DESCRIPTION

CATALYST FOR OLEFIN OLIGOMERIZ ATION AND METHOD FOR PRODUCING a-OLEFIN

TECHNICAL FIELD

[0001]

The present invention relates to a catalyst for olefin oligomerization and a method for producing a-olefin. BACKGROUND ART

[0002]

a-olefin is an industrially important monomer raw material that is produced by the oligomerization of ethylene using a metal catalyst. However, the oligomerization of ethylene usually gives α-olefin mixtures according to Schulz-Flory distribution. Therefore, the development of a catalyst system capable of selectively producing one species of a-olefin is very important industrially.

[0003]

For example, 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.

Among these catalysts for selective ethylene trimerization, a half-metallocene titanium complex (carbon-bridged Cp-Ar complex) wherein cyclop.entadiene is bonded to a substituted aryl group via a carbon atom, such as [l-(l-methyl-l-(3,5-dimethylphenyl)ethyl)-3- trimethylsilylcyclopentadienyl]titanium trichloride, has been reported to function as an efficient catalyst for ethylene trimerization under the condition of 30°C with MAO (methylaluminoxane) as an activating co-catalytic component (see e.g., Non Patent Literature 1). On the other hand, [dimethylphenylsilylcyclopentadienyl]titanium trichloride, which is a half-metallocene titanium complex (silicon-bridged Cp-Ar complex) wherein cyclopentadiene is bonded to a substituted aryl group via a silicon atom, has been reported to have low activity in ethylene trimerization reaction under the same conditions as above and to also have low 1-hexene selectivity (see Non Patent Literature 1).

[0004]

Moreover, it has been reported that a catalyst system for ethylene trimerization using a carbon-bridged Cp-Ar complex and MAO exhibits much lower activity in 1-hexene production and 1-hexene production selectivity under the high temperature condition of 80°C than that of 30°C (see Non Patent Literature 2).

[0005]

In general, by-product polyethylene is produced in the oligomerization reaction of ethylene and therefore fouls the walls of reactors, stirrers, or the like in industrial production, disadvantageously making long-term operation impracticable. Patent Literature 1 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.

CITATION LIST PATENT LITERATURE

[0006]

PATENT LITERATURE 1 : JP 2004-524959 A

NON PATENT LITERATURE

[0007]

NON PATENT LITERATURE 1 : Organometallics 2002, 21, 5122-5135.

NON PATENT LITERATURE 2: Chinese Journal of Chemistry 2006, 24, 1397-1401.

SUMMARY OF INVENTION TECHNICAL PROBLEM

[0008]

Under such circumstances, 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.

SOLUTION TO PROBLEM

[0009]

Specifically, 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

(1-1) to (1-3) into contact with each other:

wherein

M represents a transition metal atom of Group 4 of the Periodic Table of the Elements;

P XV ¹ , PIV ² , PIV ³ , IP ⁴ , PIV ⁵ , PIV ⁶ , IPV ⁷ , PXV ⁸ , PIV ⁹ , PIV ¹² , PIV ¹³ , PXV ¹⁴ , IPV ¹⁵ , PXV ¹⁶ , PXV ¹⁷ , PtV ¹⁸ , PXV ¹⁹ , PXV ²⁰ , PtV ²¹ , PXV ²⁴ , PXV ²⁵ , XPV ²⁶ - RIV ²⁷ ,

X ¹ , X ² and X ³ each independently represent

a hydrogen atom, a halogen atom,

an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,

an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,

an aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,

an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,

an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,

a substituted silyl group represented by -Si(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

an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,

an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,

an aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,

an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,

an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,

a substituted silyl group represented by -Si(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;

of R ¹ , R ² , R ³ and R ⁴ , two group bonded to two adjoining carbon atoms may be bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded, of R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ , two group bonded to two adjoining carbon atoms may be bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded, of R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ , two group bonded to two adjoining carbon atoms may be bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded, of R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ , two group bonded to two adjoining carbon atoms may be bonded to each other to form a ring together with the two carbon atoms to which the two groups are bonded, of R ⁵ , R ²⁴ , R ⁷ , R ²⁵ and R ⁹ , 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 ^I , R , R ¹ *, R" and R , 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, and R ¹⁰ and R ¹¹ may be bonded to each other to form a ring together with the silicon atom to which they are bonded.

[0010]

Moreover, 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:

(1-1)

wherein

M represents a transition metal atom of Group 4 of the Periodic Table of the

Elements;

p K 1 , ft Ix2 , _R Ex3 , _R rv4 , p rx5 , p Ix6 , p ix7 , _ρ rx8 , _p ix9 , p Ixl2 , p Ix 13 , p ixl4 , p ixl5 , p Ix 16 p 17 p 18 , p ix 19 , p ix20 , p ix21 , p ix24 , _p K25 , p K26 , p K27

, κ. , ix , X ¹ , X ² and X ³ each independently represent

a hydrogen atom, a halogen atom,

an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,

an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,

an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,

an aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,

an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,

an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,

a substituted silyl group represented by -Si(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

an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,

an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent,

an aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent,

an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,

an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent,

a substituted silyl group represented by -Si(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;

of 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 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 , R ²⁵ and R ⁹ , 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 ¹² , R ²⁶ , R ¹⁴ , R ²⁷ 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, and R ¹⁰ and R ¹¹ may be bonded to each other to form a ring together with the silicon atom to which they are bonded.

[0011]

Moreover, 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

oligomerization. ADVANTAGEOUS EFFECTS OF INVENTION

[0012]

According to the present invention, 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.

DESCRIPTION OF EMBODIMENTS

[0013]

In the present invention, oligomerization is the dimerization to decamerization of olefin, preferably the trimerization or tetramerization of ethylene, most preferably the trimerization thereof. In the present invention, the term "substituent" encompasses a halogen atom constituting a compound or a group. Furthermore, in the present invention, 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. In the present invention, the substituted cyclopentadiene compound refers to any one of them or a mixture of them.

[0014]

<Transition metal complexes (1-1) to (1-3) (catalyst component for olefin oligomerization)>

Hereinafter, the transition metal complex represented by formula (1-1) to (1-3) will be described in detail.

In the transition metal complexes (1-1) to (1-3), 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.

[0015]

In the transition metal complexes (1-1) to (1-3), the substituents R ¹ , R ² , R ³ , R ⁴ ,

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 Λ ¹ , X ² and X ³ are as defined above, and examples thereof are shown below.

[0016]

The halogen atom is a fluorine, chlorine, bromine or iodine atom and is preferably a chlorine atom.

[0017]

Examples of the "alkyl group having 1 to 20 carbon atoms" in the alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, amyl, n-hexyl, heptyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, n-tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and n-eicosyl groups. Of them, a preferable alkyl group is an alkyl group having 1 to 10 carbon atoms, and more preferable examples thereof include methyl, ethyl, isopropyl, tert-butyl and amyl groups. Moreover, the phrase "may have a halogen atom as a substituent" in the "alkyl group which may have a halogen atom as a substituent" means that a part or all of the hydrogen atoms in the alkyl group may be substituted by a halogen atom. Examples of the halogen atom are as described above. When the alkyl group has a halogen atom as a substituent, the number of its carbon atoms is preferably in the range of 1 to 20, more preferably in the range of 1 to 10. Preferable examples of the alkyl group having a halogen atom as a substituent include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, fluoroethyl, perfiuoropropyl, perfluorobutyl, perfiuoropentyl and perfluorohexyl groups.

[0018]

Examples of the "aryl group having 6 to 20 carbon atoms" in the aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent include phenyl, 2- tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6-xylyl, 3,4-xylyl, 3,5-xylyl, 2,3,4- trimethylphenyl, 2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl, 2,4,6-trimethylphenyl, 3,4,5- trimethylphenyl, 2,3,4,5-tetramethylphenyl, 2,3,4,6-tetramethylphenyl, 2,3,5,6- tetramethylphenyl, pentamethylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n- butylphenyl, sec-butylphenyl, tert-butylphenyl, n-pentylphenyl, neopentylphenyl, n-hexylphenyl, n-octylphenyl, n-decylphenyl, n-dodecylphenyl, n-tetradecylphenyl, naphthyl and anthracenyl groups. Of them, a preferable aryl group is an aryl group having 6 to 10 carbon atoms, and more preferable examples thereof include a phenyl group. Moreover, the phrase "may have a halogen atom as a substituent" in the "aryl group which may have a halogen atom as a substituent" means that a part or all of the hydrogen atoms in the aryl group may be substituted by a halogen atom. Examples of the halogen atom are as described above. When the aryl group has a halogen atom as a substituent, the number of its carbon atoms is preferably in the range of 6 to 20, more preferably in the range of 6 to 10. Preferable examples of the aryl group having a halogen atom as a substituent specifically include fluorophenyl, difluorophenyl, trifluorophenyl, tetrafluorophenyl, pentafluorophenyl, chlorophenyl, bromophenyl and iodophenyl groups.

[0019]

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, (2,3,5,6-tetramethylphenyl)methyl,

(pentamethylphenyl)methyl, (ethylphenyl)methyl, (n-propylphenyl)methyl,

(isopropylphenyl)methyl, (n-butylphenyl)methyl, (sec-butylphenyl)methyl, (tert- butylphenyl)methyl, (n-pentylphenyl)methyl, (neopentylphenyl)methyl, (n-hexylphenyl)methyl, (n-octylphenyl)methyl, (n-decylphenyl)methyl, (n-dodecylphenyl)methyl, naphthylmethyl and anthracenylmethyl groups. Of them, a preferable aralkyl group is an aralkyl group having 7 to 10 carbon atoms, and more preferable examples thereof include a benzyl group. Moreover, the phrase "may have a halogen atom as a substituent" in the "aralkyl group which may have a halogen atom as a substituent" means that a part or all of the hydrogen atoms in the aralkyl group may be substituted by a halogen atom. Examples of the halogen atom are as described above. When the aralkyl group has a halogen atom as a substituent, the number of its carbon atoms is preferably in the range of 7 to 20, more preferably in the range of 7 to 10.

[0020]

Examples of the "alkoxy group having 1 to 20 carbon atoms" in the alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy, neopentyloxy, n- hexyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy, tridecyloxy, tetradecyloxy, n-pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy, nonadecyloxy and n-eicosyloxy groups. Of them, a preferable alkoxy group is an alkoxy group having 1 to 10 carbon atoms, and more preferable examples thereof include methoxy, ethoxy and tert-butoxy groups. Moreover, the phrase "may have a halogen atom as a substituent" in the "alkoxy group which may have a halogen atom as a substituent" means that a part or all of the hydrogen atoms in the alkoxy group may be substituted by a halogen atom. Examples of the halogen atom are as described above. When the alkoxy group has a halogen atom as a substituent, the number of its carbon atoms is preferably in the range of 1 to 20, more preferably in the range of 1 to 10.

