CN1189506A - Catalysts for polymerization of Alpha-olefins, process for producing Alpha-olefin polymers, novel transition metal compounds and catalyst components for polymerization of Alpha-olefin - Google Patents

Abstract

The present invention relates to a catalyst for polymerization of alpha-olefin, which comprises: an essential component (A) of a transition metal compound, an essential component (B) of an ion exchangeable layer compound except for silicate or an inorganic silicate, and an optional component (C) of an organoaluminum compound, said component (A) being represented by the general formula (I).

Description

Catalyst for polymerization of α -olefins, process for producing α -olefin polymers, novel transition metal compounds and catalyst components for polymerization of α -olefins

The present invention relates to a catalyst for polymerizing α -olefins, a process for producing α -olefin polymers, a novel transition metal compound and a catalyst component for polymerizing α -olefins.

As the catalyst for polymerizing α -olefin, those comprising metallocene and aluminoxane have been proposed (Japanese patent application laid-open (KOKAI) No.60-35007, Japanese patent publication (KOKOKU) No.4-12283, etc.) however, since the above-mentioned catalysts are dissolved in the reaction solvent, the obtained polymer is particularly poor in properties in that the polymer has an irregular particle shape, has a low bulk density and contains a large amount of fine powder therein.

On the other hand, in order to solve the above-mentioned problems, there have been proposed catalysts obtained by supporting one or more of transition metals and organoaluminum compounds on inorganic oxides such as silica or alumina or other organic substances (Japanese patent application laid-open (KOKAI) Nos. 61-108610, 60-135408, 61-296008, 3-74412, 3-74415 and the like).

However, the polymers obtained using such catalysts contain a large amount of fine or coarse particles and impair their particle properties such as low bulk density. Further, there arise other problems that the catalyst is low in polymerization catalytic activity per unit weight of its solid component, and the obtained polymer has disadvantages such as a lower molecular weight or a lower stereoregularity as compared with that by using a catalyst which is not supported on a carrier.

The present invention aims to solve the above-mentioned problems in the prior art.

It is an object of the present invention to provide a catalyst for polymerizing α -olefin and producing a α -olefin polymer having not only a narrow composition distribution but also excellent transparency and mechanical strength, and a method for producing α -olefin polymer using said catalyst, the α -olefin polymer having no low properties such as low molecular weight or low stereoregularity caused by the catalyst supported on a carrier.

It is another object of the present invention to provide novel transition metal compounds and catalyst components (catalytically active components) for the polymerization α -olefins.

According to the results of the early studies of the present invention, it has been found that the above object can be easily achieved by using a catalyst comprising a specific transition metal compound and a specific ion-exchangeable layer compound or inorganic silicate.

In a first aspect of the invention, there is provided a catalyst for the polymerisation of α -olefins comprising:

a transition metal compound as a base component (A),

an essential component (B) of an ion-exchangeable layer compound other than a silicate or an inorganic silicate,

an optional organoaluminum compound component (C),

the component (A) is prepared fromFormula (I) represents:

wherein A is¹And A²Independently a conjugated 5-membered ring ligand, with the proviso that A¹And A²May be the same or different in one molecule, and A¹And A²Form a 7-to 10-membered fused ring comprising two adjacent carbon atoms of the conjugated 5-membered ring, the fused ring being formed by connecting two adjacent substituents on the conjugated 5-membered ring; q is A¹And A²The two conjugated 5-membered rings of (a) are bridging groups at any position of the 5-membered ring; m is a metal atom selected from elements belonging to groups 4-6 of the periodic Table of the elements; x and Y are independently a hydrogen atom, a halogen atom, a hydrocarbon group, an amino group, a halogenated hydrocarbon group, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, a phosphorus-containing hydrocarbon group or a silicon-containing hydrocarbon group.

In a second aspect of the present invention, there is provided a catalyst for the polymerisation of α -olefins comprising:

a transition metal compound as a base component (A),

an aluminumoxy compound as an essential component (D), which is an ionic compound capable of reacting with the component (A) to convert the component (A) into a cation or a Lewis acid, and

an optional fine particulate support component (E),

the component (A) is represented by the following general formula (II), (III), (IV), (V) or (VI) included in the above general formula (I): general formula (II)

Wherein R is¹、R²、R⁴And R⁵Independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms or a halogenated hydrocarbon group having 1 to 18 carbon atoms; r³And R⁶Independently is a saturated or unsaturated divalent hydrocarbon group of 3 to 10 carbon atoms, and R³And R⁶Respectively to each occurrence of R³And R⁶Form a fused ring together with two 5-membered rings, provided that R³And R⁶At least one of which has from 5 to 8 carbon atoms and forms a compound having at least one group derived from R³Or R⁶7 to 10 membered of the unsaturated bond ofA ring; r⁷And R⁸Independently a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms or a sulfur-containing hydrocarbon group having 1 to 20 carbon atoms, with the proviso that R⁷And R⁸At least one of which is a halogenated hydrocarbon group having 1 to 20 carbon atoms; m and n are independently integers from 0 to 20, provided that m and n are not both 0 at the same time; q is a bridging group of two 5-membered rings and is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a silylene or oligosilylene group which may have a hydrocarbon group or a halogenated hydrocarbon group of 1 to 20 carbon atoms, a germylene group which may have a hydrocarbon group or a halogenated hydrocarbon group of 1 to 20 carbon atoms; x and Y are independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms; m is a transition metal selected from the group consisting of elements belonging to groups 4 to 6 of the periodic Table of the elements. General formula (III)

Wherein R is¹、R²、R⁴、R⁵Q, X, Y and M have the same meaning as defined in formula (II) above; r⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵And R¹⁶Independently a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms; ar is an aryl group which may be substituted, provided that at least one of the two 7-membered rings is bonded to a halogenated hydrocarbon group having 1 to 20 carbon atoms. General formula (IV)

Wherein R is¹And R⁴Independently a hydrocarbyl group having 7 to 12 carbon atoms, a silicon-containing hydrocarbyl group having 8 to 18 carbon atoms, or a halogenated hydrocarbyl group having 7 to 12 carbon atoms; r²And R⁵Independently a hydrogen atom, having 1A hydrocarbon group of up to 10 carbon atoms, a silicon-containing hydrocarbon group of 1 to 18 carbon atoms, or a halogenated hydrocarbon group of 1 to 18 carbon atoms; r³And R⁶Independently is a saturated or unsaturated divalent hydrocarbon group having 3 to 10 carbon atoms, and R³And R⁶Respectively to each occurrence of R³And R⁶Form a fused ring together with two 5-membered rings, provided that R³And R⁶At least one of which has from 5 to 10 carbon atoms and forms a compound having at least one group derived from R³Or R⁶7 to 10 membered ring of unsaturated bond(s); r⁷And R⁸Independently a hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms or a sulfur-containing hydrocarbon group having 1 to 20 carbon atoms; m and n are independently an integer of 0 to 20, provided that m and n are not 0 at the same time, and when m or n is an integer of not less than 2, R⁷And R⁸May be bonded to each other to form a ring; q is a bridging group of two 5-membered rings and is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a silylene or oligosilylene group which may be substituted with a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms, or a germylene group which may be substituted with a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms; x and Y are independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms; m is a transition metal selected from the group consisting of elements belonging to groups 4 to 6 of the periodic Table of the elements. General formula (V)

Wherein R is¹And R⁴Independently a hydrocarbyl group having 7 to 12 carbon atoms, a silicon-containing hydrocarbyl group having 8 to 18 carbon atoms, or a halogenated hydrocarbyl group having 7 to 12 carbon atoms; r²And R⁵Independently a hydrogen atom, having 1A hydrocarbon group of up to 10 carbon atoms, a silicon-containing hydrocarbon group of 1 to 18 carbon atoms, or a halogenated hydrocarbon group of 1 to 18 carbon atoms; r³And R⁶Independently is a saturated or unsaturated divalent hydrocarbon group having 3 to 10 carbon atoms, and R³And R⁶Respectively to each occurrence of R³And R⁶Form a fused ring together with two 5-membered rings, provided that R³And R⁶At least one of which has from 5 to 10 carbon atoms and forms a compound having at least one group derived from R³Or R⁶7 to 10 membered ring of unsaturated bond(s); r⁷And R⁸Independently a hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, or a sulfur-containing hydrocarbon group having 1 to 20 carbon atoms; m and n are independently an integer of 0 to 20, provided that m and n are not 0 at the same time, and when m or n is an integer of not less than 2, R⁷And R⁸May be bonded to each other to form a ring; q is a bridging group of two 5-membered rings and is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a silylene or oligosilylene group which may be substituted with a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms, or a germylene group which may be substituted with a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms; x and Y are independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms; m is a transition metal selected from the group consisting of elements belonging to groups 4 to 6 of the periodic Table of the elements. General formula (VI)

Wherein R is¹、R²、R⁴And R⁵Independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms, or a halogenated hydrocarbon group having 1 to 18 carbon atoms; r³And R⁶Independently of each otherIs a saturated or unsaturated divalent hydrocarbon group having 3 to 10 carbon atoms, and R³And R⁶Respectively to each occurrence of R³And R⁶Form a fused ring together with two 5-membered rings, provided that R³And R⁶At least one of which has from 5 to 8 carbon atoms and forms a compound having at least one group derived from R³Or R⁶7 to 10 membered ring of unsaturated bond(s); r⁷And R⁸Independently is provided withA hydrocarbon group of 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, or a sulfur-containing hydrocarbon group having 1 to 20 carbon atoms; q is a silicon atom, a germanium atom or a tin atom; a is an unsaturated hydrocarbon group having 3 to 12 carbon atoms and forms a ring together with Q, wherein A and Q are bonded; r^aIs an unsaturated hydrocarbon group having 1 to 10 carbon atoms; m and n are independently an integer of 0 to 20, provided that m and n are not 0 at the same time, and when m or n is an integer of not less than 2, R⁷And R⁸May be bonded to each other to form a ring; 1 is an integer of 0 to 22, and when 1 is an integer of not less than 2, R^aMay be bonded to each other to form a ring; x and Y are independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms; m is a transition metal selected from the group consisting of elements belonging to groups 4 to 6 of the periodic Table of the elements.

The third aspect of the present invention provides a process for producing α -olefin polymer, which comprises contacting α -olefin with any one of the catalysts defined in the above first and second aspects to carry out the polymerization or copolymerization of α -olefin.

The fourth aspect of the present invention provides a novel transition metal compound represented by the above general formula (II).

The fifth aspect of the present invention provides a novel transition metal compound represented by the above general formula (III).

The sixth aspect of the present invention provides a novel transition metal compound represented by the above general formula (IV).

The seventh aspect of the present invention provides a novel transition metal compound represented by the above general formula (V).

An eighth aspect of the present invention provides a novel transition metal compound represented by the above general formula (VI).

The ninth aspect of the present invention provides a catalyst component for polymerizing α -olefin, comprising a transition metal compound represented by the above general formula (II).

The tenth aspect of the present invention provides a catalyst component for polymerizing α -olefin, comprising a transition metal compound represented by the above general formula (III).

An eleventh aspect of the present invention provides a catalyst component for polymerizing α -olefin, comprising a transition metal compound represented by the above general formula (IV).

The twelfth aspect of the present invention provides a catalyst component for polymerizing α -olefin, comprising a transition metal compound represented by the above general formula (V).

A thirteenth aspect of the present invention provides a catalyst component for polymerizing α -olefin, comprising a transition metal compound represented by the above general formula (VI).

The present invention is explained in detail below.

The catalyst for polymerizing α -olefin of the present invention comprises a specific transition metal compound (component A) as an essential component

The transition metal component A is explained first below. In the present invention, as the transition metal compound, those represented by the following general formula (I) can be used:

in the above general formula (I), A¹And A²For the conjugation of 5-membered ring ligands, with the proviso that A¹And A²May be the same or different in one molecule, and A¹And A²Form a 7-to 10-membered fused ring comprising two adjacent carbon atoms of the conjugated 5-membered ring, which is formed by connecting two adjacent substituents on the conjugated 5-membered ring. At the same time, from A¹And A²The conjugated 5-membered ring ligand represented may have a substituent bonded to a carbon atom in addition to the substituent bonded to the group Q.

A typical example of the above conjugated 5-membered ring ligand is cyclopentadienyl. The cyclopentadienyl group may be unsaturated, i.e. "C" having 4 hydrogen atoms₅H₄- "; or may be a substituted cyclopentadienyl group in which one or more hydrogen atoms are replaced by any of the substituents described above

Examples of the substituent are hydrocarbon groups having 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms. Specific examples of the hydrocarbon group may include methyl, ethyl, propyl, butyl, hexyl, octyl, phenyl, naphthyl, butenyl, butadienyl, triphenylhydrocarbon group, and the like.

The above hydrocarbon group may be a monovalent group bonded to the cyclopentadienyl group. Further, two substituents may be bonded to each other at their ends to form a fused ring. Typical examples of the cyclopentadienyl group having a condensed ring may include indene, fluorene, azulene, or derivatives thereof. Meanwhile, the transition metal compound used in the present invention is required to have at least one 7-to 10-membered ring as a fused ring, as described in detail below.

Examples of the substituent other than the above hydrocarbon group include hydrocarbon groups containing silicon, oxygen, nitrogen, phosphorus, boron, sulfur and the like. Typical examples of the hydrocarbon residue may include methoxy, ethoxy, phenoxy, furyl, trimethylsilyl, diethylamino, diphenylamino, pyrazolyl, indolyl, carbazolyl, dimethylphosphino, diphenylphosphino, diphenylboryl, dimethoxyboryl, thienyl, and the like.

Examples of the other substituent include halogen and a halogen-containing hydrocarbon group. Typical examples of the other substituent include a chlorine atom, a bromine atom, a fluorine atom, a trichloromethyl group, a trifluoromethyl group, a fluorophenyl group, a pentafluorophenyl group and the like.

Meanwhile, in the transition metal compound used in the present invention, a conjugated 5-membered ring ligand A¹And A²Has a 7-to 10-membered ring including two adjacent carbon atoms thereof, the fused ring being formed by connecting two adjacent substituents on the conjugated 5-membered ring. In other words, A¹And A²Must form a 7-to 10-membered fused ring comprising two adjacent carbon atoms of the conjugated 5-membered ring ligand.

Constitution A¹And A²Examples of the above ligand of at least one of the above groups may include hydroazulenyl, methylhydroazulenyl, ethylhydroazulenyl, dimethylhydroazulenyl, methylethylhydroazulenyl, methylisopropylhydroazulenyl, methylphenylisopropylhydroazulenyl, various hydrogenated azulenyl groups, bicyclo- [6.3.0]-undecyl, methyl-bicyclo- [6.3.0]-undecyl, ethyl-bicyclo- [6.3.0]-undecyl, phenyl-bicyclo- [6.3.0]-undecyl, methylphenyl-bicyclo- [6.3.0]-undecyl, ethylphenyl-bicyclo- [6.3.0]-undecyl, methyldiphenyl-bicyclo- [6.3.0]-undecyl, methyl-bicyclo- [6.3.0]Undecabdienyl, methylphenyl-bicyclo- [6.3.0]-undecenyl, ethylphenyl-bicyclo- [6.3.0]Undecabdienyl, methylisopropyl-bicyclo- [6.3.0]Undecenyl, bicyclo- [7.3.0]Dodecyl or derivatives thereof, bicyclo- [7.3.0]Dodecadienyl or derivatives thereof, bicyclo- [8.3.0]Tridecyl or derivatives thereof, bicyclo- [7.3.0]Tridecadienyl or a derivative thereof, and the like.

The above-mentioned groups may further have a substituent such as the above-mentioned hydrocarbon group, a hydrocarbon group containing silicon, oxygen, nitrogen, phosphorus, boron, sulfur and the like, a halogen or halogen-containing hydrocarbon group, and the like.

Q is A at any position of the 5-membered ring¹And A²Two bridging groups conjugated to a 5-membered ring. In other words, Q is a divalent group and functions to crosslink two conjugated 5-membered rings with each other. The type of bridging group is not particularly limited. Examples of the bridging group may include (a) a divalent hydrocarbon group or halogenated hydrocarbon group generally having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more specifically, an unsaturated divalent hydrocarbon group such as an alkylene group, cycloalkylene group, arylene group, haloalkylene group or halocycloalkylene group; (b) silylene or oligomeric silylene; (c) silylene or oligosilylene substituted with a hydrocarbon group or a halogenated hydrocarbon group generally having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms; (d) a germylene group; (e) germylene substituted with hydrocarbyl or halohydrocarbyl groups typically having 1 to 20 carbon atoms; and so on. Wherein, alkylene, arylene, methyleneSilyl groups, silylene groups substituted with hydrocarbyl groups or germylene groups substituted with hydrocarbyl or halogenated hydrocarbyl groups are preferred.

M represents a transition metal selected from the group consisting of elements belonging to groups 4 to 6 of the periodic Table. Among them, a group 4 transition metal such as titanium, zirconium or hafnium is preferable, and zirconium or hafnium is more preferable.

X and Y are independently a hydrogen atom, a halogen atom, a hydrocarbon group, an amino group, a halogenated hydrocarbon group, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, a phosphorus-containing hydrocarbon group or a silicon-containing hydrocarbon group. Each of the above hydrocarbon groups may generally have 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms. Specific examples of preferable X and Y may include methyl, isobutyl, phenyl, dimethylamino, diethylamino, and the like.

Some of the transition metal compounds represented by the above-mentioned general formula (I), i.e., the transition metal compounds represented by the following general formulae (II), (III), (IV), (V) and (VI), are novel compounds.

The novel transition metal compounds classified into the first class are explained below. The first type of transition metal compound is represented by the following general formula (II):

the novel transition metal compound represented by the general formula (II) includes a compound (a) wherein a substituent R is present when considering its relative position through a group Q¹、R²And R³And a 5-membered ring ligand having a substituent R⁴、R⁵And R⁶Is asymmetric with respect to a plane containing M, X and Y; and a compound (b) having a substituent R when considering its relative position through the group Q¹、R²And R³And a 5-membered ring ligand having a substituent R⁴、R⁵And R⁶Is asymmetric with respect to the plane containing M, X and Y.

To produce α -olefins having a high molecular weight and a high melting point, the above-mentioned compound (a), i.e., a compound in which two 5-membered rings do not have a real and specular image relationship with respect to a plane containing M, X and Y is preferably used.

In the general formula (II), R is as defined above¹、R²、R⁴And R⁵Independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms, or a silicon-containing halogenated hydrocarbon group having 1 to 18 carbon atoms.

Specific examples of the above hydrocarbon group having 1 to 10 carbon atoms include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclopentyl, cyclohexyl or methylcyclohexyl; alkenyl groups such as vinyl, propenyl or cyclohexenyl; aralkyl groups such as benzyl, phenethyl or phenylpropyl; arylalkenyl such as trans-styryl; aryl groups such as phenyl, tolyl, dimethylphenyl, ethylphenyl, trimethylphenyl, 1-naphthyl or 2-naphthyl; and so on.

Specific examples of the above silicon-containing hydrocarbon group having 1 to 18 carbon atoms include trialkylsilyl groups such as trimethylsilyl group, triethylsilyl group or t-butyldimethylsilyl group; triarylsilyl groups such as triphenylsilyl; (alkyl) (aryl) silyl groups such as dimethylphenylsilyl; alkylsilylalkyl groups such as bis (trimethylsilyl) methyl; and so on.

As the halogen atom contained in the above-mentioned halogenated hydrocarbon group having 1 to 18 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom can be used. When the halogen atom contained in the halogenated hydrocarbon group is a fluorine atom, the fluorine atom may be bonded to an arbitrary position of the hydrocarbon group. Specific examples of the halogenated hydrocarbon group may include fluoromethyl group, difluoromethyl group, trifluoromethyl group, chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl group, iodomethyl group, 2, 2, 2-trifluoroethyl group, 2, 2, 1, 1-tetrafluoroethyl group, pentafluoroethyl group, pentachloroethyl group, pentafluoropropyl group, nonafluorobutyl group, trifluorovinyl group, 1, 1-difluorobenzyl group, 1, 1, 2, 2-tetrafluorophenethyl group, o-, m-or p-fluorophenyl group, o-, m-or p-chlorophenyl group, o-, m-or p-bromophenyl group, 2, 4-, 3, 5-, 2, 6-or 2, 5-difluorophenyl group, 2, 4-, 3, 5-, 2, 6-or 2, 5-dichlorophenyl group, 2, 4, 6-trifluorophenyl group, 2, 4, 6-trichlorophenyl group, pentafluorophenyl group, Pentachlorophenyl group, 4-fluoronaphthyl group, 4-chloronaphthyl group, 2, 4-difluoronaphthyl group, heptafluoro-1-naphthyl group, heptachloro-1-naphthyl group, o-, m-, or p-trifluoromethylphenyl group, o-, m-, or p-trichlorotolyl group, 2, 4-, 3, 5-, 2, 6-, or 2, 5-bis (trifluoromethyl) phenyl group, 2, 4-, 3, 5-, 2, 6-, or 2, 5-bis (trichloromethyl) phenyl group, 2, 4, 6-tris (trifluoromethyl) phenyl group, 4-trifluoromethylnaphthyl group, 4-trichloromethylnaphthyl group, 2, 4-bis (trifluoromethyl) naphthyl group, and the like.

Wherein, for R¹And R⁴Hydrocarbon groups having 1 to 7 carbon atoms such as methyl, ethyl, propyl, butyl or benzyl are preferred,and for R²And R⁵Hydrogen atoms are preferred.

In the general formula (II), R³And R⁶Independently a saturated or unsaturated di-compound having 3 to 10 carbon atomsA monovalent hydrocarbon radical, and R³And R⁶Respectively to each occurrence of R³And R⁶Together form a fused ring. From R³Or R⁶The fused rings formed may be 5 to 12 membered rings. However, the essential requirement is that R³And R⁶At least one of which has from 5 to 10 carbon atoms and forms a compound having at least one group derived from R³Or R⁶7 to 10 membered ring of unsaturated bond(s). In this case, it is preferable that both the fused rings have 7 to 10 membered rings.

R³And R⁶Specific examples of (b) may include divalent saturated hydrocarbon groups such as a propylidene group, a butylidene group, a pentylidene group, a hexylidene group or a heptylidene group; divalent unsaturated hydrocarbon groups such as propenylene, 2-butenylene, 1, 3-butenylene, 1-pentenylene, 2-pentenylene, 1, 3-pentadienylene, 1, 4-pentadienylene, 1-hexenylene, 2-hexenylene, 3-hexenylene, 1, 3-hexadiene, 1, 4-hexadiene, 1, 5-hexadiene, 2, 4-hexadiene, 2, 5-hexadiene or 1, 3, 5-hexatriene; and so on. Among them, pentylene, 1, 3-pentadienylene, 1, 4-pentadienylene or 1, 3, 5-hexatrienylene is preferable, and 1, 3-pentadienylene or 1, 4-pentadienylene is particularly preferable.

