WO2012133928A1 - Trimerization catalyst and method for producing 1-hexene - Google Patents

Trimerization catalyst and method for producing 1-hexene Download PDF

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WO2012133928A1
WO2012133928A1 PCT/JP2012/059286 JP2012059286W WO2012133928A1 WO 2012133928 A1 WO2012133928 A1 WO 2012133928A1 JP 2012059286 W JP2012059286 W JP 2012059286W WO 2012133928 A1 WO2012133928 A1 WO 2012133928A1
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carbon atoms
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halogen atom
substituent
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PCT/JP2012/059286
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Takayuki Hishiya
Takahiro Hino
Taichi Senda
Masaya Tanimoto
Yasutoyo Kawashima
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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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/146—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of boron
    • 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
    • B01J2531/001—General concepts, e.g. reviews, relating to catalyst systems and methods of making them, the concept being defined by a common material or method/theory
    • B01J2531/002—Materials
    • B01J2531/007—Promoter-type Additives
    • 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
    • C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • C07C2531/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • C07C2531/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • 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 trimerization catalyst and a method for producing 1-hexene.
  • a-olefin is an industrially important monomer raw material that is produced by the oligomerization of ethylene using a metal catalyst.
  • the oligomerization of ethylene usually gives a-olefin mixtures according to Schulz-Flory distribution. Therefore, the development of a catalyst system capable of selectively producing one species of a-olefin is very important industrially.
  • Patent Literatures 1 and 2 and Non Patent Literature 1, for example A complex containing a titanium atom has been reported as a complex for selective trimerization of ethylene (Patent Literatures 1 and 2 and Non Patent Literature 1, for example).
  • by-product polyethylene is generally produced in the trimerization reaction of ethylene and therefore fouls the walls of reactors, stirrers, or the like in industrial production, disadvantageously making long-term operation impracticable.
  • Patent Literature 1 Non Patent Literature 1 and Patent Literature 2 have reported an example using a trimerization catalyst obtained by bringing a catalytic component comprising aluminoxane supported by a carrier into contact with a complex for trimerization.
  • NON-PATENT LITERATURE 1 ORGANOMETALLICS 2002, 21, 5122-5135.
  • an object of the present invention is to provide an ethylene trimerization catalyst that is capable of producing 1-hexene while suppressing adhesion of by-product polymers to the walls of reactors or stirrers in the trimerization reaction of ethylene.
  • a 1st aspect of the present invention relates to
  • an ethylene trimerization catalyst which is obtainable by bringing a complex for ethylene trimerization containing a titanium atom into contact with an activating co-catalytic component containing an element of Group 12 of the Periodic Table.
  • a 2nd aspect of the present invention relates to an ethylene
  • trimerization catalyst which is obtainable by bringing a complex for ethylene trimerization containing a titanium atom into contact with an activating co-catalytic component containing an element of Group 12 of the Periodic Table, the complex for ethylene trimerization being represented by any one of formulae (1-1) to (1-3):
  • Cp represents a group having a cyclopentadiene-type anionic skeleton
  • J represents a bridging group based on a single atom selected from Groups 13 to 16 of the Periodic Table of the Elements
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 each independently represent a hydrogen atom, a halogen atom,
  • hydrocarbyl group and the total number of the carbon atoms in the three R 18 groups is 1 to 20, or a disubstituted amino group represented by -N(R l9 ) 2 , wherein the two R 19 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 19 groups is 2 to 20;
  • X 1 , X 2 and X 3 each independently represent
  • a substituted silyl group represented by -Si(R 18 ) 3 wherein the three R 18 groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated
  • the two R 19 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 19 groups is 2 to 20;
  • R 6 and R 7 each independently represent
  • t o I S ' a substituted silyl group represented by -Si(R ) 3 , wherein the three R groups 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 18 groups is 1 to 20, or a disubstituted amino group represented by -N(R 19 ) 2 , wherein the two R 19 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 19 groups is 2 to 20;
  • R 1 and m each represent 1 or 0, and 1 + m is an integer equal to (valence of J - 2); of R 1 , R 2 , R 3 , R 4 and R 5 , 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 8 , R 9 , R 10 , R u and R 12 , 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 13 , R 14 , R 15 , R 16 and R 17 , 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 6 and R 7 may be bonded to each other to form a ring together with J to which they are bonded; and
  • two groups may be bonded to each other to form a ring together with Ti.
  • a 3rd aspect of the present invention relates to an ethylene trimerization catalyst which is obtainable by bringing a complex for ethylene trimerization containing a titanium atom into contact with an activating co-catalytic component containing an element of Group 12 of the Periodic Table, the complex for ethylene trimerization being r resented by any one of formulae (2-1) to (2-3):
  • R 40 , R 41 , R 42 , R 43 and R 44 each independently represent
  • a substituted silyl group represented by -Si(R 18 ) 3 wherein the three R 18 groups 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 18 groups is 1 to 20, or a disubstituted amino group represented by -N(R 19 ) 2 , wherein the two R 19 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 19 groups is 2 to 20;
  • X 4 , X 5 and X 6 each independently represent
  • a substituted silyl group represented by -Si(R 18 ) 3 wherein the three R 18 groups 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 18 groups is 1 to 20, or a disubstituted amino group represented by -N(R 19 ) 2 , wherein the two R 19 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 19 groups is 2 to 20;
  • R 29 and R 30 each independently represent
  • a substituted silyl group represented by -Si(R 18 ) 3 wherein the three R 18 groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated
  • the hydrocarbyl group, and the total number of the carbon atoms m the three R groups is 1 to 20, or a disubstituted amino group represented by -N(R 19 ) 2 , wherein the two R 19 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 19 groups is 2 to 20;
  • R , R , R and R 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;
  • 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 , R , R , R and R , 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 J1 , R", R ⁇ and R JJ , 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 , R , R , R and R , 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 , R , R , R and R , two group bonded to two adjoining carbon atoms may be bonded to each other to form a ring
  • a 4th aspect of the present invention relates to a method for producing 1-hexene using the ethylene trimerization catalyst component.
  • the present invention can provide an ethylene trimerization catalytic component that is capable of producing 1-hexene while suppressing adhesion of by-product polymers to the walls of reactors or stirrers in the trimerization reaction of ethylene.
  • 1-hexene can be produced efficiently and selectively by using a complex represented by any of formulae (1-1) to (1-3) or (2-1) to (2-3) as a complex for ethylene trimerization.
  • substituted encompasses a halogen atom constituting a compound or a group.
  • substituted cyclopentadiene compounds represented by formulae (6-1) to (6-3) have isomers each differing in the double bond position of each cyclopentadiene ring.
  • the substituted cyclopentadiene compounds refer to any of them or a mixture of them.
  • the complex for ethylene trimerization used in the present invention is a complex for ethylene trimerization containing a titanium atom.
  • Examples of the complex for ethylene trimerization containing a titanium atom can include a complex for ethylene trimerization represented by any of formulae (1-1) to (1-3) shown below, a complex for ethylene trimerization represented by any of formulae (2-1) to (2-3) shown below, and phenoxyimine titanium complexes described in Patent Literature 2.
  • the complex for ethylene trimerization is preferably a complex for ethylene trimerization represented by any of formulae (1-1) to (1-3) shown below or a complex for ethylene trimerization represented by any of formulae (2-1) to (2- 3) shown below, more preferably a complex for ethylene trimerization represented by any of formulae (2-1) to (2-3) shown below.
  • the complex for trimerization containing a titanium atom is preferable because it is free from poisoning attributed to polymerization catalytic components such as metallocene- type polymerization catalytic components or Ziegler-Natta-type solid-state polymerization catalytic component containing a titanium atom, a magnesium atom, or the like.
  • the complexes for ethylene trimerization represented by formulae (1-1) to (1-3) or (2-1) to (2-3) are more preferable because they exhibit high activity in ethylene trimerization and produce a few by-product polymers.
  • the complexes for ethylene trimerization represented by formulae (2-1) to (2-3) are most preferable because they exhibit higher activity in ethylene trimerization and a high ratio of the amount of 1-hexene produced to the amount of by-product polymers produced.
  • the complex for ethylene trimerization containing a titanium atom can include phenoxyimine titanium complexes described in Patent Literature 2. 6-Adamantyl-4-methyl-2-[N- ⁇ 2-(2-methoxyphenyl) ⁇ phenyl]imino-phenoxytitanium trichloride is preferable. These compounds can be synthesized according to, for example, a method described in Journal of Organometallic Chemistry, 2003, vol. 678, 134-141.
  • Cp, J, R 1 to R 44 and X 1 to X 6 are as defined above, and examples thereof are shown below.
  • Examples of the group having a cyclopentadiene-type anionic skeleton, represented by Cp, include rj 5 -cyclopentadienyl, r
  • the group having a cyclopentadiene-type anionic skeleton is preferably a ⁇ 5 - Cyclopentadienyl, T
  • Examples of the bridging group based on a single atom selected from Groups 13 to 16 of the Periodic Table of the Elements, represented by J, include boron, carbon, silicon, nitrogen, phosphorus, oxygen and sulfur atoms. A carbon or silicon atom is preferable, and a silicon atom is more preferable.
  • 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 a part or all of the hydrogen atoms in the alkyl group may be substituted by a halogen atom. 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, tnbromomethyl, 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-tolyl, 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 a part or all of the hydrogen atoms in the aryl group may be substituted by a halogen atom.
  • Specific examples of the halogen atom are as described above.
  • the aryl 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.
  • the aryl group having a halogen atom as a substituent can specifically include fluorophenyl,
  • 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)meth
  • 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 a part or all of the 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.
  • 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 a part or all of the 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 a part or all of the hydrogen atoms in the alkoxy group may be substituted by a halogen atom. 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 a part or all of the 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.
  • Examples of the "aralkyloxy group having 7 to 20 carbon atoms" in the aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent 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)methoxy,
  • 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 a part or all of the hydrogen atoms in the aralkyloxy group may be substituted by a halogen atom.
  • Specific examples of the halogen atom are as described above.
  • the aralkyloxy 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.
  • the R 18 groups 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 halogenated hydrocarbyl group obtained by substituting a part or all of the hydrogen atoms in the hydrocarbyl group with a halogen atom, and the total number of carbon atoms in the three R groups is in the range of
  • the total number of the carbon atoms in these three R 18 groups 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 a part or all of the hydrogen atoms in the hydrocarbyl groups of these groups with 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 a part or all of the hydrogen atoms in the hydrocarbyl groups of these groups with a halogen atom; and trisubstituted silyl group having three hydrocarbyl and/or halogenated hydrocarbyl groups, such as trimethylsilyl, tri
  • trisubstituted silyl groups are preferable, and trimethylsilyl, tert-butyldimethylsilyl and triphenylsilyl groups, and groups obtained by substituting a part or all of the hydrogen atoms in these groups with a halogen atom are more preferable.
  • the R 19 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 19 groups is 2 to 20, the R 19 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 19 groups is in the range of 2 to 20, more preferably in the range of 2 to 10.
  • the 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 19 groups may be bonded to each other to form a ring together with the nitrogen atom to which they are bonded.
  • Examples of such a disubstituted amino group include dimethylamino, diethylamino, di-n-propylamino,
  • R and R' may be bonded to each other to form a ring together with J to which they are bonded, and R 29 and R 30 may be bonded to each other to form a ring together with the silicon atom to which they are bonded.
  • R 1 , R 2 , R 3 , R 4 and R 5 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 they are bonded,
  • R , R , R , R and R 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 they are bonded, of R 24 , R 41 ,
  • 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.
  • R 8 , R 9 , R 10 , R 11 and R 12 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 they are bonded
  • R J1 , R", R and R 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 they are bonded
  • R 31 , R 43 , R 33 , R 44 and R 35 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 they two groups are bonded.
  • 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 they are
  • 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 they are bonded.
  • R , R , R , and R 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 they are bonded.
  • 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.
  • Examples thereof include cyclopropane, cyclopropene, cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, cyclohexene, cycloheptane, cycloheptene, cyclooctane, cyclooctene, benzene, naphthalene, anthracene, silacyclopropane, silacyclobutane, silacyclopentane and
  • Examples of the complexes for ethylene trimerization (1-1) to (1-3) include the following complexes:
  • titanium chloride complexes such as [1-dimethylphenylsilyl- cyclopentadienyljtitanium trichloride, [l-diethylphenylsilyl-cyclopentadienyl]titanium trichloride, [1-ethylmethylphenylsilyl -cyclopentadienyljtitanium trichloride, [1-n- butylmethylphenylsilyl-cyclopentadienyljtitanium trichloride, [ 1 -methyldiphenylsilyl- cyclopentadienyljtitanium trichloride, [ 1 -cyclohexylmethylphenylsilyl- cyclopentadienyljtitanium trichloride, [l-methyl(n-octadecyl)phenylsilyl- cyclopentadienyljtitanium t
  • examples of the complexes for ethylene trimerization (1-1) to (1-3) also include: complexes obtained by substituting a carbon atom for the silicon atom in J in the general formulae (1-1) to (1-3) in the complexes exemplified above; 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 hydride complexes obtained by substituting "hydride” therefor; alkylated titanium complexes such as methylated titanium complexes obtained by substituting "methyl” therefor; arylated titanium complexes such as phenylated titanium complexes obtained by substituting "phenyl” therefor; aralkylated titanium complexes such as benzylated titanium complexes obtained by substituting "benzyl” therefor;
  • preferable examples of the complexes for ethylene trimerization (1-1) to (1-3) also include complexes specifically exemplified later as the complexes for ethylene trimerization (2-1) to (2-3).
  • a hydrogen atom 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.
  • R , R , R and R can include cyclopentadiene substructures represented by a substructural formula (3): wherein R 20 , R 21 , R 22 and R 23 are as defined above, and at least one thereof is a substituent other than hydrogen, for example, the following substructures:
  • methylcyclopentadienyl ethylcyclopentadienyl, n-propylcyclopentadienyl, isopropylcyclopentadienyl, n-butylcyclopentadienyl, sec-butylcyclopentadienyl, tert- butylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl, tetramethylcyclopentadienyl, phenylcyclopentadienyl, benzylcyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, methyltetrahydroindenyl, dimethyltetrahydroindenyl and octahydrofluoreny 1.
  • cyclopentadiene substructure is tetramethylcyclopentadienyl, etc.
  • R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 , R 39 , R 40 , R 41 , R 42 , R 43 and R 44 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.
  • R 27 and R 28 a preferable combination of the groups represented by R 31 , R 32 , R 33 , R 34 and R 35 , a preferable combination of the groups represented by R 36 , R 37 , R 38 , R 39 and R 40 , a preferable combination of the groups represented by R 24 , R 41 , R 26 , R 42 and R 28 and a preferable combination of the groups represented by R 31 , R 43 , R 33 , R 44 and R 35 each include the following substructures represented by a substructural formula (4-1):
  • R , R , R / and R are as defined above;
  • R 31 , R 32 , R 33 , R 34 and R 35 are as defined above
  • R , R , R , R and R are as defined above;
  • R 31 , R 43 , R 33 , R 44 and R 35 are as defined above:
  • phenyl methylphenyl, dimethylphenyl, trimethylphenyl, tetramethylphenyl, pentamethylphenyl, ethylphenyl, diethylphenyl, trimethylphenyl, tetraethylphenyl, pentaethylphenyl, tert-butylphenyl, di-tert-butylphenyl, tert-butylmethylphenyl, di(tert- butyl)methylphenyl, phenylphenyl, diphenylphenyl, triphenylphenyl, tetraphenylphenyl, pentaphenylphenyl, benzylphenyl, dibenzylphenyl, tribenzylphenyl, tetrabenzylphenyl, pentabenzylphenyl, naphthyl, anthracenyl, chlorophenyl, dichlorophenyl, fluorophen
  • a preferable substructure is phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, diethylphenyl, di-tert-butylphenyl, etc.
  • R 29 and R 30 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 specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl or benzyl group.
  • Examples of a preferable combination of the groups represented by R 29 and R 30 include the following substructures represented by a substructural formula (5):
  • R 29 and R 30 are as defined above:
  • substructural formula (5) include a substructural formula wherein
  • R 29 is a methyl group
  • R 30 is
  • R 29 and R 30 are the same as each other and are
  • R 29 and R 30 are different from each other and are
  • alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent.
  • the substructure is specifically dimethylsilylene, diethylsilylene, ethylmethylsilylene, n-butylmethylsilylene, cyclohexylmethylsilylene,
  • the complex for ethylene trimerization (2-1) include transition metal complexes wherein R 25 and R 27 are each independently
  • R 30 is preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec- butyl, tert-butyl and benzyl groups.
  • the complex for ethylene trimerization (2-2) include transition metal complexes wherein R , R , R and R are each independently
  • Preferable examples of the complex for ethylene trimerization (2-3) include transition metal complexes wherein R 37 , R 39 , R 41 , R 42 , R 43 and R 44 are each independently an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent or an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent.
  • Examples of the complexes for ethylene trimerization (2-1) to (2-3) include the following complexes:
  • titanium chloride complexes such as [l-dimethylphenylsilyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [l-diethylphenylsilyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [l-cyclotetramethylene(phenyl)silyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [ 1 -ethylmethylphenylsilyl-2, 3 ,4, 5 - tetramethylcyclopentadienyl]titanium trichloride, [1- butylmethylphenylsilyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [l-methyldiphenylsilyl-2,3,4,5- tetramethylcyclopentadie
  • examples of the complexes for ethylene trimerization (2-1) to (2-3) also include titanium chloride complexes obtained by substituting "2-methylcyclopentadienyl", “3-methylcyclopentadienyl”, “2,3-dimethylcyclopentadienyl”, “2,4-dimethylcyclopentadienyl", “2, 5 -dimethy lcyclopentadieny 1 ", “2,3,5 -trimethylcyclopentadienyl " , "2-ethy lcyclopentadieny 1 " , “3-ethylcyclopentadienyl”, “2-n-propylcyclopentadienyl”, “3-n-propylcyclopentadienyl”, “2- isopropylcyclopentadienyl", “3-isopropylcyclopentadienyl", "2-n-butylcyclopentadienyl", "3-n- butyl
  • examples of the complexes for ethylene trimerization (2-1) to (2-3) also include: titanium halide complexes such as titanium fluoride complexes obtained by substituting "fluoride” for "chloride” in the complexes exemplified above, titanium bromide complexes obtained by substituting "bromide” therefor and titanium iodide complexes obtained by substituting "iodide” therefor; titanium hydride complexes obtained by substituting "hydride” therefor; alkylated titanium complexes such as methylated titanium complexes obtained by substituting "methyl” therefor; arylated titanium complexes such as phenylated titanium complexes obtained by substituting "phenyl” therefor; aralkylated titanium complexes such as benzylated titanium complexes obtained by substituting "benzyl” therefor; titanium alkoxide complexes such as titanium methoxide complexes obtained by substituting "methoxide” therefor, titanium n-butoxide
  • the complexes for ethylene trimerization (2-1), (2-2) and (2-3) can be produced from a substituted cyclopentadiene compound represented by formula (6-1), a substituted cyclopentadiene compound represented by formula (6-2) and a substituted cyclopentadiene compound represented by formula (6-3), respectively, by similar methods:
  • R , R , R , R , R , R , R , R and R are as defined above,
  • R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 30 , R 31 , R 32 , R 33 , R 34 and R 35 are as defined above, and 6-3)
  • R are as defined above.
  • the complexes for ethylene trimerization (2-1) can be described as an example.
  • the complexes for ethylene trimerization (2-1) can be produced by, for example, a production method comprising the steps of:
  • substituted cyclopentadiene compound represented by formula (6-1) (hereinafter, referred to as a "substituted cyclopentadiene compound (6-1)") with a base in the presence of an amine compound:
  • X 4 , X 5 and X 6 are as defined above; and X 7 is as defined in X 4 , X 5 and X 6 : q is 0 or 1.
  • the step of reacting the substituted cyclopentadiene compound (6-1) 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 (6-1) and the base with a transition metal compound (7) may be referred to as a "2nd reaction step”.
  • Isomers of the substituted cyclopentadiene compound (6-1) differing in the double bond osition of the cyclopentadiene ring include the following structural isomers:
  • the compound represented by formula (6-1) 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 7 is as defined above, and specific examples thereof include the same as those exemplified for X 4 , X 5 and X 6 .
  • transition metal compound (7) examples include: titanium halide such as titanium tetrachloride, titanium trichloride, titanium tetrabromide and titanium tetraiodide;
  • amidotitanium such as tetrakis(dimethylamino)titanium, dichlorobis(dimethylamino)titanium, trichloro(dimethylamino)titanium and tetrakis(diethylamino)titanium; and alkoxytitanium such as tetraisopropoxytitanium, tetra-n-butoxytitanium, dichlorodiisopropoxytitanium and
  • a preferable transition metal compound (4) is titanium tetrachloride.
  • Examples of the base reacted with the substituted cyclopentadiene compound (6- 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 cyclopentadiene compound (6-1).
  • an amine compound is used in the reaction of the substituted cyclopentadiene compound (6-1) 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 (6-1) with the base is preferably performed in the presence of a solvent.
  • the substituted cyclopentadiene compound (6-1) and the base are reacted in the solvent and then a transition metal compound (7) can be added into this reaction mixture to thereby further react the transition metal compound (7) with the reaction product of the substituted cyclopentadiene compound (6-1) and the base.
  • Solids may be deposited in the reaction mixture obtained by reacting the substituted cyclopentadiene compound (6-1) 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 (7).
  • the solvent when the solvent is used, the substituted
  • the base and the transition metal compound (7) 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, tetrahydrofiiran and 1,4-dioxane; amide solvents such as hexamethylphosphoric amide and dimethylformamide; polar solvents such as acetonitrile, propionitrile, acetone, diethyl ketone, methyl isobutyl ketone and cyclohexanone; and 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 (6-1).
  • the amount of the transition metal compound (7) 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 (6-1).
  • the reaction temperature of the 1st 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 -80 to 100°C .
  • the produced complex for ethylene trimerization (2-1) can be taken by various purification methods known in the art.
  • the complex for ethylene trimerization (2-1) of interest can be obtained by a method in which after the 1st and 2nd reaction steps, the formed
  • a compound wherein one or some of X 4 , X 5 and X 6 in any of the complexes for ethylene trimerization (2-1) to (2-3) are substituted by a hydrogen atom, an alkoxy 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, an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent, or the like can also be obtained by reacting a compound wherein X 4 , X 5 and X 6 in any of the complexes for ethylene trimerization (2-1) to (2-3) are a halogen atom with a lithium, sodium, potassium or magnesium compound having the corresponding alkyl, alkoxy, ary
  • R 42 , R 43 and R 44 are as defined above.
  • Examples of the substituted cyclopentadiene compound (6-1) include the following substituted cyclopentadiene compounds:
  • examples of the substituted cyclopentadiene compound (6-1) also include substituted cyclopentadiene compounds obtained by substituting "2- methylcyclopentadiene", “3-methylcyclopentadiene”, “2,3-dimethylcyclopentadiene”, “2,4- dimethylcyclopentadiene", "2,5-dimethyIcyclopentadiene", "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
  • substituted cyclopentadiene compound (6-2) can include the following substituted cyclopentadiene compounds:
  • l-methyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadiene 1-ethyldiphenylsilyl- 2,3,4,5-tetramethylcyclopentadiene, l-n-propyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, l-isopropyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, l-n-butyldiphenylsilyl-2,3,4,5- tetramethylcyclopentadiene, l-isobutyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1-sec- butyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, l-tert-butyldiphenylsilyl-2,3,4,5- tetramethylcyclopentadiene, 1 -cyclohexyldiphenyl
  • examples of the substituted cyclopentadiene compound (6-2) 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- butylcyclopentadiene, “
  • substituted cyclopentadiene compound (6-3) can include the following substituted cyclopentadiene compounds:
  • examples of the substituted cyclopentadiene compound (6-3) 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 compounds (6-1), (6-2) and (6-3) can be produced by similar methods comprising the steps of:
  • R , R , R and R ,2 i 3 are as defined above, and
  • R , R , R , R 2y and R 3U are as defined above, and X s is a halogen atom
  • R 24 , R 25 , R 26 , R 27 , R 28 , R 30 , R 31 , R 32 , R 33 , R 34 and R 35 are as defined above, and X 8 is a halo en atom, and
  • R 24 , R 26 , R 28 , R 31 , R 33 , R 35 , R 36 , R 37 , R 38 , R 39 , R 40 , R 41 , R 42 , R 43 and R 44 are as defined above, and X s is a halogen atom.
