WO2012133921A1 - Catalyseur d'oligomérisation d'oléfines et procédé de production d'∞-oléfine - Google Patents

Catalyseur d'oligomérisation d'oléfines et procédé de production d'∞-oléfine Download PDF

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WO2012133921A1
WO2012133921A1 PCT/JP2012/059279 JP2012059279W WO2012133921A1 WO 2012133921 A1 WO2012133921 A1 WO 2012133921A1 JP 2012059279 W JP2012059279 W JP 2012059279W WO 2012133921 A1 WO2012133921 A1 WO 2012133921A1
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carbon atoms
group
groups
bonded
halogen atom
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Takayuki Hishiya
Takahiro Hino
Taichi Senda
Masaya Tanimoto
Hidenori Hanaoka
Yasutoyo Kawashima
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • 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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
    • C07C2/34—Metal-hydrocarbon complexes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/20—Olefin oligomerisation or telomerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/46—Titanium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/02—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 catalyst for olefin oligomerization and a method for producing a-olefin.
  • 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 ⁇ -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 Literature 1 has reported that a half-metallocene titanium complex represented by the formula (Cp-B(R) n Ar)TiR 1 3 functions as a catalytic component for selective trimerization of ethylene by activation with an activating co-catalytic component.
  • a half-metallocene titanium complex carbon-bridged Cp-Ar complex
  • cyclop.entadiene is bonded to a substituted aryl group via a carbon atom
  • MAO methylaluminoxane
  • Patent Literature 1 and Non Patent Literature 1 have reported a catalyst in which a half-metallocene titanium complex wherein cyclopentadiene and a substituted aryl group are bonded via a carbon atom is supported by a carrier. Unfortunately, reaction using the catalyst is performed under the condition of 30°C, which makes industrial production difficult.
  • NON PATENT LITERATURE 1 Organometallics 2002, 21, 5122-5135.
  • an object of the present invention is to provide a catalyst for olefin oligomerization that is capable of producing oc-olefin such as 1-hexene through the oligomerization reaction of ethylene while preventing by-product polymers from adhering to the walls of reactors or stirrers even under high temperature conditions, and a method for producing a-olefin using said catalyst.
  • a 1st aspect of the present invention relates to a catalyst for olefin oligomerization obtainable by bringing a carrier, an activating co-catalytic component comprising an element of Group 13 of the Periodic Table and a transition metal complex
  • M represents a transition metal atom of Group 4 of the Periodic Table of the Elements
  • X 1 , X 2 and X 3 each independently represent
  • a substituted silyl group represented by -Si(R 22 ) 3 wherein the three R 22 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 22 groups is 1 to 20, or a disubstituted amino group represented by -N(R 23 ) 2 , wherein the two R 23 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 23 groups is 2 to 20, and
  • R 10 and R 11 each independently represent
  • a substituted silyl group represented by -Si(R 22 ) 3 wherein the three R 22 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 22 groups is 1 to 20, or a disubstituted amino group represented by -N(R 23 ) 2 , wherein the two R 23 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 23 groups is 2 to 20;
  • two group bonded to two adjoining carbon atoms may be bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded, of R 5 , R 6 , R 7 , R 8 and R 9 , two group bonded to two adjoining carbon atoms may be bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded, of R 12 , R 13 , R 14 , R 15 and R 16 , two group bonded to two adjoining carbon atoms may be bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded, of R 17 , R 18 , R 19 , R 20 and R 21 , two group bonded to two adjoining carbon atoms may be bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded, of R 5 , R 24 , R 7
  • a 2nd aspect of the present invention relates to a catalyst for olefin oligomerization in which a transition metal complex represented by any of formulae (1-1) to (1- 3) and an activating co-catalytic component comprising an element of Group 13 of the Periodic Table are supported by a carrier:
  • M represents a transition metal atom of Group 4 of the Periodic Table of the
  • X 1 , X 2 and X 3 each independently represent
  • a substituted silyl group represented by -Si(R 22 ) 3 wherein the three R 22 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 22 groups is 1 to 20, or a disubstituted amino group represented by -N(R 23 ) 2 , wherein the two R 23 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 23 groups is 2 to 20, and
  • R 10 and R 11 each independently represent
  • a substituted silyl group represented by -Si(R 22 ) 3 wherein the three R 22 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 22 groups is 1 to 20, or a disubstituted amino group represented by -N(R 23 ) 2 , wherein the two R 23 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 23 groups is 2 to 20;
  • two groups bonded to two adjoining carbon atoms may be bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded, of R 5 , R 6 , R 7 , R 8 and R 9 , two group bonded to two adjoining carbon atoms may be bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded, of R 12 , R 13 , R 14 , R 15 and R 16 , two groups bonded to two adjoining carbon atoms may be bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded, of R 17 , R 18 , R 19 , R 20 and R 21 , two groups bonded to two adjoining carbon atoms may be bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded, of R 5 , R 24 , R 7
  • a 3rd aspect of the present invention relates to a method for producing a-olefin, comprising oligomerizing olefin in the presence of the catalyst for olefin
  • a-olefin such as 1-hexene can be produced through the oligomerization reaction of ethylene while suppressing adhesion of by-product polymers to the walls of reactors or stirrers even under high temperature conditions.
  • oligomerization is the dimerization to decamerization of olefin, preferably the trimerization or tetramerization of ethylene, most preferably the trimerization thereof.
  • substituted encompasses a halogen atom constituting a compound or a group.
  • a substituted cyclopentadiene compound represented by any of formulae (5-1) to (5-3) has isomers each differing in the double bond position of each cyclopentadiene ring.
  • the substituted cyclopentadiene compound refers to any one of them or a mixture of them.
  • transition metal complex represented by formula (1-1) to (1-3) will be described in detail.
  • M represents an element of Group 4 of the Periodic Table of the Elements, and examples thereof include titanium, zirconium and hafnium atoms. Among them, a titanium atom is preferable.
  • P I 5 , I PV 6 , P Jv 7 , i Pv 8 , i Pv 9 , P I 10 , PJv 11 , P I 12 , Piv 13 , Piv 14 , Piv 15 , i Pv 16 , P rv 17 , Piv 18 , P Jtv 20 , P Jtv 21 , P Jtv 24 , P Jtv 25 , i Pv 26 , J Ptv 27 , Y ⁇ 1 , X 2 and X 3 are as defined above, and examples thereof are shown below.
  • the halogen atom is a fluorine, chlorine, bromine or iodine atom and is preferably a chlorine atom.
  • alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, amyl, n-hexyl, heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and n-eicosyl groups.
  • a preferable alkyl group is an alkyl group having 1 to 10 carbon atoms, and more preferable examples thereof 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 include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, fluoroethyl, perfiuoropropyl, perfluorobutyl, perfiuoropentyl 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 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. 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.
  • aryl group having a halogen atom as a substituent specifically include fluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, chlorophenyl, bromophenyl and iodophenyl groups.
  • 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)methyl,
  • a preferable aralkyl group is an aralkyl group having 7 to 10 carbon atoms, and more preferable examples thereof 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.
  • 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 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. 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 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 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.
  • the halogen atom are as described above.
  • the number of its carbon atoms is preferably in the range of 6 to 20, more preferably in the range of 6 to 10.
  • 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 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.