In the general formula (II), R⁷And R⁸Independently a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, or a sulfur-containing hydrocarbon group having 1 to 20 carbon atoms. However, R is required⁷And R⁸At least one of which is a halogenated hydrocarbon group having 1 to 20 carbon atoms.

Specific examples of the above hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclopentyl, cyclohexyl or methylcyclohexyl; alkenyl groups such as vinyl, propenyl or cyclohexenyl; aralkyl groups such as benzyl, phenethyl or phenylpropyl; aralkenyl such as trans-styryl; aryl radicals such as the phenyl, tolyl, dimethylphenyl, ethylphenyl, trimethylphenyl, 1-or 2-naphthyl, acenaphthenyl, phenanthryl or anthracenyl radical; and so on. Among them, an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl or cyclopropyl and an aryl group having 6 to 12 carbon atoms such as phenyl, tolyl, dimethylphenyl, ethylphenyl, trimethylphenyl, 1-naphthyl or 2-naphthyl are preferable.

As the halogen atom contained in the above-mentioned halogenated hydrocarbon group having 1 to 20 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom can be used. When the halogen atom contained in the halogenated hydrocarbon group is a fluorine atom, the fluorine atom may be bonded to an arbitrary position of the hydrocarbon group. Specific examples of the halogenated hydrocarbon group may include fluoromethyl group, difluoromethyl group, trifluoromethyl group, chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl group, iodomethyl group, 2, 2, 2-trifluoromethyl group, 2, 2, 1, 1-tetrafluoroethyl group, pentafluoroethyl group, pentachloroethyl group, pentafluoropropyl group, nonafluorobutyl group, trifluorovinyl group, 1, 1-difluorobenzyl group, 1, 1, 2, 2-tetrafluorophenethyl group, o-, m-or p-fluorophenyl group, o-, m-or p-chlorophenyl group, o-, m-or p-bromophenyl group, 2, 4-, 3, 5-, 2, 6-or 2, 5-difluorophenyl group, 2, 4-, 3, 5-, 2, 6-or 2, 5-dichlorophenyl group, 2, 4, 6-trifluorophenyl group, 2, 4, 6-trichlorophenyl group, pentafluorophenyl group, Pentachlorophenyl group, 4-fluoronaphthyl group, 4-chloronaphthyl group, 2, 4-difluoronaphthyl group, heptafluoro-1-naphthyl group, heptachloro-1-naphthyl group, o-, m-, or p-trifluoromethylphenyl group, o-, m-, or p-trichlorotolyl group, 2, 4-, 3, 5-, 2, 6-, or 2, 5-bis (trifluoromethyl) phenyl group, 2, 4-, 3, 5-, 2, 6-, or 2, 5-bis (trichloromethyl) phenyl group, 2, 4, 6-tris (trifluoromethyl) phenyl group, 4-trifluoromethylnaphthyl group, 4-trichloromethylnaphthyl group, 2, 4-bis (trifluoromethyl) naphthyl group, and the like. Among them, a fluorinated hydrocarbon group or a chlorinated hydrocarbon group is preferable, and an o-, m-or p-fluorophenyl group, an o-, m-or p-chlorophenyl group and an o-, m-or p-trifluoromethylphenyl group are particularly preferable.

Specific examples of the above oxygen-containing hydrocarbon group having 1 to 20 carbon atoms include alkoxy groups such as methoxy, ethoxy, propoxy, cyclopropoxy or butoxy; aryloxy such as phenoxy, methylphenoxy, dimethylphenoxy or naphthoxy; aralkyloxy such as benzyloxy or naphthylmethoxy; oxygen-containing heterocyclic groups such as furyl; and so on.

Specific examples of the above nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms include alkylamino groups such as methylamino, dimethylamino, ethylamino, or diethylamino; arylamino groups such as phenylamino groups or diphenylamino groups; (alkyl) (aryl) amino such as (methyl) (phenyl) amino; nitrogen-containing heterocycles such as pyrazolyl or indolyl; and so on.

In the above general formula (II), m and n are independently an integer of 0 to 20, preferably 1 to 5. When m and/or n is an integer of 2 to 20, a plurality of R⁷And R⁸May be the same or different. The integers m and n are not 0 at the same time. In other words, the divalent group R³And/or R⁶Having the above-mentioned substituent R⁷Or R⁸And a substituent R⁷And/or R⁸A halogenated hydrocarbon group having 1 to 20 carbon atoms. Further, when m or n is not less than 2, R⁷Or R⁸May be bonded to each other to form another ring. Substituent R⁷Or R⁸Can be reacted with R³Or R⁶Bonded in arbitrary positions, but the substituent R⁷Or R⁸Preferably with R³Or R⁶To the carbon atom adjacent to the 5-membered ring (carbon atom at position α).

In the general formula (II), Q is a bridging group of two 5-membered rings, and is a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or an oligosilylene group which may have a hydrocarbon group or a halogenated hydrocarbon group of 1 to 20 carbon atoms, or a germylene group which may have a hydrocarbon group or a halogenated hydrocarbon group of 1 to 20 carbon atoms. When the silylene group or germylene group has two hydrocarbon groups or halogenated hydrocarbon groups, those groups may be bonded to each other to form a ring.

Specific examples of the group Q include an alkylene group such as a methylene group, a methylmethylene group, a dimethylmethylene group, a 1, 2-ethylene group, a 1, 3-propylene group, a 1, 4-butylene group, a 1, 2-cyclohexylene group or a 1, 4-cyclohexylene group; arylalkylene groups such as (methyl) (phenyl) methylene or diphenylmethylene; a silylene group; alkylsilylene such as methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (isopropyl) silylene or di (cyclohexyl) silylene; (alkyl) (aryl) silylene groups such as methylphenylsilylene or methylphenylsilylene; arylsilylene groups such as diphenylsilylene group; haloalkylsilylene groups such as bis (chloromethyl) silylene group or bis (2-chloroethyl) silylene group; (alkyl) (haloalkyl) silylene such as methyl (4' -chlorophenyl) silylene; a bis (haloalkyl) silylene group such as bis (4-chlorophenyl) silylene group or bis (3, 5-dichlorophenyl) silylene group; a germylene group; an alkylgermylene group obtained by substituting germanium for a silicon atom of the silylene group having the above hydrocarbon group of 1 to 20 carbon atoms; alkyl aryl germylene or aryl germylene, and the like. Among them, silylene group having a hydrocarbon group of 1 to 20 carbon atoms or germylene group having 1 to 20 carbon atoms is preferable, and alkylsilylene group, alkylarylsilylene group or arylsilylene group is particularly preferable.

In the general formula (II), X and Y are independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms.

As the halogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom can be used. As the above-mentioned hydrocarbon group having 1 to 20 carbon atoms and halogenated hydrocarbon group having 1 to 20 carbon atoms, the above-mentioned pair R is exemplified⁷And R⁸The same hydrocarbon groups and halogenated hydrocarbon groups are given.

Specific examples of the above silicon-containing hydrocarbon group include trialkylsilylmethyl groups such as trimethylsilylmethyl group or triethylsilylmethyl group; di (alkyl) (aryl) silylmethyl groups such as dimethylphenylsilylmethyl, diethylphenylsilylmethyl, dimethyltolylsilylmethyl; and so on.

Specific examples of the above-mentioned oxygen-containing hydrocarbon group having 1 to 20 carbon atoms may include alkoxy groups such as methoxy, ethoxy, propoxy, cyclopropoxy or butoxy; aryloxy such as phenoxy, methylphenoxy, dimethylphenoxy or naphthoxy; aralkyloxy such as benzyloxy or naphthylmethoxy; and so on.

Specific examples of the above nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms include alkylamino groups such as methylamino, dimethylamino, ethylamino, or diethylamino; arylamino groups such as phenylamino groups or diphenylamino groups; (alkyl) (aryl) amino such as (methyl) (phenyl) amino; and so on.

In the general formula (II), X and Y are preferably a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms. Among them, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms is more preferable. While particularly preferred X and Y are a chlorine atom, a methyl group, an isobutyl group, a phenyl group, a dimethylamino group and a diethylamino group.

In the general formula (II), M represents a transition metal selected from the group consisting of elements belonging to groups 4 to 6 of the periodic Table of the elements. Among them, a group 4 transition metal such as titanium, zirconium or hafnium is preferable. Zirconium or hafnium being more preferred

The novel transition metal compound represented by the general formula (II) can be produced by any method depending on the kind of the substituent or the bonding manner thereof. Generally, the transition metal compound can be produced by the following reaction scheme. At the same time, ` H ` in the reaction scheme₂R_a"and" H₂R_b"has the following chemical formula:

furthermore, metal salts of cyclopentadienyl compounds such as the above HR_aLi or HR_bLi can be produced by addition reaction of alkyl or aryl groups as described in European patent No. 697418. More specifically, the reaction of an alkyl lithium compound or aryl lithium compound with azulene derivatives in an inert solvent produces lithium salts of dihydroazulene derivatives. For the alkyl lithium compound, methyllithium, isopropyllithium, n-butyllithium, t-butyllithium may be used. For the aryl lithium compound, phenyl lithium, p-chlorophenyl lithium, p-fluorophenyl lithium, p-trifluoromethylphenyl lithium, naphthyl lithium, or the like can be used. Further, as the inert solvent, hexane, benzene, toluene, diethyl ether, tetrahydrofuran or a mixture thereof may be used.

The novel transition metal compounds classified in the second class are explained below. The second group of transition metal compounds isSpecific compounds within the first class are represented by the following general formula (III):

in the general formula (III), R¹、R²、R⁴、R⁵Q, X, Y and M have the same meaning as defined in formula (II) above; r⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵And R¹⁶Independently a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms. Ar represents aryl Ar. However, it is required that at least one of the two 7-membered rings is substituted with a halogenated hydrocarbon group having 1 to 20 carbon atoms. As the hydrocarbon group having 1 to 20 carbon atoms or the halogenated hydrocarbon group having 1 to 20 carbon atoms, the same hydrocarbon group and halogenated hydrocarbon group as defined in the general formula (II) can be cited. Specific examples of the aryl group may include phenyl, naphthyl, anthryl, phenanthryl, and the like. These aryl groups may be substituted with 1 to 5 halogen atoms or halogenated hydrocarbon groups.

The novel transition metal compounds classified in the third class are explained below. The third type of transition metal compound is represented by the following general formula (IV):

in the general formula (IV), R¹And R⁴Independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a silicon-containing hydrocarbon group having 1 to 7 carbon atoms, or a halogenated hydrocarbon group having 1 to 6 carbon atoms.

Examples of the above-mentioned hydrocarbon group having 1 to 6 carbon atoms may include an alkyl group such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, a n-hexyl group, a cyclopropyl group, a cyclopentyl group or a cyclohexyl group; alkenyl groups such as vinyl, propenyl or cyclohexenyl; a phenyl group; and so on.

The above silicon-containing hydrocarbon group having 1 to 7 carbon atoms may include trialkylsilyl groups such as trimethylsilyl, triethylsilyl or t-butyldimethylsilyl; alkylsilylalkyl groups such as bis (trimethylsilyl) methyl; and so on.

As the halogen atom contained in the above halogenated hydrocarbon group having 1 to 6 carbon atoms, the same halogen atoms as described in the above general formula (II) can be used. When the halogen atom contained in the halogenated hydrocarbon group is, for example, a fluorine atom, the halogenated hydrocarbon group is a group substituted with a fluorine atom at any position thereof. Specific examples of the halogenated hydrocarbon group may include fluoromethyl group, difluoromethyl group, trifluoromethyl group, chloromethyl group, dichloromethyl group, trichloromethyl group, bromomethyl group, dibromomethyl group, tribromomethyl group, iodomethyl group, 2, 2, 2-trifluoromethyl group, 2, 2, 1, 1-tetrafluoroethyl group, pentafluoroethyl group, pentachloroethyl group, pentafluoropropyl group, nonafluorobutyl group, trifluorovinyl group, o-, m-or p-fluorophenyl group, o-, m-or p-chlorophenyl group, o-, m-or p-bromophenyl group, 2, 4-, 3, 5-, 2, 6-or 2, 5-difluorophenyl group, 2, 4-, 3, 5-, 2, 6-or 2, 5-dichlorophenyl group, 2, 4, 6-trifluorophenyl group, 2, 4, 6-trichlorophenyl group, pentafluorophenyl group, pentachlorophenyl group, and the like.

Wherein, for R¹And R⁴A hydrocarbon group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group or a butyl group is preferable.

In the general formula (IV), R²And R⁵Independently a hydrogen atom, having 1 to 10 carbon atomsA hydrocarbon group, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms, or a halogenated hydrocarbon group having 1 to 18 carbon atoms. Substituent R²And R⁵Specific examples of (iii) may be the same as those described in the general formula (II).

In the general formula (IV), R³Is a saturated or unsaturated divalent hydrocarbon group having 3 to 10 carbon atoms and to which R is bonded³Together the 5-membered rings of (a) form a fused ring. Thus, from R³The fused ring formed is a 5 to 12 membered ring. R³Specific examples of (b) may include divalent saturated hydrocarbon groups such as a propylenemethyl group, a butylenyl group, a pentylene group or a hexylene group; divalent unsaturated hydrocarbon groups such as propenylene, 2-butenylene, 1, 3-butenylene, 1-pentenylene, 2-pentenylene, 1, 3-pentadienylene, 1, 4-pentadienylene, 1-hexenylene, 2-hexenylene, 3-hexenylene, 1, 3-hexadiene, 1, 4-hexadiene, 1, 5-hexadiene, 2, 4-hexadiene, 2, 5-hexadiene or 1, 3, 5-hexatriene; and so on. Among them, pentylene, 1, 3-pentadienylene, 1, 4-pentadienylene or 1, 3, 5-hexatrienylene is preferable. A group of a pentylene group,1, 3-pentadienylene or 1, 4-pentadienylene are more preferable. 1, 3-pentadienylene or 1, 4-pentadienylene are particularly preferred.

In other words, R³Preferably with a bond to R³C of which 5-membered rings together form a fused ring₅A divalent saturated or unsaturated hydrocarbon group. R³More preferably pentadienylene.

In the general formula (IV), R⁶Is a saturated or unsaturated divalent hydrocarbon group having 5 to 8 carbon atoms and bonded with R⁶Together the 5-membered rings of (a) form a fused ring. Thus, from R⁶The fused rings formed are 7 to 10 membered rings. R⁶Specific examples of (b) may include divalent saturated hydrocarbon groups such as pentylene or hexylene or heptylene; divalent unsaturated hydrocarbon radicals, e.g. 1-pentenylene, 2-pentenylene, 1, 3-pentadienylene, 1, 4-pentadienylene, 1-hexenylene, 2-hexenylene, 3-hexenylene, 1, 3-hexadiene, 1, 4-hexadiene, 1, 5-hexadiene, 2, 4-hexadiene, 2, 5-hexadiene or 1, 3, 5-hexadieneA hexatrienyl group; and so on. Among them, pentylene, 1, 3-pentadienylene, 1, 4-pentadienylene or 1, 3, 5-hexatrienylene is preferable. Pentylene, 1, 3-pentadienylene or 1, 4-pentadienylene are more preferred. 1, 3-pentadienylene or 1, 4-pentadienylene are particularly preferred.

In other words, R⁶Preferably with the linkage of R⁶C of which 5-membered rings together form a fused ring₅A divalent saturated or unsaturated hydrocarbon group. R⁶More preferably pentadienylene.

In the general formula (IV), R⁷And R⁸Independently a hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, or a sulfur-containing hydrocarbon group having 1 to 20 carbon atoms, with the proviso that at least one R⁸At R relative to the 5-membered ring⁶β -or a further position for R in formula (IV)⁷And R⁸The same groups as those described in the above general formula (II) may be used except for the halogenated hydrocarbon group.

In the above general formula (IV), m and n are independently an integer of 0 to 20, and n is an integer of 1 to 16. When m or n is an integer of not less than 2, R⁷Or R⁸May be bonded to each other to form a ring. m and n are preferably integers of 1 to 5, more preferably 2 to 5. When m and/or n is an integer of not less than 2, a plurality of R⁷(or a plurality of R⁸) May be the same or different. The bond R is not particularly limited⁷R of (A) to (B)³Position or bond R of⁸R of (A) to (B)³In addition to the above definition relates to R⁸Except that R is not in the bonding position of⁷Or R⁸Preferably with R³Or R⁶To the carbon atom adjacent to the 5-membered ring (i.e., the carbon atom at position α).

In the general formula (IV), Q is a bridging group of two 5-membered rings, and is a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or an oligosilylene group which may be substituted with a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms, or a germylene group which may be substituted with a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms. For Q of the general formula (IV), the same groups as those described in the general formula (II) can be used.

In the general formula (IV), X and Y are independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms. For X and Y of the formula (IV), the same groups as those described in the formula (II) can be used.

In the general formula (IV), M is a transition metal selected from the group consisting of elements belonging to groups 4 to 6 of the periodic Table of the elements. For M of the formula (IV), the same transition metals as those described in the formula (II) can be used.

The novel transition metal compound represented by the general formula (IV) can be produced in the same manner as that for the preparation of the transition metal compound represented by the general formula (II).

The novel transition metal compounds classified in the fourth class are explained below. The fourth type of transition metal compound is represented by the following general formula (V):

in the general formula (V), R¹And R⁴Independently a hydrocarbon group having 7 to 12 carbon atoms, a silicon-containing hydrocarbon group having 8 to 18 carbon atoms, or a halogenated hydrocarbon group having 7 to 12 carbon atoms. R is as defined above¹And R⁴Specific examples of (b) may include alkyl groups such as n-heptyl, 1, 2, 2-tetramethylpropyl, n-octyl, sec-octyl, n-nonyl or cyclohexylmethyl; alkenyl such as 1-heptenyl, 2-heptenyl or cyclohexenylmethyl; aralkyl such as benzyl, 1-phenylethyl or diphenylethyl; aryl radicals such as the o-, m-or p-tolyl radical or the 2, 5-xylyl radical; and so on.

Specific examples of the above silicon-containing hydrocarbon group having 8 to 18 carbon atoms may include trialkylsilyl groups such as tripropylsilyl group, tri-n-butylsilyl group or tri-tert-butylsilyl group; (alkyl) arylsilyl groups such as dimethylphenylsilyl or methyldiphenylsilyl; alkylsilylalkyl groups such as tris (trimethylsilyl) methyl; etc. of

As the halogen atom in the above halogenated hydrocarbon group having 7 to 12 carbon atoms, the same halogen atoms as described in the above general formula (II) can be used. When the halogen atom contained in the halogenated hydrocarbon group is, for example, a fluorine atom, the halogenated hydrocarbon group is a group substituted with a fluorine atom at any position thereof. Specific examples of the halogenated hydrocarbon group may include 1, 1-difluorobenzyl, 1, 2, 2-tetrafluorophenethyl, 4-fluoronaphthyl, 4-chloronaphthyl, 2, 4-difluoronaphthyl, heptafluoro-1-naphthyl, heptachloro-1-naphthyl, o-, m-, or p-trifluoromethylphenyl, o-, m-, or p-trichloromethylphenyl, 2, 4-, 3, 5-, 2, 6-, or 2, 5-bis (trifluoromethyl) phenyl, 2, 4-, 3, 5-, 2, 6-, or 2, 5-bis (trichloromethyl) phenyl, 2, 4, 6-tris (trifluoromethyl) phenyl, 4-trifluoromethylnaphthyl, 4-trichloromethylnaphthyl, 2, 4-bis (trifluoromethyl) naphthyl and the like.

Wherein, for R¹And R⁴Hydrocarbon groups such as n-heptyl, benzyl or 1-phenylethyl are preferred. Aralkyl groups such as benzyl or 1-phenylethyl are more preferred.

In the general formula (V), R²And R⁵Independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms, or a halogenated hydrocarbon group having 1 to 18 carbon atoms. For R in the formula (V)²And R⁵The same groups as those described in the above general formula (II) can be used,

in the general formula (V), R³And R⁶Independently a saturated or unsaturated divalent hydrocarbon radical having from 3 to 10 carbon atoms, and R³And R⁶Respectively to each occurrence of R³And R⁶Form a fused ring together with two 5-membered rings, provided that R³And R⁶At least one of which has from 5 to 10 carbon atoms and forms a compound having at least one group derived from R³Or R⁶7 to 10 membered ring of unsaturated bond(s). For R in the formula (V)³And R⁶The same groups as those described in the above general formula (II) can be used.

In the general formula (V), R⁷And R⁸Independently a hydrocarbon group having 1 to 20 carbon atoms, having 1 to 20An oxygen-containing hydrocarbon group of carbon atoms, an amino group, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, or a sulfur-containing hydrocarbon group having 1 to 20 carbon atoms. For R in the formula (V)⁷And R⁸The same groups as those described in the above general formula (II) may be used except for the halogenated hydrocarbon group.

In the above general formula (V), m and n are independently an integer of 0 to 20, preferably 1 to 5. When m and/or n is an integer of 2 to 20, a plurality of R⁷(or a plurality of R⁸) May be the same or different. However, in this case, m and n are not 0 at the same time. Further, when m or n is an integer of not less than 2, R⁷Or R⁸May be bonded to each other to form another ring. Substituent R⁷Or R⁸Can be reacted with R³Or R⁶Is bonded at an arbitrary position of (b), but the substituent R⁷Or R⁸Preferably with R³Or R⁶To the carbon atom adjacent to the 5-membered ring (carbon atom at position α).

In the above general formula (V), Q is a bridging group of two 5-membered rings, and represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group or an oligosilylene group which may be substituted with a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms, or a germylene group which may be substituted with a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms. For Q of the general formula (V), the same groups as those described in the general formula (II) can be used.

In the general formula (V), X and Y are independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms. For X and Y of the formula (V), the same groups as those described in the formula (II) can be used.

In the general formula (V), M is a transition metal selected from the group consisting of elements belonging to groups 4 to 6 of the periodic Table of the elements. For M of the formula (V), the same transition metals as those described in the formula (II) can be used.

The novel transition metal compound represented by the general formula (V) can be produced in the same manner as that for the preparation of the transition metal compound represented by the general formula (II).

The novel transition metal compounds classified in the fifth class are explained below. The fifth type of transition metal compound is represented by the following general formula (VI):

in the general formula (VI), R¹、R²、R⁴And R⁵Independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms, or a halogenated hydrocarbon group having 1 to 18 carbon atoms. For R of the formula (VI)¹、R²、R⁴And R⁵The same groups as those described in the general formula (II) may be used.