  • (6-1) will be described as an example.
  • the substituted cyclopentadiene compound (8) is as follows:
  • R 20 , R 21 , R 22 and , 23 are as defined above, and
  • Examples of the substituted cyclopentadiene compound (8) include the following compounds:
  • methylcyclopentadiene 1,2-dimethylcyclopentadiene, 1,3- dimethylcyclopentadiene, 1 , 2, 3 -tnmethylcyclopentadiene, 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, ne
  • 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 (8) exemplified above may be an isomer thereof differing in the double bond position of each cyclopentadiene ring. A mixture of these isomers may also be used.
  • the halogenated silyl compound (9-1) is as follows:
  • R , R , R , R 2y and R J(J are as defined above, and X is a halogen atom.
  • halogenated sily compound (9-1) examples include the following halogenated silyl compounds:
  • chlorodimethylphenylsilane chlorodiethylphenylsilane, chlorophenyldi(n- propyl)silane, chlorodiisopropylphenylsilane, di(n-butyl)chlorophenylsilane,
  • halogenated silyl compound (9-2) 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-dimethylphenyl)silane, chloromethyl(2,4-dimethylphenyl)(3,5- dimethylphenyl)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 (9-3) examples include the following .
  • chlorotriphenylsilane chlorophenyldi(2-methylphenyl)silane, chlorophenyldi(3 - methylphenyl)silane, chlorophenyldi(4-methylphenyl)silane, chlorophenylbis(2,3- dimethylphenyl)silane, chlorophenylbis(2,4-dimethylphenyl)silane, chlorophenylbis(2, 5- dimethylphenyl)silane, chlorophenylbis(2,6-dimethylphenyl)silane, chlorophenylbis(3,5- dimethylphenyl)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(3,4,5-trimethylphenyl)silane,
  • chlorodi(2-methylphenyl)(3,5-dimethylphenyl)silane chlorodi(3- methylphenyl)(3,5-dimethylphenyl)silane, chlorodi(4-methylphenyl)(3,5-dimethylphenyl)silane, chlorobis(2,3-dimethylphenyl)(3,5-dimethylphenyl)silane, chlorobis(2,4-dimethylphenyl)(3,5- dimethylphenyl)silane, chlorobis(2,5-dimethylphenyl)(3,5-dimethylphenyl)silane, chlorobis(2,6- dimethylphenyl)(3,5-dimethylphenyl)silane, chlorotris(3,5-dimethylphenyl)silane, chloro(3,5- dimethylphenyl)bis(3,4,5-dimethylphenyl)silane.
  • Examples of the base reacted with the substituted cyclopentadiene compound (8) 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 (8).
  • 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 (8) 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
  • 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-methylaminopyridine, 3-methylaminopyridine and 4- methylaminopyridine; and
  • tertiary amines such as N,N-dimethylaniline, ⁇ , ⁇ -dimethylchloroaniline, N,N- dimethylbromoaniline, N,N-dimethylfluoroaniline, ⁇ , ⁇ -dimethylanisidine, N- methylmethylaniline, ⁇ , ⁇ -dimethylethylaniline, N,N-dimethyl-n-propylaniline, N,N- dimethylisopropylaniline, l,4-diazabicyclo[2.2.2]octane, l,5-diazabicyclo[4.3.0]non-5-ene, 1,8- diazabicycIo[5.4.0]undec-7-ene, 2-dimethylaminopyridine, 3-dimethylaminopyridine, 4- dimethylaminopyridine, trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, diisopropyle
  • 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 (8), 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 (8) 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 0 to 70°C, preferably 10 to 60°C.
  • This reaction efficiently produces a metal salt of the substituted cyclopentadiene compound (8).
  • the metal salt of the substituted cyclopentadiene compound (8) 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 (6-1) 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 (8).
  • This reaction is usually performed, for example, by mixing the base, the amine compound and the substituted cyclopentadiene compound (8) in a solvent and then adding the halogenated silyl compound (9-1) to the mixture.
  • the substituted cyclopentadiene compound (6-1) 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 (8) 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 (9-1).
  • chlorobenzene may be added to the reaction mixture as appropriate, followed by separation into organic and aqueous phases.
  • the obtained organic phase is concentrated to obtain the substituted cyclopentadiene compound (6-1).
  • the obtained substituted cyclopentadiene compound (6-1) may be purified, if necessary, by a method such as distillation and column chromatography treatment.
  • the activating co-catalytic component used in the present invention is an activating co-catalytic component containing an element of Group 12 of the Periodic Table, and examples thereof include an activating co-catalytic component obtainable by bringing the following compounds (a), (b) and (c) into contact with each other (hereinafter, referred to as an activating co-catalytic component- 1):
  • M 1 represents an atom of Group 12 of the Periodic Table.
  • M 1 is particularly preferably a zinc atom.
  • n represents the valence of M 1 .
  • M 1 is a zinc atom, n is 2.
  • L represents a hydrogen atom, a halogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and in the case where more than one L groups exist, the L groups may be the same as or different from each other.
  • the halogen atom in L include fluorine, chlorine, bromine and iodine atoms.
  • the hydrocarbyl group in L is preferably an alkyl, aryl or aralkyl group.
  • the alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert- butyl, isobutyl, n-pentyl, neopentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-pentadecyl and n- eicosyl groups.
  • the alkyl group is more preferably a methyl, ethyl, isopropyl, tert-butyl or isobutyl group.
  • the aryl group is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include phenyl, 2-tolyl, 3-tolyl, 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-butylphenyl, tert-butylphenyl, n-penty
  • aryl group is more preferably a phenyl group. All of these aryl groups may partially be substituted by, for example, an alkoxy group (e.g., methoxy and ethoxy groups), an aryloxy group (e.g., a phenoxy group) or an aralkyloxy group (e.g., a benzyloxy group).
  • the aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and examples thereof 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, (2,3, 5,6- tetramethylphenyl)methyl,
  • the aralkyl group is more preferably a benzyl group. All of these aralkyl groups may partially be substituted by, for example, an alkoxy group (e.g., methoxy and ethoxy groups), an aryloxy group (e.g., a phenoxy group) or an aralkyloxy group (e.g., a benzyloxy group).
  • the halogenated hydrocarbyl group is preferably a halogenated alkyl group having 1 to 20 carbon atoms.
  • the halogenated hydrocarbyl group include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, diiodomethyl, triiodomethyl, fluoroethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl, pentafluoroethyl, chloroethyl, dichloroethyl, trichloroethyl, tetrachloroethyl, pentachloroethyl, bromoethyl, dibromoethyl, tribromoethyl, tetrabromoethyl, pentabromo
  • perfluoropentyl perfiuorohexyl, perfluorooctyl, perfluorododecyl, perfluoropentadecyl, perfluoroeicosyl, perchloropropyl, perchlorobutyl, perchloropentyl, perchlorohexyl,
  • perchlorooctyl perchlorododecyl, perchloropentadecyl, perchloroeicosyl, perbromopropyl, perbromobutyl, perbromopentyl, perbromohexyl, perbromooctyl, perbromododecyl,
  • halogenated alkyl groups may partially be substituted by, for example, an alkoxy group (e.g., methoxy and ethoxy groups), an aryloxy group (e.g., a phenoxy group) or an aralkyloxy group (e.g., a benzyloxy group).
  • an alkoxy group e.g., methoxy and ethoxy groups
  • an aryloxy group e.g., a phenoxy group
  • aralkyloxy group e.g., a benzyloxy group
  • L is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, particularly preferably an alkyl group.
  • T 1 represents an atom of Group 15 or 16 of the Periodic Table.
  • T represents an atom of Group 15 or 16 of the Periodic Table.
  • Examples of the atom of Group 15 include nitrogen and phosphorus atoms.
  • Examples of the atom of Group 16 include oxygen and sulfur atoms.
  • T 1 is preferably a nitrogen or oxygen atom, particularly preferably an oxygen atom.
  • T' is preferably a nitrogen or oxygen atom, particularly preferably an oxygen atom.
  • t represents the valence of T 1 .
  • T 1 is an atom of Group 15, t is 3.
  • t is 2.
  • u represents the valence of T'.
  • T' is an atom of Group 15, u is 3.
  • T' is an atom of Group 16, u is 2.
  • E 1 represents an electron- withdrawing group or a group containing an electron-withdrawing group, and the E 1 groups may be the same as or different from each other in the case more than one E 1 groups exist.
  • a substituent constant ⁇ of the Hammett's rule is known as an index for electron-withdrawing properties.
  • the electron-withdrawing group include functional groups whose substituent constant ⁇ of the Hammett's rule is positive.
  • Examples of the electron-withdrawing group include fluorine, chlorine, bromine and iodine atoms, and cyano, nitro, carbonyl, sulfone and phenyl groups.
  • Examples of the group containing an electron-withdrawing group include halogenated alkyl, halogenated aryl, (halogenated alkyl)aryl, cyanated aryl, nitrated aryl, ester (alkoxycarbonyl, aralkyloxycarbonyl and aryloxycarbonyl), acyl and halogenated acyl groups.
  • halogenated alkyl group examples include fluoromethyl, chloromethyl, bromomethyl, iodomethyl, difluoromethyl, dichloromethyl, dibromomethyt, diiodomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, triiodomethyl, 2,2,2-trifluoroethyl, 2,2,2- trichloroethyl, 2,2,2-tribromoethyl, 2,2,2-triiodoethyl, 2,2,3,3,3-pentafluoropropyl, 2,2,3,3,3- pentachloropropyl, 2,2,3,3,3-pentabromopropyl, 2,2,3,3,3-pentaiodopropyl, 2,2,2-trifluoro-l- trifluoromethylethyl, 2,2,2-trichloro- 1-trichloromethylethyl, 2,2,2-tribromo- 1 - tribromomethylethyl
  • halogenated aryl group examples include 2-fluorophenyl, 3 -fluorophenyl, 4-fluorophenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-bromophenyl, 3- bromophenyl, 4-bromophenyl, 2-iodophenyl, 3-iodophenyl, 4-iodophenyl, 2,6-difluorophenyl, 3,5-difluorophenyl, 2,6-dichlorophenyl, 3,5-dichlorophenyl, 2,6-dibromophenyl, 3,5- dibromophenyl, 2,6-diiodophenyl, 3,5-diiodophenyl, 2,4,6-trifluorophenyl, 3,4,5-trifluorophenyl, 2,4,6-trichlorophenyl, 2,4,6-tribromophenyl, 2,4,6-t
  • Examples of the (halogenated alkyl)aryl group include 2-(trifluoromethyl)phenyl,
  • Examples of the cyanated aryl group include 2-cyanophenyl, 3-cyanophenyl and
  • nitrated aryl group examples include 2-nitrophenyl, 3-nitrophenyl and 4- nitrophenyl groups.
  • ester group examples include methoxycarbonyl, ethoxycarbonyl, normal propoxycarbonyl, isopropoxycarbonyl, phenoxycarbonyl, trifluoromethoxycarbonyl and pentafiuorophenoxycarbonyl groups.
  • acyl group examples include formyl, ethanoyl, propanoyl, butanoyl, trifluoroethanoyl, benzoyl, pentafluorobenzoyl, perfiuoroethanoyl, perfluoropropanoyl, perfluorobutanoyl, perfluoropentanoyl, perfluorohexanoyl, perfluoroheptanoyl,
  • E 1 is preferably a halogenated hydrocarbyl group, more preferably a halogenated alkyl or halogenated aryl group, even more preferably a fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, 2,2,2-trifluoro-l- trifluoromethylethyl, l, l-bis(trifluoromethyl)-2,2,2-trifluoroethyl, 2-fiuorophenyl, 3- fluorophenyl, 4-fluorophenyl, 2,4-difluorophenyl, 2,6-difluorophenyl, 3,4-difluorophenyl, 3,5- difluorophenyl, 2,4,6-trifluorophenyl, 3,4,5-trifluorophenyl, 2,3,5,6-tetrafluorophenyl, pentafluorophen
  • E 2 represents a hydrocarbyl group or a halogenated hydrocarbyl group.
  • the hydrocarbyl group represented by E 2 is preferably an alkyl, aryl or aralkyl group.
  • the same hydrocarbyl group as those exemplified as L in the general formula [Al] is used.
  • Examples of the halogenated hydrocarbyl group represented by E 2 include halogenated alkyl, halogenated aryl and (halogenated alkyl)aryl groups.
  • the same halogenated alkyl, halogenated aryl and (halogenated alkyl)aryl groups as those specifically exemplified as the electron- withdrawing group represented by E 1 in formula [A2] are used.
  • E 2 is preferably a halogenated hydrocarbyl group, more preferably a hydrocarbyl fluoride group.
  • the compound (a) is preferably a dialkylzinc, more preferably dimethylzinc, diethylzinc, dipropylzinc, di-normal butylzinc, diisobutylzinc, di-normal hexylzinc, diallylzinc or bis(cyclopentadienyl)zinc, particularly preferably dimethylzinc or diethylzinc.
  • the compound (b) is preferably an amine such as bis(trifluoromethyl)amine, bis(2,2,2-trifluoroethyl)amine, bis(2,2,3,3,3-pentafluoropropyl)amine, bis(2,2,2-trifluoro-l- trifiuoromethylethyl)amine, bis(l,l-bis(trifluoromethyl)-2,2,2-trifluoroethyl)amine, bis(3,4,5- trifluorophenyl)amine, bis(3,4,5-tris(trifluoromethyl)phenyl)amine, bis(3,4,5- tris(pentafluorophenyl)phenyl)amine, bis(3,5-difluoro-4-pentafluorophenylphenyl)amine, bis(4,5,6,7,8-pentafluoro-2-naphthyl)amine or bis(pentafluorophenyl)amine; alcohols such as trifluoromethanol, 2,2,2-
  • the compound (b) is more preferably bis(trifluoromethyl)amine, bis(3,4,5- trifluorophenyl)amine, bis(4,5,6,7,8-pentafiuoro-2-naphthyl)amine,
  • the compound (c) is preferably water, hydrogen sulfide, alkylamine, arylamine, aralkylamine, halogenated alkylamine, halogenated arylamine or (halogenated alkyl)arylamine, more preferably water, hydrogen sulfide, methylamine, ethylamine, n-propylamine,
  • pentafluoroaniline pentachloroa iline, pentabromoaniline, pentaiodoaniline, 2- (trifluoromethyl)aniline, 3-(trifluoromethyl)aniline, 4-(trifluoromethyl)aniline, 2,6- di(trifluoromethyl)aniline, 3,5-di(trifluoromethyl)aniline or 2,4,6-tri(trifluoromethyl)aniline.
  • the compound (c) is more preferably water, hydrogen sulfide, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, isobutylamine, n-octylamine, aniline, 2,6-xylylamine, 2,4,6-trimethylaniline, naphthylamine, anthracenylamine, benzylamine, trifluoromethylamine, pentafluoroethylamine,
  • the activating co-catalytic component- 1 can be obtained by bringing these compounds (a), (b) and (c) into contact with each other.
  • the order in which the compounds (a), (b) and (c) are brought into contact with each other is not particularly limited, and for example, the following order can be adopted:
  • the order of contact is preferably the method (1) or (2).
  • the compound of the present invention is preferably a compound obtained by bringing the compound (c) into contact with a contact product obtained by bringing the compound (a) into concact with the compound (b) or a compound obtained by bringing the compound (b) into contact with a contact product obtained by bringing the compound (a) into contact with the compound (c).
  • Such contact treatment is preferably performed in an inert gas atmosphere.
  • the contact treatment temperature is usually -100 to 200°C, preferably -80 to 150°C.
  • the contact treatment time is usually 1 minute to 36 hours, preferably 10 minutes to 24 hours.
  • Such contact treatment may be performed using a solvent, or these compounds may be brought into contact with each other directly without using a solvent.
  • the solvent used may be a nonpolar solvent inert to the compounds (a), (b) and (c), such as an aliphatic hydrocarbon or aromatic hydrocarbon solvent, or may be a polar solvent such as an ether solvent.
  • the amount of each compound used is not particularly limited.
  • y is preferably any number from 0.01 to 1.99, more preferably any number from 0.20 to 1.80, further preferably any number from 0.25 to 1.50, most preferably any number from 0.50 to 1.00.
  • z is a number determined depending on n, y and the formula (11).
  • n the valence of M 1 .
  • the starting compounds (a), (b) and/or (c) for the compound of the present invention may remain as unreacted products as a result of such contact treatment.
  • the solvent is distilled off from the product, which is then dried under reduced pressure at a temperature of 25°C or higher for 1 hour or longer.
  • the product is more preferably dried at a temperature of 60 to 200°C for 1 to 24 hours, most preferably at a temperature of 80 to 160°C for 4 to 18 hours.
  • the starting compound is not limited to the zinc compound.
  • the drying conditions are not limited to 120°C for 8 hours.
  • activating co-catalytic component can include an activating co-catalytic component obtainable by bringing the following compounds (a), (b) and (c) and a carrier (hereinafter, referred to as an activating co-catalytic component-2) into contact with each other:
  • a carrier generally used is preferably used.
  • a porous substance having a uniform particle size is preferable.
  • An inorganic substance or an organic polymer is preferably used, and an inorganic substance is more preferably used.
  • the geometric standard deviation of the particle size of the carrier based on the volume is preferably 2.5 or lower, more preferably 2.0 or lower, further preferably 1.7 or lower, from the viewpoint of the particle size distribution of the resulting polymer.
  • Examples of the inorganic substance that may be used as a carrier include inorganic oxide. Clay, clay mineral, or the like may also be used. They may be mixed for use.
  • Examples of the inorganic oxide can include Si0 2 , A1 2 0 3 , MgO, Zr0 2 , Ti0 2 , B 2 0 3 , CaO, ZnO, BaO, Th0 2 and mixtures thereof, for example, Si0 2 -MgO, Si0 2 -Al 2 0 3 , Si0 2 -Ti0 2 , Si0 2 -V 2 0 5 , Si0 2 -Cr 2 0 3 and Si0 2 -Ti0 2 -MgO.
  • Si0 2 and/or A1 2 0 3 are preferable, and particularly, Si0 2 (i.e., silica) is preferable.
  • the inorganic oxide may contain a small amount of a carbonate, sulfate, nitrate or oxide component such as Na 2 C0 3 , K 2 C0 3 , CaC0 3 , MgC0 3 , Na 2 S0 4 , A1 2 (S0 4 ) 3 , BaS0 4 , KN0 3 , Mg(N0 3 ) 2 , A1(N0 3 ) 3 , Na 2 0, K 2 0 and Li 2 0.
  • a carbonate, sulfate, nitrate or oxide component such as Na 2 C0 3 , K 2 C0 3 , CaC0 3 , MgC0 3 , Na 2 S0 4 , A1 2 (S0 4 ) 3 , BaS0 4 , KN0 3 , Mg(N0 3 ) 2 , A1
  • Examples of the clay or clay mineral include kaolin, bentonite, kibushi clay, gairome clay, allophane, hisingerite, pyrophyllite, talc, mica isinglass, montmorillonite, vermiculite, chlorite, palygorskite, kaolinite, nacrite, dickite and halloysite.
  • smectite, montmorillonite, hectorite, Laponite or saponite is preferable, and montmorillonite or hectorite is more preferable.
  • an inorganic oxide is preferably used.
  • These inorganic substances are preferably dried until substantially no water content and preferably dried by heat treatment.
  • the heat treatment is usually performed at a temperature of 100 to 1,500°C, preferably 100 to 1,000°C, more preferably 200 to 800°C, for the inorganic substance whose water content cannot be confirmed by visual observation.
  • the heating time is not particularly limited and is preferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours.
  • Further examples of the heat treatment include, but not limited to, a method in which, for example, dried inert gas (e.g., nitrogen or argon) is circulated at a constant flow rate during heating and a method in which the pressure is reduced.
  • dried inert gas e.g., nitrogen or argon
  • the inorganic oxide usually has a hydroxy group formed on the surface.
  • Modified inorganic oxide obtained by substituting active hydrogen in the surface hydroxy group by various substituents may be used as the inorganic oxide.
  • a preferable substituent is a silyl group.
  • Specific examples of the modified inorganic oxide include inorganic oxide treated by contact with trialkylchlorosilane such as trimethylchlorosilane and tert- butyldimethylchlorosilane, triarylchlorosilane such as triphenylchlorosilane,
  • dialkyldichlorosilane such as dimethyldichlorosilane, diaryldichlorosilane such as
  • diphenyldichlorosilane alkyltrichlorosilane such as methyltrichlorosilane, aryltrichlorosilane such as phenyltrichlorosilane, trialkylalkoxysilane such as trimethylmethoxysilane,
  • triarylalkoxysilane such as triphenylmethoxysilane, dialkyldialkoxysilane such as
  • diaryldialkoxysilane such as diphenyldimethoxysilane
  • alkyltrialkoxysilane such as methyltrimethoxysilane
  • aryltrialkoxysilane such as
  • phenyltrimethoxysilane tetraalkoxysilane such as tetramethoxysilane
  • alkyldisilazane such as
  • the average particle size of the inorganic substance is preferably 5 to 1000 ⁇ , more preferably 10 to 500 ⁇ ⁇ ⁇ , further preferably 10 to 100 ⁇ .
  • Its pore volume is preferably 0.1 ml/g or larger, more preferably 0.3 to 10 ml/g.
  • Its specific surface is preferably 10 to 1000 m 2 /g, more preferably 100 to 500 m 2 /g.
  • the organic polymer that may be used as a carrier can be any organic polymer, and two or more organic polymers may be used as a mixture.
  • a polymer having a functional group having active hydrogen or a non-proton-donating Lewis-basic functional group is preferable as the organic polymer.
  • the order in which the compounds (a), (b) and (c) and the carrier are brought into contact with each other is not particularly limited.
  • Such contact treatment is preferably performed in an inert gas atmosphere.
  • the treatment temperature is usually -100 to 300°C, preferably -80 to 200°C.
  • the treatment time is usually 1 minute to 200 hours, preferably 10 minutes to 100 hours.
  • such treatment may be performed using a solvent, or these compounds may be contacted directly without using a solvent.
  • a solvent that does not react with each of the components to be brought into contact with each other or a contact product obtainable by bringing them into contact with each other when the solvent is used is usually used as the solvent.
  • the amounts of the compounds (a), (b) and (c) used are not particularly limited.
  • n the valence of M 1 .
  • y is preferably any number from 0.01 to 1.99, more preferably any number from 0.10 to 1.80, further preferably any number from 0.20 to 1.50, most preferably any number from 0.30 to 1.00.
  • the preferable range of z is also determined depending on n, y and the formula (13).
  • the amount of the carrier used with respect to the compound (a) is preferably an amount that offers 0.1 mmol or larger, more preferably 0.5 to 20 mmol, of compound (a)- derived metal atoms contained in particles obtainable by bringing the compound (a) into contact with the carrier, with respect to the molar number of metal atoms contained in 1 g of the resulting activating co-catalytic component.
  • the amount can be determined appropriately to achieve the range.
  • heating is also preferably performed to further promote the reaction.
  • a solvent having a higher boiling point is preferably used to achieve a higher temperature.
  • the solvent used in the contact treatment may be replaced by a different solvent having a higher boiling point.
  • the starting compounds (a), (b) and/or (c) and/or the carrier for the activating co- catalytic component-2 obtainable by bringing the compounds (a), (b) and (c) and the carrier into contact with each other used in the present invention may remain as unreacted products as a result of such contact treatment.
  • this activating co-catalytic component-2 is applied to ethylene trimerization reaction, the unreacted products are preferably removed by washing treatment in advance.
  • a solvent for this washing treatment may be the same as or different from the solvent used in the contact.
  • Pentafluorophenol is added dropwise thereto in a equimolar amount with respect to diethylzinc and the mixture is stirred at room temperature for 10 minutes to 24 hours. Then, water is further added dropwise thereto in a 0.5 -fold molar amount with respect to diethylzinc and the mixture is stirred at room temperature for 10 minutes to 24 hours. Then, the solvent is distilled off and the residue is dried under reduced pressure at 120°C for 8 hours. To the solid component obtained by these procedures, tetrahydrofiiran and silica are added, and the mixture is stirred at 40°C for 2 hours. The solid component is washed with tetrahydrofuran and then dried under reduced pressure at 120°C for 8 hours. In this way, particles obtainable by bringing the compounds (a), (b) and (c) and the carrier into contact with each other used in the present invention can be produced.
