WO2012133919A1 - Process for producing catalyst for producing ethylenic polymer, catalyst for producing ethylenic polymer and process for producing ethylenic polymer - Google Patents

Process for producing catalyst for producing ethylenic polymer, catalyst for producing ethylenic polymer and process for producing ethylenic polymer Download PDF

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WO2012133919A1
WO2012133919A1 PCT/JP2012/059277 JP2012059277W WO2012133919A1 WO 2012133919 A1 WO2012133919 A1 WO 2012133919A1 JP 2012059277 W JP2012059277 W JP 2012059277W WO 2012133919 A1 WO2012133919 A1 WO 2012133919A1
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group
titanium trichloride
silyl
titanium
tert
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PCT/JP2012/059277
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French (fr)
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Takayuki Hishiya
Yoshinobu Nozue
Taichi Senda
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Sumitomo Chemical Company, Limited
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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
    • 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
    • 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
    • C08F4/6592—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 process for producing a catalyst for producing an ethylenic polymer, a catalyst for producing an ethylenic polymer and a process for producing an ethylenic polymer.
  • 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 ot-olefin 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 process 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 trimerization of ethylene into contact with modified methylaluminoxane (hereinafter, referred to as a "MMAO”) as an activating co-catalyst component in a reaction container has been reported.
  • a catalyst obtained by simultaneously bringing dimethylsilylene
  • the Non Patent Literature 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 also reports a process 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 trimerization of ethylene into contact with MMAO in a reactor.
  • zirconium complex 1 rac-dimethylsilylene bis(2-methylbenz[e]indenyl)zirconium dichloride
  • 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. DISCLOSURE OF THE INVENTION
  • the problem to be solved by the present invention is to provide a process for producing a catalyst capable of efficiently producing an ethylenic polymer having short chain branches even though only ethylene is used as a raw material monomer, a catalyst obtained by the production process and a process for producing an ethylenic polymer by the catalyst.
  • a first aspect of the present invention relates to a process for producing a catalyst for producing an ethylenic polymer, the process including the following steps 1 and 2.
  • step 1 the step of bringing a complex represented by formula (1), (2-1) or (2-2) and an activating co-catalyst component into contact with each other in the absence of ethylene to prepare a catalyst component (I).
  • step 2 the step of mixing the catalyst component (I) obtained in step 1 with a catalyst component (II) for olefin polymerization.
  • 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 ;
  • 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 6;
  • 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 as each other 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
  • 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 , R and R may be bonded to each other, the three X groups each may be the same as each other 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, and a substituted hydrocarbyl group, and R 28 may be bonded to Z 2 .
  • a second aspect of the present invention relates to a catalyst for producing an ethylenic polymer obtained by the production process mentioned above.
  • a third aspect of the present invention relates to a process 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 process for producing a catalyst capable of efficiently producing an ethylenic polymer having short chain branches even though only ethylene is used as a raw material monomer, a catalyst obtained by the production process and a process 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.
  • a process for producing a catalyst for producing an ethylenic polymer according to the present invention is a process including the following steps 1 and 2.
  • step 1 the step of bringing a complex and an activating co-catalyst component into contact with each other in the absence of ethylene to prepare a catalyst component (I).
  • step 2 the step of mixing the catalyst component (I) obtained in step 1 with a catalyst component ( ⁇ ) for olefin polymerization.
  • the catalyst for producing an ethylenic polymer obtained by the above-mentioned process has the catalyst component (I) and the catalyst component ( ⁇ ) for olefin polymerization.
  • the complex to be used in step 1 can oligomerize ethylene by the complex and the activating co-catalyst component to synthesize a-olefin.
  • Oligomerization of ethylene means changing of ethylene into 2 to 20-mer compound.
  • the number of carbon atoms of the a- olefin is 4 to 40.
  • the suitable complex is a complex capable of synthesizing at least one a- 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 is a compound represented by any of formula (1), the formula (2-1) a (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 .
  • M 1 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.
  • 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.
  • 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.
  • 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 amy I 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 trimethylphenyl 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.
  • 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 the carbon atoms of the substituted hydrocarbyl group is preferably 1 to 20, and more preferably 1 to 10.
  • halogenated alkyl group examples include a fluoromethyl group, a difiuoromethyl 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 the 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 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
  • 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-methylphenoxy 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.
  • halogenated hydrocarbyl groups 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, 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 12 ) 3 , wherein the three R 12 groups each 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 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 R 12 groups 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 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 bound to a silicon atom in the above-mentioned groups are substituted with a halogen atom or a halogenated hydrocarbyl group; a disubstituted silyl group having two 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 bound to a silicon atom in the above- mentioned groups are substituted with a halogen atom and/or halogenated hydrocarbyl groups; and a trisubstituted silyl group having three hydrocar
  • 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 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.
  • 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 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
  • 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 1 , R 2 , R 3 , R 4 , and R 5 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.
  • R 1 , R 2 , R 3 , R 4 and R 5 examples include the below-mentioned substructures in 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).
  • substructures 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,
  • preferable substructures are phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, or diethylphenyl.
  • R 6 and R 7 are preferably a hydrogen atom, and 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, and an aralkyl group having 7 to 20 carbon atoms.
  • 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).
  • substructures 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
  • 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).
  • substructures 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)methy lene, di(3 , 5 -diethylpheny l)methy lene, (3 , 5 -dimethylphenyl)(3 , 5-di- tert-butylphenyl)methylene, di(3,5-diphenylphenyl)methylene, and di(3,5- dibenzylphenyl)methylene.
  • 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-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.
  • X 1 , X 2 and X 3 are 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 represented by formula ( 1 -2) .
  • M 1 represents a transition metal atom of Group 4 of the periodic table of the elements
  • 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 11 , two groups bonded to the two adjoining carbon atoms may be bonded to
  • 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 l , 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 n 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, or 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, or 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, or an aralkyl group having 7 to 20 carbon atoms.
  • 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 phenyl group, a 4- methylphenyl group, a 3 -methylphenyl 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 (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 u 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 substituent other than hydrogen or a halogen atom.
  • R 8 , R 9 , R 10 and R n in formula (1-2) include the below-mentioned substructures in the substructural formula (6) in formula (1):
  • R 8 , R 9 , R 10 and R 11 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 hydrogen or a halogen atom. Examples thereof include the following substructures:
  • methylcyclopentadienyl ethylcyclopentadienyl, n-propylcyclopentadienyl, isopropylcyclopentadienyl, n-butylcyclopentadienyl, sec-butylcyclopentadienyl, tert- butylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl,
  • a preferable cyclopentadienyl substructure is tetramethylcyclopentadienyl.
  • Examples of the compound represented by formula (1) include a compound represented 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 the 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 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, 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, or 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, or 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, or an aralkyl group having 7 to 20 carbon atoms.
  • 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 phenyl group, a 4- methylphenyl group, a 3 -methylphenyl 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 carbon 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-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.
  • R 8 , R 9 , R 10 and R u 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 u is preferably a substituent other than hydrogen or a halogen atom.
  • R 8 , R 9 , R 10 and R u in formula (1-3) include the substructural formula 6) in formula (1):
  • R 8 , R 9 , R 10 and R 11 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 hydrogen or a halogen atom. Examples thereof include the following substructures.
  • methylcyclopentadienyl ethylcyclopentadienyl, n-propylcyclopentadienyl, isopropylcyclopentadienyl, n-butylcyclopentadienyl, sec-butylcyclopentadienyl, tert- butylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl,
  • preferable cyclopentadienyl substructure is tetramethylcyclopentadienyl.
  • Examples of the compound represented by formula (1) include the following compounds.
  • -methy lb is(3 , 5 -dimethylphenyl lyl-2-methyl indenyljtitanium trichloride
  • yl-2-tert-butylcyclopentadienyl]titanium trichloride l-tris(3 -dimethylpheny IS; yl-3-tert-butylcyclopentadienyl]titanium trichloride, l-tris(3 -dimethylpheny 'Si yl-2-phenylcyclopentadienyl]titanium trichloride, l-tris(3 -dimethylpheny Si yl-3 -phenylcyclopentadienyljtitanium trichloride, l-tris(3 ⁇ dimethylpheny isi yl-2-benzylcyclopentadienyl]titanium trichloride, l-tris(3 ⁇ dimethylpheny >s: yl-3 -benzylcyclopentadienyljtitanium trichloride, l-tri
  • examples of the compounds represented by formula (1) also include a compound in which a silicon atom is substituted with a carbon atom in the above-mentioned compound.
  • Preferable examples of the compounds represented by formula (1) include [1- dimethylphenylsilyl-3 -trimethylsilylcyclopentadienyl]titanium trichloride,
  • Examples of process for producing the compound represented by formula (1) include a process described in Organometallics 2002, 21, 5122-5135.
  • examples of a process for producing the compound represented by formula (1) include a process 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)
  • R 8 , R 9 , R 10 and R 11 have the same meanings as in R 8 , R 9 , R 10 and R 11 res ectivel in formula (1-2)
  • M , X , X and X have the same meanings as in M , X , X and X , respectively, in formula (1), and X u represents a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted sily group, or a disubstituted amino group, and n represents 0 or 1.
  • X u 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 as X'in formula (1).
  • 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 followin constitutional isomers.
  • the compound represented by formula (7) has isomers whose positions of the double bonds of each cyclopentadienyl ring are different from each other.
  • formula (7) shows 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, trimethylsilylmethyllithium, vinyllithium, phenyllithium, and allyllithium.
  • the amount of the base to be used is in the range from 0.5 mol to 10 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 amine compounds 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 reacted with the reaction product of the substituted cyclopentadiene compound (7) and the base. Note here that in a reaction solution obtained by allowing the substituted
  • a solid may be precipitated.
  • a solvent may be added, or the precipitated solid may be once separated by filtration, and the solvent is added to the separated solid so that the precipitated solid is dissolved or suspended, and then the transition metal compound (8) may be added.
  • 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 reaction in these steps.
  • a solvent to be used include aprotic compounds including aromatic hydrocarbon such as benzene and toluene; aliphatic hydrocarbon such as hexane and heptane; ether compounds such as diethyl ether, tetrahydrofuran and 1,4- dioxane; amide compounds such as hexamethylphosphoric amide and dimethylformamide; polar compounds such as acetonitrile, propionitrile, acetone, diethyl ketone, methyl isobutyl ketone, and cyclohexanone; halogenated hydrocarbon such as dichloromethane, dichloroethane, 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 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 a hydrogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, or a substituted hydrocarbyloxy group
  • X 1 , X 2 and X 3 are 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
  • X 1 , X 2 and X 3 are 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.
  • alkaline earth metal compound having a hydrogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group or a substituted hydrocarby
  • the above-mentioned substituted cyclopentadiene compound (7) can be produced by a step 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 a step of 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)").
  • a substituted cyclopentadiene compound represented by formula (9) hereinafter, referred to as a "substituted cyclopentadiene compound (9)
  • 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 u have the same meanings as in R 8 , R 9 , R 10 and R 11 , respectively, in formula (1-2), a compound represented by 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-dimethylcyclopentadiene, 1,3-dimethylcyclopentadiene, 1,2,3- trimethylcyclopentadiene, 1,2,4-trimethylcyclopentadiene, 1,2,3,4-tetramethylcyclopentadiene, ethylcyclopentadiene, 1,2-diethylcyclopentadiene, 1,3-diethylcyclopentadiene, 1,2,3- triethylcyclopentadiene, 1,2,4-triethylcyclopentadiene, 1,2,3,4-tetraethylcyclopentadiene, n- propylcyclopentadiene, isopropylcyclopentadiene, n-butylcyclopentadiene, sec- butylcyclopentadiene, tert-butylcyclopentadiene, n-pentylcycl
  • neopentylcyclopentadiene n-hexyl cyclopentadiene, 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, difluoroaniline, 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
  • the substituted cyclopentadiene compound (9), the base, and an 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.
  • 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.
  • 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
  • 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) which has been used for preparation of the reaction product of the substituted cyclopentadiene compound (9) and the base.
  • the base with the halogenated silicon compound (10) is usually carried out by mixing a base, an 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 a base, an 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) used in Step 1 further include compounds represented by formula (2-1) or formula (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 6; 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 as each other 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 represents a nitrogen atom or a phosphorus atom
  • Z is a group linking A to N, and the number of the shortest bonds linking A to N is 4 to 6;
  • 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 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 as each other 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 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 .
  • 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.
  • a trimethylsilyl group, a triethylsilyl group, a triphenylsilyl 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 bound to a nitrogen atom is 2 to 20, and more preferably 2 to 10.
  • R 21 , R 22 , R 23 , R 24 , and R 25 may be bonded to each other to form a ring together with the 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 the 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 preferably a phenyl group, an a-cumyl group, a tert-butyl group, or a 1- adamanthyl group, and more 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, or 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 hydrocarbyl idene 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 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, or 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, or 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 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 21 to Z 1 may be a double bond.
  • 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. The number of the shortest bonds is defined by a method described in WO2009-005003.
  • Z 1 and Z 2 include a group for forming a structure represented by the following substructure formula (2-3) by combining the following A 21 and N, or a group for forming a structure represented by the following 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 the carbon atom to which R is bonded and the carbon atom to which R is bonded
  • R and R 34 be bonded to each other to form a ring together with the carbon atom to which R 33 is bonded and the carbon atom to which R 34 is bonded
  • R 34 and R 26 bonded to A 21 may be bonded to each other to form a ring together with A 21
  • R 34 and R 28 bonded to A 22 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 as R 1 described in formula (1).
  • the number of 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.
  • a ring formed by bonding R 31 to R 32 , a ring formed by bonding R 33 to R 34 , a ring formed by bonding R 34 to R 26 , and a ring formed by bonding R 34 to R 28 may be an aliphatic ring, or an aromatic ring, or a heterocycle.
  • Examples of a process for producing the compound represented by formula (2-1) or formula (2-2) include the process described in WO2009/005003.
  • Examples of the compound represented by formula (2-1) or formula (2-2) include the following compounds.
  • Examples of preferable compounds represented by formula (2-1) or formula (2-2) include a compound represented by formula (2-a) or formula (2-b):
  • M 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
  • 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 as each other 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, and a bond linking R 26 to A 21 may be a double bond;
  • R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 and R 48 each represent a hydrogen atom and a hydrocarbyl group, 0178]
  • 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
  • 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 as each other 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 27 and R 28 represent a hydrogen atom, a halogen atom, a hydrocarbyl group, and a substituted hydrocarbyl group;
  • R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 and R 48 each represent a hydrogen atom and a hydrocarbyl group.
  • a 21 and A 22 in formula (2-a) and formula (2-b) are the same as the definition and the examples of A 21 and A 22 in formula (2-1) and formula (2- 2).
  • R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 and R 48 in formula (2-a) and formula (2-b) represent a hydrogen atom, and 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.
  • an activating co-catalyst component in step 1 for example, at least one compound selected from the compound group consisting of an organic aluminum oxy
  • Examples of the organic aluminum oxy compound include cyclic aluminoxane having a structure represented by formula: ,wherein, a represents an integer of 2 or more; and E 1 represents a hydrocarbyl group having 1 to 8 carbon atoms, and a plurality of E 1 may be the same as each other or different from each other, and linear aluminoxane having a structure represented by formula: E 2 ⁇ -Al(E 2 )-0- ⁇ bAlE 2 2 , wherein, b represents an integer of 1 or more; and E 2 represents a hydrocarbyl group having 1 to 8 carbon atoms, and a plurality of E 2 may be the same as each other or different from each other.
  • the organic aluminum oxy compound one or more of these compounds are used.
  • E 1 and E 2 include an alkyl group 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.
  • Cyclic aluminoxane in which E 1 is a methyl group or an isobutyl group and a is 2 to 40, and linear aluminoxane in which E 2 is a methyl group or an isobutyl group, and b is 1 to 40 are preferable.
  • aluminoxane is produced by a known process.
  • the process include a production process involving bringing a solution in which trialkyl aluminum (for example, trimethyl aluminum) is dissolved in an organic solvent (benzene, aliphatic hydrocarbyl, and the like) and water into contact with each other.
  • examples also include a production process involving bringing trialkyl aluminum (for example, trimethyl aluminum) into contact with a metallic salt (for example, copper sulfate hydrate) containing water of crystallization.
  • boron compound one or more boron compounds selected from the compound group consisting of the following compounds (B 1) to (B3) can be used:
  • B2 a borate compound represented by formula: T + (BQ 4 Q 5 Q 6 Q 7 ) "
  • B3 a borate compound represented by formula: (L-H) + (BQ 8 Q 9 Q 10 Q U ) "
  • B represents a trivalent boron atom
  • Q 1 , Q 2 , Q 3 , Q 4 , Q 5 , Q 6 , Q 7 , Q 8 , Q 9 , Q 10 and Q u each represents a halogen atom, a 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;
  • (L-H) + represents Broensted acid.
  • Q 1 , Q 2 , Q 3 , Q 4 , Q 5 , Q 6 , Q 7 , Q 8 , Q 9 , Q 10 and Q u 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 (BQ Q 5 Q 6 Q 7 ) “ and (BQ 8 Q 9 Q 10 Q n ) " include tetrakis(pentafluorophenyl)borate, tetrakis(2, 3,5,6- tetrafluorophenyl)borate, tetrakis(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, N,N-dialkylanilinium, dialkylammonium, and triarylphosphonium.
  • Examples of the boron compound (Bl) represented by formula: BQ Q 2 Q 3 include tris(pentafiuorophenyl)borane, tri s(2, 3 , 5 , 6-tetrafiuoropheny l)borane, tris(2, 3 , 4, 5 - tetrafluorophenyl)borane, tris(3,4,5-trifluorophenyl)borane, tris(2,3,4-trifluorophenyl)borane, and phenyl-bis(pentafiuorophenyl)borane.
  • borate compound (B2) represented by formula: T + (BQ 4 Q 5 Q 6 Q 7 ) " include ferrocenium tetrakis(pentafluorophenyl)borate, ⁇ , ⁇ -bis-trimethylsilylferrocenium tetrakis(pentafluorophenyl)borate, silver tetrakis(pentafiuorophenyl)borate, triphenyl
  • borate compound (B3) represented by formula: (L- H) + (BQ 8 Q 9 Q 10 Q u y include triethyl ammonium tetrakis(pentafluorophenyl)borate,
  • Examples of the organic aluminum compound include a compound represented by formula: E 3 C A1X'3 -C , wherein c represents a number satisfying 0 ⁇ c ⁇ 3; E 3 represents a hydrocarbyl group having 1 to 8 carbon atoms; X' represents a hydrogen atom or a halogen atom; when more than one E 3 groups exist, the E 3 groups may be the same as each other or different from each other; and when more than one X groups exist, the X groups may be the same as each other or different from each other.
  • the organic aluminum compound one or more of these compounds are used.
  • 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
  • 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
  • diisobutylaluminum hydride dihexylaluminum hydride.
  • Trialkylaluminum is preferable, triethylaluminum and triisobutylaluminum are more preferable.
  • Examples of a method for bringing a complex and an activating co-catalyst component into contact with each other in step 1 include a method mixing the complex with the acticating co-catalyst component, in the absence of ethylene, in a solvent.
  • the solvent include saturated aliphatic hydrocarbon such as butane, pentane, hexane, heptane, and octane; and aromatic hydrocarbon such as toluene and xylene.
  • the boiling point of the solvent is preferably 100°C or lower, more preferably 80°C or lower, and further preferably 65°C or lower.
  • the total amount to be used of the organic aluminum oxy compound and the organic aluminum compound is usually 0.1 mol to 10000 mol, and preferably 1 mol to 2000 mol on the basis of aluminum atom of the total amount of the organic aluminum oxy compound and the organic aluminum compound with respect to 1 mol of a transition metal atom of a complex for ethylene oligomerization.
  • the amount of the boron compound to be used is usually 0.1 mol to 100 mol and preferably 0.5 mol to 10 mol with respect to 1 mol of a transition metal atom of a complex for ethylene oligomerization.

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Abstract

An object of the present invention is to provide a process for producing a catalyst capable of efficiently producing an ethylenic polymer having short chain branches even when only ethylene is used as a raw material monomer, a catalyst obtained by the production process, and a process for producing an ethylenic polymer by the catalyst. The present invention provides a process for producing a catalyst for producing an ethylenic polymer, the process including the following steps 1 and 2: step 1: the step of bringing a complex represented by formula (1), (2-1) or (2-2) and an activating co-catalyst component into contact with each other in the absence of ethylene to prepare a catalyst component (I); and step 2: the step of mixing the catalyst component (I) obtained in step 1 with a catalyst component (II) for olefin polymerization.

Description

DESCRIPTION
PROCESS FOR PRODUCING CATALYST FOR PRODUCING ETHYLENIC POLYMER, CATALYST FOR PRODUCING ETHYLENIC POLYMER AND
PROCESS FOR PRODUCING ETHYLENIC POLYMER
TECHNICAL FIELD
[0001]
The present invention relates to a process for producing a catalyst for producing an ethylenic polymer, a catalyst for producing an ethylenic polymer and a process for producing an ethylenic polymer.
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 ot-olefin 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 process for producing an ethylenic polymer having short chain branches by using only ethylene as a raw material monomer have been studied. For example, a process 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 process 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 trimerization of ethylene into contact with modified methylaluminoxane (hereinafter, referred to as a "MMAO") as an activating co-catalyst component in a reaction container has been reported. The Non Patent Literature 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 also reports a process 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 trimerization 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.
[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. DISCLOSURE OF THE INVENTION
PROBLEMS TO BE SOLVED BY THE INVENTION
[0008]
In such circumstances, the problem to be solved by the present invention is to provide a process for producing a catalyst capable of efficiently producing an ethylenic polymer having short chain branches even though only ethylene is used as a raw material monomer, a catalyst obtained by the production process and a process for producing an ethylenic polymer by the catalyst. MEANS FOR SOLVING THE PROBLEMS
[0009]
A first aspect of the present invention relates to a process for producing a catalyst for producing an ethylenic polymer, the process including the following steps 1 and 2.
step 1 : the step of bringing a complex represented by formula (1), (2-1) or (2-2) and an activating co-catalyst component into contact with each other in the absence of ethylene to prepare a catalyst component (I).
step 2: the step of mixing the catalyst component (I) obtained in step 1 with a catalyst component (II) for olefin polymerization.
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 groups of X1, X2 and X3 may be bonded to each other to form a ring together with M1;
Figure imgf000006_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 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;
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;
Figure imgf000006_0002
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;
2 22 22
Z is a group linking A to N, and the number of the shortest bonds linking A 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, R , R and R may be bonded to each other, the three X groups each 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, and a substituted hydrocarbyl group, and R28 may be bonded to Z2.
[0010]
A second aspect of the present invention relates to a catalyst for producing an ethylenic polymer obtained by the production process mentioned above.
[0011]
A third aspect of the present invention relates to a process for producing an ethylenic polymer in which olefin including ethylene is polymerized by the catalyst for producing an ethylenic polymer.
ADVANTAGES OF THE INVENTION
[0012]
The present invention can provide a process for producing a catalyst capable of efficiently producing an ethylenic polymer having short chain branches even though only ethylene is used as a raw material monomer, a catalyst obtained by the production process and a process for producing an ethylenic polymer by the catalyst.
BEST MODE FOR CARRYING OUT THE INVENTION
[0013]
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.
[0014] _
[Process for Producing Catalyst for Producing Ethylenic Polymer]
A process for producing a catalyst for producing an ethylenic polymer according to the present invention is a process including the following steps 1 and 2.
step 1 : the step of bringing a complex and an activating co-catalyst component into contact with each other in the absence of ethylene to prepare a catalyst component (I).
step 2: the step of mixing the catalyst component (I) obtained in step 1 with a catalyst component (Π) for olefin polymerization.
