WO2012133929A1 - Procédé de production d'un complexe ion métal de transition, catalyseur de trimérisation, et procédé de production de 1-hexène - Google Patents

Procédé de production d'un complexe ion métal de transition, catalyseur de trimérisation, et procédé de production de 1-hexène Download PDF

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WO2012133929A1
WO2012133929A1 PCT/JP2012/059287 JP2012059287W WO2012133929A1 WO 2012133929 A1 WO2012133929 A1 WO 2012133929A1 JP 2012059287 W JP2012059287 W JP 2012059287W WO 2012133929 A1 WO2012133929 A1 WO 2012133929A1
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silyl
tetramethylcyclopentadienyl
dimethylphenyl
methyl
carbon atoms
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PCT/JP2012/059287
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English (en)
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Taichi Senda
Masaya Tanimoto
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Sumitomo Chemical Company, Limited
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1608—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes the ligands containing silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
    • C07C2/34—Metal-hydrocarbon complexes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/20—Olefin oligomerisation or telomerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/46—Titanium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/22—Organic complexes

Definitions

  • the present invention relates to a transition metal ion complex, a method for producing the transition metal ion complex, a catalyst for trimerization, and a method for producing 1-hexene.
  • An a-olefin is an industrially important raw material monomer that is produced by the oligomerization of ethylene using a metal catalyst.
  • the oligomerization of ethylene usually gives ⁇ -olefin mixtures according to Schulz-Flory distribution. Therefore, the development of a catalyst system capable of selectively producing one kind of ⁇ -olefin is very important industrially.
  • Patent Document 1 has reported that a half-metallocene titanium complex represented by formula (Cp-B(R) n Ar)TiR 1 3 activated with an activating co-catalyst component works as a catalyst for selective trimerization of ethylene.
  • a half-metallocene titanium complex (carbon-bridged Cp-Ar complex) comprising cyclopentadiene bonded to a substituted aryl group via a carbon atom, such as [l-(l-methyl-l-(3,5-dimethylphenyl)ethyl)-3- trimethyIsilylcyclopentadienyl]titanium trichloride, has been reported to work as an efficient catalyst for ethylene trimerization under conditions of 30°C with MAO (methylaluminoxane) as an activating co-catalyst component (see e.g., Non-Patent Document 1).
  • MAO methylaluminoxane
  • [dimethylphenylsilylcyclopentadienyl]titanium trichloride which is a half-metallocene titanium complex (silicon-bridged Cp-Ar complex) comprising cyclopentadiene bonded to a substituted aryl group via a silicon atom, has been reported to have low catalytic activity in ethylene trimerization reaction under the same conditions as above and to also have low 1-hexene selectivity (see Non-Patent Document 1).
  • Non-Patent Document 1 Organometallics 2002, 21 , 5122-5135.
  • Non-Patent Document 3 J. Am. Chem. Soc. 2009, 131, 5298-5312.
  • Non-Patent Document 4 J. Mol. Catal. A: Chem. 2006, 248, 237-247.
  • an object of the present invention is to provide a transition metal ion complex that serves as a catalyst capable of efficiently and highly selectively producing 1-hexene through the trimerization reaction of ethylene.
  • the 1 st aspect of the present invention relates to a transition metal ion complex represented by formula (1-1), (1-2) or (1-3):
  • M represents a transition metal atom of Group 4 of the Periodic Table of the Elements;
  • A represents a counter anion;
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , X 1 and X 2 each independently represent
  • a substituted silyl group represented by -Si(R ) 3 wherein the three R moieties each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the three R 22 moieties is 1 to 20, or a disubstituted amino group represented by -N(R 23 ) 2 , wherein the two R 23 moieties each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 23 moieties is 2 to 20, and
  • R 1 , R 2 , R 3 and R 4 is a halogen atom, the alkyl group, the alkoxy group, the aryl group, the aryloxy group, the aralkyl group, the aralkyloxy group, the substituted silyl group or the disubstituted amino group;
  • R 10 and R n each independently represent
  • a substituted silyl group represented by -Si(R 22 ) 3 wherein the three R 22 moieties each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the three R 22 moieties is 1 to 20, or a disubstituted amino group represented by -N(R 3 ) 2 , wherein the two R 23 moieties each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 23 moieties is 2 to 20; or
  • R 1 , R 2 , R 3 and R 4 two group 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, of R 5 , R 6 , R 7 , R 8 and R 9 , two group 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, of R 12 , R 13 , R 14 , R 15 and R 16 , two group 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, of R 17 , R 18 , R 19 , R 20 and R 21 , two group 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, and R 10 and R 11 may be bonded to
  • the 2nd aspect of the present invention relates to methods for producing the transition metal ion complex represented by formula (1-1), the transition metal ion complex represented by formula (1-2), and the transition metal ion complex represented by formula (1-3).
  • the 3rd aspect of the present invention relates to a catalyst for trimerization comprising the transition metal ion complex.
  • the 4th aspect of the present invention relates to a method for producing 1-hexene, comprising trimerizing ethylene in the presence of the catalyst for trimerization.
  • the present invention can provide a transition metal ion complex that is suitable as a catalyst capable of efficiently and highly selectively producing 1-hexene through the trimerization reaction of ethylene even under high temperature conditions.
  • the present invention can also provide a method for producing 1-hexene that does not require using an expensive activating co-catalyst component such as MAO.
  • substituted encompasses a halogen atom constituting a compound or a group.
  • transition metal ion complex (1-1), (1-2) or (1-3) (hereinafter, abbreviated to a "transition metal ion complex (1-1)", etc.) will be described in detail.
  • M represents an element of Group 4 of the Periodic Table of the Elements, and examples thereof include titanium, zirconium and hafnium atoms. Among them, a titanium atom is preferable.
  • the substituents R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , X 1 and X 2 are as defined above, and specific examples thereof are shown below.
  • the halogen atom is a fluorine, chlorine, bromine or iodine atom and is preferably a chlorine atom.
  • alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, amyl, n-hexyl, heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and n-eicosyl groups.
  • a preferable alkyl group is an alkyl group having 1 to 10 carbon atoms, and more preferable examples thereof can include methyl, ethyl, isopropyl, tert-butyl and amyl groups.
  • the phrase "may have a halogen atom as a substituent" in the "alkyl group which may have a halogen atom as a substituent” means that some or all hydrogen atoms in the alkyl group may be substituted by a halogen atom. Specific examples of the halogen atom are as described above.
  • the number of its carbon atoms is preferably in the range of 1 to 20, more preferably in the range of 1 to 10.
  • the alkyl group having a halogen atom as a substituent can include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, fluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl and perfluorohexyl groups.
  • Examples of the "aryl group having 6 to 20 carbon atoms" in the aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent include phenyl, 2- tolyl, 3-toly , 4-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, 2,3,4- trimethylphenyl, 2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl, 2,4,6-trimethylphenyl, 3,4,5- trimethylphenyl, 2,3,4,5-tetramethylphenyl, 2,3,4,6-tetramethylphenyl, 2,3,5,6- tetramethylphenyl, pentamethylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n- butylphenyl, sec-butylpheny
  • a preferable aryl group is an aryl group having 6 to 10 carbon atoms, and more preferable examples thereof can include a phenyl group.
  • the phrase "may have a halogen atom as a substituent" in the "aryl group which may have a halogen atom as a substituent” means that some or all hydrogen atoms in the aryl group may be substituted by a halogen atom.
  • Specific examples of the halogen atom are as described above.
  • the number of its carbon atoms is preferably in the range of 6 to 20, more preferably in the range of 6 to 10.
  • aryl group having a halogen atom as a substituent can specifically include fluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, chlorophenyl, bromophenyl and iodophenyl groups.
  • aralkyl group having 7 to 20 carbon atoms examples include benzyl, (2- methylphenyl)methyl, (3-methylphenyl)methyl, (4-methylphenyl)methyl, (2,3- dimethylphenyl)methyl, (2,4-dimethylphenyl)methyl, (2,5-dimethylphenyl)methyl, (2,6- dimethylphenyl)methyl, (3,4-dimethylphenyl)methyl, (3,5-dimethylphenyl)methyl, (2,3,4- trimethylphenyl)methyl, (2,3,5-trimethylphenyl)methyl, (2,3,6-trimethylphenyl)methyl, (3,4,5- trimethylphenyl)methyl, (2,4,6-trimethylphenyl)methyl, (2,3,4,5-tetramethylphenyl)methyl, (2, 3 ,4,6-tetramethylphenyl)methyl
  • a preferable aralkyl group is an aralkyl group having 7 to 10 carbon atoms, and more preferable examples thereof can include a benzyl group.
  • the phrase "may have a halogen atom as a substituent" in the "aralkyl group which may have a halogen atom as a substituent” means that some or all hydrogen atoms in the aralkyl group may be substituted by a halogen atom.
  • Specific examples of the halogen atom are as described above.
  • the aralkyl group has a halogen atom as a substituent, the number of its carbon atoms is preferably in the range of 7 to 20, more preferably in the range of 7 to 10.
  • alkoxy group having 1 to 20 carbon atoms examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy, neopentyloxy, n- hexyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy, tridecyloxy, tetradecyloxy, n-pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy, nonadecyloxy and n-eicosyloxy groups.
  • a preferable alkoxy group is an alkoxy group having 1 to 10 carbon atoms, and more preferable examples thereof can include methoxy, ethoxy and tert- butoxy groups.
  • alkoxy group which may have a halogen atom as a substituent means that some or all hydrogen atoms in the alkoxy group may be substituted by a halogen atom. Specific examples of the halogen atom are as described above.
  • the alkoxy group has a halogen atom as a substituent, the number of its carbon atoms is preferably in the range of 1 to 20, more preferably in the range of 1 to 10.
  • a preferable alkoxy group is an alkoxy group having 2 to 10 carbon atoms, and more preferable examples thereof can include ethoxy and tert-butoxy groups.
  • the phrase "may have a halogen atom as a substituent" in the "alkoxy group which may have a halogen atom as a substituent” means that some or all hydrogen atoms in the alkoxy group may be substituted by a halogen atom.
  • Specific examples of the halogen atom are as described above.
  • the alkoxy group has a halogen atom as a substituent, the number of its carbon atoms is preferably in the range of 2 to 20, more preferably in the range of 2 to 10.
  • aryloxy group is an aryloxy group having 6 to 10 carbon atoms, and more preferable examples thereof can include phenoxy, 2-methylphenoxy, 3-methylphenoxy and 4-methylphenoxy groups.