  • organic aluminum compound (B) may also be used in the trimerization reaction of ethylene:
  • compound (B) an organic aluminum compound represented by formula
  • Q 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
  • the Q 1 groups may be the same as or different from each other in the case where more than one Q 1 groups exist
  • the G groups may be the same as or different from each other in the case where more than one G groups exist.
  • examples of the hydrocarbyl group having 1 to 8 carbon atoms in Q 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 (B) represented by formula (Q 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, isobutylaluminum dichloride and hexylaluminum dichloride.
  • dialkylaluminum hydride examples include dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride and dihexylaluminum hydride.
  • the ethylene trimerization catalyst of the present invention is obtainable by bringing the complex for ethylene trimerization containing a titanium atom into contact with the activating co-catalytic component containing an element of Group 12 of the Periodic Table and is a catalyst that is capable of producing 1-hexene by ethylene trimerization.
  • a ratio (by mol) between the amounts of the catalytic components used in the present invention is not particularly limited.
  • the molar ratio between the activating co-catalytic component-1 and the complex for ethylene trimerization is usually such that the (activating co-catalytic component-1 ): (complex for ethylene trimerization) molar ratio is in the range of from 1 :1 to 10000: 1, preferably from 1 : 1 to 5000: 1, more preferably from 1 : 1 to 1000: 1.
  • the organic aluminum compound (B) When the organic aluminum compound (B) is used, it is usually used in such an amount that the (complex for ethylene trimerization) :(B) molar ratio is in the range of from 1 :0.1 to 1 : 10000, preferably from 1 : 1 to 1 : 1000.
  • the amount of the complex for ethylene trimerization used is usually 1 x 10 "6 to 1 x 10 "2 mol, preferably 1 x 10 "5 to 1 x 10 '3 mol, with respect to 1 g of the activating co-catalytic component-2.
  • the ethylene trimerization catalyst of the present invention is obtainable by bringing the activating co-catalytic component into contact with the complex for ethylene trimerization and in some cases, further with the organic aluminum compound (B).
  • a method for the contact is not particularly limited.
  • the activating co-catalytic component and the complex for ethylene trimerization, and in some cases, the organic aluminum compound (B) may be brought into contact with each other simultaneously.
  • arbitrary two components may be brought into contact with each other in advance and then brought into contact with the remaining one component, or each of these components may be brought into contact with the remaining components in any order.
  • the partial or whole procedures of this contact may be performed in a reactor, to which the components may be added in any order without particular limitations.
  • These catalytic components are preferably brought into contact with each other in a solvent.
  • the solvent include: aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane and octane; aromatic hydrocarbon solvents such as benzene and toluene; and halogenated hydrocarbon such as methylene chloride. Aliphatic hydrocarbon or aromatic hydrocarbon is preferable.
  • the concentration of each of the activating co-catalytic component- 1 and the organic aluminum compound (B) is usually 0.001 to 100 mmol/L, preferably 0.01 to 5 mmol/L, in terms of the metal atom.
  • the concentration of the complex for ethylene trimerization is usually 0.0001 to 100 mmol/L, preferably 0.01 to 10 mmol/L, in terms of the metal atom.
  • the concentration of the activating co-catalytic component-2 is usually 0.01 to 100 g L, preferably 0.1 to 10 g L.
  • the concentration of the organic aluminum compound (B) is usually 0.001 to 100 mmol/L, preferably 0.01 to 10 mmol/L, in terms of the Al atom.
  • the concentration of the complex for ethylene trimerization is usually 0.0001 to 10 mmol/L, preferably 0.001 to 10 mmol/L, in terms of the transition metal atom.
  • 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.
  • the trimerization reaction of ethylene is not particularly limited and may be, for example, trimerization reaction of ethylene 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 in a slurry state, or trimerizing gaseous ethylene.
  • 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 from normal pressure to 10 MPa, preferably in the range of from normal pressure to 5 MPa.
  • the temperature of the trimerization reaction can usually be in the range of -50°C to 220°C and is preferably in the range of 0°C to 170°C, more preferably in the range of 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.
  • the ethylene trimerization catalyst of the present invention can be used in combination with a catalytic component for olefin polymerization to thereby produce an olefin polymer having butyl branches from only ethylene without using an expensive ⁇ -olefin.
  • a catalytic component for olefin polymerization can be used as long as the complex for ethylene trimerization is not poisoned thereby.
  • Many catalytic components for polymerization may be used. Examples thereof can include Ziegler-Natta-type solid catalytic components and metallocene complexes.
  • metallocene complexes examples include metallocene complexes having one cyclopentadiene ring with a geometrically constrained structure, metallocene complexes having two cyclopentadiene rings, and metallocene complexes having three cyclopentadiene rings.
  • the complexes for polymerization include metallocene complexes highly capable of a-olefin copolymerization and having one cyclopentadiene ring with a geometrically constrained structure, and metallocene complexes highly capable of ⁇ -olefin copolymerization and having two cyclopentadiene rings.
  • More preferable examples of the complexes for polymerization include a metallocene complex having one cyclopentadiene ring with a geometrically constrained structure and bridged a metallocene complex having two cyclopentadiene rings.
  • Examples of the catalytic component for olefin polymerization include methylene(cyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride,
  • dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride dimethylsilylene(fluorenyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, methylene(tert-butylamido)(cyclopentadienyl)titanium dichloride, diphenylmethylene(tert- butylamido)(cyclopentadienyl)titanium dichloride, dimethylsilylene(tert- butylamido)(cyclopentadienyl)titanium dichloride,
  • the catalytic component for olefin polymerization is preferably methylene(cyclopentadienyI)(3,5-dimethyl-2- phenoxy)titanium dichloride, isopropylidene(tetramethylcyclopentadienyl)(3 , 5-dimethyl-2- phenoxy)titanium dichloride, diphenylmethylene(fluorenyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, dimethylsilylene(cyclopentadienyl)(2-phenoxy)titanium dichloride,
  • dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride dimethylsilylene(fiuorenyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, methylene(tert-butylamido)(cyclopentadienyl)titanium dichloride, diphenylmethylene(tert- butylamido)(cyclopentadienyl)titanium dichloride, dimethylsilylene(tert- butylamido)(cyclopentadienyl)titanium dichloride,
  • methylenebis(cyclopentadienyl)zirconium dichloride ethylenebis(indenyl)zirconium dichloride or methylenebis(indenyl)hafnium dichloride, more preferably methylene(cyclopentadienyl)(3,5- dimethyl-2-phenoxy)titanium dichloride, dimethylsilylene(tetramethylcyclopentadienyl)(3-tert- butyl-5-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(tert- butylamido)(cyclopentadienyl)titanium dichloride or ethylenebis(indenyl)zirconium dichloride.
  • the catalytic component for olefin polymerization may be used in combination with various activating co-catalytic components, may be used in combination with the activating co-catalytic component containing an element of Group 12 of the Periodic Table used in the present invention, or may be used in combination with a component usually used as an activating co-catalytic component containing an element of Group 13 of the Periodic Table, such as aluminoxane and boron-containing compounds.
  • Apparatus EX270 manufactured by JEOL Ltd.
  • Sample cell Tube (5 mm in diameter)
  • Measurement parameter Probe (5 mm in diameter), EXMOD NON, OBNUC 1H, accumulated number 16 times or more
  • Apparatus EX270 manufactured by JEOL Ltd.
  • Sample cell Tube (5 mm in diameter)
  • Measurement parameter Probe (5 mm in diameter), EXMOD BCM, OBNUC 13 C, accumulated number 256 times or more
  • Apparatus JMS-T100GC manufactured by JEOL Ltd.
  • Toluene (50 mL) was added to separate an organic phase, and the organic phase was washed with water (50 mL) twice and further washed with saturated brine (50 mL). The organic phase was dried over sodium sulfate and then filtrated. The solvent was removed from the filtrate under reduced pressure. After purification was performed by silica gel column chromatography, the resultant solid substance, to which hexane of 50°C was added, was filtrated to remove insolubles. The solvent was removed from the filtrate under reduced pressure.
  • Complex 2 [ 1 -( 1 -methyl- 1 -(3 , 5 -dimethylpheny l)ethy l)-3 - trimethylsilylcyclopentadienyl]titanium trichloride (hereinafter, referred to as "Complex 2”) was synthesized in accordance with a known method (Organometallics 2002, 21, 5122-5135.).
  • Complex 3 6-adamantyl-4-methyl-2-[N- ⁇ 2-(2-methoxyphenyl) ⁇ phenyl]imino- phenoxytitanium trichloride (hereinafter, referred to as "Complex 3”) was synthesized in accordance with a known method (WO2009/005003).
  • the fouling state was evaluated based on the amount of amorphous solids adhering to stirring blades after reaction.
  • the fouling state was determined according to the criteria: a state in which amorphous solids adhered to the whole surface of the stirring blade (poor); a state in which amorphous solids adhered to the partial (more than half) surface of the stirring blade (fair); a state in which amorphous solids adhered to the partial (less than half) surface of the stirring blade (good); and a state in which few amorphous solids adhered to the stirring blade (excellent).
  • the results are shown in Table 1.
  • TEBA triisobutylaluminum
  • ethylene was introduced so that the partial pressure of ethylene might become 2.0 MPa, and the system was stabilized.
  • 1.0 mL of a toluene solution (1 ⁇ mol/mL) of Complex 1 was added thereto and 63.5 mg of the activating co- catalytic component obtained in Preparation Example 1 was subsequently added.
  • trimerization reaction of ethylene was performed at 80°C for 30 minutes while continuously supplying ethylene gas so as to maintain the total pressure at a constant value. Ethanol (2 mL) was added to terminate the reaction. Thereafter, ethylene was purged and the content of the autoclave was decalcificated with ethanol-hydrochloric acid and filtered. 1-Hexene was obtained at an activity of 7.6 x 10 6 g/mol complex/h and a polymer was obtained at an activity of 0.64 x 10 6 g/mol complex/h. No amorphous polymer adhering to the stirrer or the like was observed.
  • Example 2 An autoclave (0.4 liter) equipped with a stirrer was dried under reduced pressure and then purged with nitrogen. Toluene (90 mL) and a hexane solution (2.2 mL) of
  • TEBA triisobutylaluminum
  • trimerization reaction of ethylene was performed at 80°C for 30 minutes while continuously supplying ethylene gas so as to maintain the total pressure at a constant value. Ethanol (2 mL) was added to terminate the reaction. Thereafter, ethylene was purged and the content of the autoclave was decalcificated with ethanol-hydrochloric acid and filtered. 1-Hexene was obtained at an activity of 1.6 x 10 6 g mol complex/h and a polymer was obtained at an activity of 0.29 x 10 6 g/mol complex/h. No amorphous polymer adhering to the stirrer or the like was observed.
  • TIBA triisobutylaluminum
  • trimerization reaction of ethylene was performed at 80°C for 30 minutes while continuously supplying ethylene gas so as to maintain the total pressure at a constant value. Ethanol (2 mL) was added to terminate the reaction. Thereafter, ethylene was purged and the content of the autoclave was decalcificated with ethanol-hydrochloric acid and filtered. 1-Hexene was obtained at an activity of 0.14 x 10 6 g/mol complex/h and a polymer was obtained at an activity of 0.81 x 10 6 g/mol complex/h. No amorphous polymer adhering to the stirrer or the like was observed.
  • trimerization reaction of ethylene was performed at 40°C for 30 minutes while continuously supplying ethylene gas so as to maintain the total pressure at a constant value. Ethanol (2 mL) was added to terminate the reaction. Thereafter, ethylene was purged and the content of the autoclave was decalcificated with ethanol-hydrochloric acid and filtered. 1-Hexene was obtained at an activity of 20.6 x 10 6 g/mol complex/h and a polymer was obtained at an activity of 0.49 x 10 6 g/mol complex/h. No amorphous polymer adhering to the stirrer or the like was observed.
  • TIBA triisobutylaluminum having a concentration of 0.93 mmol/mL were supplied. After the interior temperature of the system was elevated to 40°C, ethylene was introduced so that the partial pressure of ethylene might become 2.0 MPa, and the system was stabilized. 1.0 mL of a toluene solution (1 ⁇ /mL) of Complex 2 was added thereto and 81.8 mg of the activating co- catalytic component obtained in Preparation Example 1 was subsequently added.
  • TIBA triisobutylaluminum
  • trimerization reaction of ethylene was performed at 40°C for 30 minutes while continuously supplying ethylene gas so as to maintain the total pressure at a constant value. Ethanol (2 mL) was added to terminate the reaction. Thereafter, ethylene was purged and the content of the autoclave was decalcificated with ethanol-hydrochloric acid and filtered. 1-Hexene was obtained at an activity of 13.2 x 10 6 g/mol complex/h and a polymer was obtained at an activity of 0.55 x 10 6 g/mol complex/h. No amorphous polymer adhering to the stirrer or the like was observed.
  • trimerization reaction of ethylene was performed at 40°C for 30 minutes while continuously supplying ethylene gas so as to maintain the total pressure at a constant value. Ethanol (2 mL) was added to terminate the reaction. Thereafter, ethylene was purged and the content of the autoclave was decalcificated with ethanol-hydrochloric acid and filtered. 1-Hexene was obtained at an activity of 1.79 x 10 6 g mol complex/h and a polymer was obtained at an activity of 7.44 x 10 6 g/mol complex/h. No amorphous polymer adhering to the stirrer or the like was observed.
  • Example 1 Example 2 Example 3 Example 4
  • the present invention provides an ethylene trimerization catalytic component that is capable of producing 1-hexene while suppressing adhesion of by-product polymers to the walls of reactors or stirrers in the trimerization reaction of ethylene, the present invention is highly valuable in various fields of industries, especially in the field of ethylene trimerization catalysts and methods for producing 1-hexene.

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Abstract

Disclosed is an ethylene trimerization catalyst that is capable of suppressing adhesion of by-product polymers to the walls of reactors or stirrers in the trimerization reaction of ethylene and capable of efficiently producing 1-hexene. The ethylene trimerization catalyst is obtainable by bringing a complex for ethylene trimerization containing a titanium atom into contact with an activating co-catalytic component containing an element of Group 12 of the Periodic Table.

Description

DESCRIPTION
TRIMERIZATION CATALYST AND METHOD FOR PRODUCING 1-HEXENE
TECHNICAL FIELD
[0001]
The present invention relates to a trimerization catalyst and a method for producing 1-hexene. BACKGROUND ART
[0002]
a-olefin is an industrially important monomer raw material that is produced by the oligomerization of ethylene using a metal catalyst. However, the oligomerization of ethylene usually gives a-olefin mixtures according to Schulz-Flory distribution. Therefore, the development of a catalyst system capable of selectively producing one species of a-olefin is very important industrially.
[0003]
A complex containing a titanium atom has been reported as a complex for selective trimerization of ethylene (Patent Literatures 1 and 2 and Non Patent Literature 1, for example). However, by-product polyethylene is generally produced in the trimerization reaction of ethylene and therefore fouls the walls of reactors, stirrers, or the like in industrial production, disadvantageously making long-term operation impracticable.
Patent Literature 1, Non Patent Literature 1 and Patent Literature 2 have reported an example using a trimerization catalyst obtained by bringing a catalytic component comprising aluminoxane supported by a carrier into contact with a complex for trimerization.
CITATION LIST PATENT LITERATURE
[0004]
PATENT LITERATURE 1. JP 2004-524959 A
PATENT LITERATURE 2: WO 2009/005003
NON-PATENT LITERATURE
[0005] NON-PATENT LITERATURE 1 : ORGANOMETALLICS 2002, 21, 5122-5135.
SUMMARY OF INVENTION TECHNICAL PROBLEM
[0006]
Under such circumstances, an object of the present invention is to provide an ethylene trimerization catalyst that is capable of producing 1-hexene while suppressing adhesion of by-product polymers to the walls of reactors or stirrers in the trimerization reaction of ethylene.
SOLUTION TO PROBLEM
[0007]
Specifically, a 1st aspect of the present invention relates to
an ethylene trimerization catalyst which is obtainable by bringing a complex for ethylene trimerization containing a titanium atom into contact with an activating co-catalytic component containing an element of Group 12 of the Periodic Table.
[0008]
Moreover, a 2nd aspect of the present invention relates to an ethylene
trimerization catalyst which is obtainable by bringing a complex for ethylene trimerization containing a titanium atom into contact with an activating co-catalytic component containing an element of Group 12 of the Periodic Table, the complex for ethylene trimerization being represented by any one of formulae (1-1) to (1-3):
(1 -1)
Figure imgf000003_0001
Figure imgf000004_0001
wherein
Cp represents a group having a cyclopentadiene-type anionic skeleton; J represents a bridging group based on a single atom selected from Groups 13 to 16 of the Periodic Table of the Elements;
R1, R2, R3, R4, R5, R8, R9, R10, R11, R12, R13, R14, R15, R16 and R17 each independently represent 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 alkoxy 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 aryloxy 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,
an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
a substituted silyl group represented by -Si(R18)3, wherein the three R18 groups 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 R18 groups is 1 to 20, or a disubstituted amino group represented by -N(Rl9)2, wherein the two R19 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R19 groups is 2 to 20;
X1, X2and X3 each independently represent
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 alkoxy 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,
an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
a substituted silyl group represented by -Si(R18)3, wherein the three R18 groups 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 groups is 1 to 20, or a disubstituted amino group represented by -N(R19)2, hwerein the two R19 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R19 groups is 2 to 20;
R6 and R7 each independently represent
an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
an aryloxy 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,
an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
t o I S ' a substituted silyl group represented by -Si(R )3, wherein the three R groups 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 R18 groups is 1 to 20, or a disubstituted amino group represented by -N(R19)2, wherein the two R19 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R19 groups is 2 to 20;
1 and m each represent 1 or 0, and 1 + m is an integer equal to (valence of J - 2); of R1, R2, R3, R4 and R5, 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 R8, R9, R10, Ru and R12, 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 R13, R14, R15, R16 and R17, 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 R6 and R7 may be bonded to each other to form a ring together with J to which they are bonded; and
of X1, X2 and X3, two groups may be bonded to each other to form a ring together with Ti.
[0009]
Moreover, a 3rd aspect of the present invention relates to an ethylene trimerization catalyst which is obtainable by bringing a complex for ethylene trimerization containing a titanium atom into contact with an activating co-catalytic component containing an element of Group 12 of the Periodic Table, the complex for ethylene trimerization being r resented by any one of formulae (2-1) to (2-3):
(2-1)
Figure imgf000006_0001
Figure imgf000006_0002
Figure imgf000007_0001
wherein
p 20 p 21 R 22 p 23 p 24 p 25 p 26 p 27 p 28 p 31 p 32 p 33 c 34 p 35 D 36 p 37 p 38 p 39 iv , Jv , rv , tv , iv , I , Jts. , tv , tv , tv , tv , K , tv , K , lv , K , , rv ,
R40, R41, R42, R43 and R44 each independently represent
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 alkoxy 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 aryloxy 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,
an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
a substituted silyl group represented by -Si(R18)3, wherein the three R18 groups 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 R18 groups is 1 to 20, or a disubstituted amino group represented by -N(R19)2, wherein the two R19 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R19 groups is 2 to 20;
X4, X5 and X6 each independently represent
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 alkoxy 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,
an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
a substituted silyl group represented by -Si(R18)3, wherein the three R18 groups 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 R18 groups is 1 to 20, or a disubstituted amino group represented by -N(R19)2, wherein the two R19 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R19 groups is 2 to 20;
R29 and R30 each independently represent
an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
an aryloxy 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,
an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
a substituted silyl group represented by -Si(R18)3, wherein the three R18 groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated
1 8
hydrocarbyl group, and the total number of the carbon atoms m the three R groups is 1 to 20, or a disubstituted amino group represented by -N(R19)2, wherein the two R19 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R19 groups is 2 to 20;
at least one of R , R , R and R 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; and
of R20, R21, R22 and R23, 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 , R , R , R and R , 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 RJ1, R", R~ and RJJ, 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 , R , R , R and R , 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 R24, R41, R26, R42 and R28, 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 R31, R43, R33, R44 and R35, 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 R29 and R30 may be bonded to each other to form a ring together with the silicon atom to which they are bonded.
[0010]
Furthermore, a 4th aspect of the present invention relates to a method for producing 1-hexene using the ethylene trimerization catalyst component.
ADVANTAGEOUS EFFECTS OF INVENTION
[0011]
The present invention can provide an ethylene trimerization catalytic component that is capable of producing 1-hexene while suppressing adhesion of by-product polymers to the walls of reactors or stirrers in the trimerization reaction of ethylene.
Furthermore, according to the present invention, 1-hexene can be produced efficiently and selectively by using a complex represented by any of formulae (1-1) to (1-3) or (2-1) to (2-3) as a complex for ethylene trimerization.
DESCRIPTION OF EMBODIMENTS
[0012]
In the present invention, the term "substituent" encompasses a halogen atom constituting a compound or a group.
Furthermore, in the present invention, substituted cyclopentadiene compounds represented by formulae (6-1) to (6-3) have isomers each differing in the double bond position of each cyclopentadiene ring. In the present invention, the substituted cyclopentadiene compounds refer to any of them or a mixture of them.
[0013]
<Complex for ethylene trimerization>
[0014]
The complex for ethylene trimerization used in the present invention is a complex for ethylene trimerization containing a titanium atom. Examples of the complex for ethylene trimerization containing a titanium atom can include a complex for ethylene trimerization represented by any of formulae (1-1) to (1-3) shown below, a complex for ethylene trimerization represented by any of formulae (2-1) to (2-3) shown below, and phenoxyimine titanium complexes described in Patent Literature 2. The complex for ethylene trimerization is preferably a complex for ethylene trimerization represented by any of formulae (1-1) to (1-3) shown below or a complex for ethylene trimerization represented by any of formulae (2-1) to (2- 3) shown below, more preferably a complex for ethylene trimerization represented by any of formulae (2-1) to (2-3) shown below.
The complex for trimerization containing a titanium atom is preferable because it is free from poisoning attributed to polymerization catalytic components such as metallocene- type polymerization catalytic components or Ziegler-Natta-type solid-state polymerization catalytic component containing a titanium atom, a magnesium atom, or the like. The complexes for ethylene trimerization represented by formulae (1-1) to (1-3) or (2-1) to (2-3) are more preferable because they exhibit high activity in ethylene trimerization and produce a few by-product polymers. The complexes for ethylene trimerization represented by formulae (2-1) to (2-3) are most preferable because they exhibit higher activity in ethylene trimerization and a high ratio of the amount of 1-hexene produced to the amount of by-product polymers produced.
[0015]
Preferable examples of the complex for ethylene trimerization containing a titanium atom can include phenoxyimine titanium complexes described in Patent Literature 2. 6-Adamantyl-4-methyl-2-[N-{2-(2-methoxyphenyl)}phenyl]imino-phenoxytitanium trichloride is preferable. These compounds can be synthesized according to, for example, a method described in Journal of Organometallic Chemistry, 2003, vol. 678, 134-141.
[0016]
The complex for ethylene trimerization represented by any of formulae (1-1) to (1-3) and the complex for ethylene trimerization represented by any of formulae (2-1) to (2-3) will be described. [0017]
In the transition metal complexes (1-1) to (1-3) and (2-1) to (2-3), Cp, J, R1 to R44 and X1 to X6 are as defined above, and examples thereof are shown below.