The catalyst for producing an ethylenic polymer obtained by the above-mentioned process has the catalyst component (I) and the catalyst component (Π) for olefin polymerization.
[0015] <Step 1>
(Complex)
The complex to be used in step 1 can oligomerize ethylene by the complex and the activating co-catalyst component to synthesize a-olefin. Oligomerization of ethylene means changing of ethylene into 2 to 20-mer compound. The number of carbon atoms of the a- olefin is 4 to 40. The suitable complex is a complex capable of synthesizing at least one a- 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.
[0016]
The complex is a compound represented by any of formula (1), the formula (2-1) a (2-1) mentioned later.
Figure imgf000008_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.
[0017]
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.
[0018]
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 ri5-ethylcyclopentadienyl group, a r|5-n-propylcyclopentadienyl group, η5-isopropylcyclopentadienyl group, a r|5-n-butylcyclopentadienyl group, a r|5-sec- butylcyclopentadienyl group, a ri5-tert-butylcyclopentadienyl group, a η5- dimethylcyclopentadienyl group, a η5-trimethylcyclopentadienyl group, a η5- tetramethylcyclopentadienyl group, a r|5-phenylcyclopentadienyl group, a η5- benzylcyclopentadienyl group, a η5-indenyl group, a r|5-fluorenyl group, a η5-tetrahydroindenyl group, a r|5-methyltetrahydroindenyl group, a r|5-dimethyltetrahydroindenyl group, and a η5- octahydrofluorenyl group. A substituted cyclopentadienyl group is preferable.
[0019]
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.
[0020]
1 and m each represent 1 or 0, and 1 + m is an integer equal to (the valence of J1 -
2).
[0021]
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.
[0022]
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. A chlorine atom is preferable.
[0023]
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.
[0024]
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 amy I group.
[0025]
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 trimethylphenyl group, a diethylphenyl group, particularly preferable examples include a phenyl group, a dimethylphenyl group, and a diethylphenyl group.
[0026]
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.
[0027]
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 the carbon atoms of the substituted hydrocarbyl group is preferably 1 to 20, and more preferably 1 to 10.
[0028]
Examples of the halogenated alkyl group include a fluoromethyl group, a difiuoromethyl 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.
[0029]
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.
[0030]
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.
[0031]
Examples of the hydrocarbyloxy group 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, and more preferably 1 to 10.
[0032]
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.
[0033]
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-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-methylphenoxy group, a 3-methylphenoxy group, and a 4- methylphenoxy group.
[0034]
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 a 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.
[0035]
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 the carbon atoms of the substituted hydrocarbyloxy group is preferably 1 to 20, and more preferably 1 to 10.
[0036]
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.
[0037]
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.
[0038]
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.
[0039]
Examples of the substituted silyl group include a group represented by -Si(R12)3, wherein the three R12 groups each 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.
[0040]
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 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 R12 groups is preferably 1 to 20, and more preferably 3 to 18.
[0041]
Examples of the substituted silyl group include a monosubstituted silyl group having one 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 bound to a silicon atom in the above-mentioned groups are substituted with a halogen atom or a halogenated hydrocarbyl group; a disubstituted silyl group having two 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 bound to a silicon atom in the above- mentioned groups are substituted with a halogen atom and/or halogenated hydrocarbyl groups; and a trisubstituted silyl group having three 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-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 bound to a silicon atom in the above-mentioned groups are substituted with a halogen atom and/or halogenated hydrocarbyl groups. 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.
[0042]
Examples of the disubstituted amino group include a group represented by -
N(R13)2, wherein the two R13 groups each 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.
[0043]
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.
[0044]
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.
[0045]
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. 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.
[0046]
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.
[0047]
R1, R2, R3, R4, and R5 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.
[0048]
Examples of the preferable combination of R1, R2, R3, R4 and R5 include the below-mentioned substructures in 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).
[0049]
Examples of the substructures 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(trifluoromethyl)phenyl, and methoxyphenyl.
[0050]
Among the substructures listed herein as examples, preferable substructures are phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, or diethylphenyl.
[0051]
R6 and R7 are preferably a hydrogen atom, and 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, and an aralkyl group having 7 to 20 carbon atoms. Specific 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.
[0052]
Examples of the preferable combination of R , R and J include the below- mentioned substructures in the substructural formula (4) in formula (1) in which 1 = 1 and m = 1 are satisfied, and J1 is a silicon atom:
R6
r7> (4) wherein R6 and R7 have the same meanings as in R6 and R7, respectively, in formula (1).
[0053]
Examples of the substructures 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.
[0054]
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.
[0055]
Furthermore, examples of the preferable combination of R6, R7 and J1 include the below-mentioned substructures in the substructural formula (5) in formula (1) in which 1 = 1 and = 1 are satisfied and J1 is a carbon atom.
Figure imgf000018_0001
wherein R6 and R7 have the same meanings as in R6 and R7, respectively, in formula (1).
[0056]
Examples of the substructures 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)methy lene, di(3 , 5 -diethylpheny l)methy lene, (3 , 5 -dimethylphenyl)(3 , 5-di- tert-butylphenyl)methylene, di(3,5-diphenylphenyl)methylene, and di(3,5- dibenzylphenyl)methylene.
[0057]
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-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.
[0058]
X1, X2 and X3 are 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.
[00591
The compound represented by formula (1) can be preferably a compound represented by formula ( 1 -2) .
Figure imgf000019_0001
wherein M1 represents a transition metal atom of Group 4 of the periodic table of the elements; and
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 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, and two groups of X , X and X may be bonded to each other to form a ring together with M1.
[0060]
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.
[0061]
In formula (1-2), R1, R2, R3, R4, R5, R6, R7, X1, X2 and X3 have the same meanings as in Rl, 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).
[0062]
In formula (1-2), R8, R9, R10, and Rn 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 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).
[0063]
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.
[0064] 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, or an aralkyl group having 7 to 20 carbon atoms.
[0065]
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.
[0066]
In formula (1-2), R6 and R7 are preferably a hydrogen atom, or 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, or an aralkyl group having 7 to 20 carbon atoms. 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 phenyl group, a 4- methylphenyl group, a 3 -methylphenyl 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.
[0067]
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 thesesub structure formulas 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. [0068]
In formula (1-2), R8, R9, R10 and Ru 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 substituent other than hydrogen or a halogen atom.
[0069]
Examples of R8, R9, R10 and Rn in formula (1-2) include the below-mentioned substructures in the substructural formula (6) in formula (1):
Figure imgf000022_0001
wherein R8, R9, R10 and R11 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 hydrogen or a halogen atom. Examples thereof include the following substructures:
[0070]
methylcyclopentadienyl, ethylcyclopentadienyl, n-propylcyclopentadienyl, isopropylcyclopentadienyl, n-butylcyclopentadienyl, sec-butylcyclopentadienyl, tert- butylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl,
tetramethylcyclopentadienyl phenylcyclopentadienyl, benzylcyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, methyltetrahydroindenyl, dimethyltetrahydroindenyl, and octahydrofluoreny 1.
[0071]
Among the cyclopentadienyl substructures shown as examples herein, a preferable cyclopentadienyl substructure is tetramethylcyclopentadienyl.
[0072]
Examples of the compound represented by formula (1) include a compound represented by formula (1-3).
Figure imgf000022_0002
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 the 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.
[0073]
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.
[0074]
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 the carbon atom to which they are bonded, 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).
[0075]
In formula (1-3), 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, and 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 ) .
[0076]
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.
[0077]
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, or an aralkyl group having 7 to 20 carbon atoms.
[0078]
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.
[0079]
In formula (1-3), R6 and R7 are preferably a hydrogen atom, or 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, or an aralkyl group having 7 to 20 carbon atoms. 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 phenyl group, a 4- methylphenyl group, a 3 -methylphenyl 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.
[0080]
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 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 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.
[0081]
In formula (1-3), R8, R9, R10 and Ru 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 Ru is preferably a substituent other than hydrogen or a halogen atom.
[0082]
Examples of R8, R9, R10 and Ru in formula (1-3) include the substructural formula 6) in formula (1):
Figure imgf000025_0001
wherein R8, R9, R10 and R11 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 hydrogen or a halogen atom. Examples thereof include the following substructures.
[0083]
methylcyclopentadienyl, ethylcyclopentadienyl, n-propylcyclopentadienyl, isopropylcyclopentadienyl, n-butylcyclopentadienyl, sec-butylcyclopentadienyl, tert- butylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl,
tetramethylcyclopentadienylphenylcyclopentadienyl, benzylcyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, methyltetrahydroindenyl, dimethyltetrahydroindenyl, and octahydrofluorenyl.
[0084]
Among the cyclopentadienyl substructures shown as examples herein, preferable cyclopentadienyl substructure is tetramethylcyclopentadienyl.
[0085]
Examples of the compound represented by formula (1) include the following compounds.
[ 1 -dimethylphenylsilyl-cyclopentadienyl]titanium trichloride,
[ 1 -dimethylphenylsilyl-2-methylcyclopentadienyl]titanium trichloride,
[ 1 -dimethylphenylsilyl-3-methylcyclopentadienyl]titanium trichloride,
[l-dimethylphenylsilyl-2,3-dimethylcyclopentadienyl]titanium trichloride,
[ 1 -dimethylphenylsilyl-2,4-dimethylcyclopentadienyl]titanium trichloride,
[l-dimethylphenylsilyl-2,5-dimethylcyclopentadienyl]titanium trichloride,
[l-dimethylphenylsilyl-2,3,5-trimethylcyclopentadienyl]titanium trichloride,
[ 1 -dimethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride,
[ 1 -dimethylphenylsilyl-2-ethylcyclopentadienyl]titanium trichloride,
[ 1 -dimethylphenylsilyl-3 -ethylcyclopentadienyl]titanium trichloride,
[ 1 -dimethylphenylsilyl-2-n-propylcyclopentadienyl]titanium trichloride,
[ 1 -dimethylphenylsilyl-3 -n-propylcyclopentadienyl]titanium trichloride,
[ 1 -dimethylphenylsilyl-2-isopropylcyclopentadienyl]titanium trichloride,
[ 1 -dimethylpheny lsilyi-2-n-butylcyclopentadienyl]titanium trichloride,
[ 1 -dimethylpheny 1 sily 1-3 -n-butyl cyclopentadienyl] titanium trichloride,
[l-dimethylphenylsilyl-2-sec-butylcyclopentadienyl]titanium trichloride,
[ 1 -dimethylphenylsilyl-3 -sec-butylcyclopentadienyl]titanium trichloride,
[ 1 -dimethylphenylsilyl-2-tert-butylcyclopentadienyl]titanium trichloride,
[ 1 -dimethylphenylsilyl-3 -tert-butylcyclopentadienyl]titanium trichloride,
[ 1 -dimethylphenylsilyl-2-phenylcyclopentadienyl]titanium trichloride,
[ 1 -dimethylphenylsilyl-3 -phenylcyclopentadienyl]titanium trichloride,
[ 1 -dimethylphenylsilyl-2-benzylcyclopentadieny l]titanium trichloride,
[ 1 -dimethylphenylsilyl-3 -benzylcyclopentadienyl]titanium trichloride,
[l-dimethylphenylsilyl-indenyl]titanium trichloride,
[l-dimethylphenylsilyl-2-methylindenyl]titanium trichloride,
[9-dimethylphenylsilyl-fluorenyl]titanium trichloride,
[ 1 -dimethylphenylsilyl-tetrahydroindeny l]titanium trichloride, -dimethylphenylsi yl-2-methyltetrahydroindenyl]titanium trichloride,-dimethylphenylsi yl-octahydrofluorenyl]titanium trichloride,
086]
-di ethylphenylsi -cyclopentadienyl]titanium trichloride,
-di ethylphenylsi! -2-methylcyclopentadienyl]titanium trichloride,
-di ethylphenylsi -3 -methylcyclopentadienyljtitanium trichloride, ■d ethylphenylsi -2,3-dimethylcyclopentadienyl]titanium trichloride, -di ethylphenylsi -2,4-dimethylcyclopentadienyl]titanium trichloride, -di ethylphenylsi -2,5-dimethylcyclopentadienyl]titanium trichloride, -d ethylphenylsi -2,3,5-trimethylcyclopentadienyl]titanium trichloride, -di ethylphenylsi -2,3, 4,5-tetramethylcyclopentadienyl]titanium trichloride, -d ethylphenylsi -2-ethylcyclopentadienyl]titanium trichloride,
-d ethylphenylsi -3-ethylcyclopentadienyl]titanium trichloride,
-d ethylphenylsi 2-n-propylcyclopentadienyl]titanium trichloride, -d ethylphenyls 3 -n-propylcyclopentadienyl]titanium trichloride, -d ethylphenylsi 2- isopropylcyclopentadienyl]titanium trichloride, -d ethylphenylsi 3- isopropylcyclopentadienyl]titanium trichloride, -d ethylphenylsi 2-n-butylcyclopentadienyl]titanium trichloride,
-di ethylphenylsi -3 -n-butylcyclopentadienyl]titanium trichloride,
-di ethylphenylsi 2- sec-butylcyclopentadienyl]titanium trichloride, -d ethylphenylsi 3- sec-butylcyclopentadienyl]titanium trichloride, -di ethylphenylsi 2- tert-butylcyclopentadienyl]titanium trichloride, -di ethylphenylsi! 3- tert-butylcyclopentadienyl]titanium trichloride, -di ethylphenylsi -2-phenylcyclopentadienyl]titanium trichloride,
-di ethylphenylsi -3 -phenylcyclopentadienyl]titanium trichloride,
-d ethylphenylsi -2-benzylcyclopentadienyl]titanium trichloride,
-d ethylphenylsi -3-benzylcyclopentadienyl]titanium trichloride,
-d ethylphenylsi -indenyljtitanium trichloride,
-di ethylphenylsi -2-methyl indenyljtitanium trichloride,
-d ethylphenylsi -fluorenyl]titanium trichloride,
-d ethylphenylsi -tetrahydroindenyljtitanium trichloride,
-d ethylphenylsi -2-methyltetrahydroindenyl]titanium trichloride,
-di ethylphenylsii -octahydrofluorenyl]titanium trichloride,
087] [ 1 -cyclotetramethylene(phenyl)silyl-cyclopentadienyl]titanium trichloride,
[ 1 -cyclotetramethylene(phenyl)silyl-2-methylcyclopentadienyl]titanium trichloride,
[ 1 -cyclotetramethylene(phenyl)silyl-3-methylcyclopentadienyl]titanium trichloride,
[l-cyclotetramethylene(phenyl)silyl-2,3-dimethylcyclopentadienyl]titanium trichloride,
[ 1 -cyclotetramethylene(phenyl)silyl-2,4-dimethylcyclopentadienyl]titanium trichloride,
[l-cyclotetramethylene(phenyl)silyl-2,5-dimethylcyclopentadienyl]titanium trichloride,
[l-cyclotetramethylene(phenyl)silyl-2,3,5-trimethylcyclopentadienyl]titanium trichloride,
[l-cyclotetramethylene(phenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride,
[ 1 -cyclotetramethylene(phenyl)silyl-2- ethyl cyclopentadienyl]titanium trichloride,
[ l-cyclotetramethylene(phenyl)silyl-3- ethylcyclopentadienyl]titanium trichloride,
[ 1 -cyclotetramethylene(phenyl)silyl-2-n-propylcyclopentadienyl]titanium trichloride,
[ 1 -cyclotetramethylene(phenyl)silyl-3-n-propylcyclopentadienyl]titanium trichloride,
[ 1 -cyclotetramethylene(phenyl)silyl-2-isopropylcy clopentadienyl]titanium trichloride,
[ 1 -cyclotetramethylene(phenyl)silyl-3 -isopropylcyclopentadienyljtitanium trichloride,
[ 1 -cyclotetramethylene(phenyl)silyl-2-n-butylcyclopentadienyl]titanium trichloride,
[ 1 -cyclotetramethylene(phenyl)silyl-3 -n-butylcyclopentadienyl]titanium trichloride,
[ 1 -cyclotetramethylene(phenyl)silyl-2-sec-butylcyclopentadienyl]titanium trichloride,
[ 1 -cyclotetramethylene(phenyl)silyl-3 -sec-butyl cyclopentadienyl]titanium trichloride,
[ 1 -cyclotetramethylene(phenyl)silyl-2-tert-butylcyclopentadienyl]titanium trichloride,
[ 1 -cyclotetramethylene(phenyl)silyl-3 -tert-butylcyclopentadienyl]titanium trichloride,
[ 1 -cyclotetramethylene(phenyl)silyl-2-phenylcyclopentadienyl]titanium trichloride,
[l-cyclotetramethylene(phenyI)silyl-3-phenylcyclopentadienyl]titanium trichloride,
[ 1 -cyclotetramethylene(phenyl)silyl-2-benzylcyclopentadienyl]titanium trichloride,
[ 1 -cyclotetramethylene(phenyl)silyl-3 -benzylcyclopentadienyljtitanium 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,
[0088]
[ 1 -ethylmethylphenylsily l-cyclopentadienyl]titanium trichloride,
[ 1 -ethylmethylphenylsilyl-2-methylcyclopentadienyl]titanium trichloride,
[ 1 -ethylmethylphenylsilyl-3 -methylcyclopentadienyl]titanium trichloride, [ 1 -ethylmethylphenylsi -2,3-dimethylcyclopentadienyl]titanium trichloride,
[ 1 -ethylmethylphenylsi -2,4-dimethylcyclopentadienyl]titanium trichloride,
[ 1 -ethylmethylphenylsi -2,5-dimethylcyclopentadienyl]titanium trichloride,
[ 1 -ethylmethylphenylsi -2,3,5-trimethylcyclopentadienyl]titanium trichloride, [ 1 -ethylmethylphenylsi -2,3,4,5-tetramethylcyclopentadienyljtitanium trichloride, [ 1 -ethylmethylphenylsi -2-ethylcyclopentadienyl]titanium trichloride,
[ 1 -ethylmethylphenylsi -3 -ethy lcyclopentadienyljtitanium trichloride,
[ 1 -ethylmethylphenylsi -2-n-propylcyclopentadienyl]titanium trichloride,
[ 1 -ethylmethylphenylsi -3 -n-propylcyclopentadienyl]titanium trichloride,
[ 1 -ethylmethylphenylsi -2-isopropylcyclopentadienyl]titanium trichloride,
[ 1 -ethylmethylphenylsi -3-isopropylcyclopentadienyl]titanium trichloride,
[ 1 -ethylmethylphenylsi -2-n-butylcyclopentadienyl]titanium trichloride,
[ 1 -ethylmethylphenylsi -3 -n-butylcyclopentadienyl]titanium trichloride,
[ 1 -ethylmethylphenylsi: -2-sec-butylcyclopentadienyl]titanium trichloride,
[ 1 -ethylmethylphenylsi -3 -sec-butylcyclopentadienyl]titanium trichloride,
[1-ethylmethylphenylsi 2- tert-butylcyclopentadienyl]titanium trichloride,
[ 1 -ethylmethylphenylsi: 3- tert-butylcyclopentadienyl]titanium trichloride,
[ 1 -ethylmethylphenylsi! 2-phenylcyclopentadienyl]titanium trichloride,
[ 1 -ethylmethylphenylsi 3 -phenyl cyclopentadienyl]titanium trichloride,