  • 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 22 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 hydrocar
  • the total number of the carbon atoms in these three R 22 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, triethylsilyl, tri-n-propylsilyl, triisopropylsilyl, tri-n-butylsilyl, tri-sec-butylsilyl, tri-tert- butylsilyl, tri-isobutylsilyl, tert-butyl-dimethylsilyl, tri-n-pentylsilyl, tri-n-hexyl
  • 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 23 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 23 groups is 2 to 20
  • the R 23 groups each independently represent a hydrocarbyl group or a halogenated hydrocarbyl group, and the total number of the carbon atoms in the two R 23 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 23 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 1 , R 2 , R 3 and R 4 two groups bonded to two adjoining carbon atoms may be bonded to each other to form a ring together with the carbon atoms to which they are bonded
  • R 1( and R 11 may be bonded to each other to form a ring together with the silicon atom to which they are bonded
  • R 5 , R 6 , R 7 , R 8 and R 9 two groups bonded to two adjoining carbon atoms may be bonded to each other to form a ring together with the carbon atoms to which they are bonded
  • R 12 , R 13 , R 14 , R 15 and R 16 two group bonded to two adjoining carbon atoms may be bonded to each other to form a ring together with the two carbon atoms to which they are bonded
  • R 17 , R 18 , R 19 , R 20 and R 21 two group bonded to two adjoining carbon atoms may be bonded to each other to form a ring together with the two
  • 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.
  • R 1 , R 2 , R 3 and R 4 are each independently preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, at least one of R 1 , R 2 , R 3 and R 4 is preferably a substituent other than hydrogen.
  • R 1 , R 2 , R 3 and R 4 include the following substructures represented by a substructural formula (2):
  • R l , R 2 , R 3 and R 4 are as defined above:
  • cyclopentadienyl methylcyclopentadienyl, ethylcyclopentadienyl, n- propylcyclopentadienyl, isopropylcyclopentadienyl, n-butylcyclopentadienyl, sec- butylcyclopentadienyl, tert-butylcyclopentadienyl, dimethylcyclopentadienyl,
  • a preferable cyclopentadienyl substructure is tetramethylcyclopentadienyl, etc.
  • R 5 , R 6 , R 7 , R 8 , R 9 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 24 , R 25 , R 26 and R 27 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.
  • Examples of a preferable combination of the groups represented by R 5 , R 6 , R 7 , R s and R 9 ; a preferable combination of the groups represented by R 12 , R 13 , R 14 , R 15 and R 16 ; a preferable combination of the groups represented by R 17 , R 18 , R 19 , R 20 and R 21 ; a preferable combination of the groups represented by R 5 , R 24 , R 7 , R 25 and R 9 ; and a preferable combination of the groups represented by R 12 , R 26 , R 14 , R 27 and R 16 include the following substructures re resented by a substructural formula (3-1):
  • R 5 , R 6 , R 7 , R 8 and R 9 are as defined above;
  • R , R , R , R and R are as defined above;
  • R 17 , R 18 , R 19 R 20 and R 21 are as defined above;
  • R 5 , R 24 , R 7 R 25 and R 9 are as defined above;
  • R 12 , R 26 , R 14 , R 27 and R 16 are as defined above, respectively:
  • phenyl methylphenyl, dimethylphenyl, trimethylphenyl, tetramethylphenyl, pentamethylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, tetraethylphenyl,
  • a preferable substructure is phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, diethylphenyl, di-tert-buthylphenyl, etc.
  • R 10 and R u are preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert- butyl and benzyl group.
  • Examples of a preferable combination of the groups represented by R 10 and R u include the following substructures represented by a substructural formula (4):
  • R 10 and R 11 are as defined above:
  • a structural formula represented by the substructural formula (4) include the following:
  • R 10 is a methyl group, and R u is
  • R 10 and R u are the same as each other and are
  • R 10 and R 11 are not the same as each other and are
  • the substructure is dimethylsilylene, diethyl si lylene, ethylmethylsilylene, n- butylmethylsilylene, cyclohexylmethylsilylene, cyclotetramethylenesilylene, etc.
  • transition metal complex of the formula (1-1) include transition metal complexes wherein R 6 and R 8 are each independently
  • R 11 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 examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl and benzyl groups.
  • transition metal complex of the formula (1-2) include transition metal complexes wherein R 6 , R 8 , R 13 and R 15 are each independently
  • transition metal complex of the formula (1-3) include transition metal complexes wherein R 24 , R 25 , R 26 , R 27 , R 18 and R 20 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.
  • transition metal complexes (1-1) to (1-3) 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- tetramethylcyclopentadienyljtitanium trichloride, [l-ethylmethylphenylsilyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [l-n-butylmethylphenylsilyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [l-methyldiphenylsilyl-2,3,4,5- tetramethylcyclopentadienyl
  • examples of the transition metal complex also include titanium chloride complexes obtained by substituting "cyclopentadienyl",”2-methylcyclopentadienyl", “3- methylcyclopentadienyl", “2,3-dimethylcyclopentadienyl", “2,4-dimethylcyclopentadienyl", "2,5-dimethylcyclopentadienyl", “2,3,5-trimethylcyclopentadienyl M , "2-ethylcyclopentadienyl”, “ 3 -ethylcyclopentadienyl “ , " 2-n-propylcyclopentadieny 1" , “ 3 -n-propylcyclopentadienyl " , " 2- isopropylcyclopentadienyl", “3-isopropylcyclopentadienyl", "2-n-butylcyclopentadienyl", “3-n- butylcyclopent
  • transition metal complexes (1-1) to (1-3) also include: transition metal chloride complexes such as zirconium chloride complexes obtained by substituting "zirconium” for "titanium” in the complexes exemplified above, and hafnium chloride complexes obtained by substituting "hafnium” therefor; 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
  • transition metal complexes (1-1), (1-2) and (1-3) can be produced from a substituted cyclopentadiene compound represented by formula (5-1), a substituted cyclopentadiene compound represented by formula (5-2) and a substituted cyclopentadiene compound represented by formula (5-3), respectively, by similar methods:
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 are as defined above,
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are as defined above, and
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 7 , R 9 , R 12 , R 14 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 24 , R 25 , R 26 and R 27 are as defined above.
  • the transition metal complex (1-1) can be produced by, for example, a production method comprising the steps of reacting a substituted cyclopentadiene compound represented by formula (5-1) (hereinafter, referred to as a "substituted cyclopentadiene compound (5-1)") with a base in the presence of an amine com ound:
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 are as defined above;
  • transition metal compound represented by formula (6) (hereinafter, referred to as a "transition metal com ound (6)"):
  • the step of reacting the substituted cyclopentadiene compound (5-1) 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 (5-1) and the base with a transition metal compound (6) may be referred to as a "2nd reaction step".
  • the compound represented by formula (5-1) has isomers differing in the double bond position of each cyclopentadiene ring. In the present invention, it represents any of them or a mixture of them.
  • the substituent X 4 is as defined above, and examples thereof include the same as those exemplified for X 1 , X 2 and X 3 .
  • transition metal compound (6) 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 dichlorodiisopropoxytitanium and trichloroisopropoxytitanium.
  • examples of the transition metal compound (6) include compounds obtained by substituting "zirconium” or “hafnium” for "titanium” in these compounds. Of them, a preferable transition metal compound (6) is titanium tetrachloride.
  • Examples of the base reacted with the substituted cyclopentadiene compound (5- 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 (5-1).