  • the phrase "may have a halogen atom as a substituent" in the "aryloxy group which may have a halogen atom as a substituent” means that some or all hydrogen atoms in the aryloxy group may be substituted by a halogen atom.
  • Specific examples of the halogen atom are as described above.
  • the aryloxy group has. a halogen atom as a substituent, the number of its carbon atoms is preferably in the range of 6 to 20, more preferably in the range of 6 to 10.
  • aralkyloxy group having 7 to 20 carbon atoms examples include benzyloxy, (2-methylphenyl)methoxy, (3-methylphenyl)methoxy, (4- methylphenyl)methoxy, (2,3-dimethylphenyl)methoxy, (2,4-dimethylphenyl)methoxy, (2,5- dimethylphenyl)methoxy, (2,6-dimethylphenyl)methoxy, (3,4-dimethylphenyl)methoxy, (3,5- dimethylphenyl)methoxy, (2, 3 ,4-trimethylphenyl)methoxy, (2,3 , 5-trimethylphenyl)methoxy, (2,3,6-trimethylphenyl)methoxy, (2,4,5-trimethylphenyl)methoxy, (2,4,6- trimethylphenyl)meth
  • a preferable aralkyloxy group is an aralkyloxy group having 7 to 10 carbon atoms, and more preferable examples thereof can include a benzyloxy group.
  • the phrase "may have a halogen atom as a substituent" in the "aralkyloxy group which may have a halogen atom as a substituent” means that some or all hydrogen atoms in the aralkyloxy group may be substituted by a halogen atom.
  • the halogen atom are as described above.
  • the number of its carbon atoms is preferably in the range of 7 to 20, more preferably in the range of 7 to 10.
  • the R 22 moieties are each independently a hydrogen atom; a hydrocarbyl group such as an alkyl group having 1 to 10 carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl and n-decyl groups) and an aryl group (e.g., a phenyl group); or a phenyl group
  • the total number of the carbon atoms in these three R 22 moieties is preferably in the range of 3 to 18.
  • the substituted silyl group include: monosubstituted silyl groups having one hydrocarbyl or halogenated hydrocarbyl group, such as methylsilyl, ethylsilyl and phenylsilyl groups, and groups obtained by substituting some or all hydrogen atoms in the hydrocarbyl groups of these groups by a halogen atom; disubstituted silyl groups having two hydrocarbyl and/or halogenated hydrocarbyl groups, such as dimethylsilyl, diethylsilyl and diphenylsilyl groups, and groups obtained by substituting some or all hydrogen atoms in the hydrocarbyl groups of these groups by a halogen atom; and trisubstituted silyl group having three
  • hydrocarbyl and/or halogenated hydrocarbyl groups such as trimethylsilyl, triethylsilyl, tri-n- propylsilyl, triisopropylsilyl, tri-n-butylsilyl, tri-sec-butylsilyl, tri-tert-butylsilyl, tri-isobutylsilyl, tert-butyl-dimethylsilyl, tri-n-pentylsilyl, tri-n-hexylsilyl, tricyclohexylsilyl and triphenyl silyl groups, and groups obtained by substituting some or all hydrogen atoms in the hydrocarbyl groups of these groups by a halogen atom.
  • halogenated hydrocarbyl groups such as trimethylsilyl, triethylsilyl, tri-n- propylsilyl, triisopropylsilyl, tri-n-butylsilyl, tri-sec-
  • trisubstituted silyl groups are preferable, and trimethylsilyl, tert-butyldimethylsilyl and triphenylsilyl groups, and groups obtained by substituting some or all hydrogen atoms in these groups by a halogen atom are more preferable.
  • the R 23 moieties each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 23 moieties is 2 to 20, the R 23 moieties each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 23 moieties is in the range of 2 to 20, more preferably in the range of 2 to 10.
  • hydrocarbyl group and the halogenated hydrocarbyl group are the same as those described as a hydrocarbyl group and a halogenated hydrocarbyl group for the substituted silyl group.
  • these two R 23 moieties may be bonded to each other to form a ring together with the nitrogen atom to which R 23 moieties are bonded.
  • Examples of such a disubstituted amino group include dimethylamino, diethylamino, di-n-propylamino,
  • R 1 , R 2 , R 3 and R 4 two groups bonded to two adjoining carbon atoms may be bonded to each other to form a ring together with the carbon atoms to which the two groups are bonded, of R 5 , R 6 , R 7 , R 8 and R 9 , two groups bonded to two adjoining carbon atoms may be bonded to each other to form a ring together with the carbon atoms to which the two groups are bonded, of R 12 , R 13 , R 14 , R 15 and R 16 , two group 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, of R 17 , R 18 , R 19 , R 20 and R 21 , two group 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, and R 10 and R u may be bonded to each
  • the ring is a saturated or unsaturated hydrocarbyl ring substituted by a hydrocarbyl group having 1 to 20 carbon atoms, a saturated or unsaturated silahydrocarbyl ring substituted by a hydrocarbyl group having 1 to 20 carbon atoms, etc.
  • Specific examples thereof include cyclopropane, cyclopropene, cyclobutane, cyclobutene, cyclopentane, eyclopentene, cyclohexane, cyclohexene, cycloheptane,
  • cycloheptene cyclooctane
  • cyclooctene benzene, naphthalene, anthracene
  • silacyclopropane silacyclobutane
  • silacyclopentane silacyclohexane rings.
  • R 1 , R 2 , R 3 and R 4 are each independently 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, more preferably an alkyl group having 1 to 20 carbon atoms, even more preferably a methyl group.
  • R 1 , R 2 , R 3 and R 4 include the following substructures represented by sub structural formula (3):
  • R 1 , R 2 , R 3 and R 4 are as defined above:
  • methylcyclopentadienyl ethylcyclopentadienyl, n-propylcyclopentadienyl, isopropylcyclopentadienyl, n-butylcyclopentadienyl, sec-butylcyclopentadienyl, tert- butylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl,
  • a preferable cyclopentadienyl substructure is tetramethylcyclopentadienyl, etc.
  • R 5 , R 6 , R 7 , R 8 , R 9 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 and R 21 are each independently preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent, an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent or a substituted silyl group represented by -Si(R 22 ) 3 , wherein the three R 22 moieties each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms
  • R 6 , R 8 , R 13 , R 15 , R 18 and R 20 are each independently preferably an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent or a substituted silyl group represented by -Si(R 22 ) 3 , wherein the three R 22 moieties each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the three R 22 moieties is 1 to 20, more preferably an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent.
  • Examples of a preferable combination of the moieties represented by R 5 , R 6 , R 7 , 8 and R 9 include the following substructures represented by substructural formula (4):
  • R 5 , R 6 , R 7 R 8 and R 9 are as defined above:
  • a more preferable substructure is phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, diethylphenyl, trimethylsilylphenyl, etc.
  • Examples of a preferable combination of the moieties represented by R 12 , R 13 , R 14 , R 15 and R 16 include the following substructures represented by a substructural formula (5):
  • R , R , R , R and R lb are as defined above:
  • phenyl methylphenyl, dimethylphenyl, trimethylphenyl, tetramethylphenyl, pentamethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, diisopropylphenyl, tert- butylphenyl, di-tert-butylphenyl, tert-butylmethylphenyl, di(tert-butyl)methylphenyl, naphthyl, anthracenyl, chlorophenyl, dichlorophenyl, fluorophenyl, pentafluorophenyl,
  • sqbstructure is phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, diethylphenyl, trimethylsilylphenyl, etc.
  • Examples of a preferable combination of the moieties represented by R 17 , R 18 , R 19 , R 20 and R 21 include the following substructures represented by a substructural formula (6):
  • R 17 , R 18 , R 19 , R 20 and R 21 are as defined above: [0041]
  • phenyl methylphenyl, dimethylphenyl, trimethylphenyl, tetramethylphenyl, pentamethylphenyl, ethylphenyl, diethylphenyl, isopropylphenyl, diisopropylphenyl, tert- butylphenyl, di-tert-butylphenyl, tert-butylmethylphenyl, di(tert-butyl)methylphenyl, naphthyl, anthracenyl, chlorophenyl, dichlorophenyl, fluorophenyl, pentafluorophenyl,
  • a more preferable substructure is phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, diethylphenyl, tnmethylsilylphenyl, etc.
  • R 10 and R 11 are each independently preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl and benzyl group.
  • Examples of a preferable combination of the moieties represented by R 10 and R 11 include the following substructures represented by substructural formula (7):
  • R 10 and R u are as defined above:
  • Preferable examples thereof include substructures represented by substructural formula (7), wherein
  • R 10 and R u are the same as each other and are
  • alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent.
  • the substructure is dimethylsilylene, diethylsilylene,
  • X 1 and X 2 are each independently preferably a halogen atom, an alkyl group having 1 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms.
  • transition metal ion complex (1-1) examples include the following ion complexes:
  • dimethyltitanium cation complexes such as [ ⁇ l-dimethylphenylsilyl-2,3,4,5- tetramethylcyclopentadienyl ⁇ dimethyltitanium cation] [tetrakis(pentafluorophenyl)borate], [ ⁇ 1- diethylphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl ⁇ dimethyltitanium
  • examples of the transition metal ion complex (1-1) also include dimethyltitanium cation complexes obtained by substituting "2-methylcyclopentadienyl", “3- methylcyclopentadienyl”, “2,3-dimethylcyclopentadienyl", “2,4-dimethylcyclopentadienyl", “2,5-dimethylcyclopentadienyl”, “2,3,5-trimethylcyclopentadienyl”, “2-ethylcyclopentadienyl” “ 3 -ethylcyclopentadienyl " , "2-n-propylcyclopentadienyl " , “3 -n-propylcyclopentadienyl " , "2- isopropylcyclopentadienyl”, “3-isopropylcyclopentadienyl", "2-n-butylcyclopentadienyl M , "3-n butylcyclopen
  • examples of the transition metal ion complex (1-1) also include: dimethyl transition metal cation complexes such as dimethylzirconium cation complexes obtained by substituting "zirconium” for "titanium” in the ion complexes exemplified above, and dimethylhafnium cation complexes obtained by substituting "hafnium” therefor; dialkyltitanium cation complexes such as diethyltitanium cation complexes obtained by substituting "diethyl” for "dimethyl” in the ion complexes, dipropyltitanium cation complexes obtained by substituting "dipropyl” therefor and dibutyltitanium cation complexes obtained by substituting "dibutyl” therefor; diaryltitanium cation complexes such as diphenyltitanium cation complexes obtained by substituting "diphenyl” therefor and bis(penta
  • dialkoxytitanium cation complexes such as dimethoxytitanium cation complexes obtained by substituting "dimethoxide” therefor, di-n-butoxytitanium cation complexes obtained by substituting "di-n-butoxide” therefor and diisopropoxytitanium cation complexes obtained by substituting "diisopropoxide” therefor; diaryloxytitanium cation complexes such as
  • diaralkyloxytitanium cation complexes such as dibenzyloxytitanium cation complexes obtained by substituting "dibenzyloxide” therefor; and diamidotitanium cation complexes such as bis(dimethylamido)titanium cation complexes obtained by substituting "bis(dimethylamido)" therefor and bis(diethylamido)titanium cation complexes obtained by substituting
  • dialkyltitanium cation complexes are preferable, and dimethyltitanium cation complexes are particularly preferable.