In the general formula (VI), R³And R⁶Independently a saturated or unsaturated di-compound having 3 to 10 carbon atomsA monovalent hydrocarbon radical, and R³And R⁶Respectively to each occurrence of R³And R⁶Form a fused ring together with two 5-membered rings, provided that R³And R⁶At least one of which has from 5 to 8 carbon atoms and forms a compound having at least one group derived from R³Or R⁶7 to 10 membered ring of unsaturated bond(s). For R in the formula (VI)³And R⁶The same groups as those described in the above general formula (II) may be used except for the halogenated hydrocarbon group.

In the general formula (VI), R⁷And R⁸Independently a hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, or a sulfur-containing hydrocarbon group having 1 to 20 carbon atoms. For R in the formula (VI)⁷And R⁸The same groups as those described in the above general formula (II) may be used except for the halogenated hydrocarbon group.

In the above general formula (VI), Q is a silicon atom, a germanium atom or a tin atom, with a silicon atom and a germanium atom being preferred.

In the above general formula (VI), A is a divalent unsaturated hydrocarbon group having 3 to 12 carbon atoms and forms a ring together with Q, wherein A and Q are bonded. Specific examples of such unsaturated hydrocarbon groups include divalent unsaturated hydrocarbon groups such as propenylene, butenylene, butadienylene, pentenylene, pentadienylene, hexenylene, hexadienylene, and hexatrienylene. Among them, a divalent hydrocarbon group having 3 to 5 carbon atoms such as propenylene, butenylene, butadienylene, or pentadienylene is preferable. Butadienylene is more preferred.

In the general formula (VI), R^aIs a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms. Specific examples of such unsaturated hydrocarbon groups include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, cyclopropyl or cyclopentyl; alkenyl groups such as vinyl, propenyl, butenyl, butadienyl, hexenyl, or hexadienyl; aralkyl groups such as benzyl, phenethyl or phenylpropyl; arylalkenyl such as trans-styryl; aryl groups such as phenyl, tolyl, dimethylphenyl, ethylphenyl, trimethylphenyl, 1-naphthyl or 2-naphthyl; and so on. Among them, methyl, ethyl, n-propyl, isopropyl, propenyl, or butenyl is preferable.

In the above general formula (VI), m and n are independently 0 to 20. m and n are preferably integers of 1 to 5. When m and/or n is an integer of 2 to 20, a plurality of R⁷(or a plurality of R⁸) May be the same or different. However, in this case, m and n are not 0 at the same time. Further, when m or n is an integer of not less than 2, R⁷Or R⁸May be bonded to each other to form another ring. The bond R is not particularly limited⁷R of (A) to (B)³Position or bond R of⁸R of (A) to (B)⁶Position of (2), but R⁷Or R⁸Preferably with R³Or R⁶Is bonded to a carbon atom adjacent to the 5-membered ring (i.e., the carbon atom at the α -position). when 1 is an integer of 0 to 22, it is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and when 1 is an integer of 2 to 22, a plurality of R's are bonded^aMay be the same or different. When 1 is an integer less than 2, R^aMay be bonded to each other to form a ring.

In the general formula (VI), X and Y are independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms. For X and Y of the formula (VI), the same groups as those described in the formula (II) can be used.

In the general formula (VI), M is a transition metal selected from the group consisting of elements belonging to groups 4 to 6 of the periodic Table of the elements. For M of the formula (VI), the same transition metals as those described in the formula (II) can be used.

The novel transition metal compound represented by the general formula (VI) can be produced in the same manner as that for the preparation of the transition metal compound represented by the general formula (II). In this case, QCl in the reaction scheme exemplifying the transition metal compound represented by the general formula (II)₂Represented by the following general formula:

specific examples of the transition metal compound include the following compounds, and further, although only chemical names of these compounds are given below, two compounds having symmetric and asymmetric steric structures as described above are also included. First, the nomenclature of these transition metal compounds is better understood. The structural formula of the zirconium chloride compound (1) is given below. It should be noted that the zirconium chloride compound may also be named "methylenebis {1, 1' - (2-methyl-4-phenyl-1, 4-dihydrooxazolyl) } zirconium dichloride" if the name derived from the compound having a 1, 4-dihydroazulene skeleton before the complexation is considered.