  • an amine compound is used in the reaction of the substituted cyclopentadiene compound (5-1) 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 substituted cyclopentadiene compound (5-1) and the base are reacted in the solvent and then a transition metal compound (6) can be added into this reaction mixture to thereby further react the transition metal compound (6) with the reaction product of the substituted cyclopentadiene compound (5-1) and the base. Solids may be deposited in the reaction mixture obtained by reacting the substituted cyclopentadiene compound (5-1) 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 (6).
  • the solvent when the solvent is used, the substituted
  • the base and the transition metal compound (6) can also be added simultaneously to the solvent to thereby perform the 1st reaction step and the 2nd reaction step almost simultaneously.
  • the solvent used in the 1st reaction step or in the 1st and 2nd reaction steps is an inert solvent that does not significantly hinder the progress of the reaction associated with these steps.
  • aprotic solvents such as: aromatic hydrocarbyl solvents such as benzene and toluene; aliphatic hydrocarbyl solvents such as hexane and heptane; ether solvents such as diethyl ether, tetrahydrofuran and 1,4-dioxane; amide solvents such as hexamethylphosphoric amide and dimethylformamide; polar solvents such as acetonitrile, 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 (5-1).
  • the amount of the transition metal compound (6) 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 (5-1). [0057]
  • 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 transition metal complex (1-1) can be taken by various purification methods known in the art.
  • the transition metal complex (1-1) of interest can be obtained by a method in which after the 1 st 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.
  • R 26 and R 27 are as defined above.
  • Examples of the substituted cyclopentadiene compound (5-1) include the following substituted cyclopentadiene compounds:
  • substituted cyclopentadiene compounds such as l-dimethylphenylsilyl-2,3,4,5- tetramethylcyclopentadiene, l-diethylphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1- phenyldi(n-propyl)silyl-2,3,4,5-tetramethylcyclopentadiene, l-diisopropylphenylsilyl-2,3,4,5- tetramethylcyclopentadiene, l-di(n-butyl)phenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1- di(isobutyl)phenylsilyl-2,3,4,5-tetramethylcyclopentadiene, l-di(sec-butyl)phenylsilyl-2,3,4,5- tetramethylcyclopentadiene, l-di(tert-butyl)phenylsily
  • examples of the substituted cyclopentadiene compound (5-1) also include substituted cyclopentadiene compounds obtained by substituting "cyclopentadiene", “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- butyl
  • Examples of the substituted cyclopentadiene compound (5-2) include the following substituted cyclopentadiene compounds:
  • substituted cyclopentadiene compounds such as l-methyldiphenylsilyl-2,3,4,5- tetramethylcyclopentadiene, 1 -ethyldiphenylsilyl-2,3,4, 5-tetramethylcyclopentadiene, 1 -n- propyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, l-isopropyldiphenylsilyl-2,3,4,5- tetramethylcyclopentadiene, l-n-butyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, 1- isobutyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, l-sec-butyldiphenylsilyl-2, 3,4,5 - tetramethylcyclopentadiene, 1 -tert-butyldiphenylsilyl-2,3 ,4, 5-tetramethylcycl
  • examples of the substituted cyclopentadiene compound (5-2) also include substituted cyclopentadiene compounds obtained by substituting "cyclopentadiene", “2- methy lcyclopentadiene”, “ 3 -methy lcyclopentadiene”, “2,3-dimethylcyclopentadiene”, “2,4- dimethy lcyclopentadiene", "2,5-dimethylcyclopentadiene”, “2,3,5-trimethylcyclopentadiene”, "2- ethyl cyclopentadiene”, “3-ethylcyclopentadiene”, “2-n-propyl cyclopentadiene”, “3-n- propylcyclopentadiene”, “2-isopropylcyclopentadiene”, “3-isopropylcyclopentadiene", "2-n- butylcyclopentadiene", “3-n-butylcyclopentadiene", "2-sec-buty
  • Examples of the substituted cyclopentadiene compound (5-3) include the following substituted cyclopentadiene compounds:
  • substituted cyclopentadiene compounds such as l-triphenylsilyl-2,3,4,5- tetramethylcyclopentadiene, 1 -phenyldi(2-methylphenyl)silyl-2,3 ,4,5- 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- tetra
  • examples of the substituted cyclopentadiene compound (5-3) also include substituted cyclopentadiene compounds obtained by substituting "cyclopentadiene", “2- methylcyclopentadiene”, “3-methylcyclopentadiene”, “2,3-dimethylcyclopentadiene”, “2,4- dimethylcyclopentadiene", "2,5-dimethylcyclopentadiene”, “2,3,5-trimethylcyclopentadiene”, “2- ethylcyclopentadiene”, “ 3 -ethy lcyclopentadiene”, “2-n-propylcyclopentadiene”, “3-n- propylcyclopentadiene”, “2-isopropylcyclopentadiene”, “3-isopropylcyclopentadiene", "2-n- butylcyclopentadiene", “3-n-butylcyclopentadiene”, “2-sec-butylcyclopentadiene", "3-sec-but
  • the substituted cyclopentadiene compounds (5-1), (5-2) and (5-3) can be produced by similar methods comprising the steps of:
  • R , R , R and R are as defined above,
  • R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R ⁇ 1 1 1 1 are as defined above, and X is a halogen atom
  • R 5 , R 6 , R 7 , R 8 , R 9 , R 11 , R 12 , R 13 , R 14 , R 15 and R 16 are as defined above, and X 5 is a halogen atom, and
  • R 5 , R 7 , R 9 , R 12 , R 14 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 24 , R 25 , R 26 and R 27 are as defined above, and X 5 is a halogen atom.
  • the substituted cyclopentadiene compound (7) is as follows:
  • R , R , R and R are as defined above, and
  • Examples of the substituted cyclopentadiene compound (7) include the following compounds:
  • cyclopentadiene methylcyclopentadiene, 1,2-dimethylcyclopentadiene, 1,3- dimethylcyclopentadiene, 1,2,3-trimethylcyclopentadiene, 1, 2,4-trimethylcyclopentadiene, 1,2,3,4-tetramethylcyclopentadiene, ethylcyclopentadiene, 1,2-diethylcyclopentadiene, 1,3- diethylcyclopentadiene, 1,2,3-triethylcyclopentadiene, 1, 2,4-triethylcyclopentadiene, 1,2,3,4- tetraethylcyclopentadiene, n-propylcyclopentadiene, isopropylcyclopentadiene, n- butylcyclopentadiene, sec-butylcyclopentadiene, tert-butylcyclopentadiene, n- pentylcyclopentadiene, 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 (7) exemplified above may have an isomer thereof differing in the double bond position of each cyclopentadiene ring. A mixture of these isomers may be used.
  • the halo enated silyl compound (8-1) is as follows:
  • R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R u are as defined above, and X 5 is a halogen atom.
  • halogenated silyl compound (8-1) examples include the following halogenated silyl compounds:
  • 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,
  • halogenated silyl compound (8-2) examples include the following halogenated silyl compounds:
  • chloromethyldiphenylsilane chloroethyldiphenylsilane, chloro-n- propyldiphenylsilane, chloroisopropyldiphenylsilane, n-butylchlorodiphenylsilane,
  • 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)sil ane, tert-butylchloropheny 1(3 , 5 - dimethylphenyl)silane, chlorocyclohexylphenyl(3,5-dimethylphenyl)silane, chloro-n- octadecylpheny 1(3 , 5 -dimethy lphenyl)
  • chloromethyl(4-methylphenyl)(3,5-dimethylphenyl)silane chloromethyt(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 (8-3) examples include the following halogenated silyl compounds:
  • 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 (7) 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 (7).