[0018]
Examples of the group having a cyclopentadiene-type anionic skeleton, represented by Cp, include rj5-cyclopentadienyl, r|5-methylcyclopentadienyl, η5- dimethylcyclopentadienyl, T]5-trimethylcyclopentadienyl, ri5-tetramethylcyclopentadienyl, η5- ethylcyclopentadienyl, Ti5-n-propylcyclopentadienyl, η5-isopropylcyclopentadienyl, η5-η- butylcyclopentadienyl, η5-sec-butylcyclopentadienyl, η5-tert-butylcyclopentadienyl, η5-η- pentylcyclopentadienyl, Ti5-neopentylcyclopentadienyl, η5-n-he ylcyclope tadie yl, η5-η- octylcyclopentadienyl, η5-phenylcyclopentadienyl, r|5-naphthylcyclopentadienyl, η5- trimethylsilylcyclopentadienyl, η5-triethylsilylcyclopentadienyl, r|5-tert- butyldimethylsilylcyclopentadienyl, r|5-indenyl, η5-methylindenyl, η5-dimethylindenyl, η5- ethylindenyl, η5-n-propylindenyl, η5-isopropylinde yl, η5-n-butylindenyl, η5-sec-butylindenyl, r|5-tert-butylindenyl, η5-n-pentylί denyl, η5-neopentylindenyl, η5-n-he ylindenyl, η5-η- octylindenyl, η5-n-decylindenyl, η5-phenylindenyl, η5-methylphenyli denyl, η5- naphthylindenyl, η5-trimethylsilylindenyl, η5-triethylsilyli denyl, η5-ίειΐ- butyldimethylsilylindenyl, r|5-tetrahydroindenyl, η5-fluorenyl, η5-methylfluorenyl, η5- dimethylfluorenyl, -ethylfluorenyl, η5-diethylfluorenyl, 5-n-propylfluore yl, r|5-di-n- propylfluorenyl, r|5-isopropylfluorenyl, η5-diisopropylfluorenyl, η5-n-butylfluorenyl, ri5-sec- butylfluorenyl, r|5-tert-butylfluorenyl, η5-di-n-butylfluorenyl, η5-di-sec-butylfluorenyl, η5-di- tert-butylfluorenyl, r|5-n-pentylfluorenyl, η5-neopentylfluorenyl, 5- -hexylfluorenyl, η5-η- octylfluorenyl, ri5-n-decylfluorenyl, η5-n-dodecylfluorenyl, η5-phenylf uorenyl, η5-di- phenylfluorenyl, Ti5-methylphenylfluorenyl, η5-naphthylfluorenyl, η5-trimethylsilylfluorenyl, η5- bis-trimethylsilylfluorenyl, r|5-triethylsilylfluorenyl and η5-tert-butyldimethylsilylfluorenyl groups. The group having a cyclopentadiene-type anionic skeleton is preferably a η5- Cyclopentadienyl, T|5-methylcyclopentadienyl, η5-tert-butylcyclope tadie yl, η5- tetramethylcyclopentadienyl, r|5-indenyl or η5-fluorenyl group.
[0019]
Examples of the bridging group based on a single atom selected from Groups 13 to 16 of the Periodic Table of the Elements, represented by J, include boron, carbon, silicon, nitrogen, phosphorus, oxygen and sulfur atoms. A carbon or silicon atom is preferable, and a silicon atom is more preferable.
[0020]
The halogen atom is a fluorine, chlorine, bromine or iodine atom and is preferably a chlorine atom.
[0021]
Examples of the "alkyl group having 1 to 20 carbon atoms" in the 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. Of them, 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. Moreover, 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 a part or all of the hydrogen atoms in the alkyl group may be substituted by a halogen atom. Examples of the halogen atom are as described above. When the alkyl 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. Preferable examples of the alkyl group having a halogen atom as a substituent can include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tnbromomethyl, fluoroethyl, perfluoropropyl, perfluorobutyl, perfluoropentyl and perfluorohexyl groups.
[0022]
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-tolyl, 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-butylphenyl, tert-butylphenyl, n-pentylphenyl, neopentylphenyl, n-hexylphenyl, n-octylphenyl, n-decylphenyl, n-dodecylphenyl, n-tetradecylphenyl, naphthyl and anthracenyl groups. Of them, a preferable aryl group is an aryl group having 6 to 10 carbon atoms, and more preferable examples thereof can include a phenyl group. Moreover, 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 a part or all of the hydrogen atoms in the aryl group may be substituted by a halogen atom. Specific examples of the halogen atom are as described above. When the aryl 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. Preferable examples of the aryl group having a halogen atom as a substituent can specifically include fluorophenyl,
difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, chlorophenyl,
bromophenyl and iodophenyl groups.
[0023]
Examples of the "aralkyl group having 7 to 20 carbon atoms" in the aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent 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)methy 1, (2,3,5, 6-tetramethylpheny l)methy 1,
(pentamethylphenyl)methyl, (ethylphenyl)methyl, (n-propylphenyl)methyl,
(isopropylphenyl)methyl, (n-butylphenyl)methyl, (sec-butylphenyl)methyl, (tert- butylphenyl)methyl, (n-pentylphenyl)methyl, (neopentylphenyl)methyl, (n-hexylphenyl)methyl, (n-octylphenyl)methyl, (n-decylphenyl)methyl, (n-dodecylphenyl)methyl, naphthyl methyl and anthracenylmethyl groups. Of them, a preferable aralkyl group is an aralkyl group having 7 to 10 carbon atoms, and more preferable examples thereof can include a benzyl group. Moreover, 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 a part or all of the hydrogen atoms in the aralkyl group may be substituted by a halogen atom. Specific examples of the halogen atom are as described above. When 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.
[0024]
Examples of the "alkoxy group having 1 to 20 carbon atoms" in the alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent 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. Of them, 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. Moreover, 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 a part or all of the hydrogen atoms in the alkoxy group may be substituted by a halogen atom. Specific examples of the halogen atom are as described above. When 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.
[0025]
Examples of the "alkoxy group having 2 to 20 carbon atoms" in the alkoxy group having 2 to 20 carbon atoms which may have a halogen atom as a substituent include 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. Of them, 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. Moreover, 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 a part or all of the hydrogen atoms in the alkoxy group may be substituted by a halogen atom. Examples of the halogen atom are as described above. When 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.
[0026]
Examples of the "aryloxy group having 6 to 20 carbon atoms" in the aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent include phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2,3-dimethylphenoxy, 2,4- dimethylphenoxy, 2,5-dimethylphenoxy, 2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5- dimethylphenoxy, 2,3,4-trimethylphenoxy, 2,3,5-trimethylphenoxy, 2,3,6-trimethylphenoxy, 2,4,5-trimethylphenoxy, 2,4,6-trimethylphenoxy, 3,4,5-trimethylphenoxy, 2,3,4,5- tetramethylphenoxy, 2,3,4,6-tetramethylphenoxy, 2,3,5,6-tetramethylphenoxy,
pentamethylphenoxy, ethylphenoxy, n-propylphenoxy, isopropylphenoxy, n-butylphenoxy, sec- butylphenoxy, tert-butylphenoxy, n-hexylphenoxy, n-octylphenoxy, n-decylphenoxy, n- tetradecylphenoxy, naphthoxy and anthracenoxy groups. Of them, a preferable 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. Moreover, 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 a part or all of the hydrogen atoms in the aryloxy group may be substituted by a halogen atom. Specific examples of the halogen atom are as described above. When 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.
[0027]
Examples of the "aralkyloxy group having 7 to 20 carbon atoms" in the aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent 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)methoxy, (3,4,5-trimethylphenyl)methoxy, (2,3,4,5-tetramethylphenyl)methoxy, (2,3,4, 6-tetramethy 1 phenyl)methoxy, (2,3,5, 6-tetramethylphenyl)methoxy,
(pentamethylphenyl)methoxy, (ethylphenyl)methoxy, (n-propylphenyl)methoxy,
(isopropylphenyl)methoxy, (n-butylphenyl)methoxy, (sec-butylphenyl)methoxy, (tert- butylphenyl)methoxy, (n-hexylphenyl)methoxy, (n-octylphenyl)methoxy, (n- decylphenyl)methoxy, naphthylmethoxy and anthracenylmethoxy groups. Of them, a preferable aralkyloxy group is an aralkyloxy group having 7 to 10 carbon atoms, and more preferable examples thereof can include a benzyloxy group. Moreover, 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 a part or all of the hydrogen atoms in the aralkyloxy group may be substituted by a halogen atom. Specific examples of the halogen atom are as described above. When the aralkyloxy 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.
[0028]
In the substituted silyl group represented by -Si(R18)3, wherein the three R18 groups each independently represent a hydrogen atom, a hydrocarbyl group or a halogenated
18
hydrocarbyl group, and the total number of the carbon atoms in the three R groups is 1 to 20, the R18 groups 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 halogenated hydrocarbyl group obtained by substituting a part or all of the hydrogen atoms in the hydrocarbyl group with a halogen atom, and the total number of carbon atoms in the three R groups is in the range of 1 to 20. The total number of the carbon atoms in these three R18 groups is preferably in the range of 3 to 18. Examples of 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 a part or all of the hydrogen atoms in the hydrocarbyl groups of these groups with 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 a part or all of the hydrogen atoms in the hydrocarbyl groups of these groups with 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 tnphenylsilyl groups, and groups obtained by substituting a part or all of the hydrogen atoms in the hydrocarbyl groups of these groups with a halogen atom. Of them, trisubstituted silyl groups are preferable, and trimethylsilyl, tert-butyldimethylsilyl and triphenylsilyl groups, and groups obtained by substituting a part or all of the hydrogen atoms in these groups with a halogen atom are more preferable.
[0029]
In the disubstituted amino group represented by -N(R19)2, wherein the two R19 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R19 groups is 2 to 20, the R19 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R19 groups is in the range of 2 to 20, more preferably in the range of 2 to 10. The 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. Moreover, these two R19 groups may be bonded to each other to form a ring together with the nitrogen atom to which they are bonded. Examples of such a disubstituted amino group include dimethylamino, diethylamino, di-n-propylamino,
diisopropylamino, di-n-butylamino, di-sec-butylamino, di-tert-butylamino, di-isobutylamino, tert-butylisopropylamino, di-n-hexylamino, di-n-octylamino, di-n-decylamino, diphenylamino, bistrimethylsilylamino, bis-tert-butyldimethylsilylamino, pyrrolyl, pyrrolidinyl, piperidinyl, carbazolyl, dihydroindolyl and dihydroisoindolyl groups, and groups obtained by substituting a part or all of the hydrogen atoms in these groups with a halogen atom. Of them,
dimethylamino, diethylamino, pyrrolidinyl and piperidinyl groups, and groups obtained by substituting a part or all of the hydrogen atoms in these groups with a halogen atom are preferable.
[0030]
6 7
R and R' may be bonded to each other to form a ring together with J to which they are bonded, and R29 and R30 may be bonded to each other to form a ring together with the silicon atom to which they are bonded.
Of R1, R2, R3, R4 and R5, two groups bonded to two adjoining carbon atoms may be bonded to each other to form a ring together with the carbon atoms to which they are bonded,
24 25 6 27 28
of R , R , R , R and R , 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 they are bonded, of R24, R41,
26 42 28
R , R" and R'e, 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 R8, R9, R10, R11 and R12, 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 they are bonded, of RJ1, R", R and R", 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 they are bonded, and of R31, R43, R33, R44 and R35, 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 they two groups are bonded.
Of R13, R14, R15, R16 and R17, 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 they are
36 37 38 39 40
bonded, and of RJO, R", RJS, Rw and Rw, 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 they are bonded.
20 21 22 23
Of R , R , R , and R", 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 they are bonded.
In this context, 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. Examples thereof include cyclopropane, cyclopropene, cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, cyclohexene, cycloheptane, cycloheptene, cyclooctane, cyclooctene, benzene, naphthalene, anthracene, silacyclopropane, silacyclobutane, silacyclopentane and
silacyclohexane rings.
[0031] Examples of the complexes for ethylene trimerization (1-1) to (1-3) include the following complexes:
[0032]
titanium chloride complexes such as [1-dimethylphenylsilyl- cyclopentadienyljtitanium trichloride, [l-diethylphenylsilyl-cyclopentadienyl]titanium trichloride, [1-ethylmethylphenylsilyl -cyclopentadienyljtitanium trichloride, [1-n- butylmethylphenylsilyl-cyclopentadienyljtitanium trichloride, [ 1 -methyldiphenylsilyl- cyclopentadienyljtitanium trichloride, [ 1 -cyclohexylmethylphenylsilyl- cyclopentadienyljtitanium trichloride, [l-methyl(n-octadecyl)phenylsilyl- cyclopentadienyljtitanium trichloride, [l-triphenylsilyl-cyclopentadienyl]titanium trichloride, [1- tri(4-n-butylphenyl)silyl-cyclopentadienyl]titanium trichloride, [l-tri(3-methylphenyl)silyl- cyclopentadienyl Jtitanium trichloride, [ 1 -tri(3 -isopropylphenyl)silyl-cyclopentadienyl Jtitanium trichloride, [l-dimethyl(3,5-dimethylphenyl)silyl-cyclopentadienyl]titatiium trichloride, [1- dimethyl(3,5-di-n-hexylphenyl)silyl-cyclopentadienylJtitanium trichloride, [l-n-butylmethyl(3,5- dimethylphenyl)silyl-cyclopentadienyl]titanium trichloride, [ 1 -tris(3,5-dimethylphenyl)silyl- cyclopentadienyljtitanium trichloride, [l-tris(3,5-diethylphenyl)silyl-cyclopentadienyl]titanium trichloride, [ 1 -tris(3, 5-diisopropylphenyl)silyl-cyclopentadienyl]titanium trichloride, [ 1 -tris(3, 5- di-tert-butylphenyl)silyl-cyclopentadienylJtitanium trichloride, [ 1 -tris(3 ,5-di-n- hexylphenyl)silyl-cyclopentadienylJtitanium trichloride, [ 1 -n-butylmethyl(2,4,6- trimethylphenyl)silyl-cyclopentadienyl]titanium trichloride, [1-n- butylmethyl(pentamethylphenyl)silyl-cyclopentadienylJtitanium trichloride, [l-(3,5-di-tert- butylphenyl)bis(3 ,5-dimethylphenyl)silyl-cyclopentadienylJtitanium trichloride, [ 1 -(3, 5-di-tert- butylphenyl)(3,5-diethylphenyl)(3,5-dimethylphenyl)sityl-cyclopentadienylJtitanium trichloride, [l-tris(3,5-diphenylphenyl)silyl-cyclopentadienyl]titanium trichloride and [l-tris(3,5- dibenzylphenyl)silyl-cyclopentadienylJtitanium trichloride.
[0033J
Moreover, examples of the complexes for ethylene trimerization (1-1) to (1-3) also include: complexes obtained by substituting a carbon atom for the silicon atom in J in the general formulae (1-1) to (1-3) in the complexes exemplified above; 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 hydride complexes obtained by substituting "hydride" therefor; alkylated titanium complexes such as methylated titanium complexes obtained by substituting "methyl" therefor; arylated titanium complexes such as phenylated titanium complexes obtained by substituting "phenyl" therefor; aralkylated titanium complexes such as benzylated titanium complexes obtained by substituting "benzyl" therefor; titanium alkoxide complexes such as titanium methoxide complexes obtained by substituting "methoxide" therefor, titanium n-butoxide complexes obtained by substituting "n- butoxide" therefor and titanium isopropoxide complexes obtained by substituting "isopropoxide" therefor; titanium aryloxide complexes such as titanium phenoxide complexes obtained by substituting "phenoxide" therefor; titanium aralkyloxide complexes such as titanium benzyloxide complexes obtained by substituting "benzyloxide" therefor; and titanium amide complexes such as titanium dimethylamide complexes obtained by substituting "dimethylamide" therefor and titanium diethylamide complexes obtained by substituting "diethylamide" therefor.
[0034]
Moreover, preferable examples of the complexes for ethylene trimerization (1-1) to (1-3) also include complexes specifically exemplified later as the complexes for ethylene trimerization (2-1) to (2-3).
[0035]
Hereinafter, the complexes for ethylene trimerization (2-1) to (2-3) will be described.
In the complexes for ethylene trimerization (2-1) to (2-3), at least one of R20, R2!, R22 and R23 is a substituent other than hydrogen, and R20, R21, R22 and R23 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.
[0036]
Examples of R , R , R and R can include cyclopentadiene substructures represented by a substructural formula (3):
Figure imgf000019_0001
wherein R20, R21, R22 and R23 are as defined above, and at least one thereof is a substituent other than hydrogen, for example, the following substructures:
[0037]
methylcyclopentadienyl, ethylcyclopentadienyl, n-propylcyclopentadienyl, isopropylcyclopentadienyl, n-butylcyclopentadienyl, sec-butylcyclopentadienyl, tert- butylcyclopentadienyl, dimethylcyclopentadienyl, trimethylcyclopentadienyl, tetramethylcyclopentadienyl, phenylcyclopentadienyl, benzylcyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, methyltetrahydroindenyl, dimethyltetrahydroindenyl and octahydrofluoreny 1.
[0038]
Of the cyclopentadiene substructures exemplified above, a preferable
cyclopentadiene substructure is tetramethylcyclopentadienyl, etc.
[0039]
In the complexes for ethylene trimerization (2-1) to (2-3), R , R , R , R , R ,
R31, R32, R33, R34, R35, R36, R37, R38, R39, R40, R41, R42, R43 and R44 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.
[0040]
Examples of a preferable combination of the groups represented by R , R , R ,
R27 and R28, a preferable combination of the groups represented by R31, R32, R33, R34 and R35, a preferable combination of the groups represented by R36, R37, R38, R39 and R40, a preferable combination of the groups represented by R24, R41, R26, R42 and R28 and a preferable combination of the groups represented by R31, R43, R33, R44 and R35 each include the following substructures represented by a substructural formula (4-1):
Figure imgf000020_0001
wherein R , R , R , R / and R are as defined above;
a substructural formula 4-2):
Figure imgf000020_0002
wherein R31, R32, R33, R34 and R35 are as defined above
a substructural formula (4-3) thereof: defined above;
Figure imgf000021_0002
wherein R , R , R , R and R are as defined above;
a substructural formula (4-5):
Figure imgf000021_0003
wherein R31, R43, R33, R44 and R35 are as defined above:
[0041]
phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, tetramethylphenyl, pentamethylphenyl, ethylphenyl, diethylphenyl, trimethylphenyl, tetraethylphenyl, pentaethylphenyl, tert-butylphenyl, di-tert-butylphenyl, tert-butylmethylphenyl, di(tert- butyl)methylphenyl, phenylphenyl, diphenylphenyl, triphenylphenyl, tetraphenylphenyl, pentaphenylphenyl, benzylphenyl, dibenzylphenyl, tribenzylphenyl, tetrabenzylphenyl, pentabenzylphenyl, naphthyl, anthracenyl, chlorophenyl, dichlorophenyl, fluorophenyl, pentafluorophenyl, bis(trifluoromethyl)phenyl and methoxyphenyl.
[0042]
Of the substructures exemplified above, a preferable substructure is phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, diethylphenyl, di-tert-butylphenyl, etc.
[0043]
In the complexes for ethylene trimerization (2-1), R29 and R30 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 specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl or benzyl group.
[0044]
Examples of a preferable combination of the groups represented by R29 and R30 include the following substructures represented by a substructural formula (5):
Figure imgf000022_0001
wherein R29 and R30 are as defined above:
[0045]
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 and cyclotetramethylenesilylene.
[0046]
Preferable examples of the substructural formula (5) include a substructural formula wherein
R29 is a methyl group, and R30 is
an alkyl group having 2 to 20 carbon atoms which may have a halogen atom as a substituent, a substructural formula wherein
R29 and R30 are the same as each other and are
an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, and a structural formula wherein
R29 and R30 are different from each other and are
an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent.
The substructure is specifically dimethylsilylene, diethylsilylene, ethylmethylsilylene, n-butylmethylsilylene, cyclohexylmethylsilylene,
cyclotetramethylenesilylene, etc.
[0047]
Preferable examples of the complex for ethylene trimerization (2-1) include transition metal complexes wherein R25 and R27 are each independently
an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent or an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent.
[0048] In the complex for ethylene trimerization (2-2), R30 is preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec- butyl, tert-butyl and benzyl groups.
[0049]
Preferable examples of the complex for ethylene trimerization (2-2) include transition metal complexes wherein R , R , R and R are each independently
an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent or an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent.
[0050] .
Preferable examples of the complex for ethylene trimerization (2-3) include transition metal complexes wherein R37, R39, R41, R42, R43 and R44 are each independently an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent or an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent.
[0051]
Examples of the complexes for ethylene trimerization (2-1) to (2-3) include the following complexes:
[0052]
titanium chloride complexes such as [l-dimethylphenylsilyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [l-diethylphenylsilyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [l-cyclotetramethylene(phenyl)silyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [ 1 -ethylmethylphenylsilyl-2, 3 ,4, 5 - tetramethylcyclopentadienyl]titanium trichloride, [1- butylmethylphenylsilyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [l-methyldiphenylsilyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [l-methylbis(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [l-cyclohexylmethylphenylsilyl-2,3,4,5- tetramethylcyclopentadienyljtitanium trichloride, [ 1 -methyl(n-octadecyl)phenylsilyl-2,3 ,4,5- tetramethylcyclopentadienyljtitanium trichloride, [l-triphenylsilyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [l-tri(4-n-buthylphenylsilyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [l-tri(3-methylphenyl)silyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [ 1 -tri(3 -isopropylphenyl)silyl-2, 3 ,4, 5- tetramethy lcyclopentadieny l]titanium trichloride, [ 1 -dimethy 1(3 , 5 -dimethylpheny l)silyl-2, 3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [l-dimethyl(3,5-di-n-hexylphenyl)silyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [l-n-buthylmethyl(3,5-dimethylphenyl)silyl- 2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride, [l-tris(3,5-dimethylphenyl)silyl- 2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride, [l-tris(3,5-diethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [l-tris(3,5-diisopropylphenyl)silyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [ 1 -tris(3 , 5-di-tert-butylphenyl)silyl-2, 3 ,4, 5 - tetramethylcyclopentadienyl]titanium trichloride, [l-tris(3,5-di-n-hexylphenyl)silyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [ 1 -n-butylmethyl(2,4,6-trimethylphenyl)silyl- 2,3,4, 5-tetramethylcyclopentadienyl]titanium trichloride, [ 1 -n-butyl
methyl(pentamethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride, [1- (3 , 5-di-tert-butylphenyl)bis(3 , 5-dimethylphenyl)silyl-2,3 ,4, 5- tetramethylcyclopentadienyljtitanium trichloride, [ 1 -(3,5-di-tert-butylphenyl)(3,5- diethylphenyl)(3,5-dimethyIphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride, [l-tris(3,5-diphenylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride and [l-tris(3,5-dibenzylphenyl)silyl-2,3,4,5-tetraniethylcyclopentadienyl]titanium trichloride.
[0053]
Moreover, examples of the complexes for ethylene trimerization (2-1) to (2-3) also include titanium chloride complexes obtained by substituting "2-methylcyclopentadienyl", "3-methylcyclopentadienyl", "2,3-dimethylcyclopentadienyl", "2,4-dimethylcyclopentadienyl", "2, 5 -dimethy lcyclopentadieny 1 ", "2,3,5 -trimethylcyclopentadienyl " , "2-ethy lcyclopentadieny 1 " , "3-ethylcyclopentadienyl", "2-n-propylcyclopentadienyl", "3-n-propylcyclopentadienyl", "2- isopropylcyclopentadienyl", "3-isopropylcyclopentadienyl", "2-n-butylcyclopentadienyl", "3-n- butylcyclopentadienyl", "2-sec-butylcyclopentadienyl", "3-sec-butylcyclopentadienyl", "2-tert- butylcyclopentadienyl", "3-tert-butylcyclopentadienyl", "2-phenylcyclopentadienyl", "3- phenylcyclopentadienyl", "2-benzylcyclopentadienyl", "3-benzylcyclopentadienyl", "indenyl", "2-methylindenyl", "fluorenyl", "tetrahydroindenyl", "2-methyltetrahydroindenyl" or
"octahydrofluorenyl" for "2,3,4,5-tetramethylcyclopentadienyl" in the complexes exemplified above.
[0054]
Furthermore, examples of the complexes for ethylene trimerization (2-1) to (2-3) also include: titanium halide complexes such as titanium fluoride complexes obtained by substituting "fluoride" for "chloride" in the complexes exemplified above, titanium bromide complexes obtained by substituting "bromide" therefor and titanium iodide complexes obtained by substituting "iodide" therefor; titanium hydride complexes obtained by substituting "hydride" therefor; alkylated titanium complexes such as methylated titanium complexes obtained by substituting "methyl" therefor; arylated titanium complexes such as phenylated titanium complexes obtained by substituting "phenyl" therefor; aralkylated titanium complexes such as benzylated titanium complexes obtained by substituting "benzyl" therefor; titanium alkoxide complexes such as titanium methoxide complexes obtained by substituting "methoxide" therefor, titanium n-butoxide complexes obtained by substituting "n-butoxide" therefor and titanium isopropoxide complexes obtained by substituting "isopropoxide" therefor; titanium aryloxide complexes such as titanium phenoxide complexes obtained by substituting "phenoxide" therefor; titanium aralkyloxide complexes such as titanium benzyloxide complexes obtained by substituting "benzyloxide" therefor; and titanium amide complexes such as titanium
dimethylamide complexes obtained by substituting "dimethylamide" therefor and titanium diethylamide complexes obtained by substituting "diethylamide" therefor.