(1) Methylenebis {1, 1' - (2-methyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride; (2) methylenebis {1, 1' - (4-hydroazulenyl) } zirconium dichloride; (3) methylenebis {1, 1' - (2-methyl-4-hydroazulenyl) } zirconium dichloride; (4) methylenebis {1, 1' - (2, 4-dimethyl-4-hydroazulenyl) } zirconium dichloride; (5) methylenebis {1, 1' - (2-ethyl-4-hydroazulenyl) } zirconium dichloride; (6) methylenebis {1, 1' - (2-ethyl-4-methyl-4-hydroazulenyl) } zirconium dichloride; (7) methylenebis {1, 1' - (2-ethyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride; (8) methylenebis {1, 1' - (2, 4,4-trimethylazulenyl) } zirconium dichloride; (9) methylenebis {1, 1' - (2-methyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (10) methylenebis {1, 1' - (2-methyl-4-phenyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (11) methylenebis {1, 1' - (4-methyl-4-hydroazulenyl) } zirconium dichloride; (12) methylenebis {1, 1' - (4-phenyl-4-hydroazulenyl) } zirconium dichloride; (13) methylenebis {1, 1' - (4-isopropyl-4-hydroazulenyl) } zirconium dichloride; (14) methylenebis {1, 1' - (4-naphthyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride; (15) methylenebis {1, 1' - (2-phenyl-4-hydroazulenyl) } zirconium dichloride;(16) methylenebis {1, 1' - (2-benzyl-4-hydroazulenyl) } zirconium dichloride; (17) methylenebis {1, 1' - (2-styryl-4-hydroazulenyl) } zirconium dichloride; (18) methylenebis {1, 1' - (2-tert-butyl-4-hydroazulenyl) } zirconium dichloride; (19) methylenebis (1, 1' -cyclopentacyclooctenyl) zirconium dichloride; (20) methylenebis {1, 1' - (4-methylcyclopentaenocyclooctenyl) } zirconium dichloride; (21) methylenebis {1, 1' - (4-ethylcyclopentacyclooctenyl) } zirconium dichloride; (22) methylenebis {1, 1' - (4-phenylcyclopentacyclooctenyl) } zirconium dichloride; (23) methylenebis {1, 1' - (2-ethyl-4-phenylcyclopentacyclooctenyl) } zirconium dichloride; (24) methylenebis {1, 1' - (4-methyl-4, 5, 6, 7, 8-hexahydrocyclopentacyclooctenyl) } zirconium dichloride; (25) methylenebis (9-bicyclo [8.3.0 ]]Tridecan-2-methylpentene) zirconium dichloride; (26) methylenebis (9-bicyclo [8.3.0 ]]Tridecane-2, 12-dimethylpentenyl) zirconium dichloride; (27) methylenebis (9-bicyclo [8.3.0 ]]Tridecane-2, 12-dimethyloctahydropentenyl) zirconium dichloride; (28) methylenebis (9-bicyclo [8.3.0 ]]Tridecane-2-phenyl, 12-diethylpentenyl) zirconium dichloride; (29) ethylene bis {1, 1' - (4-hydroazulenyl) } zirconium dichloride; (30) ethylene bis {1, 1' - (2-methyl-4-hydroazulenyl) } zirconium dichloride; (31) ethylene bis {1, 1' - (2, 4-dimethyl-4-hydroazulenyl) } zirconium dichloride; (32) ethylene bis {1, 1' - (2-methyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride; (33) ethylene bis {1, 1' - (2-ethyl-4-hydroazulenyl) } zirconium dichloride; (34) ethylene bis {1, 1' - (2-ethyl-4-methyl-4-hydroazulenyl) } zirconium dichloride; (35) ethylene bis {1, 1' - (2-ethyl-4-phenyl-4-hydroazulenyl) } dichlorideZirconium; (36) ethylene bis (1, 1 '- (2, 4, 4-trimethylazulenyl) } zirconium dichloride, (37) ethylene bis {1, 1' - (2-methyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride, (38) ethylene bis {1, 1 '- (2-methyl-4-phenyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride, (39) ethylene bis {1, 1' - (4-methyl-4-hydroazulenyl) } zirconium dichloride, (40) ethylene bis {1, 1 '- (4-phenyl-4-hydroazulenyl) } zirconium dichloride, (41) ethylene bis {1, 1' - (4-isopropyl-4-hydroazulenyl) } zirconium dichloride, (42) ethylene bis {1, 1' - (4-naphthyl-4-hydroazulenyl) } zirconium dichloride; (43) ethylene bis {1, 1' - (2-phenyl-4-hydroazulenyl) } zirconium dichloride; (44) ethylene bis {1, 1' - (2-benzyl-4-hydroazulenyl) } zirconium dichloride;(45) ethylene bis {1, 1' - (2-styryl-4-hydroazulenyl) } zirconium dichloride; (46) ethylene bis {1, 1' - (2-tert-butyl-4-hydroazulenyl) } zirconium dichloride; (47) ethylenebis (1, 1' -cyclopentacyclooctenyl) zirconium dichloride; (48) ethylenebis {1, 1' - (4-methylcyclopentaenocyclooctenyl) } zirconium dichloride; (49) ethylenebis {1, 1' - (4-ethylcyclopentacyclooctenyl) } zirconium dichloride; (50) ethylenebis {1, 1' - (4-phenylcyclopentacyclooctenyl) } zirconium dichloride; (51) ethylene bis (1, 1 '- (2-ethyl-4-phenylcyclopentacyclooctenyl) } zirconium dichloride, (52) ethylene bis {1, 1' - (4-methyl-4, 5, 6, 7, 8, 9-hexahydrocyclopentacyclooctenyl) } zirconium dichloride, (53) ethylene bis (9-bicyclo [8.3.0 ]]Tridecan-2-methylpentene) zirconium dichloride; (54) ethylene bis (9-bicyclo [8.3.0 ]]Tridecane-2, 12-dimethylpentenyl) zirconium dichloride; (55) ethylene bis (9-bicyclo [8.3.0 ]]Tridecane-2, 12-dimethyloctahydropentenyl) zirconium dichloride; (56) ethylene bis (9-bicyclo [8.3.0 ]]Tridecane-2-phenyl, 12-ethylpentenyl) zirconium dichloride; (57) ethylene (1-indenyl) {1- (4-hydroazulenyl } zirconium dichloride, (58) ethylene {1- (2-methylindenyl) } {1- (2-methyl-4-hydroazulenyl) } zirconium dichloride, (59) ethylene {1- (2-methyl-4, 5-benzindenyl) } {1- (2, 4-dimethyl-4-hydroazulenyl) } zirconium dichloride, (60) ethylene {1- (2-methyl-4-phenylindenyl) } {1- (2-methyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride, (61) ethylene {1- (2-ethyl-4-phenylindenyl) } {1- (2-ethyl-4-hydroazulenyl) } zirconium dichloride, (62) ethylene {1- (2, 4-dimethylcyclopentaDienyl) } {1- (2-ethyl-4-methyl-4-hydroazulenyl) } zirconium dichloride; (63) ethylene {1- (2-methyl-4, 5-benzoindenyl) } {1- (2-ethyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride; (64) ethylene {1- (2-methyl-4-phenylindenyl) } {1- (2, 4, 4-trimethylazulenyl) } zirconium dichloride; (65) ethylene {1- (2-methyltetrahydroindenyl) } {1- (2-methyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (66) ethylene {1- (4-tert-butyl-2-methylcyclopentadienyl) } {1- (2-methyl-4-phenyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (67) ethylene {1- (2-ethyl-4-phenylindenyl) } {1- (4-methyl-4-hydroazulenyl) } zirconium dichloride;(68) ethylene {1- (2-phenylindenyl) } {1- (4-phenyl-4-hydroazulenyl) } zirconium dichloride; (69) ethylene {1- (2-propyl-4-phenylindenyl) } {1- (4-isopropyl-4-hydroazulenyl) } zirconium dichloride; (70) ethylene {1- (2-tert-butylindenyl) } {1- (4-naphthyl-4-hydroazulenyl) } zirconium dichloride; (71) dimethylmethylenebis {1, 1' - (4-hydroazulenyl) } zirconium dichloride; (72) dimethylmethylenebis {1, 1' - (2-methyl-4-hydroazulenyl) } zirconium dichloride; (73) dimethylmethylenebis {1, 1' - (2, 4-dimethyl-4-hydroazulenyl) } zirconium dichloride; (74) dimethylmethylenebis {1, 1' - (2-methyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride; (75) dimethylmethylenebis {1, 1' - (2-ethyl-4-hydroazulenyl) } zirconium dichloride; (76) dimethylmethylenebis {1, 1' - (2-ethyl-4-methyl-4-hydroazulenyl) } zirconium dichloride; (77) dimethylmethylenebis {1, 1' - (2-ethyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride; (78) dimethylmethylenebis {1, 1' - (2, 4, 4-trimethylazulenyl) } zirconium dichloride; (79) dimethylmethylenebis {1, 1' - (2-methyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (80) dimethylmethylenebis {1, 1' - (2-methyl-4-phenyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (81) dimethylmethylenebis {1, 1' - (4-methyl-4-hydroazulenyl) } zirconium dichloride; (82) dimethylmethylenebis {1, 1' - (4-phenyl-4-hydroazulenyl) } zirconium dichloride; (83) dimethylmethylenebis {1, 1' - (4-isopropyl-4-hydroazulenyl) } zirconium dichloride; (84) dimethylmethylenebis {1, 1' - (4-naphthyl-4-hydroazulenyl) } zirconium dichloride; (85) dimethylmethylenebis {1, 1' - (2-phenyl-4-hydroazulenyl) } zirconium dichloride; (86) dimethyl methylene bis {1, 1' - (2-benzyl-4-hydroazulenyl) } dichloroZirconium is treated; (87) dimethylmethylenebis {1, 1' - (2-styryl-4-hydroazulenyl) } zirconium dichloride; (88) dimethylmethylenebis {1, 1' - (2-tert-butyl-4-hydroazulenyl) } zirconium dichloride; (89) dimethylmethylenebis (1, 1' -cyclopentacyclooctenyl) zirconium dichloride; (90) dimethylmethylenebis {1, 1' - (4-methylcyclopentaenocyclooctenyl) } zirconium dichloride; (91) dimethylmethylenebis {1, 1' - (4-ethylcyclopentacyclooctenyl) } zirconium dichloride; (92) dimethylmethylenebis {1, 1' - (4-phenylcyclopentacyclooctenyl) } zirconium dichloride; (93) dimethylmethylenebis {1, 1' - (2-ethyl-4-phenylcyclopentacyclooctenyl) } zirconium dichloride; (94) dimethylmethylenebis {1, 1' - (4-methyl-4, 5, 6, 7, 8, 9-hexahydrocyclopentacyclooctenyl) } zirconium dichloride; (95) dimethylmethylenebis (9-bicyclo [8.3.0 ]]Tridecan-2-methylpentene) zirconium dichloride;(96) dimethylmethylenebis (9-bicyclo [8.3.0 ]]Tridecane-2, 12-dimethylpentenyl) zirconium dichloride; (97) dimethylmethylenebis (9-bicyclo [8.3.0 ]]Tridecane-2, 12-dimethyloctahydropentenyl) zirconium dichloride; (98) dimethylmethylenebis (9-bicyclo [8.3.0 ]]Tridecane-2-phenyl, 12-ethylpentenyl) zirconium dichloride; (99) dimethylmethylene (1-indenyl) {1- (4-hydroazulenyl } zirconium dichloride, (100) dimethylmethylene {1- (2-methylindenyl) } {1- (2-methyl-4-hydroazulenyl) } zirconium dichloride, (101) dimethylmethylene {1- (2-methyl-4, 5-benzindenyl) } {1- (2, 4-dimethyl-4-hydroazulenyl) } zirconium dichloride, (102) dimethylmethylene {1- (2-methyl-4-phenylindenyl) } {1- (2-methyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride, (103) dimethylmethylene {1- (2-ethyl-4-phenylindenyl) } {1- (2-ethyl-4-hydroazulenyl) } bis (zirconium dichloride) Zirconium chloride; (104) dimethylmethylene {1- (2, 4-dimethylcyclopentadienyl) } {1- (2-ethyl-4-methyl-4-hydroazulenyl) } zirconium dichloride; (105) dimethylmethylene {1- (2-methyl-4, 5-benzoindenyl) } {1- (2-ethyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride; (106) dimethylmethylene {1- (2-methyl-4-phenylindenyl) } {1- (2, 4, 4-trimethylazulenyl) } zirconium dichloride; (107) dimethylmethylene {1- (2-methyltetrahydroindenyl) } {1- (2-methyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (108) dimethylmethylene {1- (4-tert-butyl-2-methylcyclopentadienyl) } {1- (2-methyl-4-phenyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (109) dimethylmethylene {1- (2-ethyl-4-phenylindenyl) } {1- (4-methyl-4-hydroazulenyl) } zirconium dichloride; (110) dimethylmethylene {1- (2-phenylindenyl) } {1- (4-phenyl-4-hydroazulenyl)) zirconium dichloride; (111) dimethylmethylene {1- (2-propyl-4-phenylindenyl) } {1- (4-isopropyl-4-hydroazulenyl) } zirconium dichloride; (112) dimethylmethylene {1- (2-tert-butylindenyl) } {1- (4-naphthyl-4-hydroazulenyl) } zirconium dichloride;(113)2, 3-dibutylenebis {1, 1' - (2-methyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride; (114) dimethylsilylenebis {1, 1' - (4-hydroazulenyl) } zirconium dichloride; (115) dimethylsilylenebis {1, 1' - (2-methyl-4-hydroazulenyl) } zirconium dichloride; (116) dimethylsilylenebis {1, 1' - (2, 4-dimethyl-4-hydroazulenyl) } zirconium dichloride; (117) dimethylsilylenebis {1, 1' - (2-methyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride; (118) dimethylsilylenebis {1, 1' - (2-ethyl-4-hydroazulenyl) } zirconium dichloride; (119) dimethylsilylenebis {1, 1' - (2-ethyl-4-methyl-4-hydroazulenyl) } zirconium dichloride; (120) dimethylsilylenebis {1, 1' - (2-ethyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride; (121) dimethylsilylenebis {1, 1' - (2, 4, 4-trimethylazulenyl) } zirconium dichloride; (122) dimethylsilylenebis {1, 1' - (2-methyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (123) dimethylsilylenebis {1, 1' - (2-methyl-4-phenyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (124) dimethylsilylenebis {1, 1' - (4-methyl-4-hydroazulenyl) } zirconium dichloride; (125) dimethylsilylenebis {1, 1' - (4-phenyl-4-hydroazulenyl) } zirconium dichloride; (126) dimethylsilylenebis {1, 1' - (4-isopropyl-4-hydroazulenyl) } zirconium dichloride; (127) dimethylsilylenebis {1, 1' - (4-naphthyl-4-hydroazulenyl) } zirconium dichloride; (128) dimethylsilylenebis {1, 1' - (2-phenyl-4-hydroazulenyl) } zirconium dichloride; (129) dimethylsilylenebis {1, 1' - (2-benzyl-4-hydroazulenyl) } zirconium dichloride; (130) dimethylsilylenebis {1, 1' - (2-styryl-4-hydroazulenyl) } zirconium dichloride; (131) dimethylsilylenebis {1, 1' - (2-tert-butyl-4-hydroazulenyl) } zirconium dichloride; (132) dimethylsilylenebis (1, 1' -cyclopentanocyclooctan)Alkenyl) zirconium dichloride; (133) dimethylsilylenebis {1, 1' - (4-methylcyclopentanenyl) cyclooctenyl) } zirconium dichloride; (134) dimethylsilylenebis {1, 1' - (4-ethylcyclopentacyclooctenyl) } zirconium dichloride; (135) dimethylsilylenebis {1, 1' - (4-phenylcyclopentacyclooctenyl) } zirconium dichloride; (136) dimethylsilylenebis {1, 1' - (2-ethyl-4-phenylcyclopentacyclooctenyl) } zirconium dichloride; (137) dimethylsilylenebis {1, 1' - (4-methyl-4, 5, 6, 7, 8, 9-hexahydrocyclopentacyclooctenyl) } zirconium dichloride; (138) dimethylsilylenebis (9-bicyclo [8.3.0 ]]Tridecan-2-methylpentene) zirconium dichloride; (139) dimethylsilylenebis (9-bicyclo [8.3.0 ]]Tridecane-2, 12-dimethylpentenyl) dichlorideZirconium; (140) dimethylsilylenebis (9-bicyclo [8.3.0 ]]Tridecane-2, 12-dimethyloctahydropentenyl) zirconium dichloride; (141) dimethylsilylenebis (9-bicyclo [8.3.0 ]]Tridecane-2-phenyl, 12-ethylpentenyl) zirconium dichloride; (142) dimethylsilylene (1-indenyl) {1- (4-hydroazulenyl } zirconium dichloride, (143) dimethylsilylene {1- (2-methylindenyl) } {1- (2-methyl-4-hydroazulenyl) } zirconium dichloride, (144) dimethylsilylene {1- (2-methyl-4, 5-benzindenyl) } {1- (2, 4-dimethyl-4-hydroazulenyl) } zirconium dichloride, (145) dimethylsilylene {1- (2-methyl-4-phenylindenyl) } {1- (2-methyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride, (146) dimethylsilylene {1- (2-ethyl-4-phenylindenyl) } {1- (2-ethyl-4-hydroazulenyl) } zirconium dichloride, (146) dimethylsilylene {1- (2-ethyl-4-phenylindenyl) } zirconium dichloride Azulenyl) } zirconium dichloride; (147) dimethylsilylene {1- (2, 4-dimethylcyclopentadienyl) } {1- (2-ethyl-4-methyl-4-hydroazulenyl) } zirconium dichloride; (148) dimethylsilylene {1- (2-methyl-4, 5-benzoindenyl) } {1- (2-ethyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride; (149) dimethylsilylene {1- (2-methyl-4-phenylindenyl) } {1- (2, 4, 4-trimethylazulenyl) } zirconium dichloride; (150) dimethylsilylene {1- (2-methyltetrahydroindenyl) } {1- (2-methyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (151) dimethylsilylene {1- (4-tert-butyl-2-methylcyclopentadienyl) } {1- (2-methyl-4-phenyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (152) dimethylsilylene {1- (2-ethyl-4-phenylindenyl) } {1- (4-methyl-4-hydroazulenyl) } zirconium dichloride; (153) IIMethylsilylene {1- (2-phenylindenyl) } {1- (4-phenyl-4-hydroazulenyl) } zirconium dichloride; (154) dimethylsilylene {1- (2-propyl-4-phenylindenyl) } {1- (4-isopropyl-4-hydroazulenyl) } zirconium dichloride; (155) dimethylsilylene {1- (2-tert-butylindenyl) } {1- (4-naphthyl-4-hydroazulenyl) } zirconium dichloride;(156) (methyl) (phenyl) silylene bis {1, 1' - (4-hydroazulenyl) } zirconium dichloride; (157) (methyl) (phenyl) silylene bis {1, 1' - (2-methyl-4-hydroazulenyl) } zirconium dichloride; (158) (methyl) (phenyl) silylene bis {1, 1' - (2, 4-dimethyl-4-hydroazulenyl) } zirconium dichloride; (159) (methyl) (phenyl) silylenebis {1, 1' - (2-methyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride; (160) (methyl) (phenyl) silylene bis {1, 1' - (2-ethyl-4-hydroazulenyl) } zirconium dichloride; (161) (methyl) (phenyl) silylenebis {1, 1' - (2-ethyl-4-methyl-4-hydroazulenyl) } zirconium dichloride; (162) (methyl) (phenyl) silylenebis {1, 1' - (2-ethyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride; (163) (methyl) (phenyl) silylenebis {1, 1' - (2, 4, 4-trimethylazulenyl) } zirconium dichloride; (164) (methyl) (phenyl) silylene bis {1, 1' - (2-methyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (165) (methyl) (phenyl) silylenebis {1, 1' - (2-methyl-4-phenyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (166) diphenylsilylene bis {1, 1' - (4-hydroazulenyl) } zirconium dichloride; (167) diphenylsilylene bis {1, 1' - (2-methyl-4-hydroazulenyl) } zirconium dichloride; (168) diphenylsilylene bis {1, 1' - (2, 4-dimethyl-4-hydroazulenyl) } zirconium dichloride; (169) diphenylsilylene bis {1, 1' - (2-methyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride; (170) diphenylsilylene bis {1, 1' - (2-ethyl-4-hydroazulenyl) } zirconium dichloride; (171) diphenylsilylene bis {1, 1' - (2-ethyl-4-methyl-4-hydroazulenyl) } zirconium dichloride; (172) diphenylsilylene bis {1, 1' - (2-ethyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride; (173) diphenylsilylene bis {1, 1' - (2, 4, 4-trimethylazulenyl) } zirconium dichloride; (174) diphenylsilylene bis {1, 1' - (2-methyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (175) diphenylsilylene bis {1, 1' - (2-methyl-4-phenyl-4, 5, 6, 7, 8-pentahydroazulenyl) } dichlorideZirconium; (176) tetramethyldisilylenebis {1, 1' - (4-hydroazulenyl) } zirconium dichloride; (177) tetramethyldisilylenebis {1, 1' - (2-methyl-4-hydroazulenyl) } zirconium dichloride; (178) tetramethyldisilylenebis {1, 1' - (2, 4-dimethyl-4-hydroazulenyl) } zirconium dichloride; (179) tetramethyldisilylenebis {1, 1' - (2-methyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride;(180) tetramethyldisilylenebis {1, 1' - (2-ethyl-4-hydroazulenyl) } zirconium dichloride; (181) tetramethyldisilylenebis {1, 1' - (2-ethyl-4-methyl-4-hydroazulenyl) } zirconium dichloride; (182) tetramethyldisilylenebis {1, 1' - (2-ethyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride; (183) tetramethyldisilylenebis {1, 1' - (2, 4, 4-trimethylazulenyl) } zirconium dichloride; (184) tetramethyldisilylenebis {1, 1' - (2-methyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (185) tetramethyldisilylenebis {1, 1' - (2-methyl-4-phenyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (186) dimethylgermylidene bis {1, 1' - (4-hydroazulenyl) } zirconium dichloride; (187) dimethylgermylidene bis {1, 1' - (2-methyl-4-hydroazulenyl) } zirconium dichloride; (188) dimethylgermylidene bis {1, 1' - (2, 4-dimethyl-4-hydroazulenyl) } zirconium dichloride; (189) dimethylgermylidene bis {1, 1' - (2-methyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride; (190) dimethylgermylidene bis {1, 1' - (2-ethyl-4-hydroazulenyl) } zirconium dichloride; (191) dimethylgermylidene bis {1, 1' - (2-ethyl-4-methyl-4-hydroazulenyl) } zirconium dichloride; (192) dimethylgermylidene bis {1, 1' - (2-ethyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride; (193) dimethylgermylidene bis {1, 1' - (2, 4, 4-trimethylazulenyl) } zirconium dichloride; (194) dimethylgermylidene bis {1, 1' - (2-methyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (195) dimethylgermylidenebis {1, 1' - (2-methyl-4-phenyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (196) dimethylsilylenebis {1, 1' - (2-trifluoromethyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride; (197) dimethylsilylenebis {1, 1' - (2-ethyl-4-indolyl-4-hydroazulenyl) } zirconium dichloride; (198) dimethylsilylenebis {1, 1' - (2-ethyl-4-phenoxy-4-hydroazulenyl) } zirconium dichloride; (199) dimethylsilylene groupBis {1, 1' - (2-fluoro-4-pyrazolyl-4-hydroazulenyl) } zirconium dichloride; (200) dimethylsilylenebis {1, 1' - (2-methyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride; (201) cyclohexylidenebis {1, 1' - (2-methyl-4-furyl-4-hydroazulenyl) } zirconium dichloride; (202) dimethylsilylenebis {1, 1' - (2-benzyl-4-phenyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (203) dimethylsilylenebis {1, 1' - (2-benzyl-4- (4-chlorophenyl) -4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (204) dimethylsilylenebis {1, 1' - (2-benzyl-4- (4-fluorophenyl) -4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride;(205) dimethylsilylenebis {1, 1' - (2-benzyl-4- (1-naphthyl) -4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (206) dimethylsilylenebis {1, 1' - (2-benzyl-4- (2-naphthyl) -4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (207) dimethylsilylenebis {1, 1' - (2-benzyl-4-phenyl-7-isopropyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (208) dimethylsilylenebis [1, 1' - {2- (1-phenylethyl) -4-phenyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (209) dimethylsilylenebis [1, 1' - {2- (1-phenylethyl) -4-phenyl-7-isopropyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (210) 9-silafluorene-9, 9-diylbis {1, 1' - (2-methyl-4-phenyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (211) 1-silaindene-1, 1-diylbis {1, 1' - (2-methyl-4-phenyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (212) tetramethyl-1-silacyclopentadiene-1, 1-diylbis {1, 1' - (2-methyl-4-phenyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (213) 1-silacycle-3-pentene-1, 1-diylbis {1, 1' - (2-methyl-4-phenyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (214) dimethylmethylenebis {1, 1' - (2-methyl-4- (4-fluorophenyl) -4-hydroazulenyl) } zirconium dichloride; (215) dimethylmethylenebis {1, 1' - (2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl) } zirconium dichloride; (216) dimethylmethylenebis [1, 1' - (2-methyl-4- (4-trifluoromethylphenyl) -4-hydroazulenyl) } zirconium dichloride; (217) ethylene bis {1, 1' - (2-methyl-4- (4-fluorophenyl) -4-hydroazulenyl) } zirconium dichloride; (218) ethylene bis {1, 1' - (2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl) } zirconium dichloride; (219) Ethylene bis [1, 1' - (2-methyl-4- (4-trifluoromethylphenyl) -4-hydroazulenyl) } zirconium dichloride; (220) trimethylene bis {1, 1' - (2-methyl-4- (4-fluorophenyl) -4-hydroazulenyl) } zirconium dichloride; (221) trimethylene bis {1, 1' - (2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl) } zirconium dichloride; (222) trimethylene bis [1, 1' - (2-methyl-4- (4-trifluoromethylphenyl) -4-hydroazulenyl) } zirconium dichloride; (223) dimethylsilylenebis {1, 1' - (2-methyl-4-trifluoromethyl-4-hydroazulenyl }]Zirconium dichloride; (224) dimethylsilylenebis [1,' - (2-methyl-4- (2-fluorophenyl) -4-hydroazulenyl }]Dichloroation ofZirconium; (225) dimethylsilylenebis [1, 1' - (2-methyl-4- (3-fluorophenyl) -4-hydroazulenyl ] }]Zirconium dichloride; (226) dimethylsilylenebis [1, 1' - (2-methyl-4- (4-fluorophenyl) -4-hydroazulenyl ] }]Zirconium dichloride; (227) dimethylsilylenebis [1, 1' - (2-ethyl-4- (4-fluorophenyl) -4-hydroazulenyl ] }]Zirconium dichloride; (228) dimethylsilylenebis [1, 1' - (2-methyl-4- (2-chlorophenyl) -4-hydroazulenyl }]Zirconium dichloride; (229) dimethylsilylenebis [1, 1' - (2-methyl-4- (3-chlorophenyl) -4-hydroazulenyl }]Zirconium dichloride; (230) dimethylsilylenebis [1, 1' - (2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl }]Zirconium dichloride; (231) dimethylsilylenebis [1, 1' - (2-ethyl-4- (4-chlorophenyl) -4-hydroazulenyl }]Zirconium dichloride; (232) dimethylsilylenebis [1, 1' - (2-methyl-4- (2-trifluoromethylphenyl) -4-hydroazulenyl } group]Zirconium dichloride; (233) dimethylsilylenebis [1, 1' - (2-methyl-4- (3-trifluoromethylphenyl) -4-hydroazulenyl } group]Zirconium dichloride; (234) dimethylsilylenebis [1, 1' - (2-methyl-4- (4-trifluoromethylphenyl) -4-hydroazulenyl } group]Zirconium dichloride; (235) dimethylsilylenebis [1, 1' - (2-ethyl-4- (4-trifluoromethylphenyl) -4-hydroazulenyl ] }]Zirconium dichloride; (236) dimethylsilylenebis [1, 1' - (2-methyl-4- (2, 4-difluorophenyl) -4-hydroazulenyl }]Zirconium dichloride; (237) dimethylsilylenebis [1, 1' - (2-methyl-4- (2, 5-difluorophenyl) -4-hydroazulenyl }]Zirconium dichloride; (238) dimethylsilylenebis [1, 1' - (2-methyl-4- (2, 6-difluorophenyl) -4-hydroazulenyl }]Zirconium dichloride; (239) dimethylsilylenebis [1, 1' - (2-methyl-4- (3, 5-difluorophenyl) -4-hydroazulenyl }]Dichloro (phenyl) methaneZirconium is treated; (240) dimethylsilylene bis[1, 1' - (2-methyl-4- (2, 4, 6-trifluorophenyl) -4-hydroazulenyl } group]Zirconium dichloride; (241) dimethylsilylene [1- { 2-methyl-4- (4-fluorophenyl) -4-hydroazulenyl }][1- { 2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl } group]Zirconium dichloride; (242) dimethylsilylenebis [1, 1' - (2-methyl-4- (4-fluorophenyl) -6-isopropyl-4-hydroazulenyl }]Zirconium dichloride; (243) dimethylsilylenebis [1, 1' - (2, 8-dimethyl-4- (4-fluorophenyl) -4-hydroazulenyl ] }]Zirconium dichloride; (244) dimethylsilylenebis [1, 1' - (2-methyl-4- (4-chlorophenyl) -6-isopropyl-4-hydroazulenyl }]Zirconium dichloride; (245) dimethylsilylenebis [1, 1' - (2-methyl-4- (4-chlorophenyl) -7-isopropyl-4-hydroazulenyl }]Zirconium dichloride; (246) dimethylsilylenebis [1, 1' - (2, 8-dimethyl-4- (4-chlorophenyl) -4-hydroazulenyl }]Zirconium dichloride; (247) dimethylsilylenebis [1, 1' - (2-methyl-4- (4-trifluoromethylphenyl) -6-isopropyl-4-hydroazulenyl } group]Zirconium dichloride; (248) dimethylsilylenebis [1, 1' - (2-methyl-4- (4-trifluoromethylphenyl) -7-isopropyl-4-hydroazulenyl } group]Zirconium dichloride; (249) dimethylsilylenebis [1, 1' - (2-methyl-4- (4-fluorophenyl) -7-isopropyl-4-hydroazulenyl }]Zirconium dichloride; (250) dimethylsilylenebis [1, 1' - (2-ethyl-4- (4-chlorophenyl) -7-isopropyl-4-hydroazulenyl }]Zirconium dichloride; (251) dimethylsilylenebis [1, 1' - (2-ethyl-4- (4-fluorophenyl) -7-isopropyl-4-hydroazulenyl }]Zirconium dichloride; (252) dimethylsilylenebis [1, 1' - (2-ethyl-4- (4-trifluoromethylphenyl) -7-isopropyl-4-hydroazulenyl }]Zirconium dichloride; (253) dimethylsilylenebis [1, 1' - (2-ethyl-4- (4-chlorophenyl) -7-isopropyl-4-hydroazulenyl }]Zirconium dichloride; (254) dimethylsilylenebis [1, 1' - (2-ethyl-4- (4-fluorophenyl) -7-phenyl-4-hydroazulenyl }]IIZirconium chloride; (255) dimethylsilylenebis [1, 1' - (2-ethyl-4- (4-trifluoromethylphenyl) -7-phenyl-4-hydroazulenyl } group]Zirconium dichloride; (256) diphenylsilylene bis [1, 1' - (2-ethyl-4- (4-chlorophenyl) -7-isopropyl-4-hydroazulenyl }]Zirconium dichloride; (257) diphenylsilylene bis [1, 1' - (2-ethyl-4- (4-fluorophenyl) -7-isopropyl-4-hydroazulenyl }]Zirconium dichloride; (258) diphenylsilylene bis [1, 1' - (2-ethyl-4- (4-trifluoromethylphenyl) -7-isopropyl-4-hydroazulenyl }]Zirconium dichloride; (259) (methyl) (phenyl) methyleneSilyl bis [1, 1' - (2-ethyl-4- (4-chlorophenyl) -7-isopropyl-4-hydroazulenyl }]Zirconium dichloride; (260) (methyl) (phenyl) silylene bis [1, 1' - (2-ethyl-4- (4-fluorophenyl) -7-isopropyl-4-hydroazulenyl }]Zirconium dichloride; (261) (methyl) (phenyl) silylene bis [1, 1' - (2-ethyl-4- (4-trifluoromethylphenyl) -7-isopropyl-4-hydroazulenyl }]Zirconium dichloride; (262) dimethylsilylenebis [1, 