[ 1 -ethylmethylphenylsi 2-benzylcyclopentadienyl]titanium trichloride,
[ 1 -ethylmethylphenylsi -3-benzylcycIopentadienyl]titanium trichloride,
[ 1 -ethylmethylphenylsi -indenyl]titanium trichloride,
[1 -ethylmethylphenylsi! -2-methyl indenyljtitanium trichloride,
[9-ethylmethylphenylsi -fluorenyljtitanium trichloride,
[ 1 -ethylmethylphenylsi -tetrahydroindenyl]titanium trichloride,
[ 1 -ethylmethylphenylsi -2-methyltetrahydroindenyl]titanium trichloride,
[9-ethylmethylphenylsi -octahydrofluorenyl]titanium trichloride,
[0089]
[ 1 -n-butylmethylpheny yl-cyclopentadienyl]titanium trichloride,
[ 1 -n-butylmethylpheny yl-2-methylcyclopentadienyl]titanium trichloride,
[ 1 -n-butylmethylpheny yl-3 -methylcyclopentadienyl]titanium trichloride,
[ 1 -n-butylmethylpheny! yl-2,3-dimethylcyclopentadienyl]titanium trichloride, [ 1 -n-butylmethylpheny y 1-2, 4-dimethylcyclopentadieny l]titanium trichloride, [ 1 -n-butylmethylpheny yl-2,5-dimethylcyclopentadienyl]titanium trichloride, 1 -n-butylmethylpheny yl-2,3,5-trimethylcyclopentadienyl]titanium trichloride, 1 -n-butylmethylpheny yl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride, 1 -n-butylmethylpheny yl-2-ethylcyclopentadienyl]titanium trichloride,
1 -n-butylmethylphenyi yl-3-ethylcyclopentadienyl]titanium trichloride,
1 -n-butylmethylpheny yl-2-n-propylcyclopentadienyl]titanium trichloride, 1 -n-butylmethylpheny yl-3-n-propylcyclopentadienyl]titanium trichloride, 1 -n-butylmethylpheny yl-2-isopropylcyclopentadienyl]titanium trichloride, 1 -n-butylmethylpheny y 1-3 -isopropylcyclopentadienyl]titanium trichloride, 1 -n-butylmethylpheny yl-2-n-butylcyclopentadienyl]titanium trichloride,
1 -n-butylmethylpheny yl-3-n-butylcyclopentadienyl]titanium trichloride,
1 -n-butylmethylpheny yl-2-sec-butylcyclopentadienyl]titanium trichloride, 1 -n-butylmethylpheny yl-3 -sec-butylcyclopentadienyl]titanium trichloride, 1 -n-butylmethylpheny yl-2-tert-butylcyclopentadienyl]titanium trichloride, 1 -n-butylmethylpheny yl-3-tert-butylcyclopentadienyl]titanium trichloride, 1 -n-butylmethylpheny yl-2-phenylcyclopentadienyl]titanium trichloride,
1 -n-butylmethylpheny yl-3 -phenyl cyclopentadienyl]titanium trichloride,
1 -n-butylmethylpheny yl-2-benzylcyclopentadienyl]titanium trichloride,
1 -n-butylmethylpheny yl-3 -benzyl cyclopentadienyljtitanium trichloride,
1 -n-butylmethylpheny yl-indenyl]titanium trichloride,
1 -n-butylmethylpheny yl-2-methylindenyl]titanium trichloride,
9-n-butylmethylpheny yl-fluorenyl]titanium trichloride,
1 -n-butylmethylpheny yl-tetrahydroindenyl]titanium trichloride,
1 -n-butylmethylpheny yl-2-methyltetrahydroindenyl]titanium trichloride,
9-n-butylmethylpheny yl-octahydrofluorenyl]titanium trichloride,
0090]
1 -methy ldiphenylsilyl-cyclopentadienyl]titanium trichloride,
l-methyldiphenylsilyl-2-methylcyclopentadienyl]titanium trichloride,
l-methyldiphenylsilyl-3-methylcyclopentadienyl]titanium trichloride,
l-methyldiphenylsilyl-2,3-dimethylcyclopentadienyl]titanium trichloride, l-methyldiphenylsilyl-2,4-dimethylcyclopentadienyl]titanium trichloride, l-methyldiphenylsilyl-2,5-dimethylcyclopentadienyl]titanium trichloride, l-methyldiphenylsilyl-2,3,5-trimethylcyclopentadienyl]titanium trichloride, l-methyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride, l-methyldiphenylsilyl-2-ethylcyclopentadienyl]titanium trichloride, -methyldip heny Is lyl-3-ethylcyclopentadienyl]titanium trichloride,
-methyldiphenyls lyl-2-n-propylcyclopentadienyl]titanium trichloride,
-methyldiphenyls lyl-3 -n-propylcyclopentadienyl]titanium trichloride,
-methyldiphenyls lyl-2-isopropylcyclopentadienyl]titanium trichloride,
-methyldiphenyls lyl-2-n-butylcyclopentadienyl]titanium trichloride,
-methyldiphenyls: lyl-3-n-butylcyclopentadienyl]titanium trichloride,
-methyldiphenyls! lyI-2-sec-butylcyclopentadienyl]titanium trichloride,
-methyldiphenyls lyl-3 -sec-butylcyclopentadienyl]titanium trichloride,
-methyldiphenyls lyl-2-tert-butylcyclopentadienyl]titanium trichloride,
-methyldiphenyls lyl-3-tert-butylcyclopentadienyl]titanium trichloride,
-methyldiphenyls lyl-2-phenylcyclopentadienyl]titanium trichloride,
-methyldiphenyls lyl-3 -phenylcyclopentadienyl]titanium trichloride,
-methyldiphenyls: lyl-2-benzylcyclopentadienyl]titanium trichloride,
-methyldiphenyls lyl-3 -benzylcyclopentadienyljtitanium trichloride,
-methyldiphenyls: lyl-indenyl]titanium trichloride,
-methyldiphenyls lyl-2-methylindenyl]titanium trichloride,
-methyldiphenyls: lyl-fluorenyl]titanium trichloride,
-methyldiphenyls: lyl-tetrahydroindenyl]titanium trichloride,
-methyldiphenyls lyl-2-methyltetrahydroindenyl]titanium trichloride,
-methyldiphenyls lyl-octahydrofluorenyl]titanium trichloride,
091]
-methylb s(3,5-dimethylphenyl)s lyl-cyclopentadienyl]titanium trichloride,
-methylb s(3 , 5 -dimethylpheny l)s lyl-2-methylcyclopentadienyl]titanium trichloride,
-methylb s(3 , 5 -dimethy lpheny l)s lyl-3-methylcyclopentadienyl]titanium trichloride,
-methylb s(3,5-dimethylphenyl)s lyl-2,3 -dimethylcyclopentadienyljtitanium trichloride,-methylb s(3 , 5 -dimethy lphenyl)s lyl-2,4-dimethylcyclopentadienyl]titanium trichloride,-methylb s(3 , 5 -dimethy lpheny l)s: lyl-2, 5-dimethylcyclopentadienyl]titanium trichloride,-methylb s(3 , 5 -dimethy lphenyl)s; lyl-2,3, 5-trimethylcyclopentadienyl]titanium trichloride,-methylb s(3 , 5 -dimethylphenyl)s: lyl-2,3, 4, 5-tetramethylcyclopentadienyl]titanium trichloride,-methylb s(3 , 5 -dimethy lpheny l)s; lyl-2-ethylcyclopentadienyl]titanium trichloride,
-methylb s(3 , 5-dimethylphenyl)s lyl-3 -ethy lcyclopentadieny l]titanium trichloride,
-methylb s(3 , 5 -dimethy lpheny l)s lyl-2-n-propylcyclopentadienyl]titanium trichloride,-methylb s(3,5-dimethylphenyl)s lyl-3 -n-propylcyclopentadienyl]titanium trichloride,-methylb s(3 , 5-dimethylphenyl)s lyl-2-isopropylcyclopentadienyl]titanium trichloride, -methy lb is(3 , 5 -dimethy lpheny 1 lyl-2-n-butylcyclopentadienyl]titanium trichloride, -methy lbis(3 , 5 -dimethylphenyl lyl-3 -n-butylcyclopentadienyl]titanium trichloride, -methylbis(3, 5-dimethylphenyl lyl-2-sec-butylcyclopentadienyl]titanium trichloride, -methylbis(3, 5-dimethylphenyl lyl-3-sec-butylcyclopentadienyl]titanium trichloride, -methylbis(3, 5-dimethylphenyl lyl-2-tert-butylcyclopentadienyl]titanium trichloride, -methylbis(3 , 5-dimethylphenyl lyl-3-tert-butylcyclopentadienyl]titanium trichloride, -methylbis(3 , 5-dimethylphenyl lyl-2-phenylcyclopentadienyl]titanium trichloride, -methylbis(3 , 5-dimethylphenyl lyl-3 -phenyl cyclopentadienyljtitanium trichloride, -methylbis(3 , 5-dimethylphenyl lyl-2-benzylcyclopentadienyl]titanium trichloride, -methylbis(3 , 5-dimethylphenyl lyl-3-benzylcyclopentadienyl]titanium trichloride, -methylbis(3 ,5 -dimethylphenyl lyl-indenyl]titanium trichloride,
-methy lb is(3 , 5 -dimethylphenyl lyl-2-methyl indenyljtitanium trichloride,
-methylbis(3, 5-dimethylphenyl lyl-fluorenyl]titanium trichloride,
-methy lbis(3 , 5 -dimethylphenyl Iyl-tetrahydroindenyl]titanium trichloride,
-methylbis(3, 5-dimethylphenyl lyl-2-methyltetrahydroindenyl]titanium trichloride,-methylbis(3 , 5 -dimethylphenyl lyl-octahydrofluorenyl]titanium trichloride,
092]
-cyclohexylmethylpheny silyl-cyclopentadienyl]titanium trichloride,
-cyclohexylmethylpheny silyl-2-methylcyclopentadienyl]titanium trichloride,
-cyclohexylmethylpheny silyl-3-methylcyclopentadienyl]titanium trichloride,
-cyclohexylmethylpheny silyl-2,3 -dimethylcyclopentadienyljtitanium trichloride, -cyclohexylmethylpheny silyl-2,4-dimethylcyclopentadienyl]titanium trichloride, -cyclohexylmethylpheny silyl-2, 5-dimethylcyclopentadienyl]titanium trichloride, -cyclohexylmethylpheny silyl-2,3, 5-trimethylcyclopentadienyl]titanium trichloride, -cyclohexylmethylpheny silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride, -cyclohexylmethylpheny silyl-2-ethylcyclopentadienyl]titanium trichloride,
-cyclohexylmethylpheny silyl-3 -ethylcyclopentadienyljtitanium trichloride,
-cyclohexylmethylpheny silyl-2-n-propylcyclopentadienyl]titanium trichloride, -cyclohexylmethylpheny silyl-3-n-propylcyclopentadienyl]titanium trichloride, -cyclohexylmethylpheny silyl-2-isopropylcyclopentadienyl]titanium trichloride, -cyclohexylmethylpheny silyl-3 -isopropyl cyclopentadienyljtitanium trichloride, -cyclohexylmethylpheny silyl-2-n-butylcyclopentadienyl]titanium trichloride,
-cyclohexylmethylpheny silyl-3 -n-butylcyclopentadienyl]titanium trichloride,
-cyclohexylmethylpheny silyl-2-sec-butylcyclopentadienyl]titanium trichloride, -cyclohexylmethylphenylsii 3-sec-butylcyclopentadienyl]titanium trichloride,
-cyclohexylmethylphenylsii 2-tert-butylcyclopentadienyl]titanium trichloride,
-cyclohexylmethylphenylsii -3 -tert-butylcyclopentadienyl]titanium trichloride,
-cyclohexylmethylphenylsii 2-phenylcyclopentadienyl]titanium trichloride,
-cyclohexylmethylphenylsii 3 -phenylcyclopentadienyljtitanium trichloride,
-cyclohexylmethylphenylsii -2-benzylcyclopentadienyl]titanium trichloride,
-cyclohexylmethylphenylsii 3 -benzyl cyclopentadienyI]titanium trichloride,
-cyclohexylmethylphenylsii indenyl]titanium trichloride,
-cyclohexylmethylphenylsii 2-methylindenyl]titanium trichloride,
-cyclohexylmethylphenylsil fluorenyljtitanium trichloride,
-cyclohexylmethylphenylsii tetrahydroindenyljtitanium trichloride,
-cyclohexylmethylphenylsii 2-methyltetrahydroindenyl]titanium trichloride,
-cyclohexylmethylphenylsil octahydrofluorenyljtitanium trichloride,
093]
-methy n-octadecyl)phenylsi l-cyclopentadienyl]titanium trichloride,
-methy n-octadecyl)phenylsi l-2-methylcyclopentadienyl]titanium trichloride,
-methy n-octadecyl)phenylsi yl-3-methylcyclopentadienyl]titanium trichloride,
-methy n-octadecyl)phenylsi yl-2,3-dimethylcyclopentadienyl]titanium trichloride,-methy n-octadecyl)phenylsi yl-2,4-dimethylcyclopentadienyl]titanium trichloride,-methy n-octadecyl)phenylsi yl-2, 5-dimethylcyclopentadienyl]titanium trichloride, -methyl n-octadecyl)phenylsi yl-2, 3 , 5-trimethylcyclopentadienyl]titanium trichloride, -methyl n-octadecyl)phenylsi yl-2,3 ,4, 5-tetramethylcyclopentadienyl]titanium trichloride, -methyl n-octadecyl)phenylsi yl-2-ethylcyclopentadienyl]titanium trichloride,
-methy! n-octadecyl)phenyl si yl-3 -ethy lcyclopentadieny l]titanium trichloride,
-methyl n-octadecyl)phenylsi yl-2-n-propylcyclopentadienyl]titanium trichloride, -methyl n-octadecyl)phenylsi yl-3-n-propylcyclopentadienyl]titanium trichloride, -methyl n-octadecyl)phenylsi yl-2-isopropylcyclopentadienyl]titanium trichloride, -methyl n-octadecyl)phenylsi yl-3-isopropylcyclopentadienyl]titanium trichloride, -methyl n-octadecyl)phenylsi yl-2-n-butylcyclopentadienyl]titanium trichloride,
-methyl n-octadecyl)phenylsi yl-3-n-butylcyclopentadienyl]titanium trichloride,
-methyl n-octadecyl)phenylsi yl-2-sec-butylcyclopentadienyl]titanium trichloride, -methyl n-octadecyl)phenylsi yl-3-sec-butylcyclopentadienyl]titanium trichloride, -methyl n-octadecyl)phenyl si i-2-tert-butylcyclopentadienyl]titanium trichloride, -methyl n-octadecyl)phenylsi yl-3 -tert-butylcyclopentadienyl]titanium trichloride, 1 -methyl(n-octadecyl)phenylsilyl-2-phenylcyclopentadienyl]titanium trichloride,
1 -methyl(n-octadecyl)phenylsilyl-3 -phenyl cyclopentadienyljtitanium trichloride,
1 -methyl(n-octadecyl)phenylsilyl-2-benzylcyclopentadienyl]titanium trichloride,
1 -methyl(n-octadecyl)phenylsilyl-3-benzylcyclopentadienyl]titanium trichloride,
1 -methyl(n-octadecyl)phenylsilyl-indenyl]titanium trichloride,
1 -methyl(n-octadecyl)phenylsilyl-2-methylindenyl]titanium trichloride,
9-methyl(n-octadecyl)phenylsilyl-fluorenyl]titanium trichloride,
1 -methyl(n-octadecyl)pheny lsilyl-tetrahydroindenyl]titanium trichloride,
1 -methyl(n-octadecyl)phenylsilyl-2-methyltetrahydroindenyl]titanium trichloride,
9-methyl(n-octadecyl)phenylsilyl-octahydrofluorenyl]titanium trichloride,
0094]
1 -triphenylsilyl-cyclopentadienyljtitanium trichloride,
1 -triphenylsilyl-2-methy lcyclopentadienyljtitanium trichloride,
1 -triphenylsilyl-3-methylcyclopentadienyl]titanium trichloride,
l-triphenylsilyl-2,3-dimethylcyclopentadienyl]titanium trichloride,
1 -triphenylsilyl-2,4-dimethylcyclopentadienyl]titanium trichloride,
1 -triphenylsilyl-2, 5-dimethylcyclopentadienyl]titanium trichloride,
1 -triphenylsilyl-2,3 , 5-trimethylcyclopentadienyl]titanium trichloride,
1 -triphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride,
1 -triphenylsilyl-2-ethylcyclopentadienyl]titanium trichloride,
l-triphenylsilyl-3-ethylcyclopentadienyl]titanium trichloride,
1 -triphenylsilyl-2-n-propylcyclopentadienyl]titanium trichloride,
1 -triphenylsilyl-3-n-propylcyclopentadienyl]titanium trichloride,
1 -triphenylsilyl-2-isopropyl cyclopentadienyljtitanium 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-butylcyclopentadienyl]titanium trichloride,
1 -triphenylsilyl-2-tert-butylcyclopentadienyl]titanium trichloride,
1 -triphenylsilyl-3 -tert-butylcyclopentadieny ljtitanium trichloride,
1 -triphenylsilyl-2-phenylcyclopentadienyl]titanium trichloride,
1 -triphenylsilyl-3 -phenylcyclopentadienyl]titanium trichloride,
1 -triphenylsilyl-2 -benzylcyclopentadienyljtitanium trichloride, l-triphenylsilyl-3-benzylcyclopentadienyl]titanium trichloride,
l-triphenylsilyl-indenyl]titanium trichloride,
1 -triphenylsily l-2-methylindenyl]titanium trichloride,
-triphenylsilyl-fluorenyl]titanium trichloride,
1 -triphenylsilyl-tetrahydroindenyl]titanium trichloride,
1 -tripheny lsilyl-2-methyltetrahydroindenyl]titanium trichloride,
-triphenylsilyl-octahydrofluorenyl]titanium trichloride,
095]
1 -tri(4-n-butylphenyl)s lyl-cyclopentadienyl]titanium trichloride,
1 -tri(4-n-butylphenyl) s lyl-2-methylcyclopentadienyl]titanium trichloride, l-tri(4-n-butylphenyl)s: lyl-3-methylcyclopentadienyl]titanium trichloride,
1 -tri(4-n-butylphenyl)si lyl-2, 3 -dimethylcyclopentadienyljtitanium trichloride, 1 -tri(4-n-butylphenyl)s Iyl-2,4-dimethylcyclopentadienyl]titanium trichloride, 1 -tri(4-n-butylphenyl)s lyl-2,5-dimethylcyclopentadienyl]titanium trichloride, 1 -tri(4-n-butylphenyl)s lyl-2, 3 , 5-trimethylcyclopentadienyl]titanium trichloride, 1 -tri(4-n-butylphenyl)s lyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride, 1 -tri(4-n-butylphenyl)s lyl-2-ethylcyclopentadienyl]titanium trichloride,
1 -tri(4-n-butylphenyl)s ly 1-3 -ethylcyclopentadienyl]titanium trichloride,
1 -tri(4-n-butylphenyl)s lyl-2-n-propylcyclopentadienyl]titanium trichloride, 1 -tri(4-n-butylphenyl)s lyl-3 -n-propylcyclopentadienyl]titanium trichloride, 1 -tri(4-n-butylphenyl)s lyl-2-isopropylcyclopentadienyl]titanium trichloride, 1 -tri(4-n-butylphenyl)s lyl-3 -isopropylcyclopentadienyljtitanium trichloride, 1 -tri(4-n-butylphenyl)s lyl-2-n-butylcyclopentadienyl]titanium trichloride,
1 -tri(4-n-butylphenyl)s: lyl-3 -n-butylcyclopentadienyl]tttanium trichloride,
1 -tri(4-n-butylphenyl)s: lyl-2-sec-butylcyclopentadienyl]titanium trichloride, 1 -tri(4-n-butylphenyl)s! lyl-3 -sec-butylcyclopentadienyl]titanium trichloride, 1 -tri(4-n-butylphenyl)s lyl-2-tert-butylcyclopentadienyl]titanium trichloride, 1 -tri(4-n-butylphenyl)s lyl-3 -tert-butylcyclopentadienyl]titanium trichloride, 1 -tri(4-n-butylphenyl)s lyl-2 -phenylcyclopentadienyljtitanium trichloride,
1 -tri(4-n-butylphenyl)s lyl-3 -phenylcyclopentadienyl]titanium trichloride,
1 -tri(4-n-butylphenyl) s lyl-2-benzylcyclopentadienyl]titanium trichloride,
1 -tri(4-n-butylphenyl)s lyl-3 -benzylcyclopentadienyljtitanium trichloride,
1 -tri(4-n-butylphenyl)s lyl-indenyl]titanium trichloride,
1 -tri(4-n-butylphenyl)s lyl-2-methyl indenyl]titanium trichloride, 9-tri(4-n- butylphenyl)silyl-fluorenyl]titanium trichloride,
1 -tri(4-n-butylphenyl)silyl-tetrahydroindenyl]titanium trichloride,
1 -tri(4-n-butylphenyl)silyl-2-methyltetrahydroindenyl]titanium trichloride,
9-tri(4-n-butylphenyl)silyl-octahydrofluorenyl]titanium trichloride,
0096]
l-tri(3-methylphenyl)silyl-cyclopentadienyl]titanium trichloride,
1 -tri(3 -methylphenyl)silyl-2-methylcyclopentadienyl]titanium trichloride, l-tri(3-methylphenyl)silyl-3-methylcyclopentadienyl]titanium trichloride, l-tri(3-methylphenyl)silyl-2,3-dimethylcyclopentadienyl]titanium trichloride, l-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, 1 -tri(3-methylphenyl)silyl-2-ethylcyclopentadienyl]titanium trichloride,
1 -tri(3 -methylphenyl)silyl-3 -ethylcyclopentadienyljtitanium trichloride,
1 -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-isopropylcyclopentadienyI]titanium trichloride, 1 -tri(3 -methylphenyl)silyl-2-n-butylcyclopentadienyl]titanium trichloride, l-tri(3-methylphenyl)silyl-3-n-butylcyclopentadienyl]titanium trichloride, l-tri(3-methylphenyl)silyl-2-sec-butylcyclopentadienyl]titanium trichloride, l-tri(3-methylphenyl)silyl-3-sec-butylcyclopentadienyl]titanium trichloride, l-tri(3-methylphenyl)silyl-2-tert-butylcyclopentadienyl]titanium trichloride, 1 -tri(3 -methylphenyl)silyl-3 -tert-butylcyclopentadienyl]titanium trichloride, 1 -tri(3 -methylphenyl)silyl-2-phenylcyclopentadienyl]titanium trichloride,
1 -tri(3 -methylphenyl)silyl-3 -phenyl cyclopentadienyljtitanium trichloride,
1 -tri(3 -methylphenyl)silyl-2-benzylcyclopentadienyl]titanium trichloride,
1 -tri(3 -methylphenyl)silyl-3 -benzylcyclopentadienyljtitanium trichloride,
1 -tri(3 -methylphenyl)silyl-indenyl]titanium trichloride,
l-tri(3-methylphenyl)silyl-2-methyl indenyl]titanium trichloride,
9-tri(3-methylphenyl)silyl-fluorenyl]titanium trichloride,
l-tri(3-methylphenyl)silyl-tetrahydroindenyl]titanium trichloride,
l-tri(3-methylphenyl)silyl-2-methyltetrahydroindenyl]titanium trichloride, -tri(3-methylphenyl)silyl-octahydrofluorenyl]titaniuni trichloride,
097]
1 -tri(3-isopropylphenyl)silyl-cyclopentadienyl]titanium trichloride,
1 -tri(3 -isopropylphenyl)silyl-2-methylcyclopentadienyl]titanium trichloride,
1 -tri(3 -isopropylphenyl)silyl-3 -methyl cyclopentadienyl]titanium trichloride, l-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, l-tri(3-isopropylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride,
1 -tri(3 -isopropylphenyl)silyl-2-ethylcyclopentadienyl]titanium trichloride,
1 -tri(3 -isopropylphenyl)silyl-3 -ethylcyclopentadienyljtitanium trichloride,
1 -tri(3 -isopropylphenyl)silyl-2-n-propylcyclopentadienyl]titanium trichloride, l-tri(3-isopropylphenyl)silyl-3-n-propylcyclopentadienyl]titanium 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 -isopropylphenyl)silyl-3 -n-butylcyclopentadienyl]titanium trichloride, l-tri(3-isopropylphenyl)silyl-2-sec-butylcyclopentadienyl]titanium trichloride, l-tri(3-isopropylphenyl)silyl-3-sec-butylcyclopentadienyl]titanium trichloride, l-tri(3-isopropylphenyl)silyl-2-tert-butylcyclopentadienyl]titanium trichloride,
1 -tri(3 -isopropylphenyl)silyl-3 -tert-butylcyclopentadienyl]titanium trichloride,
1 -tri(3 -isopropylphenyl)silyl-2-phenylcyclopentadienyl]titanium trichloride, l-tri(3-isopropylphenyl)silyl-3-phenylcyclopentadienyl]titanium trichloride,
1 -tri(3 -isopropylphenyl)silyl-2-benzylcyclopentadienyl]titanium trichloride, l-tri(3-isopropylphenyl)silyl-3-benzylcyclopentadienyl]titanium trichloride,
1 -tri(3 -isopropylphenyl)silyl-indenyl]titanium trichloride,
1 -tri(3 -isopropylphenyl)silyl-2-methylindenyl]titanium trichloride,
9-tri(3 -isopropylphenyl)silyl-fluorenyl]titanium trichloride,
1 -tri(3 -isopropylphenyl)silyl-tetrahydroindenyl]titanium trichloride,
l-tri(3-isopropylphenyl)silyl-2-methyltetrahydroindenyl]titanium trichloride,
9-tri(3-isopropylphenyl)silyl-octahydrofluorenyl]titanium trichloride,
0098]
1 -dimethyl(3 , 5 -dimethylphenyl) sily l-cyclopentadieny l]titanium trichloride, -dimethyl(3,5-dimethylphenyl)silyl-2-methylcyclopentadienyl]titanium trichloride, l-dimethyl(3,5-dimethylphenyl)silyl-3-methylcyclopentadienyl]titanium trichloride,
-dimethyl(3,5-dimethylphenyl)silyl-2,3-dimethylcyclopentadienyl]titanium trichloride, -dimethyl(3,5-dimethylphenyl)silyl-2,4-dimethylcyclopentadienyl]titanium trichloride, l-dimethyl(3,5-dimethylphenyl)silyl-2,5-dimethylcyclopentadienyl]titanium trichloride, " 1 -dimethyl(3,5-dimethylphenyl)silyl-2,3,5-trimethylcyclopentadienyl]titanium trichloride, " 1 -dimethyl (3 , 5 -dimethylphenyl) silyl-2, 3 ,4, 5 -tetramethy Icy clopentadieny ljtitanium trichloride, ~ 1 -dimethyl(3 , 5-dimethylphenyl)silyl-2-ethylcyclopentadienyl]titanium trichloride,