[0021]

Examples of the "alkoxy group having 2 to 20 carbon atoms" in the alkoxy group having 2 to 20 carbon atoms which may have a halogen atom as a substituent include ethoxy, n- propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy, neopentyloxy, n-hexyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy, tridecyloxy, tetradecyloxy, n- pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy, nonadecyloxy and n-eicosyloxy groups. Of them, a preferable alkoxy group is an alkoxy group having 2 to 10 carbon atoms, and more preferable examples thereof include ethoxy and tert-butoxy groups. Moreover, the phrase "may have a halogen atom as a substituent" in the "alkoxy group which may have a halogen atom as a substituent" means that a part or all of the hydrogen atoms in the alkoxy group may be substituted by a halogen atom. Examples of the halogen atom are as described above. When the alkoxy group has a halogen atom as a substituent, the number of its carbon atoms is preferably in the range of 2 to 20, more preferably in the range of 2 to 10.

[0022]

Examples of the "aryloxy group having 6 to 20 carbon atoms" in the aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent include phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2,3-dimethylphenoxy, 2,4- dimethylphenoxy, 2,5-dimethylphenoxy, 2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5- dimethylphenoxy, 2,3,4-trimethylphenoxy, 2,3,5-trimethylphenoxy, 2,3,6-trimethylphenoxy, 2,4,5-trimethylphenoxy, 2,4,6-trimethylphenoxy, 3,4,5-trimethylphenoxy, 2,3,4,5- tetramethylphenoxy, 2,3 ,4,6-tetramethylphenoxy, 2,3 , 5,6-tetramethylphenoxy,

pentamethylphenoxy, ethylphenoxy, n-propylphenoxy, isopropylphenoxy, n-butylphenoxy, sec- butylphenoxy, tert-butylphenoxy, n-hexylphenoxy, n-octylphenoxy, n-decylphenoxy, n- tetradecylphenoxy, naphthoxy and anthracenoxy groups. Of them, a preferable aryloxy group is an aryloxy group having 6 to 10 carbon atoms, and more preferable examples thereof include phenoxy, 2-methylphenoxy, 3-methylphenoxy and 4-methylphenoxy groups. Moreover, the phrase "may have a halogen atom as a substituent" in the "aryloxy group which may have a halogen atom as a substituent" means that a part or all of the hydrogen atoms in the aryloxy group may be substituted by a halogen atom. Examples of the halogen atom are as described above. When the aryloxy group has a halogen atom as a substituent, the number of its carbon atoms is preferably in the range of 6 to 20, more preferably in the range of 6 to 10.

[0023]

Examples of the "aralkyloxy group having 7 to 20 carbon atoms" in the aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent include benzyloxy, (2-methylphenyl)methoxy, (3-methylphenyl)methoxy, (4- methylphenyl)methoxy, (2,3-dimethylphenyl)methoxy, (2,4-dimethylphenyl)methoxy, (2,5- dimethylphenyl)methoxy, (2,6-dimethylphenyl)methoxy, (3,4-dimethylphenyl)methoxy, (3,5- dimethylphenyl)methoxy, (2,3,4-trimethylphenyl)methoxy, (2,3,5-trimethylphenyl)methoxy, (2,3,6-trimethylphenyl)methoxy, (2,4,5-trimethylphenyl)methoxy, (2,4,6- trimethylphenyl)methoxy, (3,4,5-trimethylphenyl)methoxy, (2,3,4,5-tetramethylphenyl)methoxy, (2,3,4,6-tetramethylphenyl)methoxy, (2,3,5,6-tetramethylphenyl)methoxy,

(pentamethylphenyl)methoxy, (ethylphenyl)methoxy, (n-propylphenyl)methoxy,

(isopropylphenyl)methoxy, (n-butylphenyl)methoxy, (sec-butylphenyl)methoxy, (tert- butylphenyl)methoxy, (n-hexylphenyl)methoxy, (n-octylphenyl)methoxy, (n- decylphenyl)methoxy, naphthylmethoxy and anthracenylmethoxy groups. Of them, a preferable aralkyloxy group is an aralkyloxy group having 7 to 10 carbon atoms, and more preferable examples thereof include a benzyloxy group. Moreover, the phrase "may have a halogen atom as a substituent" in the "aralkyloxy group which may have a halogen atom as a substituent" means that a part or all of the hydrogen atoms in the aralkyloxy group may be substituted by a halogen atom. Examples of the halogen atom are as described above. When the aralkyloxy group has a halogen atom as a substituent, the number of its carbon atoms is preferably in the range of 7 to 20, more preferably in the range of 7 to 10.

[0024]

In the 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, 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 hydrocarbyl group obtained by substituting a part or all of the hydrogen atoms in the hydrocarbyl group with a halogen atom, and the total number of the carbon atoms in the three R ²² groups is in the range of 1 to 20. The total number of the carbon atoms in these three R ²² groups is preferably in the range of 3 to 18. Examples of the substituted silyl group include: monosubstituted silyl groups having one hydrocarbyl or halogenated hydrocarbyl group, such as methylsilyl, ethylsilyl and phenylsilyl groups, and groups obtained by substituting a part or all of the hydrogen atoms in the

hydrocarbyl groups of these groups with a halogen atom; disubstituted silyl groups having two hydrocarbyl and/or halogenated hydrocarbyl groups, such as dimethylsilyl, diethylsilyl and diphenylsilyl groups, and groups obtained by substituting a part or all of the hydrogen atoms in the hydrocarbyl groups of these groups with a halogen atom; and trisubstituted silyl group having three hydrocarbyl and/or halogenated hydrocarbyl groups, such as trimethylsilyl, triethylsilyl, tri-n-propylsilyl, triisopropylsilyl, tri-n-butylsilyl, tri-sec-butylsilyl, tri-tert- butylsilyl, tri-isobutylsilyl, tert-butyl-dimethylsilyl, tri-n-pentylsilyl, tri-n-hexylsilyl, tricyclohexylsilyl and triphenylsilyl groups, and groups obtained by substituting a part or all of the hydrogen atoms in the hydrocarbyl groups of these groups with a halogen atom. Of them, trisubstituted silyl groups are preferable, and trimethylsilyl, tert-butyldimethylsilyl and triphenylsilyl groups, and groups obtained by substituting a part or all of the hydrogen atoms in these groups with a halogen atom are more preferable.

[0025]

In the 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, 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. Moreover, 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,

diisopropylamino, di-n-butylamino, di-sec-butylamino, di-tert-butylamino, di-isobutylamino, tert-butylisopropylamino, di-n-hexylamino, di-n-octylamino, di-n-decylamino, diphenylamino, bistrimethylsilylamino, bis-tert-butyldimethylsilylamino, pyrrolyl, pyrrolidinyl, piperidinyl, carbazolyl, dihydroindolyl and dihydroisoindolyl groups, and groups obtained by substituting a part or all of the hydrogen atoms in these groups with a halogen atom. Of them,

dimethylamino, diethylamino, pyrrolidinyl and piperidinyl groups, and groups obtained by substituting a part or all of the hydrogen atoms in these groups with a halogen atom are preferable.

[0026]

Of 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, of R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ , two groups bonded to two adjoining carbon atoms may be bonded to each other to form a ring together with the carbon atoms to which they 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 they 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 they are bonded, of R ⁵ , R ²⁴ , R ⁷ R ²⁵ 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, and of R ¹² , R ²⁶ , R ¹⁴ , R ²⁷ 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. In this context, the ring is a saturated or unsaturated hydrocarbyl ring substituted by a hydrocarbyl group having 1 to 20 carbon atoms, a saturated or unsaturated silahydrocarbyl ring substituted by a hydrocarbyl group having 1 to 20 carbon atoms, etc. Examples thereof include cyclopropane, cyclopropene, cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, cyclohexene, cycloheptane, cycloheptene, cyclooctane, cyclooctene, benzene, naphthalene, anthracene, silacyclopropane, silacyclobutane, silacyclopentane and silacyclohexane rings.

[0027]

In the transition metal complexes (1-1) to (1-3), 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.

[0028]

Examples of R ¹ , R ² , R ³ and R ⁴ include the following substructures represented by a substructural formula (2):

wherein R ^l , R ² , R ³ and R ⁴ are as defined above:

[0029]

cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, n- propylcyclopentadienyl, isopropylcyclopentadienyl, n-butylcyclopentadienyl, sec- butylcyclopentadienyl, tert-butylcyclopentadienyl, dimethylcyclopentadienyl,

trimethylcyclopentadienyl, tetramethylcyclopentadienyl, phenylcyclopentadienyl,

benzylcyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, methyltetrahydroindenyl, dimethyltetrahydroindenyl and octahydrofluorenyl.

[0030]

Of the cyclopentadienyl substructures exemplified above, a preferable cyclopentadienyl substructure is tetramethylcyclopentadienyl, etc.

[0031]

In the transition metal complexes (1-1) to (1-3), 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.

[0032]

8

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):

wherein R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are as defined above;

the followin substructures represented by a substructural formula

wherein R , R , R , R and R are as defined above;

the followin substructures represented by a substructural formula

wherein R ¹⁷ , R ¹⁸ , R ¹⁹ R ²⁰ and R ²¹ are as defined above;

the followin substructures represented by a substructural formula

wherein R ⁵ , R ²⁴ , R ⁷ R ²⁵ and R ⁹ are as defined above;

the following substructures represented by a substructural formula (3-5): and

wherein R ¹² , R ²⁶ , R ¹⁴ , R ²⁷ and R ¹⁶ are as defined above, respectively:

[0033]

phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, tetramethylphenyl, pentamethylphenyl, ethylphenyl, diethylphenyl, triethylphenyl, tetraethylphenyl,

pentaethylphenyl, tert-butylphenyl, di-tert-butylphenyl, tert-butylmethylphenyl, di(tert- butyl)methylphenyl, phenylphenyl, diphenylphenyl, triphenylphenyl, tetraphenylphenyl, pentaphenylphenyl, benzylphenyl, dibenzylphenyl, tribenzylphenyl, tetrabenzylphenyl, pentabenzylphenyl, naphthyl, anthracenyl, chlorophenyl, dichlorophenyl, fluorophenyl, pentafluorophenyl, bis(trifluoromethyl)phenyl, methoxyphenyl.

[0034]

Of the substructures exemplified above, a preferable substructure is phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, diethylphenyl, di-tert-buthylphenyl, etc.

[0035]

In the transition metal complexes (1-1), 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.