1' - (2-ethyl-4- (4-chlorophenyl) -7-isopropyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (263) dimethylsilylenebis [1, 1' - (2-ethyl-4- (4-fluorophenyl) -7-isopropyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (264) dimethylsilylenebis [1, 1' - (2-ethyl-4- (4-trifluoromethylphenyl) -7-isopropyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (265) dimethylsilylene [1- { 2-ethyl-4- (4-chlorophenyl) -7-isopropyl-4-hydroazulenyl }]{1- (2-methyl-4, 5-benzoindenyl) } zirconium dichloride; (266) dimethylsilylene [1- { 2-ethyl-4- (4-fluorophenyl) -7-isopropyl-4-hydroazulenyl }]{1- (2-methyl-4, 5-benzoindenyl) } zirconium dichloride; (267) dimethylsilylene [1- { 2-ethyl-4- (4-trifluoromethylphenyl) -7-isopropyl-4-hydroazulenyl }]{1- (2-methyl-4, 5-benzoindenyl) } zirconium dichloride; (268) dimethylsilylene [1- { 2-ethyl-4- (4-chlorophenyl) -7-isopropyl-4-hydroazulenyl }]{1- (2-methyl-4-phenylindenyl) } zirconium dichloride; (269) dimethylsilylene [1- { 2-ethyl-4- (4-fluorophenyl) -7-isopropyl-4-hydroazulenyl }]{1-(2-methyl-4-phenylindenyl) } zirconium dichloride; (270) dimethylsilylene [1- { 2-ethyl-4- (4-trifluoromethylphenyl) -7-isopropyl-4-hydroazulenyl }]{1- (2-methyl-4-phenylindenyl) } zirconium dichloride; (271) dimethylsilylenebis [1, 1' - { 2-benzyl-4- (4-chlorophenyl) -4-hydroazulenyl }]Zirconium dichloride; (272) dimethylsilylenebis [1, 1' - { 2-benzyl-4- (4-fluorophenyl) -4-hydroazulenyl }]Zirconium dichloride; (273) dimethylsilylenebis [1, 1' - { 2-benzyl-4- (4-chlorophenyl) -7-isopropyl-4-hydroazulenyl }]Zirconium dichloride; (274) dimethylsilylenebis [1, 1' - { 2-benzyl-4- (4-fluorophenyl) -7-isopropyl-4-hydroazulenyl } group]Zirconium dichloride; (275) diphenylsilylene bis [1, 1' - { 2-benzyl-4- (4-chlorophenyl) -4-hydroazulenyl }]Zirconium dichloride; (276) diphenylsilylene bis [1, 1' - { 2-benzyl-4- (4-fluorophenyl) -4-hydroazuleneRadical }]Zirconium dichloride; (277) (methyl) (phenyl) silylene bis [1, 1' - { 2-benzyl-4- (4-chlorophenyl) -4-hydroazulenyl }]Zirconium dichloride; (278) (methyl) (phenyl) silylene bis [1, 1' - { 2-benzyl-4- (4-fluorophenyl) -4-hydroazulenyl }]Zirconium dichloride; (279) dimethylsilylenebis [1- { 2-benzyl-4- (4-chlorophenyl) -4-hydroazulenyl }]{1- (2-methyl-4, 5-benzoindenyl) } zirconium dichloride; (280) dimethylsilylene [1- { 2-benzyl-4- (4-fluorophenyl) -4-hydroazulenyl }]{1- (2-methyl-4, 5-benzoindenyl) } zirconium dichloride; (281) dimethylsilylene [1- { 2-benzyl-4- (4-chlorotolyl) -4-hydroazulenyl }]{1- (2-methyl-4-phenylindenyl) } zirconium dichloride; (282) dimethylsilylene [1- { 2-benzyl-4- (4-fluorophenyl) -4-hydroazulenyl }]{1- (2-methyl-4-phenylindenyl) } zirconium dichloride; (283) dimethylsilylene [1, 1' - {2, 8-dimethyl-4- (4-trifluoromethylphenyl) -4-hydroazulenyl } group]Zirconium dichloride; (284) dimethylsilylenebis [1, 1' - { 2-methyl-4- (4-fluoro-1-naphthyl) -4-hydroazulenyl }]Zirconium dichloride; (285) dimethylsilylenebis [1, 1' - { 2-methyl-4- (4-fluoro-2-naphthyl) -4-hydroazulenyl }]Dichloroation ofZirconium; (286) dimethylsilylenebis [1, 1' - { 2-methyl-4- (4-chloro-2-naphthyl) -4-hydroazulenyl }]Zirconium dichloride; (287) (methyl) (phenyl) silylene bis [1, 1' - { 2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl }]Zirconium dichloride; (288) (methyl) (phenyl) silylene bis [1, 1' - { 2-methyl-4- (4-trifluoromethylphenyl) -4-hydroazulenyl }]Zirconium dichloride; (289) diphenylsilylene bis [1, 1' - { 2-methyl-4- (4-fluorophenyl) -4-hydroazulenyl }]Zirconium dichloride; (290) diphenylsilylene bis [1, 1' - { 2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl }]Zirconium dichloride; (291) diphenylsilylene bis [1, 1' - { 2-methyl-4- (4-trifluoromethylphenyl) -4-hydroazulenyl }]Zirconium dichloride; (292) dimethylgermylidenebis [1, 1' - { 2-methyl-4- (4-fluorophenyl) -4-hydroazulenyl }]Zirconium dichloride; (293) dimethylgermylidenebis [1, 1' - { 2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl }]Zirconium dichloride; (294) dimethylgermylidene bis [1, 1' - { 2-methyl-4- (4-trifluoromethylphenyl) -4-hydroazulenyl }]Zirconium dichloride; (295) dimethylsilylene [1- { 2-methyl-4- (4-fluorophenyl) -4-hydroazulenyl }]{1- (2-methyl-4-hydroazulenyl) } zirconium dichloride; (296) dimethylsilylene [1- { 2-ethyl-4- (4-fluorophenyl) -4-dihydroazulenyl group}]{1- (2-ethyl-4-hydroazulenyl) } zirconium dichloride; (297) dimethylsilylene [1- { 2-methyl-4- (4-chlorophenyl) -4-dihydroazulenyl }]{1- (2-methyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride; (298) dimethylsilylene [1- { 2-methyl-4- (4-trifluoromethylphenyl) -4-dihydroazulenyl }]{1- (2-methyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride; (299) dimethylsilylene [1- { 2-methyl-4- (4-fluorophenyl) -4-dihydroazulenyl }]{1- (2-methyl-4-phenyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (300) dimethylsilylene [1- { 2-methyl-4- (4-fluorophenyl) -4-hydroazulenyl }]{1- (2-methyl-4- (4-fluorophenyl) -4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (301) dimethylsilylene [1- { 2-ethyl-4- (4-fluorophenyl) -4-hydroazulenyl }]{1- (2-ethyl-4-phenyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (302) dimethylsilylene [1- { 2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl }]{1- (2-methyl-4-phenyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (303) dimethylsilylene [1- { 2-methyl-4- (4-trifluoromethylphenyl) -4-hydroazulenyl }]{1- (2-methyl-4-phenyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (304) dimethylsilylene [1- { 2-methyl-4- (4-fluorophenyl) -4-hydroazulenyl }]{1- (2-methyl-4-phenylindenyl) } zirconium dichloride; (305) dimethylsilylene [1- { 2-ethyl-4- (4-fluorophenyl) -4-hydroazulenyl }]{1- (2-ethyl-4-phenylindenyl) } zirconium dichloride; (306) dimethylsilylene [1- { 2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl }]{1- (2-methyl-4-phenylindenyl) } zirconium dichloride; (307) dimethylsilylene [1- { 2-methyl-4- (4-trifluoromethylphenyl) -4-hydroazulenyl }]{1- (2-methyl-4-phenylindenyl) } zirconium dichloride; (308) dimethylsilylene [1- { 2-methyl-4- (4-trifluoromethylphenyl) -4-hydroazulenyl }]{1- (2-methyl-4, 5-benzoindenyl) } zirconium dichloride; (309) dimethylsilylene [1- { 2-methyl-4- (4-fluorophenyl) -4-hydroazulenyl }]{1- (2-methyl-4, 5-benzoindenyl) } zirconium dichloride; (310) dimethylsilylene [1- { 2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl }]{1- (2-methyl-4, 5-benzoindenyl) } zirconium dichloride; (311) dimethylsilylene [1- { 2-methyl-4- (4-chlorophenyl) -4, 5, 6, 7, 8-pentahydroazulenyl } group]{1- (2-methyl-4-phenylindenyl) } zirconium dichloride; (312) dimethylsilylene [1- { 2-methyl-4- (4-fluorophenyl) indenyl]]{1- (2-methyl-4-phenyl-4-Hydroazulenyl)) Zirconium dichloride; (313) dimethylsilylene [1- { 2-ethyl-4- (4-fluorophenyl) indenyl }]{1- (2-ethyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride; (314) dimethylsilylene [1- { 2-methyl-4- (4-chlorophenyl) indenyl }]{1- (2-methyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride; (315) dimethylsilylene [1- { 2-methyl-4- (4-trifluoromethylphenyl) indenyl }]{1- (2-methyl-4-Phenyl-4-hydroazulenyl) } zirconium dichloride; (316) dimethylsilylene [1- { 2-methyl-4- (4-trifluoromethylphenyl) indenyl }]{1- (2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl) } zirconium dichloride; (317) dimethylsilylenebis [1- { 2-methyl-4- (4-fluorophenyl) cyclopentacyclooctenyl } zirconium dichloride; (318) dimethylsilylenebis [1, 1' - { 2-ethyl-4- (4-chlorophenyl) cyclopentacyclooctenyl } zirconium dichloride; (319) dimethylsilylenebis [1, 1' - { 2-methyl-5- (4-trifluoromethylphenyl) cyclopentacyclooctenyl } zirconium dichloride; (320) 9-silafluorene-9, 9-diylbis {1, 1' - (2-methyl-4- (4-fluorophenyl) -4-hydroazulenyl) } zirconium dichloride; (321) 9-silafluorene-9, 9-diylbis {1, 1' - (2-methyl-4- (4-trifluoromethylphenyl) -4-hydroazulenyl) } zirconium dichloride; (322) 1-silaindene-1, 1-diylbis {1, 1' - (2-methyl-4- (4-fluorophenyl) -4-hydroazulenyl) } zirconium dichloride; (323) 1-silaindene-1, 1-diylbis {1, 1' - (2-methyl-4- (4-trifluoromethylphenyl) -4-hydroazulenyl) } zirconium dichloride; (324) tetramethyl-1-silacyclopentadiene-1, 1-diylbis [1, 1' - { 2-methyl-4- (4-fluorophenyl) -4-hydroazulenyl } group]Zirconium dichloride; (325) tetramethyl-1-silacyclopentadiene-1, 1-diylbis [1, 1' - { 2-methyl-4- (4-trifluoromethylphenyl) -4-hydroazulenyl } group]Zirconium dichloride; 326) 1-silacycle-3-pentene-1, 1-diylbis [1, 1' - (2-methyl-4- (4-fluorophenyl) -4-hydroazulenyl) } zirconium dichloride; (327) 1-silacycle-3-pentene-1, 1-diylbis [1, 1' - (2-methyl-4- (4-trifluoromethylphenyl) -4-hydroazulenyl) } zirconium dichloride; (328) (4-fluorophenyl) methylsilylene [1, 1' - (2-methyl-4- (4-fluorophenyl) -4-hydroazulenyl) } zirconium dichloride; (329) (4-chlorophenyl) methylsilylenebis [1, 1' - (2-methyl-4- (4-fluorophenyl) -4-hydroazulenyl) } zirconium dichloride; (330) (chloromethyl) methylsilylenebis [1, 1' - (2-methyl-4- (4-trifluoromethylphenyl) -4-hydroazulenyl) }Zirconium dichloride; (331) (4-fluorophenyl) methylsilylene [1, 1' - { 2-methyl4- (4-fluorophenyl) -4-hydroazulenyl }]{1- (2-ethyl-4-phenylindenyl }]Zirconium dichloride; (332) dimethylsilylenebis {1, 1' - (2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl) } zirconium dichloride; (333) dimethylsilylenebis {1, 1' - (2-ethyl-4-phenyl-7-isopropyl-4-hydroazulenyl) } zirconium dichloride; (334) dimethylsilylenebis {1, 1' - (2-propyl-4-phenyl-7-isopropyl-4-hydroazulenyl) } zirconium dichloride; (335) dimethylsilylenebis {1, 1' - (2-isopropyl-4-phenyl-7-isopropyl-4-hydroazulenyl) } zirconium dichloride; (336) dimethylsilylenebis {1, 1' - (2-phenyl-4-phenyl-7-isopropyl-4-hydroazulenyl) } zirconium dichloride; (337) dimethylsilylenebis {1, 1' - (2-trimethylsilylmethyl-4-phenyl-7-isopropyl-4-hydroazulenyl) } zirconium dichloride; (338) dimethylsilylenebis {1, 1' - (2-methyl-4- (1-naphthyl) -7-isopropyl-4-hydroazulenyl) } zirconium dichloride; (339) dimethylsilylenebis [1, 1' - { 2-methyl-4- (2-naphthyl) -7-isopropyl-4-hydroazulenyl } group]Zirconium dichloride; (340) dimethylsilylenebis [1, 1' - { 2-ethyl-4- (1-naphthyl) -7-isopropyl-4-hydroazulenyl } group]Zirconium dichloride; (341) dimethylsilylenebis [1, 1' - { 2-ethyl-4- (2-naphthyl) -7-isopropyl-4-hydroazulenyl }]Zirconium dichloride; (342) dimethylsilylenebis {1, 1' - (2-ethyl-4-phenyl-7-phenyl-4-hydroazulenyl) } zirconium dichloride; (343) dimethylsilylenebis [1, 1' - { 2-ethyl-4- (1-naphthyl) -7-phenyl-4-hydroazulenyl })]Zirconium dichloride; (344) dimethylsilylenebis [1, 1' - { 2-ethyl-4- (2-naphthyl) -7-phenyl-4-hydroazulenyl } group]Zirconium dichloride; (345) diphenylsilylene bis [1, 1' - { 2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl }]Dichloroation ofZirconium; (346) diphenylsilylene bis [1, 1' - (2-ethyl-4-phenyl-7-isopropyl-4-hydroazulenyl) } zirconium dichloride; (347) diphenylsilylene bis {1, 1' - (2-propyl-4-phenyl-7-isopropyl-4-hydroazulenyl) } zirconium dichloride; (348) diphenylsilylene bis {1, 1' - (2-isopropyl-4-phenyl-7-isopropyl-4-hydroazulenyl) } zirconium dichloride; (349) diphenylsilylene bis {1, 1' - (2-phenyl-4-phenyl-7-isopropyl-4-hydroazulenyl) } zirconium dichloride; (350) diphenylsilylene bis {1, 1' - (2-trimethylsilylmethyl-4-phenyl-7-isopropyl-4-hydroazulenyl) } zirconium dichloride; (351) diphenylsilyleneYylbis [1, 1' - { 2-ethyl-4- (1-naphthyl) -7-isopropyl-4-hydroazulenyl } ]]Zirconium dichloride; (352) diphenylsilylene bis [1, 1' - { 2-methyl-4- (2-naphthyl) -7-isopropyl-4-hydroazulenyl }]Zirconium dichloride; (353) (methyl) (phenyl) silylenebis [1, 1' - (2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl) } zirconium dichloride; (354) (methyl) (phenyl) silylenebis {1, 1' - (2-ethyl-4-phenyl-7-isopropyl-4-hydroazulenyl) } zirconium dichloride; (355) (methyl) (phenyl) silylene bis [1, 1' - { 2-ethyl-4- (1-naphthyl) -7-isopropyl-4-hydroazulenyl }]Zirconium dichloride; (356) (methyl) (phenyl) silylene bis {1, 1' - (2-ethyl-4- (2-naphthyl) -7-isopropyl-4-hydroazulenyl }]Zirconium dichloride; (357) dimethylsilylenebis {1, 1' - (2-methyl-4-phenyl-7-isopropyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (358) dimethylsilylenebis {1, 1' - (2-ethyl-4-phenyl-7-isopropyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (359) dimethylsilylenebis {1, 1' - (2-ethyl-4- (1-naphthyl) -7-isopropyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (360) dimethylsilylenebis [1, 1' - { 2-ethyl-4- (2-naphthyl) -7-isopropyl-4, 5, 6, 7, 8-pentaHydrogen azulenyl group }]Zirconium dichloride; (361) dimethylsilylene {1- (2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl) } {1- (2-methyl-4, 5-benzoindenyl) } zirconium dichloride; (362) dimethylsilylene {1- (2-ethyl-4-phenyl-7-isopropyl-4-hydroazulenyl) } {1- (2-methyl-4, 5-benzoindenyl) } zirconium dichloride; (363) dimethylsilylene {1- (2-ethyl-4- (1-naphthyl) -7-isopropyl-4-hydroazulenyl) } {1- (2-methyl-4, 5-benzoindenyl) } zirconium dichloride; (364) dimethylsilylene {1- (2-ethyl-4- (2-naphthyl) -7-isopropyl-4-hydroazulenyl) } {1- (2-methyl-4, 5-benzoindenyl) } zirconium dichloride; (365) dimethylsilylene {1- (2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl) } {1- (2-methyl-4-phenylindenyl) } zirconium dichloride; (366) dimethylsilylene {1- (2-ethyl-4-phenyl-7-isopropyl-4-hydroazulenyl }]{1- (2-methyl-4-phenylindenyl) } zirconium dichloride; (367) dimethylsilylene {1- (2-ethyl-4- (1-naphthyl) -7-isopropyl-4-hydroazulenyl } group]{1- (2-methyl-4-phenylindenyl) } zirconium dichloride; (368) dimethylsilylene {1- (2-ethyl-4- (2-naphthyl) -7-isopropyl-4-hydroazulenyl } group]{1- (2-methyl-4-benzene)Indenyl) } zirconium dichloride; (369) methylenebis [1, 1' - { 2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl }]Zirconium dichloride; (370) methylenebis [1, 1' - { 2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl }]Zirconium dichloride; (371) methylenebis [1, 1' - { 2-methyl-6-isopropyl-4-hydroazulenyl }]Zirconium dichloride; (372) methylenebis {1, 1' - (2-ethyl-4, 7-diisopropyl-4, 5, 6, 7, 8-pentahydroazulenyl }]Zirconium dichloride; (373) methylenebis {1, 1' - (4, 6-dimethylcyclopentacyclooctenyl) } zirconium dichloride; (374) methylenebis {1, 1' - (4-methyl-6-isopropylcyclopentacyclooctenyl)]Zirconium dichloride; (375) methylenebis {1, 1' - (2-methyl-5-phenylcyclopentacyclooctenyl) } zirconium dichloride; (376) ethylene bis {1, 1' - (2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl) } zirconium dichloride; (377) ethylene bis {1, 1' - (2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl) } zirconium dichloride; (378) ethylene bis {1, 1' - (2-methyl-6-isopropyl-4-hydroazulenyl) } zirconium dichloride; (379) ethylene bis {1, 1' - (2-ethyl-4, 7-diisopropyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride;(380) ethylenebis {1, 1' - (4, 6-dimethylcyclopentacyclooctenyl) } zirconium dichloride; (381) ethylenebis {1, 1' - (4-methyl-6-isopropylcyclopentacyclooctenyl) } zirconium dichloride; (382) ethylenebis {1, 1' - (4-methyl-5-phenylcyclopentacyclooctenyl) } zirconium dichloride; (383) ethylene { (1- (2, 4, 7-trimethylindenyl) } {1- (2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl) } zirconium dichloride, (384) ethylene { (1- (2-ethyl-4, 5-benzindenyl) } {1- (2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl) } zirconium dichloride, (385) dimethylmethylenebis {1, 1 '- (2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl) } zirconium dichloride, (386) dimethylmethylenebis {1, 1' - (2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl) } zirconium dichloride, (387) dimethylmethylenebis Bis {1, 1' - (2-methyl-6-isopropyl-4-hydroazulenyl) } zirconium dichloride; (388) dimethylmethylenebis {1, 1' - (2-ethyl-4, 7-diisopropyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (389) dimethylmethylenebis {1, 1' - (4, 6-dimethylcyclopentano-cyclooctenyl }]Zirconium dichloride; (390) dimethylmethylenebis {1, 1' - (4-methyl-6-isopropylcyclopentacycloocteneRadical }]Zirconium dichloride; (391) dimethylmethylenebis {1, 1' - (2-methyl-5-phenylcyclopentacyclooctenyl }]Zirconium dichloride; (392) dimethylmethylene { (1- (2, 4, 7-trimethylindenyl) } {1- (2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl } methyl-ethyl-methyl-4-methyl-ethyl-methyl-4-hydroazulenyl-methyl-ethyl-methyl-ethyl-methyl]Zirconium dichloride; (393) dimethylmethylene { (1- (2-ethyl-4, 5-benzindenyl) } {1- (2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl) } zirconium dichloride, (394) dimethylsilylenebis {1, 1 ' - (2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl) } zirconium dichloride, (395) dimethylsilylenebis {1, 1 ' - (2-methyl-6-isopropyl-4-hydroazulenyl) } zirconium dichloride, (396) dimethylsilylenebis {1, 1 ' - (2-ethyl-4, 7-diisopropyl-4-hydroazulenyl) } zirconium dichloride, (397) dimethylsilylenebis {1, 1' - (4, 6-dimethylcyclopentano-cyclooctenyl) }]Zirconium dichloride; (398) dimethylsilylenebis {1, 1' - (4-methyl-6-isopropylcyclopentacyclooctenyl })]Zirconium dichloride;(399) dimethylsilylenebis {1, 1' - (2-methyl-5-phenylcyclopentacyclooctenyl }]Zirconium dichloride; (400) dimethylsilylene { (1- (2, 4, 7-trimethylindenyl) } {1- (2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl }]Zirconium dichloride; (401) dimethylsilylene { (1- (2-ethyl-4, 5-benzindenyl) } {1- (2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl) } zirconium dichloride, (402) (methyl) (phenyl) silylene bis {1, 1 ' - (2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl) } zirconium dichloride, (403) (methyl) (phenyl) silylene bis {1, 1 ' - (2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl) } zirconium dichloride, (404) diphenylsilylene bis {1, 1 ' - (2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl) } zirconium dichloride, (405) tetramethylbissilylene Silylene bis {1, 1' - (2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl) } zirconium dichloride; (406) tetramethyldisilylenebis {1, 1' - (2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl) } zirconium dichloride; (407) dimethylgermylidene bis {1, 1' - (2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl) } zirconium dichloride; (408) dimethylgermylidene bis {1, 1' - (2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl) } zirconium dichloride; (409) dimethylsilylenebis {1, 1' - (2-benzyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride; (410) dimethylsilylenebis {1, 1' - (2-heptyl-4-phenyl-4-hydro-genAzulenyl) } zirconium dichloride; (411) dimethylsilylenebis {1, 1' - (2-octyl 4-phenyl-4-hydroazulenyl) } zirconium dichloride; (412) dimethylsilylenebis {1, 1' - (2- (1-phenylethyl) -4-phenyl-4-hydroazulenyl) } zirconium dichloride; (413) dimethylsilylenebis {1, 1' - (2- (2-phenylethyl) -4-phenyl-4-hydroazulenyl) } zirconium dichloride; (414) dimethylsilylenebis {1, 1' - (2- (1-naphthyl) -4-phenyl-4-hydroazulenyl) } zirconium dichloride; (415) dimethylsilylenebis {1, 1' - (2- (2-naphthyl) -4-phenyl-4-hydroazulenyl) } zirconium dichloride; (416) dimethylsilylenebis {1, 1' - (2-dimethylphenylsilyl-4-phenyl-4-hydroazulenyl) }Zirconium dichloride; (417) dimethylsilylenebis [1, 1' - { 2-benzyl-4- (1-naphthyl) -4-hydroazulenyl) } zirconium dichloride; (418) dimethylsilylenebis [1, 1' - { 2-benzyl-4- (2-naphthyl) -4-hydroazulenyl) } zirconium dichloride; (419) dimethylsilylenebis {1, 1' - (2-benzyl-4-phenyl-7-isopropyl-4-hydroazulenyl) } zirconium dichloride; (420) dimethylsilylenebis {1, 1' - (2-heptyl-4-phenyl-7-isopropyl-4-hydroazulenyl) } zirconium dichloride; (421) dimethylsilylenebis {1, 1' - (2-octyl-4-phenyl-7-isopropyl-4-hydroazulenyl) } zirconium dichloride; (422) dimethylsilylenebis [1, 1' - {2- (1-phenethyl) -4-phenyl-7-isopropyl-4-hydroazulenyl) } zirconium dichloride; (423) dimethylsilylenebis [1, 1' - {2- (2-phenylethyl) -4-phenyl-7-isopropyl-4-hydroazulenyl) } zirconium dichloride; (424) dimethylsilylenebis [1, 1' - {2- (1-naphthyl) -4-phenyl-7-isopropyl-4-hydroazulenyl) } zirconium dichloride; (425) dimethylsilylenebis [1, 1' - {2- (2-naphthyl) -4-phenyl-7-isopropyl-4-hydroazulenyl) } zirconium dichloride; (426) dimethylsilylenebis {1, 1' - (2-dimethylphenylsilyl-4-phenyl-7-isopropyl-4-hydroazulenyl) } zirconium dichloride; (427) dimethylsilylenebis [1, 1' - { 2-benzyl-4- (1-naphthyl) -7-isopropyl-4-hydroazulenyl) } zirconium dichloride; (428) dimethylsilylenebis [1, 1' - { 2-benzyl-4- (2-naphthyl) -7-isopropyl-4-hydroazulenyl) } zirconium dichloride; (429) diphenylsilylene bis [1, 1' - { 2-benzyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride; (430) diphenylsilylene bis [1, 1' - { 2-benzyl-4- (1-naphthyl) -4-hydroazulenyl) } zirconium dichloride; (431) diphenylsilylene bis [1, 1' - { 2-benzyl-4- (2-naphthyl)) -4-hydroazulenyl) } zirconium dichloride; (432) diphenylsilylene bis {1, 1' - (2-benzyl-4-phenyl-7-isopropyl-4-hydroazulenyl) } zirconium dichloride; (433) diphenylsilylene bis [1, 1' - {2- (1-phenethyl) -4-phenyl-4-hydroazulenyl) } zirconium dichloride;(434) diphenylsilylene bis [1, 1' - {2- (1-phenethyl) -4-phenyl-7-isopropyl-4-hydroazulenyl) } zirconium dichloride; (435) (methyl) (phenyl) silylene bis {1, 1' - (2-benzyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride; (436) (methyl) (phenyl) silylene bis [1, 1' - { 2-benzyl-4- (1-naphthyl) -4-hydroazulenyl) } zirconium dichloride; (437) (methyl) (phenyl) silylene bis [1, 1' - { 2-benzyl-4- (2-naphthyl) -4-hydroazulenyl) } zirconium dichloride; (438) (methyl) (phenyl) silylene bis {1, 1' - (2-benzyl-4-phenyl-7-isopropyl-4-hydroazulenyl) } zirconium dichloride; (439) (methyl) (phenyl) silylene bis [1, 1' - {2- (1-phenethyl) -4-phenyl-4-hydroazulenyl) } zirconium dichloride; (440) (methyl) (phenyl) silylenebis [1, 1' - {2- (1-phenethyl) -4-phenyl-7-isopropyl-4-hydroazulenyl) } zirconium dichloride; (441) dimethylsilylene {1- (2-benzyl-4-phenyl-4-hydroazulenyl) } { (1- (2-methyl-4, 5-benzindenyl) } zirconium dichloride, (442) dimethylsilylene [1- (2-benzyl-4- (1-naphthyl) -4-hydroazulenyl) } { (1- (2-methyl-4, 5-benzindenyl) } zirconium dichloride, (443) dimethylsilylene [1- (2-benzyl-4- (2-naphthyl) -4-hydroazulenyl) } { (1- (2-methyl-4, 5-benzindenyl) } zirconium dichloride, (444) dimethylsilylene [1- { 2-benzyl-4-phenyl-7-isopropyl-4-hydroazulenyl ] } zirconium dichloride, (444) dimethylsilylene [1- { 2-benzyl-4-phenyl-7-isopropyl-4-hydroazulenyl } zirconium dichloride Azulene radical }]{ (1- (2-methyl-4, 5-benzindenyl) } zirconium dichloride, (445) dimethylsilylene [1- {2- (1-phenethyl) -4-phenyl-4-hydroazulenyl) } { (1- (2-methyl-4, 5-benzindenyl) } zirconium dichloride, (446) dimethylsilylene [1- {2- (1-phenethyl) -4-phenyl-7-isopropyl-4-hydroazulenyl) } { (1- (2-methyl-4, 5-benzindenyl) } zirconium dichloride, (447) dimethylsilylene {1- (2-benzyl-4-phenyl-4-hydroazulenyl } 447 }]{ (1- (2-methyl-phenylindenyl) } zirconium dichloride, (448) dimethylsilylene [1- { 2-benzyl-4- (1-naphthyl) -4-hydroazulenyl) } { (1- (2-methyl-phenylindenyl) } zirconium dichloride, (449) dimethylsilylene [1- { 2-benzyl-4- (2-naphthyl) -4-hydroazulenyl) } { (1- (2-methyl-phenyl-azulenyl) } zirconium dichlorideIndenyl) } zirconium dichloride; (450) dimethylsilylene [1- { 2-benzyl-4-phenyl ]-7-isopropyl-4-hydroazulenyl }]{ (1- (2-methyl-phenylindenyl) } zirconium dichloride, (451) dimethylsilylene [1- {2- (1-phenethyl) -4-phenyl-4-hydroazulenyl) } { (1- (2-methyl-phenylindenyl) } zirconium dichloride, (452) dimethylsilylene [1- {2- (1-phenethyl) -4-phenyl-7-isopropyl-4-hydroazulenyl) } { (1- (2-methyl-phenylindenyl) } zirconium dichloride, (453) 9-silafluorene-9, 9-diylbis {1, 1' - (2-methyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride, (454) 9-silafluorene-9, 9-diylbis {1, 1' - (2-ethyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride; (455) 9-silafluorene-9, 9-diylbis {1, 1' - (2, 8-dimethyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride; (456) 9-silafluorene-9, 9-diylbis {1, 1' - (2-methyl-4- (1-naphthyl) -4-hydroazulenyl) } zirconium dichloride; (457) 9-silafluorene-9, 9-diyl {1- (2-methyl-4-phenyl-4-hydroazulenyl) } {1- (2-methyl-4-phenyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (458) 9-silafluorene-9, 9-diyl {1- (2-methyl-4-phenyl-4-hydroazulenyl) } {1- (2-methyl-4-phenylindenyl) } zirconium dichloride; (459) 1-silaindene-1, 1-diylbis {1, 1' - (2-methyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride; (460) 1-silaindene-1, 1-diylbis {1, 1' - (2-ethyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride; (461) 1-silaindene-1, 1-diylbis {1, 1' - (2, 8-dimethyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride; (462) 1-silaindene-1, 1-diylbis {1, 1' - (2-methyl-4- (1-naphthyl) -4-hydroazulenyl) } zirconium dichloride; (463) 1-silaindene-1, 1-diyl {1- (2-methyl-4-phenyl-4-hydroazulenyl) } {1- (2-methyl-4-phenyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (464) 1-silaindene-1, 1-diyl {1- (2-methyl-4-phenyl-4-hydroazulenyl) } {1- (2-methyl-4-phenylindenyl) } zirconium dichloride; (465) tetramethyl-1-silacyclopentadienyl-1, 1-diylbis {1, 1' - (2-methyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride; (466) tetramethyl-1-silacyclopentadienyl-1, 1-diylbis {1, 1' - (2-ethyl-4-phenyl-4-hydroazulene)Yl) } zirconium dichloride; (467) tetramethyl-1-silacyclopentadienyl-1, 1-diylbis {1, 1' - (2, 8-dimethyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride; (468) tetramethyl-1-silacyclopentadienyl-1, 1-diylbis {1, 1' - (2-methyl-4- (1-naphthyl) -4-hydroazulenyl) } zirconium dichloride; (469) tetramethyl-1-silacyclopentadienyl-1, 1-diyl{1- (2-methyl-4-phenyl-4-hydroazulenyl) } {1- (2-methyl-4-phenyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (470) tetramethyl-1-silacyclopentadienyl-1, 1-diyl {1- (2-methyl-4-phenyl-4-hydroazulenyl) } {1- (2-methyl-4-phenylindenyl) } zirconium dichloride; (471) 1-silacycle-3-pentene-1, 1-diylbis {1, 1' - (2-methyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride; (472) 1-silacycle-3-pentene-1, 1-diylbis {1, 1' - (2-ethyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride; (473) 1-silacycle-3-pentene-1, 1-diylbis {1, 1' - (2, 8-dimethyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride; (474) 1-silacycle-3-pentene-1, 1-diylbis {1, 1' - (2-methyl-4- (1-naphthyl) -4-hydroazulenyl) } zirconium dichloride; (475) 1-silacycle-3-pentene-1, 1-diylbis {1- (2-methyl-4-phenyl-4-hydroazulenyl) } {1- (2-methyl-4-phenyl-4, 5, 6, 7, 8-pentahydroazulenyl) } zirconium dichloride; (476) 1-silacyclo-3-pentene-1, 1-diylbis {1- (2-methyl-4-phenyl-4-hydroazulenyl) } {1- (2-methyl-4-phenylindenyl) } zirconium dichloride;