  • transition metal ion complex (1-2) examples include the following ion complexes:
  • dimethyltitanium cation complexes such as [ ⁇ l-methyldiphenylsilyl-2,3,4,5- tetramethy Icyclopentadieny 1 ⁇ dimethyltitanium cation][tetrakis(pentafluorophenyl)borate], [ ⁇ 1- ethyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadienyl ⁇ dimethyltitanium
  • examples of the transition metal ion complex (1-2) also include dimethyltitanium cation complexes obtained by substituting "2-methylcyclopentadienyl", “3- methylcyclopentadienyl”, “2,3-dimethylcyclopentadienyl", “2,4-dimethylcyclopentadienyl", “2,5-dimethylcyclopentadienyl”, “2,3,5-trimethylcyclopentadienyl”, “2-ethylcyclopentadienyl”, “3-ethylcyclopentadienyl”, “2-n-propylcyclopentadienyl", “3-n-propylcyclopentadienyl”, “2- isopropylcyclopentadienyl", “3-isopropylcyclopentadienyl", “2-n-butylcyclopentadienyl”, “3-n- butylcyclopentadieny 1 " ,
  • examples of the transition metal ion complex (1-2) also include: dimethyl transition metal cation complexes such as dimethylzirconium cation complexes obtained by substituting "zirconium” for "titanium” in the ion complexes exemplified above, and dimethylhafnium cation complexes obtained by substituting "hafnium” therefor; dialkyltitanium cation complexes such as diethyltitanium cation complexes obtained by substituting "diethyl” for "dimethyl” in the ion complexes, dipropyltitanium cation complexes obtained by substituting "dipropyl” therefor and dibutyltitanium cation complexes obtained by substituting "dibutyl” therefor; diaryltitanium cation complexes such as diphenyltitanium cation complexes obtained by substituting "diphenyl” therefor and bis(penta
  • dialkoxytitanium cation complexes such as dimethoxytitanium cation complexes obtained by substituting "dimethoxide” therefor, di-n-butoxytitanium cation complexes obtained by substituting "di-n-butoxide” therefor and diisopropoxytitanium cation complexes obtained by substituting "diisopropoxide” therefor; diaryloxytitanium cation complexes such as
  • diaralkyloxytitanium cation complexes such as dibenzyloxytitamum cation complexes obtained by substituting "dibenzyloxide” therefor; and diamidotitanium cation complexes such as bis(dimethylamido)titanium cation complexes obtained by substituting "bis(dimethylamido)” therefor and bis(diethylamido)titanium cation complexes obtained by substituting "bis(diethylamido)” therefor.
  • dialkyltitanium cation complexes are preferable, and dimethyltitanium cation complexes are particularly preferable.
  • transition metal ion complex (1-3) examples include the following ion complexes:
  • dimethyltitanium cation complexes such as [ ⁇ l-triphenylsilyl-2,3,4,5- tetramethylcyclopentadienyl ⁇ dimethyltitanium cation][tetrakis(pentafluorophenyl)borate], [ ⁇ 1 phenyldi(2-methylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl ⁇ dimethyltitanium cation] [tetrakis(pentafluorophenyl)borate], [ ⁇ 1 -phenyldi(3 -methylphenyl)silyl-2, 3,4,5- tetramethylcyclopentadienyl ⁇ dimethyltitanium cation] [tetrakis(pentafluorophenyl)borate], [ ⁇ 1 phenyldi(4-methylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl ⁇ d
  • examples of the transition metal ion complex (1-3) also include dimethyltitanium cation complexes obtained by substituting "2-methylcyclopentadienyl", “3- methylcyclopentadienyl”, “2,3-dimethylcyclopentadienyl", “2,4-dimethylcyclopentadienyl", “2,5-dimethylcyclopentadienyl”, “2,3,5-trimethylcyclopentadienyl”, “2-ethylcyclopentadienyl”, “ 3 -ethylcyclopentadienyl " , " 2-n-propylcyclopentadienyl " , “3 -n-propylcyclopentadienyl " , "2- isopropylcyclopentadienyl”, “3-isopropylcyclopentadienyl", “2-n-butylcyclopentadienyl”, “3-n- butylcyclopent
  • examples of the transition metal ion complex (1-3) also include: dimethyl transition metal cation complexes such as dimethylzirconium cation complexes obtained by substituting "zirconium” for "titanium” in the ion complexes exemplified above, and dimethylhafnium cation complexes obtained by substituting "hafnium” therefor; dialkyltitanium cation complexes such as diethyltitanium cation complexes obtained by substituting "diethyl” for "dimethyl” in the ion complexes, dipropyltitanium cation complexes obtained by substituting "dipropyl” therefor and dibutyltitanium cation complexes obtained by substituting "dibutyl” therefor; diaryltitanium cation complexes such as diphenyltitanium cation complexes obtained by substituting "diphenyl” therefor and bis(penta
  • dialkoxytitanium cation complexes such as dimethoxytitanium cation complexes obtained by substituting "dimethoxide” therefor, di-n-butoxytitanium cation complexes obtained by substituting "di-n-butoxide” therefor and diisopropoxytitanium cation complexes obtained by substituting "diisopropoxide” therefor; diaryloxytitanium cation complexes such as
  • diaralkyloxytitanium cation complexes such as dibenzyloxytitanium cation complexes obtained by substituting "dibenzyloxide” therefor; and diamidotitanium cation complexes such as bis(dimethylamido)titanium cation complexes obtained by substituting "bis(dimethylamido)" therefor and bis(diethylamido)titanium cation complexes obtained by substituting
  • dialkyltitanium cation complexes are preferable, and dimethyltitanium cation complexes are particularly preferable.
  • A represents a counter anion.
  • the counter anion is an anion that can stabilize the cation of the element of Group 4 of the Periodic Table represented by M, and examples thereof include: anions of boron compounds such as tris(pentafluorophenyl)methylborate,
  • the counter anion is preferably tris(pentafluorophenyl)methylborate, tetrakis(pentafluorophenyl)borate, tris(pentafluorophenyl)methylaluminate, tetrakis(pentafluorophenyl)aluminate, etc., more preferably tetrakis(pentafluorophenyl)borate.
  • transition metal ion complex represented by the formula (1-1), (1-2) or (1-3) include [ ⁇ l-dimethylphenylsilyl-2,3,4,5- tetramethylcyclopentadienyl ⁇ dimethyltitanium cation] [tetrakis(pentafluorophenyl)borate], [ ⁇ 1- dimethyl(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl ⁇ dimethyltitanium cation][tetrakis(pentafluorophenyl)borate], [ ⁇ l-dimethyl(3,5-diethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadienyl ⁇ dimethyltitanium cation] [tetrakis(pentafluorophenyl)borate], [ ⁇ 1- dimethy 1(5 -methyl-3 -trimethylsily 1-3 ,
  • transition metal ion complexes (1-1), (1-2) and (1-3) can be produced from a transition metal complex represented by formula (2-1) (hereinafter, abbreviated to a “transition metal complex (2-1)”), a transition metal complex represented by formula (2-2) (hereinafter, abbreviated to a “transition metal complex (2-2)”) and a transition metal complex represented by formula (2-3) (hereinafter, abbreviated to a “transition metal complex (2-3)”), respectively, by similar methods:
  • 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 M are as defined above, and X 3 represents an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent or ay have a halogen atom as a substituent,
  • X 3 represents
  • an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent or an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent, and
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , X 1 , X 2 and M are as defined above, and
  • X 3 represents
  • transition metal ion complex (1-1) the transition metal ion complex (1-1) will be described as an example.
  • the transition metal ion complex (1-1) can be produced by a method comprising the step of reacting the transition metal complex (2-1) with one or more compounds selected from the compound group consisting of the following compounds (Dl), (D2) and (D3)
  • transition metal complex (2-1) examples include the following complexes:
  • trimethyltitanium complexes such as [l-dimethylphenylsilyl-2,3,4,5- tetramethylcyclopentadienyl]trimethyltitanium, [l-diethylphenylsilyl-2,3,4,5- tetramethylcyclopentadienyl]trimethyltitanium, [ 1 -phenyldi(n-propyl)silyl-2, 3 ,4, 5 - tetramethylcyclopentadienyl]trimethyltitanium, [ 1 -diisopropylphenylsilyl-2,3,4,5- tetramethylcyclopentadienyl]trimethyltitanium, [l-di(n-butyl)phenylsilyl-2,3,4,5- tetramethylcyclopentadienyl]trimethyltitanium, [ 1 -di(isobutyl)phenylsilyl-2,3,4,5- tetramethylcycl
  • examples of the transition metal complex (2-1) also include trimethyltitanium complexes obtained by substituting "2-methylcyclopentadienyl", “3- methy lcyclopentadieny 1 " , “2,3 -dimethy lcyclopentadieny 1 " , “2, 4-dimethy Icy clopentadienyl " , “2,5 -dimethylcy clopentadienyl” , “2,3,5 -trimethylcy clopentadienyl “ , "2-ethy lcyclopentadieny 1 " , “3-ethylcyclopentadienyl”, “2-n-propylcyclopentadienyl”, “3-n-propylcyclopentadienyl”, “2- isopropylcyclopentadieny 1” , " 3 -isopropylcy clopentadienyl " , "
  • examples of the transition metal complex (2-1) also include:
  • trimethyl transition metal complexes such as trimethylzirconium complexes obtained by substituting "zirconium” for “titanium” in the complexes exemplified above, and
  • trimethylhafnium complexes obtained by substituting "hafnium” therefor trimethylhafnium complexes obtained by substituting "hafnium” therefor; trialkyltitanium complexes such as triethyltitanium complexes obtained by substituting "triethyl” for “trimethyl” in the complexes, tripropyltitanium complexes obtained by substituting "tripropyl” therefor and tributyltitanium complexes obtained by substituting "tributyl” therefor; triaryltitanium complexes such as triphenyltitanium complexes obtained by substituting "triphenyl” therefor and
  • tris(pentafluorophenyl)titanium complexes obtained by substituting "tris(pentafluorophenyl)" therefor; triaralkyltitanium complexes such as tribenzyltitanium complexes obtained by substituting "tribenzyl” therefor; dialkoxy(alkyl)titanium complexes such as
  • dimethoxy(methyl)titanium complexes obtained by substituting "dimethoxy(methyl)" therefor; diaryloxy(alkyl)titanium complexes such as diphenoxy(methyl)titanium complexes obtained by substituting "diphenoxy(methyl)" therefor; diaralkyloxy(alkyl)titanium complexes such as dibenzyloxy(methyl)titanium complexes obtained by substituting "dibenzyloxy(methyl)” therefor; and diamido(alkyl)titanium complexes such as bis(dimethylamido)(methyl)titanium complexes obtained by substituting "bis(dimethylamido)(methyl)" therefor and
  • bis(diethylamido)(methyl) therefor.