[0055]
<Methods for producing complexes for ethylene trimerization (2-1) to (2-3)>
The complexes for ethylene trimerization (2-1), (2-2) and (2-3) can be produced from a substituted cyclopentadiene compound represented by formula (6-1), a substituted cyclopentadiene compound represented by formula (6-2) and a substituted cyclopentadiene compound represented by formula (6-3), respectively, by similar methods:
(6-1)
Figure imgf000025_0001
wherein R , R , R , R , R , R , R , R , R , R and R are as defined above,
-2)
Figure imgf000025_0002
wherein R20, R21, R22, R23, R24, R25, R26, R27, R28, R30, R31, R32, R33, R34 and R35 are as defined above, and 6-3)
Figure imgf000026_0001
wherein R20, R21, R22, R23, R24, R26, R28, R31, R33, R35, R36, R37, R38, R39, R40, R41, R42, R43 and
R are as defined above.
Hereinafter, the complexes for ethylene trimerization (2-1) will be described as an example. The complexes for ethylene trimerization (2-1) can be produced by, for example, a production method comprising the steps of:
reacting the substituted cyclopentadiene compound represented by formula (6-1) (hereinafter, referred to as a "substituted cyclopentadiene compound (6-1)") with a base in the presence of an amine compound:
Figure imgf000026_0002
wherein R20, R21, R22, R23, R24, R25, R26, R27, R28, R29 and R30 are as defined above; and reacting the reaction product of the substituted cyclopentadiene compound (6-1) and the base with a transition metal compound represented by formula (7) (hereinafter, referred to as a "transition metal compound (7)"):
Figure imgf000026_0003
wherein X4, X5 and X6 are as defined above; and X7 is as defined in X4, X5 and X6: q is 0 or 1. Hereinafter, the step of reacting the substituted cyclopentadiene compound (6-1) with a base in the presence of an amine compound may be referred to as a "1st reaction step", and the step of reacting the reaction product of the substituted cyclopentadiene compound (6-1) and the base with a transition metal compound (7) may be referred to as a "2nd reaction step".
[0056] Isomers of the substituted cyclopentadiene compound (6-1) differing in the double bond osition of the cyclopentadiene ring include the following structural isomers:
Figure imgf000027_0001
The compound represented by formula (6-1) 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.
[0057]
In the transition metal compound (7), the substituent X7 is as defined above, and specific examples thereof include the same as those exemplified for X4, X5 and X6.
[0058]
Examples of the transition metal compound (7) include: titanium halide such as titanium tetrachloride, titanium trichloride, titanium tetrabromide and titanium tetraiodide;
amidotitanium such as tetrakis(dimethylamino)titanium, dichlorobis(dimethylamino)titanium, trichloro(dimethylamino)titanium and tetrakis(diethylamino)titanium; and alkoxytitanium such as tetraisopropoxytitanium, tetra-n-butoxytitanium, dichlorodiisopropoxytitanium and
trichloroisopropoxytitanium. Of them, a preferable transition metal compound (4) is titanium tetrachloride.
[0059]
Examples of the base reacted with the substituted cyclopentadiene compound (6- 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. [0060]
The amount of the base used may be in the range of 0.5 to 5 moles per mole of the substituted cyclopentadiene compound (6-1).
[0061]
In the reaction of the substituted cyclopentadiene compound (6-1) with the base in the 1st reaction step, an amine compound is used. Examples of such an amine compound 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-butylamine, diisopropylethylamine, tri-n-octylamine, tri-n-decylamine, triphenylamine, N,N-dimethylaniline, N,N,N N'-tetramethylethylenediamine, N-methylpyrrolidine and 4-dimethylaminopyridine. The amount of such an amine compound used is preferably 10 moles or smaller, more preferably in the range of 0.5 to 10 moles, even more preferably in the range of 1 to 5 moles, per mole of the base.
[0062]
In the 1st reaction step, the reaction of the substituted cyclopentadiene compound (6-1) with the base is preferably performed in the presence of a solvent. Moreover, when the solvent is used, the substituted cyclopentadiene compound (6-1) and the base are reacted in the solvent and then a transition metal compound (7) can be added into this reaction mixture to thereby further react the transition metal compound (7) with the reaction product of the substituted cyclopentadiene compound (6-1) and the base. Solids may be deposited in the reaction mixture obtained by reacting the substituted cyclopentadiene compound (6-1) and the base. In this case, 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 (7). Moreover, when the solvent is used, the substituted
cyclopentadiene compound (6-1), the base and the transition metal compound (7) can also be added simultaneously to the solvent to thereby perform the 1st reaction step and the 2nd reaction step almost simultaneously.
[0063]
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. Examples of such a solvent include 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, tetrahydrofiiran and 1,4-dioxane; amide solvents such as hexamethylphosphoric amide and dimethylformamide; polar solvents such as acetonitrile, propionitrile, acetone, diethyl ketone, methyl isobutyl ketone and cyclohexanone; and 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 (6-1).
[0064]
The amount of the transition metal compound (7) 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 (6-1).
[0065]
The reaction temperature of the 1st 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 -80 to 100°C .
[0066]
From the reaction mixture thus obtained through the 1st and 2nd reaction steps, the produced complex for ethylene trimerization (2-1) can be taken by various purification methods known in the art. For example, the complex for ethylene trimerization (2-1) of interest 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, which is then collected by filtration.
[0067]
Moreover, a compound wherein one or some of X4, X5 and X6 in any of the complexes for ethylene trimerization (2-1) to (2-3) are substituted by a hydrogen atom, an alkoxy 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, an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent, or the like can also be obtained by reacting a compound wherein X4, X5 and X6 in any of the complexes for ethylene trimerization (2-1) to (2-3) are a halogen atom with a lithium, sodium, potassium or magnesium compound having the corresponding alkyl, alkoxy, aryl, aralkyl or aralkyloxy group.
[0068]
<Substituted cyclopentadiene compounds (6-1) to (6-3 )>
[0069]
In the substituted cyclopentadiene compounds (6-1) to (6-3), the substituents R20
TJ21 p22 p23 β24 R25 β26 R27 R28 p29 p30 p31 p32 R33 p34 Ώ35 p 36 p37 p38 D 39 D40 D41 I , is. , is. , Is. , is. , is. , is. , is. , is. , is. , is. , is. , is. , is. , is. , is. , is. , is. , K. , rv , tv
R42, R43 and R44 are as defined above.
[0070]
Examples of the substituted cyclopentadiene compound (6-1) include the following substituted cyclopentadiene compounds:
[0071]
l-dimethylphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1-diethylphenylsilyl- 2,3,4,5-tetramethylcyclopentadiene, 1 -phenyldi(n-propyl)silyl-2,3,4,5- tetramethylcyclopentadiene, 1 -diisopropylphenylsilyl-2,3,4, 5-tetramethylcyclopentadiene, 1 - di(n-butyl)phenylsilyl-2,3,4,5-tetramethylcyclopentadiene, l-di(isobutyl)phenylsilyl-2,3,4,5- tetramethylcyclopentadiene, l-di(sec-butyl)phenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1- di(tert-butyl)phenylsilyl-2,3,4,5-tetramethylcyclopentadiene, l-ethylmethylphenylsilyl-2,3,4,5- tetramethylcyclopentadiene, l-methylphenyl(n-propyl)silyl-2,3,4,5-tetramethylcyclopentadiene, l-methylphenyl(isopropyl)silyl-2,3,4,5-tetramethylcyclopentadiene, 1-n-butylmethylphenylsilyl 2, 3 ,4, 5 -tetramethylcyclopentadiene, 1 -isobutylmethylpheny lsilyl-2, 3,4,5- tetramethylcyclopentadiene, 1 -sec-butylmethylphenylsilyl-2,3 ,4, 5 -tetramethylcyclopentadiene, l-tert-butylmethylphenyIsilyl-2,3,4,5-tetramethylcyclopentadiene, 1- cyclohexylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, l-methyl(n- octadecyl)phenylsilyl-2,3,4,5-tetramethylcyclopentadiene,
[0072]
l-dimethyl(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene, 1- diethyl(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene, l-(3,5- dimethylphenyl)di(n-propyl)silyl-2,3,4, 5-tetramethylcyclopentadiene, 1 -diisopropyl(3 , 5- dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene, l-di(n-butyl)(3,5- dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene, 1 -di(isobutyl)(3,5- dimethylphenyl)silyl-2,3,4,5-tetramethyIcyclopentadiene, l-di(sec-butyl)(3,5- dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene, l-di(tert-butyl)(3,5- dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene, l-ethylmethyl(3,5- dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene, l-methyl(3,5-dimethylphenyl)(n- propyl)silyl-2,3,4,5-tetramethylcyclopentadiene, l-methyl(3,5-dimethylphenyl)(isopropyl)silyl- 2, 3 ,4, 5 -tetramethylcyclopentadiene, 1 -n-butylmethyl(3 , 5-dimethylphenyl)silyl-2,3 ,4, 5- tetramethy lcyclopentadiene, 1 -isobuty lmethy 1(3 , 5 -dimethylpheny 1) sily 1-2, 3 , 4, 5 - tetramethylcyclopentadiene, l-sec-butylmethyl(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethy lcyclopentadiene, 1 -tert-butylmethyl(3 , 5 -dimethylphenyl)sily 1-2, 3,4,5- tetramethylcyclopentadiene, l-cyclohexylmethyl(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-methyl(n-octadecyl)(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene.
[0073]
Moreover, examples of the substituted cyclopentadiene compound (6-1) also include substituted cyclopentadiene compounds obtained by substituting "2- methylcyclopentadiene", "3-methylcyclopentadiene", "2,3-dimethylcyclopentadiene", "2,4- dimethylcyclopentadiene", "2,5-dimethyIcyclopentadiene", "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", "2-tert-butylcyclopentadiene", "3-tert-butylcyclopentadiene", "2- phenylcyclopentadiene", "3-phenylcyclopentadiene", "2-benzylcyclopentadiene", "3- benzylcyclopentadiene", "indene", "2-methylindene", "fluorene", "tetrahydroindene", "2- methyltetrahydroindene" or "octahydrofluorene" for "2,3,4,5-tetramethylcyclopentadiene" in the substituted cyclopentadiene compounds exemplified above.
[0074]
Specific examples of the substituted cyclopentadiene compound (6-2) can include the following substituted cyclopentadiene compounds:
[0075]
l-methyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1-ethyldiphenylsilyl- 2,3,4,5-tetramethylcyclopentadiene, l-n-propyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, l-isopropyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, l-n-butyldiphenylsilyl-2,3,4,5- tetramethylcyclopentadiene, l-isobutyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1-sec- butyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, l-tert-butyldiphenylsilyl-2,3,4,5- tetramethylcyclopentadiene, 1 -cyclohexyldiphenylsilyl-2, 3 ,4, 5-tetramethylcyclopentadiene, 1 -n- octadecyldiphenylsilyl-2,3,4, 5-tetramethylcyclopentadiene, 1 -methylphenyl(2- methylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene, l-methylphenyl(3-methylphenyl)silyl- 2,3,4,5-tetramethylcyclopentadiene, l-methylphenyl(4-methylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-methylphenyl(2,3-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-methylphenyl(2,4-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-methylphenyl(2,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-methylphenyl(2,6-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-methylphenyl(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-methylphenyl(3,4,5-trimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene,
[0076]
l-ethylphenyl(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene, 1-n- propylphenyl(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene, 1- isopropylphenyl(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene, 1-n- butylphenyl(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene, l-isobutylphenyl(3,5- dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene, l-sec-butylphenyl(3,5- dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene, l-tert-butylphenyl(3,5- dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene, l-cyclohexylphenyl(3,5- dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene, l-n-octadecylphenyl(3,5- dimethylphenyl)silyl-2,3, 4, 5-tetramethylcyclopentadiene, l-methyl(2-methylphenyl)(3,5- dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene, l-methyl(3-methylphenyl)(3,5- dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene, l-methyl(4-methylphenyl)(3,5- dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene, l-methyl(2,3-dimethylphenyl)(3,5- dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene, l-methyl(2,4-dimethylphenyl)(3,5- dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene, l-methyl(2,5-dimethylphenyl)(3,5- dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene, l-methylphenyl(2,6- dimethylphenyl)(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene, l-methylbis(3,5- dimethylphenyl)silyl-2, 3 ,4, 5-tetramethylcyclopentadiene, 1 -methyl(3 , 5-dimethylphenyl)(3 ,4,5- trimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene.
[0077]
Moreover, examples of the substituted cyclopentadiene compound (6-2) 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- butylcyclopentadiene", "2-tert-butylcyclopentadiene", "3-tert-butylcyclopentadiene", "2- phenylcyclopentadiene", "3-phenylcyclopentadiene", "2-benzylcyclopentadiene", "3- benzylcyclopentadiene", "indene", "2-methylindene", "fluorene", "tetrahydroindene", "2- methyltetrahydroindene" or "octahydrofluorene" for "2,3,4,5-tetramethylcyclopentadiene" in the substituted cyclopentadiene compounds exemplified above.
[0078]
Specific examples of the substituted cyclopentadiene compound (6-3) can include the following substituted cyclopentadiene compounds:
[0079]
1 -triphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1 -phenyldi(2- methylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene, l-phenyldi(3-methylphenyl)silyl- 2,3,4,5-tetramethylcyclopentadiene, l-phenyldi(4-methylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-phenylbis(2,3-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-phenylbis(2,4-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-phenylbis(2,5-dimethylphenyl)silyl-2,3,4,5- tetramethy lcyclopentadiene, 1 -pheny lbi s(2, 6-dimethy lpheny l)si lyl-2, 3,4,5- tetramethylcyclopentadiene, l-phenylbis(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-phenylbis(3,4,5-trimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene,
[0080]
l-diphenyl(2-methylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene, 1- diphenyl(3-methylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene, l-diphenyl(4- methylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene, l-diphenyl(2,3-dimethylphenyl)silyl- 2,3,4,5-tetramethylcyclopentadiene, l-diphenyl(2,4-dimethylphenyl)silyl-2,3,4,5- tetramethy lcyclopentadiene, 1 -dipheny 1(2, 5 -dimethy lpheny l)sily 1-2, 3,4,5- tetramethylcyclopentadiene, l-diphenyl(2,6-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-diphenyl(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, 1 -diphenyl(3 ,4, 5-trimethylphenyl)silyl-2, 3 ,4, 5- tetramethylcyclopentadiene,
[0081]
l-phenyl(2-methylphenyl)(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-phenyl(3-methylphenyl)(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-phenyl(4-methylphenyl)(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-phenyl(2,3-dimethylphenyl)(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-phenyl(2,4-dimethylphenyl)(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-phenyl(2,5-dimethylphenyl)(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-phenyl(2,6-dimethylphenyl)(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-phenyl(3,5-dimethylphenyl)(3,4,5-trimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene,
[0082]
l-di(2-methylphenyl)(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-di(3-methylphenyl)(3,5-dimethylphenyl)siIyl-2,3,4,5- tetramethylcyclopentadiene, l-di(4-methylphenyl)(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-bis(2,3-dimethylphenyl)(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-bis(2,4-dimethylphenyl)(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-bis(2,5-dimethylphenyl)(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-bis(2,6-dimethylphenyl)(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-tris(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene, l-(3,5-dimethylphenyl)bis(3,4,5-trimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene.
[0083]
Moreover, examples of the substituted cyclopentadiene compound (6-3) 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", "2-tert-butylcyclopentadiene", "3-tert-butylcyclopentadiene", "2- phenylcyclopentadiene", "3-phenylcyclopentadiene", "2-benzylcyclopentadiene", "3- benzylcyclopentadiene", "indene", "2-methylindene", "fluorene", "tetrahydroindene", "2- methyltetrahydroindene" or "octahydrofluorene" for "2,3,4,5-tetramethylcyclopentadiene" in the substituted cyclopentadiene compounds exemplified above.
[0084]
<Methods for producing substituted cyclopentadiene compounds (6-1) to (6-3)>
The substituted cyclopentadiene compounds (6-1), (6-2) and (6-3) can be produced by similar methods comprising the steps of:
reacting a substituted cyclopentadiene compound represented by formula (8) (hereinafter, abbreviated to a "substituted cyclopentadiene compound (8)") with a base;
reacting the reaction product of the substituted cyclopentadiene compound (8) and the base with a halogenated silyl compound represented by formula (9-1) (hereinafter, abbreviated to a "halogenated silyl compound (9-1)"), and
reacting the substituted cyclopentadiene compound (8) with a base;
reacting the reaction product of the substituted cyclopentadiene compound (8) and the base with a halogenated silyl compound represented by formula (9-2) (hereinafter, abbreviated to a "halogenated silyl compound (9-2)"), and
reacting the substituted cyclopentadiene compound (8) with a base; and
reacting the reaction product of the substituted cyclopentadiene compound (8) and the base with a halogenated silyl compound represented by formula (9-3) (hereinafter, abbreviated to a "halogenated silyl compound (9-3)"), respectively:
Figure imgf000035_0001
wherein R , R , R and R ,2i3 are as defined above, and
Figure imgf000035_0002
represents
Figure imgf000035_0003
wherein R , R , R , R , R , R2y and R3U are as defined above, and Xs is a halogen atom,
wherein R24, R25, R26, R27, R28, R30, R31, R32, R33, R34 and R35 are as defined above, and X8 is a halo en atom, and
Figure imgf000036_0002
wherein R24, R26, R28, R31, R33, R35, R36, R37, R38, R39, R40, R41, R42, R43 and R44 are as defined above, and Xs is a halogen atom.
Hereinafter, a method for producing the substituted cyclopentadiene compound
(6-1) will be described as an example.
[0085]
The substituted cyclopentadiene compound (8) is as follows:
Figure imgf000036_0003
wherein R20, R21, R22 and , 23 are as defined above, and
Figure imgf000036_0004
[0086]
Examples of the substituted cyclopentadiene compound (8) include the following compounds:
[0087]
methylcyclopentadiene, 1,2-dimethylcyclopentadiene, 1,3- dimethylcyclopentadiene, 1 , 2, 3 -tnmethylcyclopentadiene, 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, neopentylcyclopentadiene, n-hexylcyclopentadiene, n- octylcyclopentadiene, phenylcyclopentadiene, naphthylcyclopentadiene,
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- hexyltetrahydroindene, 2-cyclohexyltetrahydroindene, 2-n-octyltetrahydroindene, 2-n- decyltetrahydroindene, 2-phenyltetrahydroindene, 2-benzyltetrahydroindene, 2- naphthyltetrahydroindene, 2-methoxytetrahydroindene, 2-phenoxytetrahydroindene, 2- benzyloxytetrahydroindene, 2-dimethylaminotetrahydroindene, 2-trimethylsilyltetrahydroindene, fluorene and octahydrofluorene.
[0088]
The substituted cyclopentadiene compounds (8) exemplified above may be an isomer thereof differing in the double bond position of each cyclopentadiene ring. A mixture of these isomers may also be used.
[0089]
The halogenated silyl compound (9-1) is as follows:
Figure imgf000038_0001
wherein R , R , R , R , R , R2y and RJ(J are as defined above, and X is a halogen atom.
[0090]
Examples of the halogenated sily compound (9-1) include the following halogenated silyl compounds:
[0091]
chlorodimethylphenylsilane, chlorodiethylphenylsilane, chlorophenyldi(n- propyl)silane, chlorodiisopropylphenylsilane, di(n-butyl)chlorophenylsilane,
di(isobutyl)chlorophenylsilane, di(sec-butyl)chlorophenylsilane, di(tert- butyl)chlorophenylsilane, chloroethylmethylphenylsilane, chloromethylphenyl(n-propyl)silane, chloromethylphenyl(isopropyl)silane, n-butylchloromethylphenylsilane,
isobutylchloromethylphenylsilane, sec-butylchloromethylphenylsilane, tert- butylchloromethylphenylsilane, chlorocyclohexylmethylphenylsilane, chloromethyl(n- octadecyl)phenylsilane,
[0092]
chlorodimethyl(3,5-dimethylphenyl)silane, chlorodiethyl(3,5- dimethylphenyl)silane, chloro(3,5-dimethylphenyl)di(n-propyl)silane, chlorodiisopropyl(3,5- dimethylphenyl)silane, di(n-butyl)chloro(3,5-dimethylphenyl)silane, di(isobutyl)chloro(3,5- dimethylphenyl)silane, di(sec-butyl)chloro(3, 5-dimethylphenyl)silane, di(tert-butyl)chloro(3, 5- dimethylphenyl)silane, chloroethylmethyl(3,5-dimethylphenyl)silane, chloromethy 1(3,5 - dimethylphenyl)(n-propyl)silane, chloromethyl(3,5-dimethylphenyl)(isopropyl)silane, n- butylchloromethyl(3,5-dimethylphenyl)silane, isobutylchloromethyl(3,5-dimethylphenyl)silane, sec-butylchloromethy 1(3 , 5 -dimethy lphenyl)silane, tert-butylchloromethy 1(3 , 5 - dimethylphenyl)silane, chlorocyclohexylmethyl(3,5-dimethylphenyl)silane, chloromethyl(n- octadecyl)(3,5-dimethylphenyl)silane.
[0093]
Compounds obtained by substituting "fluoro", "bromo" or "iodo" for "chloro" in these compounds exemplified above are also included therein.
[0094] Examples of the halogenated silyl compound (9-2) include the following halogenated silyl compounds:
[0095]
chloromethyldiphenylsilane, chloroethyldiphenylsilane, chloro-n- propyldiphenylsilane, chloroisopropyldiphenylsilane, n-butylchlorodiphenylsilane,
isobutylchlorodiphenylsilane, sec-butylchlorodiphenylsilane, tert-butylchlorodiphenylsilane, chlorocyclohexyldiphenylsilane, chloro-n-octadecyldiphenylsilane, chloromethylphenyl(2- methylphenyl)silane, chloromethylphenyl(3-methylphenyl)silane, chloromethylphenyl(4- methylphenyl)silane, chloromethylphenyl(2,3-dimethylphenyl)silane, chloromethylpheny 1(2,4- dimethylphenyl)silane, chloromethylphenyl(2,5-dimethylphenyl)silane, chloromethylphenyl(2,6- dimethylphenyl)silane, chloromethylphenyl(3,5-dimethylphenyl)silane,
chloromethylphenyl(3,4,5-trimethylphenyl)silane,
[0096]
chloroethylphenyl(3 , 5-dimethylphenyl)silane, chloro-n-propylphenyl(3 , 5- dimethylphenyl)silane, chloroisopropylphenyl(3,5-dimethylphenyl)silane, n- butylchlorophenyl(3 , 5-dimethylphenyl)silane, isobutylchlorophenyl(3 , 5-dimethylphenyl)silane, sec-butylchloropheny 1(3 , 5 -dimethy lpheny l)silane, tert-butylchloropheny 1(3 , 5 - dimethylphenyl)silane, chlorocyclohexylphenyl(3,5-dimethylphenyl)silane, chloro-n- octadecylpheny 1(3 , 5 -dimethylpheny l)silane, chloromethyl(2-methy lp heny 1)(3 , 5 - dimethylphenyl)silane, chloromethyl(3-methylphenyl)(3,5-dimethylphenyl)silane,
chloromethyl(4-methylphenyl)(3,5-dimethylphenyl)silane, chloromethyl(2,3- dimethylphenyl)(3,5-dimethylphenyl)silane, chloromethyl(2,4-dimethylphenyl)(3,5- dimethylphenyl)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.
[0097]
Compounds obtained by substituting "fluoro", "bromo" or "iodo" for "chloro" in these compounds exemplified above are also included therein.