  • 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 (7) 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,N- dimethylethylaniline, N,N-dimethyl-n-propylaniline, N,N-dimethylisopropylaniline, 1,4- diazabicyclo[2.2.2]octane, l,5-diazabicyclo[4.3.0]non-5-ene, l,8-diazabicyclo[5.4.0]undec-7- ene, 2-dimethylaminopyridine, 3-dimethylaminopyridine, 4-dimethylaminopyridine,
  • trimethylamine triethylamine, tri-n-propylamine, tri-n-butylamine, diisopropylethylamine, tri-n- octylamine, tri-n-decylamine and triphenylamine.
  • primary or secondary amines more preferably primary amines are used.
  • the amount of such an amine compound used is usually in the range of 0.001- to 2-fold by mol, preferably 0.01- to 0.5-fold by mol, with respect to the base.
  • the reaction is usually performed in a solvent inert to the reaction.
  • a solvent include aprotic solvents such as: aromatic hydrocarbyl solvents such as benzene, toluene and xylene; aliphatic hydrocarbyl solvents such as pentane, hexane, heptane, octane and cyclohexane; ether solvents such as diethyl ether, methyl t-butyl ether, tetrahydrofuran and 1,4-dioxane; amide solvents such as hexamethylphosphoric amide, dimethylformamide, dimethylacetamide and N- methylpyrrolidone; and halogen solvents such as chlorobenzene and dichlorobenzene. These solvents are used
  • the substituted cyclopentadiene compound (7), 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 (7) 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 (7).
  • the metal salt of the substituted cyclopentadiene compound (7) 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 (5-1) 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 (7).
  • This reaction is usually performed, for example, by mixing the base, the amine compound and the substituted cyclopentadiene compound (7) in a solvent and then adding the halogenated silyl compound (8-1) to the mixture.
  • the substituted cyclopentadiene compound (5-1) 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. [0103]
  • the amount of the substituted cyclopentadiene compound (7) 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 (8-1).
  • 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 (5-1).
  • the obtained substituted cyclopentadiene compound (8-1) may be purified, if necessary, by a method such as distillation and column chromatography treatment.
  • the activating co-catalytic component is an activating co-catalytic component comprising an element of Group 13 of the Periodic Table, and examples thereof include compounds (A), (B) and (C) shown below. These compounds may be used in combination: compound (A): one or more aluminum compounds selected from the compound group consisting of the following compounds (Al), (A2) and (A3):
  • Al an organic aluminum compound represented by formula (E 1 ) a Al(G) 3-a ,
  • E 1 represents a hydrocarbyl group having 1 to 8 carbon atoms
  • E 2 and E 3 each independently represent a hydrocarbyl group having 1 to 8 carbon atoms, an alkoxy group containing an electron- withdrawing group or an aryloxy group containing an electron- withdrawing group
  • G represents a hydrogen atom or a halogen atom
  • a represents an integer of 1 to 3
  • b represents an integer of 2 or more
  • c represents an integer of 1 or more
  • the E 1 groups may be the same or different from each other
  • the G groups may be the same or different from each other.
  • a plurality of E 2 groups may be the same or different from each other; and a plurality of E 3 groups may be the same or different from each other;
  • compound (B) one or more boron compounds selected from the compound group consisting of the following compounds (Bl), (B2) and (B3):
  • compound (C) one or more borate compounds selected from the compound group consisting of the following compounds (CI) and (C2):
  • B represents a trivalent boron
  • Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 and Y 8 are the same as or different from each other and each represent a halogen atom, a hydrocarbyl group having 1 to 100 carbon atoms which may have a halogen atom as a substituent, a hydrocarbylsilyl group having 1 to 100 carbon atoms, an alkoxy group having 1 to 100 carbon atoms or a dihydrocarbylamino group having 2 to 100 carbon atoms; at least one of Y 1 , Y 2 , Y 3 and Y 4 and at least one of Y 5 , Y 6 , Y 7 and Y 8 each have an active hydrogen site represented by formula (U-H), wherein U represents O, S, NR or PR, and R represents a hydrocarbyl group, a trihydrocarbylsilyl group, a
  • T + represents an inorganic or organic cation
  • (L- H) + represents Broensted acid.
  • examples of the hydrocarbyl group having 1 to 8 carbon atoms in E 1 , E 2 and E 3 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.
  • E 2 and E 3 may be an alkoxy group containing an electron-withdrawing group or an aryloxy group containing an electron- withdrawing group.
  • 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.
  • alkoxy group containing an electron- withdrawing group in E 2 and E 3 examples include fluoromethoxy, chloromethoxy, bromomethoxy, iodomethoxy, difluoromethoxy, dichloromethoxy, dibromomethoxy, diiodomethoxy, trifluoromethoxy, trichloromethoxy, tribromomethoxy, triiodomethoxy, 2,2,2-trifluoroethoxy, 2,2,2-trichloroethoxy, 2,2,2- tribromoethoxy, 2,2,2-triiodoethoxy, pentafluoroethoxy, pentachloroethoxy, pentabromoethoxy, pentaiodoethoxy, 2,2,3,3, 3-pentafluoropropoxy, 2,2,3,3,3-pentachloropropoxy, 2,2,3,3,3- pentabromopropoxy, 2,2,3,3,3- pentabromopropoxy, 2,2,3,3,3- pentabromopropoxy, 2,
  • Examples of the aryloxy group containing an electron-withdrawing group in E 2 and E 3 include 2-fluorophenoxy, 3-fluorophenoxy, 4-fluorophenoxy, 2,3-difluorophenoxy, 2,4- difluorophenoxy, 2,5-difluorophenoxy, 2,6-difluorophenoxy, 3,4-difluorophenoxy, 3,5- difluorophenoxy, 2,3,4-trifluorophenoxy, 2,3,5-trifluorophenoxy, 2,3,6-trifluorophenoxy, 2,4,5- trifluorophenoxy, 2,4,6-trifluorophenoxy, 3,4,5-trifluorophenoxy, 2,3,4,5-tetrafluorophenoxy, 2,3,4,6-tetrafluorophenoxy, 2,3,5,6-tetrafluorophenoxy, 2,3,4,5,6-pentafluorophenoxy, 2,3,5,6- tetrafluoro-4-trifluoromethylphenoxy, 2-chloroph
  • Examples of the organic aluminum compound (Al) represented by formula (E 1 )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.
  • 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.
  • Examples of E 2 and E 3 in the cyclic aluminoxane (A2) having a structure represented by formula ⁇ -Al(E 2 )-0- ⁇ b and the linear aluminoxane (A3) having a structure represented by formula E 3 ⁇ -Al(E 3 )-0- ⁇ cAlE 3 2 include: alkyl groups such as methyl, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, normal pentyl and neopentyl groups; alkoxy groups containing an electron- withdrawing group, such as trifluoromethoxy and 1, 1- bis(trifluoromethyl)-2,2,2-trifluoroethoxy groups; and aryloxy groups containing an electron- withdrawing group, such as 4-fluorophenoxy, 3,4,5-trifluorophenoxy and 2,3,4,5,6- pentafluorophenoxy groups, b is an integer of 2 or more, and c is an integer of 1 or more.