[0036]

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):

wherein R ¹⁰ and R ¹¹ are as defined above:

[0037]

dimethylsilylene, diethyl silylene, ethylmethylsilylene, di(n-propyl)silylene, methyl(n-propyl)silylene, di(n-butyl)silylene, n-butylmethylsilylene, n-hexylmethylsilylene, methyl(n-octyl)silylene, n-decylmethylsilylene, methyl(n-octadecyl)silylene,

cyclohexylmethylsilylene and cyclotetramethylenesilylene.

[0038]

Preferable examples of a structural formula represented by the substructural formula (4) include the following:

a substructural formula wherein

R ¹⁰ is a methyl group, and R ^u is

an alkyl group having 2 to 20 carbon atoms which may have a halogen atom as a substituent; a structural formula wherein

R ¹⁰ and R ^u are the same as each other and are

an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent; or a structural formula wherein

R ¹⁰ and R ¹¹ are not the same as each other and are

an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent; specifically, the substructure is dimethylsilylene, diethyl si lylene, ethylmethylsilylene, n- butylmethylsilylene, cyclohexylmethylsilylene, cyclotetramethylenesilylene, etc.

[0039]

Preferable examples of the transition metal complex of the formula (1-1) include transition metal complexes wherein R ⁶ and R ⁸ 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.

[0040]

In the transition metal complex (1-2), 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.

[0041]

Preferable examples of the 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

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.

[0042]

Preferable examples of the 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.

[0043]

Examples of the transition metal complexes (1-1) to (1-3) include the following complexes:

[0044]

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]titanium trichloride, [l-methylbis(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethyl cyclopentadienyljtitanium trichloride, [l-cyclohexylmethylphenylsilyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [l-methyl(n-octadecyl)phenylsilyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [l-triphenylsilyl-2,3,4,5- tetramethylcyclopentadienyljtitanium trichloride, [l-tri(4-n-butylphenyl)silyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [l-tri(3-methylphenyl)silyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [ 1 -tri(3 -isopropylphenyl)silyl-2, 3 ,4, 5- tetramethylcyclopentadieny l]titanium trichloride, [ 1 -dimethyl(3 , 5 -dimethylphenyl)silyl-2, 3 ,4, 5- tetramethylcyclopentadienyl]titanium trichloride, [l-dimethyl(3,5-di-n-hexylphenyl)silyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [l-n-butylmethyl(3,5-dimethylphenyl)silyl- 2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride, [l-tris(3,5-dimethylphenyl)silyl- 2,3,4,5-tetramethylcyclopentadienyljtitanium trichloride, [l-tris(3,5-diethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadienyljtitanium trichloride, [l-tris(3,5-diisopropylphenyl)silyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [ 1 -tris(3, 5-di-tert-butylphenyl)silyl-2,3 ,4, 5- tetramethylcyclopentadienyl]titanium trichloride, [l-tris(3,5-di-n-hexylphenyl)silyl-2,3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [ 1 -n-butylmethyl(2,4,6-trimethylphenyl)silyl- 2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride, [1-n- butylmethyl(pentamethylphenyl)silyl-2,3,4,5-tetramethylcyclo pentadienyl]titanium trichloride, [ 1 -(3 , 5 -di-tert-butylphenyl)bi s(3 , 5 -dimethy lphenyl)silyl-2, 3,4,5- tetramethylcyclopentadienyl]titanium trichloride, [ 1 -(3 , 5-di-tert-butylphenyl)(3 , 5 - diethylphenyl)(3,5-dimethyl phenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]titanium trichloride, [l-tris(3,5-diphenylphenyl)silyl-2,3,4,5-tetramethylcyclopen tadienyl]titanium trichloride, [l-tris(3,5-dibenzylphenyl)silyl-2,3,4,5-tetramethylcyclopen tadienyl]titanium trichloride.

[0045]

Moreover, 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- butylcyclopentadienyl", "2-sec-butylcyclopentadienyl", "3-sec-butylcyclopentadienyl", "2-tert- butylcyclopentadienyl", "3-tert-butylcyclopentadienyl", "2-phenylcyclopentadienyl", "3- phenylcyclopentadienyl", "2-benzylcyclopentadienyl", "3-benzylcyclopentadienyl", "indenyl", "2-methylindenyl", "fluorenyl", "tetrahydroindenyl", "2-methyltetrahydroindenyl" or

"octahydrofluorenyl" for "2,3,4,5-tetramethylcyclopentadieny in the complexes exemplified above.

[0046]

Furthermore, examples of the 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 as benzylated titanium complexes obtained by substituting "benzyl" therefor; titanium alkoxide complexes such as titanium methoxide complexes obtained by substituting "methoxide" therefor, titanium n-butoxide complexes obtained by substituting "n- butoxide" therefor and titanium isopropoxide complexes obtained by substituting "isopropoxide" therefor; titanium aryloxide complexes such as titanium phenoxide complexes obtained by substituting "phenoxide" therefor; titanium aralkyloxide complexes such as titanium benzyloxide complexes obtained by substituting "benzyloxide" therefor; and titanium amide complexes such as titanium dimethylamide complexes obtained by substituting "dimethylamide" therefor and titanium diethylamide complexes obtained by substituting "diethylamide" therefor.

[0047]

<Methods for producing transition metal complexes (1-1) to (l-3)>

The 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:

5-1)

wherein 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,

-2)

wherein 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

-3)

wherein 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.

Hereinafter, the transition metal complex (1-1) will be described as an example. 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:

wherein 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; and

reacting the reaction product of the substituted cyclopentadiene compound (5-1) and the base with a transition metal compound represented by formula (6) (hereinafter, referred to as a "transition metal com ound (6)"):

wherein M, X ¹ , X ² and X ³ are as defined above; and X ⁴ is as defined in X ¹ , X ² and X ³ ; m is 0 or 1. Hereinafter, 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".

[0048]

Isomers of the substituted cyclopentadiene compound (5-1) differing in the double

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.

[0049]

In the transition metal compound (6), 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 .

[0050]

Examples of the transition metal compound (6) 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. Moreover, 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.

[0051]

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.

[0052]

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).

[0053]

In the reaction of the substituted cyclopentadiene compound (5-1) with the base in the 1st reaction step, an amine compound is used. Examples of such an amine compound include: primary amine compounds such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, tert-butylamine, n-octylamine, n-decylamine, aniline and ethylenediamine; secondary amine compounds such as dimethylamine, diethylamine, di-n- propylamine, diisopropylamine, di-n-butylamine, di-tert-butylamine, di-n-octylamine, di-n- decylamine, pyrrolidine, hexamethyldisilazane and diphenylamine; and tertiary amine compounds such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, diisopropylethylamine, tri-n-octylamine, tri-n-decylamine, triphenylamine, N,N-dimethylaniline, Ν,Ν,Ν',Ν'-tetramethylethylenediamine, N-methylpyrrolidine and 4-dimethylaminopyridine. The amount of such an amine compound used is preferably 10 moles or smaller, more preferably in the range of 0.5 to 10 moles, even more preferably in the range of 1 to 5 moles, per mole of the base.

[0054]

In the 1st reaction step, the reaction of the substituted cyclopentadiene compound

(5-1) with the base is preferably performed in the presence of a solvent. Moreover, when the solvent is used, 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. In this case, the solvent may be further added until the deposited solid is dissolved; or the deposited solid may be temporarily separated by filtration or the like, and the solvent may be added to the separated solid for dissolution or suspension, followed by the addition of a transition metal compound (6). Moreover, when the solvent is used, the substituted

cyclopentadiene compound (5-1), 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.

[0055]

The solvent used in the 1st reaction step or in the 1st and 2nd reaction steps is an inert solvent that does not significantly hinder the progress of the reaction associated with these steps. Examples of such a solvent include aprotic solvents such as: aromatic hydrocarbyl solvents such as benzene and toluene; aliphatic hydrocarbyl solvents such as hexane and heptane; ether solvents such as diethyl ether, 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).

[0056]

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.

[0058]

From the reaction mixture thus obtained through the 1st and 2nd reaction steps, the produced transition metal complex (1-1) can be taken by various purification methods known in the art. For example, 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.

[0059]

Moreover, a compound wherein one or some of X ¹ , X ² and X ³ in the transition metal complexes (1-1) to (1-3) are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, an aryl group having 6 to 20 carbon atoms which may have a halogen atom as a substituent, an aryloxy group having 6 to 20 carbon atoms which may have a halogen atom as a substituent, an aralkyl group having 7 to 20 carbon atoms which may have a halogen atom as a substituent, an aralkyloxy group having 7 to 20 carbon atoms which may have a halogen atom as a substituent, or the like can also be obtained by reacting a compound wherein X ¹ , X ² and X ³ in the transition metal complexes (1-1) to (1-3) are a halogen atom with a lithium, sodium, potassium or magnesium compound having the

corresponding alkyl, alkoxy, aryl, aryloxy, aralkyl or aralkyloxy group.

[0060]

Substituted cyclopentadiene compounds (5-1) to(5-3)>

[0061]

In the substituted cyclopentadiene compounds (5-1) to (5-3), the substituents R ¹ ,

TJ 2 _p 3 _β 4 _p 5 p 6 p 7 p 8 p 9 10 p l l p 12 p 13 p 14 p 15 p 16 p 17 p 18 p 19 p20 p 21 p 24 p 25 XV , XV , XV , IV , IV , IV , IV , IV , IV , ix , IV , JY , IV , rv , Jv , jv , xV , xV , iv , iv , xV , is. ,

R ²⁶ and R ²⁷ are as defined above.