  • trialkyltitanium complexes are preferable, and trimethyltitanium complexes are particularly preferable.
  • transition metal complex (2-2) examples include the following complexes: [0085]
  • trimethyltitanium complexes such as [l-methyldiphenylsilyl-2,3,4,5- tetramethylcyclopentadienyljtrimethyltitanium, [l-ethyldiphenylsilyl-2,3,4,5- tetramethylcyclopentadienyljtrimethyltitanium, [l-n-propyldiphenylsilyl-2,3,4,5- tetramethylcyclopentadienyl]trimethyltitanium, [l-isopropyldiphenylsilyl-2,3,4,5- tetramethylcyclopentadienyl]trimethyltitanium, [l-n-butyldiphenylsilyl-2,3,4,5- tetramethylcyclopentadienyljtrimethyltitanium, [l-isobutyldiphenylsilyl-2,3,4,5- tetramethylcyclopentadienyl]trimethyltitanium, [l
  • examples of the transition metal complex (2-2) also include trimethyltitanium complexes obtained by substituting "2-methylcyclopentadienyl", “3- methylcyclopentadienyl”, “2,3-dimethylcyclopentadienyl”, “2,4-dimethylcyclopentadienyl”, “2,5 -dimethylcyclopentadieny 1 " , “2,3,5 -trimethylcyclopentadieny 1 " , “2-ethylcy clopentadieny 1 " , “3-ethylcyclopentadienyl”, 2-n-propylcyclopentadienyr*, "3-n-propylcyclopentadienyl", “2- isopropylcyclopentadienyl” , “ 3 -isopropylcyclopentadienyl” , " 2-n-butylcyclopentadienyl " , " 3
  • examples of the transition metal complex (2-2) also include:
  • trimethyl transition metal complexes such as trimethylzirconium complexes obtained by substituting "zirconium” for “titanium” in the complexes exemplified above, and
  • trimethylhafnium complexes obtained by substituting "hafnium” therefor trimethylhafnium complexes obtained by substituting "hafnium” therefor; trialkyltitanium complexes such as triethyltitanium complexes obtained by substituting "triethyl” for “trimethyl” in the complexes, tripropyltitanium complexes obtained by substituting "tripropyl” therefor and tributyltitanium complexes obtained by substituting "tributyl” therefor; triaryltitanium complexes such as triphenyltitanium complexes obtained by substituting "triphenyl” therefor and
  • tris(pentafluorophenyl)titanium complexes obtained by substituting "tris(pentafluorophenyl)" therefor; triaralkyltitanium complexes such as tribenzyltitanium complexes obtained by substituting "tribenzyl” therefor; dialkoxy(alkyl)titanium complexes such as
  • dimethoxy(methyl)titanium complexes obtained by substituting "dimethoxy(methyl)" therefor; diaryloxy(alkyl)titanium complexes such as diphenoxy(methyl)titanium complexes obtained by substituting "diphenoxy(methyl)" therefor; diaralkyloxy(alkyl)titanium complexes such as dibenzyloxy(methyl)titanium complexes obtained by substituting "dibenzyloxy(methyl)” therefor; and diamido(alkyl)titanium complexes such as bis(dimethylamido)(methyl)titanium complexes obtained by substituting "bis(dimethylamido)(methyl)" therefor and
  • bis(diethylamido)(methyl) therefor.
  • trialkyltitanium complexes are preferable, and trimethyltitanium complexes are particularly preferable.
  • transition metal complex (2-3) examples include the following complexes:
  • trimethyltitanium complexes such as [l-triphenylsilyl-2,3,4,5- tetramethylcyclopentadienyljtrimethyltitanium, [l-phenyldi(2-methylphenyl)silyl-2,3,4,5- tetramethylcyclopentadienyljtrimethyltitamum, [l-phenyldi(3-methylphenyl)silyl-2,3,4,5- tetramethylcyclopentadienyl]trimethyltitanium, [l-phenyldi(4-methylphenyl)silyl-2,3,4,5- tetramethylcyclopentadienyl]trimethyltitanium, [ 1 -phenylbis(2, 3 -dimethylphenyl)silyl-2, 3 ,4, 5 - tetramethylcyclopentadienyl]trimethyltitanium, [l-phenylbis(2,4-dimethylphenyl)sily
  • examples of the transition metal complex (2-3) also include trimethyltitanium complexes obtained by substituting "2-methylcyclopentadienyl", “3- methylcyclopentadienyl”, “2,3-dimethylcyclopentadienyl", “2,4-dimethylcyclopentadienyl", “2,5-dimethylcyclopentadienyl”, “2,3,5-trimethylcyclopentadienyl”, “2-ethylcyclopentadienyl”, “ 3 -ethylcyclopentadienyl " , "2-n-propylcyclopentadieny 1" , “ 3 -n-propylcyclopentadienyl " , "2- isopropylcyclopentadieny 1 " , “ 3 -i sopropylcyclopentadieny 1 " , " 2-n-butylcyclopentadienyl " , “ 3 -n- butylcycl
  • examples of the transition metal complex (2-3) also include:
  • trimethyl transition metal complexes such as trimethylzirconium complexes obtained by substituting "zirconium” for “titanium” in the complexes exemplified above, and
  • trimethylhafnium complexes obtained by substituting "hafnium” therefor trimethylhafnium complexes obtained by substituting "hafnium” therefor; trialkyltitanium complexes such as triethyltitanium complexes obtained by substituting "triethyl” for “trimethyl” in the complexes, tripropyltitanium complexes obtained by substituting "tripropyl” therefor and tributyltitanium complexes obtained by substituting "tributyl” therefor; triaryltitanium complexes such as triphenyltitanium complexes obtained by substituting "triphenyl” therefor and
  • tris(pentafluorophenyl)titanium complexes obtained by substituting "tris(pentafluorophenyl)" therefor; triaralkyltitanium complexes such as tribenzyltitanium complexes obtained by substituting "tribenzyl” therefor; dialkoxy(alkyl)titanium complexes such as
  • dimethoxy(methyl)titanium complexes obtained by substituting "dimethoxy(methyl)" therefor; diaryloxy(alkyl)titanium complexes such as diphenoxy(methyl)titanium complexes obtained by substituting "diphenoxy(methyl)" therefor; diaralkyloxy(alkyl)titanium complexes such as dibenzyloxy(methyl)titanium complexes obtained by substituting "dibenzyloxy(methyl)” therefor; and diamido(alkyl)titanium complexes such as bis(dimethylamido)(methyl)titanium complexes obtained by substituting "bis(dimethylamido)(methyl)" therefor and
  • bis(diethylamido)(methyl) therefor.
  • trialkyltitanium complexes are preferable, and trimethyltitanium complexes are particularly preferable.
  • the method for reacting the transition metal complex (2-1) with the compound (D) can usually be performed by adding the transition metal complex (2-1) to a solvent and then adding the compound (D) to the mixture.
  • the amount of the compound (D) used is usually in the range of 0.5 to 5 moles, preferably 0.7 to 1.5 moles, per mole of the transition metal complex (2-1).
  • the reaction temperature is usually in the range of from -100°C to the boiling point of the solvent, preferably from -80°C to +60°C.
  • the reaction is usually performed in a solvent inert to the reaction.
  • a solvent include aprotic solvents such as: aromatic hydrocarbon solvents such as benzene and toluene; aliphatic hydrocarbon solvents such as hexane and heptane; ether solvents such as diethyl ether, tetrahydrofiiran and 1,4-dioxane; and halogen solvents such as dichloromethane, dichloroethane, chlorobenzene, dichlorobenzene, bromobenzene and dibromobenzene.
  • solvents are used alone or as a mixture of two or more thereof, and the amount thereof used is usually 1 to 200 parts by weight, preferably 3 to 50 parts by weight, per part by weight of the transition metal complex (2-1).
  • the transition metal ion complex (1-1) of interest can be obtained from the obtained reaction mixture by a usual method, for example, a method in which the formed precipitates are filtered off, and the filtrate is then concentrated to deposit a transition metal complex (1-1), which is then collected by filtration.
  • the compound (D) used in the production of the transition metal ion complexes (1-1) to (1-3) is one or more compounds selected from the group consisting of the compounds (Dl), (D2) and (D3) described above.
  • Q 1 , Q 2 , Q 3 , Q 4 , Q 5 , Q 6 , Q 7 , Q 8 , Q 9 , Q 10 and Q 11 are preferably a halogen atom or a hydrocarbyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent.
  • examples of the inorganic cation represented by T + include a ferrocenium cation, an alkyl-substituted ferrocenium cation, and a silver cation.
  • Examples of the organic cation include a triphenylmethyl cation.
  • Examples of (DQ 4 Q 5 Q 6 Q 7 ) “ and (DQ 8 Q 9 Q 10 Q U ) " include tetrakis(pentafluorophenyl)borate, tetrakis(2,3,5,6- tetrafluoropheny l)borate, tetraki s(2, 3 ,4, 5 -tetrafluorophenyl)borate, tetraki s(3 , 4, 5 - trifluorophenyl)borate, tetrakis(2,3,4-trifluorophenyl)borate,
  • Examples of the Broensted acid represented by (L-H) + include trialkyl-substituted ammonium, ⁇ , ⁇ -dialkylanilinium, dialkylammonium and triarylphosphonium.
