WO2012133936A1 - Catalyseur de production de polymère à base d'éthylène et son procédé de production - Google Patents

Catalyseur de production de polymère à base d'éthylène et son procédé de production Download PDF

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WO2012133936A1
WO2012133936A1 PCT/JP2012/059295 JP2012059295W WO2012133936A1 WO 2012133936 A1 WO2012133936 A1 WO 2012133936A1 JP 2012059295 W JP2012059295 W JP 2012059295W WO 2012133936 A1 WO2012133936 A1 WO 2012133936A1
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titanium trichloride
titanium
tert
silyl
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Takayuki Hishiya
Takahiro Hino
Taichi Senda
Masaya Tanimoto
Yasutoyo Kawashima
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged

Definitions

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

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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Abstract

L'invention vise à produire un catalyseur apte à la production efficace d'un polymère éthylénique possédant une ramification à chaîne courte même lorsque seulement de l'éthylène est utilisée comme monomère manière première, ainsi qu'un procédé de production de polymère éthylénique par le catalyseur. Un catalyseur pour la production d'un polymère éthylénique est divulgué, préparé à partir d'un complexe (I) représenté par la formule (1), (2-1) ou (2-2), un complexe pour la polymérisation d'oléfine, un composant co-catalyseur d'activation et un support, le complexe (I) et le complexe pour la polymérisation d'oléfines étant portés par le support.
PCT/JP2012/059295 2011-03-30 2012-03-29 Catalyseur de production de polymère à base d'éthylène et son procédé de production Ceased WO2012133936A1 (fr)

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US10124326B2 (en) 2014-09-30 2018-11-13 Sumitomo Chemical Company, Limited Modified solid polyalkylaluminoxane and catalyst for olefin oligomerization reaction

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KR102546537B1 (ko) * 2021-05-10 2023-06-23 지에스칼텍스 주식회사 올레핀 중합용 메탈로센 담지 촉매 조성물 및 이의 제조 방법

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