[0062]

Examples of the substituted cyclopentadiene compound (5-1) include the following substituted cyclopentadiene compounds:

[0063]

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)phenylsilyl-2,3,4,5-tetramethylcyclopentadie ne, 1- ethylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, l-methylphenyl(n-propyl)silyl- 2,3,4,5-tetramethylcyclopentadiene, l-methylphenyl(isopropyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-n-butylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadien e, 1- isobutylmethylphenylsilyl-2,3,4,5-tetramethylcyclopentadiene , 1-sec-butylmethylphenylsilyl- 2,3,4,5-tetramethylcyclopentadiene, l-tert-butylmethylphenylsilyl-2,3,4,5- tetramethylcyclopentadiene, 1 -cyclohexylmethylphenylsilyl-2, 3 ,4, 5-tetramethylcyclopentadiene, l-methyl(n-octadecyl)phenylsilyl-2,3,4,5-tetramethylcyclopen tadiene,

[0064]

l-dimethyl(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclo pentadiene, 1- diethyl(3 , 5-dimethylphenyl)silyl-2,3 ,4, 5 -tetramethylcyclopentadiene, 1 -(3, 5- dimethylphenyl)di(n-propyl)silyl-2,3,4,5-tetramethylcyclopen tadiene, l-diisopropyl(3,5- dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene, l-di(n-butyl)(3,5- dimethylphenyl)silyl-2,3 ,4,5-tetramethylcyclopentadiene, 1 -di(isobutyl)(3 , 5- dimethylphenyl)silyl-2,3 ,4, 5 -tetramethylcyclopentadiene, 1 -di(sec-butyl)(3 ,5- dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene, l-di(tert-butyl)(3,5- dimethy lpheny 1) sily 1-2, 3 ,4, 5 -tetramethylcyclopentadiene, 1 -ethylmethy 1(3 , 5 - dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene, l-methyl(3,5-dimethylphenyl)(n- propyl)silyl-2,3,4,5-tetramethylcyclopentadiene, l-methyl(3,5-dimethylphenyl)(isopropyl)silyl- 2,3,4,5-tetramethylcyclopentadiene, l-n-butylmethyl(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-isobutylmethyl(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, 1 -sec-butylmethyl(3 , 5-dimethylphenyl)silyl-2,3 ,4, 5- tetramethylcyclopentadiene, 1 -tert-butylmethy 1(3 , 5 -dimethylphenyl)silyl-2, 3,4,5- tetramethylcyclopentadiene, 1 -cyclohexylmethyl(3 , 5-dimethylphenyl)silyl-2,3 ,4, 5- tetramethylcyclopentadiene, l-methyl(n-octadecyl)(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene.

[0065]

Moreover, 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- butylcyclopentadiene", "2-tert-butylcyclopentadiene", "3-tert-butylcyclopentadiene", "2- phenylcyclopentadiene", "3-phenylcyclopentadiene", "2-benzylcyclopentadiene", "3- benzylcyclopentadiene", "indene", "2-methylindene", "fluorene", "tetrahydroindene", "2- methyltetrahydroindene" or "octahydro fluorene" for "2,3,4,5-tetramethylcyclopentadiene" in the substituted cyclopentadiene compounds exemplified above.

[0066]

Examples of the substituted cyclopentadiene compound (5-2) include the following substituted cyclopentadiene compounds:

[0067]

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-tetramethylcyclopentadiene, 1 - cyclohexyldiphenylsilyl-2,3,4,5-tetramethylcyclopentadiene, l-n-octadecyldiphenylsilyl-2,3,4,5- tetramethylcyclopentadiene, l-methylphenyl(2-methylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, 1 -methylphenyl(3-methylphenyl)silyl-2,3 ,4, 5- tetramethylcy clopentadiene, 1 -methy lpheny l(4-methylphenyl) si ly 1-2, 3 , 4, 5 - tetramethylcyclopentadiene, l-methylphenyl(2,3-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-methylphenyl(2,4-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-methylphenyl(2,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-methylphenyl(2,6-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-methylphenyl(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, 1 -methylphenyl(3 ,4, 5-trimethylphenyl)silyl-2, 3 ,4, 5- tetramethylcyclopentadiene,

[0068]

l-ethylphenyl(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcy clopentadiene, 1-n- propylphenyl(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyc lopentadiene, 1- isopropylphenyl(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethyl cyclopentadiene, 1-n- butylphenyl(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcycl opentadiene, l-isobutylphenyl(3,5- dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene, l-sec-butylphenyl(3,5- dimethy lphenyl) silyl-2, 3,4,5 -tetramethy lcyclopentadiene, 1 -tert-butylpheny 1(3 , 5 - dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene, l-cyclohexylphenyl(3,5- dimethylphenyl)silyl-2, 3 ,4, 5-tetramethylcyclopentadiene, 1 -n-octadecylphenyl(3 ,5- dimethylphenyl)silyl-2, 3 ,4, 5-tetramethylcyclopentadiene, 1 -methyl(2-methylphenyl)(3 , 5 - dimethy lphenyl) silyl-2, 3 ,4, 5 -tetramethy lcyclopentadiene, 1 -methyl(3 -methylphenyl)(3 , 5 - dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene, l-methyl(4-methylphenyl)(3,5- dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene, l-methyl(2,3-dimethylphenyl)(3,5- dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene, l-methyl(2,4-dimethylphenyl)(3,5- dimethylphenyl)silyl-2,3 ,4, 5-tetramethylcyclopentadiene, 1 -methyl(2, 5-dimethylphenyl)(3 , 5- dimethylphenyl) silyl-2, 3 ,4, 5 -tetramethylcyclopentadiene, 1 -methylphenyl(2, 6- dimethylphenyl)(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethyl cyclopentadiene, l-methylbis(3,5- dimethylphenyl)silyl-2, 3 ,4, 5-tetramethylcyclopentadiene, 1 -methyl(3 , 5-dimethylphenyl)(3 ,4, 5 - trimethylphenyl)silyl-2,3, 4, 5-tetramethylcyclopentadiene.

[0069]

Moreover, 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-butylcyclopentadiene", "3-sec- butylcyclopentadiene", "2-tert-butylcyclopentadiene", "3-tert-butylcyclopentadiene", "2- phenylcyclopentadiene", " 3 -pheny lcyclopentadiene", "2-benzylcyclopentadiene", "3- benzylcyclopentadiene", "indene", "2-methylindene", "fluorene", "tetrahydroindene", "2- methyltetrahydroindene" or "octahydrofluorene" for "2,3, 4, 5-tetramethylcyclopentadiene" in the substituted cyclopentadiene compounds exemplified above.

[0070]

Examples of the substituted cyclopentadiene compound (5-3) include the following substituted cyclopentadiene compounds:

[0071]

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- tetramethylcyclopentadiene, l-phenylbis(2,6-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-phenylbis(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-phenylbis(3,4,5-trimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene,

[0072]

l-diphenyl(2-methylphenyl)silyl-2,3,4,5-tetramethylcyclopent adiene, 1- diphenyl(3-methylphenyl)silyl-2,3,4,5-tetramethylcyclopentad iene, l-diphenyl(4- methylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene, l-diphenyl(2,3-dimethylphenyl)silyl- 2,3,4,5-tetramethylcyclopentadiene, l-diphenyl(2,4-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-diphenyl(2,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-diphenyl(2,6-dimethylphenyl)silyl-2,3,4,5- tetramethy lcyclopentadiene, 1 -dipheny 1(3 , 5 -dimethy lpheny l)silyl-2, 3,4,5- tetramethylcyclopentadiene, l-diphenyl(3,5-diethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, 1 -diphenyl(3 ,4, 5-trimethylphenyl)silyl-2,3 ,4, 5 - tetramethylcyclopentadiene,

[0073]

l-phenyl(2-methylphenyl)(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-phenyl(3-methylphenyl)(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-phenyl(4-methylphenyl)(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-phenyl(2,3-dimethylphenyl)(3,5-dimethylphenyl)silyl-2,3,4, 5- tetramethylcyclopentadiene, l-phenyl(2,4-dimethylphenyl)(3,5-dimethylphenyl)silyl-2,3,4, 5- tetramethylcyclopentadiene, l-phenyl(2,5-dimethylphenyl)(3,5-dimethylphenyl)silyl-2,3,4, 5- tetramethylcyclopentadiene, 1 -phenyl(2,6-dimethylphenyl)(3 , 5-dimethylphenyl)silyl-2,3,4, 5- tetramethylcyclopentadiene, 1 -phenyl(3 , 5 -dimethy lpheny 1)(3 ,4, 5-trimethylphenyl)silyl-2, 3 ,4, 5- tetramethylcyclopentadiene,

[0074]

1 -di(2-methylphenyl)(3 , 5-dimethylphenyl)silyl-2,3 ,4, 5 - tetramethylcyclopentadiene, 1 -di(3-methylphenyl)(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-di(4-methylphenyl)(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-bis(2,3-dimethylphenyl)(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-bis(2,4-dimethylphenyl)(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethy lcyclopentadiene, 1 -bis(2, 5 -dimethy lpheny 1)(3 , 5 -dimethy lpheny l)sily 1-2, 3,4,5- tetramethylcyclopentadiene, 1 -bis(2,6-dimethylphenyl)(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadiene, l-tris(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopent adiene, l-(3,5-dimethylphenyl)bis(3,4,5-dimethylphenyl)silyl-2,3,4,5 -tetramethylcyclopentadiene.

[0075]

Moreover, 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- butylcyclopentadiene", "2-tert-butylcyclopentadiene", "3-tert-butylcyclopentadiene", "2- phenylcyclopentadiene", "3-phenylcyclopentadiene", "2-benzylcyclopentadiene", "3- benzylcyclopentadiene", "indene", "2-methylindene", "fluorene", "tetrahydroindene", "2- methyltetrahydroindene" or "octahydrofluorene" for "2,3,4,5-tetramethylcyclopentadiene" in the substituted cyclopentadiene compounds exemplified above.

[0076]

<Methods for producing substituted cyclopentadiene compounds (5-1) to (5-3)>

The substituted cyclopentadiene compounds (5-1), (5-2) and (5-3) can be produced by similar methods comprising the steps of:

reacting a substituted cyclopentadiene compound represented by formula (7) (hereinafter, abbreviated to a "substituted cyclopentadiene compound (7)") with a base; and

reacting the reaction product of the substituted cyclopentadiene compound (7) and the base with a halogenated silyl compound represented by formula (8-1) (hereinafter, abbreviated to a

"halogenated silyl compound (8-1)"),

reacting the substituted cyclopentadiene compound (7) with a base; and

reacting the reaction product of the substituted cyclopentadiene compound (7) and the base with a halogenated silyl compound represented by formula (8-2) (hereinafter, abbreviated to a

"halogenated silyl compound (8-2)"), and

reacting the substituted cyclopentadiene compound (7) with a base; and

reacting the reaction product of the substituted cyclopentadiene compound (7) and the base with a halogenated silyl compound represented by formula (8-3) (hereinafter, abbreviated to a

"halogenated silyl compound (8-3)"), respectively:

wherein R , R , R and R are as defined above,

the moiety represents

wherein 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,

wherein 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

wherein 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.

Hereinafter, a method for producing the substituted cyclopentadiene compound (5-1) will be described as an example.