further, as the transition metal compound of the present invention, there can be also exemplified those in which one or two chlorine atoms constituting the groups X and Y in the general formula (I) are substituted with a hydrogen atom, a fluorine atom, a bromine atom, an iodine atom, a methyl group, a phenyl group, a fluorophenyl group, a benzyl group, a methoxy group, a dimethylamino group, a diethylamino group or the like. Further, there may be also exemplified those compounds in which zirconium as the central metal M of each of the compounds is substituted with titanium, hafnium, tantalum, niobium, vanadium, tungsten, molybdenum or the like. Among them, compounds containing a group 4 transition metal such as zirconium, titanium or hafnium are preferable, and compounds containing zirconium or hafnium are particularly preferable.

The catalyst (1) for polymerizing α -olefin of the first aspect of the invention is explained below, the catalyst (1) comprising the transition metal compound (component A) and a specific ion-exchangeable layer compound or inorganic silicate (component B) as essential components, and an organoaluminum compound (component C) as an optional component.

First, as for component B, an inorganic silicate other than silicate or an ion-exchangeable layer compound (hereinafter referred to simply as "ion-exchangeable layer compound") is explained below.

As the above-mentioned ion-exchangeable layer compound as the component (B), hexagonal close-packed type, antimony type, CdCl having a layered crystal structure are exemplified₂Form or CdI₂Specific examples of the ion-exchangeable layer may include crystalline polyvalent metal acid salts such as α -Zr (HAsO)₄)₂·H₂O、α-Zr(HPO₄)₂、α-Zr(KPO₄)₂·3H₂O、α-Ti(HPO₄)₂、α-Ti(HAsO₄)₂·H₂O、α-Sn(HPO₄)₂·H₂O、γ-Zr(HPO₄)₂、γ-Ti(HPO₄)₂Or gamma-Ti (NH)₄PO₄)₂·H₂O。

The above-mentioned ion-exchangeable layer compound may be treated with a salt and/or an acid, if necessary. An ion-exchangeable layer compound other than a silicate (neither treated with a salt nor with an acid) has a crystal structure of: a layer formed by ionic bonding or the like is laid in parallel on another layer (having weak bonding force between layers), and thus the layers contain mutually exchangeable ions.

As the above inorganic silicate as the component (B), clay mineral, zeolite, diatomaceous earth and the like can be mentioned. These inorganic silicates may be synthetic products or naturally mined ores. Specific examples of the clay or clay mineral may include allophane-type clay or clay mineral such as allophane; kaolinite-like clays or clay minerals such as dickite, nacrite, kaolin or silica-rich kaolin, halloysite-like clays or clay minerals such as halloysite or halloysite; serpentine clays or clay-like minerals such as olivine, serpentine or antigorite; smectite clays or clay minerals such as montmorillonite, sauconite, beidellite, nontronite, saponite or hectorite; vermiculite minerals such as vermiculite; mica minerals such as illite, sericite or glauconite; a stevensite; sepiolite; palygorskite; nontronite; a plurality of sections of clay; gairome clay ferrosilicon soil; pyrophyllite; (ii) chlorites; and so on. These inorganic silicates may be in the form of mixed layers thereof. Examples of the synthetic inorganic silicate include synthetic mica, synthetic hectorite, synthetic saponite, and synthetic taeniolite.

Among the above inorganic silicates, kaolinite-based clays or clay minerals, halloysite-based clays or clay minerals, serpentine-based clays and clay minerals, smectite-based clays or clay minerals, vermiculite minerals, mica minerals, synthetic micas, synthetic hectorites, synthetic saponites or synthetic taeniolite are preferable. Particularly preferred synthetic inorganic silicates are montmorillonite, vermiculite, synthetic mica, synthetic hectorite, synthetic saponite and synthetic taeniolite. These inorganic silicates may be used in their untreated form or may be used after being subjected to treatments such as grinding by a ball mill, sieving, and the like. Further, these inorganic silicates may be used alone or in the form of a mixture of any two or more thereof.

The above-mentioned ion-exchangeable layer compounds other than silicates and inorganic silicates as component (B) can be treated with salts and/or acids to control the acid strength of these solid compounds. Meanwhile, when these compounds are treated with a salt, an ionic complex, a molecular complex or an organic derivative may be formed, and thus it is possible to suitably change the surface area and interlayer distance thereof. In particular, the exchangeable ions present between the layers can be replaced by other, more bulky ions by virtue of the ion-exchange properties of these compounds, resulting in a layer material with an increased interlayer distance.

If these compounds are not subjected to the above-mentioned pretreatment, it is preferable that the metal cations contained therein be ion-exchanged by cations derived from the following salts and/or acids.

The salt used for the above ion exchange may be a compound comprising a cation containing at least one atom selected from the group consisting of groups 1 to 14, preferably a compound comprising a cation containing at least one atom selected from the group consisting of groups 1 to 14 and at least one anion derived from an atom or radical selected from the group consisting of a halogen atom, an inorganic acid and an organic acid, more preferably a compound comprising a cation containing at least one atom selected from the group consisting of groups 2 to 14 and at least one atom selected from the group consisting of Cl, Br, I, F, PO₄、SO₄、NO₃、CO₃、C₂O₄、ClO₄、OOCCH₃、CH₃COCHCOCH₃、OCl₂、O(NO₃)₂、O(ClO₄)₂、O(SO₄)、OH、O₂Cl₂、OCl₃OOCH and OOCCH₂CH₃The anionic compound of (1). These salts may be used alone or in the form of a mixture of any two or more of them.

The acid used for the above ion exchange may be selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid and oxalic acid. These acids may be used alone or in the form of a mixture of two or more thereof. The salt treatment may be used in combination with the acid treatment. As a method in which the salt treatment and the acid treatment are used in combination, the following methods can be mentioned: a method of performing an acid treatment after a salt treatment, a method of performing a salt treatment after an acid treatment, a method of performing a salt and acid treatment simultaneously, and a method of performing a salt and acid treatment simultaneously after a salt treatment. Further, the acid treatment has an ion exchange effect such that impurities can be removed from the surface of the component (B) and a cationic moiety such as Al, Fe, Mg or Li contained in the crystal structure can be eluted therefrom.

The treatment conditions for the salt or acid treatment are not particularly limited. However, suitable concentrations of salt or acid are typically 0.1 to 30 wt%; the treatment temperature is generally from room temperature to the melting point of the solvent used; the treatment time is generally from 5 minutes to 24 hours, so that at least part of the compound to be treated is dissolved. In addition, salts and acids are generally used in the form of aqueous solutions.

The component (B) thus prepared generally has a pore volume of not less than 0.1cc/g, more preferably 0.3 to 5cc/g (as determined by mercury penetration method with respect to a radius of not less than 20 Å.) this component (B) generally contains absorbed water or interlayer water.

According to the present invention, component (B) is preferably used after removing the above-mentioned absorbed water or interlayer water. The method of removing water is not particularly limited, but dehydration methods such as heating, heating in the presence of a flowing gas, heating under reduced pressure, azeotropic distillation with an organic solvent, and the like can be used. The heating may be carried out at a temperature at which no absorption water and interlayer water are present. The heating temperature is usually not lower than 100 ℃ and preferably not lower than 150 ℃. However, the use of temperatures that cause damage to the crystal structure should be avoided. The heating time is usually not less than 0.5 hour, preferably not less than 1 hour. When the suction is conducted at a temperature of 200 ℃ under a pressure of 1mmHg for 2 hours, the weight loss of the thus-treated component is preferably not less than 3% by weight. According to the present invention, it is preferable that the weight loss of the component (B) is adjusted to not less than 3% by weight based on the total weight of the component (B) with respect to the component (B) used, and the weight loss of the component (B) is also maintained when the component (B) is contacted with the essential component (A) and the following optional component (C).

The organoaluminum compound (component (C)) is explained in detail below. As component (C), an organoaluminum compound represented by the following general formula (VII) can be preferably used:

AlR_aP_3-a(VII) wherein R is a hydrocarbyl group having 1 to 20 carbon atoms; p is a hydrogen atom, a halogen atom, an alkoxy group or a siloxy group; "a" is a number satisfying 0 < a.ltoreq.3.

Specific examples of the organoaluminum compound represented by the above-mentioned general formula (VII) may include trialkylaluminums such as trimethyllithium, triethylaluminum, tripropylaluminum or triisobutylaluminum, halogen-or alkoxy-containing alkylaluminum such as diethylaluminum monochloride or monomethoxydiethylaluminum and the like, among which trialkylaluminums may be preferably used, and among them, for the catalyst (1) for polymerizing α -olefin of the first aspect of the present invention, aluminoxane such as methylaluminoxane and the like may be used as the component (C).

The catalyst (1) for polymerizing α -olefin can be prepared by contacting the essential components (A) and (B) and optionally (C) with each other, the contacting method is not particularly limited, but the following methods (i) to (v) can be cited.

When or after the respective components are contacted with each other, a polymer such as polyethylene or polypropylene or an inorganic oxide solid component such as silica or alumina may coexist or may also participate in the contact.

Furthermore, the contact between the respective components may be carried out in an inert gas such as nitrogen in the presence of an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene or xylene. Furthermore, the contact is preferably carried out at a temperature of-20 ℃ to the boiling point of the solvent used, more preferably from room temperature to the boiling point of the solvent used.

The amount of the component (A) used is usually 10 based on 1g of the component (B)^-4To 10mmol, preferably 10^-3To 5 mmol. The amount of the component (C) used is usually 0.01 to 10 based on 1g of the component (B)⁴mmol, preferably 0.1 to 100 mmol. Further, the atomic ratio between the transition metal and aluminum contained in the component (A) is usually 1/0.01 to 1/10⁶Preferably 1/0.1 to 1/10⁵。

The catalyst thus prepared may be used without washing, or may be used after washing. Furthermore, the catalyst may be used in combination with another component (C') composed of a compound similar to the component (C), if necessary. In other words, when the component (A) and/or (B) and the component (C) are used for preparing the catalyst, another component (C') may be added separately from the component (C) for preparing the catalyst to the reaction system. In this case, the amount of the other component (C ') added may be selected so that the atomic ratio of the transition metal contained in the component (A) to the aluminum contained in the other component (C') added is from 1/0 to 1/10⁴。

The catalyst (2) for polymerizing α -olefin of the second aspect of the invention is explained in detail below, the catalyst (2) may contain, as essential components, (i) a novel transition metal compound represented by the above-mentioned general formula (II), (III), (IV), (V) or (VI) (component (A)) and (II) an aluminumoxy compound, (component (D)) an ionic compound capable of reacting with the component (A) to convert the component (A) into a cation or a Lewis acid, and (III) a fine particle carrier (component (E)) as an optional component.

As the above aluminumoxy compound, those represented by the following general formulae (VIII), (IX) and (X) can be exemplified:

in the above general formulae (VIII), (IX) and (X), R⁹Is a hydrogen atom or a hydrocarbon group preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, provided that when a plurality of R's are present in the same molecule⁹When R is equal to⁹May be the same or different; p is an integer from 0 to 40, preferably from 2 to 30.

The compounds represented by the general formulae (VIII) and (IX) are also referred to as "aluminoxanes" and can be obtained by reacting at least one trialkylaluminum with water. Specific examples of the compounds represented by the general formulae (VIII) and (IX) may include (i) a compound obtained by reacting one trialkylaluminum with water, such as methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane or isobutylaluminoxane, (ii) a compound obtained by reacting two trialkylaluminums with water, such as methylethylaluminoxane, methylbutylaluminoxane or methylisobutylaluminoxane, and the like. Among them, methylaluminoxane and methylisobutylaluminoxane are preferable.

The above-mentioned aluminoxanes may be used in the form of mixtures within one group or between groups. Aluminoxanes can be prepared under various known conditions. Specifically, the following methods can be used to prepare these aluminoxanes: (a) a method of reacting trialkylaluminum with water in the presence of a suitable organic solvent such as toluene, benzene or ether; (b) a method of reacting trialkylaluminum with a salt containing crystal water such as copper sulfate or aluminum sulfate hydrate; (c) a method of reacting trialkylaluminum with moisture impregnated in silica gel or the like; (d) a method of mixing trimethylaluminum and triisobutylaluminum and then reacting the mixed trialkylaluminum directly with water in the presence of a suitable organic solvent such as toluene, benzene or ether; (e) a method of mixing trimethylaluminum and triisobutylaluminum and then reacting the mixed trialkylaluminum with a salt containing crystal water such as copper sulfate or hydrate of aluminum sulfate while heating; (f) a method of impregnating water into silica gel or the like, treating the silica gel or the like impregnated with water with triisobutylaluminum, and then treating with trimethylaluminum; (g) a method of preparing methylaluminoxane and isobutylaluminoxane by a known method, and then mixing the two components in a predetermined mixing ratio to react them under heating; and (h) a method in which a salt containing water of crystallization, such as copper sulfate pentahydrate and trimethylaluminum, is added to an aromatic hydrocarbon solvent, such as benzene or toluene, and then these components are allowed to react at a temperature of between about-40 ℃ and about 40 ℃.

The molar ratio of water to trimethylaluminum used is generally from 0.5 to 1.5. The methylaluminoxane prepared by the above method is a linear or cyclic organoaluminum polymer.

The compound represented by the general formula (X) can be produced by reacting at least one trialkylaluminum with an alkylboronic acid represented by the following formula (XI) in a molar ratio of from 10: 1 to 1: 1.

R¹⁰-B-(OH)₂(XI) wherein R¹⁰Is a hydrocarbon group or a halogenated hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.

Specific examples of the compound represented by the general formula (XI) include the following reaction products: (a) a reaction product obtained by the reaction of trimethylaluminum and methylboronic acid according to the molar ratio of 2: 1; (b) triisobutyl aluminum and methyl boric acid react according to the mol ratio of 2: 1 to obtain a reaction product; (c) a reaction product obtained by the mutual reaction of trimethylaluminum, triisobutylaluminum and methylboronic acid according to the molar ratio of 1: 1; (d) a reaction product obtained by the reaction of trimethylaluminum and ethylboric acid according to the molar ratio of 2: 1; and (e) a reaction product obtained by reacting triethylaluminum with butyl boronic acid in a molar ratio of 2: 1.

Also, as the ionic compound capable of reacting with component (a) to convert component (a) into a cation, there can be cited those compounds represented by the general formula (XII):

[K]e⁺[Z]e^- (XII)

in the general formula (XII), K represents a cationic component. Examples of cations include carbonium cations,  onium cations, ammonium cations, oxonium cations, sulfonium cations, phosphonium cations, or the like. Furthermore, it is also possible to use metal cations, which tend to reduce themselves, organometallic cations or the like.

Specific examples of the above cation may include triphenylcarbenium, diphenylcarbenium, cycloheptatriylium, indene onium, triethylammonium, tripropylammonium, tributylammonium, N, N-dimethylammonium ion, dipropylammonium ion, dicyclohexylammonium ion, triphenylphosphonium, trimethylphosphonium, tris (dimethylphenyl) phosphonium, tris (methylphenyl) phosphonium, triphenylsulfonium, triphenyloxonium, triethyloxonium, pyrylium, silver ion, gold ion, platinum ion, copper ion, palladium ion, mercury ion, iron ion or the like.

In the general formula (XII), Z represents an anionic component (generally a non-conjugated component) which constitutes a counter anion to the cation formed by the conversion of component (A). Examples of the anion Z include anions of organoboron compounds, anions of organoaluminum compounds, anions of organogallium compounds, anions of organophosphorus compounds, anions of organoarsenic compounds, and anions of organoantimony compounds. Specific examples of these organic compounds are the following: (a) tetraphenylboron, tetrakis (3, 4, 5-trifluorophenyl) boron, tetrakis {3, 5-bis (trifluoromethyl) phenyl } boron, tetrakis {3, 5-di (tert-butyl) phenyl } boron, tetrakis (pentafluorophenyl) boron, or the like; (b) tetraphenylaluminum, tetrakis (3, 4, 5-trifluorophenyl) aluminum, tetrakis {3, 5-bis (trifluoromethyl) phenyl } aluminum, tetrakis (3, 5-di (tert-butyl) phenyl) aluminum, tetrakis (pentafluorophenyl) aluminum, or the like; (c) tetraphenylgallium, tetrakis (3, 4, 5-trifluorophenyl) gallium, tetrakis {3, 5-bis (trifluoromethyl) phenyl } gallium, tetrakis (3, 5-di (tert-butyl) phenyl) gallium, tetrakis (pentafluoro) phenylgallium, or the like; (d) tetraphenylphosphonium, tetrakis (pentafluorophenyl) phosphonium, or the like; (e) tetraphenylarsenic, tetrakis (pentafluorophenyl) arsenal, or the like; (f) tetraphenylantimony, tetrakis (pentafluorophenyl) antimony, or the like; and (g) decaborate, undecaborate, carbadecaborate, decachlorodecaborate, or the like.

Further, as the Lewis acid, especially those capable of converting component (A) into a cation, various organoboron compounds, halogenated metal compounds, solid acids or the like can be exemplified. Specific examples of lewis acids are the following: (a) organoboron compounds, such as triphenylboron, tris (3, 5-difluorophenyl) boron or tris (pentafluorophenyl) boron; (b) halogenated metal compounds such as aluminum chloride, aluminum bromide, aluminum iodide, magnesium chloride, magnesium bromide, magnesium iodide, magnesium chlorobromide, magnesium chloroiodide, magnesium bromoiodide, magnesium chlorohydride, magnesium chlorohydroxide, magnesium hydrobromide, magnesium alkoxychloride or magnesium alkoxybromide; and (c) a solid acid such as alumina or silica-alumina.

In the catalyst (2) for the polymerization of α -olefin, the fine particle carrier as the optionally selected component (E) may be composed of an inorganic or organic compound, and is a particulate matter generally having a particle diameter of 5 μm to 5mm, preferably 10 μm to 2 mm.

As the aforementioned inorganic carrier, oxides such as SiO are exemplified₂，Al₂O₃，MgO，ZrO，TiO₂，B₂O₃Or ZnO; composite oxides such as SiO₂-MgO，SiO₂-Al₂O₃，SiO₂-TiO₂，SiO₂-CrO₃Or SiO₂-Al₂O₃-MgO; or the like.

As the aforementioned organic carriers, fine particles of porous polymers (e.g., polymers or copolymers of α -olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene or 4-methyl-1-pentene), polymers or copolymers of aromatic unsaturated hydrocarbons such as styrene or divinylbenzene, or the like can be exemplified, and these organic carriers have a specific surface area of usually 20 to 1,000m²Per g, preferably from 50 to 700m²In terms of/g, and the pore volume is usually not less than 0.1cm³In terms of/g, preferably not less than 0.3cm³G, more preferably not less than 0.8cm³/g。

The catalyst (2) for the α -olefin polymerization contains, as other optional components besides the fine-particle carrier, for example protic compounds such as H₂O, methanol, ethanol or butanol; electron-donating compounds such as ethers, esters or amines; alkoxy-containing compounds such as phenyl borate, dimethylmethoxyaluminum, phenyl phosphite, tetraethoxysilane or diphenyldimethoxysilane; or the like.

As still other optionally used components other than the above-mentioned compounds, tri-lower alkylaluminum such as trimethylaluminum, triethylaluminum or triisobutylaluminum; halogen-containing alkylaluminum such as diethylaluminum chloride, diisobutylaluminum chloride or methylaluminum sesquichloride; alkyl aluminum hydrides such as diethyl aluminum hydride; alkoxy-containing alkylaluminum such as diethylaluminum ethoxide or dimethylbutylaluminum butoxide; aryloxy group-containing alkylaluminum such as diethylphenoxyaluminum.

Incidentally, it is preferable that, as further optionally used components, one or more of the above-mentioned lower alkyl aluminum, halogen-containing alkyl aluminum, alkyl aluminum hydride, alkoxy-containing alkyl aluminum or aryloxy-containing alkyl aluminum may be contained in the catalyst (2) for α -olefin polymerization together with the aluminumoxy compound, the ionic compound or the Lewis acid.

The catalyst (2) for α -olefin polymerization can be prepared by allowing the components (A) and (D) to contact inside and outside of a reactor and in the presence or absence of a monomer to be polymerized.

The contact between the various components can be carried out under an atmosphere containing an inert gas such as nitrogen or in the presence of an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene or xylene. Also, the contacting can be carried out at a temperature between-20 ℃ and the boiling point of the solvent used, preferably room temperature and the boiling point of the solvent used. The catalyst thus produced can be used as it is without washing or after washing. Furthermore, the obtained catalyst can be used in admixture with other components, if desired.

