenyl)zirconium diphenoxide were added, and the temperature in the reactor was made to be 50°C and the mixture was stirred for two hours.
Subsequently, the temperature in the reactor was lowered to 30°C, and ethylene, hydrogen, a particulate solid catalyst component prepared in the same manner as in the method described in Examples 1 ( 1 ) and (2) of JP- A-2009-79182 [the amount of racemic ethylene-bis( 1 - indenyl)zirconium diphenoxide to be added per 1 g of the particulate solid catalyst component was 126 μηιοΐ] and triisobutylaluminum were added thereto, and polymerization was started.
After the polymerization was started, the polymerization temperature in the reactor was adjusted to 30°C, and the polymerization reaction was carried out for 0.5 hours. Subsequently, the mixture was raised to 50°C over 30 minutes, and the polymerization reaction was then carried out at 50°C for 6.5 hours. Furthermore, during the polymerization, ethylene and hydrogen were supplied to the reactor.
As a result of the polymerization, a prepolymerized catalyst component in which the amount of prepolymerized ethylene was 35.9 g per 1 g of the particulate solid catalyst component was obtained. Hereinafter, the prepolymerized catalyst component is referred to as
"solid component D".
[0358]
The inside of a 0.4 L autoclave was dried, 90 mL of toluene was charged into the autoclave, 2 mmol of triisobutylaluminum was added thereto, ethylene was supplied to the autoclave so that the ethylene pressure might become 2 MPa, and the temperature in the autoclave was adjusted to 40°C. Into the autoclave, 115 mg of solid component B prepared in Example 5 was added, and then 74 mg of solid component D was added, and polymerization was carried out at 40°C for 30 minutes while the ethylene pressure was kept at 2 MPa. Into the autoclave, 2 mL of ethanol was added to stop the reaction. The autoclave was cooled, and a polymerization product was taken out. The obtained polymerization product was decalcified with hydrochloric acid - ethanol, the polymerization product was taken out by filtration operation, and the polymerization product was dried under reduced pressure to obtain 24.6 g of a polymer. The number of butyl branches of the polymer was 9.2 (branches/ 1000 C).
Furthermore, Mw of the polymer was 91 ,000, and Mn thereof was 51 ,000.
[0359]
Example 10
Under nitrogen atmosphere, 5 mL of anhydrous toluene was charged into a 100 mL-flask at room temperature. Into the flask, 198 mg of Si02 / MAO, 1.98 mL of a toluene solution of [l-tris(3,5-diethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride having a concentration of 1 mmol L, and 0.40 μιηοΐ of racemic ethylene-bis(l- indenyl)zirconium diphenoxide were added and the mixture inside the flask was stirred for 5 minutes. After the stirring was stopped, the solvent was removed from the mixture by evaporation under reduced pressure, and dried under reduced pressure for one hour to obtain a solid (hereinafter, referred to as "solid component IV").
[0360]
Into a 5 L autoclave, 50 g of dried NaCl was placed, and the inside of the autoclave was substituted with argon. The inside temperature of the autoclave was adjusted to 40°C, and ethylene was supplied to the autoclave so that the ethylene pressure might become 2 MPa. Subsequently, 1 mmol of triisobutylaluminum was added into the autoclave, and 128 mg of solid component IV was added thereto, and ethylene was polymerized by gas phase polymerization at 40°C for 30 minutes. After the reaction, 2 mL of ethanol was added into the autoclave to stop the reaction. The autoclave was cooled, and 200 mL of toluene was supplied thereto and the mixture was stirred. Toluene slurry in the autoclave was recovered and filtered, and the obtained solid was then added to 1 L of water. NaCl was dissolved in the mixture while the mixture was stirred for 30 minutes. Residual solid component was recovered by suction filtration, and further washed with ethanol and dried to obtain 4.9 g of a polymer. The number of butyl branches of the polymer was 25.0 (branches/ 1000 C). Furthermore, Mw of the polymer was 47,000, and Mn thereof was 22,000.
[0361]
Example 11
Under nitrogen atmosphere, 5 mL of anhydrous toluene was charged into a 1 OOmL-flask at room temperature. Into the flask, 216 mg of Si02 / MAO, 4.3 mL of a toluene solution of 6-adamanthyl-4-methyl-2-[N-{2-(2-methoxyphenyl)} phenyl] imino-phenoxy titanium trichloride having a concentration of 1 mmol/L, and 0.86 μιηοΐ of racemic ethylene- bis(l-indenyl)zirconium diphenoxide were added, and the mixture inside the flask was stirred for 5 minutes. After the stirring was stopped, the solvent was removed from the mixture by evaporation under reduced pressure, and then the product was dried under reduced pressure for one hour to obtain a solid (hereinafter, referred to as "solid component V").