  • aluminoxanes are prepared by various methods. The methods are not particularly limited, and they may be prepared according to methods known in the art. For example, a solution containing trialkylaluminum (e.g., trimethylaluminum) dissolved in an appropriate organic solvent (e.g., benzene or aliphatic hydrocarbyl) is brought into contact with water to prepare the aluminoxanes.
  • an appropriate organic solvent e.g., benzene or aliphatic hydrocarbyl
  • preparation methods include a method in which trialkylaluminum (e.g., trimethylaluminum) is brought into contact with metal salt (e.g., copper sulfate hydrate) containing crystalline water, and a method in which the compound thus obtained is brought into contact with an alcohol containing an electron- withdrawing group or phenol containing an electron-withdrawing group.
  • metal salt e.g., copper sulfate hydrate
  • Q 1 , Q 2 , Q 3 , Q 4 , Q 5 , Q 6 , Q 7 , Q 8 , Q 9 , Q 10 and Q 11 are preferably a halogen atom or a hydrocarbyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent.
  • the inorganic cation in T + include a ferrocenium cation, an alkyl-substituted ferrocenium cation and a silver cation.
  • Examples of the organic cation in T + include a triphenylmethyl cation.
  • Examples of (BQ 4 Q 5 Q 6 Q 7 ) “ and (BQ 8 Q 9 Q 10 Q U ) " include tetrakis(pentafluorophenyl)borate, tetrakis(2,3,5,6- tetrafluorophenyl)borate, tetrakis(2,3,4,5-tetrafluorophenyl)borate, tetrakis(3,4,5- trifluorophenyl)borate, tetrakis(2,3,4-trifluorophenyl)borate, phenyltris(pentafluorophenyl)borate and tetrakis(3,5-bistrifluoromethylphenyl)borate.
  • Examples of the Broensted acid represented by (L-H) + include trialkyl- substituted ammonium, ⁇ , ⁇ -dialkylanilinium, dialkylammonium and triarylphosphonium.
  • Examples of the boron compound (Bl) represented by formula BQ 1 Q 2 Q 3 include tris(pentafluorophenyl)borane, tris(2, 3 , 5 ,6-tetrafluoropheny l)borane, tris(2, 3 ,4, 5 - tetrafluorophenyl)borane, tris(3,4,5-trifluorophenyl)borane, tris(2,3,4-trifluorophenyl)borane and phenylbis(pentafluorophenyl)borane.
  • borate compound (B2) represented by formula T + (BQ 4 Q 5 Q 6 Q 7 ) " examples include ferrocenium tetrakis(pentafluorophenyl)borate, ⁇ , ⁇ -bis-trimethylsilylferrocenium tetrakis(pentafluorophenyl)borate, silver tetrakis(pentafluorophenyl)borate, triphenylmethyl tetrakis(pentafluorophenyl)borate and triphenylmethyl tetrakis(3,5- bistrifluoromethylphenyl)borate.
  • borate compound (B3) represented by formula (L- H) + (BQ 8 Q 9 Q 10 Q n ) " include triethylammonium tetrakis(pentafluorophenyl)borate,
  • Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 and Y 8 are preferably a halogen atom or a hydrocarbyl group having 1 to 100 carbon atoms which may have a halogen atom as a substituent, and at least one of Y 1 , Y 2 , Y 3 and Y 4 and at least one of Y 5 , Y 6 , Y 7 and Y 8 each have an active hydrogen site represented by formula (U-H), wherein U represents O, S, NR or PR, and R represents a hydrocarbyl group, a trihydrocarbylsilyl group, a trihydrocarbylgermyl group or hydrogen.
  • U-H active hydrogen site represented by formula (U-H)
  • T + represents an inorganic or organic cation
  • (L-H) + represents Broensted acid.
  • examples of the inorganic cation in T + include a ferrocenium cation, an alkyl- substituted ferrocenium cation and a silver cation.
  • examples of the organic cation in T + include a triphenylmethyl cation. Examples of (BY 1 Y 2 Y 3 Y 4 ) " and (BY 5 Y 6 Y 7 Y 8 ) " include
  • triphenyl(hydroxyphenyl)borate diphenyl-di(hydroxyphenyl)borate, triphenyl(2,4- dihydroxyphenyl)borate, tri(p-tolyl)(hydroxyphenyl)borate,
  • Tris(pentafluorophenyl)(4-hydroxybutyl)borate tris(pentafluorophenyl)(4- hydroxycyclohexyl)borate, tris(pentafluorophenyl)(4-(4'-hydroxyphenyl)phenyl)borate and tris(pentafluorophenyl)(6-hydroxy-2-naphthyl)borate.
  • Tris(pentafluorophenyl)(4- hydroxyphenyl)borate is preferable.
  • preferable anions are the borates exemplified above whose functional hydroxy group is substituted by a functional amino NHR group.
  • R is preferably methyl, ethyl or t-butyl.
  • Examples of the Broensted acid represented by (L-H) + include trialkyl- substituted ammonium, ⁇ , ⁇ -dialkylanilinium, dialkylammonium and triarylphosphonium.
  • borate compound (CI) represented by formula T + (BY 1 Y 2 Y 3 Y 4 ) " examples include ferrocenium tris(pentafluorophenyl)(4-hydroxyphenyl)borate, silver
  • borate compound (C2) represented by formula (L- H) + (BY 5 Y 6 Y 7 Y 8 ) ' include triethylammonium tris(pentafluorophenyl)(4-hydroxyphenyl)borate, tripropylammonium tris(pentafluorophenyi)(4-hydroxyphenyl)borate, tri(normal
  • butyl)ammonium tris(pentafluorophenyl)(4-hydroxyphenyl)borate
  • N,N-diethylanilinium tris(pentafluorophenyl)(4-hydroxyphenyl)borate
  • the compound (C) can be synthesized according to a method described in JP 1999-503113 A.
  • a porous substance is preferably used as a carrier.
  • An inorganic substance or an organic polymer is more preferably used, and an inorganic substance is further preferably used.
  • inorganic substance used as a carrier examples include inorganic oxide and magnesium compounds.
  • inorganic oxide and magnesium compounds examples include inorganic oxide and magnesium compounds.
  • clay, clay mineral and zeolite may also be used. They may be mixed for use.
  • Examples of the inorganic oxide used as a carrier 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 - A1 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 or A1 2 0 3 is preferable, and Si0 2 is more preferable.
  • These inorganic oxides 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(N0 3 ) 3 , Na 2 0, K 2 0 and Li 2 0.
  • the inorganic oxide usually has a hydroxy group 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.
  • the substituent is preferably a silyl group.
  • 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
  • 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.
  • magnesium compounds used as a carrier include: magnesium halide such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride; alkoxy magnesium halide such as methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride and octoxy magnesium chloride; aryloxy magnesium halide such as phenoxy magnesium chloride and methylphenoxy magnesium chloride; alkoxymagnesium such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium and 2-ethylhexoxymagnesium; aryloxymagnesium such as phenoxymagnesium and dimethylphenoxymagnesium; and carboxylate of magnesium such as magnesium laurate and magnesium stearate.