l-dimethyl(3,5-dimethylphenyl)silyl-3-ethylcyclopentadienyl]titanium trichloride,
l-dimethyl(3,5-dimethylphenyl)silyl-2-n-propylcyclopentadienyl]titanium trichloride, l-dimethyl(3,5-dimethylphenyl)silyl-3-n-propylcyclopentadienyl]titanium trichloride, l-dimethyl(3,5-dimethylphenyl)silyl-2-isopropylcyclopentadieriyl]titanium trichloride, ' 1 -dimethyl(3 , 5-dimethylphenyl)silyl-3-isopropylcyclopentadienyl]titanium trichloride, l-dimethyl(3,5-dimethylphenyl)silyl-2-n-butylcyclopentadienyl]titanium trichloride,
1 -dimethyl(3,5-dimethylphenyl)silyl-3-n-butylcyclopentadienyl]titanium trichloride, l-dimethyl(3,5-dimethylphenyl)silyl-2-sec-butylcyclopentadienyl]titanium trichloride, -dimethyl(3,5-dimethylphenyl)silyl-3-sec-butylcyclopentadienyl]titanium trichloride, l-dimethyl(3,5-dimethylphenyl)silyl-2-tert-butylcyclopentadienyl]titanium trichloride, l-dimethyl(3,5-dimethylphenyl)silyl-3-tert-butylcyclopentadienyl]titanium trichloride, l-dimethyl(3,5-dimethylphenyl)silyl-2-phenylcyclopentadienyl]titanium trichloride, l-dimethyl(3,5-dimethylphenyl)silyl-3-phenylcyclopentadienyl]titanium trichloride, l-dimethyl(3,5-dimethylphenyl)silyl-2-benzylcyclopentadienyl]titanium trichloride,
' 1 -dimethyl(3 , 5-dimethylphenyl)silyl-3 -benzylcyclopentadienyl]titanium trichloride, l-dimethyl(3,5-dimethylphenyl)silyl-indenyl]titanium trichloride,
l-dimethyl(3,5-dimethylphenyl)silyl-2-methyl indenyl]titanium trichloride,
9-dimethyl(3,5-dimethylphenyl)silyl-fluorenyl]titanium trichloride,
-dimethyl(3,5-dimethylphenyl)silyl-tetrahydroindenyl]titanium trichloride,
1 -dimethyl(3 , 5 -dimethylphenyl)silyl-2-methyltetrahydroindenyl]titanium trichloride,
9-dimethyl(3,5-dimethylphenyl)silyl-octahydrofluorenyl]titanium trichloride,
0099]
1 -dimethyl(3,5-di-n-hexylphenyl)silyl-cyclopentadienyl]titanium trichloride,
l-dimethyl(3,5-di-n-hexylphenyl)silyl-2-methylcyclopentadienyl]titanium trichloride, l-dimethyl(3,5-di-n-hexylphenyl)silyl-3-methylcyclopentadienyl]titanium trichloride, l-dimethyl(3,5-di-n-hexylphenyl)silyl-2,3-dimethylcyclopentadienyl]titanium trichloride, l-dimethyl(3,5-di-n-hexylphenyl)silyl-2,4-dimethylcyclopentadienyl]titanium trichloride, l-dimethyl(3,5-di-n-hexylphenyl)silyl-2,5-dimethylcyclopentadienyl]titanium trichloride, l-dimethyl(3,5-di-n-hexylphenyl)silyl-2,3,5-trimethylcyclopentadienyl]titanium trichloride, 1 -dimethyl(3 , 5-di-n-hexylphenyl)silyl-2, 3 ,4, 5-tetramethy Icyclopentadienyljtitanium trichloride, l-dimethyl(3,5-di-n-hexylphenyl)silyl-2-ethylcyclopentadienyl]titanium trichloride,
l-dimethyl(3,5-di-n-hexylphenyl)silyl-3-ethylcyclopentadienyl]titanium trichloride,
1 -dimethyl(3,5-di-n-hexylphenyl)silyl-2-n-propylcyclopentadienyl]titanium trichloride, 1 -dimethyl(3 , 5-di-n-hexylphenyl)silyl-3 -n-propylcyclopentadienyl]titanium trichloride, l-dimethyl(3,5-di-n-hexylphenyl)silyl-2-isopropylcyclopentadienyl]titanium trichloride, 1 -dimethyl(3,5-di-n-hexylphenyl)silyl-3-isopropylcyclopentadienyl]titanium trichloride, l-dimethyl(3,5-di-n-hexylphenyl)silyl-2-n-butylcyclopentadienyl]titanium trichloride, l-dimethyl(3,5-di-n-hexylphenyl)silyl-3-n-butylcyclopentadienyl]titanium trichloride, l-dimethyl(3,5-di-n-hexylphenyl)silyl-2-sec-butylcyclopentadienyl]titanium trichloride, 1 -dimethyl(3 , 5-di-n-hexylphenyl)silyl-3 -sec-butylcyclopentadienyl]titanium trichloride, 1 -dimethyl(3 ,5-di-n-hexylphenyl)silyl-2-tert-butylcyclopentadienyl]titanium trichloride, 1 -dimethyl(3,5-di-n-hexylphenyl)silyl-3-tert-butylcyclopentadienyl]titanium trichloride, l-dimethyl(3,5-di-n-hexylphenyl)silyl-2-phenylcyclopentadienyl]titanium trichloride,
1 -dimethy 1(3 , 5-di-n-hexylphenyl)sily 1-3 -phenylcy clopentadienyl]titanium trichloride, l-dimethyl(3,5-di-n-hexylphenyl)silyl-2-benzylcyclopentadienyl]titanium trichloride, l-dimethyl(3,5-di-n-hexylphenyl)silyl-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 indenyljtitanium trichloride,
9-dimethyl(3,5-di-n-hexylphenyl)silyl-fluorenyl]titanium trichloride,
1 -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,
0100]
l-n-butylmethyl(3,5-dimethylphenyl)silyl-cyclopentadienyl]titanium trichloride,
l-n-butylmethyl(3,5-dimethylphenyl)silyl-2-methylcyclopentadienyl]titanium trichloride, l-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, l-n-butylmethyl(3,5-dimethylphenyl)silyl-2,5-dimethyIcyclopentadienyl]titanium trichloride, -n-butylmethyl(3,5-dimethylphenyl)siIyl-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 -dimethylpheny l)sily 1-3 -n-propylcyclopentadieny ljtitanium trichloride, [l-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, [l-n-butylmethyl(3,5-dimethylphenyl)silyl-3-n-butylcyclopentadienyI]titanium trichloride, [ 1 -n-butylmethyl(3 , 5-dimethylphenyl)silyl-2-sec-butylcyclopentadienyl]titanium trichloride, [l-n-butylmethyl(3,5-dimethylphenyl)silyl-3-sec-butylcyclopentadienyl]titanium trichloride, [l-n-butylmethyl(3,5-dimethylphenyl)silyl-2-tert-butylcyclopentadienyl]titanium trichloride, [ 1 -n-butylmethyl(3 , 5-dimethylphenyl)sily 1-3 -tert-butylcyclopentadienyl]titanium trichloride, [l-n-butylmethyl(3,5-dimethylphenyl)silyl-2-phenylcyclopentadienyl]titanium trichloride, [ 1 -n-butylmethyl(3 , 5-dimethylphenyl)silyl-3 -phenylcyclopentadienyl]titanium trichloride, [l-n-butylmethyl(3,5-dimethylphenyl)silyl-2-benzylcyclopentadienyl]titanium trichloride, [l-n-butylmethyl(3,5-dimethylphenyl)silyl-3-benzylcyclopentadienyl]titanium trichloride, [ 1 -n-butylmethyl(3 , 5-dimethylphenyl)silyl-indenyl]titanium trichloride,
[l-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,
[0101]
[l-tris(3,5-dimethylphenyl)silyl-cyclopentadienyl]titanium trichloride,
[l-tris(3,5-dimethylphenyl)silyl-2-methylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3,5-dimethylphenyl)silyl-3-methylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-dimethylphenyl)silyl-2,3-dimethylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-dimethylphenyl)silyl-2,4-dimethylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-dimethylphenyl)silyl-2,5-dimethylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3 , 5 -dimethylpheny l)silyl-2, 3 , 5 -trimethy Icy clopentadieny ljtitanium trichloride,
[l-tris(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride, [l-tris(3,5-dimethylphenyl)silyl-2-ethylcyclopentadienyl]titanium trichloride, l-tris(3 ■dimethylpheny is: y 1-3 -ethylcyclopentadienyljtitanium trichloride, l-tris(3 ■dimethylpheny is: yl-2-n-propylcyclopentadienyl]titanium trichloride, l-tris(3 ■dimethylpheny: IS: yl-3 -n-propylcyclopentadienyl]titanium trichloride, l-tris(3 ■dimethylpheny! IS: yl-2-isopropylcyclopentadienyl]titanium trichloride, l-tris(3 -dimethylpheny IS: yl-3 -isopropylcyclopentadienyljtitanium trichloride, l-tris(3 ■dimethylpheny! IS: yl-2-n-butylcyclopentadienyl]titanium trichloride, l-tris(3 ■dimethylpheny! IS! yl-3 -n-butylcyclopentadienyl]titanium trichloride, l-tris(3 -dimethylpheny IS: yl-2-sec-butylcyclopentadienyl]titanium trichloride, l-tris(3 -dimethylpheny! IS! yl-3 -sec-butylcyclopentadienyl]titanium trichloride, l-tris(3 -dimethylpheny! IS! yl-2-tert-butylcyclopentadienyl]titanium trichloride, l-tris(3 -dimethylpheny IS; yl-3-tert-butylcyclopentadienyl]titanium trichloride, l-tris(3 -dimethylpheny 'Si yl-2-phenylcyclopentadienyl]titanium trichloride, l-tris(3 -dimethylpheny Si yl-3 -phenylcyclopentadienyljtitanium trichloride, l-tris(3 ■dimethylpheny isi yl-2-benzylcyclopentadienyl]titanium trichloride, l-tris(3 ■dimethylpheny >s: yl-3 -benzylcyclopentadienyljtitanium trichloride, l-tris(3 -dimethylpheny 'S; yl-indenyl]titanium trichloride,
l-tris(3 ■dimethylpheny 'SI yl-2-methylindenyl]titanium trichloride,
9-tris(3 ■dimethylpheny si yl-fluorenyl]titanium trichloride,
l-tris(3 ■dimethylpheny 'S! yl-tetrahydroindenyl]titanium trichloride,
l-tris(3 -dimethylpheny 'S yl-2-methyltetrahydroindenyl]titanium trichloride,
9-tris(3 -dimethylpheny s yl-octahydrofluorenyl]titanium trichloride,
0102]
l-tris(3 •diethylphenyl -cyclopentadienyljtitanium trichloride,
l-tris(3 ■diethylphenyl -2-methylcyclopentadienyl]titanium trichloride, l-tris(3 ■diethylphenyl 3 -methylcyclopentadienyl]titanium trichloride, l-tris(3 -diethylphenyl -2, 3 -dimethylcyclopentadienyl]titanium trichloride, -tris(3 -diethylphenyl 2,4-dimethylcyclopentadienyl]titanium trichloride,
;i-tris(3 -diethylphenyl -2,5-dimethylcyclopentadienyl]titanium trichloride, l-tris(3 -diethylphenyl 2,3,5-trimethylcyclopentadienyl]titanium trichloride, l-tris(3 ■diethylphenyl -2, 3,4, 5-tetramethylcyclopentadienyl]titanium trichloride, l-tris(3 -diethylphenyl -2-ethylcyclopentadienyl]titanium trichloride,
l-tris(3 ■diethylphenyl -3-ethylcyclopentadienyl]titanium trichloride,
l-tris(3 ■diethylphenyl -2-n-propylcyclopentadienyl]titanium trichloride, l-tris(3 -diethylphenyl -3 -n-propylcyclopentadienyl]titanium trichloride, l-tris(3,5-diethylphenyl)silyl-2-isopropylcyclopentadienyl]titanium trichloride, l-tris(3,5-diethylphenyl)silyl-3-isopropylcyclopentadienyl]titanium trichloride, l-tris(3,5-diethylphenyl)silyl-2-n-butylcyclopentadienyl]titanium trichloride,
l-tris(3,5-diethylphenyl)silyl-3-n-butylcyclopentadienyl]titanium trichloride,
l-tris(3,5-diethylphenyl)silyl-2-sec-butylcyclopentadienyl]titanium trichloride,
l-tris(3,5-diethylphenyl)silyl-3 -sec-butyl cyclopentadienyl]titanium trichloride,
1 -tris(3, 5-diethylphenyl)silyl-2-tert-butylcyclopentadienyl]titanium trichloride,
l-tris(3,5-diethylphenyl)silyl-3-tert-butylcyclopentadienyl]titanium trichloride,
1 -tris(3 , 5-diethylphenyl)silyl-2-phenylcyclopentadienyl]titanium trichloride,
l-tris(3,5-diethylphenyl)silyl-3-phenylcyclopentadienyl]titanium trichloride,
l-tris(3,5-diethylphenyl)silyl-2-benzylcyclopentadienyl]titanium trichloride,
l-tris(3,5-diethylphenyl)silyl-3-benzylcyclopentadienyl]titanium trichloride,
1 -tris(3 , 5-diethylphenyl)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,
l-tris(3,5-diethylphenyl)silyl-2-methyltetrahydroindenyl]titanium trichloride,
9-tris(3,5-diethylphenyl)silyl-octahydrofluorenyl]titanium trichloride,
0103]
l-tris(3,5-diisopropylphenyl)silyl-cyclopentadienyl]titanium trichloride,
l-tris(3,5-diisopropylphenyl)sityl-2-methylcyclopentadienyl]titanium trichloride, l-tris(3,5-diisopropylphenyl)silyl-3-methylcyclopentadienyl]titanium trichloride, l-tris(3,5-diisopropylphenyl)silyl-2,3-dimethylcyclopentadienyl]titanium trichloride, l-tris(3,5-diisopropylphenyl)silyl-2,4-dimethylcyclopentadienyl]titanium trichloride, l-tris(3,5-diisopropylphenyl)silyl-2,5-dimethylcyclopentadienyl]titanium trichloride, l-tris(3,5-diisopropylphenyl)silyl-2,3,5-trimethylcyclopentadienyl]titanium trichloride, l-tris(3,5-diisopropylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride, l-tris(3,5-diisopropylphenyl)silyl-2-ethylcyclopentadienyl]titanium trichloride,
l-tris(3,5-diisopropylphenyl)silyl-3-ethylcyclopentadienyl]titanium trichloride,
l-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, l-tris(3,5-diisopropylphenyl)silyl-2-n-butylcyclopentadienyl]titanium trichloride, l-tris(3 5 -diisopropylphenyl) s lyl-3 -n-butylcyclopentadienyl]titanium trichloride, l-tris(3 5-diisopropylphenyl)s lyl-2-sec-butylcyclopentadienyl]titanium trichloride, l-tris(3 5-diisopropylphenyl)s lyl-3 -sec-butylcyclopentadieny l]titanium trichloride, l-tris(3 5-diisopropylphenyl)s lyl-2-tert-butylcyclopentadienyl]titanium trichloride, l-tris(3 5-diisopropylphenyl)si lyl-3-tert-butylcyclopentadienyl]titanium trichloride, l-tris(3 5-diisopropylphenyl)si lyl-2-phenylcyclopentadienyl]titanium trichloride, l-tris(3 5-diisopropylphenyl)si lyl-3 -phenylcyclopentadienyljtitanium trichloride, l-tris(3 5-diisopropylphenyl)si lyl-2-benzylcyclopentadienyl]titanium trichloride, l-tris(3 5 -dii sopropylphenyl)s lyl-3-benzylcyclopentadienyl]titanium trichloride, l-tris(3 5 -dii sopropylphenyl) s lyl-indenyl]titanium trichloride,
l-tris(3 5 -diisopropylphenyl) s lyl-2-methyl indenyl]titanium trichloride,
9-tris(3 5-diisopropylphenyl)s lyl-fluorenyl]titanium trichloride,
l-tris(3 5-diisopropylphenyl)s lyl-tetrahydroindenyl]titanium trichloride,
l-tris(3 5-diisopropylphenyl)s! lyl-2-methyltetrahydroindenyl]titanium trichloride,
9-tris(3 5-diisopropylphenyl)si lyl-octahydrofluorenyl]titanium trichloride,
0104]
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, l-tris(3 5 tert-butylphenyl)silyl-2,3,5-trimethylcyclopentadienyl]titanium trichloride, l-tris(3 5 tert-butylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride,
;i-tris(3 5 tert-butylphenyl)silyl-2-ethylcyclopentadienyl]titanium trichloride,
l-tris(3 5-di tert-butylphenyl)silyl-3-ethylcyclopentadienyl]titanium trichloride,
;i-tris(3 5-di tert-butylphenyl)silyl-2-n-propylcyclopentadienyl]titanium trichloride, l-tris(3 5-di tert-butylphenyl)silyl-3-n-propylcyclopentadienyl]titanium 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,
;i-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,
;i-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, ri-tris(3 5-di-tert-butylphenyl)silyl-3-tert-butylcyclopentadienyl]titanium trichloride, l-tris(3 5-di-tert-butylphenyl)silyl-2-phenylcyclopentadienyl]titanium trichloride,
[l-tris(3 5-di-tert-butylphenyl)silyl-3-phenylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3 5-di-tert-butylphenyl)silyl-2-benzylcyclopentadienyl]titanium trichloride,
[l-tris(3 5-di-tert-butylphenyl)silyl-3-benzylcyclopentadienyl]titanium trichloride,
[l-tris(3 5-di-tert-butylphenyl)silyl-indenyl]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,
-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-butylpheny 1) silyl-octahydrofluoreny ljtitanium trichloride,
[0105]
tris(3 5-di-n-hexylphenyl)silyl-cyclopentadienyl]titanium trichloride,
! l-tris(3 5-di-n-hexylphenyl)silyl-2-methylcyclopentadienyl]titanium trichloride,
-tris(3 5-di-n-hexylphenyl)silyl-3-methylcyclopentadienyl]titanium trichloride,
! l-tris(3 5-di-n-hexylphenyl)silyl-2,3-dimethylcyclopentadienyl]titanium trichloride, ;i-tris(3 5-di-n-hexylphenyl)silyl-2,4-dimethylcyclopentadienyl]titanium trichloride,
[ l-tris(3 5-di-n-hexylphenyl)silyl-2,5-dimethylcyclopentadienyl]titanium trichloride, tris(3 5-di-n-hexylphenyl)silyl-2,3,5-trimethylcyclopentadienyl]titanium trichloride, -tris(3 5-di-n-hexylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride, l-tris(3 5-di-n-hexylphenyl)silyl-2-ethylcyclopentadienyl]titanium trichloride,
-tris(3 5-di-n-hexylphenyl)silyl-3-ethylcyclopentadienyl]titanium trichloride,
-tris(3 5-di-n-hexylphenyl)silyl-2-n-propylcyclopentadienyl]titanium trichloride, -tris(3 5-di-n-hexylphenyl)silyl-3-n-propylcyclopentadienyl]titanium trichloride,
[l-tris(3 5-di-n-hexylphenyl)silyl-2-isopropylcyclopentadienyl]titanium trichloride,
-tris(3 5-di-n-hexylphenyl)silyl-3-isopropylcyclopentadienyl]titanium trichloride,
[l-tris(3 5-di-n-hexylphenyl)silyl-2-n-butylcyclopentadienyl]titanium trichloride,
[l-tris(3 5-di ■n-hexylphenyl)silyl-3-n-butylcyclopentadienyl]titaniurn trichloride,
[l-tris(3 5-di-n-hexylphenyl)silyl-2-sec-butylcyclopentadienyl]titanium trichloride,
-tris(3 5-di-n-hexylphenyl)silyl-3-sec-butylcyclopentadienyl]titanium trichloride,
[l-tris(3 5-di-n-hexylphenyl)silyl-2-tert-butylcyclopentadienyl]titanium trichloride,
[l-tris(3 5-di■n-hexylphenyl)silyl-3-tert-butylcyclopentadienyl]titanium trichloride,
[l-tris(3 5-di-n-hexylphenyl)silyl-2-phenylcyclopentadienyl]titanium trichloride, [ 1 -tris(3 , 5 -di-n-hexy lpheny l)sily 1-3 -phenylcyclopentadienyljtitanium trichloride, [l-tris(3,5-di-n-hexylphenyl)silyl-2-benzylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-di-n-hexylphenyl)silyl-3-benzylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3 , 5-di-n-hexylphenyl)silyl-indenyl]titanium trichloride,
[l-tris(3,5-di-n-hexylphenyl)silyl-2-methyl indenyl]titanium trichloride,
[9-tris(3,5-di-n-hexylphenyl)silyl-fluorenyl]titanium trichloride,
[l-tris(3,5-di-n-hexylphenyl)silyl-tetrahydroindenyl]titanium trichloride,
[l-tris(3,5-di-n-hexylphenyl)silyl-2-methyltetrahydroindenyl]titanium trichloride,
[9-tris(3,5-di-n-hexylphenyl)silyl-octahydrofIuorenyl]titanium trichloride,
[0106]
[ 1 -n-butylmethyl(2,4,6-trimethylphenyl)silyl-cyclopentadienyl]titanium trichloride,
[ 1 -n-butylmethyl(2,4,6-trimethylphenyl)silyl-2-methylcyclopentadienyl]titanium trichloride, [ 1 -n-butylmethyl(2,4,6-trimethylphenyl)silyl-3 -methylcyclopentadienyl]titanium trichloride, [ 1 -n-butylmethyl(2,4,6-trimethylphenyl)silyl-2,3 -dimethylcyclopentadienyljtitanium 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-trirnethylphenyl)silyl-2,3,5-trimethylcyclopentadienyl]titanium trichloride,
[l-n-butylmethyl(2,4,6-trimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride,
[ 1 -n-butylmethyl(2,4,6-trimethylphenyl)silyl-2-ethylcyclopentadienyl]titanium trichloride,
[ 1 -n-butylmethyl(2,4,6-trimethylphenyl)silyl-3 -ethylcyclopentadienyl]titanium trichloride,
[ 1 -n-butylmethyl(2,4,6-trimethylphenyl)silyl-2-n-propylcyclopentadienyl]titanium trichloride, [l-n-butylmethyl(2,4,6-trimethylphenyl)silyl-3-n-propylcyclopentadienyl]titanium trichloride, [l-n-butylmethyl(2,4,6-trimethylphenyl)silyl-2-isopropylcyclopentadienyl]titanium trichloride, [l-n-butylmethyl(2,4,6-trimethylphenyl)silyl-3-isopropylcyclopentadienyl]titanium trichloride, [ 1 -n-butylmethyl(2,4,6-trimethylphenyl)silyl-2-n-butylcyclopentadienyl]titanium trichloride, [ 1 -n-butylmethyl(2,4,6-trimethylphenyl)silyl-3-n-butylcyclopentadienyl]titanium trichloride, [ 1 -n-butylmethyl(2,4,6-trimethylphenyl)silyl-2-sec-butylcyclopentadienyl]titanium trichloride, [l-n-butylmethyl(2,4,6-trimethylphenyl)silyl-3-sec-butylcyclopentadienyl]titanium trichloride, [ 1 -n-butylmethyl(2,4,6-trimethylphenyl)silyl-2-tert-butylcyclopentadienyl]titanium trichloride, [l-n-butylmethyl(2,4,6-trimethylphenyl)silyl-3-tert-butylcyclopentadienyl]titanium trichloride, [ 1 -n-butylmethyl(2,4,6-trimethylphenyl)silyl-2-phenylcyclopentadienyl]titanium trichloride, [ 1 -n-butylmethyl(2,4,6-trimethylphenyl)silyl-3 -phenylcyclopentadienyljtitanium trichloride, [ 1 -n-butylmethyl(2,4,6-trimethylphenyl)si ilyl-2-benzylcyclopentadienylJtitanium trichloride, [ 1 -n-butylmethyl(2,4,6-trimethy lpheny l)s ii lyl-3-benzylcyclopentadienylJtitanium trichloride, [ 1 -n-butylmethyl(2,4,6-trimethylphenyl)si ilyl-indenyijtitanium trichloride,
[ 1 -n-butylmethyl(2,4,6-trimethylphenyl)si ilyl-2-methyl indenyljtitanium trichloride,
[9-n-butylmethyl(2,4,6-trimethylphenyl)si ilyl-fluorenyljtitanium trichloride,
[ 1 -n-butylmethyl(2,4,6-trimethylphenyl)s iilyl-tetrahydroindenyljtitanium trichloride,
[ 1 -n-butylmethyl(2,4,6-trimethylphenyl)si ilyl-2-methyltetrahydroindenyl]titanium trichloride, [9-n-butylmethyl(2,4,6-trimethylphenyl)si ilyl-octahydrofluorenyl]titanium trichloride,
[0107]
[ 1 -n-butylmethy l(pentamethylphenyl)silyl -cyclopentadienyljtitanium trichloride,
[ 1 -n-butylmethyl(pentamethylphenyl)sily) -2-methylcyclopentadienyl]titanium trichloride, [ 1 -n-butylmethyl(pentamethylphenyl)silyl -3 -methyl cyclopentadienyljtitanium trichloride, [ 1 -n-butylmethyl(pentamethylphenyl)silyl -2,3-dimethylcyclopentadienylJtitanium trichloride, [ 1 -n-butylmethyl(pentamethylphenyl)sily] -2,4-dimethylcyclopentadienylJtitanium trichloride, [ 1 -n-butylmethyl(pentamethylphenyl)silyl -2, 5 -dimethylcyclopentadienyljtitanium trichloride, [ 1 -n-butylmethyl(pentamethylphenyl)silyl -2,3,5-trimethylcyclopentadienylJtitanium trichloride, [ 1 -n-butylmethyl(pentamethylphenyl)silyl -2,3,4,5 -tetramethy lcyclopentadieny 1 Jtitanium trichloride,
[l-n-butylmethyl(pentamethylphenyl)silyl [-2-ethylcyclopentadienyl]titanium trichloride,
[ 1 -n-butylmethyl(pentamethylphenyl)silyl [-3 -ethyl cyclopentadienyljtitanium trichloride,