[0098]
Examples of the halogenated silyl compound (9-3) include the following .
halogenated silyl compounds:
[0099]
chlorotriphenylsilane, chlorophenyldi(2-methylphenyl)silane, chlorophenyldi(3 - methylphenyl)silane, chlorophenyldi(4-methylphenyl)silane, chlorophenylbis(2,3- dimethylphenyl)silane, chlorophenylbis(2,4-dimethylphenyl)silane, chlorophenylbis(2, 5- dimethylphenyl)silane, chlorophenylbis(2,6-dimethylphenyl)silane, chlorophenylbis(3,5- dimethylphenyl)silane, chlorophenylbis(3,4,5-trimethylphenyl)silane,
[0100]
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(3,4,5-trimethylphenyl)silane,
[0101]
chlorophenyl(2-methylphenyl)(3,5-dimethylphenyl)silane, chlorophenyl(3- methylphenyl)(3,5-dimethylphenyl)silane, chlorophenyl(4-methylphenyl)(3,5- dimethylphenyl)silane, chlorophenyl(2,3-dimethylphenyl)(3,5-dimethylphenyl)silane, chlorophenyl(2,4-dimethylphenyl)(3,5-dimethylphenyl)silane, chlorophenyl(2,5~
dimethylphenyl)(3,5-dimethylphenyl)silane, chlorophenyl(2,6-dimethylphenyl)(3,5- dimethylphenyl)silane, chlorophenyl(3,5-dimethylphenyl)(3,4,5-trimethylphenyl)silane,
[0102]
chlorodi(2-methylphenyl)(3,5-dimethylphenyl)silane, chlorodi(3- methylphenyl)(3,5-dimethylphenyl)silane, chlorodi(4-methylphenyl)(3,5-dimethylphenyl)silane, chlorobis(2,3-dimethylphenyl)(3,5-dimethylphenyl)silane, chlorobis(2,4-dimethylphenyl)(3,5- dimethylphenyl)silane, chlorobis(2,5-dimethylphenyl)(3,5-dimethylphenyl)silane, chlorobis(2,6- dimethylphenyl)(3,5-dimethylphenyl)silane, chlorotris(3,5-dimethylphenyl)silane, chloro(3,5- dimethylphenyl)bis(3,4,5-dimethylphenyl)silane.
[0103]
Compounds obtained by substituting "fluoro", "bromo" or "iodo" for "chloro" in these compounds exemplified above are also included therein.
[0104]
Examples of the base reacted with the substituted cyclopentadiene compound (8) 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. The amount thereof used 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 (8). 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.
[0105]
In the step of reacting the substituted cyclopentadiene compound (8) with a base, an amine compound may be used. Examples of such an amine compound include: primary anilines such as aniline, chloroaniline, bromoaniline, fluoroaniline, dichloroaniline,
dibromoaniline, difluoroanitine, trichloroaniline, tribromoaniline, trifluoroaniline,
tetrachloroaniline, tetrabromoaniline, tetrafluoroaniline, pentachloroaniline, pentafluoroaniline, nitroaniline, dinitroaniline, hydroxyaniline, phenylenediamine, anisidine, dimethoxyaniline, trimethoxyaniline, ethoxyaniline, diethoxyaniline, triethoxyaniline, n-propoxyaniline, isopropoxyaniline, n-butoxyaniline, sec-butoxyaniline, isobutoxyaniline, t-butoxyaniline, phenoxyaniline, methylaniline, ethylaniline, n-propylaniline, isopropylaniline, n-butylaniline, sec-butylaniline, isobutylaniline, t-butylaniline, dimethylaniline, diethylaniline, di-n- propylaniline, diisopropylaniline, di-n-butylaniline, di-sec-butylaniline, diisobutylaniline, di-t- butylaniline, trimethylaniline, triethylaniline, diisopropylaniline, phenylaniline, benzylaniline, aminobenzoic acid, methyl aminobenzoate, ethyl aminobenzoate, n-propyl aminobenzoate, isopropyl aminobenzoate, n-butyl aminobenzoate, isobutyl aminobenzoate, sec-butyl aminobenzoate and t-butyl aminobenzoate, and other primary amines including naphthylamine, naphthylmethylamine, benzylamine, propylamine, butylamine, pentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, 2-aminopyridine, 3-aminopyridine and 4- aminopyridine;
[0106]
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-methylaminopyridine, 3-methylaminopyridine and 4- methylaminopyridine; and
[0107]
tertiary amines such as N,N-dimethylaniline, Ν,Ν-dimethylchloroaniline, N,N- dimethylbromoaniline, N,N-dimethylfluoroaniline, Ν,Ν-dimethylanisidine, N- methylmethylaniline, Ν,Ν-dimethylethylaniline, N,N-dimethyl-n-propylaniline, N,N- dimethylisopropylaniline, l,4-diazabicyclo[2.2.2]octane, l,5-diazabicyclo[4.3.0]non-5-ene, 1,8- diazabicycIo[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. Preferably primary or secondary amines, more preferably primary amines are used.
[0108]
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. Examples of such 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 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 each cyclopentadiene.
[0109]
For the reaction, for example, the substituted cyclopentadiene compound (8), 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 (8) 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 0 to 70°C, preferably 10 to 60°C. This reaction efficiently produces a metal salt of the substituted cyclopentadiene compound (8). The metal salt of the substituted cyclopentadiene compound (8) 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.
[0110]
The reaction for obtaining the substituted cyclopentadiene compound (6-1) is usually performed in a solvent inert to the reaction. Examples of such 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 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 (8). This reaction is usually performed, for example, by mixing the base, the amine compound and the substituted cyclopentadiene compound (8) in a solvent and then adding the halogenated silyl compound (9-1) to the mixture. However, even when a method is adopted in which these components are mixed simultaneously, the substituted cyclopentadiene compound (6-1) 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.
[0111]
The amount of the substituted cyclopentadiene compound (8) 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 (9-1).
[0112]
After completion of the reaction, water, an aqueous sodium bicarbonate solution, an aqueous sodium carbonate solution, an aqueous ammonium chloride solution or an aqueous solution of hydrochloric acid or the like is added to the obtained reaction mixture. Then, organic and aqueous phases are separated to obtain a solution of the substituted cyclopentadiene compound (6-1) as the organic phase. When a water-compatible solvent is used in the reaction or when the amount of the solvent used in the reaction is too small to easily separate organic and aqueous phases, a water-insoluble organic solvent such as toluene, ethyl acetate or
chlorobenzene may be added to the reaction mixture as appropriate, followed by separation into organic and aqueous phases. The obtained organic phase is concentrated to obtain the substituted cyclopentadiene compound (6-1). The obtained substituted cyclopentadiene compound (6-1) may be purified, if necessary, by a method such as distillation and column chromatography treatment.
[0113]
<Activating co-catalytic component>
The activating co-catalytic component used in the present invention is an activating co-catalytic component containing an element of Group 12 of the Periodic Table, and examples thereof include an activating co-catalytic component obtainable by bringing the following compounds (a), (b) and (c) into contact with each other (hereinafter, referred to as an activating co-catalytic component- 1):
(a) : a compound represented by formula [Al]:
[Al],
(b) : a compound represented by formula [A2]:
El TlH [A2], and
(c) : a compound represented by formula [A3]:
E2 U-2T'H2 [A3], wherein
M1 represents an atom of Group 12 of the Periodic Table; n represents the valence of M1; L represents a hydrogen atom, a halogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group; in the case where more than one L groups exist, the L groups may be the same as or different from each other; E1 represents an electron- withdrawing group or a group containing an electron-withdrawing group; E2 represents a hydrocarbyl group or a halogenated hydrocarbyl group; in the case where more than one E1 groups exist, the E1 groups may be the same as or different from each other; T1 represents an atom of Group 15 or 16 of the Periodic Table; t represents the valence of T1; T' represents an atom of Group 15 or 16 of the Periodic Table; and u represents the valence of T'.
[0114]
In formula [Al], M1 represents an atom of Group 12 of the Periodic Table.
Specific examples thereof include zinc, cadmium and mercury atoms. M1 is particularly preferably a zinc atom. In formula [Al], n represents the valence of M1. For example, when M1 is a zinc atom, n is 2.
[0115]
In formula [Al], L represents a hydrogen atom, a halogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group, and in the case where more than one L groups exist, the L groups may be the same as or different from each other. Examples of the halogen atom in L include fluorine, chlorine, bromine and iodine atoms. The hydrocarbyl group in L is preferably an alkyl, aryl or aralkyl group.
[0116]
In this context, the alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert- butyl, isobutyl, n-pentyl, neopentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-pentadecyl and n- eicosyl groups. The alkyl group is more preferably a methyl, ethyl, isopropyl, tert-butyl or isobutyl group.
[0117]
The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include phenyl, 2-tolyl, 3-tolyl, 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-butylphenyl, tert-butylphenyl, n-pentylphenyl,
neopentylphenyl, n-hexylphenyl, n-octylphenyl, n-decylphenyl, n-dodecylphenyl, n- tetradecylphenyl, naphthyl and anthracenyl groups. The aryl group is more preferably a phenyl group. All of these aryl groups may partially be substituted by, for example, an alkoxy group (e.g., methoxy and ethoxy groups), an aryloxy group (e.g., a phenoxy group) or an aralkyloxy group (e.g., a benzyloxy group).
[0118]
The aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, and examples thereof 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, (2,3, 5,6- tetramethylphenyl)methyl, (pentamethylphenyl)methyl, (ethylphenyl)methyl, (n- propylphenyl)methyl, (isopropylphenyl)methyl, (n-butylphenyl)methyl, (sec- butylphenyl)methyl, (tert-butylphenyl)methyl, (n-pentylphenyl)methyl,
(neopentylphenyl)methyl, (n-hexylphenyl)methyl, (n-octylphenyl)methyl, (n- decylphenyl)methyl, (n-tetradecylphenyl)methyl, naphthylmethyl and anthracenylmethyl groups. The aralkyl group is more preferably a benzyl group. All of these aralkyl groups may partially be substituted by, for example, an alkoxy group (e.g., methoxy and ethoxy groups), an aryloxy group (e.g., a phenoxy group) or an aralkyloxy group (e.g., a benzyloxy group).
[0119]
The halogenated hydrocarbyl group is preferably a halogenated alkyl group having 1 to 20 carbon atoms. Examples of the halogenated hydrocarbyl group include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, diiodomethyl, triiodomethyl, fluoroethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl, pentafluoroethyl, chloroethyl, dichloroethyl, trichloroethyl, tetrachloroethyl, pentachloroethyl, bromoethyl, dibromoethyl, tribromoethyl, tetrabromoethyl, pentabromoethyl, perfluoropropyl, perfluorobutyl,
perfluoropentyl, perfiuorohexyl, perfluorooctyl, perfluorododecyl, perfluoropentadecyl, perfluoroeicosyl, perchloropropyl, perchlorobutyl, perchloropentyl, perchlorohexyl,
perchlorooctyl, perchlorododecyl, perchloropentadecyl, perchloroeicosyl, perbromopropyl, perbromobutyl, perbromopentyl, perbromohexyl, perbromooctyl, perbromododecyl,
perbromopentadecyl and perbromoeicosyl groups. All of these halogenated alkyl groups may partially be substituted by, for example, an alkoxy group (e.g., methoxy and ethoxy groups), an aryloxy group (e.g., a phenoxy group) or an aralkyloxy group (e.g., a benzyloxy group).
[0120]
In formula [Al], L is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group, particularly preferably an alkyl group.
[0121]
In formula [A2], T1 represents an atom of Group 15 or 16 of the Periodic Table.
In the general formula [A3], T represents an atom of Group 15 or 16 of the Periodic Table.
Examples of the atom of Group 15 include nitrogen and phosphorus atoms. Examples of the atom of Group 16 include oxygen and sulfur atoms. T1 is preferably a nitrogen or oxygen atom, particularly preferably an oxygen atom. T' is preferably a nitrogen or oxygen atom, particularly preferably an oxygen atom. In formula [A2], t represents the valence of T1. When T1 is an atom of Group 15, t is 3. When T1 is an atom of Group 16, t is 2. In formula [A3], u represents the valence of T'. When T' is an atom of Group 15, u is 3. When T' is an atom of Group 16, u is 2.
[0122]
In formula [A2], E1 represents an electron- withdrawing group or a group containing an electron-withdrawing group, and the E1 groups may be the same as or different from each other in the case more than one E1 groups exist. For example, a substituent constant σ of the Hammett's rule is known as an index for electron-withdrawing properties. Examples of the electron-withdrawing group include functional groups whose substituent constant σ of the Hammett's rule is positive.
[0123]
Examples of the electron-withdrawing group include fluorine, chlorine, bromine and iodine atoms, and cyano, nitro, carbonyl, sulfone and phenyl groups. Examples of the group containing an electron-withdrawing group include halogenated alkyl, halogenated aryl, (halogenated alkyl)aryl, cyanated aryl, nitrated aryl, ester (alkoxycarbonyl, aralkyloxycarbonyl and aryloxycarbonyl), acyl and halogenated acyl groups.
[0124]
Examples of the halogenated alkyl group include fluoromethyl, chloromethyl, bromomethyl, iodomethyl, difluoromethyl, dichloromethyl, dibromomethyt, diiodomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, triiodomethyl, 2,2,2-trifluoroethyl, 2,2,2- trichloroethyl, 2,2,2-tribromoethyl, 2,2,2-triiodoethyl, 2,2,3,3,3-pentafluoropropyl, 2,2,3,3,3- pentachloropropyl, 2,2,3,3,3-pentabromopropyl, 2,2,3,3,3-pentaiodopropyl, 2,2,2-trifluoro-l- trifluoromethylethyl, 2,2,2-trichloro- 1-trichloromethylethyl, 2,2,2-tribromo- 1 - tribromomethylethyl, 2,2,2-triiodo- 1-triiodomethylethyl, 1 , l-bis(trifluoromethyl)-2,2,2- trifluoroethyl, 1 , 1 -bis(trichloromethyl)-2,2,2-trichloroethyl, 1 , l-bis(tribromomethyl)-2,2,2- tribromoethyl and l,l-bis(triiodomethyl)-2,2,2-triiodoethyl groups.
[0125]
Examples of the halogenated aryl group include 2-fluorophenyl, 3 -fluorophenyl, 4-fluorophenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-bromophenyl, 3- bromophenyl, 4-bromophenyl, 2-iodophenyl, 3-iodophenyl, 4-iodophenyl, 2,6-difluorophenyl, 3,5-difluorophenyl, 2,6-dichlorophenyl, 3,5-dichlorophenyl, 2,6-dibromophenyl, 3,5- dibromophenyl, 2,6-diiodophenyl, 3,5-diiodophenyl, 2,4,6-trifluorophenyl, 3,4,5-trifluorophenyl, 2,4,6-trichlorophenyl, 2,4,6-tribromophenyl, 2,4,6-triiodophenyl, pentafluorophenyl,
pentachlorophenyl, pentabromophenyl and pentaiodophenyl groups.
[0126]
Examples of the (halogenated alkyl)aryl group include 2-(trifluoromethyl)phenyl,
3- (trifluoromethyl)phenyl, 4-(trifIuoromethyl)phenyl, 2,6-bis(trifluoromethyl)phenyl, 3,5- bis(trifluoromethyl)phenyl and 2,4,6-tris(trifluoromethyl)phenyl groups.
[0127]
Examples of the cyanated aryl group include 2-cyanophenyl, 3-cyanophenyl and
4- cyanophenyl groups.
[0128]
Examples of the nitrated aryl group include 2-nitrophenyl, 3-nitrophenyl and 4- nitrophenyl groups.
[0129]
Examples of the ester group include methoxycarbonyl, ethoxycarbonyl, normal propoxycarbonyl, isopropoxycarbonyl, phenoxycarbonyl, trifluoromethoxycarbonyl and pentafiuorophenoxycarbonyl groups. [0130]
Examples of the acyl group include formyl, ethanoyl, propanoyl, butanoyl, trifluoroethanoyl, benzoyl, pentafluorobenzoyl, perfiuoroethanoyl, perfluoropropanoyl, perfluorobutanoyl, perfluoropentanoyl, perfluorohexanoyl, perfluoroheptanoyl,
perfiuorooctanoyl, perfluorononanoyl, perfluorodecanoyl, perfluoroundecanoyl and
perfluorododecanoyl groups.
[0131]
E1 is preferably a halogenated hydrocarbyl group, more preferably a halogenated alkyl or halogenated aryl group, even more preferably a fluoromethyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 2,2,3,3,3-pentafluoropropyl, 2,2,2-trifluoro-l- trifluoromethylethyl, l, l-bis(trifluoromethyl)-2,2,2-trifluoroethyl, 2-fiuorophenyl, 3- fluorophenyl, 4-fluorophenyl, 2,4-difluorophenyl, 2,6-difluorophenyl, 3,4-difluorophenyl, 3,5- difluorophenyl, 2,4,6-trifluorophenyl, 3,4,5-trifluorophenyl, 2,3,5,6-tetrafluorophenyl, pentafluorophenyl, 2,3,5,6-tetrafluoro-4-trifluoromethylphenyl, 2,3,5,6-tetrafluoro-4- pentafluorophenylphenyl, perfluoro-l-naphthyl, perfluoro-2-naphthyl, chloro methyl, dichloromethyl, trichloromethyl, 2,2,2-trichloroethyl, 2,2,3,3,3-pentachloropropyl, 2,2,2- trichloro- 1 -tnchloromethylethyl, 1 , 1 -bis(trichloromethyl)-2,2,2-trichloroethyl, 4-chlorophenyl, 2,6-dichlorophenyl, 3,5-dichlorophenyl, 2,4,6-trichlorophenyl or pentachlorophenyl group, particularly preferably a fluoroalkyl or fluoroaryl group, further preferably a trifluoromethyl, 2,2,2-trifluoro-l-trifluoromethylethyl, 1, l-bis(trifluoromethyl)-2,2,2-trifluoroethyl, 3,5- difluorophenyl or pentafluorophenyl group, most preferably a 3,4,5-trifluorophenyl group.
[0132]
In formula [A3], E2 represents a hydrocarbyl group or a halogenated hydrocarbyl group. The hydrocarbyl group represented by E2 is preferably an alkyl, aryl or aralkyl group. The same hydrocarbyl group as those exemplified as L in the general formula [Al] is used. Examples of the halogenated hydrocarbyl group represented by E2 include halogenated alkyl, halogenated aryl and (halogenated alkyl)aryl groups. The same halogenated alkyl, halogenated aryl and (halogenated alkyl)aryl groups as those specifically exemplified as the electron- withdrawing group represented by E1 in formula [A2] are used.
[0133]
In formula [A3], E2 is preferably a halogenated hydrocarbyl group, more preferably a hydrocarbyl fluoride group.
[0134]
The compound (a) is preferably a dialkylzinc, more preferably dimethylzinc, diethylzinc, dipropylzinc, di-normal butylzinc, diisobutylzinc, di-normal hexylzinc, diallylzinc or bis(cyclopentadienyl)zinc, particularly preferably dimethylzinc or diethylzinc.
[0135]
The compound (b) is preferably an amine such as bis(trifluoromethyl)amine, bis(2,2,2-trifluoroethyl)amine, bis(2,2,3,3,3-pentafluoropropyl)amine, bis(2,2,2-trifluoro-l- trifiuoromethylethyl)amine, bis(l,l-bis(trifluoromethyl)-2,2,2-trifluoroethyl)amine, bis(3,4,5- trifluorophenyl)amine, bis(3,4,5-tris(trifluoromethyl)phenyl)amine, bis(3,4,5- tris(pentafluorophenyl)phenyl)amine, bis(3,5-difluoro-4-pentafluorophenylphenyl)amine, bis(4,5,6,7,8-pentafluoro-2-naphthyl)amine or bis(pentafluorophenyl)amine; alcohols such as trifluoromethanol, 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropanol, 2,2,2-trifluoro-l- trifluoromethylethanol or l,l-bis(trifluoromethyl)-2,2,2-trifluoroethanol; phenols such as 2- fluorophenol, 3-f uorophenol, 4-fluorophenol, 2,6-difluorophenol, 3,5-difluorophenol, 2,4,6- trifluorophenol, 3,4,5-trifluorophenol, pentafluorophenol, 2-(trifluoromethyl)phenol, 3- (trifluoromethyl)phenol, 4-(trifluoromethyl)phenol, 2,6-bis(trifluoromethyl)phenol, 3,5- bis(trifluoromethyl)phenol, 2,4,6-tris(trifiuoromethyl)phenol, 3,4,5-trifluorophenol, 3,4,5- tris(trifluoromethyl)phenol, 3 ,4, 5-tris(pentafluorophenyl)phenol, 3 , 5-difluoro-4- pentafluorophenylphenol or 4,5,6, 7,8-pentafluoro-2-naphthol; carboxylic acids such as pentafiuorobenzoic acid or trifluoroacetic acid; and sulfonic acids such as
trifluoromethanesulfonic acid.
[0136]
The compound (b) is more preferably bis(trifluoromethyl)amine, bis(3,4,5- trifluorophenyl)amine, bis(4,5,6,7,8-pentafiuoro-2-naphthyl)amine,
bis(pentafluorophenyl)amine, trifluoromethanol, 2,2,2-trifIuoro-l-trifluoromethylethanol, 1, 1- bis(trifluoromethyl)-2,2,2-trifluoroethanol, 4-fluorophenol, 2,6-difluorophenol, 2,4,6- trifiuorophenol, 3,4,5-trifluorophenol, 4,5,6,7,8-pentafluoro-2-naphthol, pentafluorophenol, 4- (trifiuoromethyl)phenol, 2,6-bis(trifluoromethyl)phenol or 2,4,6-tris(trifluoromethyl)phenol, further preferably l,l-bis(trifluoromethyl)-2,2,2-trifluoroethanol, 3,5-difluorophenol, 3,4,5- trifluorophenol, pentafluorophenol or l, l-bis(trifluoromethyl)-2,2,2-trifluoroethanol, particularly preferably 3,4,5-trifluorophenol.
[0137]
The compound (c) is preferably water, hydrogen sulfide, alkylamine, arylamine, aralkylamine, halogenated alkylamine, halogenated arylamine or (halogenated alkyl)arylamine, more preferably water, hydrogen sulfide, methylamine, ethylamine, n-propylamine,
isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, isobutylamine, n-pentylamine, neopentylamine, amylamine, n-hexylamine, n-octylamine, n-decylamine, n-dodecylamine, n- pentadecylamine, n-eicosylamine, allylamine, cyclopentadienylamine, aniline, 2-tolylamine, 3- tolylamine, 4-tolylamine, 2,3-xylylamine, 2,4-xylylamine, 2,5-xylylamine, 2,6-xylylamine, 3,4- xylylamine, 3,5-xylylamine, 2,3,4-trimethylaniline, 2,3,5-trimethylaniline, 2,3,6- trimethylaniline, 2,4,6-trimethylaniline, 3,4,5-trimethylaniline, 2,3,4,5-tetramethylaniline, 2,3,4,6-tetramethylaniline, 2,3,5,6-tetramethylaniline, pentamethylaniline, ethylaniline, n- propylaniline, isopropylaniline, n-butylaniline, sec-butylaniline, tert-butylaniline, n- pentylaniline, neopentylaniline, n-hexylani ine, n-octylaniline, n-decylaniline, n-dodecylaniline, n-tetradecylaniline, naphthylamine, anthracenylamine,
[0138]
benzylamine, (2-methylphenyl)methylamine, (3-methylphenyl)methylamine, (4- methylphenyl)methylamine, (2,3-dimethylphenyl)methylamine, (2,4- dimethylphenyl)methylamine, (2, 5-dimethylphenyl)methylamine, (2,6- dimethylphenyl)methylamine, (3 ,4-dimethylphenyl)methylamine, (3,5- dimethylphenyl)methylamine, (2,3,4-trimethylphenyl)methylamine, (2,3,5- trimethylphenyl)methylamine, (2,3,6-trimethylphenyl)methylamine, (3,4,5- trimethylphenyl)methylamine, (2,4,6-trimethylphenyl)methylamine, (2,3,4,5- tetramethylphenyl)methylamine, (2,3,4,6-tetramethylphenyl)methylamine, (2,3,5,6- tetramethylphenyl)methylamine, (pentamethylphenyl)methylamine, (ethylphenyl)methylamine, (n-propylphenyl)methylamine, (isopropylphenyl)methylamine, (n-butylphenyl)methylamine, (sec-butylphenyl)methylamine, (tert-butylphenyl)methylamine, (n-pentylphenyl)methylamine, (neopentylphenyl)methylamine, (n-hexylphenyl)methylamine, (n-octylphenyl)methylamine, (n- decylphenyl)methylamine, (n-tetradecylphenyl)methylamine, naphthylmethylamine, anthracenylmethylamine, fluoromethylamine, chloromethylamine, bromomethylamine, iodomethylamine, difluoromethylamine, dichloromethylamine, dibromomethylamine, diiodomethylamine, trifluoromethylamine, trichloromethylamine, tribromomethylamine, triiodomethylamine, 2,2,2-trifluoroethylamine, 2,2,2-trichloroethylamine, 2,2,2- tribromoethylamine, 2,2,2-triiodoethylamine, 2,2,3,3, 3-pentafluoropropylamine, 2,2,3,3,3- pentachloropropylamine, 2,2,3,3 , 3-pentabromopropylamine, 2, 2, 3 , 3 , 3 -pentaiodopropylamine, 2,2,2-trifluoro-l-trifluoromethylethylamine, 2,2,2-trichloro-l-trichloromethylethylamine, 2,2,2- tribromo- 1 -tribromomethylethylamine, 2,2,2-triiodo- 1 -triiodomethylethylamine, 1,1- bis(trifluoromethyl)-2,2,2-trifluoroethylamine, 1 , 1 -bis(trichloromethyl)-2,2,2- trichloroethylamine, 1 , 1 -bis(tribromomethyl)-2,2,2-tribromoethylamine, 1 , 1 -bis(triiodomethyl)- 2,2,2-triiodoethylamine, [0139]
2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 2-chloroaniline, 3-chloroaniline, 4-chloroaniline, 2-bromoaniline, 3-bromoaniline, 4-bromoaniline, 2-iodoaniline, 3-iodoaniline, 4-iodoaniline, 2,6-difluoroaniline, 3,5-difluoroaniline, 2,6-dichloroaniline, 3,5-dichloroaniline, 2,6-dibromoaniline, 3,5-dibromoaniline, 2,6-diiodoaniline, 3,5-diiodoaniline, 2,4,6- trifluoroaniline, 2,4,6-trichloroaniline, 2,4,6-tribromoaniline, 2,4,6-triiodoaniline,
pentafluoroaniline, pentachloroa iline, pentabromoaniline, pentaiodoaniline, 2- (trifluoromethyl)aniline, 3-(trifluoromethyl)aniline, 4-(trifluoromethyl)aniline, 2,6- di(trifluoromethyl)aniline, 3,5-di(trifluoromethyl)aniline or 2,4,6-tri(trifluoromethyl)aniline.