  • Examples of the compound (Dl) represented by formula OQ l Q 2 Q 3 include tris(pentafluorophenyl)borane, tris(2, 3,5, 6-tetrafluoropheny l)borane, tris(2, 3 ,4, 5 - tetrafluorophenyl)borane, tris(3,4,5-trifIuorophenyl)borane, tris(2,3,4-trifluorophenyl)borane, phenylb i s(pentafiuoropheny l)borane, tris(pentafluorophenyl)alane, tris(2, 3 , 5 ,6- tetrafluorophenyl)alane, tris(2,3,4,5-tetrafiuorophenyl)alane, tris(3,4,5-trifiuorophenyl)alane, tris(2,3,4-trifluorophenyl)alane and pheny
  • the compound (Dl) is preferably tris(pentafiuorophenyl)borane or tris(pentafluorophenyl)alane, most preferably tris(pentafluorophenyl)borane.
  • Examples of the compound (D2) represented by formula T + (DQ 4 Q 5 Q 6 Q 7 ) ' include ferrocenium tetrakis(pentafluorophenyl)borate, 1, ⁇ -dimethylferrocenium
  • the compound (D2) is preferably triphenylmethyl tetrakis(pentafiuorophenyl)borate or triphenylmethyl tetrakis(pentafluorophenyl)aluminate, most preferably triphenylmethyl tetrakis(pentafluorophenyl)borate.
  • Examples of the compound (D3) represented by formula (L-H) + (DQ 8 Q 9 Q 10 Q U ) " include triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium
  • the compound (D3) is preferably tri(normal
  • the transition metal complex (2-1) can be obtained by reacting a transition metal complex represented by formula (2-1) wherein X 3 is a halogen atom (hereinafter, abbreviated to a "transition metal halide complex (2-1)”) with a lithium, sodium, potassium or magnesium compound having an alkyl, aryl or aralkyl group corresponding to X 3 .
  • the transition metal complex (2-2) can be obtained by reacting a transition metal complex represented by formula (2- 2) wherein X 3 is a halogen atom (hereinafter, abbreviated to a "transition metal halide complex (2-2)”) with a lithium, sodium, potassium or magnesium compound having an alkyl, aryl or aralkyl group corresponding to X 3 .
  • the transition metal complex (2-3) can be obtained by reacting a transition metal complex represented by formula (2-3) wherein X 3 is a halogen atom (hereinafter, abbreviated to a "transition metal halide complex (2-3)”) with a lithium, sodium, potassium or magnesium compound having an alkyl, aryl or aralkyl group corresponding to X 3 .
  • X 3 is a halogen atom (hereinafter, abbreviated to a "transition metal halide complex (2-3)”) with a lithium, sodium, potassium or magnesium compound having an alkyl, aryl or aralkyl group corresponding to X 3 .
  • transition metal halide complex (2-1) examples include the following complexes:
  • titanium chloride complexes such as [l-dimethylphenylsilyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [ 1 -diethylphenylsilyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [l-phenyldi(n-propyl)silyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [ 1 -diisopropylphenylsilyl-2,3 ,4, 5- tetramethylcyclopentadienyl]titanium trichloride, [l-di(n-butyl)phenylsilyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [l-di(isobutyl)phenylsilyl-2,
  • examples of the transition metal halide complex (2-1) also include titanium chloride complexes obtained by substituting "2-methylcyclopentadienyl", “3- methylcyclopentadieny 1 " , “2,3 -dimethy lcyclopentadienyl “ , “ 2,4-dimethy lcyclopentadieny 1 " , “2,5 -dimethy lcyclopentadieny 1 " , “2,3,5 -trimethylcyclopentadienyl “ , " 2-ethy lcyclopentadieny 1 " , “ 3 -ethylcyclopentadienyl “ , " 2-n-propylcyclopentadieny 1 " , “3 -n-propylcyclopentadienyl “ , "2- isopropylcyclopentadienyl", “3-isopropylcyclopentadienyl", "2-n-butylcycl
  • examples of the transition metal halide complex (2-1) also include: transition metal chloride complexes such as zirconium chloride complexes obtained by substituting "zirconium” for "titanium” in the complexes exemplified above, and hafnium chloride complexes obtained by substituting "hafnium” therefor; and titanium halide complexes such as titanium fluoride complexes obtained by substituting "fluoride” for "chloride” in the complexes, titanium bromide complexes obtained by substituting "bromide” therefor and titanium iodide complexes obtained by substituting "iodide” therefor.
  • transition metal chloride complexes such as zirconium chloride complexes obtained by substituting "zirconium” for "titanium” in the complexes exemplified above, and hafnium chloride complexes obtained by substituting "hafnium” therefor
  • titanium halide complexes such as titanium fluoride complexes obtained
  • transition metal halide complex (2-2) can include the following complexes:
  • titanium chloride complexes such as [l-methyldiphenylsilyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [l-ethyldiphenylsilyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [ l-n-propyldiphenylsilyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [l-isopropyldiphenylsilyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [l-n-butyldiphenylsilyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [l-isobutyldiphenylsilyl-2,3,4,5- tetramethylcyclopentadie
  • examples of the transition metal halide complex (2-2) also include titanium chloride complexes obtained by substituting "2-methylcyclopentadienyl", “3- methylcyclopentadienyl”, “2,3-dimethylcyclopentadienyl", “2,4-dimethylcyclopentadienyl", “2,5-dimethylcyclopentadienyl”, “2,3,5-trimethylcyclopentadienyl”, "2-ethylcyclopentadienyl”, “ 3 -ethylcyclopentadienyl” , "2-n-propylcyclopentadieny 1 " , “3 -n-propylcyclopentadieny " , " 2- isopropylcyclopentadieny 1 " , “ 3 -i sopropylcyclopentadienyl " , "2-n-butylcyclopentadienyl " , “ 3 -n- butylcyclopen
  • examples of the transition metal halide complex (2-2) also include: titanium halide complexes such as zirconium chloride complexes obtained by substituting "zirconium” for "titanium” in the complexes exemplified above, and hafnium chloride complexes obtained by substituting "hafnium” therefor; and titanium halide complexes such as titanium fluoride complexes obtained by substituting "fluoride” for "chloride” in the complexes, titanium bromide complexes obtained by substituting "bromide” therefor and titanium iodide complexes obtained by substituting "iodide” therefor.
  • titanium halide complexes such as zirconium chloride complexes obtained by substituting "zirconium” for "titanium” in the complexes exemplified above, and hafnium chloride complexes obtained by substituting "hafnium” therefor
  • titanium halide complexes such as titanium fluoride complexes obtained
  • transition metal halide complex (2-3) examples include the following complexes:
  • titanium chloride complexes such as [l-triphenylsilyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [l-phenyldi(2-methylphenyl)silyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [l-phenyldi(3-methylphenyl)silyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [l-phenyldi(4-methylphenyl)silyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [l-phenylbis(2,3-dimethylphenyl)silyl-2,3,4,5 tetramethylcyclopentadienyl]titanium trichloride, [l-phenylbis(2,3-dimethylphen
  • examples of the transition metal halide complex (2-3) also include titanium chloride complexes obtained by substituting "2-methylcyclopentadienyl", “3- methylcyclopentadienyl”, “2,3-dimethylcyclopentadienyl", “2,4-dimethylcyclopentadienyl", "2,5-dimethylcyclopentadienyl", “2,3,5-trimethylcyclopentadienyl”, "2-ethylcyclopentadienyl”, “3-ethylcyclopentadienyl”, “2-n-propylcyclopentadienyl", “3-n-propylcyclopentadienyl”, “2- isopropylcyclopentadienyl", “3-isopropylcyclopentadienyl", "2-n-butylcyclopentadienyl", “3-n- butylcyclopentadienyl”, “2-sec-butylcycl
  • transition metal halide complex (2-3) also include: titanium halide complexes such as zirconium chloride complexes obtained by substituting
  • zirconium for "titanium” in the complexes exemplified above, and hafnium chloride complexes obtained by substituting "hafnium” therefor; and titanium halide complexes such as titanium fluoride complexes obtained by substituting "fluoride” for "chloride” in the complexes, titanium bromide complexes obtained by substituting "bromide” therefor and titanium iodide complexes obtained by substituting "iodide” therefor.
  • the transition metal halide complexes (2-1), (2-2) and (2-3) can be produced from a substituted cyclopentadiene compound represented by formula (8-1) (hereinafter, abbreviated to a "substituted cyclopentadiene compound (8-1)”), a substituted cyclopentadiene compound represented by formula (8-2) (hereinafter, abbreviated to a “substituted cyclopentadiene compound (8-2)”) and a substituted cyclopentadiene compound represented by formula (8-3) (hereinafter, abbreviated to a "substituted cyclopentadiene compound (8-3)”), respectively, by similar methods:
  • R , R z , R J , R , R , R , R , R , R 9 R and R . 1 1 1 1 are as defined above,
  • R , R R 3 , R R , R°, R', R e , R v , R , R , R", R , R and R lb are as defined above, and
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , and R 21 are as defined above.
  • transition metal halide complex (2-1) will be described as an example.
  • the transition metal halide complex (2-1) can be produced by, for example, a method comprising the steps of:
  • transition metal compound (9) a transition metal compound represented by formula (9) (hereinafter, referred to as a "transition metal compound (9)"):
  • the step of reacting the substituted cyclopentadiene compound (8-1) with a base in the presence of an amine compound may be referred to as a “1st reaction step”
  • the step of reacting the reaction product of the substituted cyclopentadiene compound (8-1) and the base with a transition metal compound (9) may be referred to as a "2nd reaction step”.
  • the substituted cyclopentadiene compound (8-1) has isomers differing in the double bond position of each cyclopentadiene ring. In the present invention, it represents any of them or a mixture of them.
  • the substituent X 4 is as defined above, and examples thereof include the same as those exemplified for X 1 and X 2 .
  • transition metal compound (9) examples include: titanium halide such as titanium tetrachloride, titanium trichloride, titanium tetrabromide and titanium tetraiodide;
  • amidotitanium such as dichlorobis(dimethylamino)titanium and
  • transition metal compound (9) examples include compounds obtained by substituting "zirconium” or “hafnium” for "titanium” in these compounds. Of them, a preferable transition metal compound (9) is titanium tetrachloride.
  • Examples of the base reacted with the substituted cyclopentadiene compound (8- 1) in the 1st reaction step include organic alkali metal compounds typified by organic lithium compounds such as methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert- butyllithium, lithiumtrimethylsilyl acetylide, lithium acetylide, trimethylsilylmethyllithium, vinyllithium, phenyllithium and allyllithium.