Likewise, when the components (A), (D) and (E) are previously contacted with each other, the contacting can be carried out in the presence of the monomer to be polymerized, i.e., α -olefin, to partially polymerize α -olefin (so-called prepolymerization). more specifically, α -olefin such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane or styrene is subjected to prepolymerization and, if necessary, washed prior to the polymerization reaction.

The amounts of components (A) and (D) used are arbitrarily selected. For example, for solution polymerization, component (A) is generally used in an amount of 10^-7-10²mmol/L (calculated as transition metal), preferably 10^-4In the range of-1 mmol/L. In the case where an aluminumoxy compound is used as the component (D), the molar ratio of Al to the transition metal is usually in the range of 10 to 10⁵Preferably 100-2X 10⁴More preferably 100-10⁴In the above range, on the other hand, in the case where an ionic compound or a Lewis acid is used as the component (D), the molar ratio of the ionic compound or Lewis acid to the transition metal is usually in the range of 0.1 to 1,000, preferably 0.5 to 100, more preferably 1 to 50.

The method for producing α -olefin according to the present invention will be explained in detail below, the above catalyst and α -olefin are contacted with each other to polymerize or copolymerize α -olefin according to the present invention, the catalyst for polymerizing α -olefin according to the present invention is suitable not only for solution polymerization using a solvent but also for liquid phase non-solvent polymerization, gas phase polymerization or melt polymerization using substantially no solvent, and these polymerization reactions can be carried out in a continuous manner or in a batch manner.

As solvents for the solution polymerization, mention may be made of inert saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene or toluene. These solvents can be used alone or as a mixture of two or more thereof. The polymerization temperature is generally between-78 ℃ and 250 ℃, preferably between-20 ℃ and 100 ℃. The pressure of the olefin in the reaction system is not particularly limited, but is preferably from normal pressure to 2,000kgf/cm²G (gauge pressure), more preferably from atmospheric pressure to 50kgf/cm²G (gauge pressure) in addition, the molecular weight of the obtained α -olefin polymer can be controlled by a suitable method such as appropriately selecting the reaction temperature and reaction temperature to be used or introducing hydrogen.

As the crude α -olefin, α -olefin generally having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms can be used α -olefin specific examples may include ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-nonadecene or the like, the catalyst according to the present invention is preferably used for the stereoregular polymerization of α -olefin having 3 to 10 carbon atoms, especially for the polymerization of propylene.

Further, the catalyst according to the present invention is used not only for the homopolymerization of the above-mentioned α -olefin but also for the copolymerization of α -olefin with other monomer as other monomer copolymerizable with α -olefin, there can be exemplified conjugated diolefins or non-conjugated diolefins such as butadiene, 1, 4-hexadiene, 7-methyl-1, 6-octadiene, 1, 8-nonadiene or 1, 9-decadiene, cyclic olefins such as cyclopropene, cyclobutene, cyclopentene, norbornene or dicyclopentadiene, or the like, the polymerization or copolymerization of α -olefin can be carried out in a plurality of steps, the reaction conditions of which are different from each other, namely, in a so-called multi-step polymerization mode including, for example, a prepolymerization of propylene and a copolymerization of ethylene with polypropylene prepared by the prepolymerization.

As described above, according to the polymerization method of the present invention, α -olefin polymers having a narrow molecular weight distribution and a narrow composition distribution can be obtained, and excellent in transparency and mechanical strength and exhibiting good flowability.

Also, in the case of carrying out the polymerization reaction of propylene using the catalyst of the present invention, a crystalline polypropylene showing a high tacticity value [ mmmm ] (e.g., not less than 90%) and having the following unique peak defect amounts can be obtained: 0.5-2.0 mol% 2, 1-inversion and 0.06-0.40 mol% 1, 3-insertion. The amount of peak defects is calculated according to the following formula:

2, 1-inversion percentage (%) (Y/X) × 1,000 × 1/5,

the 1, 3-insertion percentage (%) - (Z/X) × 1,000 × 1/5,

x is the sum of the integrated values from 27ppm to 48ppm,

Y＝(A①+A②+A③+A④+A⑤+A⑥)/6，

Z＝(A⑦+A⑧+A⑨)/6

in the above equation, A ①, A ②, A ③, A ④, A ⑤, A ⑥, A ⑦, A ⑧, A ⑨ are areas at 42.3ppm, 35.9ppm, 38.6ppm, 30.6ppm, 36.0ppm, 31.5ppm, 31.0ppm, 37.2ppm and 27.4ppm, respectively, and represent the ratios between the amounts of carbon atoms present at the respective sites of the following partial structures (I) and (II):partial structure (II):

particularly, in the case of using the catalyst containing the transition metal compound represented by the general formulae (II) to (VI) according to the present invention, α -olefin polymer, which has no decrease in molecular weight and no impairment of stereoregularity, can exhibit a high molecular weight and a high melting point, and is therefore suitable for extrusion processing or injection molding processing and can be produced at a high yield.

That is, in the novel transition metal compounds represented by the general formulae (II) and (III), due to the group R³And R⁶Each forming a fused ring having not less than 7 members, to which is attached a substituent R⁷And R⁸In a spatial arrangement such that with respect to the 5-membered ring and R³Or R⁶The planes of the fused rings formed are inclined at an angle. Also, substituent R⁷And R⁸Contains halogen atoms, which are sterically bulky compared to hydrogen atoms. The halogen atom is used to provide suitable steric hindrance and a suitable configuration (it cannot be obtained solely from the hydrocarbon group). As a result, the effect of regulating the direction of polymer chain growth and the direction of monomer coordination is enhanced, thereby improving the stereoregularity of the obtained polymer and further increasing the melting point thereof.

Further, it is considered that the halogen atom exerts an electric effect on the central position metal (for example, zirconium and hafnium), and that the electric effect and the above-mentioned steric structure can effectively prevent the chain transfer reaction, thereby increasing the molecular weight of the obtained polymer. In addition, due to the radicals R³Or R⁶The 7-to 10-membered ring formed having a double bond, substituent R⁷And R⁸Is restricted and tightly fixes the ligand configuration. For this reason, it is generally considered that the substituent R is present even when the polymerization temperature is increased⁷And R⁸The effect of regulating the growth direction of the polymer chain and the coordination direction of the monomer is not lost, and a high molecular weight polymer having excellent stereoregularity is obtained.

In the novel transition metal compound represented by the general formula (IV), the substituent R is⁶Forming a condensed ring having not less than 7 members, the substituent R attached thereto⁸Having a spatial arrangement such that with respect to the 5-membered ring and R⁶The planes of the fused rings formed are inclined at an angle. Also, substituent R⁸At R⁶Upper is equivalent to 5These conditions allow the transition metal compound to have a bulky steric structure, thereby providing it with suitable steric hindrance and suitable configurationThe same effect as given by the transition metal compound of the formula (II) is obtained.

In the novel transition metal compound represented by the general formula (V), the substituent R is³And R⁶Forming a condensed ring having not less than 7 members, the substituent R attached thereto⁷And R⁸In a spatial arrangement such that with respect to the 5-membered ring and R³Or R⁶The planes of the fused rings formed are inclined at an angle. Also, the relatively bulky R¹And R⁴Bonded to a 5-membered ring. These conditions give the transition metal compound a relatively bulky steric structure, which gives it a suitable steric hindrance and a suitable configuration. As a result, the same effects as provided by the transition metal compound of the general formula (II) can be obtained.

Further, in the novel transition metal compound represented by the general formula (VI), R is a substituent³And R⁶Each forming a fused ring having not less than 7 members, to which is attached a substituent R⁷And R⁸In a spatial arrangement such that with respect to the 5-membered ring and R³Or R⁶The planes of the fused rings formed are inclined at an angle. Also, a cyclic substituent A is attached to the crosslinking group Q. These conditions lead to sterically bulky structures and suitable configurations of the transition metal compounds. As a result, the same effects as provided by the transition metal compound of the general formula (II) can be obtained. Moreover, due to the radicals R³Or R⁶The 7-to 10-membered ring and the radical A formed containing a double bond, the substituent R⁷，R⁸And R^aIs restricted to tightly fix the configuration of the ligand. For this reason, it is generally considered that, even if the polymerization reaction temperature is increased, it is possible to obtain a high molecular weight polymer having excellent stereoregularity.

Examples

The present invention is described in detail below by way of examples, which are not intended to limit the scope of the present invention. Incidentally, in the following examples, all the catalyst preparation methods and polymerization methods were carried out in a purified nitrogen atmosphere. Also, the solvents were dehydrated with MA-4A and then degassed by bubbling with purified nitrogen before they were used in these processes. Further, the activity per unit weight of each catalyst component means "catalytic activity" and is represented by the unit "g of polymer/g of solid catalyst component", while the activity per unit weight of each complex component means "complex activity" and is represented by the unit "g of polymer/g of complex component".

(1) Measurement of Melt Flow Rate (MFR)

6g of an acetone solution containing 0.6% by weight of heat stability (BHT) was added to 6g of the obtained polymer. After drying, the polymer was added to a melt indexer (230 ℃ C.) and held under a load of 2.16kg for 5 minutes. Thereafter, the polymer was extruded to measure the amount of the extruded polymer. Based on the amount of extruded polymer thus measured, the amount per 10 minutes was calculated and used as a value of MFR.

(2) Measurement of molecular weight distribution

The molecular weight distribution of the obtained polymer was determined from the Q value (Mw/Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer as measured by Gel Permeation Chromatography (GPC). The measurement of the molecular weight was carried out by using o-dichlorobenzene as a solvent at 135 ℃ by a GPC apparatus (150 CV type manufactured by Waters).

(3) Measurement of melting Point

The melt flow rate of the obtained polymer was measured after the polymer was heated twice from 20 ℃ to 200 ℃ at a heating rate of 10 ℃/min using a Differential Scanning Calorimeter (DSC) manufactured by e.i. dupont.

(4) Measurement of tacticity

A300 mg sample of the polymer was dissolved in a mixed solvent composed of 2.5ml of o-dichlorobenzene and 0.5ml of benzene-d 6 (deuterated). The obtained solution was subjected to Nuclear Magnetic Resonance (NMR) analysis by using a JEOL EX-270 spectrometer. NMR analysis was carried out at a temperature of 130 ℃ for an irradiation time of 0.744 sec and a pulse delay of 2.256 sec, and 20,000 cumulative repetitions were carried out to determine the tacticity of the obtained polymer.

Example 1

(1) Chemical treatment of clay minerals

30g of 35% hydrochloric acid solution are diluted with 70ml of desalted water. Next, 11.7g of commercial montmorillonite ("KUNIPIA F" manufactured by kunmine INDUSTRIES co., ltd.) was dispersed in the diluted solution. The resulting dispersion was heated to its boiling point while stirring and boiled for 2 hours. Thereafter, the product was sufficiently washed with desalted water, and after predrying, dried at 200 ℃ for 2 hours under reduced pressure to obtain component (B).

(2) Preparation of solid catalyst component

3.0g of the chemically treated montmorillonite obtained in (1) above was charged into a 100ml flask and dispersed in 20ml of toluene to obtain a slurry. Continuously, 1.3ml of triethylaluminum was added to the slurry under stirring and at room temperature. After the slurry was stirred at room temperature for 1 hour, the supernatant was removed, and the solid residue was washed with toluene to obtain a solid catalyst component.

(3) Synthesis of dimethylsilylenebis {1, 1' - (2-methyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride (component (A)):

(a) synthesis of racemic and meso mixtures:

2.22g of 2-methylazulene produced according to the method described in Japanese patent application laid-open (KOKAI) No.62-207232 was dissolved in 30ml of hexane. 15.6ml of a cyclohexane/diethyl ether solution of phenyllithium (1.0 eq.) were added gradually to the hexane solution obtained above at 0 ℃. After stirring at room temperature for 1 hour, the resulting solution was cooled to-78 ℃ and then mixed with 30ml of tetrahydrofuran. This solution was mixed with 0.95ml of dimethyldichlorosilane and the temperature was raised to room temperature. The solution was further heated to 50 ℃ and stirred for 1.5 hours. After addition of the aqueous ammonium chloride solution, the solution was separated into an aqueous phase and an organic phase. The organic phase is dried over magnesium sulfate and the solvent is removed under reduced pressure. The crude product thus obtained was purified by column chromatography (hexane: dichloromethane ═ 5: 1) to obtain 1.48g of dimethylbis {1, 1' - (2-methyl-4-phenyl-1, 4-dihydroazulenyl) silane.

768g of the dimethylbis {1, 1' - (2-methyl-4-phenyl-1, 4-dihydroazulenyl) silane thus obtained are dissolved in 15ml of diethyl ether. 1.98ml of a hexane solution of n-butyllithium (1.64mol/L) was added dropwise to the solution at-78 ℃ and the solution was stirred for 12 hours while gradually raising the temperature to room temperature. The solvent was removed under reduced pressure, thereby obtaining a solid component. The obtained solid component was washed with hexane, then dried, and solidified under reduced pressure. 20ml of a mixed solvent composed of toluene and diethyl ether (40: 1) was added to the dried product, and 325mg of zirconium tetrachloride was further added at-60 ℃. The mixture was stirred for 15 hours while gradually raising the temperature to room temperature. The obtained solution was concentrated under reduced pressure and then mixed with hexane to obtain a racemic and meso mixture of dimethylsilylenebis {1, 1' - (2-methyl-4-phenyl-4-hydroazulenyl) zirconium dichloride in the form of a precipitate (the mixture showed the spectral data described below).

(b) Purification of racemic compound:

887mg of the racemic and meso mixture produced above was dissolved in 30ml of dichloromethane and placed in a Pyrex vessel equipped with a 100W high pressure mercury lamp. The solution was irradiated (300nm-600nm) for 30 minutes at normal pressure while stirring to increase the percentage of racemic compound in the mixture, and the solvent was removed under stirring under reduced pressure. 7ml of toluene were added to the yellow solid obtained. After stirring, the mixture was allowed to stand to precipitate a yellow solid, and then the supernatant was removed. A similar washing procedure was repeated 3 times using 4ml of toluene, 2ml of toluene and 2ml of hexane. The solid product thus obtained was dried and solidified under reduced pressure to obtain 437mg of a racemic compound of dimethylsilylenebis {1, 1' - (2-methyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride.

(c) Of racemic compounds¹Chemical shifts of H-NMR:

300MHz，C₆D₆(ppm)δ0.51(s，6H，Si(CH₃)₂)，1.92(s，6H，CH₃) 5.30(brd, 2H), 5.75-5.95(m, 6H), 6.13(s, 2H), 6.68(d, J ═ 14Hz, 2H), 7.05-7.20(m, 2H, aromatic), 7.56(d, J ═ 7Hz, 4H)

(d) Of meso compounds¹Chemical shifts of H-NMR:

300MHz，C₆D₆(ppm)δ0.44(s，6H，Si(CH₃)₂)，0.59(s，6H，SiCH₃)，1.84(s，6H，CH₃) 5.38(br d, 2H), 5.75-6.00(m, 6H), 6.13(s, 2H), 6.78(d, J ═ 14Hz, 2H), 7.00-7.20(m, 2H, aromatic), 7.56(d, J ═ 7Hz, 4H)

(4) Polymerization of propylene

0.5mmol (in terms of Al atom) of triethylaluminum (produced by TOSOH AKZO CORP.) and 100mg of the solid catalyst component obtained in the above item (2) were charged into a 2-liter stirring autoclave. On the other hand, 0.975mg (1.5. mu. mol) of the racemic compound prepared above as component (A) was diluted with 3ml of toluene and added to a catalyst feeder equipped with a safety diaphragm. Thereafter, 1,500ml of propylene was added to the autoclave, and then the contents of the autoclave were heated to 70 ℃. Continuously, the pressure will be 80kgf/cm²Argon gas of G was introduced into the catalyst feeder to rupture the safety diaphragm, so that the component (A) was supplied to the autoclave to initiate polymerization of propylene.

After the polymerization was carried out for 2 hours, 166.5g of polypropylene was obtained after unreacted monomers were purged. Through measurement, it was confirmed that the catalyst activity was 1665 and the complex activity was 17.1X 10⁴. Further, it was confirmed that the obtained polypropylene had a melting point (Tm) of 150.1 ℃, a Melt Flow Rate (MFR) of 2.5 and a weight average molecular weight (Mw) of 3.1X 10⁵And a Q value (Mw/Mn) of 2.8.¹³Measurement of the C-NMR spectrum showed [ mmmm]Is 98.9%, 2, 1-inversion is 0.9% and 1, 3-insertion is 0.08%. The results are shown in tables 1 and 2.

Reference example 1

< polymerization of Polypropylene >

4mmol (calculated as Al atom) of methylaluminoxane ("MMAO" manufactured by TOSOH AKZO CORP. and 0.26mg (0.4. mu. mol) of the racemic compound obtained in example 1 were charged into a 2-liter stirring autoclave. Further, 1,5000ml of propylene was charged into an autoclave, and then the contents of the autoclave were heated to 70 ℃ to effect propyleneFor 1 hour, thereby obtaining 43.5g of polypropylene. Through measurement, it was confirmed that the complex activity was 16.7X 10⁴And the obtained polypropylene had a melting point (Tm) of 150.9 ℃, a Melt Flow Rate (MFR) of 1.3 and a weight average molecular weight (Mw) of 3.5X 10⁵And a Q value (Mw/Mn) of 2.7. In addition to this, the present invention is,¹³measurement of the C-NMR spectrum showed [ mmmm]Is 99.0%, 2, 1-The inversion was 0.9% and the 1, 3-insertion was 0.10%. The results are shown in tables 1 and 2.

Example 2

< polymerization of propylene >

The same process as defined in example 1(3) was conducted except that the polymerization temperature was changed to 80 ℃ to obtain 235g of polypropylene. By measurement, it was confirmed that the catalyst activity was 2350 and the complex activity was 24.1X 10⁴And the obtained polypropylene had a melting point (Tm) of 148.8 ℃, a Melt Flow Rate (MFR) of 8.5 and a weight average molecular weight (Mw) of 2.1X 10⁵And a Q value (Mw/Mn) of 2.7. In addition to this, the present invention is,¹³measurement of the C-NMR spectrum showed [ mmmm]It was 98.8%, 0.9% for 2, 1-inversion and 0.06% for 1, 3-insertion. The results are shown in tables 1 and 2.

Example 3

< polymerization of propylene >

500ml of dried and degassed toluene, 0.5mmol (in terms of Al atom) of triethylaluminum (produced by TOSOHAKZO CORP., Ltd.) and 100mg of the solid catalyst component obtained in the above example 1(2) were charged into a 1.5 liter stirred autoclave whose inside was sufficiently dried and whose inside atmosphere had been replaced with propylene gas. The autoclave was charged with 4. mu. mol of the racemic compound obtained in example 1 while maintaining 20 ℃. Thereafter, the reaction system in the autoclave was heated to 70 ℃ to initiate polymerization of propylene while adjusting the pressure of propylene in the autoclave to 5kgf/cm²G. After the polymerization was continued for 1 hour, unreacted propylene was discharged to obtain a slurry containing a polymer. The slurry was filtered and dried to recover 17g of polypropylene. Further, the filtrate was concentrated to recover 0.05g of polypropylene dissolved in the filtrate. After the measurement, the measurement result is obtained,it has been demonstrated that the catalyst activity is 170 and the complex activity is 0.65X 10⁴And the obtained polypropylene had a melting point (Tm) of 150.9 ℃, a Melt Flow Rate (MFR) of 3.5 and a weight average molecular weight (Mw) of 3.0X 10⁵And a Q value (Mw/Mn) of 2.8. In addition to this, the present invention is,¹³measurement of the C-NMR spectrum showed [ mmmm]Is 99.0%, 2, 1-inversion is 0.7% and 1, 3-insertion is 0.10%. The results are shown in tables 1 and 2.

Example 4

(1) Chemical treatment of clay minerals

3kg of commercial montmorillonite was ground to a fine powder by a vibrating ball mill and dispersed in 16 liters of a 3% hydrochloric acid solution. The dispersion was heated to 90 ℃ and held for 3 hours while being stirred, to obtain an aqueous slurry of chemically treated montmorillonite. Continuously, after the solid content of the aqueous slurry is adjusted to 15%, the slurry is sprayed by means of a spray dryer to granulate the solid components, followed by washing with desalted water. The particles thus obtained have a spherical shape.

Then, 10.0g of the chemically treated montmorillonite obtained above was charged into a 200ml flask and heated and dehydrated to dryness at 200 ℃ under reduced pressure for 2 hours. It was confirmed that the weight of montmorillonite was reduced by 1.3g as a result of heating and dehydration drying.

(2) Preparation of solid catalyst component

3.0g of the chemically treated montmorillonite obtained in (1) above was charged into a 100ml flask and dispersed in 20ml of toluene to obtain a slurry. Continuously, 1.3ml of triethylaluminum was added to the slurry under stirring and at room temperature. After allowing the two components to contact at room temperature for 1 hour, the supernatant was removed, and the solid residue was washed with toluene to obtain a solid catalyst component.

(3) Polymerization of propylene

0.5mmol (in terms of Al atom) of triethylaluminum (produced by TOSOH AKZO CORP., Ltd.), 100mg of the solid catalyst component obtained in the above item (2) and 750g of liquid propylene were charged into a 2-liter stirring autoclave. Subsequently, the contents of the autoclave were heated to 70 ℃ and then charged with 5.0ml of a solution containing dimethylmethylene as a complex componentSolution of silyl bis {1, 1' - (2-methyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride (2.0. mu. mol/ml) in toluene. The polymerization of propylene was allowed to proceed at 70 ℃ for 2 hours while stirring. After the polymerization was completed, unreacted propylene was discharged to obtain 180g of polypropylene. As a result of measurement, it was confirmed that the catalyst activity was 1800 and the complex activity was 2.7X 10⁴. Further, it was confirmed that the obtained polypropylene had a melting point (Tm) of 148.4 ℃, a Melt Flow Rate (MFR) of 11.1 and a weight average molecular weight (Mw) of 1.9X 10⁵And a Q value (Mw/Mn) of 2.7.¹³Measurement of the C-NMR spectrum showed [ mmmm]Is 98.8%, 2, 1-inversion is 0.9% and 1, 3-insertion is 0.10%. The results are shown in tables 1 and 2.