[0140]
The compound (c) is more preferably water, hydrogen sulfide, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, isobutylamine, n-octylamine, aniline, 2,6-xylylamine, 2,4,6-trimethylaniline, naphthylamine, anthracenylamine, benzylamine, trifluoromethylamine, pentafluoroethylamine,
perfiuoropropylamine, perfluorobutylamine, perfluoropentylamine, perfluorohexylamine, perfluorooctylamine, perfluorododecylamine, perfluoropentadecylamine, perfluoroeicosylamine, 2-fluoroaniline, 3-fluoroaniline, 4-fluoroaniline, 2,6-difluoroaniline, 3,5-difluoroaniline, 2,4,6- trifluoroaniline, pentafluoroaniline, 2-(trifluoromethyl)aniline, 3-(trifluoromethyl)aniline, 4- (trifluoromethyl)aniline, 2,6-bis(trifluoromethyl)aniline, 3,5-bis(trifluoromethyl)aniline or 2,4,6- tris(trifluoromethyl)aniline, particularly preferably water, trifluoromethylamine,
perfluorobutylamine, perfluorooctylamine, perfluoropentadecylamine, 2-fluoroaniline, 3- fluoroaniline, 4-fluoroaniline, 2,6-difluoroaniline, 3,5-difluoroaniline, 2,4,6-trifluoroaniline, pentafluoroaniline, 2-(trifluoromethyl)aniline, 3-(trifluoromethyl)aniline, 4- (trifluoromethyl)aniline, 2,6-bis(trifluoromethyl)aniline, 3,5-bis(trifluoromethyl)aniline or 2,4,6- tris(trifluoromethyl)aniline, most preferably water or pentafluoroaniline.
[0141]
The activating co-catalytic component- 1 can be obtained by bringing these compounds (a), (b) and (c) into contact with each other. The order in which the compounds (a), (b) and (c) are brought into contact with each other is not particularly limited, and for example, the following order can be adopted:
(1) a method in which the compounds (a) and (b) are brought into contact with each other and then bought into contact with the compound (c),
(2) a method in which the compounds (a) and (c) are brought into contact with each other and then brought into contact with the compound (b), and (3) a method in which the compounds (b) and (c) are brought into contact with each other and then brought into contact with the compound (a).
The order of contact is preferably the method (1) or (2). Specifically, the compound of the present invention is preferably a compound obtained by bringing the compound (c) into contact with a contact product obtained by bringing the compound (a) into concact with the compound (b) or a compound obtained by bringing the compound (b) into contact with a contact product obtained by bringing the compound (a) into contact with the compound (c).
[0142]
Such contact treatment is preferably performed in an inert gas atmosphere. The contact treatment temperature is usually -100 to 200°C, preferably -80 to 150°C. The contact treatment time is usually 1 minute to 36 hours, preferably 10 minutes to 24 hours. Moreover, such contact treatment may be performed using a solvent, or these compounds may be brought into contact with each other directly without using a solvent. The solvent used may be a nonpolar solvent inert to the compounds (a), (b) and (c), such as an aliphatic hydrocarbon or aromatic hydrocarbon solvent, or may be a polar solvent such as an ether solvent.
[0143]
The amount of each compound used is not particularly limited. When a molar ratio among the amounts of the compounds used is defined as (a):(b):(c) = l .y:z, preferably, y and z substantially satisfy the following formula (11): n = y + 2z (11), wherein n represents the valence of M1.
In the formula (11), y is preferably any number from 0.01 to 1.99, more preferably any number from 0.20 to 1.80, further preferably any number from 0.25 to 1.50, most preferably any number from 0.50 to 1.00. In the formula (11), z is a number determined depending on n, y and the formula (11).
[0144]
When a molar ratio among the amounts of the compounds used is defined as (a):(b):(c) = 1 :y:z, more preferably, y and z substantially satisfy the following formula (12):
0 < |n - y - 2z| < 0.2 (12), wherein
n represents the valence of M1.
[0145]
The starting compounds (a), (b) and/or (c) for the compound of the present invention may remain as unreacted products as a result of such contact treatment. Moreover, after such contact treatment, preferably, the solvent is distilled off from the product, which is then dried under reduced pressure at a temperature of 25°C or higher for 1 hour or longer. The product is more preferably dried at a temperature of 60 to 200°C for 1 to 24 hours, most preferably at a temperature of 80 to 160°C for 4 to 18 hours.
[0146]
Hereinafter, examples of a method for producing the activating co-catalytic component- 1 wherein M1 is a zinc atom, the compound (b) is pentafluorophenol, and the compound (c) is water will be shown in more detail. A hexane solution of diethylzinc is added to tetrahydrofuran as a solvent and the mixture is cooled to 0°C. Pentafluorophenol is added dropwise thereto in a equimolar amount with respect to diethylzinc and the mixture is stirred at room temperature for 10 minutes to 24 hours. Then, water is further added dropwise thereto in a 0.5 -fold molar amount with respect to diethylzinc and the mixture is stirred at room
temperature for 10 minutes to 24 hours. Then, the solvent is distilled off and the residue is then dried under reduced pressure at 120°C for 8 hours. This method can be adopted in the present invention. Of course, the compounds used in such treatment are not limited to
pentafluorophenol or water, and the starting compound is not limited to the zinc compound. In addition, the drying conditions are not limited to 120°C for 8 hours.
[0147]
Another example of the activating co-catalytic component can include an activating co-catalytic component obtainable by bringing the following compounds (a), (b) and (c) and a carrier (hereinafter, referred to as an activating co-catalytic component-2) into contact with each other:
(a) : a compound represented by formula [Al]:
[Al],
(b) : a compound represented by formula [A2]:
Figure imgf000053_0001
(c) : a compound represented by formula [A3]:
E2 U-2T'H2 [A3], wherein
M1 represents an atom of Group 12 of the Periodic Table; n represents the valence of M1; L represents a hydrogen atom, a halogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group; in the case where more than one L groups exist, the L groups may be the same as or different from each other; E1 represents an electron-withdrawing group or a group containing an electron-withdrawing group; E2 represents a hydrocarbyl group or a halogenated hydrocarbyl group; in the case where more than one E1 groups exist, the E1 groups may be the same as or different from each other; T1 represents an atom of Group 15 or 16 of the Periodic Table; t represents the valence of T1; T" represents an atom of Group 15 or 16 of the Periodic Table; and u represents the valence of T'.
[0148]
A carrier generally used is preferably used. A porous substance having a uniform particle size is preferable. An inorganic substance or an organic polymer is preferably used, and an inorganic substance is more preferably used. The geometric standard deviation of the particle size of the carrier based on the volume is preferably 2.5 or lower, more preferably 2.0 or lower, further preferably 1.7 or lower, from the viewpoint of the particle size distribution of the resulting polymer.
[0149]
Examples of the inorganic substance that may be used as a carrier include inorganic oxide. Clay, clay mineral, or the like may also be used. They may be mixed for use. Examples of the inorganic oxide can include Si02, A1203, MgO, Zr02, Ti02, B203, CaO, ZnO, BaO, Th02 and mixtures thereof, for example, Si02-MgO, Si02-Al203, Si02-Ti02, Si02-V205, Si02-Cr203 and Si02-Ti02-MgO. Among these inorganic oxides, Si02 and/or A1203 are preferable, and particularly, Si02 (i.e., silica) is preferable. The inorganic oxide may contain a small amount of a carbonate, sulfate, nitrate or oxide component such as Na2C03, K2C03, CaC03, MgC03, Na2S04, A12(S04)3, BaS04, KN03, Mg(N03)2, A1(N03)3, Na20, K20 and Li20.
[0150]
Examples of the clay or clay mineral include kaolin, bentonite, kibushi clay, gairome clay, allophane, hisingerite, pyrophyllite, talc, mica isinglass, montmorillonite, vermiculite, chlorite, palygorskite, kaolinite, nacrite, dickite and halloysite. Among them, smectite, montmorillonite, hectorite, Laponite or saponite is preferable, and montmorillonite or hectorite is more preferable.
[0151]
Of these inorganic substances, an inorganic oxide is preferably used. These inorganic substances are preferably dried until substantially no water content and preferably dried by heat treatment. The heat treatment is usually performed at a temperature of 100 to 1,500°C, preferably 100 to 1,000°C, more preferably 200 to 800°C, for the inorganic substance whose water content cannot be confirmed by visual observation. The heating time is not particularly limited and is preferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours. Further examples of the heat treatment include, but not limited to, a method in which, for example, dried inert gas (e.g., nitrogen or argon) is circulated at a constant flow rate during heating and a method in which the pressure is reduced.
[0152]
Moreover, the inorganic oxide usually has a hydroxy group formed on the surface. Modified inorganic oxide obtained by substituting active hydrogen in the surface hydroxy group by various substituents may be used as the inorganic oxide. A preferable substituent is a silyl group. Specific examples of the modified inorganic oxide include inorganic oxide treated by contact with trialkylchlorosilane such as trimethylchlorosilane and tert- butyldimethylchlorosilane, triarylchlorosilane such as triphenylchlorosilane,
dialkyldichlorosilane such as dimethyldichlorosilane, diaryldichlorosilane such as
diphenyldichlorosilane, alkyltrichlorosilane such as methyltrichlorosilane, aryltrichlorosilane such as phenyltrichlorosilane, trialkylalkoxysilane such as trimethylmethoxysilane,
triarylalkoxysilane such as triphenylmethoxysilane, dialkyldialkoxysilane such as
dimethyldimethoxysilane, diaryldialkoxysilane such as diphenyldimethoxysilane,
alkyltrialkoxysilane such as methyltrimethoxysilane, aryltrialkoxysilane such as
phenyltrimethoxysilane, tetraalkoxysilane such as tetramethoxysilane, alkyldisilazane such as
1,1,1,3,3,3-hexamethyldisilazane, tetrachlorosilane, or the like.
[0153]
The average particle size of the inorganic substance is preferably 5 to 1000 μη , more preferably 10 to 500 μηι, further preferably 10 to 100 μιη. Its pore volume is preferably 0.1 ml/g or larger, more preferably 0.3 to 10 ml/g. Its specific surface is preferably 10 to 1000 m2/g, more preferably 100 to 500 m2/g.
[0154]
The organic polymer that may be used as a carrier can be any organic polymer, and two or more organic polymers may be used as a mixture. A polymer having a functional group having active hydrogen or a non-proton-donating Lewis-basic functional group is preferable as the organic polymer.
[0155]
The order in which the compounds (a), (b) and (c) and the carrier are brought into contact with each other is not particularly limited.
[0156]
Such contact treatment is preferably performed in an inert gas atmosphere. The treatment temperature is usually -100 to 300°C, preferably -80 to 200°C. The treatment time is usually 1 minute to 200 hours, preferably 10 minutes to 100 hours. Moreover, such treatment may be performed using a solvent, or these compounds may be contacted directly without using a solvent.
[0157]
A solvent that does not react with each of the components to be brought into contact with each other or a contact product obtainable by bringing them into contact with each other when the solvent is used is usually used as the solvent.
[0158]
The amounts of the compounds (a), (b) and (c) used are not particularly limited. When a molar ratio among the amounts of the compounds used is defined as (a):(b):(c) = l :y:z, preferably, y and z substantially satisfy the following formula (13):
|n - y - 2z| < 1 (13), wherein
n represents the valence of M1.
In the formula (13), y is preferably any number from 0.01 to 1.99, more preferably any number from 0.10 to 1.80, further preferably any number from 0.20 to 1.50, most preferably any number from 0.30 to 1.00. In the formula (13), the preferable range of z is also determined depending on n, y and the formula (13).
[0159]
In the preparation of the activating co-catalytic component-2 obtainable by bringing the compounds (a), (b) and (c) and the carrier into contact with each other used in the present invention, the amount of the carrier used with respect to the compound (a) is preferably an amount that offers 0.1 mmol or larger, more preferably 0.5 to 20 mmol, of compound (a)- derived metal atoms contained in particles obtainable by bringing the compound (a) into contact with the carrier, with respect to the molar number of metal atoms contained in 1 g of the resulting activating co-catalytic component. Thus, the amount can be determined appropriately to achieve the range.
[0160]
After the contact treatment as described above, heating is also preferably performed to further promote the reaction. For the heating, a solvent having a higher boiling point is preferably used to achieve a higher temperature. For this purpose, the solvent used in the contact treatment may be replaced by a different solvent having a higher boiling point.
[0161]
The starting compounds (a), (b) and/or (c) and/or the carrier for the activating co- catalytic component-2 obtainable by bringing the compounds (a), (b) and (c) and the carrier into contact with each other used in the present invention may remain as unreacted products as a result of such contact treatment. However, when this activating co-catalytic component-2 is applied to ethylene trimerization reaction, the unreacted products are preferably removed by washing treatment in advance. A solvent for this washing treatment may be the same as or different from the solvent used in the contact.
[0162]
Hereinafter, examples of a method for producing the activating co-catalytic component-2 wherein M1 is a zinc atom, the compound (b) is pentafluorophenol, the compound (c) is water, and the carrier is silica will be shown in more detail. A hexane solution of diethylzinc is added to tetrahydrofuran as a solvent and the mixture is cooled to 3°C.
Pentafluorophenol is added dropwise thereto in a equimolar amount with respect to diethylzinc and the mixture is stirred at room temperature for 10 minutes to 24 hours. Then, water is further added dropwise thereto in a 0.5 -fold molar amount with respect to diethylzinc and the mixture is stirred at room temperature for 10 minutes to 24 hours. Then, the solvent is distilled off and the residue is dried under reduced pressure at 120°C for 8 hours. To the solid component obtained by these procedures, tetrahydrofiiran and silica are added, and the mixture is stirred at 40°C for 2 hours. The solid component is washed with tetrahydrofuran and then dried under reduced pressure at 120°C for 8 hours. In this way, particles obtainable by bringing the compounds (a), (b) and (c) and the carrier into contact with each other used in the present invention can be produced.
[0163]
<Organic aluminum compound>
The following organic aluminum compound (B) may also be used in the trimerization reaction of ethylene:
compound (B): an organic aluminum compound represented by formula
(Q1)aAl(G)3-a, wherein
Q1 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; the Q1 groups may be the same as or different from each other in the case where more than one Q1 groups exist; and the G groups may be the same as or different from each other in the case where more than one G groups exist.
[0164]
In the compound (B), examples of the hydrocarbyl group having 1 to 8 carbon atoms in Q1, 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. [0165]
Examples of the organic aluminum compound (B) represented by formula (QI)aAl(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.
Examples of the alkylaluminum dichloride include methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride and hexylaluminum dichloride. Examples of the dialkylaluminum hydride include dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride and dihexylaluminum hydride.
[0166]
<Ethylene trimerization catalyst>
The ethylene trimerization catalyst of the present invention is obtainable by bringing the complex for ethylene trimerization containing a titanium atom into contact with the activating co-catalytic component containing an element of Group 12 of the Periodic Table and is a catalyst that is capable of producing 1-hexene by ethylene trimerization.
[0167]
A ratio (by mol) between the amounts of the catalytic components used in the present invention is not particularly limited. When the activating co-catalytic component-1 is used, the molar ratio between the activating co-catalytic component-1 and the complex for ethylene trimerization is usually such that the (activating co-catalytic component-1 ): (complex for ethylene trimerization) molar ratio is in the range of from 1 :1 to 10000: 1, preferably from 1 : 1 to 5000: 1, more preferably from 1 : 1 to 1000: 1. When the organic aluminum compound (B) is used, it is usually used in such an amount that the (complex for ethylene trimerization) :(B) molar ratio is in the range of from 1 :0.1 to 1 : 10000, preferably from 1 : 1 to 1 : 1000.
When the activating co-catalytic component-2 is used, the amount of the complex for ethylene trimerization used is usually 1 x 10"6 to 1 x 10"2 mol, preferably 1 x 10"5 to 1 x 10'3 mol, with respect to 1 g of the activating co-catalytic component-2. Moreover, when the organic aluminum compound (B) is used, it is usually preferably used in such an amount that the complex for ethylene trimerization: (B) ratio = 1 :0.01 to 1 : 10000, more preferably 1 :0.1 to 1 :5000, most preferably 1 : 1 to 1 :2000.
[0168] The ethylene trimerization catalyst of the present invention is obtainable by bringing the activating co-catalytic component into contact with the complex for ethylene trimerization and in some cases, further with the organic aluminum compound (B). A method for the contact is not particularly limited. For example, the activating co-catalytic component and the complex for ethylene trimerization, and in some cases, the organic aluminum compound (B) may be brought into contact with each other simultaneously. Alternatively, of them, arbitrary two components may be brought into contact with each other in advance and then brought into contact with the remaining one component, or each of these components may be brought into contact with the remaining components in any order. Moreover, the partial or whole procedures of this contact may be performed in a reactor, to which the components may be added in any order without particular limitations.
[0169]
These catalytic components are preferably brought into contact with each other in a solvent. Examples of the solvent include: aliphatic hydrocarbon solvents such as butane, pentane, hexane, heptane and octane; aromatic hydrocarbon solvents such as benzene and toluene; and halogenated hydrocarbon such as methylene chloride. Aliphatic hydrocarbon or aromatic hydrocarbon is preferable.
[0170]
When the activating co-catalytic component- 1 is used and the catalytic components are brought into contact with each other in a solvent, the concentration of each of the activating co-catalytic component- 1 and the organic aluminum compound (B) is usually 0.001 to 100 mmol/L, preferably 0.01 to 5 mmol/L, in terms of the metal atom. Moreover, the concentration of the complex for ethylene trimerization is usually 0.0001 to 100 mmol/L, preferably 0.01 to 10 mmol/L, in terms of the metal atom.
[0171]
When the activating co-catalytic component-2 is used and the catalytic components are brought into contact with each other in a solvent, the concentration of the activating co-catalytic component-2 is usually 0.01 to 100 g L, preferably 0.1 to 10 g L. The concentration of the organic aluminum compound (B) is usually 0.001 to 100 mmol/L, preferably 0.01 to 10 mmol/L, in terms of the Al atom. The concentration of the complex for ethylene trimerization is usually 0.0001 to 10 mmol/L, preferably 0.001 to 10 mmol/L, in terms of the transition metal atom.
[0172]
<Method for producing l-hexene> 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.
[0173]
The trimerization reaction of ethylene is not particularly limited and may be, for example, trimerization reaction of ethylene 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 in a slurry state, or trimerizing gaseous ethylene.
[0174]
The trimerization reaction can be performed by any of batch, semi-continuous and continuous methods.
[0175]
The pressure of ethylene in the trimerization reaction is usually in the range of from normal pressure to 10 MPa, preferably in the range of from normal pressure to 5 MPa.
[0176]
The temperature of the trimerization reaction can usually be in the range of -50°C to 220°C and is preferably in the range of 0°C to 170°C, more preferably in the range of 50°C to 120°C.
[0177]
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.
[0178]
<Catalytic component for olefin polymerization>
The ethylene trimerization catalyst of the present invention can be used in combination with a catalytic component for olefin polymerization to thereby produce an olefin polymer having butyl branches from only ethylene without using an expensive α-olefin. Any catalytic component for olefin polymerization can be used as long as the complex for ethylene trimerization is not poisoned thereby. Many catalytic components for polymerization may be used. Examples thereof can include Ziegler-Natta-type solid catalytic components and metallocene complexes. Examples of the metallocene complexes include metallocene complexes having one cyclopentadiene ring with a geometrically constrained structure, metallocene complexes having two cyclopentadiene rings, and metallocene complexes having three cyclopentadiene rings. Preferable examples of the complexes for polymerization include metallocene complexes highly capable of a-olefin copolymerization and having one cyclopentadiene ring with a geometrically constrained structure, and metallocene complexes highly capable of α-olefin copolymerization and having two cyclopentadiene rings. More preferable examples of the complexes for polymerization include a metallocene complex having one cyclopentadiene ring with a geometrically constrained structure and bridged a metallocene complex having two cyclopentadiene rings.
[0179]
Examples of the catalytic component for olefin polymerization include methylene(cyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride,
isopropylidene(tetramethylcyclopentadienyl)(3 ,5-dimethyl-2-phenoxy)titanium dichloride, diphenylmethylene(fluorenyl)(3,5-dimethyl-2-phenoxy)titanium dichloride,
dimethylsilylene(cyclopentadienyl)(2-phenoxy)titanium dichloride,
dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(fluorenyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, methylene(tert-butylamido)(cyclopentadienyl)titanium dichloride, diphenylmethylene(tert- butylamido)(cyclopentadienyl)titanium dichloride, dimethylsilylene(tert- butylamido)(cyclopentadienyl)titanium dichloride,
diphenylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,
diphenylsilylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,
methylenebis(cyclopentadienyl)zirconium dichloride, ethylenebis(indenyl)zirconium dichloride, methylenebis(indenyl)hafnium dichloride, bis(cyclopentadienyl)zirconium dichloride, bis(indenyl)zirconium dichloride and bis(fiuorenyl)zirconium dichloride. The catalytic component for olefin polymerization is preferably methylene(cyclopentadienyI)(3,5-dimethyl-2- phenoxy)titanium dichloride, isopropylidene(tetramethylcyclopentadienyl)(3 , 5-dimethyl-2- phenoxy)titanium dichloride, diphenylmethylene(fluorenyl)(3,5-dimethyl-2-phenoxy)titanium dichloride, dimethylsilylene(cyclopentadienyl)(2-phenoxy)titanium dichloride,
dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(fiuorenyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium dichloride, methylene(tert-butylamido)(cyclopentadienyl)titanium dichloride, diphenylmethylene(tert- butylamido)(cyclopentadienyl)titanium dichloride, dimethylsilylene(tert- butylamido)(cyclopentadienyl)titanium dichloride,
diphenylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,
diphenylsilylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,
methylenebis(cyclopentadienyl)zirconium dichloride, ethylenebis(indenyl)zirconium dichloride or methylenebis(indenyl)hafnium dichloride, more preferably methylene(cyclopentadienyl)(3,5- dimethyl-2-phenoxy)titanium dichloride, dimethylsilylene(tetramethylcyclopentadienyl)(3-tert- butyl-5-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(tert- butylamido)(cyclopentadienyl)titanium dichloride or ethylenebis(indenyl)zirconium dichloride.
[0180]
The catalytic component for olefin polymerization may be used in combination with various activating co-catalytic components, may be used in combination with the activating co-catalytic component containing an element of Group 12 of the Periodic Table used in the present invention, or may be used in combination with a component usually used as an activating co-catalytic component containing an element of Group 13 of the Periodic Table, such as aluminoxane and boron-containing compounds.
EXAMPLES
[0181]
The present invention will be described by way of Reference Examples,
Preparation Examples and Examples.
<Production of transition metal complex>
Physical properties were measured in accordance with the following methods.