  • organic alkali metal compounds typified by organic lithium compounds such as methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert- butyllithium, lithiumtrimethylsilyl acetylide, lithium acetylide, trimethylsilylmethyllithium, vinyllithium, phenyllithium and allyllithium.
  • the amount of the base used may be in the range of 0.5 to 5 moles per mole of the substituted cyclopentadienyl compound (8-1).
  • an amine compound is used in the reaction of the substituted cyclopentadiene compound (8-1) with the base in the 1st reaction step.
  • an amine compound examples include: primary amine compounds such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, tert-butylamine, n-octylamine, n-decylamine, aniline and ethylenediamine; secondary amine compounds such as dimethylamine, diethylamine, di-n- propylamine, diisopropylamine, di-n-butylamine, di-tert-butylamine, di-n-octylamine, di-n- decylamine, pyrrolidine, hexamethyldisilazane and diphenylamine; and tertiary amine compounds such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-buty
  • the reaction of the substituted cyclopentadiene compound (8-1) with the base is preferably performed in the presence of a solvent.
  • the solvent is used, the substituted cyclopentadiene compound (8-1) and the base are reacted in the solvent and then a transition metal compound (9) can be added into this reaction mixture to thereby further react the transition metal compound (9) with the reaction product of the substituted
  • cyclopentadiene compound (8-1) and the base Solids may be deposited in the reaction mixture obtained by reacting the substituted cyclopentadiene compound (8-1) and the base.
  • the solvent may be further added until the deposited solid is dissolved; or the deposited solid may be temporarily separated by filtration or the like, and the solvent may be added to the separated solid for dissolution or suspension, followed by the addition of a transition metal compound (9).
  • the substituted cyclopentadiene compound (8-1), the base and the transition metal compound (9) can also be added simultaneously to the solvent to thereby perform the 1st reaction step and the 2nd reaction step almost simultaneously.
  • the solvent used in the 1st reaction step or in the 1st and 2nd reaction steps is an inert solvent that does not significantly hinder the progress of the reaction associated with these steps.
  • aprotic solvents such as: aromatic hydrocarbyl solvents such as benzene and toluene; aliphatic hydrocarbyl solvents such as hexane and heptane; ether solvents such as diethyl ether, tetrahydrofuran and 1,4-dioxane; amide solvents such as hexamethylphosphoric amide and dimethylformamide; polar solvents such as
  • acetonitrile acetonitrile, propionitrile, acetone, diethyl ketone, methyl isobutyl ketone and cyclohexanone
  • halogen solvents such as dichloromethane, dichloroethane, chlorobenzene and
  • dichlorobenzene These solvents can be used alone or as a mixture of two or more thereof, and the amount thereof used is preferably 1 to 200 parts by weight, more preferably 3 to 50 parts by weight, per part by weight of the substituted cyclopentadiene compound (8-1).
  • the amount of the transition metal compound (9) used is preferably in the range of 0.5 to 3 moles, more preferably in the range of 0.7 to 1.5 moles, per mole of the substituted cyclopentadiene compound (8-1).
  • the reaction temperature of the 1 st and 2nd reaction steps needs only to be a temperature between -100°C and the boiling point of the solvent inclusive and is preferably in the range of from -80 to +100°C.
  • the produced transition metal complex (2-1) wherein X 3 is a halogen atom can be taken by various purification methods known in the art.
  • the transition metal complex (2-1) of interest wherein X 3 is a halogen atom can be obtained by a method in which after the 1st and 2nd reaction steps, the formed precipitates are filtered off, and the filtrate is then concentrated to deposit a transition metal complex (2-1) wherein X 3 is a halogen atom, which is then collected by filtration.
  • the substituents R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 and R 21 are as defined above.
  • Examples of the substituted cyclopentadiene compound (8-1) include the following substituted cyclopentadiene compounds:
  • substituted cyclopentadiene compounds such as l-dimethylphenylsilyl-2, 3,4,5- tetramethylcyclopentadiene, 1 -diethylphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1 - phenyldi(n-propyl)silyl-2,3,4,5-tetramethylcyclopentadiene, l-diisopropylphenylsilyl-2,3,4,5- tetramethylcyclopentadiene, l-di(n-butyl)phenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1- di(isobutyl)phenylsilyl-2,3,4,5-tetramethylcyclopentadiene, l-di(sec-butyl)phenylsilyl-2, 3,4,5 - tetramethylcyclopentadiene, 1 -di(tert-butyl)pheny
  • examples of the substituted cyclopentadiene compound (8-1) also include substituted cyclopentadiene compounds obtained by substituting "2- methylcyclopentadiene", “3-methylcyclopentadiene”, “2,3-dimethylcyclopentadiene”, “2,4- dimethylcyclopentadiene", "2,5-dimethylcyclopentadiene”, “2,3,5-trimethylcyclopentadiene”, "2- ethylcyclopentadiene”, “3-ethylcyclopentadiene”, “2-n-propylcyclopentadiene”, “3-n- propylcyclopentadiene”, “2-isopropylcyclopentadiene”, “3-isopropylcyclopentadiene", "2-n- butylcyclopentadiene", “3-n-butylcyclopentadiene”, “2-sec-butylcyclopentadiene”, "3-sec- butylcyclopentadiene, “
  • Examples of the substituted cyclopentadiene compound (8-2) include the following substituted cyclopentadiene compounds:
  • substituted cyclopentadiene compounds such as l-methyldiphenylsilyl-2,3,4,5- tetramethylcyclopentadiene, l-ethyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1-n- propyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, l-isopropyldiphenylsilyl-2,3,4,5- tetramethylcyclopentadiene, 1 -n-butyldiphenylsilyl-2, 3 ,4, 5-tetramethylcyclopentadiene, 1 - isobutyIdiphenylsilyl-2,3 ,4, 5 -tetramethylcyclopentadiene, 1 -sec-butyldiphenylsilyl-2,3,4, 5- tetramethylcyclopentadiene, 1 -tert-butyldiphenylsilyl-2,3,4,5-te
  • examples of the substituted cyclopentadiene compound (8-2) also include substituted cyclopentadiene compounds obtained by substituting "2- methylcyclopentadiene", “3-methylcyclopentadiene”, “2,3-dimethylcyclopentadiene”, “2,4- dimethylcyclopentadiene", “2,5-dimethylcyclopentadiene”, “2,3,5-trimethylcyclopentadiene”, "2- ethylcyclopentadiene”, “3-ethylcyclopentadiene”, “2-n-propylcyclopentadiene”, “3-n- propylcyclopentadiene “ , "2-isopropylcyclopentadiene " , “3 -isopropylcyclopentadiene " , " 2-n- butylcyclopentadiene”, “3-n-butylcyclopentadiene”, “2-sec-butylcyclopentadiene", "3-sec- buty
  • Examples of the substituted cyclopentadiene compound (8-3) include the following substituted cyclopentadiene compounds:
  • substituted cyclopentadiene compounds such as l-triphenylsilyl-2,3,4,5- tetramethylcyclopentadiene, 1 -phenyldi(2-methylphenyl)silyl-2,3 ,4, 5- tetramethy lcyclopentadiene, 1 -phenyldi(3 -methylphenyl)silyl-2, 3 ,4, 5- tetramethylcyclopentadiene, l-phenyldi(4-methylphenyl)silyl-2,3,4,5- tetramethy lcyclopentadiene, 1 -pheny lb is(2, 3 -dimethy lpheny l)silyl-2, 3,4,5- tetramethylcyclopentadiene, l-phenylbis(2,4-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-phenylbis(2,5-d
  • examples of the substituted cyclopentadiene compound (8-3) also include substituted cyclopentadiene compounds obtained by substituting "2- methylcyclopentadiene", “3-methylcyclopentadiene”, “2,3-dimethylcyclopentadiene", “2,4- dimethylcyclopentadiene", “2,5-dimethylcyclopentadiene”, “2,3,5-trimethylcyclopentadiene”, "2- ethylcyclopentadiene”, “3-ethylcyclopentadiene”, “2-n-propylcyclopentadiene”, “3-n- propylcyclopentadiene”, “2-isopropylcyclopentadiene”, “3-isopropylcyclopentadiene", "2-n- butylcyclopentadiene", “3-n-butylcyclopentadiene”, “2-sec-butylcyclopentadiene”, "3-sec- butylcyclopentadiene, “
  • the substituted cyclopentadiene compound (8-1) can be produced by a method comprising the steps of:
  • the substituted cyclopentadiene compound (8-2) can be produced by a method comprising the steps of:
  • the substituted cyclopentadiene compound (8-3) can be produced by a method comprising the steps of:
  • halogenated silyl compound (11-3) represented by a formula (11-3) (hereinafter, abbreviated to a “halogenated silyl compound (11-3)”), respectively:
  • R d R 4 are as defined above, and
  • R 7 , R 8 , R 9 , R 10 and R 11 are as defined above, and X 5 is a halogen atom,
  • R 5 , R 6 , R 7 , R 8 , R 9 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are as defined above, and X 5 is a halogen atom, and
  • R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R n , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 and R 21 are as defined above, and X 5 is a halogen atom.
  • the substituted cyclopentadiene compound (10) is as follows:
  • R 1 , R 2 , R 3 and R 4 are as defined above, and
  • Examples of the substituted cyclopentadiene compound (10) include the following compounds:
  • methylcyclopentadiene 1,2-dimethylcyclopentadiene, 1,3- dimethylcyclopentadiene, 1,2,3-trimethylcyclopentadiene, 1,3,4-trimethylcyclopentadiene, 1,2,3,4-tetramethylcyclopentadiene, ethylcyclopentadiene, 1,2-diethylcyclopentadiene, 1,3- diethylcyclopentadiene, 1,2,3-triethylcyclopentadiene, 1,3,4-triethylcyclopentadiene, 1,2,3,4- tetraethylcyclopentadiene, n-propylcyclopentadiene, isopropylcyclopentadiene, n- butylcyclopentadiene, sec-butylcyclopentadiene, tert-butylcyclopentadiene, n- pentylcyclopentadiene, neopentylcyclopenta
  • trimethylsilylcyclopentadiene triethylsilylcyclopentadiene, tert- butyldimethylsilylcyclopentadiene, indene, 2-methylindene, tetrahydroindene, 2- methyltetrahydroindene, 3-methyltetrahydroindene, 2,3-dimethyltetrahydroindene, 2- ethyltetrahydroindene, 2-n-propyltetrahydroindene, 2-isopropyltetrahydroindene, 2-n- butyltetrahydroindene, 2-sec-butyltetrahydroindene, 2-tert-butyltetrahydroindene, 2-n- pentyltetrahydroindene, 2-neopentyltetrahydroindene, 2-amyltetrahydroindene, 2-n- hexyltetrahydroin
  • the substituted cyclopentadiene compounds (10) exemplified above may have isomers differing in the double bond position of each cyclopentadiene ring. A mixture of these isomers may be used.