[0362]
Into a 5 L autoclave, 50 g of dried NaCl was placed, and the inside of the autoclave was substituted with argon. The inside temperature of the autoclave was adjusted to 40°C, and ethylene was supplied to the autoclave so that the ethylene pressure might become 2 MPa. Subsequently, 1 mmol of triisobutylaluminum was added into the autoclave, and 125 mg of solid component V was added thereto, and ethylene was polymerized by gas phase
polymerization at 40°C for 30 minutes. After the reaction, 2 mL of ethanol was added into the autoclave to stop the reaction,. The autoclave was cooled, and 200 mL of toluene was supplied thereto and the mixture was stirred. Toluene slurry in the autoclave was recovered and filtered, and then the obtained solid was added to 1 L of water. NaCl was dissolved in the mixture while the mixture was stirred for 30 minutes. Residual solid component was recovered by suction filtration, and further washed with ethanol and dried to obtain 4.7 g of a polymer. The number of butyl branches of the polymer was 2.3 (branches/ 1000 C) .
[0363]
Example 12
Under nitrogen atmosphere, 5 mL of anhydrous toluene was charged into a 100 niL-flask at room temperature. Into the flask, 244 mg of Si02 / MAO, 0.48 mL of a toluene solution of complex 1 having a concentration of 1 mmol/L, and 0.40 μπιοΐ of
dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride were added, and the mixture in the flask was stirred for 5 minutes. After stirring was stopped, the solvent was removed from the mixture by evaporation under reduced pressure, and then dried under reduced pressure for one hour to obtain a solid (hereinafter, referred to as "solid component VI").
[0364]
Into a 5 L autoclave, 50 g of dried NaCl was placed, and the inside of the autoclave was substituted with argon. The inside temperature of the autoclave was adjusted to 70°C, and ethylene was supplied to the autoclave so that the ethylene pressure might become 2 MPa. Subsequently, 1 mmol of triisobutylaluminum was added into the autoclave, and 112 mg of solid component VT was added thereto, and ethylene was polymerized by gas phase polymerization at 70°C for 30 minutes. After the reaction, ethanol was added into the autoclave to stop the reaction. The autoclave was cooled, and 200 mL of toluene was supplied thereto and the mixture was stirred. Toluene slurry in the autoclave was recovered and filtered, and then the obtained solid was added to 1 L of water. NaCl was dissolved in the mixture while the mixture was stirred for 30 minutes. Residual solid component was recovered by suction filtration, and further washed with ethanol and dried to obtain 1.9 g of a polymer. The number of butyl branches of the polymer was 11.4 (branches/ 1000 C).

Claims

[Claim 1]
A catalyst for producing an ethylenic polymer, the catalyst being made from a complex (I) represented by the following formula (1), (2-1) or (2-2), a complex for olefin polymerization, an activating co-catalyst component, and a carrier, wherein the complex (I) and the complex for olefin polymerization are supported by the carrier:
Figure imgf000128_0001
wherein M1 represents a transition metal atom of Group 4 of the periodic table of the elements; Cp represents a group having a cyclopentadiene-type anionic skeleton;
J1 represents an atom selected from Groups 13 to 16 of the periodic table of the elements;
1 and m each represent 1 or 0, and 1 + m is an integer equal to (the valence of J1 - 2); and
R , R , R , R , R , R , R , X , X and X each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, or a disubstituted amino group, of R1, R2, R3, R4 and R5, two groups bonded to two adjoining carbon atoms may be bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded, R and R may be bonded to each other to form a ring together with J1 to which they are bonded, and two groups of X1, X2 and X3 may be bonded to each other to form a ring together with M1;
Figure imgf000128_0002
wherein M represents a transition metal atom of Group 4 of the periodic table of the elements;
A21 represents an oxygen atom, a nitrogen atom, a phosphorus atom or a sulfur atom;
Z1 is a group linking A21 to N, in which the number of the shortest bonds linking A21 to N is 4 to
6;
a bond linking A21 to Z1 may be a double bond;
R21, R22, R23, R24, R25 and X4 each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, or a disubstituted amino group, two or more groups of R21, R22, R23, R24 and R25 may be bonded to each other, the three X4 groups may be the same as each other or different from each other, and two or more X4 groups may be bonded to each other to form a ring together with M2; and
R26 represents a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbylidene group, or a substituted hydrocarbylidene group, a bond linking R26 to A21 may be a double bond, and R26 may be bonded to Z1;
Figure imgf000129_0001
2
wherein M represents a transition metal atom of Group 4 of the periodic table of the elements;
22
A represents a nitrogen atom or a phosphorus atom;
Z2 is a group linking A22 to N, and the number of the shortest bonds linking A22 to N is 4 to 6; R21, R22, R23, R24, R25 and X4 each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, or a disubstituted amino group, two or more groups of R21, R22, R23, R24 and R25 may be bonded to each other, the three X4 groups may be the same as each other or different from each other, and two or more X4 groups may be bonded to each other to form a ring together with M2; and
R27 and R28 represent a hydrogen atom, a halogen atom, a hydrocarbyl group, or a substituted hydrocarbyl group, and R28 may be bonded to Z2.