[ 1 -n-butylmethyl(pentatnethylphenyl)silyl [-2-n-propylcyclopentadienylJtitanium trichloride, [ 1 -n-butylmethyl(pentamethylphenyl)silyl ί-3 -n-propylcyclopentadienyl]titanium trichloride, [ 1 -n-butylmethyl(pentamethylphenyl)silyl [-2-isopropylcyclopentadienyl]titanium trichloride, [ 1 -n-butylmethyl(pentamethylphenyl)silyl l-3-isopropylcyclopentadienyl]titanium trichloride, [ 1 -n-butylmethyl(pentamethylphenyl)silyl [-2-n-butylcyclopentadienyl]titanium trichloride, [ 1 -n-butylmethyl(pentamethylphenyl)silyl [-3 -n-butylcyclopentadieny l]titanium trichloride, [ 1 -n-butylmethyl(pentamethylphenyl)silyl -2-sec-butylcyc opentadienylJtitanium trichloride, [ 1 -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-butyl cyclopentadienyljtitanium trichloride, [ 1 -n-butyltnethy l(pentamethylphenyl)silyl -2-phenylcyclopentadienylJtitanium 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 -benzylcyclopentadienyljtitanium trichloride, 1 -n-butylmethyl(pentamethylphenyl)silyl-indenyl]titanium trichloride,
1 -n-butylmethyl(pentamethylphenyl)silyl-2-methyl indenyl]titanium trichloride,
L9-n-butylmethyl(pentamethylphenyl)silyl-fluorenyl]titanium trichloride,
: 1 -n-butylmethy l(pentamethylphenyl)silyl-tetrahydroindenyl]titanium trichloride,
1 -n-butylmethyl(pentamethylphenyl)silyl-2-methyltetrahydroindeny l]titanium trichloride,
^9-n-butylmethyl(pentamethylphenyl)silyl-octahydrofluorenyl]titanium trichloride,
;0108]
-(3,5-di-tert-butylphenyl)bis(3,5-dimethylphenyl)silyl-cyclopentadienyl]titanium trichloride, -(3,5-di-tert-butylphenyl)bis(3,5-dimethylphenyl)silyl-2-methylcyclopentadienyl]titanium
:richloride,
"l-(3,5-di-tert-butylphenyl)bis(3,5-dimethylphenyl)silyl-3-methylcyclopentadienyl]titanium :richloride,
;i-(3,5-di-tert-butylphenyl)bis(3,5-dimeth^
xichloride,
-(3,5-di-tert-butylphenyl)bis(3,5-dimethylphenyl)silyl-2,4-dimethylcyclopentadienyl]titanium xichloride,
1 -(3 , 5 -di-tert-butylphenyl)bi s(3 , 5 -dimethy Ipheny l)sily 1-2, 5 -dimethylcyclopentadieny IJtitanium :richloride,
~ 1 -(3, 5-di-tert-butylphenyl)bis(3 , 5-dimethylphenyl)silyl-2, 3,5- :rimethylcyclopentadienyl]titanium trichloride,
-(3,5-di-tert-butylphenyl)bis(3,5-dimethylphenyl)silyl-2,3,4,5- :etramethylcyclopentadienyl]titanium trichloride,
l-(3,5-di-tert-butylphenyl)bis(3,5-dimethylphenyl)silyl-2-ethylcyclopentadienyl]titanium :richloride,
-(3,5-di-tert-butylphenyl)bis(3,5-dimethylphenyl)silyl-3-ethylcyclopentadienyl]titanium xichloride,
-(3,5-di-tert-butylphenyl)bis(3,5-dimethylphenyl)silyl-2-n-propylcyclopentadienyl]titanium :richloride,
l-(3,5-di-tert-butylphenyl)bis(3,5-dimethylphenyl)silyl-3-n-propylcyclopentadienyl]titanium xichloride,
l-(3,5-di-tert-butylphenyl)bis(3,5-dimethylphenyl)silyl-2-isopropylcyclopentadienyl]titanium :richloride,
l-(3,5-di-tert-butylphenyl)bis(3,5-dimethylphenyl)silyl-3-isopropylcyclopentadienyl]titanium ;richloride, [l-(3,5-di-tert-butylphenyl)bis(3,5-dimethylphen^
trichloride,
[l-(3,5-di-tert-butylphenyl)bis(3,5-dimethylphenyI)silyl-3-n-butylcyclopentadienyl]titanium trichloride,
[l-(3,5-di-tert-butylphenyl)bis(3,5-dimethylphenyl)silyl-2-sec-butylcyclopentadienyl]titanium trichloride,
[l-(3,5-di-tert-butylphenyl)bis(3,5-dimethylphenyl)silyl-3-sec-butylcyclopentadienyl]titanium trichloride,
[l-(3,5-di-tert-butylphenyl)bis(3,5-dimethylphenyl)silyl-2-tert-butylcyclopentadienyl]titaniurn trichloride,
[l-(3,5-di-tert-butylphenyl)bis(3,5-dimethylphenyl)silyl-3-tert-butylcyclopentadienyl]titanium trichloride,
[l-(3,5-di-tert-butylphenyl)bis(3,5-dimethylphenyl)silyl-2-phenylcyclopentadienyl]titanium trichloride,
[l-(3,5-di-tert-butylphenyl)bis(3,5-dimethylphenyl)silyl-3-phenylcyclopentadienyl]titanium trichloride,
[l-(3,5-di-tert-butylphenyl)bis(3,5-dimethylphenyl)silyl-2-benzylcyclopentadienyl]titanium trichloride,
[ 1 -(3, 5-di-tert-butylphenyl)bis(3 , 5-dimethylphenyl)silyl-3 -benzy lcyclopentadienyl]titanium trichloride,
[l-(3,5-di-tert-butylphenyl)bis(3,5-dimethylphenyl)silyl-indenyl]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, [0109]
[ 1 -(3 , 5 -di-tert-butylphenyl)(3 , 5 -diethy lphenyl)(3 , 5 -dimethylphenyl) silyl- cyclopentadienyl]titanium trichloride,
[ 1 -(3, 5-di-tert-butylphenyl)(3 ,5-diethylphenyl)(3 , 5-dimethylphenyl)silyl-2- methylcyclopentadienyl]titanium trichloride,
[ 1 -(3 , 5 -di-tert-butylpheny 1)(3 , 5 -diethy lpheny 1)(3 , 5 -dimethylphenyl) silyl-3- methylcyclopentadienyljtitanium trichloride, [l-(3,5-di-tert-butylphenyl)(3,5-diethylphenyl)(3,5-dimethylphenyl)silyl-2,3- dimethylcyclopentadienyl]titanium trichloride,
[ 1 -(3 , 5 -di-tert-butylpheny 1)(3 , 5 -diethylpheny 1)(3 , 5 -dimethylphenyl) sily 1-2,4- dimethylcyclopentadienyljtitanium trichloride,
[ 1 -(3 , 5 -di-tert-butylpheny 1)(3 , 5 -diethy lphenyl)(3 , 5 -dimethylphenyl) silyl-2, 5 - dimethylcyclopentadienyl]titanium trichloride,
[ 1 -(3 , 5-di-tert-butylpheny 1)(3 , 5 -diethy lpheny 1)(3 , 5 -dimethylphenyl) silyl-2, 3 , 5 - trimethylcyclopentadienyl]titanium trichloride,
[ 1 -(3 , 5 -di-tert-butylpheny 1)(3 , 5 -diethylpheny 1)(3 , 5 -dimethylphenyl) silyl-2, 3 , 4, 5 - tetramethylcyclopentadienyljtitanium trichloride,
[ 1 -(3 , 5 -di-tert-butylpheny 1)(3 , 5 -diethylpheny 1)(3 , 5 -dimethylphenyl) silyl-2- ethylcyclopentadienyl]titanium trichloride,
[l-(3,5-di-tert-butylphenyl)(3,5-diethylphenyl)(3,5-dimethylphenyl)silyl-3- ethylcyclopentadienyl]titanium trichloride,
[ 1 -(3 , 5 -di-tert-butylpheny 1)(3 , 5 -diethy lpheny 1)(3 , 5 -dimethylphenyl) sily 1-2 -n- propylcyclopentadienyl]titanium trichloride,
[ 1 -(3 , 5 -di-tert-butylpheny 1)(3 , 5 -diethy lpheny 1)(3 , 5 -dimethylphenyl) sily 1-3 -n- propylcyclopentadienyl]titanium trichloride,
[ 1 -(3 , 5 -di-tert-butylpheny 1)(3 , 5 -diethy lpheny 1)(3 , 5 -dimethylphenyl)sily 1-2- isopropylcyclopentadienyl]titanium trichloride,
[ 1 -(3 , 5 -di-tert-butylpheny 1)(3 , 5 -diethy lpheny 1)(3 , 5 -dimethylphenyl) silyl-3 - isopropylcyclopentadienyl]titanium trichloride,
[ 1 -(3 , 5 -di-tert-butylpheny 1)(3 , 5 -diethy lpheny 1)(3 , 5 -dimethylphenyl) sily 1-2-n- butylcyclopentadienyl]titanium trichloride,
[ 1 -(3,5-di-tert-butylphenyl)(3, 5-diethylphenyl)(3 , 5-dimethylphenyl)silyl-3-n- butylcyclopentadienyljtitanium trichloride,
[ 1 -(3 , 5 -di-tert-butylpheny 1)(3 , 5 -diethy lpheny 1)(3 , 5-dimethylphenyl) sily 1-2-sec- butylcyclopentadienyljtitanium trichloride,
[ 1 -(3, 5-di-tert-butylphenyl)(3 , 5 -diethy lpheny 1)(3 , 5-dimethylphenyl)silyl-3 -sec- butylcyclopentadienyl]titanium trichloride,
[ 1 -(3, 5 -di-tert-butylpheny 1)(3 , 5 -diethylpheny 1)(3 , 5 -dimethylphenyl) silyl-2-tert- butylcyclopentadienyljtitanium trichloride,
[ 1 -(3 , 5 -di-tert-butylpheny 1)(3 , 5 -diethy lpheny 1)(3 , 5 -dimethylphenyl) silyl-3 -tert- butylcyclopentadienyljtitanium trichloride, [ 1 -(3 , 5 -di-tert-butylphenyl)(3 , 5 -diethy lpheny 1)(3 , 5 -dimethylphenyl)silyl-2- phenylcyclopentadienyljtitanium trichloride,
[ 1 -((3 , 5 -di-tert-buty lpheny 1)(3 , 5 -diethy lpheny 1)(3 , 5 -dimethylphenyl) sily 1-3 - phenylcyclopentadienyljtitanium trichloride,
[l-(3,5-di-tert-butylphenyl)(3,5-diethylphenyl)(3,5-dimethylphenyl)silyl-2- benzylcyclopentadienyl]titanium trichloride,
[ 1 -(3 , 5 -di-tert-butylphenyl)(3 , 5 -diethy lphenyl)(3 , 5 -dimethylphenyl) sily 1-3 - benzylcyclopentadienyl]titanium trichloride,
[l-(3,5-di-tert-butylphenyl)(3,5-diethylphenyl)(3,5-dimethylphenyl)silyl-indenyl]titanium trichloride,
[ 1 -(3 , 5 -di-tert-butylphenyl)(3 , 5 -diethy lphenyl)(3 , 5 -dimethylphenyl) silyl-2-methyl indenyljtitanium trichloride,
[9-(3 , 5 -di-tert-butylpheny 1)(3 , 5 -diethy lphenyl)(3 , 5 -dimethylphenyl) silyl-fluorenyl] titanium trichloride,
[ 1 -(3 , 5 -di-tert-buty lpheny 1)(3 , 5 -diethy lpheny 1)(3 , 5 -dimethylphenyl) sily 1- tetrahydroindenyl]titanium trichloride,
[ 1 -(3 , 5 -di-tert-butylpheny 1)(3 , 5 -diethy lpheny 1)(3 , 5 -dimethylphenyl) sily 1-2- methyltetrahydroindenyl]titanium trichloride,
[9-(3 , 5 -di-tert-butylpheny 1)(3 , 5 -diethy lphenyl)(3 , 5 -dimethylphenyl) sily 1- octahydrofluorenyl]titanium trichloride,
[0110]
[ 1 -tris(3 , 5-diphenylphenyl)silyl-cyclopentadienyl]titanium trichloride,
[l-tris(3,5-diphenylphenyl)silyl-2-methylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-diphenylphenyl)silyl-3-methylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3 , 5 -diphenyiphenyl)silyl-2,3 -dimethylcyclopentadienyljtitanium trichloride,
[l-tris(3,5-diphenylphenyl)silyl-2,4-dimethylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-diphenylphenyl)silyl-2j5-dimethylcyclopentadienyl]titanium trichloride,
[l-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-dipheny lphenyl)silyl-3 -ethyl cyclopentadienyl]titanium trichloride,
[ 1 -tris(3 , 5-diphenylphenyl)silyl-2-n-propylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-diphenylphenyl)silyl-3-n-propylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3 , 5-diphenylphenyl)silyl-2-isopropylcyclopentadienyl]titanium trichloride, -tris(3,5-diphenylphenyl)silyl-3-isopropylcyclopentadienyl]titanium trichloride, -tris(3,5-diphenylphenyl)silyl-2-n-butylcyclopentadienyl]titanium trichloride, l-tris(3,5-diphenylphenyl)silyl-3-n-butylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3 , 5 -dipheny lphenyl)silyl-2-sec-butylcyclopentadieny l]titanium trichloride, 1 -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, l-tris(3,5-diphenylphenyl)silyl-2-phenylcyclopentadienyl]titanium trichloride, l-tris(3,5-diphenylphenyl)silyl-3-phenylcyclopentadienyl]titanium trichloride,i-tris(3,5-diphenylphenyl)silyl-2-benzylcyclopentadienyl]titanium trichloride, l-tris(3,5-diphenylphenyl)silyl-3-benzylcyclopentadienyl]titanium trichloride, l-tris(3,5-diphenylphenyl)silyl-indenyl]titanium trichloride,
l-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,
9-tris(3 , 5 -diphenylphenyl)silyl-octahydrofluorenyl]titanium trichloride,
0111]
[ 1 -tris(3 , 5-dibenzylphenyl)silyl-cyclopentadienyl]titanium trichloride,
l-tris(3,5-dibenzylphenyl)silyl-2-methylcyclopentadienyl]titanium trichloride,
1 -tris(3 , 5-dibenzylphenyl)silyl-3 -methylcyclopentadieny l]titanium trichloride, l-tris(3,5-dibenzylphenyl)silyl-2,3-dimethylcyclopentadienyl]titanium trichloride, 1 -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, 1 -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, l-tris(3,5-dibenzylphenyl)silyl-3-n-propylcyclopentadienyl]titanium trichloride, l-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, [ 1 -tris(3 , 5-dibenzylphenyl)silyl-2-sec-butylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3,5-dibenzylphenyl)silyl-3-sec-butylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-dibenzylphenyl)silyl-2-tert-butylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3 , 5-dibenzylphenyl)silyl-3 -tert-butylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3, 5-dibenzylphenyl)siIyl-2-phenylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-dibenzylphenyl)silyl-3-phenylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-dibenzylphenyl)silyl-2-benzylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3 , 5-dibenzylphenyl)silyl-3 -benzylcyclopentadienyl]titanium trichloride,
[ 1 -tris(3 , 5-dibenzylphenyl)silyl-indenyl]titanium trichloride,
[l-tris(3,5-dibenzylphenyl)silyl-2-methyl indenyl]titanium 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]titanium trichloride,
[9-tris(3,5-dibenzylphenyl)silyl-octahydrofluorenyl]titanium trichloride;
[0112]
a chlorinated zirconium compound in which "titanium" is substituted with "zirconium" in the above-mentioned compound;
a chlorinated hafnium compound in which "titanium" is substituted with "hafnium" in the above- mentioned compound;
a fluorinated titanium compound in which "chloride" is substituted with "fluoride" in the above- mentioned compound;
a brominated titanium compound in which "chloride" is substituted with "bromide" in the above- mentioned compound;
an iodinated titanium compound in which "chloride" is substituted with "iodide" in the above- mentioned compound;
a hydrogenated titanium compound in which "chloride" is substituted with "hydride" in the above-mentioned compound;
a methylated titanium compound in which "chloride" is substituted with "methyl" in the above- mentioned compound;
a phenylated titanium compound in which "chloride" is substituted with "phenyl" in the above- mentioned compound;
a benzylated titanium compound in which "chloride" is substituted with "benzyl" in the above- mentioned compound;
a methoxidated titanium compound in which "chloride" is substituted with "methoxide" in the above-mentioned compound;
a n-butoxylated titanium compound in which "chloride" is substituted with "n-butoxide" in the above-mentioned compound;
an isopropoxylated titanium compound in which "chloride" is substituted with "isopropoxide" in the above-mentioned compound;
a phenoxyiated titanium compound in which "chloride" is substituted with "phenoxide" in the above-mentioned compound;
a benziloxidated titanium compound in which "chloride" is substituted with "benziloxide" in the above-mentioned compound;
a dimethylamidated titanium compound in which "chloride" is substituted with "dimethylamide" in the compound; and
a diethylamidated titanium compound in which "chloride" is substituted with "diethylamide" in the above-mentioned compound.
[0113]
Furthermore, examples of the compounds represented by formula (1) also include a compound in which a silicon atom is substituted with a carbon atom in the above-mentioned compound.
[0114]
Preferable examples of the compounds represented by formula (1) include [1- dimethylphenylsilyl-3 -trimethylsilylcyclopentadienyl]titanium trichloride,
[l-tris(3,5-dimethylphenyl)silyl-3-trimethylsilylcyclopentadienyl]titanium trichloride,
[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,
[l-methyl(n-octadecyl)phenylsilyl-2,3,4,5-tetramethylcyclopentadienyl]titanium 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-tetramethylcyclopentadienyl]titanium trichloride, [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,
[ 1 -methyl di(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- tetramethylcyclopentadienyljtitanium trichloride.
[0115]
Examples of process for producing the compound represented by formula (1) include a process described in Organometallics 2002, 21, 5122-5135.
[0116]
Furthermore, examples of a process for producing the compound represented by formula (1) include a process 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.
0117]
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 R11 res ectivel in formula (1-2),
Figure imgf000054_0002
wherein M , X , X and X have the same meanings as in M , X , X and X , respectively, in formula (1), and Xu represents a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbyloxy group, a substituted hydrocarbyloxy group, a substituted sily group, or a disubstituted amino group, and n represents 0 or 1.
[0118]
In formula (7), the meanings of the groups to be used in Rl, R2, R3, R4, R5, R6, R7, R8, R9, R10, and R11, the examples of groups, and the preferable groups are the same as in the meanings of the groups, the examples of groups, and the preferable groups described in formulae
(1) and (1-2).
[0119]
In formula (8), the meanings of the groups to be used in M1, X1, X2 and X3, the examples of groups, and the preferable groups are the same as in the meanings of the groups, the examples of groups, and the preferable groups described in formula (1).
[0120]
Xu 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 as X'in formula (1).
[0121]
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 followin constitutional isomers.
Figure imgf000055_0001
the compound represented by formula (7) has isomers whose positions of the double bonds of each cyclopentadienyl ring are different from each other. In the present invention, formula (7) shows any one of them or a mixture of them.
[0122]
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.
[0123]
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, trimethylsilylmethyllithium, vinyllithium, phenyllithium, and allyllithium.
[0124]
The amount of the base to be used is in the range from 0.5 mol to 10 mol with respect to 1 mol of the substituted cyclopentadienyl compound (7).
[0125]
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 amine compounds 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.
[0126]
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 reacted with the reaction product of the substituted cyclopentadiene compound (7) and the base. Note here that in a reaction solution obtained by allowing the substituted
cyclopentadiene compound (7) and the base to be reacted with each other, a solid may be precipitated. 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 is added to the separated solid so that the precipitated solid is dissolved or suspended, and then the transition metal compound (8) may be added. 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.
[0127]
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 reaction in these steps, is used. Examples of such a solvent to be used include aprotic compounds including aromatic hydrocarbon such as benzene and toluene; aliphatic hydrocarbon such as hexane and heptane; ether compounds such as diethyl ether, tetrahydrofuran and 1,4- dioxane; amide compounds such as hexamethylphosphoric amide and dimethylformamide; polar compounds such as acetonitrile, propionitrile, acetone, diethyl ketone, methyl isobutyl ketone, and cyclohexanone; 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).
[0128]
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).
[0129]
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.
[0130]
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.
Furthermore, in the compound represented by formula (1) in which a part or all of X1, X2 and X3 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 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 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.
[0132]
The above-mentioned substituted cyclopentadiene compound (7) can be produced by a step 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 a step of 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)").
[0133]
Figure imgf000058_0001
wherein R8, R9, R10 and Ru have the same meanings as in R8, R9, R10 and R11, respectively, in formula (1-2), a compound represented by formula:
Figure imgf000058_0002
is any of the following compounds or a mixture thereof,
Figure imgf000059_0001
Figure imgf000059_0002
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.
[0134]
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.
[0135]
Examples of the substituted cyclopentadiene compound (9) include methylcyclopentadiene, 1,2-dimethylcyclopentadiene, 1,3-dimethylcyclopentadiene, 1,2,3- trimethylcyclopentadiene, 1,2,4-trimethylcyclopentadiene, 1,2,3,4-tetramethylcyclopentadiene, ethylcyclopentadiene, 1,2-diethylcyclopentadiene, 1,3-diethylcyclopentadiene, 1,2,3- triethylcyclopentadiene, 1,2,4-triethylcyclopentadiene, 1,2,3,4-tetraethylcyclopentadiene, n- propylcyclopentadiene, isopropylcyclopentadiene, n-butylcyclopentadiene, sec- butylcyclopentadiene, tert-butylcyclopentadiene, n-pentylcyclopentadiene,
neopentylcyclopentadiene, n-hexyl cyclopentadiene, n-octylcyclopentadiene,
phenylcyclopentadiene, naphthylcyclopentadiene, trimethylsilylcyclopentadiene,
triethylsilylcyclopentadiene, and tert-butyldimethylsilylcyclopentadiene.
[0136]
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. [0137]
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).
[0138]
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, difluoroaniline, trichloroaniline, tribromoaniline,
trifiuoroaniline, 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, isobutylaniline, t-butylaniline, dimethylaniline, 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.
[0139]
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.
[0140]
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).
[0141]
In the reaction between the substituted cyclopentadiene compound (9) and the base, the substituted cyclopentadiene compound (9), the base, and an 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.
[0142]
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.
[0143]
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.
[0144]
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 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, dimethyl acetamide, 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) which has been used for preparation of the reaction product of the substituted cyclopentadiene compound (9) and the base.