  • the halogenated silyl compound (11-1) is as follows:
  • R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R u are as defined above, and X 5 is a halogen atom.
  • halogenated silyl compound (11-1) examples include the following halogenated silyl compounds:
  • chlorodimethylphenylsilane chlorodiethylphenylsilane, chlorophenyldi(n- propyl)silane, chlorodiisopropylphenylsilane, di(n-butyl)chlorophenylsilane,
  • chloroethylmethyl(3,5-diethylphenyl)silane chloromethyl(3,5-diethylphenyl)(n-propyl)silane, chloromethyl(3,5-diethylphenyl)(isopropyl)silane, n-butylchloromethy 1(3, 5 -diethylphenyl) silane, isobutylchloromethyl(3,5-diethylphenyl)silane, sec-butylchloromethyl(3,5-diethylphenyl)silane, tert-buty lchloromethyl(3 , 5 -diethylpheny l)silane, chlorocyclohexy Imethy 1(3 , 5 - diethylphenyl)silane, chloromethyl(n-octadecyl)(3, 5 -diethylphenyl) silane,
  • halogenated silyl compound (11-2) examples include the following halogenated silyl compounds:
  • chloromethyldiphenylsilane chloroethyldiphenylsilane, chloro-n- propyldiphenylsilane, chloroisopropyldiphenylsilane, n-butylchlorodiphenylsilane,
  • chloromethyl(4-methylphenyl)(3,5-dimethylphenyl)silane chloromethyl(2,3- dimethylphenyl)(3,5-ditnethylphenyl)silane, chloromethyl(2,4-dimethylphenyl)(3,5- ditnethylphenyl)silane, chloromethyl(2,5-dimethylphenyl)(3,5-dimethylphenyl)silane, chloromethylphenyl(2,6-dimethylphenyl)(3,5-dimethylphenyl)silane, chloromethylbis(3,5- dimethylphenyl)silane, chloromethyl(3,5-dimethylphenyl)(3,4,5-trimethylphenyl)silane,
  • halogenated silyl compound (11-3) examples include the following halogenated silyl compounds:
  • chlorotriphenylsilane chlorophenyldi(2-methylphenyl)silane, chloropheny ldi(3 - methylphenyl)silane, chlorophenyldi(4-methylphenyl)silane, chlorophenylbis(2, 3 - dimethylphenyl)silane, chlorophenylbis(2,4-dimethylphenyl)silane, chloropheny lb is(2, 5- dimethylphenyl)silane, chlorophenylbis(2,6-dimethylphenyl)silane, chlorophenylbis(3,5- dimethylphenyl)silane, chlorophenylbis(3,5-diethylphenyl)silane, chlorophenylbis(5-methyl-3- trimethylsilyl-phenyl)silane, chlorophenylbis(3,4,5-trimethylphenyl)silane,
  • chlorodiphenyl(2-methylphenyl)silane chlorodiphenyl(3-methylphenyl)silane, chlorodiphenyl(4-methylphenyl)silane, chlorodiphenyl(2,3-dimethylphenyl)silane,
  • chlorodiphenyl(2,4-dimethylphenyl)silane chlorodiphenyl(2,5-dimethylphenyl)silane, chlorodiphenyl(2,6-dimethylphenyl)silane, chlorodiphenyl(3,5-dimethylphenyl)silane, chlorodiphenyl(3,5-diethylphenyl)silane, chlorodiphenyl(5-methyl-3-trimethylsilyl- phenyl)silane, chlorodiphenyl(3,4,5-trimethylphenyl)silane,
  • chlorodi(2-methylphenyl)(3,5-diethylphenyl)silane chlorodi(3- methylphenyl)(3,5-diethylphenyl)silane, chlorodi(4-methylphenyl)(3,5-diethylphenyl)silane, chlorobis(2,3-dimethylphenyl)(3,5-diethylphenyl)silane, chlorobis(2,4-dimethylphenyl)(3,5- diethylphenyl)silane, chlorobis(2,5-dimethylphenyl)(3,5-diethylphenyl)silane, chlorobis(2,6- dimethylphenyl)(3,5-diethylphenyl)silane, chlorotris(3,5-diethylphenyl)silane, chloro(3,5- diethylphenyl)bis(3,4,5-dimethylphenyl)silane,
  • Examples of the base reacted with the substituted cyclopentadiene compound (10) include: alkali metal hydride such as lithium hydride, sodium hydride and potassium hydride; alkaline earth metal hydride such as calcium hydride; and organic alkali metal compounds typified by organic lithium compounds such as methyllithium, ethyllithium, n-butyllithium, sec- butyllithium, tert-butyllithium, lithiumtrimethylsilyl acetylide, lithium acetylide,
  • trimethylsilylmethyllithium, vinyllithium, phenyllithium and allyllithium is usually in the range of 0.5- to 3 -fold by mol, preferably 0.9- to 2-fold by mol, with respect to the substituted cyclopentadiene compound (10).
  • a usual commercially available mineral oil-containing product can be used directly as sodium hydride or potassium hydride. Of course, the mineral oil may be removed, for use, by washing with a hydrocarbyl solvent such as hexane.
  • an amine compound may be used in the step of reacting the substituted cyclopentadiene compound (10) with a base.
  • an amine compound include: primary anilines such as aniline, chloroaniline, bromoaniline, fluoroaniline, dichloroaniline,
  • 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
  • aminobenzoate and t-butyl aminobenzoate and other primary amines including naphthylamine, naphthylmethylamine, benzylamine, propylamine, butylamine, pentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, 2-aminopyridine, 3-aminopyridine and 4- aminopyridine;
  • secondary amines such as N-methylaniline, N-ethylaniline, diphenylamine, N- methylchloroaniline, N-methylbromoaniline, N-methylfluoroaniline, N-methylanisidine, N- methylmethylaniline, N-methylethylaniline, N-methyl-n-propylaniline, N- methylisopropylaniline, diethylamine, dipropylamine, diisopropylamine, dipentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, morpholine, piperidine, 2,2,6,6- tetramethylpiperidine, pyrrolidine, 2-methylamino pyridine, 3-methylaminopyridine and 4- methylaminopyridine; and
  • tertiary amines such as N,N-dimethylaniline, ⁇ , ⁇ -dimethylchloroaniline, N,N- dimethylbromoaniline, N,N-dimethylfluoroaniline, ⁇ , ⁇ -dimethylanisidine, N,N- dimethylethylaniline, N,N-dimethyl-n-propylaniline, N,N-dimethylisopropylaniline, 1,4- diazabicyclo[2.2.2]octane, l,5-diazabicyclo[4.3.0]non-5-ene, l,8-diazabicyclo[5.4.0]undec-7- ene, 2-dimethylaminopyridine, 3-dimethylaminopyridine, 4-dimethylaminopyridine,
  • trimethylamine triethylamine, tri-n-propylamine, tri-n-butylamine, diisopropylethylamine, tri-n- octylamine, tri-n-decylamine and triphenylamine.
  • primary or secondary amines more preferably primary amines are used.
  • the amount of such an amine compound used is usually in the range of 0.001- to 2-fold by mol, preferably 0.01- to 0.5-fold by mol, with respect to the base.
  • the reaction is usually performed in a solvent inert to the reaction.
  • a solvent include aprotic solvents such as: aromatic hydrocarbyl solvents such as benzene, toluene and xylene; aliphatic hydrocarbyl solvents such as pentane, hexane, heptane, octane and cyclohexane; ether solvents such as diethyl ether, methyl t-butyl ether, tetrahydrofuran and 1,4-dioxane; amide solvents such as hexamethylphosphoric amide, dimethylformamide, dimethylacetamide and N- methylpyrrolidone; and halogen solvents such as chlorobenzene and dichlorobenzene. These solvents are used
  • the substituted cyclopentadiene compound (10), the base and the amine compound may be mixed simultaneously in a solvent, or the base and the amine compound are mixed in advance and then the substituted cyclopentadiene compound (10) may be added to the mixture.
  • the reaction temperature is not particularly limited, and a temperature region that eliminates the need of low temperature equipment is industrially preferable and is, for example, in the range of from 0 to 70°C, preferably from 10 to 60°C.
  • This reaction efficiently produces a metal salt of the substituted cyclopentadiene compound (10).
  • the metal salt of the substituted cyclopentadiene compound (10) thus obtained may be used directly in the form of the reaction mixture or may be taken from the reaction mixture. The former case usually suffices.
  • the reaction for obtaining the substituted cyclopentadiene compound (8-1) is usually performed in a solvent inert to the reaction.
  • a solvent include aprotic solvents such as: aromatic hydrocarbyl solvents such as benzene, toluene and xylene; aliphatic hydrocarbyl solvents such as pentane, hexane, heptane, octane and cyclohexane; ether solvents such as diethyl ether, methyl t-butyl ether, tetrahydrofuran and 1,4-dioxane; amide solvents such as hexamethylphosphoric amide, dimethylformamide, dimethylacetamide and N- methylpyrrolidone; and halogen solvents such as chlorobenzene and dichlorobenzene.
  • aromatic hydrocarbyl solvents such as benzene, toluene and xylene
  • solvents are used alone or as a mixture of two or more thereof, and the amount thereof used is usually in the range of 1- to 200-fold by weight, preferably 3- to 30-fold by weight, with respect to the substituted cyclopentadiene compound (10).
  • This reaction is usually performed, for example, by mixing the base, the amine compound and the substituted cyclopentadiene compound (10) in a solvent and then adding the halogenated silyl compound (11-1) to the mixture.
  • the substituted cyclopentadiene compound (8-1) of interest is produced.
  • the reaction temperature is not particularly limited, and a temperature region that eliminates the need of low temperature equipment is industrially advantageous and is, for example, in the range of 0 to 70°C, preferably 10 to 60°C.
  • the amount of the substituted cyclopentadiene compound (10) used is usually in the range of 0.5- to 5-fold by mol, preferably 0.8- to 3-fold by mol, with respect to the halogenated silyl compound (11-1).
  • the obtained substituted cyclopentadiene compound (8-1) may be purified, if necessary, by a method such as distillation and column chromatography treatment.
  • the catalyst for trimerization of the present invention is a catalyst for trimerization comprising the transition metal ion complex (1-1), (1-2) or (1-3). These transition metal ion complexes can be used as catalysts for ethylene trimerization without being brought into contact with an additional activating co-catalyst component.