[Claim 2]
The catalyst according to claim 1, comprising component (X),
wherein component (X) is particles obtained by bringing the complex (I), the complex for olefin polymerization, the activating co-catalyst component, and the carrier into contact with each other.
[Claim 3]
The catalyst according to claim 1, comprising component (A) and component (B), wherein component (A) is particles obtained by bringing the complex (I), the activating co-catalyst component and the carrier into contact with each other; and
component (B) is particles obtained by bringing the complex for olefin polymerization, the activating co-catalyst component and the carrier into contact with each other.
[Claim 4]
The catalyst according to claim 1, comprising component (X), and both or one of component (A) and component (B),
wherein component (X) is particles obtained by bringing the complex (I), the complex for olefin polymerization, the activating co-catalyst component, and the carrier into contact with each other;
component (A) is particles obtained by bringing the complex (I), the activating co-catalyst component and the carrier into contact with each other; and
component (B) is particles obtained by bringing the complex for olefin
polymerization, the activating co-catalyst component and the carrier into contact with each other.
[Claim 5]
The catalyst according to any one of claims 1 to 4, wherein the compound represented by formula (1) is a compound represented by formula (1-2):
Figure imgf000130_0001
wherein M1 represents a transition metal atom of Group 4 of the periodic table of the elements; R1, R2, R3, R4, R5, R6, R7, R8, R9, R10 and R11 represent a hydrogen atom, a halogen atom, or a hydrocarbyl group having 1 to 20 carbon atoms;
at least one of R8, R9, R10 and Ru is a halogen atom, or a hydrocarbyl group having 1 to 20 carbon atoms; and
X1, X2 and X3 each represent a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, or a substituted hydrocarbyloxy group.
[Claim 6]
The catalyst according to any one of claims 1 to 6, wherein the complex for olefin olymerization is a compound represented by formula (11) or (12):
Figure imgf000130_0002
wherein M3 represents a transition metal atom of Group 4 of the periodic table of the elements; Cp1 represents a group having a cyclopentadiene-type anionic skeleton; J2 represents a group linking Cp1 to A2 by one or two atoms of Group 14 of the periodic table of the elements;
A2 represents a group linking J2 to M3, the linking group being a group bonded to M3 at its atom of Group 15 of the periodic table of the elements or atom of Group 16 of the periodic table of the elements, or a group having a cyclopentadiene-type anionic skeleton; and
X5 and X6 each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, or a disubstituted amino group;
Figure imgf000131_0001
wherein M4 represents a transition metal atom of Group 4 of the periodic table of the elements;
Cp2 and Cp3 represent a group having a cyclopentadiene-type anionic skeleton; and
X7 and X8 each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted silyl group, or a disubstituted amino group.
[Claim 7]
A method for producing the catalyst according to claim 2, comprising the step of: bringing the complex (I), the complex for olefin polymerization, the activating co- catalyst component and the carrier into contact with each other in a solvent, and then removing the solvent to obtain component (X).
[Claim 8]
A method for producing the catalyst according to claim 3, comprising the steps of: bringing the complex (I), the activating co-catalyst component and the carrier into contact with each other in a solvent, and then removing the solvent to obtain component (A); and bringing the complex for olefin polymerization, the activating co-catalyst component and the carrier into contact with each other in a solvent, and then removing the solvent to obtain component (B).
[Claim 9]
A method for producing the catalyst according to claim 4, comprising the steps of: bringing the complex (I), the complex for olefin polymerization, the activating co- catalyst component and the carrier into contact with each other in a solvent, and then removing the solvent to obtain component (X); and
bringing the complex (I), the activating co-catalyst component and the carrier into contact with each other in a solvent, and then removing the solvent to obtain component (A); and/or
bringing the complex for olefin polymerization, the activating co-catalyst component and the carrier into contact with each other in a solvent, and then removing the solvent to obtain component (B).
[Claim 10]
A method for producing an ethylenic polymer, comprising polymerizing olefin including ethylene by the catalyst according to any of claims 1 to 6.
[Claim 11]
The method for producing an ethylenic polymer according claim 10, wherein the olefin including ethylene is polymerized by gas phase polymerization method.
PCT/JP2012/059295 2011-03-30 2012-03-29 Catalyst for producing ethylene-based polymer and method for producing the same Ceased WO2012133936A1 (en)

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