[0145]
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 a base, an 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 a base, an 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.
[0146]
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 phase and an aqueous phase, and a solution containing the substituted cyclopentadiene compound (7) is obtained as the organic phase. When a solvent is removed from the organic phase by a known method, the substituted cyclopentadiene compound (7) can be obtained.
[0147]
Examples of the complex (I) used in Step 1 further include compounds represented by formula (2-1) or formula (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 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;
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.
[0148]
Figure imgf000063_0001
wherein M2 represents a transition metal atom of Group 4 of the periodic table of the elements; A represents a nitrogen atom or a phosphorus atom;
Z is a group linking A to N, and the number of the shortest bonds linking A to N is 4 to 6;
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 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.
[0149]
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.
[0150]
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).
[0151]
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.
[0152]
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. A trimethylsilyl group, a triethylsilyl group, a triphenylsilyl 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.
[0153]
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 bound to a nitrogen atom is 2 to 20, and more preferably 2 to 10.
[0154]
Two or more of R21, R22, R23, R24, and R25 may be bonded to each other to form a ring together with the carbon atoms on a benzene ring to which R21 to R24 are bonded, or the carbon atom may form a ring together with the 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.
[0155]
R21 is preferably a phenyl group, an a-cumyl group, a tert-butyl group, or a 1- adamanthyl group, and more preferably a 1-adamanthyl group.
[0156]
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.
[0157]
R22, R24, and R25 are more preferably a hydrogen atom.
[0158]
X4 is more preferably a halogen atom or an alkyl group, and further preferably a chlorine atom, a bromine atom, or a methyl group.
[0159]
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.
[0160]
R26 represents a hydrogen atom, a halogen atom, a hydrocarbyl group, a substituted hydrocarbyl group, a hydrocarbylidene group, or a substituted hydrocarbyl idene 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).
[0161]
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. [0162]
In R26, the number of 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.
[0163]
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.
[0164]
R26 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.
[0165]
R27 and R28 each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, or 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).
[0166]
In R and R , the number of carbon atoms of a hydrocarbyl group and a substituted hydrocarbyl group is preferably 1 to 10, and more preferably 1 to 5.
[0167]
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.
[0168]
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.
[0169]
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.
[0170]
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 A21 to Z1 may be a double bond. Z2 is a group linking A22 to N, and the number of the shortest bonds linking A22 to N is 4 to 6. The number of the shortest bonds is defined by a method described in WO2009-005003.
[0171]
Examples of Z1 and Z2 include a group for forming a structure represented by the following substructure formula (2-3) by combining the following A21 and N, or a group for forming a structure represented by the following substructure formula (2-4) by combining the following A22 and N:
Figure imgf000067_0001
wherein A and A have the same meanings as in A 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, and R31 and R32 may be bonded to each other to form a ring together with the carbon atom to which R is bonded and the carbon atom to which R is bonded, and R and R34 be bonded to each other to form a ring together with the carbon atom to which R33 is bonded and the carbon atom to which R34 is bonded, and R34 and R26 bonded to A21 may be bonded to each other to form a ring together with A21, and R34 and R28 bonded to A22 may be bonded to each other to form a ring together with A22.
[0172]
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 as R1 described in formula (1).
[0173]
In R , R , R , and R , the number of 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. [0174]
A ring formed by bonding R31 to R32, a ring formed by bonding R33 to R34, 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.
[0175]
Examples of a process for producing the compound represented by formula (2-1) or formula (2-2) include the process described in WO2009/005003.
[0176]
Examples of the compound represented by formula (2-1) or formula (2-2) include the following compounds.
Figure imgf000068_0001
Figure imgf000068_0002
Figure imgf000068_0003
Figure imgf000069_0001
Figure imgf000070_0001
Examples of preferable compounds represented by formula (2-1) or formula (2-2) include a compound represented by formula (2-a) or formula (2-b):
Figure imgf000071_0001
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;
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 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;
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
R41, R42, R43, R44, R45, R46, R47 and R48 each represent a hydrogen atom and a hydrocarbyl group, 0178]
Figure imgf000071_0002
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;
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 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;
R27 and R28 represent a hydrogen atom, a halogen atom, a hydrocarbyl group, and a substituted hydrocarbyl group;
R41, R42, R43, R44, R45, R46, R47 and R48 each represent a hydrogen atom and a hydrocarbyl group.
[0179]
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).
[0180]
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).
[0181]
The definition, the examples and the preferable atoms and groups of R21, R22, R23, 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).
[0182]
The definitions, examples and preferable groups of R , R and R 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).
[0183]
R41, R42, R43, R44, R45, R46, R47 and R48 in formula (2-a) and formula (2-b) represent a hydrogen atom, and 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.
[0184]
(Activating co-catalyst Component)
As an activating co-catalyst component in step 1, for example, at least one compound selected from the compound group consisting of an organic aluminum oxy
compound, a boron compound, and an organic aluminum compound.
[0185] Examples of the organic aluminum oxy compound include cyclic aluminoxane having a structure represented by formula:
Figure imgf000073_0001
,wherein, a represents an integer of 2 or more; and E1 represents a hydrocarbyl group having 1 to 8 carbon atoms, and a plurality of E1 may be the same as each other or different from each other, and linear aluminoxane having a structure represented by formula: E2{-Al(E2)-0-}bAlE2 2, wherein, b represents an integer of 1 or more; and E2 represents a hydrocarbyl group having 1 to 8 carbon atoms, and a plurality of E2 may be the same as each other or different from each other. As the organic aluminum oxy compound, one or more of these compounds are used.
[0186]
Examples of E1 and E2 include an alkyl group 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. Cyclic aluminoxane in which E1 is a methyl group or an isobutyl group and a is 2 to 40, and linear aluminoxane in which E2 is a methyl group or an isobutyl group, and b is 1 to 40 are preferable.
[0187]
The above-mentioned aluminoxane is produced by a known process. Examples of the process include a production process involving bringing a solution in which trialkyl aluminum (for example, trimethyl aluminum) is dissolved in an organic solvent (benzene, aliphatic hydrocarbyl, and the like) and water into contact with each other. Examples also include a production process involving bringing trialkyl aluminum (for example, trimethyl aluminum) into contact with a metallic salt (for example, copper sulfate hydrate) containing water of crystallization.
[0188]
As the boron compound, one or more boron compounds selected from the compound group consisting of the following compounds (B 1) to (B3) can be used:
(Bl): a boron compound represented by formula: BQ'Q2Q3
(B2): a borate compound represented by formula: T+(BQ4Q5Q6Q7)" (B3): a borate compound represented by formula: (L-H)+(BQ8Q9Q10QU)" wherein, B represents a trivalent boron atom, Q1, Q2, Q3, Q4, Q5, Q6, Q7, Q8, Q9, Q10 and Qu each represents a halogen atom, a 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 Broensted acid.
[0189] In the compounds (Bl) to (B3), preferable examples of Q1, Q2, Q3, Q4, Q5, Q6, Q7, Q8, Q9, Q10 and Qu 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 (BQ Q5Q6Q7)" and (BQ8Q9Q10Qn)" include tetrakis(pentafluorophenyl)borate, tetrakis(2, 3,5,6- tetrafluorophenyl)borate, tetrakis(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, N,N-dialkylanilinium, dialkylammonium, and triarylphosphonium.
[0190]
Examples of the boron compound (Bl) represented by formula: BQ Q2Q3 include tris(pentafiuorophenyl)borane, tri s(2, 3 , 5 , 6-tetrafiuoropheny l)borane, tris(2, 3 , 4, 5 - tetrafluorophenyl)borane, tris(3,4,5-trifluorophenyl)borane, tris(2,3,4-trifluorophenyl)borane, and phenyl-bis(pentafiuorophenyl)borane.
[0191]
Examples of the borate compound (B2) represented by formula: T+(BQ4Q5Q6Q7)" include ferrocenium tetrakis(pentafluorophenyl)borate, Ι,Γ-bis-trimethylsilylferrocenium tetrakis(pentafluorophenyl)borate, silver tetrakis(pentafiuorophenyl)borate, triphenyl
methyltetrakis(pentafluorophenyl)borate, and triphenyl methyltetrakis(3,5-bis- trifiuoromethylphenyl)borate.
[0192]
Examples of the borate compound (B3) represented by formula: (L- H)+(BQ8Q9Q10Quy 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(pentafiuorophenyl)borate, dicyclohexylammonium tetrakis(pentafluorophenyl)borate, triphenylphosphonium
tetrakis(pentafluorophenyl)borate, tri(methylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, and tri(bis-trimethylsilylphenyl)phosphonium
tetrakis(pentafluorophenyl)borate.
[0193]
Examples of the organic aluminum compound include a compound represented by formula: E3 CA1X'3-C, wherein c represents a number satisfying 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 groups exist, the E3 groups may be the same as each other or different from each other; and when more than one X groups exist, the X groups may be the same as each other or different from each other. As the organic aluminum compound, one or more of these compounds are used.
[0194]
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, triethylaluminum and triisobutylaluminum are more preferable.
[0195]
(Contact of Complex and Activating Co-catalyst Component)
Examples of a method for bringing a complex and an activating co-catalyst component into contact with each other in step 1 include a method mixing the complex with the acticating co-catalyst component, in the absence of ethylene, in a solvent. Examples of the solvent include saturated aliphatic hydrocarbon such as butane, pentane, hexane, heptane, and octane; and aromatic hydrocarbon such as toluene and xylene. The boiling point of the solvent is preferably 100°C or lower, more preferably 80°C or lower, and further preferably 65°C or lower.
[0196]
When an organic aluminum oxy compound and/or an organic aluminum compound are used as an activating co-catalyst component, the total amount to be used of the organic aluminum oxy compound and the organic aluminum compound is usually 0.1 mol to 10000 mol, and preferably 1 mol to 2000 mol on the basis of aluminum atom of the total amount of the organic aluminum oxy compound and the organic aluminum compound with respect to 1 mol of a transition metal atom of a complex for ethylene oligomerization. When a boron compound is used as the activating co-catalyst component, the amount of the boron compound to be used is usually 0.1 mol to 100 mol and preferably 0.5 mol to 10 mol with respect to 1 mol of a transition metal atom of a complex for ethylene oligomerization.
[0197]
When the complex and the activating co-catalyst component are brought into contact with each other in a solvent, the concentration of the complex and the concentration of the activating co-catalyst component in the solvent are each usually 0.01 mmol/1 to 300 mmol/1, preferably 0.03 mmol/1 to 100 mmol/1, and more preferably 0.05 mmol 1 to 50 mmol/1.
[0198]
The temperature at which the complex and the activating co-catalyst component are brought into contact with each other is usually -100°C to 200°C, preferably -50°C to 150°C, and more preferably 0°C to 100°C. In particular, at the initial time of reaction, the reaction is preferably carried out at a low temperature in order to suppress heat generation.
[0199]
The catalyst component (I) obtained by bringing the complex and the activating co-catalyst component into contact with each other can be stored by appropriate storage methods before it is used in step 2. Examples of the storage method include a method of storing the catalyst component (I) in a container filled with an inert gas.
[0200]
<Step 2>
(Catalyst Component (II) for Olefin Polymerization)
Examples of the catalyst component (II) for olefin polymerization include a catalyst component obtained by bringing a solid catalyst component containing titanium, magnesium and halogen into contact with an organic aluminum compound, and a catalyst component obtained by bringing a complex for olefin polymerization into contact with an activating co-catalyst component.
[0201]
Examples of the solid catalyst component containing titanium, magnesium and halogen include a solid catalyst component described in JP S63-142008 A, JP H5-339319 A, JP H6- 179720 A, JP H9-31119 A, JP HI 1 -228628 A, JP H11 -80234 A, and JP HI 1 -322833 A.
Furthermore, examples of the organic aluminum compound include a compound described in the activating co-catalyst component in step 1 mentioned above.
[0202]
Examples of a method for bringing the solid catalyst component containing titanium, magnesium and halogen into contact with the organic aluminum compound include a method mixing the solid catalyst component with the organic aluminum compound in a solvent. Examples of the solvent include saturated aliphatic hydrocarbon such as butane, pentane, hexane, heptane, and octane; and aromatic hydrocarbon such as toluene and xylene.
[0203]
The amount of the organic aluminum compound to be used for bringing the solid catalyst component containing titanium, magnesium and halogen into contact with the organic aluminum compound is usually 1 mol to 1000 mol and preferably 5 mol to 500 mol with respect to 1 mol of the titanium atom in the solid catalyst component.
[0204]
Examples of a complex for olefin polymerization include a compound represented by formula (11) or (12). Note here that olefin polymerization means the changing of olefin into a polymer, and 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.
0205]
Figure imgf000077_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 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.] 0206]
Figure imgf000078_0001
[wherein M4 represents a transition metal atom of Group 4 of the periodic table of the elements; Cp2 and Cp3 each 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.]
[0207]
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.
[0208]
Examples of the group having a cyclopentadiene-type anionic skeleton of Cp1, Cp2 and Cp3 and A2 include a ri5-cyclopentadienyl group, a r|5-methylcyclopentadienyl group, a ri5-tert-butylcyclopentadienyl group, a r|5-tetramethylcyclopentadienyl group, a r|5-indenyl group, a ri5-fluorenyl group, and a η5-azulenyl group.
[0209]
Examples of J2 include -SiR2-, -CR2-, -SiR2SiR2-, -CR2CR2-, -CR=CR-, - CR2SiR2-, or -GeR2-. Herein, R represents a hydrogen atom, a hydrocarbyl group having less than 20 carbon atoms, a halogenated hydrocarbyl group having less than 20 carbon atoms, or a group represented by -Si(R')3 having less 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 as each other or different from each other.
[0210]
Examples of the hydrocarbyl group having less 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-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 less 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 less 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.
[0211]
Preferable examples of J2 include -SiR2-, -C 2-, and -CR2CR2-. Furthermore, preferable examples of R include a hydrogen atom and a methyl group.
[0212]
In A2, examples of 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 include -0-, -S-, -NR-, -PR-, and groups represented by formulae (i) to (iv). Herein, R represents a hydrogen atom, a hydrocarbyl group having less than 20 carbon atoms, a halogenated hydrocarbyl group having less than 20 carbon atoms, or a group represented by -Si(R")3 having less 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 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 substituent bonded to the two carbon atoms may form a ring together with the two carbon atoms to which the substituents are bonded.
0213]
Figure imgf000080_0001
[0214]
Examples of the hydrocarbyl group having less 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 less 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 less 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 tncyclohexylsilyl 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.
[0215]
In A2, examples of 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, 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, and a phenyl group.
[0216]
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.
[0217]
Examples of X 5, X6, X7, X8, and a hydrocarbyl group of the substituent 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 carbon atoms of the hydrocarbyl group is preferably 1 to 20.
[0218]
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 a methyl group, an ethyl group, an isopropyl group, a tert-butyl group and an amyl group.
[0219]
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-tetradecylphenyl 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.
[0220]
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.
[0221]
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.
[0222]
Examples of the halogenated alkyl group include a fluoromethyl group, a difluoromethyl group, a tnfluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, a dibromomethyl group, a tribromomethyl group, an iodomethyl group, a diiodomethyl group, a triiodomethyl group, a fluoroethyl 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 perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, a perfluorohexyl group, a perfluorooctyl group, a
perfiuorododecyl group, a perfiuoropentadecyl 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 perbromo pentadecyl group, and a perbromoeicosyl group. The halogenated alkyl group is preferably a halogenated alkyl group having 1 to 20 carbon atoms.
[0223]
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.
[0224]
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. [0225]
Examples of X5, 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 1 to 20.
[0226]
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-icoxoxy 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.
[0227]
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-tetradecyl 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.
[0228]
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 a 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.
[0229]
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.
[0230]
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.
[0231]
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.
[0232]
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.
[0233]
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 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.
[0234]
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.
[0235]
Examples of the substituted silyl group include a monosubstituted silyl group having one 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 bound to a silicon atom in the above-mentioned groups are substituted with a halogen atom or a halogenated hydrocarbyl group; a disubstituted silyl group having two 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 bound to a silicon atom in the above- mentioned groups are substituted with a halogen atom and/or halogenated hydrocarbyl groups; and a trisubstituted silyl group having three 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-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 bound to a silicon atom in the above-mentioned groups are substituted with a halogen atom and/or halogenated hydrocarbyl groups. 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.
[0236]
Examples of X5, X6, X7, X8, and the disubstituted amino group of the substituent on the benzene ring of the groups represented by formulas (i) to (iv) include a group represented by -N(Rl5)2, wherein the two R15 groups each 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 groups are bonded.
[0237]
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 groups is preferably 2 to 20, and more preferably 2 to 10.
[0238]
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.
[0239]
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 the 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 the 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.
[0240]
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.
[0241]
Preferable examples of X5, X6, X7, and X8 include a halogen atom and a hydrocarbyloxy group having 1 to 20 carbon atoms.
[0242]
Examples of processes for producing the compounds represented by the above- mentioned formula (11) or (12) include processes described in JP H3-163088 A, JP H3-188092 A, JP H4-268307 A, JP H6-206890 A, and JP H9-87313 A.
[0243]
Examples of the compounds represented by the above-mentioned formula (11) or (12) include the following compounds.
[0244]
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 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:
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,
[0245]
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,
[0246]
diphenylmethylene(tert-butylamido)(cyclopentadienyl)titanium dichloride,
diphenylmethylene(cyclohexylamido)(cyclopentadienyl)titanium dichloride,
diphenylmethylene(phenylamido)(cyclopentadienyl)titanium dichloride,
diphenylmethylene(benzylamido)(cyclopentadienyl)titanium dichloride, diphenylmethylenel butylphosphido)(cyclopentadienyl)titanium dichloride,
diphenylmethylene(cyclohexylphosphido)(cyclopentadienyl)titanium dichloride,
diphenylmethylene(phenylphosphido)(cyclopentadienyl)titanium dichloride,
diphenylmethylene(benzylphosphido)(cyclopentadienyl)titanium dichloride,
[0247]
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,
[0248]
dimethylsilylene(tert-butylamido)(cyclopentadienyl)titanium dichloride, dimethylsilylene (cyclohexylamido)(cyclopentadienyl)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, [0249]
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,
diphenylsilyIene(benzylphosphido)(cyclopentadienyl)titanium dichloride,
[0250]
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;
[0251]
a compound in which titanium is changed to zirconium or hafnium in the above-mentioned compound; a compound in which cyclopentadienyl is changed to methylcyclopentadienyl, n- butylcyclopentadienyl, t-butylcyclopentadienyl, tetramethylcyclopentadienyl, indenyl or fluorenyl in the above-mentioned compound; a compound in which t-butylamide is changed to an oxygen atom or a sulfur atom in the above-mentioned compound; and a compound in which chloride is changed to bromide, iodide, hydride, methyl, phenyl, benzyl, methoxide, n-butoxide, isopropoxide, phenoxide, benzyloxide, dimethyl amide or diethyl amide in the above-mentioned compound.
[0252]
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,
[0253]
methylene(methylcyclopentadieny t)(3 , 5-dimethyl-2-phenoxy)titanium dichloride,
methylene(methylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride,
methylene(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,
[0254]
methy lene(tert-butylcyclopentadienyl)(3 , 5 -dimethy l-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, methylene(tert-butylcyclopentadienyl)(3 -phenyl-2-phenoxy)titanium dichloride, methylene(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, [0255]
methy lene(tetramethy lcyclopentadieny 1)(3 , -dimethy l-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,
[0256]
methylene(trimethylsilylcyclopentadienyl)(3 , 5-dimethyl-2-phenoxy)titanium dichloride, methylene(trimethylsilylcyclopentadienyl)(3-tert-butyI-2-phenoxy)titanium dichloride, methylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniuni dichloride, methylene(trimethylsilylcyclopentadienyl)(3-phenyl-2-phenoxy)titanium dichloride,
methylene(trimethylsilylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2- phenoxy)titanium dichloride, methylene(trimethylsilylcyclopentadienyl)(3-trimethylsilyl-5- methyl-2-phenoxy)titanium dichloride, methylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5- methoxy-2-phenoxy)titanium dichloride, methylene(trimethylsilylcyclopentadienyl)(3-tert-butyl- 5-chloro-2-phenoxy)titanium dichloride,
[0257]
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,
[0258]
isopropylidene(cyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride,
isopropylidene(cyc!opentadienyl)(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,
[0259]
i sopropylidene(methy Icy clopentadieny 1)(3 , 5 -dimethy l-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,
[0260]
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,
[0261]
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,
[0262]
isopropylidene(trimethylsilylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniuni dichloride, isopropylidene(trimethylsilylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, isopropyHdene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, isopropylidene(trimethylsilylcyclopentadienyl)(3-phenyl-2-phenoxy)titanium dichloride, isopropylidene(trimethylsilylcyclopentadienyl)(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,
[0263]
isopropylidene(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(fiuorenyl)(3-tert-butyl-5-chloro-2- phenoxy)titanium dichloride,
[0264]
diphenylmethylene(cyclopentadienyl)(3 , 5 -dimethyl-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,
[0265]
diphenylmethylene(methylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, diphenylmethylene(methylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, diphenylmethylene(methylcyclopentadienyl)(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- methyl-2-phenoxy)titanium dichloride, diphenylmethylene(methylcyclopentadienyl)(3-tert- butyl-5-methoxy-2-phenoxy)titanium dichloride, diphenylmethylene(methylcyclopentadienyl)(3- tert-butyl-5-chloro-2-phenoxy)titanium dichloride,
[0266]
diphenylmethylene(tert-butylcyclopentadienyl)(3,5-dimethyl-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, diphenyl methylene(tert-butylcyclopentadienyl)(3 -pheny l-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,
[0267]
diphenylmethylene(tetramethylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, diphenylmethylene(tetramethylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, diphenylmethylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-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)titaniuni dichloride, diphenylmethylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-chloro-2- phenoxy)titanium dichloride,
[0268]
diphenylmethylene(trimethylsilytcyclopentadienyl)(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)titanium dichloride, diphenylmethylene(trimethylsilylcyclopentadienyl)(3-tert-butyl -5-chloro-2- phenoxy)titanium dichloride,
[0269]
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; [0270]
a compound in which titanium is changed to zirconium or hafnium in the above- mentioned compound; a compound in which chloride is changed to bromide, iodide, hydride, methylphenyl, benzyl, methoxide, n-butoxide, isopropoxide, phenoxide, benzyloxide, dimethyl amide or diethyl amide in the above-mentioned compound; a compound in which
(cyclopentadienyl) is changed to (dimethylcyclopentadienyl), (trimethylcyclopentadienyl), (n- butylcyclopentadienyl), (tert-butyldimethylsilylcyclopentadienyl) or (indenyl); a compound in which 3,5-dimethyl-2-phenoxy in the above-mentioned compound is changed to 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 the above-mentioned compound; and a compound in which methylene is changed to diethyl methylene in the above-mentioned compound.