  • the method for producing 1-hexene according to the present invention is a method for producing 1-hexene from ethylene and is a method for producing 1-hexene by trimerizing ethylene in the presence of the catalyst for trimerization.
  • transition metal ion complex (1-1), (1-2) or (1-3) of the present invention is used as a catalyst for trimerization in the production of 1-hexene
  • water in a reactor for performing trimerization reaction is preferably removed.
  • a compound (A) shown below can be used.
  • 1-hexene is produced by trimerizing ethylene in the presence of the catalyst for trimerization and the compound (A) .
  • E 1 represents a hydrocarbyl group having 1 to 8 carbon atoms
  • G represents a hydrogen atom or a halogen atom
  • a represents an integer of 1 to 3; in the case that more than one E l moieties exist, the E 1 moieties may be the same as or different from each other; and in the case that more than one G moieties exist, the G moieties may be the same as or different from each other.
  • examples of the hydrocarbyl group having 1 to 8 carbon atoms in E 1 include alkyl groups having 1 to 8 carbon atoms.
  • examples of the alkyl groups having 1 to 8 carbon atoms include methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, normal pentyl and neopentyl groups.
  • Examples of the organic aluminum compound (A) represented by formula (E I ) a Al(G)3-a include trialkylaluminum, dialkylaluminum chloride, alkylaluminum dichloride and dialkylaluminum hydride.
  • Examples of the trialkylaluminum include trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum and trihexylaluminum.
  • Examples of the dialkylaluminum chloride include dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride and dihexylaluminum chloride.
  • alkylaluminum dichloride examples include methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutyl aluminum dichloride and hexyl aluminum dichloride.
  • dialkylaluminum hydride examples include dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride and dihexylaluminum hydride.
  • the concentration of the transition metal ion complex is usually 0.0001 to 5 mmol/L, preferably 0.001 to 1 mmol/L.
  • the concentration of the compound (A) is usually 0.01 to 500 mmol L, preferably 0.1 to 100 mmol/L, in terms of the aluminum atom.
  • the tnmerization reaction of ethylene is not particularly limited and may be, for example, trimerization reaction using aliphatic hydrocarbyl (e.g., butane, pentane, hexane, heptane and octane), aromatic hydrocarbyl (e.g., benzene and toluene) or halogenated hydrocarbyl (e.g., methylene dichloride and chlorobenzene) as a solvent, trimerization reaction in a slurry state, or trimerization reaction in ethylene in a gas state.
  • aliphatic hydrocarbyl e.g., butane, pentane, hexane, heptane and octane
  • aromatic hydrocarbyl e.g., benzene and toluene
  • halogenated hydrocarbyl e.g., methylene dichloride and chlorobenzene
  • the trimerization reaction can be performed by any of batch, semi-continuous and continuous methods.
  • the pressure of ethylene in the trimerization reaction is usually in the range of normal pressure to 10 MPa, preferably in the range of normal pressure to 5 MPa.
  • the temperature of the trimerization reaction can usually be in the range of from - 50°C to +220°C and is preferably in the range of from 0°C to 170°C, more preferably in the range of from 50°C to 120°C.
  • the time of the trimerization reaction can generally be determined appropriately according to the reaction apparatus of interest and can be in the range of 1 minute to 20 hours.
  • Sample cell Tube (5 mm in diameter)
  • Measurement parameter Probe (5 mm in diameter), OBNUC 3 ⁇ 4 PULPROG zg30, accumulated number 16 times or more
  • Sample cell Tube (5 mm in diameter)
  • Measurement parameter Probe (5 mm in diameter), OBNUC 13 C, PULPROG zgpg30, accumulated number 256 times or more
  • sodium hydride (0.49 g, 20.45 mmol in terms of sodium hydride) dispersed in mineral oil and tetrahydrofuran (23 mL) were mixed. This mixture was heated to 50°C and aniline (0.13 g, 1.36 mmol) was added and stirred at 50°C for one hour. To this, a solution of l,2,3,4-tetramethylcyclopenta-l,3-diene (1.83 g, 15.00 mmol) in tetrahydrofuran (6 mL) was added dropwise and stirred at 50°C for 3.5 hours. This was cooled to 0°C.
  • the resultant mixture was cooled to - 78°C and a solution of titanium tetrachloride (0.42 g, 2.20 mmol) dissolved in toluene (2 mL) was added dropwise at the same temperature. After the mixture was gradually warmed to room temperature, stirring was performed at room temperature overnight. After completion of the reaction, the solvent was removed under reduced pressure. Thereafter, the residue, to which heptane was added, was filtrated to remove insoluble materials.
  • the solvent was removed under reduced pressure to obtain a mixture of [l-tris(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride and 2,2'-bis ⁇ tris(3,5-dimethylphenyl)silyl ⁇ - l ⁇ ' ⁇ ' ⁇ '-octamethyl-S ⁇ '-bi-l ⁇ -cyclopentadienyl as orange solids. Furthermore, the resultant mixture, to which diethyl ether was added, was filtrated to remove insoluble materials. The solvent was removed from the filtrate under reduced pressure. Pentane was added and the mixture was cooled to -20°C.
  • the resultant mixture was cooled to - 78°C and a solution of titanium tetrachloride (1.46 g, 7.70 mmol) dissolved in toluene (8 mL) was added dropwise at the same temperature. After the mixture was gradually warmed to room temperature, stirring was performed at room temperature overnight. After completion of the reaction, the solvent was removed under reduced pressure. Thereafter, heptane was added to the residue, and insoluble materials were removed by filtration. The solvent was removed from the filtrate under reduced pressure. Pentane was added and cooling to -20°C was performed.
  • the resultant mixture was added at -78°C to a solution of tetrachlorosilane (4.45 g, 26.19 mmol) dissolved in diethyl ether (44 mL). After stirring was performed at -78°C for 10 minutes, the mixture was gradually warmed to room temperature. After completion of the reaction, the solvent was removed under reduced pressure. Thereafter, hexane was added to the residue, and hexane-insoluble parts was removed by filtration through celite. The solvent was removed from the filtrate under reduced pressure to obtain chlorotris(5-methyl-3-trimethylsilyl- phenyl)silane (13.10 g, yield 90.4%) as a light yellow oil.
  • potassium hydride (0.88 g, 21.82 mmol in terms of potassium hydride) dispersed in mineral oil was washed with hexane. Tetrahydrofuran (38 mL) was added and this mixture was warmed to 50°C. A solution of 1,2,3,4-tetramethylcyclopenta- 1,3-diene (2.00 g, 16.37 mmol) dissolved in tetrahydrofuran (8 mL) was added dropwise and stirred at 50°C for one hour.
  • Sample cell Tube (5 mm in diameter)
  • Measurement parameter Probe (5 mm in diameter), OBNUC 3 ⁇ 4 PULPROG zg30, accumulated number 16 times or more
  • tetrakis(pentafluorophenyl)borate (197.7 mg, 0.21 mmol) dissolved in bromobenzene (1.7 mL) was added dropwise. The resultant reddish brown mixture was stirred at room temperature for 10 minutes. Hexane was added and the mixture was cooled to -20°C to precipitate a solid. The resultant solid was filtered, washed with a small amount of pentane, and then dried under reduced pressure to obtain ion complex 3 (180.2 mg, yield 74.4%) as a yellow solid.
  • Trimerization activity was analyzed using gas chromatography (Shimadzu GC- 2010, DB-1 column).
  • ion complex 6 [tetrakis(pentafluorophenyl)borate]
  • Example 11 An autoclave (0.4 liter) equipped with a stirrer was dried under reduced pressure and purged with argon. Toluene (90 mL) was supplied. After the interior temperature of the system was increased to 80°C, a hexane solution (0.43 mL) of triisobutylaluminum (TIB A) having a concentration of 0.93 mmol/mL was placed and ethylene was further introduced so as to obtain a partial pressure of 0.5 MPa. After temperature and pressure were stabilized, 3.0 ⁇ of ion complex 5 was weighed and placed in a solid state in the reactor. A reaction was performed at 80°C for 30 minutes while continuously supplying ethylene gas so as to maintain the whole pressure at a constant value.
  • TIB A triisobutylaluminum

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Abstract

Un objet de la présente invention est de pourvoir à un complexe métal de transition Cp-Ar à pont silicium qui sert de composant catalytique capable de produire de manière efficace et très sélective du 1-hexène par la réaction de trimérisation de l'éthylène. Le complexe ion métal de transition selon l'invention est représenté par l'une quelconque des formules (1-1) à (1-3), etc. : où M représente un atome de métal de transition du Groupe 4 de la Classification périodique des éléments ; A représente un contre-ion ; R1, R2, R3, R4, R5, R6, R7, R8, R9, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, X1 et X2 représentent chacun indépendamment un atome d'hydrogène ou autre ; R10 et R11 représentent chacun indépendamment un atome d'hydrogène ou autre.
PCT/JP2012/059287 2011-03-29 2012-03-29 Procédé de production d'un complexe ion métal de transition, catalyseur de trimérisation, et procédé de production de 1-hexène WO2012133929A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004524959A (ja) * 2001-02-22 2004-08-19 ステフティング ダッチ ポリマー インスティテュート オレフィンの三量化のための触媒系
WO2011040555A1 (fr) * 2009-09-30 2011-04-07 住友化学株式会社 Complexe de métaux de transition, procédé de préparation desdits complexes de métaux de transition, catalyseur de trimérisation, procédé de préparation de 1-hexène, procédé de préparation d'un polymère d'éthylène, composé de cyclopentadiène substitué, et procédé de préparation dudit composé de cyclopentadiène substitué

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004524959A (ja) * 2001-02-22 2004-08-19 ステフティング ダッチ ポリマー インスティテュート オレフィンの三量化のための触媒系
WO2011040555A1 (fr) * 2009-09-30 2011-04-07 住友化学株式会社 Complexe de métaux de transition, procédé de préparation desdits complexes de métaux de transition, catalyseur de trimérisation, procédé de préparation de 1-hexène, procédé de préparation d'un polymère d'éthylène, composé de cyclopentadiène substitué, et procédé de préparation dudit composé de cyclopentadiène substitué

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PATRICK J. W. DECKERS ET AL.: "Catalytic Trimerization of Ethene with Highly Active Cyclopentadienyl-Arene Titanium Catalysts", ORGANOMETALLICS, vol. 21, no. 23, 2002, pages 5122 - 5135, XP001132361, DOI: doi:10.1021/om020765a *
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