  • magnesium halide such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride
  • alkoxy magnesium halide such as methoxy magnesium chloride, ethoxy
  • alkoxymagnesium is preferable, and magnesium chloride or butoxymagnesium is more preferable.
  • Examples of the clay or clay mineral used as a carrier 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.
  • zeolite used as a carrier examples include zeolites of CFI, AFI, MAZ, AET, DON, FAU, CLO, VFI, ABW, ACO, AEI, AEL, AEN, AFQ AFN, AFO, AFR, AFS, AFT, AFX, AFY, AHT, ANA, APC, APD, AST, AS V, ATN, ATO, ATS, ATT, ATV, AWO and AWW types.
  • the inorganic substance used as a carrier is preferably an inorganic oxide.
  • the temperature of the heat treatment is usually 100 to 1500°C, preferably 100 to 1000°C, more preferably 200 to 800°C.
  • the time of the heat treatment is not particularly limited and is preferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours.
  • Examples of the method for the heat treatment include, but not limited to, a method in which after heating of the inorganic substance, for example, dried inert gas (e.g., nitrogen or argon) is circulated at a constant flow rate for a few hours or longer, and a method in which the pressure is reduced for a few hours.
  • dried inert gas e.g., nitrogen or argon
  • the average particle size of the carrier comprising the inorganic substance is preferably 5 to 1000 ⁇ , more preferably 10 to 500 ⁇ , even more preferably 10 to 100 ⁇ .
  • the pore volume of the carrier comprising the inorganic substance is preferably 0.1 ml/g or larger, more preferably 0.3 to 10 ml/g.
  • the specific surface of the carrier comprising the inorganic substance is preferably 10 to 1000 m 2 /g, more preferably 100 to 500 m 2 /g.
  • the organic polymer used as a carrier is not particularly limited, and two or more organic polymers may be used as a mixture.
  • a polymer having a group having active hydrogen and/or a non-proton-donating Lewis-basic group is preferable.
  • the group having active hydrogen is not particularly limited as long as it has active hydrogen.
  • Examples thereof include primary amino, secondary amino, imino, amide, hydrazide, amidino, hydroxy, hydroperoxy, carboxyl, formyl, carbamoyl, sulfonic acid, sulfinic acid, sulfenic acid, thiol, thioformyl, pyrrolyl, imidazolyl, piperidyl, indazolyl and carbazolyl groups.
  • a primary amino, secondary amino, imino, amide, imide, hydroxy, formyl, carboxyl, sulfonic acid or thiol group is preferable.
  • a primary amino, secondary amino, amide or hydroxy group is particularly preferable.
  • These groups may have a halogen atom or a hydrocarbyl group having 1 to 20 carbon atoms as a substituent.
  • the non-proton-donating Lewis-basic group is not particularly limited as long as it is a group having a Lewis base moiety free from an active hydrogen atom.
  • Examples thereof include pyridyl, N-substituted imidazolyl, N-substituted indazolyl, nitrile, azide, N-substituted imino, ⁇ , ⁇ -substituted amino, ⁇ , ⁇ -substituted aminooxy, ⁇ , ⁇ , ⁇ -substituted hydrazino, nitroso, nitro, nitrooxy, furyl, carbonyl, thiocarbonyl, alkoxy, alkyloxycarbonyl, N,N-substituted carbamoyl, thioalkoxy, substituted sulfinyl, substituted sulfonyl and substituted sulfonic acid groups.
  • Heterocyclic groups are preferable, and aromatic heterocyclic groups having oxygen and/or nitrogen atoms in the ring are more preferable.
  • a pyridyl, N-substituted imidazolyl or N-substituted indazolyl group is particularly preferable, with a pyridyl group most preferred.
  • These groups may have a halogen atom or a hydrocarbyl group having 1 to 20 carbon atoms as a substituent.
  • the amount of the group having active hydrogen and the non-proton-donating Lewis-basic group in the polymer is preferably 0.01 to 50 mmol/g, more preferably 0.1 to 20 mmol/g, in terms of the molar amount of the group per unit gram of the polymer.
  • the polymer having such group(s) can be obtained, for example, by homopolymerizing monomers having the group having active hydrogen and/or the non-proton-donating Lewis-basic group and one or more polymerizable unsaturated groups or by
  • a polymerizable bridged monomer having two or more polymerizable unsaturated groups is preferably used as at least one of the additional monomers.
  • Examples of such monomers having the group having active hydrogen and/or the non-proton-donating Lewis-basic group and one or more polymerizable unsaturated groups include monomers having the group having active hydrogen and one or more polymerizable unsaturated groups, and monomers having the group having a Lewis base moiety free from an active hydrogen atom and one or more polymerizable unsaturated groups.
  • Examples of such polymerizable unsaturated groups include: alkenyl groups such as vinyl and allyl; and alkynyl groups such as an ethyne group.
  • Examples of the monomers having the group having active hydrogen and one or more polymerizable unsaturated groups include vinyl group-containing primary amine, vinyl group-containing secondary amine, vinyl group-containing amide compounds and vinyl group- containing hydroxy compounds.
  • Examples thereof include N-( 1 -ethenyl)amine, N-(2- propenyl)amine, N-(l-ethenyl)-N-methylamine, N-(2-propenyl)-N-methylamine, 1- ethenylamide, 2-propenylamide, N-methyl-(l-ethenyl)amide, N-methyl-(2-propenyl)amide, vinyl alcohol, 2-propen-l-ol and 3-buten-l-ol.
  • Examples of the monomers having the non-proton-donating Lewis-basic group and one or more polymerizable unsaturated groups include vinylpyridine, vinyl (N-substituted) imidazole and vinyl (N-substituted) indazole.
  • additional monomers having one or more polymerizable unsaturated groups include olefin and aromatic vinyl compounds and specifically include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-l-pentene and styrene. Ethylene or styrene is preferable. These monomers may be used in combination of two or more thereof.
  • examples of the polymerizable bridged monomer having two or more polymerizable unsaturated groups include divinylbenzene.
  • the average particle size of the carrier comprising the organic polymer is preferably 5 to 1000 ⁇ , more preferably 10 to 500 ⁇ .
  • the pore volume of the carrier comprising the organic polymer is preferably 0.1 ml/g or larger, more preferably 0.3 to 10 ml/g.
  • the specific surface of the carrier comprising the organic polymer is preferably 10 to 1000 m 2 /g, more preferably 50 to 500 m 2 /g.
  • These organic polymers used as a carrier are preferably dried, for use, by heat treatment.
  • the temperature of the heat treatment is usually 30 to 400°C, preferably 50 to
  • the time of the heat treatment is not particularly limited and is preferably 10 minutes to 50 hours, more preferably 1 hour to 30 hours.
  • Examples of the method for the heat treatment include, but not limited to, a method in which after heating of the organic polymer, for example, dried inert gas (e.g., nitrogen or argon) is circulated at a constant flow rate for a few hours or longer, and a method in which the pressure is reduced for a few hours.
  • dried inert gas e.g., nitrogen or argon
  • 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, even more preferably 1.7 or lower.
  • the carrier is preferably an inorganic substance, more preferably an inorganic oxide, most preferably Si0 2 .
  • the catalyst for olefin oligomerization of the present invention is obtainable by bringing a carrier, a transition metal complex represented by any one of formulae (1-1) to (1-3) and an activating co-catalytic component comprising an element of Group 13 of the Periodic Table into contact with each other.