[0077]

The substituted cyclopentadiene compound (7) is as follows:

wherein R , R , R and R are as defined above, and

the moiety represents

[0078]

Examples of the substituted cyclopentadiene compound (7) include the following compounds:

[0079]

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, neopentylcyclopentadiene, n-hexylcyclopentadiene, n- octylcyclopentadiene, phenylcyclopentadiene, naphthylcyclopentadiene,

trimethylsilylcyclopentadiene, triethylsilylcyclopentadiene, tert- butyldimethylsilylcyclopentadiene, indene, 2-methylindene, tetrahydroindene, 2- methyltetrahydroindene, 3-methyltetrahydroindene, 2,3-dimethyltetrahydroindene, 2- ethyltetrahydroindene, 2-n-propyltetrahydroindene, 2-isopropyltetrahydroindene, 2-n- butyltetrahydroindene, 2-sec-butyltetrahydroindene, 2-tert-butyltetrahydroindene, 2-n- pentyltetrahydroindene, 2-neopentyltetrahydroindene, 2-amyltetrahydroindene, 2-n- hexyltetrahydroindene, 2-cyclohexyltetrahydroindene, 2-n-octyltetrahydroindene, 2-n- decyltetrahydroindene, 2-phenyltetrahydroindene, 2-benzyltetrahydroindene, 2- naphthyltetrahydroindene, 2-methoxytetrahydroindene, 2-phenoxytetrahydroindene, 2- benzyloxytetrahydroindene, 2-dimethylaminotetrahydroindene, 2-trimethylsilyltetrahydroindene, fluorene and octahydrofluorene.

[0080]

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.

[0081]

The halo enated silyl compound (8-1) is as follows:

wherein 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.

[0082]

Examples of the halogenated silyl compound (8-1) include the following halogenated silyl compounds:

[0083]

chlorodimethylphenylsilane, chlorodiethylphenylsilane, chlorophenyldi(n- propyl)silane, chlorodiisopropylphenylsilane, di(n-butyl)chlorophenylsilane, di(isobutyl)chlorophenylsilane, di(sec-butyl)chlorophenylsilane, di(tert- butyl)chlorophenylsilane, chloroethylmethylphenylsilane, chloromethylphenyl(n-propyl)silane, chloromethylphenyl(isopropyl)silane, n-butylchloromethylphenylsilane,

isobutylchloromethylphenylsilane, sec-butylchloromethylphenylsilane, tert- butylchloromethylphenylsilane, chlorocyclohexylmethylphenylsilane, chloromethyl(n- octadecyl)phenylsilane,

[0084]

chlorodimethyl(3 , 5-dimethylphenyl)silane, chlorodiethyl(3 , 5- dimethylphenyl)silane, chloro(3,5-dimethylphenyl)di(n-propyl)silane, chlorodiisopropyl(3,5- dimethylphenyl)silane, di(n-butyl)chloro(3,5-dimethylphenyl)silane, di(isobutyl)chloro(3,5- dimethylphenyl)silane, di(sec-butyl)chloro(3,5-dimethylphenyl)silane, di(tert-butyl)chloro(3,5- dimethylphenyl)silane, chloroethylmethyl(3,5-dimethylphenyl)silane, chloromethyl(3,5- dimethylphenyl)(n-propyl)silane, chloromethyl(3,5-dimethyIphenyl)(isopropyl)silane, n- butylchloromethyl(3,5-dimethylphenyl)silane, isobutylchloromethyl(3,5-dimethylphenyl)silane, sec-butylchloromethyl(3,5-dimethylphenyl)silane, tert-butylchloromethyl(3,5- dimethylphenyl)silane, chlorocyclohexylmethyl(3,5-dimethylphenyl)silane, chloromethyl(n- octadecyl)(3 , 5 -dimethylpheny 1) silane .

[0085]

Compounds obtained by substituting "fluoro", "bromo" or "iodo" for "chloro" in these compounds exemplified above are also included therein.

[0086]

Examples of the halogenated silyl compound (8-2) include the following halogenated silyl compounds:

[0087]

chloromethyldiphenylsilane, chloroethyldiphenylsilane, chloro-n- propyldiphenylsilane, chloroisopropyldiphenylsilane, n-butylchlorodiphenylsilane,

isobutylchlorodiphenylsilane, sec-butylchlorodiphenylsiiane, tert-butylchlorodiphenylsilane, chlorocyclohexyldiphenyl silane, chloro-n-octadecyldiphenylsilane, chloromethylphenyl(2- methylphenyl)silane, chloromethylphenyl(3 -methylphenyl)silane, chloromethylphenyl(4- methylphenyl)silane, chloromethylphenyl(2,3-dimethylphenyl)silane, chloromethylpheny 1(2,4- dimethylphenyl)silane, chloromethylphenyl(2,5-dimethylphenyl)silane, chloromethylphenyl(2,6 dimethylphenyl)silane, chloromethylphenyl(3,5-dimethylphenyl)silane, chloro methylphenyl(3, 5 diethylphenyl)silane,

[0088] 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)silane, chloromethyl(2-methy lpheny 1)(3 , 5 - dimethylphenyl)silane, chloromethyl(3-methylphenyl)(3,5-dimethylphenyl)silane,

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)si lane, chloromethylbis(3,5- dimethylphenyl)silane, chloromethyl(3,5-dimethylphenyl)(3,4,5-trimethylphenyl)silan e.

[0089]

Compounds obtained by substituting "fluoro", "bromo" or "iodo" for "chloro" in these compounds exemplified above are also included therein.

[0090]

Examples of the halogenated silyl compound (8-3) include the following halogenated silyl compounds:

[0091]

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,

[0092]

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,

[0093]

chlorophenyl(2-methylphenyl)(3,5-dimethylphenyl)silane, chlorophenyl(3- methy lpheny 1)(3 , 5 -dimethylpheny l)silane, chlorophenyl(4-methy lpheny 1)(3 , 5 - dimethylphenyl)silane, chlorophenyl(2,3-dimethylphenyl)(3,5-dimethylphenyl)silane, chlorophenyl(2,4-dimethylphenyl)(3,5-dimethylphenyl)silane, chlorophenyl(2,5- dimethylphenyl)(3,5-dimethylphenyl)silane, chlorophenyl(2,6-dimethylphenyl)(3,5- dimethylphenyl)silane, chlorophenyl(3,5-dimethylphenyl)(3,4,5-trimethylphenyl)silan e,

[0094]

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.

[0095]

Compounds obtained by substituting "fluoro", "bromo" or "iodo" for "chloro" in these compounds exemplified above are also included therein.

[0096]

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. The amount thereof used is usually in the range of 0.5- to 3-fold by mol, preferably 0.9- to 2-fold by mol, with respect to the substituted cyclopentadiene compound (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.

[0097]

In the step of reacting the substituted cyclopentadiene compound (7) with a base, an amine compound may be used. Examples of such an amine compound include: primary anilines such as aniline, chloroaniline, bromoaniline, fluoroaniline, dichloroaniline,

dibromoaniline, difluoroaniline, trichloroaniline, tribromoaniline, trifluoroaniline,

tetrachloroaniline, tetrabromoaniline, tetrafluoroaniline, pentachloroaniline, pentafluoroaniline, nitroaniline, dinitroaniline, hydroxyaniline, phenylenediamine, anisidine, dimethoxyaniline, trimethoxyaniline, ethoxyaniline, diethoxyaniline, triethoxyaniline, n-propoxyaniline, isopropoxyaniline, n-butoxyaniline, sec-butoxyaniline, isobutoxyaniline, t-butoxyaniline, phenoxyaniline, methylaniline, ethylaniline, n-propylaniline, isopropylaniline, n-butylaniline, sec-butylaniline, isobutylaniline, t-butylaniline, dimethylaniline, diethylaniline, di-n- propylaniline, diisopropylaniline, di-n-butylaniline, di-sec-butylaniline, diisobutylaniline, di-t- butylaniline, trimethylaniline, triethylaniline, diisopropylaniline, phenylaniline, benzylaniline, aminobenzoic acid, methyl aminobenzoate, ethyl aminobenzoate, n-propyl aminobenzoate, isopropyl aminobenzoate, n-butyl aminobenzoate, isobutyl aminobenzoate, sec-butyl aminobenzoate and t-butyl aminobenzoate, and other primary amines including naphthylamine, naphthylmethylamine, benzylamine, propylamine, butylamine, pentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, 2-aminopyridine, 3-aminopyridine and 4- aminopyridine;

[0098]

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

[0099]

tertiary amines such as N,N-dimethylaniline, Ν,Ν-dimethylchloroaniline, N,N- dimethylbromoaniline, N,N-dimethylfluoroaniline, Ν,Ν-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. Preferably primary or secondary amines, more preferably primary amines are used.

[0100]

The amount of such an amine compound used is usually in the range of 0.001- to 2-fold by mol, preferably 0.01- to 0.5-fold by mol, with respect to the base. The reaction is usually performed in a solvent inert to the reaction. Examples of such a solvent include aprotic solvents such as: aromatic hydrocarbyl solvents such as benzene, toluene and xylene; aliphatic hydrocarbyl solvents such as pentane, hexane, heptane, octane and cyclohexane; ether solvents such as diethyl ether, methyl t-butyl ether, tetrahydrofuran and 1,4-dioxane; amide solvents such as hexamethylphosphoric amide, dimethylformamide, dimethylacetamide and N- methylpyrrolidone; and halogen solvents such as chlorobenzene and dichlorobenzene. These solvents are used alone or as a mixture of two or more thereof, and the amount thereof used is usually in the range of 1- to 200-fold by weight, preferably 3- to 30-fold by weight, with respect to each cyclopentadiene.

[0101]

For the reaction, for example, 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.

[0102]

The reaction for obtaining the substituted cyclopentadiene compound (5-1) is usually performed in a solvent inert to the reaction. Examples of such a solvent include aprotic solvents such as: aromatic hydrocarbyl solvents such as benzene, toluene and xylene; aliphatic hydrocarbyl solvents such as pentane, hexane, heptane, octane and cyclohexane; ether solvents such as diethyl ether, methyl t-butyl ether, tetrahydrofuran and 1,4-dioxane; amide solvents such as hexamethylphosphoric amide, dimethylformamide, dimethylacetamide and N- methylpyrrolidone; and halogen solvents such as chlorobenzene and dichlorobenzene. These solvents are used alone or as a mixture of two or more thereof, and the amount thereof used is usually in the range of 1- to 200-fold by weight, preferably 3- to 30-fold by weight, with respect to the substituted cyclopentadiene compound (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. However, even when a method is adopted in which these components are mixed simultaneously, 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).