(1) Proton nuclear magnetic resonance spectrum ^H-NMR)
Apparatus: EX270 manufactured by JEOL Ltd.
Sample cell: Tube (5 mm in diameter)
Measurement solvent: CDC13
Sample concentration: 10 mg/0.5 mL (CDCI3)
Measurement temperature: Room temperature (about 25°C)
Measurement parameter: Probe (5 mm in diameter), EXMOD NON, OBNUC 1H, accumulated number 16 times or more
Repeat time: ACQTM 6 seconds, PD 1 second
Internal standard: CDCI3 (7.26 ppm)
[0182]
(2) Carbon nuclear magnetic resonance spectrum (13C-NMR)
Apparatus: EX270 manufactured by JEOL Ltd.
Sample cell: Tube (5 mm in diameter)
Measurement solvent: CDCI3
Sample concentration: 30 mg/0.5 mL (CDCI3) Measurement temperature: Room temperature (about 25°C)
Measurement parameter: Probe (5 mm in diameter), EXMOD BCM, OBNUC 13C, accumulated number 256 times or more
Repeat time: ACQTM 1.79 seconds, PD 1.21 seconds
Internal standard: CDC13 (77.0 ppm)
[0183]
(3) Mass spectrum
[Electron ionization mass spectrometry (EI-MS)]
Apparatus: JMS-T100GC manufactured by JEOL Ltd.
Ionization voltage: 70 eV
Ion source temperature: 230°C
Acceleration voltage: 7 kV
MASS RANGE: m/z 35-800
[0184]
[Reference Example 1]
" Synthesis of [ 1 -tris(3 , 5 -dimethylphenyl)silyl-2, 3 ,4, 5- tetramethylcyclopentadienyl]titanium trichloride (hereinafter, referred to as "Complex 1")"
[0185]
"Synthesis of l-tris(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene" Under a nitrogen atmosphere, sodium hydride (0.49 g, 20.45 mmol in terms of sodium hydride) dispersed in mineral oil and tetrahydrofuran (23 mL) were mixed. The mixture was heated to 50°C and aniline (0.13 g, 1.36 mmol) was added thereto and the mixture was stirred at 50°C for one hour. To this, a solution dissolving 1,2,3,4-tetramethylcyclopenta- 1,3-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. To this solution, a solution dissolving chlorotris(3,5-dimethylphenyl)silane (5.17 g, 13.64 mmol) in toluene (6 mL) was added dropwise and the mixture was stirred at room temperature for 3 hours, and thereafter, stirred at 50°C for 22 hours. The resultant mixture was added dropwise at 0°C to a 10% aqueous sodium carbonate solution (40 mL). Toluene (50 mL) was added to separate an organic phase, and the organic phase was washed with water (50 mL) twice and further washed with saturated brine (50 mL). The organic phase was dried over sodium sulfate and then filtrated. The solvent was removed from the filtrate under reduced pressure. After purification was performed by silica gel column chromatography, the resultant solid substance, to which hexane of 50°C was added, was filtrated to remove insolubles. The solvent was removed from the filtrate under reduced pressure. The resultant solid substance was washed with a small amount of hexane and then dried under reduced pressure to obtain l-tris(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene (1.49 g, yield 23.4%).
1 H-NMR (CDC13 , δ ppm): 1.54 (s, 6H), 1.60 (s, 6H), 2.27 (s, 18H), 3.73 (s, 1H), 6.98 (s, 3H), 7.17 (s, 6H)
Mass Spec (EI-MS, m/z): 464 (M+ )
[0186]
"Synthesis of Complex 1 "
Under a nitrogen atmosphere, to a toluene solution (20 mL) of l-tris(3,5- dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene (0.93 g, 2.00 mmol) and triethylamine (1.01 g, 10.00 mmol), a 1.67 M hexane solution of n-butyllithium (1.32 mL, 2.20 mmol) was added dropwise at -78°C. The mixture was gradually warmed to room temperature, and the mixture was stirred room temperature for 5 hours. The resultant mixture was cooled to -78°C and a solution dissolving titanium tetrachloride (0.42 g, 2.20 mmol) in toluene (2 mL) was added dropwise at the same temperature. After the mixture was gradually warmed to room
temperature, the mixture was stirred 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 insolubles. The solvent was removed from the filtrate under reduced pressure. Furthermore, the resultant residue, to which diethyl ether was added, was filtrated to remove insolubles. The solvent was removed from the filtrate under reduced pressure. Pentane was added and the mixture was cooled to -20°C. The resultant solid substance was filtrated, washed with a small amount of pentane, and then dried under reduced pressure to obtain Complex 1 (0.03 g, yield 2.7%) as an orange solid.
1 H-NMR (CDCb , δ ppm): 2.03 (s, 6H), 2.27 (s, 18H), 2.36 (s, 6H), 7.06 (s, 3H), 7.20 (s, 6H) 1 3 C-NMR (CDCI3 , δ ppm): 14.52, 17.83, 21.41, 131.63, 132.93, 134.60, 137.03, 142.26, 146.34 Mass Spec (EI-MS, m z): 616 (W )
[0187]
[ 1 -( 1 -methyl- 1 -(3 , 5 -dimethylpheny l)ethy l)-3 - trimethylsilylcyclopentadienyl]titanium trichloride (hereinafter, referred to as "Complex 2") was synthesized in accordance with a known method (Organometallics 2002, 21, 5122-5135.).
[0188]
6-adamantyl-4-methyl-2-[N- { 2-(2-methoxyphenyl) } phenyl]imino- phenoxytitanium trichloride (hereinafter, referred to as "Complex 3") was synthesized in accordance with a known method (WO2009/005003).
[0189]
<Production of activating co-catalytic component>
(1) Elemental analysis
Zn: A sample was added to an aqueous sulfuric acid solution (1 mol/L) and a metal component was then extracted by soni cation. The obtained liquid portion was subjected to ICP emission spectroscopy for quantification.
F: A sample was burned in a flask filled with oxygen and the resulting combustion gas was absorbed into an aqueous sodium hydroxide solution (10%). The aqueous solution thus obtained was subjected to quantification using an ion electrode method.
[0190]
<Production of l-hexene>
(1) Trimerization activity
Analysis was conducted using a gas chromatography (Shimadzu GC-2010, DB-1 column).
(2) Evaluation of fouling state
The fouling state was evaluated based on the amount of amorphous solids adhering to stirring blades after reaction. The fouling state was determined according to the criteria: a state in which amorphous solids adhered to the whole surface of the stirring blade (poor); a state in which amorphous solids adhered to the partial (more than half) surface of the stirring blade (fair); a state in which amorphous solids adhered to the partial (less than half) surface of the stirring blade (good); and a state in which few amorphous solids adhered to the stirring blade (excellent). The results are shown in Table 1.
[0191]
[Preparation Example 1] Preparation of activating co-catalytic component
Under a nitrogen atmosphere, dehydrated toluene (70 mL), a 51 wt% hexane solution of diethylzinc (14.2 mL) and dehydrated hexane (10.8 mL) were added to a 200 mL flask. After the flask was cooled to 0°C in an ice bath, 3,4,5-trifluorophenol (5.55 g) was added thereto with stirring. After the addition, the mixture was heated to 40°C and stirred for 1 hour. Thereafter, the mixture was cooled to room temperature, water (0.79 mL) was added thereto and the mixture was further stirred for 1.5 hours. Thereafter, the mixture was heated to 40°C, stirred for 2 hours, further heated to 80°C and stirred for 2 hours. Thereafter, filtration, washing and drying was performed to obtain an activating co-catalytic component as a white powder. The yield was 8.34 g. The result of elemental analysis (wt%) was Zn: 34% and F: 18%. [0192]
[Reference Example (preparation example of Si02/MAO)]
Under a nitrogen atmosphere, 1 g of dried silica (Sylopol 948 manufactured by Grace Davison; 50% volume-average particle size = 55 μιη; pore volume = 1.67 ml/g; specific surface = 325 m2/g) was weighed into a 200 mL flask, to which dehydrated toluene (15 mL) was then added. After the flask was cooled to 0°C in an ice bath, 3.5 mol/L MAO (manufactured by Tosoh Corp.) (5.0 mL, 17.5 mmol) diluted with toluene was gradually added over 30 minutes with stirring using a dropping funnel. After the dropwise addition, the mixture was heated to 95°C and stirred for 4 hours. After completion of the reaction, the mixture was cooled to room temperature and the supernatant was removed by decantation. Toluene (15 mL) was further added thereto and the mixture was stirred. Thereafter, the mixture was left standing and the supernatant was removed again by decantation. This washing procedure was performed three times. Finally, the resulting product was dried under reduced pressure at 100°C for 1 hour to obtain the intended solid (also referred to as Si02/MAO). The yield was 1.2 g. The result of elemental analysis (wt%) was Si: 24% and Al: 19%.
[0193]
[Example 1]
An autoclave (0.4 liter) equipped with a stirrer was dried under reduced pressure and then purged with nitrogen. Toluene (90 mL) and a hexane solution (2.2 mL) of
triisobutylaluminum (TEBA) having a concentration of 0.93 mmol/mL were supplied. After the interior temperature of the system was elevated to 80°C, ethylene was introduced so that the partial pressure of ethylene might become 2.0 MPa, and the system was stabilized. 1.0 mL of a toluene solution (1 μmol/mL) of Complex 1 was added thereto and 63.5 mg of the activating co- catalytic component obtained in Preparation Example 1 was subsequently added. A
trimerization reaction of ethylene was performed at 80°C for 30 minutes while continuously supplying ethylene gas so as to maintain the total pressure at a constant value. Ethanol (2 mL) was added to terminate the reaction. Thereafter, ethylene was purged and the content of the autoclave was decalcificated with ethanol-hydrochloric acid and filtered. 1-Hexene was obtained at an activity of 7.6 x 106 g/mol complex/h and a polymer was obtained at an activity of 0.64 x 106 g/mol complex/h. No amorphous polymer adhering to the stirrer or the like was observed.
[0194]
[Example 2] An autoclave (0.4 liter) equipped with a stirrer was dried under reduced pressure and then purged with nitrogen. Toluene (90 mL) and a hexane solution (2.2 mL) of
triisobutylaluminum (TEBA) having a concentration of 0.93 mmol/mL were supplied. After the interior temperature of the system was elevated to 80°C, ethylene was introduced so that the partial pressure of ethylene might become 2.0 MPa, and the system was stabilized. 1.0 mL of a toluene solution (1 μηιοΙ/mL) of Complex 2 was added thereto and 62.5 mg of the activating co- catalytic component obtained in Preparation Example 1 was subsequently added. A
trimerization reaction of ethylene was performed at 80°C for 30 minutes while continuously supplying ethylene gas so as to maintain the total pressure at a constant value. Ethanol (2 mL) was added to terminate the reaction. Thereafter, ethylene was purged and the content of the autoclave was decalcificated with ethanol-hydrochloric acid and filtered. 1-Hexene was obtained at an activity of 1.6 x 106 g mol complex/h and a polymer was obtained at an activity of 0.29 x 106 g/mol complex/h. No amorphous polymer adhering to the stirrer or the like was observed.
[0195]
[Example 3]
An autoclave (0.4 liter) equipped with a stirrer was dried under reduced pressure and then purged with nitrogen. Toluene (90 mL) and a hexane solution (2.2 mL) of
triisobutylaluminum (TIBA) having a concentration of 0.93 mmol/mL were supplied. After the interior temperature of the system was elevated to 80°C, ethylene was introduced so that the partial pressure of ethylene might become 2.0 MPa, and the system was stabilized. 1.0 mL of a toluene solution (1 μηιοΙ/ηιΕ) of Complex 3 was added thereto and 54.6 mg of the activating co- catalytic component obtained in Preparation Example 1 was subsequently added. A
trimerization reaction of ethylene was performed at 80°C for 30 minutes while continuously supplying ethylene gas so as to maintain the total pressure at a constant value. Ethanol (2 mL) was added to terminate the reaction. Thereafter, ethylene was purged and the content of the autoclave was decalcificated with ethanol-hydrochloric acid and filtered. 1-Hexene was obtained at an activity of 0.14 x 106 g/mol complex/h and a polymer was obtained at an activity of 0.81 x 106 g/mol complex/h. No amorphous polymer adhering to the stirrer or the like was observed.
[0196]
[Example 4]
An autoclave (0.4 liter) equipped with a stirrer was dried under reduced pressure and then purged with nitrogen. Toluene (90 mL) and a hexane solution (2.2 mL) of triisobutylaluminum (TIBA) having a concentration of 0.93 mmol/mL were supplied. After the interior temperature of the system was elevated to 40°C, ethylene was introduced so that the partial pressure of ethylene might become 2.0 MPa, and the system was stabilized. 1.0 mL of a toluene solution (1 μηιοΙ/mL) of Complex 1 was added thereto and 59.1 mg of the activating co- catalytic component obtained in Preparation Example 1 was subsequently added. A
trimerization reaction of ethylene was performed at 40°C for 30 minutes while continuously supplying ethylene gas so as to maintain the total pressure at a constant value. Ethanol (2 mL) was added to terminate the reaction. Thereafter, ethylene was purged and the content of the autoclave was decalcificated with ethanol-hydrochloric acid and filtered. 1-Hexene was obtained at an activity of 20.6 x 106 g/mol complex/h and a polymer was obtained at an activity of 0.49 x 106 g/mol complex/h. No amorphous polymer adhering to the stirrer or the like was observed.
[0197]
[Example 5]
An autoclave (0.4 liter) equipped with a stirrer was dried under reduced pressure and then purged with nitrogen. Toluene (90 mL) and a hexane solution (2.2 mL) of
triisobutylaluminum (TIBA) having a concentration of 0.93 mmol/mL were supplied. After the interior temperature of the system was elevated to 40°C, ethylene was introduced so that the partial pressure of ethylene might become 2.0 MPa, and the system was stabilized. 1.0 mL of a toluene solution (1 μηιοΙ/mL) of Complex 2 was added thereto and 81.8 mg of the activating co- catalytic component obtained in Preparation Example 1 was subsequently added. A
trimerization reaction of ethylene was performed at 40°C for 30 minutes while continuously supplying ethylene gas so as to maintain the total pressure at a constant value. Ethanol (2 mL) was added to terminate the reaction. Thereafter, ethylene was purged and the content of the autoclave was decalcificated with ethanol-hydrochloric acid and filtered. 1-Hexene was obtained at an activity of 13.2 x 106 g/mol complex/h and a polymer was obtained at an activity of 0.55 x 106 g/mol complex/h. No amorphous polymer adhering to the stirrer or the like was observed.
[0198]
[Example 6]
An autoclave (0.4 liter) equipped with a stirrer was dried under reduced pressure and then purged with nitrogen. Toluene (90 mL) and a hexane solution (2.2 mL) of triisobutylaluminum (TIBA) having a concentration of 0.93 mmol/mL were supplied. After the interior temperature of the system was elevated to 40°C, ethylene was introduced so that the partial pressure of ethylene might become 2.0 MPa, and the system was stabilized. 1.0 mL of a toluene solution (1 μπιοΙ/mL) of Complex 3 was added thereto and 49.7 mg of the activating co- catalytic component obtained in Preparation Example 1 was subsequently added. A
trimerization reaction of ethylene was performed at 40°C for 30 minutes while continuously supplying ethylene gas so as to maintain the total pressure at a constant value. Ethanol (2 mL) was added to terminate the reaction. Thereafter, ethylene was purged and the content of the autoclave was decalcificated with ethanol-hydrochloric acid and filtered. 1-Hexene was obtained at an activity of 1.79 x 106 g mol complex/h and a polymer was obtained at an activity of 7.44 x 106 g/mol complex/h. No amorphous polymer adhering to the stirrer or the like was observed.
[0199]
[Comparative Example 1]
An autoclave (0.4 liter) equipped with a stirrer was dried under reduced pressure and then purged with nitrogen. Toluene (90 mL) and a toluene solution (0.35 mL) of methylaluminoxane (TMAO-s manufactured by Tosoh Finechem Corp.) having a Al
concentration of 3.6 mmol mL were supplied. After the interior temperature of the system was elevated to 80°C, ethylene was introduced so that the partial pressure of ethylene might become 2.0 MPa, and the system was stabilized. 0.25 mL of a toluene solution (1 μηιοΙ/mL) of
Complex 1 was added thereto. A trimerization reaction of ethylene was performed at 80°C for 60 minutes while continuously supplying ethylene gas so as to maintain the total pressure at a constant value. Ethanol (2.0 mL) was added to terminate the reaction. Thereafter, ethylene was purged and the content of the autoclave was decalcificated with ethanol-hydrochloric acid and filtered. 1-Hexene was obtained at an activity of 16.9 x 106 g/mol complex/h and a polymer was obtained at an activity of 0.65 x 106 g/mol complex/h.
[0200]
[Table 1]
Example 1 Example 2 Example 3 Example 4
Good Good Good Good
Comparative
Example 5 Example 6
Example
Good Good Poor INDUSTRIAL APPLICABILITY
Since the present invention provides an ethylene trimerization catalytic component that is capable of producing 1-hexene while suppressing adhesion of by-product polymers to the walls of reactors or stirrers in the trimerization reaction of ethylene, the present invention is highly valuable in various fields of industries, especially in the field of ethylene trimerization catalysts and methods for producing 1-hexene.

Claims

[Claim 1]
An ethylene trimerization catalyst which is obtainable by bringing a complex for ethylene trimerization containing a titanium atom into contact with an activating co-catalytic component containing an element of Group 12 of the Periodic Table.
[Claim 2]
The catalyst according to claim 1, wherein the complex for ethylene trimerization formulae (1-1) to (1-3):
Figure imgf000071_0001
wherein
Cp represents a group having a cyclopentadiene-type anionic skeleton; J represents a bridging group based on a single atom selected from Groups 13 to 16 of the Periodic Table of the Elements;
R1, Pv2, R3, R4, R5, R8, R9, R10, Ru, R12, R13, R14, R15, R16 and R17 each independently represent 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 alkoxy 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 aryloxy 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,
an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
a substituted silyl group represented by -Si(R18)3, wherein the three R18 groups 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 R18 groups is 1 to 20, or a disubstituted amino group represented by -N(RI9)2, wherein the two R19 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R19 groups is 2 to 20, and
X1, X2and X3 each independently represent
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 alkoxy 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,
an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
a substituted silyl group represented by -Si(R18)3, wherein the three R18 groups 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 R18 groups is 1 to 20, or a disubstituted amino group represented by -N(R19)2, wherein the two R19 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R19 groups is 2 to 20, and
R6 and R7 each independently represent
an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
an aryloxy 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,
an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
a substituted silyl group represented by -Si(R18)3, wherein the three R18 groups 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 R18 groups is 1 to 20, or a disubstituted amino group represented by -N(R19)2, wherein the two R19 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R19 groups is 2 to 20;
1 and m each represent 1 or 0, and 1 + m is an integer equal to (valence of J - 2); of R1, R2, R3, R4 and R5, 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 R8, R9, R10, Ru and R12, 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 R13, R14, R15, R16 and R17, 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 R6 and R7 may be bonded to each other to form a ring together with J to which they are bonded, and
of X1, X2 and X3, two groups may be bonded to each other to form a ring together with Ti.
[Claim 3]
The catalyst according to claim 2, wherein J in the general formulae (1-1) to (1-3) is a silicon atom.
[Claim 4] The catalyst according to claim 3, wherein the complex for ethylene trimerization is a complex represented by any one of general formulae (2-1) to (2-3):
Figure imgf000074_0001
Figure imgf000074_0002
Figure imgf000074_0003
wherein
p20 p21 p22 p23 p24 p25 p26 p27 p28 p31 p32 p33 p34 p35 p36 37 p38 p39 I ,iv , I , Is. , tv , rv ,rv , iv , iv , rv ,Jv ,rv ,iv , rv , tv ,rv ,rv ,
R0, R41, R42, R43 and R44 each independently represent
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 alkoxy 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 aryloxy 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,
an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
a substituted silyl group represented by -Si(R18)3, wherein the three R18 groups 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 R18 groups is 1 to 20, or a disubstituted amino group represented by -N(RI9)2, wherein the two R19 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R19 groups is 2 to 20;
X4, X5 and X6 each independently represent
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 alkoxy 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,
an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
a substituted silyl group represented by -Si(R18)3, wherein the three R18 groups 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 R18 groups is 1 to 20, or a disubstituted amino group represented by -N(R19)2, wherein the two R19 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R19 groups is 2 to 20;
R29 and R30 each independently represent
an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,
an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, an aryloxy 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,
an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,
a substituted silyl group represented by -Si(R18)3, wherein the three R18 groups 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 R18 groups is 1 to 20, or a disubstituted amino group represented by -N(R19)2, wherein the two R19 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R19 groups is 2 to 20; and
at least one of R20, R21, R22 and R23 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;
of R20, R21, R22 and R23, 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 , R , R , R and R , 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 R31, R32, R33, R34 and R35, 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 R36, R37, R38, R39 and R40, 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 R24, R41, R26, R42 and R28, 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 R31, R43, R33, R44 and R35, 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 R29 and R30 may be bonded to each other to form a ring together with the silicon atom to which they are bonded.
[Claim 5]
The catalyst according to claim 4, wherein R20, R21, R22 and R23 are a methyl group.
[Claim 6]
The catalyst according to claim 4 or 5, wherein the complex for ethylene trimerization is represented by the general formula (2-3).
[Claim 7]
The catalyst according to claim 6, wherein
R37, R39, R41, R42, R43 and R44 are each independently
an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent or
an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent.
[Claim 8]
The catalyst according to claim 1, wherein the activating co-catalytic component is a component obtainable by bringing the following compounds (a), (b) and (c) into contact with each other:
(a) : a compound represented by formula [Al]:
Figure imgf000077_0001
(b) : a compound represented by formula [A2]:
Ε ^ΤΉ [A2], and
(c) : a compound represented by formula [A3]:
E2 U,2T'H2 [A3], wherein
M1 represents an atom of Group 12 of the Periodic Table; n represents the valence of M1; L represents a hydrogen atom, a halogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group; in the case where more than one L groups exist, the L groups may be the same as or different from each other; E1 represents an electron-withdrawing group or a group containing an electron-withdrawing group; E2 represents a hydrocarbyl group or a halogenated hydrocarbyl group; in the case where more than one E1 groups exist, the E1 groups may be the same as or different from each other; T1 represents an atom of Group 15 or 16 of the Periodic Table; t represents the valence of T1; T' represents an atom of Group 15 or 16 of the Periodic Table; and u represents the valence of T'.
[Claim 9]
The catalyst according to claim 1, wherein the activating co-catalytic component is a particle obtainable by bringing the following compounds (a), (b), (c) and a carrier into contact with each other:
(a) : a compound represented by formula [Al]:
Figure imgf000077_0002
(b) : a compound represented by formula [A2]:
Figure imgf000078_0001
(c): a compound represented by formula [A3]:
Ε2„.2ΤΉ2 [A3], wherein
M1 represents an atom of Group 12 of the Periodic Table; n represents the valence of M1; L represents a hydrogen atom, a halogen atom, a hydrocarbyl group or a halogenated hydrocarbyl group; in the case where more than one L groups exist, the L groups may be the same as or different from each other; E1 represents an electron- withdrawing group or a group containing an electron-withdrawing group; E2 represents a hydrocarbyl group or a halogenated hydrocarbyl group; in the case where more than one El groups exist, the E1 groups may be the same as or different from each other; T1 represents an atom of Group 15 or 16 of the Periodic Table; t represents the valence of T1; Γ represents an atom of Group 15 or 16 of the Periodic Table; and u represents the valence of T'.
[Claim 10]
A method for producing 1-hexene, comprising trimerizing ethylene in the presence of the catalyst according to any one of claims 1 to 9.
PCT/JP2012/059286 2011-03-30 2012-03-29 Trimerization catalyst and method for producing 1-hexene WO2012133928A1 (en)

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Citations (2)

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JP2004524959A (en) * 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 Catalyst system for olefin trimerization.
WO2009005003A1 (en) * 2007-07-04 2009-01-08 Mitsui Chemicals, Inc. Transition metal complex compound, olefin polymerization catalyst containing the compound, and method for producing olefin polymer performed in the presence of the catalyst

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JP2004524959A (en) * 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 Catalyst system for olefin trimerization.
WO2009005003A1 (en) * 2007-07-04 2009-01-08 Mitsui Chemicals, Inc. Transition metal complex compound, olefin polymerization catalyst containing the compound, and method for producing olefin polymer performed in the presence of the catalyst

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Title
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