  • the catalyst is capable of producing a-olefin from olefin by oligomerization, preferably, selectively producing 1-hexene from ethylene.
  • the catalyst for olefin oligomerization in which a transition metal complex and an activating co-catalytic component are supported by a carrier refers to a catalyst obtainable in a solid state by bringing the carrier, the transition metal complex and the activating co-catalytic component into contact with each other in a solvent, followed by removal of the solvent by appropriate treatment such as filtration, decantation or distilling off of the solvent under reduced pressure.
  • the catalyst for olefin oligomerization in which a transition metal complex and an activating co-catalytic component are supported by a carrier is preferably used for suppressing adhesion of by-product polymers to the walls of reactors or stirrers. Furthermore, a supported catalyst for olefin oligomerization obtainable by bringing a solid component comprising the activating co-catalytic component supported by the carrier into contact with the transition metal complex in a solvent, followed by removal of the solvent is more preferably used for enhancing catalytic activity in 1-hexene synthesis.
  • the catalyst for olefin oligomerization of the present invention is obtainable by bringing the carrier, the transition metal complex represented by any of formulae (1-1) to (1-3) and the activating co-catalytic component (A) and/or the compound (B) into contact with each other.
  • a method for this contact is not particularly limited. In this method, two or more of the components (Al) to (A3) may be used as the activating co-catalytic component (A).
  • Examples of the contact method include methods shown below.
  • the method 2 is preferable:
  • method 1 a method in which a contact product obtained by bringing the transition metal complex into contact with the activating co-catalytic components (A) and/or (B) is brought into contact with the carrier,
  • method 2 a method in which a contact product obtained by bringing the activating co-catalytic components (A) and/or (B) into contact with the carrier is brought into contact with the transition metal complex,
  • method 3 a method in which a contact product obtained by bringing the transition metal complex into contact with the carrier is brought into contact with the activating co- catalytic components (A) and/or (B), and
  • method 4 a method in which these three components are brought into contact with each other simultaneously.
  • 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.
  • the carrier, the transition metal complex and the activating co-catalytic component are preferably brought into contact with each other in a solvent.
  • a solvent include: aliphatic hydrocarbyl such as butane, pentane, hexane, heptane and octane; aromatic hydrocarbyl such as benzene and toluene; and halogenated hydrocarbyl such as methylene dichloride. These solvents can be used alone or as a mixture of two or more thereof.
  • 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 carrier.
  • the temperature for bringing the carrier, the transition metal complex and the activating co-catalytic component into contact with each other is usually -30°C to the boiling point of the solvent, preferably -10°C to 120°C.
  • the reaction time is not particularly limited.
  • the ratio of each component for bringing the carrier, the transition metal complex and the activating co-catalytic component (A) into contact with each other is 0.01 to 20 parts by weight of the transition metal complex and 10 to 300 parts by weight of the activating co- catalytic component (A) per 100 parts by weight of the carrier, preferably 0.05 to 10 parts by weight of the transition metal complex and 20 to 200 parts by weight of the activating co- catalytic component (A) per 100 parts by weight of the carrier.
  • the ratio of each component for bringing the carrier, the transition metal complex and the activating co-catalytic component (B) into contact with each other is 0.01 to 20 parts by weight of the transition metal complex and 0.1 to 60 parts by weight of the activating co- catalytic component (B) per 100 parts by weight of the carrier, preferably 0.05 to 10 parts by weight of the transition metal complex and 0.2 to 30 parts by weight of the activating co- catalytic component (B) per 100 parts by weight of the carrier.
  • the catalyst for olefin oligomerization is obtainable by bringing the carrier, the transition metal complex and the activating co-catalytic component (C) into contact with each other.
  • a method in which the activating co-catalytic component (A) is further used in combination therewith is preferable.
  • a method for this contact is not particularly limited. In this method, two or more of the components (Al) to (A3) may be used as the activating co- catalytic component (A).
  • the carrier, the transition metal complex, the activating co-catalytic component (C) and the activating co-catalytic component (A) 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 two components in any order or a contact product obtained by bringing these two components into contact with each other in advance, or, of them arbitrary three components may be brought into contact with each other in advance and then brought into contact with the remaining one component. Alternatively, each of these components may be brought into contact with the remaining components in any order.
  • Examples thereof include the following contact methods:
  • method 5 a method in which a contact product obtained by bringing into contact the activating co-catalytic component (A) with the carrier is brought into contact with the activating co-catalytic component (C) and then brought into contact with the transition metal complex,
  • method 6 a method in which a contact product obtained by bringing the activating co-catalytic component (A) into contact with the activating co-catalytic component (C) is brought into contact with the carrier and then brought into contact with the transition metal complex,
  • method 7 a method in which a contact product obtained by bringing the carrier into contact with the activating co-catalytic component (A) is brought into contact with the transition metal complex and then brought into contact with the activating co-catalytic component (C), and
  • method 8 a method in which a contact product obtained by bringing the carrier into contact with the activating co-catalytic component (A) is brought into contact with the activating co-catalytic component (C) and then brought into contact with the transition metal complex.
  • the methods 6, 7 and 8 are preferable, and the methods 6 and 8 are more preferable.
  • 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.
  • the carrier, the transition metal complex, the activating co-catalytic component is the carrier, the transition metal complex, the activating co-catalytic component
  • the activating co-catalytic component (C) are preferably brought into contact with each other in a solvent.
  • the solvent include: aliphatic hydrocarbyl such as butane, pentane, hexane, heptane and octane; aromatic hydrocarbyl such as benzene and toluene; and halogenated hydrocarbyl such as methylene dichloride. These solvents can be used alone or as a mixture of two or more thereof. The amount thereof used is preferably 1 to 200 parts by weight, more preferably 3 to 50 parts by weight, per one part by weight of the carrier.
  • the temperature for bringing the carrier, the transition metal complex, the activating co-catalytic component (A) and the activating co-catalytic component (C) into contact with each other is usually -30°C to the boiling point of the solvent, preferably -10°C to 120°C.
  • the reaction time is not particularly limited.
  • the ratio of each component for bringing the carrier, the transition metal complex, the activating co-catalytic component (A) and the activating co-catalytic component (C) into contact with each other is 0.01 to 20 parts by weight of the transition metal complex, 10 to 300 parts by weight of the activating co-catalytic component (A) and 1 to 30 parts by weight of the activating co-catalytic component (C) per 100 parts by weight of the carrier, preferably 0.05 to 10 parts by weight of the transition metal complex, 20 to 200 parts by weight of the activating co-catalytic component (A) and 2 to 15 parts by weight of the activating co-catalytic component (C) per 100 parts by weight of the carrier.
  • the method for producing a-olefin of the present invention is a method for producing a dimer to a decamer by olefin oligomerization in the presence of the catalyst for olefin oligomerization, preferably, producing a trimer or a tetramer from ethylene, most preferably, producing 1-hexene by ethylene trimerization.
  • the oligomerization reaction of ethylene is not particularly limited and can be, for example, oligomerization reaction using aliphatic hydrocarbyl (butane, pentane, hexane, heptane, octane, etc.), aromatic hydrocarbyl (benzene, toluene, etc.) or halogenated hydrocarbyl
  • the oligomerization reaction of ethylene can be performed by any of batch, semi- continuous and continuous methods.