[0104]

After completion of the reaction, water, an aqueous sodium bicarbonate solution, an aqueous sodium carbonate solution, an aqueous ammonium chloride solution or an aqueous solution of hydrochloric acid or the like is added to the obtained reaction mixture. Then, organic and aqueous phases are separated to obtain a solution of the substituted cyclopentadiene compound (5-1) as the organic phase. When a water-compatible solvent is used in the reaction or when the amount of the solvent used in the reaction is too small to easily separate organic and aqueous phases, a water-insoluble organic solvent such as toluene, ethyl acetate or

chlorobenzene may be added to the reaction mixture as appropriate, followed by separation into organic and aqueous phases. The obtained organic phase is concentrated to obtain the substituted cyclopentadiene compound (5-1). The obtained substituted cyclopentadiene compound (8-1) may be purified, if necessary, by a method such as distillation and column chromatography treatment.

[0105]

<Activating co-catalytic component>

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 ,

(A2): a cyclic aluminoxane having the structure represented by formula {-A1(E ² )-

0-}b, and

(A3): a linear aluminoxane having the structure represented by formula E ³ {- Al(E ³ )-0-} _c Al(E ³ ) ₂ , wherein

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; in the case where more than one E ¹ groups exist, the E ¹ groups may be the same or different from each other; and in the case where more than one G groups exist, 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):

(Bl): a boron compound represented by formula BQ^Q ³ ,

(B2): a borate compound represented by formula T ⁺ (BQ Q ⁵ Q ⁶ Q ⁷ ) ^" , and

(B3): a borate compound represented by formula (L-H) ⁺ (BQ ⁸ Q ⁹ Q ¹⁰ Q ⁿ ) ^" , wherein B represents a trivalent boron; Q ¹ , Q ² , Q ³ , Q ⁴ , Q ⁵ , Q ⁶ , Q ⁷ , Q ⁸ , Q ⁹ , Q ¹⁰ and Q ¹¹ are the same as or different from each other and each represent a halogen atom, a hydrocarbyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, a hydrocarbylsilyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a halogen atom as a substituent or a dihydrocarbylamino group having 2 to 20 carbon atoms which may have a halogen atom as a substituent; T ⁺ represents an inorganic or organic cation; and (L-H) ⁺ represents Broensted acid; and

compound (C): one or more borate compounds selected from the compound group consisting of the following compounds (CI) and (C2):

(CI): a borate compound represented by formula T ⁺ (BY ¹ Y ² Y ³ Y ⁴ ) ^" , and

(C2): a borate compound represented by formula (L-H) ⁺ (BYVY ⁷ Y ⁸ ) ^" , wherein

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

trihydrocarbylgermyl group or hydrogen; T ⁺ represents an inorganic or organic cation; and (L- H) ⁺ represents Broensted acid.

[0106]

In the compounds (Al) to (A3), 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. [0107]

E ² and E ³ may be an alkoxy group containing an electron-withdrawing group or an aryloxy group containing an electron- withdrawing group. For example, a substituent constant σ of the Hammett's rule is known as an index for electron-withdrawing properties. Examples of the electron-withdrawing group include functional groups whose substituent constant σ of the Hammett's rule is positive.

[0108]

Examples of the electron-withdrawing group include fluorine, chlorine, bromine and iodine atoms, and cyano, nitro, carbonyl, sulfone and phenyl groups.

[0109]

Examples of the alkoxy group containing an electron- withdrawing group in E ² and E ³ 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-pentaiodopropoxy, heptafluoropropoxy, heptachloropropoxy, heptabromopropoxy, heptaiodopropoxy, 2,2,2-trifluoro-l-trifluoromethylethoxy, 2,2,2-trichloro- 1 -trichloromethylethoxy, 2,2,2-tribromo- 1 -tribromomethylethoxy, 2,2,2-triiodo- 1 - triiodomethylethoxy, 1 , 1 -bis(trifluoromethyl)-2,2,2-trifluoroethoxy, 1 , 1 -bis(trichloromethyl)- 2,2,2-trichloroethoxy, 1 , 1 -bis(tribromomethyl)-2,2,2-tribromoethoxy, 1 , 1 -bis(triiodomethyl)- 2,2,2-triiodoethoxy, ΙΗ,ΙΗ-perfluorobutoxy, ΙΗ,ΙΗ-perfluoropentoxy, ΙΗ, ΙΗ- perfluorohexanoxy and ΙΗ,ΙΗ-perfluorooctanoxy groups. Preferable examples thereof include a l,l-bis(trifluoromethyl)-2,2,2-trifluoroethoxy group.

[0110]

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-chlorophenoxy, 3-chlorophenoxy, 4-chlorophenoxy, 2,3- dichlorophenoxy, 2,4-dichlorophenoxy, 2,5-dichlorophenoxy, 2,6-dichlorophenoxy, 3,4- dichlorophenoxy, 3,5-dichlorophenoxy, 2,3,4-trichlorophenoxy, 2,3,5-trichlorophenoxy, 2,3,6- trichlorophenoxy, 2,4,5-trichlorophenoxy, 2,4,6-trichlorophenoxy, 3,4,5-trichlorophenoxy,

2,3,4,5-tetrachlorophenoxy, 2,3,4,6-tetrachlorophenoxy, 2,3,5,6-tetrachlorophenoxy, 2,3,4,5,6- pentachlorophenoxy, 2,3,5,6-tetrachloro-4-trichloromethylphenoxy, 2-bromophenoxy, 3- bromophenoxy, 4-bromophenoxy, 2,3-dibromophenoxy, 2,4-dibromophenoxy, 2,5- dibromophenoxy, 2,6-dibromophenoxy, 3,4-dibromophenoxy, 3,5-dibromophenoxy, 2,3,4- tribromophenoxy, 2,3,5-tribromophenoxy, 2,3,6-tribromophenoxy, 2,4,5-tribromophenoxy, 2,4,6- tribromophenoxy, 3,4,5-tribromophenoxy, 2,3,4,5-tetrabromophenoxy, 2,3,4,6- tetrabromophenoxy, 2,3,5,6-tetrabromophenoxy, 2,3,4,5,6-pentabromophenoxy, 2,3,5,6- tetrabromo-4-tribromomethylphenoxy, 2-iodophenoxy, 3-iodophenoxy, 4-iodophenoxy, 2,3- diiodophenoxy, 2,4-diiodophenoxy, 2,5-diiodophenoxy, 2,6-diiodophenoxy, 3,4-diiodophenoxy, 3,5-diiodophenoxy, 2,3,4-triiodophenoxy, 2,3,5-triiodophenoxy, 2,3,6-triiodophenoxy, 2,4,5- triiodophenoxy, 2,4,6-triiodophenoxy, 3,4,5-triiodophenoxy, 2,3,4,5-tetraiodophenoxy, 2,3,4,6- tetraiodophenoxy, 2,3,5,6-tetraiodophenoxy, 2,3,4,5, 6-pentaiodophenoxy and 2,3,5,6-tetraiodo-4- tribromomethylphenoxy groups. Preferable examples thereof include 3,4,5-trifluorophenoxy and 2,3,4,5,6-pentafluorophenoxy groups.

[0111]

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.

Examples of the alkylaluminum dichloride include methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride and hexylaluminum dichloride. Examples of the dialkylaluminum hydride include dimethylaluminum hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride and dihexylaluminum hydride.

[0112]

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. Preferably, E ² and E ³ are each independently a methyl group, an isobutyl group or a 3,4,5- trifluorophenoxy group, b is 2 to 40, and C is 1 to 40.

[0113]

These 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. Further examples of the 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.

[0114]

In the compounds (Bl) to (B3), Q ¹ , Q ² , Q ³ , Q ⁴ , Q ⁵ , Q ⁶ , Q ⁷ , Q ⁸ , Q ⁹ , Q ¹⁰ and Q ¹¹ are preferably a halogen atom or a hydrocarbyl group having 1 to 20 carbon atoms which may have a halogen atom as a substituent. Examples of the inorganic cation 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, Ν,Ν-dialkylanilinium, dialkylammonium and triarylphosphonium.

[0115]

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.

[0116]

Examples of the borate compound (B2) represented by formula T ⁺ (BQ ⁴ Q ⁵ Q ⁶ Q ⁷ ) ^" include ferrocenium tetrakis(pentafluorophenyl)borate, Ι,Γ-bis-trimethylsilylferrocenium tetrakis(pentafluorophenyl)borate, silver tetrakis(pentafluorophenyl)borate, triphenylmethyl tetrakis(pentafluorophenyl)borate and triphenylmethyl tetrakis(3,5- bistrifluoromethylphenyl)borate.

[0117]

Examples of the borate compound (B3) represented by formula (L- H) ⁺ (BQ ⁸ Q ⁹ Q ¹⁰ Q ⁿ ) ^" include triethylammonium tetrakis(pentafluorophenyl)borate,

tripropylammonium tetrakis(pentafluorophenyl)borate, tri(normal butyl)ammonium

tetrakis(pentafluorophenyl)borate, tri(normal butyl)ammonium tetrakis(3,5- bistrifluoromethylphenyl)borate, N,N-bis-trimethylsilylanilinium

tetrakis(pentafluorophenyl)borate, Ν,Ν-dimethylanilinium tetrakis(pentafluorophenyl)borate, Ν,Ν-diethylanilinium tetrakis(pentafluorophenyl)borate, N,N-2,4,6-pentamethylanilinium tetrakis(pentafluorophenyl)borate, N,N-bis-trimethylsilylanilinium tetrakis(3,5- bistrifluoromethylphenyl)borate, diisopropylammonium tetrakis(pentafluorophenyl)borate, dicyclohexylammonium tetrakis(pentafluorophenyl)borate, triphenylphosphonium

tetrakis(pentafluorophenyl)borate, tri(methylphenyl)phosphonium

tetrakis(pentafluorophenyl)borate and tri(bis-trimethyIsilylphenyl)phosphonium

tetrakis(pentafluorophenyl)borate.

[0118]

In the compounds (CI) to (C2), 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. T ⁺ represents an inorganic or organic cation, and (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)(hydroxyphenyl)borate, tris(2,4-dimethylphenyl)(hydroxyphenyl)borate, tris(3,5-dimethylphenyl)(hydroxyphenyl)borate, tris(3,5-di-trifluoromethyl- phenyl)(hydroxyphenyl)borate, tris(pentafluorophenyl)(2-hydroxyethyl)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. In addition, 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, Ν,Ν-dialkylanilinium, dialkylammonium and triarylphosphonium.

[0119]

Examples of the borate compound (CI) represented by formula T ⁺ (BY ¹ Y ² Y ³ Y ⁴ ) ^" include ferrocenium tris(pentafluorophenyl)(4-hydroxyphenyl)borate, silver

tris(pentafluorophenyl)(4-hydroxyphenyl)borate and tnphenylmethyl tris(pentafluorophenyl)(4- hydroxypheny l)borate .