[0271]
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,
[0272]
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, dimethylsilylene(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, dimethylsilyiene(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,
[0273]
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,
[0274]
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, dimethylsilylene(tert-butylcyclopentadienyl)(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)titanium dichloride, dimethylsilylene(tert-butylcyclopentadienyl)(3 - tert-butyl-5-methoxy-2-phenoxy)titanium dichloride, dimethylsilylene(tert- butylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titanium dichloride,
dimethylsilylene(tert-butylcyclopentadienyl)(3,5-diamyl-2-phenoxy)titanium dichloride,
[0275] 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,
[0276]
dimethylsilylene(trimethylsilylcyclopentadienyl)(2-phenoxy)titanium dichloride,
dimethylsilylene(trimethylsilylcyclopentadienyl)(3-methyl-2-phenoxy)titaniuni dichloride, dimethylsilylene(trimethylsilylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, dimethylsilylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride, dimethyIsilyIene(trimethylsilylcyclopentadienyl)(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(trimethylsilylcyciopentadienyl)(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,
[0277]
dimethylsiiylene(indenyl)(2-phenoxy)titanium dichloride, dimethylsilylene(indenyl)(3-methyl-2- phenoxy)titanium dichloride, dimethylsilylene(indenyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, dimethylsilylene (indenyl)(3-tert-butyl-2-phenoxy)titanium dichloride,
dimethylsilylene(indenyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(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,
[0278]
dimethylsilylene(fluorenyl)(2-phenoxy)titanium dichloride, dimethylsilylene(fluorenyl)(3- methyl-2-phenoxy)titanium dichloride, dimethylsilylene(fluorenyl)(3,5-dimethyl-2- phenoxy)titanium dichloride, dimethylsilylene(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;
[0279]
a compound in which (cyclopentadienyl) is changed to (dimethylcyclopentadienyl),
(trimethylcyclopentadienyl), (ethylcyclopentadienyl), (n-propylcyclopentadienyl),
(isopropylcyclopentadienyl), (sec-butylcyclopentadienyl), (isobutylcyclopentadienyl), (tert- butyldimethylsilylcyclopentadienyl), (phenylcyclopentadienyl), (methylindenyl) or
(phenyhndenyl) in the above-mentioned compound; a compound in which 2-phenoxy is changed to 3-phenyl-2-phenoxy, 3-trimethylsilyl-2-phenoxy or 3-tert-butyldimethylsilyl-2-phenoxy in the above-mentioned compound; a compound in which dimethylsilylene is changed to
diethylsilylene, diphenylsilylene or dimethoxy silylene in the above-mentioned compound; a compound in which titanium is changed to zirconium or hafnium in the above-mentioned compound; and a compound in which chloride is changed to bromide, iodide, hydride, methylphenyl, benzyl, methoxide, n-butoxide, isopropoxide, phenoxide, benzyloxide, dimethylamide or diethylamide in the above-mentioned compound.
[0280] a compound represented by formula (11) in which A2 is a group having a cyclopentadiene-type anionic skeleton:
methylenebis(cyclopentadienyl)zirconium dichloride,
tsopropylidenebis(cyclopentadienyl)zirconium dichloride,
diphenylmethylenebis(cyclopentadienyl)zirconium dichloride, 1,2-ethylene- bis(cyclopentadienyl)zirconium dichloride, dimethylsilylenebis(cyclopentadienyl)zirconium dichloride, diphenylsilylenebis(cyclopentadienyl)zirconium dichloride, 1,2- tetramethyldisilylenebis(cyclopentadienyl)zirconium dichloride,
[0281]
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- tetramethyldisilylenebis(methylcyclopentadienyl)zirconium dichloride,
[0282]
methylenebis(n-butylcyclopentadienyl)zirconium dichloride, isopropylidenebis(n- butylcyclopentadienyl)zirconium dichloride, diphenylmethylene bis(n- butylcyclopentadienyl)zirconium dichloride, l,2-ethylene-bis(n- butylcyclopentadienyl)zirconium dichloride, dimethylsilylenebis(n- butylcyclopentadienyl)zirconium dichloride, diphenylsilylene bis(n- butylcyclopentadienyl)zirconium dichloride, 1 ,2-tetramethyldisilylenebis(n- butylcyclopentadienyl)zirconium dichloride,
[0283]
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, 1 ,2-tetramethyldisilylenebis(tert- butylcyclopentadienyl)zirconium dichloride,
[0284]
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- tetramethyldisilylenebis(tetramethylcyclopentadienyl)zirconium dichloride,
[0285]
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- tetramethyldisilylenebis(indenyl)zirconium dichloride,
[0286]
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- tetramethyldisilylenebis(fluorenyl)zirconium dichloride,
[0287]
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- tetramethyldisilylenebis(azulenyl)zirconium dichloride,
[0288]
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-azulenyi]zirconium dichloride, diphenylsilylenebis[2-ethyl-4-(2-fluoro-4-biphenylyl)-4H-azulenyl]zirconium dichloride, 1 ,2- tetramethyldisilylenebis[2-ethyl-4-(2-fluoro-4-biphenylyl)-4H-azulenyl]zirconium dichloride, [0289]
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, [0290]
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,
[0291]
methylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,
isopropylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride,
diphenylmethylene(cyclopentadieny l)(fluorenyl)zirconium dichloride, 1 ,2-ethylene- (cyclopentadienyl)(fluorenyl)zirconium dichloride,
dimethylsilylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,
diphenylsilylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, 1 ,2- tetramethyldisilylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,
[0292]
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)zirconium 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, 1 ,2-tetramethyldisilylene(3-tert-butyl-5- methylcyclopentadienyl)(3,6-di-tert-butylfluorenyl)zirconium dichloride;
[0293]
a compound in which zirconium is changed to hafnium or titanium in the above-mentioned compound; a compound in which cyclopentadienyl is changed to methylcyclopentadienyl, n- butylcyclopentadienyl, t-butylcyclopentadienyl, tetramethylcyclopentadienyl, indenyl or fluorenyl in the above-mentioned compound; and a compound in which chloride is changed to bromide, iodide, hydride, methyl, phenyl, benzyl, methoxide, n-butoxide, isopropoxide, phenoxide, benzyloxide, dimethylamide or diethylamide.
[0294]
Compounds 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,
[0295]
(cyclopentadienyl)(methylcyclopentadienyl)zirconium dichloride, (cyclopentadienyl)(n- butylcyclopentadienyl)zirconium dichloride, (cyclopentadienyl)(t- butylcyclopentadienyl)zirconium dichloride,
(cyclopentadienyl)(pentamethylcyclopentadienyl)zirconium dichloride,
(cyclopentadienyl)(indenyl)zirconium dichloride, (cyclopentadienyl)(fluorenyl)zirconium dichloride;
[0296]
a compound in which zirconium is changed to titanium or hafnium in the above-mentioned compound; a compound in which cyclopentadienyl is changed to methylcyclopentadienyl, n- butylcyclopentadienyl, t-butylcyclopentadienyl, tetramethylcyclopentadienyl, indenyl or fluorenyl in the above-mentioned compound; a compound in which chloride is changed to bromide, iodide, hydride, methyl, phenyl, benzyl, methoxide, n-butoxide, isopropoxide, phenoxide, benzyloxide, dimethylamide or diethyl amide in the above-mentioned compound.
[0297]
[Activating Co-catalyst Component]
As the activating co-catalyst component, for example, at least one compound selected from the group consisting of an organic aluminum oxy compound, a boron compound, and an organic aluminum compound is used. Examples of the organic aluminum oxy compound, the boron compound and the organic aluminum compound include compounds described as the activating co-catalyst component in step 1.
[0298] Furthermore, as the activating co-catalyst component that is to be brought into contact with the complex for olefin polymerization, a zinc compound can be used. Examples of the zinc compound include a zinc compound (a compound obtained by bringing dialkylzinc, fluorinated phenol, and water into contact with each other, a compound obtained by bringing dialkylzinc, fluorinated phenol, water, and silica into contact with each other, and the like) described in JP 2001-247612 A and WO 2002/051878.
[0299]
Examples of the zinc compound include a compound obtained by bringing the following component (a), component (b) and component (c), optionally, a carrier, into contact with each other.
(a) dialkylzinc
(b) fluorinated phenol
(c) H20
[0300]
Examples of dialkylzinc include dimethylzinc, diethylzinc, dipropylzinc, di-n- butylzinc, diisobutylzinc, and di-n-hexylzinc. Preferable example is dimethylzinc or diethylzinc.
[0301]
Examples of fluorinated phenol include 2-fluorophenol, 3 -fluorophenol, 4- fluorophenol, 2,4-difluorophenol, 2,6-difluorophenol, 3,4-difluorophenol, 3,5-difluorophenol, 2,4,6-trifluorophenol, 3,4,5-trifluorophenol, 2,3,5,6-tetrafluorophenol, and pentafiuorophenol. Preferable examples are 3,4,5-trifluorophenol and pentafiuorophenol.
[0302]
Preferably, in the amount of component (a), component (b) and component (c) to be used for preparing a zinc compound, y and z satisfy the following formula in which component (b) is y mol and component (c) is z mol with respect to 1 mol of component (a).
0 < |2 - y - 2z| < 1
Furthermore, y is preferably 0.01 to 1.99, more preferably 0.1 to 1.8, further preferably 0.2 to 1.5, and particularly preferably 0.3 to 1.
[0303]
The temperature at which component (a), component (b) and component (c) are brought into contact with each other is usually -100°C to 200°C, and preferably -80°C to 150°C. The contact time is usually 1 minute to 200 hours, and preferably 10 minutes to 100 hours.
Component (a), component (b) and component (c) are brought into contact with each other in a solvent. Examples of the solvent include di-n-butyl ether, methyl-tert-butyl ether, 1,4-dioxane, tetrahydrofuran, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-l- propanol, 3 -methyl- 1-butanol, and cyclohexanol, and preferable examples include
tetrahydrofuran, methanol, ethanol, 1-propanol or 2-propanol.
[0304]
Examples of a process for producing a catalyst component (Π) for olefin polymerization obtained by bringing the complex for olefin polymerization and the activating co-catalyst component into contact with each other include a process described in the below- mentioned step 3.
[0305]
The catalyst component (II) for olefin polymerization may be a catalyst component obtained by bringing the solid catalyst component containing titanium, magnesium and halogen, the organic aluminum compound and the carrier into contact with each other, or may be a catalyst component obtained by bringing the complex for olefin polymerization and the activating co-catalyst component and, in addition to the components, the carrier into contact with each other. Furthermore, the catalyst component (II) for olefin polymerization may be a component obtained by preliminary olefin polymerization in the presence of the catalyst component.
[0306]
[Mixture of Catalyst Component (I) Obtained in Step 1 and Catalyst Component (II) for Olefin Polymerization]
The catalyst component (I) obtained in step 1 and the catalyst component (Π) for olefin polymerization are mixed with each other in a solvent, an inert gas, or an olefin gas.
Examples of the solvent include saturated aliphatic hydrocarbon such as butane, pentane, hexane, heptane, and octane; and aromatic hydrocarbon such as toluene and xylene. Examples of the inert gas include a nitrogen gas, a helium gas, and an argon gas. Examples of the olefin gas include an ethylene gas. Preferably, the mixing is carried out in the presence of olefin.
Furthermore, when the catalyst component (I) and the catalyst component (Π) for olefin polymerization are mixed, an activating co-catalyst component may be further mixed.
[0307]
In the present invention, "the catalyst component (I) and the catalyst component (II) for olefin polymerization are mixed with each other" means that the catalyst component (I) and the catalyst component (II) for olefin polymerization are present together in a specific space such as inside of a container. Examples of preferable mixing state include a state in which the catalyst component (I) and the catalyst component (II) for olefin polymerization form a composition, and a state in which the catalyst component (I) and the catalyst component (II) for olefin polymerization are dispersed in a solvent or a polymerization medium (in a fluid bed when a gas phase polymerization reactor is used, or in a polymerization solvent when a solution polymerization reactor and a slurry polymerization reactor are used).
[0308]
The mixing ratio of the catalyst component (I) and the catalyst component (Π) for olefin polymerization is usually 0.001 to 100, preferably 0.01 to 50, more preferably 0.02 to 10, and further preferably 0.05 to 5 as a ratio of mol of a transition metal atom in the catalyst component (I) and mol of a transition metal atom in the catalyst component (II) for olefin polymerization (mol of a transition metal atom in the catalyst component (I) / mol of a transition metal atom in the catalyst component (II) for olefin polymerization).
[0309]
The temperature at which the catalyst component (I) and the catalyst component (II) for olefin polymerization are mixed is usually 0°C to 120°C, and preferably 10°C to 90°C.
[0310]
The catalyst component (I) and the catalyst component (II) for olefin polymerization may be previously mixed and then the mixture is supplied to a polymerization reactor, or the catalyst component (I) and the catalyst component (Π) for olefin polymerization may be supplied to a polymerization reactor separately, and they may be mixed in the
polymerization reactor.
[0311]
In mixing the catalyst component (I) and the catalyst component (Π) for olefin polymerization, the catalyst component (I) which has been dissolved or dispersed in an organic solvent and the catalyst component (II) for olefin polymerization may be mixed with each other, or the catalyst component (I) and the catalyst component (II) for olefin polymerization which has been dissolved or dispersed in an organic solvent may be mixed with each other, or the catalyst component (I) which has been dissolved or dispersed in an organic solvent and the catalyst component (II) for olefin polymerization which hase been dissolved or dispersed in an organic solvent may be mixed with other. Preferably, the catalyst component (I) is previously dissolved or dispersed in an organic solvent and then mixed with the catalyst component (II) for olefin polymerization. Preferable examples of the organic solvent include saturated aliphatic hydrocarbon such as butane, pentane, hexane, heptane, and octane. Furthermore, when the catalyst component (I) which has been dissolved or dispersed in an organic solvent and the catalyst component (Π) for olefin polymerization which has been dissolved or dispersed in an organic solvent are mixed with each other, an organic solvent in which the catalyst component (I) has been dissolved or dispersed is preferably a compound having high affinity with an organic solvent in which the catalyst component (Π) for olefin polymerization has been dissolved or dispersed, and is more preferably a compound that is the same as the organic solvent in which the catalyst component (Π) for olefin polymerization has been dissolved or dispersed.
[0312]
[Preparation Step of Catalyst Component (Π) for Olefin Polymerization]
(Step 3 and Step 4)
A process for producing a catalyst for producing an ethylenic polymer according to the present invention may include the step of preparing a catalyst component (II) for olefin polymerization. Examples of the step include a step including step 3, and a step including steps 3 and 4 mentioned below:
step 3: the step of bringing a complex for olefin polymerization and an activating co-catalyst component into contact with each other.
step 4: the step of prepolymerizing olefin in the presence of the catalyst component obtained in step 3.
[0313]
The complex for olefin polymerization and the activating co-catalyst component are brought into contact with each other by, for example, mixing the complex for olefin polymerization and the activating co-catalyst component in a solvent. Examples of the solvent include saturated aliphatic hydrocarbon such as butane, pentane, hexane, heptane, and octane; and aromatic hydrocarbon such as toluene and xylene. The mixing may be carried out in the presence of olefin.
[0314]
When the organic aluminum oxy compound and/or the organic aluminum compound are used, the total amount to be used of the organic aluminum oxy compound and the organic aluminum compound is usually 0.1 mol to 10000 mol and preferably 5 mol to 2000 mol on the basis of an aluminum atom of the total amount of the organic aluminum oxy compound and the organic aluminum compound with respect to 1 mol of a transition metal atom of the complex for olefin polymerization. When a boron compound is used, the amount of the boron compound to be used is usually 0.1 mol to 100 mol and preferably 0.5 mol to 10 mol with respect to 1 mol of the transition metal atom in the complex for olefin polymerization. When a zinc compound is used, the amount of the zinc compound to be used is usually 0.1 mol to 10000 mol and preferably 3 mol to 2000 mol on the basis of a zinc atom with respect to 1 mol of the transition metal atom in the complex for olefin polymerization.
[0315]
When the complex for olefin polymerization and the activating co-catalyst component are brought into contact with each other in a solvent, the concentration of the complex for olefin polymerization in the solvent and the concentration of the activating co- catalyst component in the solvent are each usually 0.001 mmol/1 to 100 mmol/1, preferably 0.05 mmol/1 to 50 mmol/1, and more preferably 0.1 mmol/1 to 30 mmol/1.
[0316]
The temperature at which the complex for olefin polymerization and the activating co-catalyst component are brought into contact with each other is usually 0°C to 80°C.
[0317]
In step 3, by using a carrier, the complex for olefin polymerization, the activating co-catalyst component and the carrier may be brought into contact with each other. The complex for olefin polymerization, the activating co-catalyst component and the carrier may be brought into contact with each other at the same time, or the components may be brought into contact with each other in an arbitrary order. For example, the complex for olefin
polymerization and the activating co-catalyst component may be brought into contact with each other, and the obtained component may be brought into contact with the carrier; or the complex for olefin polymerization and the carrier may be brought into contact with each other, and the obtained component may be brought into contact with the activating co-catalyst component; or the activating co-catalyst component and the carrier may be brought into contact with each other, and the obtained component may be brought into contact with the complex for olefin
polymerization. As mentioned above, as component (a), component (b), component (c) and the carrier are brought into contact with each other to prepare a zinc compound, the activating co- catalyst component and the carrier may be brought into contact with each other in the presence of the carrier to prepare an activating co-catalyst component.
[0318]
Furthermore, in step 3, two type or more of activating co-catalyst components may be used, and the same type of activating co-catalyst component may be used separately twice or more times. When two types or more of activating co-catalyst components are used (in this case, the two types of the activating co-catalyst components are defined as promoter component 1 and promoter component 2) and when the activating co-catalyst component is used separately twice or more times (in this case, the two separated aaivating co-catalyst components are defined as promoter component 1 and promoter component 2), examples of a method for bringing the complex for olefin polymerization, the activating co-catalyst component and the carrier into contact with each other include a method of bringing promoter component 1 and the carrier into contact with each other to prepare component (1), and bringing component (1) and the complex for olefin polymerization into contact with each other to prepare component (2), followed by bringing component (2) and promoter component 2 into contact with each other; and a method of bringing promoter component 1 and the carrier into contact with each other to prepare component (1), bringing the complex for olefin polymerization and promoter component 2 into contact with each other to prepare component (2), followed by bringing component (1) and component (2) into contact with each other.
[0319]
As a carrier, porous materials are used suitably, an inorganic material or an organic polymer is used more suitably, and an inorganic material is used further suitably.
[0320]
Examples of the inorganic material to be used for the carrier include inorganic oxide, clay, and clay mineral. One or more of them may be used.
[0321]
Examples of the inorganic oxide to be used for the carrier can include Si0 , 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. Note here that the above-mentioned inorganic oxide may contain a small amount of components of carbonate, sulfate, nitrate, and oxide, such as, Na2C03, K2C03, CaC03, MgC03, Na2S04, A12(S04)3, BaS04, KN03, Mg(N03)2, A1(N03)3, Na20, K20, and Li20.
[0322]
Furthermore, the inorganic oxide usually has a hydroxyl group on the surface thereof, and as the inorganic oxide, it is preferable to use modified inorganic oxide in which active hydrogen on the surface hydroxyl group is substituted with various substituents. The modified inorganic oxide can be obtained by bringing an inorganic oxide and a modifier into contact with each other, and examples of the modifier include trialkylchlorosilane such as trimethylchlorosilane and tert-butyldimethylchlorosilane, triarylchlorosilane such as
triphenylchlorosilane, dialkyldichlorosilane such as dimethyldichlorosilane, diaryldichlorosilane such as diphenyldichlorosilane, alkyltrichlorosilane such as methyltrichlorosilane,
aryltrichlorosilane such as phenyltrichlorosilane, trialkylalkoxysilane such as trimethylmethoxysilane, triarylalkoxysilane such as triphenylmethoxysilane,
dialkyldialkoxysilane such as dimmethyldimethoxysilane, diaryldialkoxysilane such as diphenyldimethoxysilane, alkyltrialkoxysilane such as methyltrimethoxysilane,
aryltrialkoxysilane such as phenyltrimethoxysilane, tetraalkoxysilane such as tetramethoxysilane, alkyldisilazane such as 1, 1, 1,3,3,3-hexamethyldisilazane and tetrachlorosilane.
[0323]
Examples of treatment for bringing the inorganic oxide and the modifier into contact with each other include a method of bringing inorganic oxide and tnalkylaluminum into contact with each other, followed by bringing the obtained product into contact with
dialkylamine (diethylamine, diphenylamine, and the like), alcohol (methanol, ethanol, and the like) or phenol.
[0324]
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.
[0325]
As the inorganic material, 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 is 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 a method for drying by heating include a method of drying by allowing an inert gas (for example, nitrogen, argon, or the like) obtained by drying while heating an inorganic material to flow at a constant flow rate, a method of heating by reducing pressure under reduced pressure, and the like.
[0326]
The average particle diameter of the inorganic material is usually 1 μηι to 5000 μπι, preferably 5 μπι to 1000 μπι, more preferably 10 μπι to 500 μιιι, 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. [0327]
The organic polymer can be obtained by polymerizing monomers having one or more polymerizable unsaturated groups. Examples of the monomer include ethylene, ot-olefin, an aromatic vinyl compound, and cyclic olefin. Specific 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 monomer is ethylene and styrene.
[0328]
The average particle diameter of the organic polymer is usually 1 μπι to 5000 μπι, preferably 5 μπι to 1000 μπι, and more preferably 10 μπι to 500 μηι. 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.
[0329]
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 a method for drying by heating include a method of drying by allowing an inert gas (for example, nitrogen, argon, or the like) obtained by dying while heating an organic polymer to flow at a constant flow rate, and a method of drying by heating under reduced pressure.
[0330]
The geometrical standard deviation of particles of the carrier on the basis of the volume is preferably 2.5 or less, more preferably 2 or less, and further preferably 1.7 or less.
[0331]
The step of preparing the catalyst component for olefin polymerization may include the above-mentioned step 4 of carrying out prepolymerization in the presence of a component in which the complex for olefin polymerization is brought into contact with the activating co-catalyst component or a component in which a complex for olefin polymerization, the activating co-catalyst component and the carrier into contact with each other. A
prepolymerization method is described below.
[0332]
[Prepolymerization] In the prepolymerization, a small amount of olefin is polymerized. Examples of the olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-l- pentene, cyclopentene, and cyclohexene. One or more of them are used. In the
prepolymerization, preferably, ethylene is homopolymerized or ethylene and oc-olefin are copolymerized. More preferably, ethylene is homopolymerized.
[0333]
The amount of the polymer produced by prepolymerization is usually 0.01 g to 1000 g, preferably 0.05 g to 500 g, more preferably 0.1 g to 200 g, and further preferably 5 g to 50 g with respect to 1 g of a catalyst component before the prepolymerization is carried out (for example, a catalyst component obtained by bringing a solid catalyst component containing titanium, magnesium and halogen and the organic aluminum compound into contact with each other, a catalyst component obtained by bringing the solid catalyst component containing titanium, magnesium and halogen, the organic aluminum compound and the carrier into contact with each other, a catalyst component obtained by bringing the complex for olefin
polymerization and the activating co-catalyst component into contact with each other, and a catalyst component obtained by bringing the complex for olefin polymerization, the activating co-catalyst component and the carrier into contact with each other).
[0334]
The prepolymerization is carried out usually by a slurry polymerization method. For the prepolymerization, any of a batch method, a semi-batch method, and a continuous method may be employed. Furthermore, in the prepolymerization, a chain transfer agent such as hydrogen may be added.
[0335]
When the prepolymerization is carried out by a slurry polymerization method, as the solvent, hydrocarbon having less than 20 carbon atoms is preferably used. Examples of the solvent include saturated aliphatic hydrocarbon such as propane, normal butane, isobutane, normal pentane, isopentane, normal hexane, cyclohexane, heptane, octane, and decane; and aromatic hydrocarbon such as benzene, toluene, and xylene. One or more thereof are used.
[0336]
When the prepolymerization is carried out by a slurry polymerization method, the concentration of the catalyst component in the slurry before the prepolymerization is carried out is usually 0.1 g to 600 g and preferably 0.5 g to 300 g with respect to 1 liter of the solvent.
[0337]
A temperature of prepolymerization is usually -20°C to 100°C and preferably 0°C to 80°C. Furthermore, the partial pressure of olefins in a gas phase portion in the prepolymerization is usually 0.01 MPa to 5 MPa and preferably 0.1 MPa to 2 MPa (note here that this is not applied to olefins which are liquid at pressures and temperatures of
prepolymerization). Prepolymerization time is usually 2 minutes to 15 hours.