  • the pressure of ethylene in the oligomerization reaction is usually normal pressure to 10 MPa, preferably in the range of normal pressure to 5 MPa.
  • the temperature of the oligomerization reaction of ethylene 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 oligomerization reaction of ethylene can generally be determined appropriately according to the reaction apparatus of interest and is typically in the range of 1 minute to 20 hours.
  • the concentration of the transition metal complex used as a catalytic component is usually 0.0001 to 5 mmol/L, preferably 0.001 to 1 mmol/L.
  • the concentration of the activating co-catalytic component (A) is usually 0.01 to 500 mmol/L, preferably, 0.1 to 100 mmol/L, in terms of the aluminum atom.
  • the concentration of the activating co-catalytic component (B) is usually 0.0001 to 5 mmol/L, preferably 0.001 to 1 mmol/L.
  • the concentration of the activating co-catalytic component (C) is usually 0.0001 to 5 mmol/L, preferably 0.001 to 1 mmol/L.
  • the catalyst for oligomerization of the present invention can be used in combination with a catalytic component for olefin polymerization to thereby produce a branched olefin polymer.
  • a catalytic component for olefin polymerization can be used as long as the catalyst for oligomerization is not poisoned thereby.
  • Many catalytic components for polymerization may be used. Examples thereof include Ziegler-Natta-type solid catalytic components and metallocene complexes.
  • metallocene complexes examples include metallocene complexes having one cyclopentadiene ring and 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 -olefin copolymerization and having one cyclopentadiene ring and a geometrically constrained structure, and metallocene complexes highly capable of a-olefin copolymerization and having two cyclopentadiene rings.
  • More preferable examples of the complexes for polymerization include metallocene complexes in which a metallocene complex having one cyclopentadiene ring and a geometrically constrained structure is bridged with two cyclopentadiene rings.
  • the olefin polymerization is the conversion of olefin to a polymer.
  • the molecular weight of the polymer is larger than that of an oligomer and is generally 10,000 or larger.
  • Examples of the catalytic component for polymerization include
  • 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 polymerization is preferably methylene(cyclopentadienyl)(3,5-dimethyl-2- phenoxy)titanium dichloride, isopropylidene(tetramethylcyclopentadienyl)(3,5-dimethyl-2- phenoxy)titanium dichloride, diphenylmethylehe(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,
  • methylenebis(cyclopentadiehyl)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 aforementioned catalytic component for polymerization can be used in combination with the activating co-catalytic component (A) and the activating co-catalytic component (B).
  • Ethylene can be polymerized in the presence of the catalytic component for olefin oligomerization combined with the catalytic component for olefin polymerization to thereby produce an ethylene polymer.
  • the polymerization may be performed by supplying only ethylene as a raw material monomer or supplying ethylene and a monomer copolymerizable with ethylene.
  • 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-T 100GC manufactured by JEOL Ltd.
  • Ion source temperature 230°C Acceleration voltage: 7 kV
  • 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 saline (50 mL). The organic phase was dried over sodium sulfate and then filtrated. The solvent was removed under reduced pressure. After purification was performed by silica gel column chromatography, the resultant solid substance, to which hexane at 50°C was added, was filtrated to remove insolubles. The solvent was removed from the filtrate under reduced pressure.
  • 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
  • triisobutylaluminum (TIBA) having a concentration of 0.93 mmol/mL were supplied.
  • TIBA triisobutylaluminum
  • ethylene was introduced so that the partial pressure of ethylene might become 2.0 MPa, and the system was stabilized.
  • 120 mg of the supported catalyst for olefin oligomerization obtained above was added thereto.
  • 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 (2.0 mL) was added to terminate the reaction.
  • 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 2.02 x 10 6 g/mol complex/h and a polymer was obtained at an activity of 0.48 x 10 6 g/mol complex/h.
  • triisobutylaluminum (TIB A) having a concentration of 0.93 mmol/mL were supplied.
  • ethylene was introduced so that the partial pressure of ethylene might become 2.0 MPa, and the system was stabilized.
  • 132 mg of the supported catalyst for olefin oligomerization obtained above was added thereto.
  • a trimerization reaction of ethylene was performed at 40°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 27.9 x 10 6 g/mol complex/h and a polymer was obtained at an activity of 2.46 x 10 6 g/mol complex/h.
  • triisobutylaluminum (TIB A) having a concentration of 0.93 mmol/mL were supplied.
  • ethylene was introduced so that the partial pressure of ethylene might become 2.0 MPa, and the system was stabilized.
  • 106 mg of the supported catalyst for olefin oligomerization obtained above was added thereto.
  • a trimerization reaction of ethylene was performed at 40°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 38.1 x 10 6 g/mol complex/h and a polymer was obtained at an activity of 2.56 x 10 6 g/mol complex/h.
  • triisobutylaluminum (TIBA) having a concentration of 0.93 mmol/mL were supplied.
  • TIBA triisobutylaluminum
  • ethylene was introduced so that the partial pressure of ethylene might become 2.0 MPa, and the system was stabilized.
  • 123 mg of the supported catalyst for olefin oligomerization obtained above was added thereto.
  • 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 (2.0 mL) was added to terminate the reaction.
  • 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 2.28 x 10 6 g/mol complex/h and a polymer was obtained at an activity of 1.45 x 10 6 g/mol complex/h.
  • Atrimerization 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 10 6 g/mol complex/h and a polymer was obtained at an activity of 0.65 x 10 6 g/mol complex/h.
  • the catalyst of the present invention can produce an a-olefin such as 1- hexene through the oligomerization reaction of ethylene while suppressing adhesion of byproduct polymers to the walls of reactors or stirrers even under high temperature conditions, the present invention is highly valuable in various fields of industries, especially in the field of catalysts for olefin oligomerization.

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Abstract

L'invention concerne un catalyseur d'oligomérisation d'oléfine apte à produire de l'∞-oléfine telle qu'1-hexène, par la réaction d'oligomérisation d'éthylène et la supression simultanée de l'adhérence des sous-produits polymères aux parois des réacteurs ou agitateurs, même dans des conditions de températures élevées, ainsi qu'un procédé de production d'∞-oléfine à l'aide de ce catalyseur. Le catalyseur d'oligomérisation d'oléfine s'obtient par la mise en contact d'un support, d'un composant co-catalytique d'activation comprenant un élément du Groupe 13 du tableau périodique et un complexe de métaux de transition représenté par une des formules (1-1) à (1-3).
PCT/JP2012/059279 2011-03-30 2012-03-29 Catalyseur d'oligomérisation d'oléfines et procédé de production d'∞-oléfine Ceased WO2012133921A1 (fr)

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EP3202822A4 (fr) * 2014-09-30 2018-05-30 Sumitomo Chemical Company Limited Polyalkylaluminoxane solide modifié et catalyseur pour la réaction d'oligomérisation d'oléfines
CN109206292A (zh) * 2017-07-06 2019-01-15 中国石油化工股份有限公司 一种乙烯齐聚制α-烯烃的方法
CN110431125A (zh) * 2017-03-14 2019-11-08 沙特阿拉伯石油公司 乙烯低聚反应生成α-烯烃的方法
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EP3202822A4 (fr) * 2014-09-30 2018-05-30 Sumitomo Chemical Company Limited Polyalkylaluminoxane solide modifié et catalyseur pour la réaction d'oligomérisation d'oléfines
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