[0120]

Examples of the 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, N,N-2,4,6-pentamethylanilinium

tris(pentafluorophenyl)(4-hydroxyphenyl)borate, diisopropylammonium

tris(pentafluorophenyl)(4-hydroxyphenyl)borate, dicyclohexylammonium

tris(pentafluorophenyl)(4-hydroxyphenyl)borate, triphenylphosphonium

tris(pentafluorophenyl)(4-hydroxyphenyl)borate and tri(methylphenyl)phosphonium

tris(pentafluorophenyl)(4-hydroxyphenyl)borate.

[0121]

The compound (C) can be synthesized according to a method described in JP 1999-503113 A.

[0122]

(Carrier)

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.

Examples of the inorganic substance used as a carrier include inorganic oxide and magnesium compounds. For example, clay, clay mineral and zeolite may also be used. They may be mixed for use.

[0123]

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. Among these inorganic oxides, 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.

[0124]

Moreover, 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

dimethyldichlorosilane, diaryldichlorosilane such as diphenyldichlorosilane, alkyltrichlorosilane such as methyltrichlorosilane, aryltrichlorosilane such as phenyltrichlorosilane,

trialkylalkoxysilane such as trimethylmethoxysilane, triarylalkoxysilane such as

triphenylmethoxysilane, dialkyldialkoxysilane such as dimethyldimethoxysilane,

diaryldialkoxysilane such as diphenyldimethoxysilane, alkyltrialkoxysilane such as

methyltrimethoxysilane, aryltrialkoxysilane such as phenyltrimethoxysilane, tetraalkoxysilane such as tetramethoxysilane, alkyldisilazane such as 1,1,1,3,3,3-hexamethyldisilazane, tetrachlorosilane, or the like.

[0125]

Examples of the 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. Among them, magnesium halide or

alkoxymagnesium is preferable, and magnesium chloride or butoxymagnesium is more preferable.

[0126] 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. Among them, smectite, montmorillonite, hectorite, Laponite or saponite is preferable, and montmorillonite or hectorite is more preferable.

[0127]

Examples of the zeolite used as a carrier 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.

[0128]

The inorganic substance used as a carrier is preferably an inorganic oxide.

[0129]

These inorganic substances used as a carrier are preferably dried for use by heat treatment. 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.

[0130]

The average particle size of the carrier comprising the inorganic substance is preferably 5 to 1000 μπι, more preferably 10 to 500 μπι, even more preferably 10 to 100 μιη. 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.

[0131]

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.

[0132]

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.

[0133]

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, Ν,Ν-substituted amino, Ν,Ν-substituted aminooxy, Ν,Ν,Ν-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.

[0134]

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.

[0135]

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

copolymerizing this monomer with additional monomer(s) having one or more polymerizable unsaturated groups. Moreover, a polymerizable bridged monomer having two or more polymerizable unsaturated groups is preferably used as at least one of the additional monomers.

[0136]

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.

[0137]

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.

[0138]

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.

[0139]

Examples of the 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.

Moreover, examples of the polymerizable bridged monomer having two or more polymerizable unsaturated groups include divinylbenzene.

[0140]

The average particle size of the carrier comprising the organic polymer is preferably 5 to 1000 μπι, more preferably 10 to 500 μιη. 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.

[0141]

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

200°C, more preferably 70 to 150°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 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.

[0142]

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.

[0143]

The carrier is preferably an inorganic substance, more preferably an inorganic oxide, most preferably Si0 ₂ .

[0144]

(Catalyst for olefin oligomerization)

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.

[0145]

In the present invention, 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.

[0146]

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.

[0147]

Hereinafter, a case in which the activating co-catalytic component (A) and/or the activating co-catalytic component (B) are used as the activating co-catalytic component will be described.

[0148]

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.

Moreover, the partial or whole procedures of this contact may be performed in a reactor, to which the components may be added in any order without particular limitations.

[0149]

The carrier, the transition metal complex and the activating co-catalytic component are preferably brought into contact with each other in a solvent. Examples of 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 part by weight of the carrier.

[0150]

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. [0151]

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.

[0152]

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.

[0153]

Next, a case in which the activating co-catalytic component (C) is used as the activating co-catalytic component will be described.

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. Alternatively, of them, 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.

Moreover, the partial or whole procedures of this contact may be performed in a reactor, to which the components may be added in any order without particular limitations.

[0154]

The carrier, the transition metal complex, the activating co-catalytic component

(A) and the activating co-catalytic component (C) are preferably brought into contact with each other in a solvent. Examples of 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.

[0155]

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.

[0156]

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.

[0157]

<Method for producing a-olefin>

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.

[0158]

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

(methylene dichloride, chlorobenzene, etc.) as a solvent, oligomerization reaction in a slurry state, or oligomerizing gaseous ethylene.

[0159]

The oligomerization reaction of ethylene can be performed by any of batch, semi- continuous and continuous methods.

[0160]

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.

[0161]

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.

[0162]

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.

[0163]

When the oligomerization reaction is performed in a solvent, 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.

[0164]

<Catalytic component for olefin polymerization>

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. Any 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. Examples of the metallocene complexes 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. Preferable examples of 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.

In this context, 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.

[0165]

Examples of the catalytic component for polymerization include

methylene(cyclopentadienyl)(3 , 5-dimethyl-2-phenoxy)titanium dichloride,

isopropylidene(tetramethylcyclopentadienyl)(3 , 5-dimethyl-2-phenoxy)titanium dichloride, diphenylmethylene(fluorenyl)(3,5-dimethyl-2-phenoxy)titanium dichloride,

dimethylsilylene(cyclopentadienyl)(2-phenoxy)titanium dichloride,

dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-buty l-5-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(fluorenyl)(3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene(tert-butylamido)(cyclopentadienyl)titanium dichloride, diphenylmethylene(tert- butylamido)(cyclopentadienyl)titanium dichloride, dimethylsilylene(tert- butylamido)(cyclopentadienyl)titanium dichloride,

diphenylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,

diphenylsilylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,

methylenebis(cyclopentadienyl)zirconium dichloride, ethylenebis(indenyl)zirconium dichloride, methylenebis(indenyl)hafnium dichloride, bis(cyclopentadienyl)zirconium dichloride, bis(indenyl)zirconium dichloride and bis(fluorenyl)zirconium 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-buty l-5-methyl-2-phenoxy)titanium dichloride, dimethylsilylene(fluorenyl)(3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene(tert-butylamido)(cyclopentadienyl)titanium dichloride, diphenylmethylene(tert- butylamido)(cyclopentadienyl)titanium dichloride, dimethylsilylene(tert- butylamido)(cyclopentadienyl)titanium dichloride,

diphenylmethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,

diphenylsilylene(cyclopentadienyl)(fluorenyl)zirconium dichloride,

methylenebis(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.

[0166]

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).

[0167]

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. EXAMPLES

[0168]

The present invention will be described by way of Reference Examples, Examples and Comparative Examples.

<Production of transition metal complex>

Physical properties were measured in accordance the following methods.

(1) Proton nuclear magnetic resonance spectrum ('H-NMR)

Apparatus: EX270 manufactured by JEOL Ltd.

Sample cell: Tube (5 mm in diameter)

Measurement solvent: CDC1 ₃

Sample concentration: about 10 mg/0.5 mL (CDCI ₃ )

Measurement temperature: Room temperature (about 25°C)

Measurement parameter: Probe (5 mm in diameter), EXMOD NON, OBNUC 1H, accumulated number 16 times or more

Repeat time: ACQTM 6 seconds, PD 1 second

Internal standard: CDCI ₃ (7.26 ppm)

[0169]

(2) Carbon nuclear magnetic resonance spectrum ( ¹³ C-NMR)

Apparatus: EX270 manufactured by JEOL Ltd.

Sample cell: Tube (5 mm in diameter)

Measurement solvent: CDCI ₃

Sample concentration: about 30 mg/0.5 mL (CD01 ₃ )

Measurement temperature: Room temperature (about 25°C)

Measurement parameter: Probe (5 mm in diameter), EXMOD BCM, OBNUC ¹³ C, accumulated number 256 times or more

Repeat time: ACQTM 1.79 seconds, PD 1.21 seconds

Internal standard: CDC1 ₃ (77.0 ppm)

[0170]

(3) Mass spectrum

[Electron ionization mass spectrometry (EI-MS)]

Apparatus: JMS-T 100GC manufactured by JEOL Ltd.

Ionization voltage: 70 eV

Ion source temperature: 230°C Acceleration voltage: 7 kV

MASS RANGE: m/z 35-800

[0171]

[Reference Example 1]

"Synthesis of [l-tris(3,5-dimethylphenyl)silyl-2,3,4,5- tetramethylcyclopentadienyljtitanium trichloride (hereinafter, referred to as "complex 1")"

[0172]

"Synthesis of l-tris(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopent adiene" Under a nitrogen atmosphere, sodium hydride (0.49 g, 20.45 mmol in terms of sodium hydride) dispersed in mineral oil and tetrahydrofuran (23 mL) were mixed. This mixture was increased in temperature to 50°C and aniline (0.13 g, 1.36 mmol) was added and stirred at 50°C for one hour. To this, a solution dissolving l,2,3,4-tetramethylcyclopenta-l,3- diene (1.83 g, 15.00 mmol) in tetrahydrofuran (6 mL) was added dropwise and stirred at 50°C for 3.5 hours. This was cooled to 0°C. To this solution, a solution dissolving chlorotris(3,5- dimethylphenyl)silane (5.17 g, 13.64 mmol) in toluene (6 mL) was added dropwise and stirred at room temperature for 3 hours, and thereafter, stirred at 50°C for 22 hours. The resultant mixture was added dropwise at 0°C to a 10% aqueous sodium carbonate solution (40 mL).

Toluene (50 mL) was added to separate an organic phase, and the organic phase was washed with water (50 mL) twice and further washed with saturated 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 resultant solid substance was washed with a small amount of hexane and then dried under reduced pressure to obtain 1- tris(3,5-dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentad iene (1.49 g, yield 23.4%).