[0338]
[Process for Producing Ethylenic Polymer]
In a process for producing an ethylenic polymer according to the present invention, polymerization of olefins including ethylene is 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 process is a production process involving carrying out polymerization by supplying only ethylene as a raw material monomer or supplying ethylene and a monomer capable of being copolymerized with ethylene.
[0339]
Examples of the monomer capable of being copolymerized with 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; cyclic olefin such as norbornene; alkenyl aromatic hydrocarbyl such as styrene; unsaturated carboxylic acid such as acrylic acid and methacrylic acid; 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.
[0340]
Examples of the polymerization method include a solvent polymerization method using aliphatic hydrocarbyl such as butane, pentarie, hexane, heptane, and octane; aromatic hydrocarbyl such as benzene and toluene; halogenated hydrocarbyl such as methylene dichloride 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 polymerization by the solution polymerization method, and then carrying out polymerization by the gas phase polymerization method, and a method of carrying out polymerization by the slurry polymerization method, and then carrying out polymerization by the gas phase polymerization method. Furthermore, both a continuous polymerization method and a batch polymerization method can be employed. In addition, both a single-stage polymerization method and a multi-stage polymerization method may be carried out. A preferable method is the slurry polymerization method or the gas phase polymerization method, and a more preferable method is the gas phase polymerization method.
[0341]
In the gas phase polymerization method, polymerization is preferably carried out in a condensed mode. When the polymerization is carried out in a condensed mode, as a condensable inert component to be supplied to a fluid bed of the gas phase polymerization reactor, easily volatile liquid hydrocarbon is used. Examples of the condensable inert component include saturated hydrocarbon having 4 to 10 carbon atoms, such as n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane, isohexane, n-heptane, and n-octane. The condensable inert component is preferably saturated hydrocarbon having 4 to 6 carbon atoms, and more preferably saturated hydrocarbon having 5 to 6 carbon atoms. The
concentration of the condensable inert component in a recycle gas is preferably 5 mol% to 60 mol%.
[0342]
When the catalyst for producing an ethylenic polymer or the catalyst component (I) and the catalyst component (Π) for olefin polymerization are supplied to a polymerization reactor, the catalyst for producing an ethylenic polymer, which has been dissolved or dispersed in an organic solvent, may be supplied to the polymerization reactor, or the catalyst component (I) which has been dissolved or dispersed in an organic solvent may be supplied to the
polymerization reactor, or the catalyst component (II) for olefin polymerization, which has been dissolved or dispersed in an organic solvent, may be supplied to the polymerization reactor.
[0343]
Preferably, the catalyst for producing an ethylenic polymer, the catalyst component (I) and the catalyst component (II) for olefin polymerization are supplied to the polymerization reactor in a state in which they are dissolved or dispersed in an organic solvent. Examples of the organic solvent include saturated aliphatic hydrocarbon such as butane, pentane, hexane, heptane, and octane.
[0344]
When the catalyst for producing an ethylenic polymer, the catalyst component (I) and the catalyst component (II) for olefin polymerization are supplied to the polymerization reactor in a state in which they are dissolved or dispersed in an organic solvent, the concentration of the catalyst for producing an ethylenic polymer in a liquid in which the catalyst for producing an ethylenic polymer is dissolved or dispersed, the concentration of the catalyst component (I) in a liquid in which the catalyst component (I) is dissolved or dispersed, and the concentration of the catalyst component (Π) for olefin polymerization in a liquid in which the catalyst component (II) for olefin polymerization is dissolved or dispersed are preferably 0.1 μπιοΙ/L to 10 mmol L and more preferably 0.5 μπιοΙ/L to 1 mmol L on the basis of the transition metal atom.
[0345]
When the catalyst for producing an ethylenic polymer or the catalyst component (I) and the catalyst component (Π) for olefin polymerization are supplied to a gas phase polymerization reactor in a state in which they are dissolved or dispersed in the organic solvent, it is preferable to use a compound whose boiling point is lower than the polymerization reaction temperature as the organic solvent. Examples of the compound include butane, pentane, and hexane.
[0346]
Furthermore, when the catalyst for producing an ethylenic polymer, the catalyst component (I) and the catalyst component (II) for olefin polymerization are supplied to a gas phase polymerization reactor in a state in which they are dissolved or dispersed in the organic solvent, a liquid in which they are each dissolved or dispersed is preferably supplied to a gas phase polymerization reactor in a mist form.
[0347]
When the catalyst for producing an ethylenic polymer, the catalyst component (I) and the catalyst component (II) for olefin polymerization are supplied to a solution
polymerization reactor or a slurry polymerization reactor in a state in which they are dissolved or dispersed in the organic solvent, the organic solvent is preferably a compound having high affinity with the polymerization solvent, and is more preferably a compound which is the same as the polymerization solvent ;
[0348]
A polymerization pressure is preferably a normal pressure to 5 MPa. A polymerization time is generally appropriately determined based on the types of target polymers and reaction devices, but the polymerization time is 1 minute to 20 hours. Furthermore, a chain transfer agent such as hydrogen can be added for modulating the molecular weight of an ethylenic polymer.
[0349]
The polymerization temperature is usually 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 lower, and more preferably 100°C or lower.
[0350]
Examples of the process for producing ethylenic polymer will now be described below.
<Gas Phase Polymerization Method>
(1) A process for producing an ethylenic polymer by polymerizing olefins including ethylene in a gas phase polymerization reactor, the process including: previously bringing a complex and an activating co-catalyst component into contact with each other in a solvent in the absence of ethylene in a tank to prepare a catalyst component (I) (step 1); and transporting a liquid containing the catalyst component (I) to the gas phase polymerization reactor through a tube (ethylene is supplied into the tube if necessary), allowing the liquid containing the catalyst component (I) to blow (in a mist form if necessary) into the gas phase polymerization reactor in which ethylene, the catalyst component for olefin polymerization and polymer particles are present, and mixing the catalyst component (I) and the catalyst component for olefin polymerization with each other in the gas phase polymerization reactor (step 2).
(2) A process for producing an ethylenic polymer by polymerizing olefins including ethylene in a gas phase polymerization reactor, the process including: preparing a solution in which a complex is dissolved in a solvent (a complex solution) and a solution in which an activating co-catalyst component is dissolved in a solvent (a co-catalyst component solution), individually, in separate tanks, connecting a tube for transporting the complex solution to a tube for transporting the co-catalyst component solution to each other before an inlet port of the polymerization reactor so that the flow of the complex solution during transport to the polymerization reactor and the flow of the co-catalyst component solution during transport to the polymerization reactor join together, and thereby bringing the complex and the activating co- catalyst component into contact with each other in the tube to prepare a catalyst component (I) (step 1); (if necessary, supplying ethylene to a mixture solution of the complex solution and the co-catalyst component solution after the flow of the complex solution and the flow of the co- catalyst component solution during transport to the polymerization reactor join together);
allowing a liquid containing the catalyst component (Γ) to blow (in a mist form if necessary) into a gas phase polymerization reactor in which ethylene, the catalyst component for olefin polymerization and polymer particles are present, and mixing the catalyst component (I) and the catalyst component for olefin polymerization with each other in the gas phase polymerization reactor (step 2).
[0351]
(3) A process for producing an ethylenic polymer by polymerizing olefins including ethylene in a gas phase polymerization reactor, the process including: previously bringing the complex and the activating co-catalyst component into contact with each other in the absence of ethylene to prepare a catalyst component (I) (step 1); bringing the complex for olefin polymerization and the activating co-catalyst component into contact with each other in the absence of olefin or in the presence of olefin to prepare a catalyst component for olefin polymerization (step 3); then carrying out prepolymerization of an olefin in a solvent in the presence of the catalyst component for olefin polymerization (step 4); after prepolymerization is finished, putting the catalyst component (I) prepared in step 1 into a liquid after
prepolymerization has been carried out, stirring the liquid and thereby mixing the catalyst component (I) and the catalyst component for olefin polymerization with each other to prepare a catalyst for producing an ethylenic polymer (step 2); and then removing a part of the solvent in a liquid after mixing by a flash operation and the like if necessary, and supplying the catalyst for producing an ethylenic polymer in a slurry state to the inside of the gas phase polymerization reactor.
(4) A process for producing an ethylenic polymer by polymerizing olefins including ethylene in a gas phase polymerization reactor, the process including: previously bringing the complex and the activating co-catalyst component into contact with each other in the absence of ethylene to prepare a catalyst component (I) (step 1); bringing the complex for olefin polymerization and the activating co-catalyst component into contact with each other in the absence of olefin or in the presence of olefin to prepare a catalyst component for olefin polymerization (step 3); then carrying out prepolymerization of an olefin in a solvent in the presence of the catalyst component for olefin polymerization (step 4); after prepolymerization is finished, putting the catalyst component (I) prepared in step 1 into a liquid after
prepolymerization has been carried out, stirring the liquid and thereby mixing the catalyst component (I) and the catalyst component for olefin polymerization with each other (step 2); and then removing the solvent from the liquid after mixing by a flash operation and the like, and taking out a catalyst for producing an ethylenic polymer in which the catalyst component (I) is adsorbed to the catalyst component for olefin polymerization, which has been subjected to prepolymerization, and supplying the catalyst for producing an ethylenic polymer to the inside of the gas phase polymerization reactor in a powder state or a slurry state (in this case, the catalyst for producing an ethylenic polymer is dispersed in a solvent so as to have a slurry state). Note here that in this process, the catalyst for producing an ethylenic polymer is preferably supplied in a slurry state.
[0352]
(5) A process for producing an ethylenic polymer by polymerizing olefins including ethylene in a gas phase polymerization reactor, the process including: previously bringing the complex and the activating co-catalyst component into contact with each other in the absence of ethylene to prepare a catalyst component (I) (step 1); mixing the catalyst component (I) and ethylene with each other in a container, allowing the obtained mixture to blow (in a mist form if necessary) into a gas polymerization reactor in which ethylene, the catalyst component for olefin polymerization and polymer particles are present, and mixing the catalyst component (I) and the catalyst component for olefin polymerization with each other in the gas phase polymerization reactor (step 2).
(6) A process for producing an ethylenic polymer by polymerizing olefins including ethylene in a gas phase polymerization reactor, the process including: previously bringing the complex and the activating co-catalyst component into contact with each other in the absence of ethylene to prepare a catalyst component (I) (step 1); in the gas phase
polymerization method in which polymerization is carried out in a condensed mode, dissolving or dispersing the catalyst component (I) in a condensable inert component to be used for the condensed mode, previously or in a tube for transporting a condensable inert component to a basic polymerization reactor, supplying (in a mist form if necessary) the catalyst component (I) together with the condensable inert component into the gas phase polymerization reactor in which ethylene, the catalyst component for olefin polymerization and polymer particles are present, and mixing the catalyst component (I) and the catalyst component for olefin
polymerization with each other in the gas phase polymerization reactor (step 2).
[0353]
[Slurry Polymerization Method, Solution Polymerization Method]
(1) A process for producing an ethylenic polymer by polymerizing olefins including ethylene in a polymerization reactor, the process including: previously bringing a complex and an activating co-catalyst component into contact with each other in a solvent in the absence of ethylene in a tank to prepare a catalyst component (I) (step 1); transporting a liquid containing the catalyst component (I) to the polymerization reactor through a tube (ethylene is supplied into the tube if necessary), supplying a liquid containing the catalyst component (I) to the polymerization reactor in which ethylene and the catalyst component for olefin
polymerization are present, and mixing the catalyst component (I) and the catalyst component for olefin polymerization with each other in the polymerization reactor (step 2).
(2) A process for producing an ethylenic polymer by polymerizing olefins including ethylene in.a polymerization reactor, the process including: preparing a solution in which a complex is dissolved in a solvent (a complex solution) and a solution in which an activating co-catalyst component is dissolved in a solvent (a co-catalyst component solution), individually, in separate tanks, connecting a tube for transporting the complex solution to a tube for transporting the co-catalyst component solution to each other before an inlet port of the polymerization reactor so that the flow of the complex solution during transport to the polymerization reactor and the flow of the co-catalyst component solution during transport to the polymerization reactor join together, and thereby bringing the complex and the activating co- catalyst component into contact with each other in the tube to prepare a catalyst component (I) (step 1); (if necessary, supplying ethylene to a mixture solution of the complex solution and the co-catalyst component solution after the flow of the complex solution and the flow of the co- catalyst component solution during transport to the polymerization reactor join together);
supplying a liquid containing the catalyst component (I) to a polymerization reactor in which ethylene and the catalyst component for olefin polymerization are present, and mixing the catalyst component (I) and the catalyst component for olefin polymerization with each other in the polymerization reactor (step 2).
[0354]
(3) A process for producing an ethylenic polymer by polymerizing olefins including ethylene in a polymerization reactor, the process including: previously bringing the complex and the activating co-catalyst component into contact with each other in the absence of ethylene to prepare a catalyst component (I) (step 1); bringing the complex for olefin
polymerization and the activating co-catalyst component into contact with each other in the absence of olefin or in the presence of olefin to prepare a catalyst component for olefin polymerization (step 3); then carrying out prepolymerization of an olefin in a solvent in the presence of the catalyst component for olefin polymerization (step 4); after prepolymerization is finished, putting the catalyst component (I) prepared in step 1 into a liquid after
prepolymerization has been carried out, stirring the liquid and thereby mixing the catalyst component (I) and the catalyst component for olefin polymerization with each other to prepare a catalyst for producing an ethylenic polymer (step 2); and then removing a part of the solvent in a liquid after mixing by a flash operation and the like if necessary, and supplying the catalyst for producing an ethylenic polymer in a slurry state into the polymerization reactor.
(4) A process for producing an ethylenic polymer by polymerizing olefins including ethylene in a polymerization reactor, the process including: previously bringing the complex and the activating co-catalyst component into contact with each other in the absence of ethylene to prepare a catalyst component (I) (step 1); bringing the complex for olefin
polymerization and the activating co-catalyst component into contact with each other in the absence of olefin or in the presence of olefin to prepare a catalyst component for olefin polymerization (step 3); then carrying out prepolymerization of an olefin in a solvent in the presence of the catalyst component for olefin polymerization (step 4); after prepolymerization is finished, putting the catalyst component (I) prepared in step 1 into a liquid after
prepolymerization has been carried out, stirring the liquid and thereby mixing the catalyst component (I) and the catalyst component for olefin polymerization with each other (step 2); and then removing the solvent from a liquid after mixing by a flash operation and the like, taking out a catalyst for producing an ethylenic polymer in which the catalyst component (I) is adsorbed to the catalyst component for olefin polymerization, which has been subjected to
prepolymerization, and supplying the catalyst for producing an ethylenic polymer into the polymerization reactor in a powder state or a slurry state (in this case, the catalyst for producing an ethylenic polymer is dispersed in a solvent so as to have a slurry state). Note here that in this process, the catalyst for producing an ethylenic polymer is preferably supplied in a slurry state.
[0355]
(5) A process for producing an ethylenic polymer by polymerizing olefins including ethylene in a polymerization reactor, the process including: previously bringing the complex and the activating co-catalyst component into contact with each other in the absence of ethylene to prepare a catalyst component (I) (step 1); mixing the catalyst component (I) and ethylene with each other in a container, supplying the obtained mixture to a slurry
polymerization reactor or a solution polymerization reactor in which ethylene, the catalyst component for olefin polymerization and polymer particles are present, and mixing the catalyst component (I) and the catalyst component for olefin polymerization with each other in the polymerization reactor (step 2). In this process, a temperature at which the catalyst component (I) and ethylene are mixed with each other is preferably 0°C to 80°C, and a temperature at which the catalyst component (I) and the catalyst component for olefin polymerization are mixed with each other in a polymerization reactor is preferably 30°C to 200°C.
[0356]
A process 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.
[0357]
The ethylenic polymer obtained by the production process of the present invention is molded into various molded products (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; and a cross-linking foaming.
[0358]
The ethylenic polymer may be blended with the known resin and 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.
[0359]
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 blow bottle, a squeeze bottle, and the like.
[EXAMPLES]
[0360]
The present invention will be described with reference to Examples. Examples were analyzed by the following methods.
[0361]
<Analysis of Transition Metal Complex>
(1) Proton nuclear magnetic resonance spectrum ('H-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 (CDCI3)
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) [0362]
(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: CDCI3 (77.0 ppm)
[0363]
(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
[0364]
<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 total 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 total 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).
[0365]
(5) Measurement of molecular weight
A weight average molecular weight in terms of polystyrene and a number average molecular weight were measured by gel permeation chromatography (GPC) under the following conditions (1) to (8). Next, from "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 (11 / 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: Waters 150C 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 μL·
(7) Detector: differential refractometry
(8) Molecular weight standard substance: standard polystyrene
[0366]
Test Example
"Synthesis of [l-tris(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride (hereinafter, referred to as a "complex 1 ")"
[0367]
"Synthesis of l-tris(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene"
Under the nitrogen atmosphere, sodium hydride (0.49 g, 20.45 mmol as sodium hydride) dispersed in mineral oil and tetrahydrofuran (23 mL) were added. The mixture was heated to 50°C, aniline (0.13 g, 1.36 mmol) was added thereto, and the mixture was stirred at 50°C for one hour. Asolution of l,2,3,4-tetramethylcyclopenta-l,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 this 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, and an 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 concentrated under reduced pressure. 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 concentrated from a filtrate under reduced pressure. 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- MR (CDC13, 6 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 (JVT)
[0368]
"Synthesis of complex 1 "
Under the 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 mixture was gradually warmed to room temperature, and then the solution was stirred at room temperature over night. After reaction, the solvent was concentrated under reduced pressure, heptane was added to the residue and the obtained product was filtered to remove insolubles, and the solvent was concentrated from the filtrate under reduced pressure. Furthermore, diethyl ether was added to the obtained residue and the obtained product was filtered to remove insolubles, and the solvent was concentrated from the filtrate 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-NMR (CDC13, 5 ppm): 2.03 (s, 6H), 2.27 (s, 18H), 2.36 (s, 6H), 7.06 (s, 3H), 7.20 (s, 6H) 13C-NMR (CDC , 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 (IVf)
[0369]
Example 1
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 in the reactor was stirred for two hours. Next, 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 process described in Examples 1 ( 1 ) and (2) of JP 2009-79182 A [the amount of racemic ethy lene-bis( 1 - indenyl)zirconium diphenoxide per 1 g of the particulate solid catalyst component was 126 μπιοΐ] and triisobutylaluminum were added thereto, and polymerization was started.
After polymerization was started, the polymerization temperature in the reactor was adjusted to 30°C, and the polymerization was carried out for 0.5 hours. Next, the mixture was raised to 50°C over 30 minutes, and then the polymerization was carried out at 50°C for 6.5 hours. Furthermore, during the polymerization, ethylene and hydrogen were supplied in 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.
[0370]
The inside of a 100-mL flask was purged with nitrogen, 5 mL of toluene was supplied into the flask, and then 2.5 mL of a toluene solution of complex 1 (concentration of the complex 1: 1 mmol/L) was supplied thereto. After that, 0.14 mL of a toluene solution of an organic aluminum oxy compound (TMAO manufactured by Tosoh Corporation, 9.0 wt% (3.3 mmol/g)) was supplied. Next, 287 mg of a catalyst component for prepolymerization was supplied into the flask, and the mixture in the flask was stirred for 5 minutes. After that, the solvent was removed by evaporation under reduced pressure, followed by drying under reduced pressure for one hour to obtain a solid component.
[0371] The inside of a 0.4 L autoclave was purged with argon, and 90 mL of heptane was supplied into the autoclave. The inside temperature of the autoclave was adjusted to 40°C, and ethylene was supplied into the autoclave so that the ethylene pressure might become 2 MPa. Next, 2 mmol of triisobutylaluminum was supplied into the autoclave, 36 mg of the above- mentioned solid component was then supplied to start a polymerization reaction by a slurry polymerization method. After 30 minutes, 2 mL of ethanol was supplied into the autoclave to stop the reaction. As a result of the reaction, 2.4 g of a polymer was obtained, the number of butyl branches of the polymer was 5.7 (branches/1000 C). Furthermore, Mw of the polymer was 124000, and Mn thereof was 54000.
[0372]
Example 2
Into a 5 L autoclave, 50 g of 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 pressure might become 2 MPa. Next, 1 mmol of triisobutylaluminum was supplied into the autoclave, and 127 mg of the solid component prepared in Example 1 was further supplied thereto to start a polymerization reaction by a gas phase polymerization method. After 60 minutes, 2 mL of ethanol was supplied into the autoclave to stop the reaction. The autoclave was cooled, then ethylene inside the autoclave was purged, and 200 mL of toluene was supplied into the autoclave and the mixture was stirred. The toluene slurry in the autoclave was recovered and filtered. 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 components were recovered by suction filtration, and further washed with ethanol and dried. As a result of the reaction, 6.9 g of a polymer was obtained. The number of butyl branches of the polymer was 13.0 (branches/ 1000 C). Furthermore, Mw of the polymer was 113000, and Mn thereof was 47000.
[0373]
Example 3
Into a 100-mL flask the inside of which was purged with nitrogen, 5 mL of toluene was supplied, and then 2.5 mL of a toluene solution of complex 1 (concentration of the complex 1 : 1 mmol/L) was supplied thereto. After that, 0.028 mL of a toluene solution of an organic aluminum oxy compound (TMAO manufactured by Tosoh Corporation, 9.0 wt% (3.3 mmol/g)) was supplied. Into the flask, 275 mg of the catalyst component for
prepolymerization, which had been prepared in Example 1, was supplied and the mixture in the flask was stirred for 5 minutes. Then, the solvent was removed by evaporation under reduced pressure, followed by drying under reduced pressure for one hour to obtain a solid component.
[0374]
The gas phase polymerization reaction of ethylene was carried out in the same manner as in Example 2 except that 127 mg of the solid component prepared in this Example was used instead of the solid component prepared in Example 1. As a result of the reaction, 4.6 g of a polymer was obtained. The number of butyl branches of the polymer was 13.5
(branches/ 1000 C). Furthermore, Mw of the polymer was 83000, and Mn thereof was 35000.

Claims

1. A process for producing a catalyst for producing an ethylenic polymer, the process comprising the following steps 1 and 2:
step 1 : the step of bringing a complex represented by formula (1), (2-1) or (2-2) and an activating co-catalyst component into contact with each other in the absence of ethylene to prepare a catalyst component (I); and
step 2: the step of mixing the catalyst component (I) obtained in step 1 with a n polymerization:
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
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 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;
Figure imgf000128_0002
wherein M2 represents a transition metal atom of Group 4 of the periodic table of the elements;
21
A 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 A to Z 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
R 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 ma be a double bond, and R26 may be bonded to Z1;
Figure imgf000129_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;
Z is a group linking A to N, and the number of the shortest bonds linking A to N is 4 to 6; 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 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
97 9R
R and R each represent a hydrogen atom, a halogen atom, a hydrocarbyl group, or a substituted hydrocarbyl group, and R28 may be bonded to Z2.
2. The process according to claim 1, further comprising the following step 3:
step 3: the step of bringing the complex for olefin polymerization and the activating co-catalyst component into contact with each other to prepare a catalyst component (II) for olefin polymerization.
3. The process according to claim 2, wherein step 3 is the step of bringing the complex for olefin polymerization, the activating co-catalyst component and the carrier into contact with each other.
4. The process according to claim 2 or 3, further comprising the following step 4: step 4: the step of prepolymerizing olefin in the presence of the catalyst component obtained in step 2.
5. The process according to claim 1, wherein the complex is a compound
(1):
Figure imgf000130_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 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.
6. A catalyst for producing an ethylenic polymer obtained by the process according to any one of claims 1 to 5.
7. A process for producing an ethylenic polymer, comprising polymerizing olefins including ethylene by a catalyst according to claim 6.
8. The process according to claim 7, wherein the olefins including ethylene are polymerized by gas phase polymerization method.
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