¹ H-NMR (CDC1 ₃ , 5 ppm): 1.54 (s, 6H), 1.60 (s, 6H), 2.27 (s, 18H), 3.73 (s, 1H), 6.98 (s, 3H), 7.17 (s, 6H)

Mass Spec (EI-MS, m/z): 464 (M ⁺ )

[0173]

" Synthesis of Complex 1 "

Under a nitrogen atmosphere, to a toluene solution (20 mL) of l-tris(3,5- dimethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadiene (0.93 g, 2.00 mmol) and triethylamine (1.01 g, 10.00 mmol), a 1.67 M hexane solution (1.32 mL, 2.20 mmol) of n-butyllithium was added dropwise at -78°C. After the mixture was gradually warmed to room temperature, the mixture was stirred at room temperature for 5 hours. The resultant mixture was cooled to -78°C and a solution dissolving titanium tetrachloride (0.42 g, 2.20 mmol) in toluene (2 mL) was added dropwise at the same temperature. After the mixture was gradually warmed to room

temperature, the mixture was stirred at room temperature overnight. After completion of the reaction, the solvent was removed under reduced pressure. Thereafter, the residue, to which heptane was added, was filtrated to remove insolubles. The solvent was removed from the filtrate under reduced pressure. Furthermore, the resultant residue, to which diethyl ether was added, was filtrated to remove insolubles. The solvent was removed from the filtrate under reduced pressure. Pentane was added and the mixture was cooled to -20°C The resultant solid substance was filtrated, washed with a small amount of pentane, and then dried under reduced pressure to obtain complex 1(0.03 g, yield 2.7%) as an orange solid.

¹ H-NMR (CDC1 ₃ , δ ppm): 2.03 (s, 6H), 2.27 (s, 18H), 2.36 (s, 6H), 7.06 (s, 3H), 7.20 (s, 6H) ^{1 3} C-NMR (CDCI ₃ , δ ppm): 14.52, 17.83, 21.41, 131.63, 132.93, 134.60, 137.03, 142.26, 146.34 Mass Spec (EI-MS, m/z): 616 (IVf )

[0174]

<Production of l-hexene>

(1) Trimerization activity

Analysis was conducted using gas chromatography (Shimadzu GC-2010, DB-1 column).

(2) Evaluation of fouling state

The fouling state was evaluated based on the amount of amorphous solids adhering to stirring blades after reaction. The fouling state was determined according to the criteria: a state in which amorphous solids adhered to the whole surface of the stirring blade (poor); a state in which amorphous solids adhered to the partial (more than half) surface of the stirring blade (fair); a state in which amorphous solids adhered to the partial (less than half) surface of the stirring blade (good); and a state in which few amorphous solids adhered to the stirring blade (excellent). The results are shown in Table 1.

[0175]

[Reference Example (preparation example of Si0 ₂ /MAO)]

Under a nitrogen atmosphere, 1 g of dried silica (Sylopol 948 manufactured by Grace Davison; 50% volume-average particle size = 55 μπι; pore volume = 1.67 ml/g; specific surface = 325 m /g) was weighed into a 200 mL flask, to which dehydrated toluene (15 mL) was then added. After the flask was cooled to 0°C in an ice bath, 3.5 mol/L MAO (manufactured by Tosoh Corp.) (5.0 mL, 17.5 mmol) diluted with toluene was gradually added over 30 minutes with stirring using a dropping funnel. After the dropwise addition, the mixture was heated to 95°C and stirred for 4 hours. After completion of the reaction, the mixture was cooled to room temperature and the supernatant was removed by decantation. Toluene (15 mL) was further added thereto and the mixture was stirred. Thereafter, the mixture was left standing and the supernatant was removed again by decantation. This washing procedure was performed three times. Finally, the resulting product was dried under reduced pressure at 100°C for 1 hour to obtain the intended solid (also referred to as Si0 ₂ /MAO). The yield was 1.2 g. The result of elemental analysis (wt%) was Si: 24% and Al: 19%.

[0176]

[Example 1]

An autoclave (0.4 liter) equipped with a stirrer was dried under reduced pressure and then purged with nitrogen. Toluene (90 mL) and a hexane solution (2.2 mL) of

triisobutylaluminum (TEBA) having a concentration of 0.93 mmol/mL were supplied. After the interior temperature of the system was elevated to 80°C, ethylene was introduced so that the partial pressure of ethylene might become 2.0 MPa, and the system was stabilized. 1.0 mL of a toluene solution (1 μιηοΙ/mL) of complex 1 was added thereto and 95.3 mg of Si0 ₂ /MAO obtained in Reference Example was subsequently added. A trimerization reaction of ethylene was performed at 80°C for 30 minutes while continuously supplying ethylene gas so as to maintain the total pressure at a constant value. After 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 subjected to filtration. 1-Hexene was obtained at an activity of 1.8 x 10 ⁶ g/mol complex/h and a polymer was obtained at an activity of 0.21 x 10 ⁶ g/mol complex/h.

[0177]

[Example 2]

Under a nitrogen atmosphere, toluene (5 mL) was added to a flask, complex 1 (2.5 μηιοΐ) and Si0 ₂ /MAO (247 mg) obtained in Reference Example were added and the mixture was stirred for 5 minutes. The solvent toluene was distilled off under reduced pressure to obtain a supported catalyst for olefin oligomerization.

An autoclave (0.4 liter) equipped with a stirrer was dried under reduced pressure and then purged with nitrogen. Toluene (90 mL) and a hexane solution (2.2 mL) of triisobutylaluminum (TIB A) having a concentration of 0.93 mmol/mL were supplied. After the interior temperature of the system was elevated to 80°C, ethylene was introduced so that the partial pressure of ethylene might become 2.0 MPa, and the system was stabilized. 152 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. 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 2.01 x 10 ⁶ g mol complex/h and a polymer was obtained at an activity of 0.34 x 10 ⁶ g/mol complex/h.

[0178]

[Example 3]

Under a nitrogen atmosphere, toluene (5 mL) was added to a flask, [l-tris(3,5- diethylphenyl)silyl-2,3,4,5-tetramethylcyclopentadienyl]tita nium trichloride (hereinafter, referred to as "complex 2") (2 μιηοΐ) and Si0 ₂ /MAO (183 mg) obtained in Reference Example were added and the mixture was stirred for 5 minutes The solvent toluene was distilled off under reduced pressure to obtain a supported catalyst for olefin oligomerization.

An autoclave (0.4 liter) equipped with a stirrer was dried under reduced pressure and then purged with nitrogen. Toluene (90 mL) and a hexane solution (2.2 mL) of

triisobutylaluminum (TIBA) having a concentration of 0.93 mmol/mL were supplied. After the interior temperature of the system was elevated to 80°C, ethylene was introduced so that the partial pressure of ethylene might become 2.0 MPa, and the system was stabilized. 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. 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 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.

[0179]

[Example 4]

Under a nitrogen atmosphere, toluene (5 mL) was added to a flask, complex 2 (0.2 μπιοΐ) and Si0 ₂ /MAO (210 mg) obtained in Reference Example were added and the mixture was stirred for 5 minutes. The solvent toluene was distilled off under reduced pressure to obtain a supported catalyst for olefin oligomerization.

An autoclave (0.4 liter) equipped with a stirrer was dried under reduced pressure and then purged with nitrogen. Toluene (90 mL) and a hexane solution (2.2 mL) of

triisobutylaluminum (TIB A) having a concentration of 0.93 mmol/mL were supplied. After the interior temperature of the system was elevated to 40°C, ethylene was introduced so that the partial pressure of ethylene might become 2.0 MPa, and the system was stabilized. 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.

[0180]

[Example 5]

Under a nitrogen atmosphere, toluene (5 mL) was added to a flask, complex 1 (0.2 μπιοΐ) and Si0 ₂ /MAO (194 mg) obtained in Reference Example were added and the mixture was stirred for 5 minutes. The solvent toluene was distilled off under reduced pressure to obtain a supported catalyst for olefin oligomerization.

An autoclave (0.4 liter) equipped with a stirrer was dried under reduced pressure and then purged with nitrogen. Toluene (90 mL) and a hexane solution (2.2 mL) of

triisobutylaluminum (TIB A) having a concentration of 0.93 mmol/mL were supplied. After the interior temperature of the system was elevated to 40°C, ethylene was introduced so that the partial pressure of ethylene might become 2.0 MPa, and the system was stabilized. 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.

[0181] [Example 6]

Under a nitrogen atmosphere, toluene (5 mL) was added to a flask, complex 1 (2 μπιοΐ) and Si0 ₂ MAO (220 mg) obtained in Reference Example were added and the mixture was stirred for 5 minutes. The solvent toluene was distilled off under reduced pressure to obtain a supported catalyst for olefin oligomerization.

An autoclave (0.4 liter) equipped with a stirrer was dried under reduced pressure and then purged with nitrogen. Heptane (90 mL) and a hexane solution (2.2 mL) of

triisobutylaluminum (TIBA) having a concentration of 0.93 mmol/mL were supplied. After the interior temperature of the system was elevated to 80°C, ethylene was introduced so that the partial pressure of ethylene might become 2.0 MPa, and the system was stabilized. 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. 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 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.

[0182]

[Example 7]

Under a nitrogen atmosphere, toluene (5 mL) was added to a flask, complex 1 (2 μπιοΐ) and Si0 ₂ /MAO (220 mg) obtained in Reference Example were added and the mixture was stirred for 5 minutes. The solvent toluene was distilled off under reduced pressure to obtain a supported catalyst for olefin oligomerization.

Dried NaCl (50 g) was placed in an autoclave (5 L), which was then purged with argon. The interior temperature was adjusted to 40°C and ethylene was supplied into the autoclave so that the partial pressure of ethylene might become 2.0 MPa. Next,

triisobutylaluminum (1 mmol) was added into the autoclave and the supported catalyst for olefin oligomerization (118 mg) obtained above was added to trimerize ethylene in gas-phase polymerization at 40°C for 60 minutes. After completion of the reaction, ethanol was added into the autoclave to terminate the reaction. The interior temperature of the autoclave was decreased to room temperature and toluene (60 mL) was further added under pressure. The autoclave was depressurized and then opened and the toluene solution remaining in the system was analyzed by gas chromatography. Further, a mixture of NaCl and a polymer was taken out and NaCl was removed by addition of water to the mixture. The obtained solid was dried by heating and the solid yield was then measured. As a result, 1-hexene was obtained at an activity of 3.6 x 10 ⁶ g/mol complex/h and a polymer was obtained at an activity of 0.18 x 10 ⁶ g/mol complex/h.

[0183]

[Comparative Example 1]

An autoclave (0.4 liter) equipped with a stirrer was dried under reduced pressure and then purged with nitrogen. Toluene (90 mL) and a toluene solution (0.35 mL) of methylaluminoxane (TMAO-s manufactured by Tosoh Finechem Corp.) having a Al concentration of 3.6 mmol/mL were supplied. After the interior temperature of the system was elevated to 80°C, ethylene was introduced so that the partial pressure of ethylene might become 2.0 MPa, and the system was stabilized. 0.25 mL of a toluene solution (1 μιηοΙ/mL) of complex 1 was added thereto. 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.

[0184]

[Table 1]

Evaluation of Fouling State

[0185]

INDUSTRIAL APPLICABILITY

Since 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.