Example 5

< copolymerization of propylene and ethylene >

0.5mmol (in terms of Al atom) of triethylaluminum, 100mg of the solid catalyst component obtained in example 1 and 750g of liquid propylene were charged into a 2-liter stirring autoclave. The contents of the autoclave were then heated to 70 ℃ and 3.0ml of a toluene solution containing dimethylsilylenebis {1, 1' - (2-methyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride (2.0. mu. mol/ml) as a complex component was added to the autoclave along with pressurized ethylene. The ethylene feed was continued so that the molar percentage of (ethylene)/(propylene + ethylene) in the gas composition in the autoclave was 3.5 mol%. Under these conditions, the polymerization of propylene was allowed to proceed at 70 ℃ for 2 hours while stirring. After the polymerization was completed, unreacted propylene and unreacted ethylene were discharged to obtain 230g of a polypropylene/ethylene copolymer. Measured and provedThe actual catalyst activity was 3830 and the complex activity was 5.9X 10⁴The polypropylene/ethylene copolymer thus obtained had an ethylene content of 0.8 mol%, a melting point (Tm) of 141.7 ℃, a Melt Flow Rate (MFR) of 9.7 and a weight average molecular weight (Mw) of 2.1X 10⁵And a Q value (Mw/Mn) of 2.6.¹³Measurement of the C-NMR spectrum showed [ mmmm]Is 98.8%, 2, 1-inversion is 0.8% and 1, 3-insertion is 0.08%. The results are shown in tables 1 and 2.

Comparative example 1

(1) Synthesis of dimethylsilylenebis {1, 1' - (2-methyl-4, 5-benzoindenyl) } zirconium dichloride:

dimethylsilylenebis {1, 1' - (2-methyl-4, 5-benzoindenyl) } zirconium dichloride was synthesized according to the method described in Japanese patent application laid-open (KOKAI) No. 8-208733.

(2) Polymerization of propylene

The same procedure as in example 1 was repeated except that the above-mentioned compound (in item (1)) was used as the component (A) and the polymerization time was 1 hour, to obtain 160g of polypropylene. As a result of measurement, it was confirmed that the catalyst activity was 1600 and the complex activity was 5.8X 10⁴The obtained polypropylene had a melting point (Tm) of 132.0 ℃, a Melt Flow Rate (MFR) of 200, and a weight average molecular weight (Mw) of 1.1X 10⁵And a Q value (Mw/Mn) of 2.2.¹³Measurement of the C-NMR spectrum showed [ mmmm]Was 95.1%, 2, 1-inversion was 0.8% and 1, 3-insertion rate was not detected. The results are shown in tables 1 and 2.

Comparative example 2

< polymerization of propylene >

The same operational procedures as defined in reference example 1 were repeated except that the above-mentioned compound synthesized in comparative example 1 was used as the component (A) and the polymerization temperature was adjusted to 70 ℃ to obtain 155.2g of polypropylene. Through measurement, it was confirmed that the complex activity was 67.5X 10⁴The obtained polypropylene had a melting point (Tm) of 151.5 ℃, a Melt Flow Rate (MFR) of 2.0, and a weight average molecular weight (Mw) of 3.8X 10⁵And a Q value (Mw/Mn) of 2.1.¹³Measurement of the C-NMR spectrum showed [ mmmm]Was 95.5%, 2, 1-inversion was 0.4% and 1, 3-insertion rate was not detected. The results are shown in tables 1 and 2.

TABLE 1

	Catalyst and process for preparing same		Polymerisation reaction Condition	Evaluation (catalyst Performance)
						Components (A)	Component (C)	Catalyst and process for preparing same Activity of	Reactivity of the Complex (×104)
	Example 1	(1)*		Triethyl aluminum	70 ℃/body/2 Hr					1665	17.1
Reference example 1			(1)			MMAO	70 ℃/body 1Hr	-	16.7
	Example 2	(1)		Triethyl aluminum	80 deg.C/body/2 Hr					2350	24.1
Example 3			(1)			Triethyl aluminum	70℃，5kgf/cm2G/ Slurry/1 Hr	170	0.65
	Example 4	(1)		Triethyl aluminum	70 ℃/body/2 Hr					1800	2.7
Example 5			(1)			Triethyl aluminum	70 ℃/body + ethylene /2Hr	3830	5.9
	Comparative example 1	(2)**		Triethyl aluminum	70 deg.C/body/1 Hr					1600	5.8
Comparative example 2			(2)			MMAO	70 deg.C/body/1 Hr	-	67.5

Note: (1)*: dimethylsilylenebis {1, 1' - (2-methyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride;

(2)**: dimethylsilylenebis {1, 1' - (2-methyl-4, 5-benzoindenyl) } zirconium dichloride

TABLE 2

	Properties of the Polymer
					Melting Point (. degree.C.)	MFR (g/10min)	Mw (×105)	Q (Mw/Mn)
	Example 1	150.1	2.5	3.1					2.8
Reference examples					150.9	1.3	3.5	2.7
	Example 2	148.8	8.5	2.1					2.7
Example 3					150.9	3.5	3.0	2.8
	Example 4	148.4	11.1	1.9					2.7
Example 5					141.7	9.7	2.1	2.6
	Comparative example 1	132.0	200	1.1					2.2
Comparative example 2					151.5	2.0	3.8	2.1

Table 2 (continuation)

	Properties of the Polymer
				[mmmm](％)	2.1-(mol％)	1.3-(mol％)
	Example 1	98.9	0.9				0.08
Reference examples				99.0	0.9	0.10
	Example 2	98.8	0.9				0.06
Example 3				99.0	0.7	0.10
	Example 4	98.8	0.9				0.1 0
Example 5				98.8	0.8	0.08
	Comparative example 1	95.1	0.8				Not detected
Comparative example 2				95.5	0.4	To detect

Example 6

(1) Synthesis of dimethylsilylenebis {1, 1' - (2-ethyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride as component (A):

(a) synthesis of tosyl tropolone

25.58g (210mmol) of tropolone were dissolved in 30ml of pyridine. 60ml of a pyridine solution containing 40.77g (214mmol) of tosyl chloride was added to the solution containing tropolone at room temperature. After stirring at room temperature overnight, water was added to the resulting reaction solution to precipitate a crystallized product. The crystallized product was isolated by filtration and dried at 50 ℃ under reduced pressure to obtain 57.61g of tosyltropolone (yield: 99.5%)

(b) Synthesis of 3-propionyl cycloheptatriene furan-2-one

8.07g (29.2mmol) of tosyltropolone and 6.2ml (43.8mmol) of ethyl propionylacetate are suspended in 30ml of ethanol. A solution containing sodium ethoxide prepared from 60ml ethanol and 806mg (35.1mmol) sodium was added to the suspension at 0 ℃. The mixture was stirred at room temperature overnight and then heated at 50 ℃ for 45 minutes. The resulting reaction solution was concentrated to twice its original concentration. Water was added to the concentrated solution to obtain a crystalline product. The crystalline product was isolated from the reaction solution by filtration. Further, the filtrate was concentrated to crystallize the reaction product remaining therein. The crystalline product obtained from the filtrate was also separated from the solution by filtration. The thus-obtained product was mixed together from the reaction solution and the filtrate and dried under reduced pressure to obtain 3.62g of 3-propionylcycloheptafuran-2-one (yield: 61%).

(c) Synthesis of 1-cyano-2-ethyl azulene-3-carboxylic acid

3.62g (17.9mmol) of 3-propionylcycloheptafuran-2-one and 3.8ml (35.8mmol) of ethyl cyanoacetate are dissolved in 50ml of ethanol. This solution was mixed with a sodium methoxide solution prepared from 80ml ethanol and 1.65g (71.7mmol) sodium at 0 ℃. After the mixed solution was stirred at room temperature overnight, the obtained reaction solution was concentrated to twice its original concentration. The concentrated solution is diluted with 200ml of water and extracted with dichloromethane. Thereafter, the aqueous phase of the extraction operation is mixed with dilute hydrochloric acid to acidify the aqueous phase, thereby obtaining a crystalline product. After filtration, the crystalline product was dried under reduced pressure to obtain 3.73g of 1-cyano-2-ethylazulene-3-carboxylic acid (yield: 93%).

(d) Synthesis of 2-Ethylazulene

3.7g (16.4mmol) of 1-cyano-2-ethylazulene-3-carboxylic acid obtained above were separated into two portions, i.e. about 1g and the remaining portion. 30ml of 75% sulfuric acid were added to the first portion, i.e. about 1g of 1-cyano-2-ethylazulene-3-carboxylic acid and heated to 90 ℃ before the remaining portion of 1-cyano-2-ethylazulene-3-carboxylic acid was gradually added. The mixture was heated to 90 ℃ for 2 hours and then at 120 ℃ for 2 hours. The obtained reaction solution was added to an aqueous solution containing 35g of sodium hydroxide, followed by extraction with a mixed solution of hexane and ethyl acetate. The organic phase of the extraction was removed under reduced pressure. The obtained crude product was purified by silica gel column chromatography to obtain 1.71g of 2-ethylazulene (yield: 67%).

(e) Synthesis of bis {1, 1' - (2-ethyl-4-phenyl-1, 4-dihydroazulenyl) } dimethylsilane

A solution of 10.9mmol (0.1M) phenyllithium in diethyl ether/cyclohexane was added to 20ml of a solution of 1.7g (10.9mmol) 2-ethylazulene in hexane at 0 ℃. After stirring at room temperature for 1.5 hours, the solution was mixed with 20ml of tetrahydrofuran at 0 ℃. Further, 0.66ml (5.45mmol) of dichlorodimethylsilane was added to the solution at-78 ℃ and then stirred at room temperature for 1 hour and then held at 50 ℃ for 3 hours. After the mixed solution was left at room temperature overnight, an aqueous solution of ammonium chloride was added to the obtained reaction solution. The solution was separated into aqueous and organic phases. The organic phase was dried over magnesium sulfate and the solvent was removed under reduced pressure. The obtained crude product was purified by column chromatography using a mixed solvent composed of hexane and dichloromethane (10: 1 to 5: 1) as an eluent, to obtain 1.07g of bis {1, 1' - (2-ethyl-4-phenyl-1, 4-dihydroazulenyl) } dimethylsilane (yield 37%).

(f) Synthesis of dimethylsilylenebis {1, 1' - (2-ethyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride:

a hexane solution containing 6.62mmol of n-butyllithium was added to 15ml of an ether solution containing 3.32mmol of bis {1, 1' - (2-ethyl-4-phenyl-1, 4-dihydroazulenyl) } dimethylsilane produced above at-78 ℃. After stirring overnight at room temperature, the solvent was removed under reduced pressure. 10ml of toluene and 0.25ml of diethyl ether were added to the product to form a solution, and 775mg (3.32mmol) of zirconium tetrachloride were added to the solution at-70 ℃. The obtained solution was gradually warmed to room temperature and stirred at room temperature for 3 hours. The solution was successively filtered through celite, and the obtained solid component was washed with 6ml of toluene and 6ml of hexane. The solid component thus obtained was dissolved in 30ml of dichloromethane, and the solvent was removed under reduced pressure. To the resulting concentrated solution was added 10ml of hexane to form a precipitate. The precipitate was separated from the solution, followed by drying and solidification under reduced pressure, to obtain 450mg of a racemic and meso mixture of dimethylsilylenebis {1, 1' - (2-ethyl-4-phenyl-4-hydroazulenyl) zirconium dichloride (yield: 20%).

(g) Purification of racemic compound:

400mg of the racemic and meso mixture produced above were dissolved in 15ml of dichloromethane and placed in a Pyrex vessel equipped with a 100W high-pressure mercury vapor lamp. The solution was irradiated with light at normal pressure for 10 minutes while stirring to increase the percentage of racemic compound in the mixture. The dichloromethane was then removed by stirring under reduced pressure. The obtained yellow solid was mixed with 5ml of toluene to form a solution, and then the solution was stirred. After filtering the solution, the obtained solid component was washed with 6ml of hexane to obtain 173mg of a racemic compound of dimethylsilylenebis {1, 1' - (2-ethyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride.

Process for producing racemic compound obtained above¹Chemical shifts of H-NMR were as follows:

300MHz，CDCl₃(ppm)1.00(s，6H，SiMe₂)，1.05(t，³J＝8Hz，6H，CH₃CH₂)，2.42(sext，³J＝8Hz，²J＝15Hz，2H，CH₃CHH′)，2.60(sext，³J＝8Hz，²J＝15Hz，2H，CH₃CHH'), 4.94(br s, 2H, 4-H), 5.83-5.95(m, 4H), 5.99(s, 2H), 6.08-6.12(m, 2H), 6.75(d, 2H, 8-H), 7.2-7.4(m, l0H, aromatic).

(2) Polymerization of propylene

0.45mmol of triethylaluminum, a slurry of the chemically treated clay mineral described in example 11(2) below, and 700ml of liquid propylene were charged in a 1 liter stirred autoclave under a nitrogen atmosphere and at room temperature. Further, 1.5. mu. mol of a racemic compound of dimethylsilylenebis {1, 1' - (2-ethyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride produced in the above item (1) was dissolved in toluene, and the solution was then charged into the autoclave together with high-pressure argon gas which passed through a safety diaphragm. The contents of the autoclave were heated to 80 ℃ and polymerization of propylene was carried out for 1 hour. Then, unreacted propylene was discharged to terminate the polymerization reaction of propylene, thereby obtaining 180g of polypropylene. By measurement, it was confirmed that the catalyst activity was 3600 and the complex activity was 17.6X 10⁴The obtained polypropylene had a melting point (Tm) of 149.2 ℃, a Melt Flow Rate (MFR) of 11 and a weight average molecular weight (Mw) of 20X 10⁵And a Q value (Mw/Mn) of 2.5.

Reference example 2

< polymerization of propylene >

4mmol (calculated as Al atom) of methylaluminoxane ("MMAO" manufactured by TOSOH AKZO CORP. RTM.) and a toluene solution containing 0.27mg of a racemic compound of dimethylsilylenebis {1, 1' - (2-ethyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride were charged into a 2-liter stirred autoclave. Further, 1,500ml of propylene was charged into the autoclave. The contents of the autoclave were heated to 70 ℃ and polymerization of propylene was carried out for 1 hour to obtain 239g of polypropylene. By measurement, it was confirmed that the complex activity was 87.2X 10⁴And the obtained polypropylene had a melting point (Tm) of 155.2 ℃, a Melt Flow Rate (MFR) of 0.6 and a weight average molecular weight (Mw) of 4.7X 10⁵And a Q value (Mw/Mn) of 3.1.

Example 7

(1) Chemical treatment of clay minerals

10g of spodumene (Li-HT from TOPY KOGYO CO., LTD.) was weighed and charged into a 300ml round bottom flask. 100ml of desalted water was introduced into the flask to form a slurry. The slurry was added to a mechanical stirrer. While stirring the slurry, 8.9ml of TiCl4 (EXTRA-HIGH GRADE produced by KISHIDA CHEMICAL co., ltd.) was gradually added dropwise at room temperature. The slurry was further stirred for 3 hours, and then filtered to separate a solid component. The obtained solid component was washed with water until the pH of the filtrate became 5.0. After drying at 100 ℃ for 3 hours, the filter cake obtained is powdered in a porcelain mortar and sieved through a sieve to separate particles having a particle size of not more than 105 μm. The thus-obtained pellets were dried at 200 ℃ under reduced pressure for 2 hours to obtain component (B).

(2) Preparation of solid catalyst component

Weighing 1.2g of TiCl obtained in the above item (1)₄Treated spodumene and charged to a 100ml flask under nitrogen atmosphere. 12ml of toluene was added to the flask to form a slurry. A toluene solution of triethylaluminum (0.9mol/L) was prepared separately. Containing TiCl while stirring₄6.4ml of a separately prepared toluene solution of triethylaluminium were added to the treated spodumene slurry at room temperatureInto the slurry. The slurry was stirred at room temperature for 1 hour and then washed with toluene until the washing efficiency reached 1/100. The measurement confirmed that the concentration of the slurry was 52.6 mg/ml.

(3) Polymerization of propylene

0.45mmol of triisobutylaluminum, 1.9ml of the catalyst slurry obtained in the above item (2) and 1,500ml of liquid propylene were charged into a 2-liter stirring autoclave at room temperature under a nitrogen stream. Separately, 2.0mg (3.0. mu. mol) of dimethylsilylenebis {1, 1' - (2-methyl-4-phenyl-4-hydroazulenyl) } dichloroThe zirconium oxide was dissolved in 1.6ml of toluene to prepare a solution. The solution was introduced into the autoclave together with high pressure argon which broke the safety diaphragm. The contents of the autoclave were heated to 80 ℃ and the propylene polymerization was allowed to proceed at this temperature for 1 hour. Then, unreacted propylene was discharged to terminate the polymerization reaction of propylene, thereby obtaining 110g of polypropylene. As a result of measurement, it was confirmed that the catalyst activity was 1100 and the complex activity was 5.5X 10⁴The obtained polypropylene had a melting point (Tm) of 147.0 ℃, a Melt Flow Rate (MFR) of 24.2 and a weight average molecular weight (Mw) of 1.7X 10⁵And a Q value (Mw/Mn) of 2.9.

Example 8

(1) Chemical treatment of clay minerals

10g of spodumene (Li-HT from TOPY KOGYO CO., LTD.) was weighed and charged into a 300ml round bottom flask. 100ml of desalted water was introduced into the flask to form a slurry. The slurry was added to a mechanical stirrer. While stirring the slurry, 25ml at room temperature will contain 19.3mg of AlCl₃(EXTRA-HIGH GRADE manufactured by Wato Pure chemical Industries, Ltd.) was gradually added dropwise. The slurry was further stirred for 3 hours, and then filtered to separate a solid component. The obtained solid component was washed with water until the pH of the filtrate became 5.0. After drying at 100 ℃ for 3 hours, the filter cake obtained is powdered in a porcelain mortar and sieved through a sieve to separate particles having a particle size of not more than 105 μm. The thus-obtained pellets were dried at 200 ℃ under reduced pressure for 2 hours to obtain component (B).

(2) Preparation of solid catalyst component

1.1g of AlCl obtained in the above item (1) was weighed₃Treated spodumene and charged to a 100ml flask under nitrogen atmosphere. 10ml of toluene was added to the flask to form a slurry. While stirring containing AlCl₃5.5ml of triethylaluminum in toluene (0.91mol/L) were added to the slurry at room temperature, simultaneously with the treated spodumene slurry. The slurry was stirred at room temperature for 1 hour and then washed with toluene until the washing efficiency reached 1/100. The measurement confirmed that the concentration of the slurry was 35.7 mg/ml.

(3) Polymerization of propylene

0.45mmol of triisobutylaluminum, 2.8ml of the catalyst component slurry obtained in the above item (2) and 1,500ml of liquid propylene were charged into a 2-liter stirring autoclave at room temperature under a nitrogen flow. Separately, 2.0mg (3.0. mu. mol) of dimethylsilylenebis {1, 1' - (2-methyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride was dissolved in 1.6ml of toluene to prepare a solution. The solution was introduced into the autoclave together with high pressure argon which broke the safety diaphragm. The contents of the autoclave were heated to 80 ℃ and the propylene polymerization was allowed to proceed at this temperature for 1 hour. Then, unreacted propylene was discharged to terminate the polymerization reaction of propylene, thereby obtaining 68g of polypropylene. As a result of measurement, it was confirmed that the catalyst activity was 660 and the complex activity was 3.4X 10⁴Obtained byThe polypropylene of (A) had a melting point (Tm) of 147.3 ℃ and a Melt Flow Rate (MFR) of 24.2. Example 9

(1) Synthesis of dimethylsilylenebis {1, 1' - (2-methyl-4-phenyl-4-hydroazulenyl) } hafnium dichloride:

(a) synthesis of racemic and meso mixtures:

3.22g of 2-methylazulene were dissolved in 30ml of hexane. 21ml of a cyclohexane/diethyl ether solution of phenyllithium (1.0 eq.) were added gradually to the hexane solution obtained above at 0 ℃. After stirring at room temperature for 1.5 hours, the resulting solution was cooled to-78 ℃ and then mixed with 30ml of tetrahydrofuran. To the solution were added 45. mu. mol of 1-methylimidazole and 1.37ml of dimethyldichlorosilane, and the temperature thereof was elevated to room temperature. The solution was further stirred for 1 hour. After addition of the aqueous ammonium chloride solution, the solution was separated into an aqueous phase and an organic phase. The organic phase was dried over magnesium sulfate and the solvent was removed by stirring under reduced pressure, thereby obtaining 5.84g of crude bis {1, 1' - (2-methyl-4-phenyl-1, 4-dihydroazulenyl) dimethylsilane.

The crude bis {1, 1' - (2-methyl-4-phenyl-1, 4-dihydroazulenyl) dimethylsilane product thus obtained was dissolved in 30ml of diethyl ether. 14.2ml of a hexane solution of n-butyllithium (1.64mol/L) was added dropwise to the solution at-78 ℃ and then the temperature of the solution was raised to room temperature and stirred at room temperature for 12 hours. The solution was stirred under reduced pressure to remove the solvent. Then, 80ml of a mixture of toluene and dimethyl ether (40: 1) was added to the solution. Further, the solution was mixed with 3.3g of hafnium tetrachloride at-60 ℃ and the temperature thereof was gradually raised to room temperature, followed by stirring at room temperature for 4 hours. The obtained solution was concentrated under reduced pressure to obtain a solid product. The solid product obtained was washed with toluene and extracted with dichloromethane to obtain 1.74g of a racemic and meso mixture of dimethylsilylenebis {1, 1' - (2-methyl-4-phenyl-4-hydroazulenyl) hafnium dichloride.

(b) Purification of racemic compound:

1.74g of the racemic and meso mixture prepared by repeating the above reaction was dissolved in 30ml of dichloromethane and placed in a Pyrex vessel equipped with a 100W high-pressure mercury lamp. The solution was irradiated with light at normal pressure for 40 minutes while stirring to increase the percentage of racemic compound in the mixture, and dichloromethane was removed by stirring under reduced pressure. 10ml of toluene were added to the obtained yellow solid. After stirring, the mixture was filtered to separate a solid component therefrom. The solid component thus obtained was washed with 8ml of toluene and 4ml of hexane to obtain 917mg of a racemic compound of dimethylsilylenebis {1, 1' - (2-methyl-4-phenyl-4-hydroazulenyl) } hafnium dichloride.

(2) Polymerization of propylene

The same operation was carried out as described in example 13(2) except that 1.12mg of the racemic compound obtained in the above item (1) was used as the component (A) and the polymerization time was changed to 35 minutes, to obtain 163g of polypropylene. ThroughMeasurement confirmed that the catalyst activity was 3260 and the complex activity was 25.0X 10⁴. Further, it was confirmed that the obtained polypropylene had a melting point (Tm) of 152.7 ℃, a Melt Flow Rate (MFR) of 0.8, and a weight average molecular weight (Mw) of 4.1X 10⁵And a Q value (Mw/Mn) of 2.6.

Reference example 3

4mmol (calculated as Al atom) of methylaluminoxane ("MMAO" manufactured by TOSOH AKZO CORP. and containing 0.298mg of the racemic compound obtained in the above item (1) of example 9 were charged into a 2-liter stirring autoclave. Further, 1,500ml of propylene was charged into the autoclave. The contents of the autoclave were heated to 70 ℃ and polymerization of propylene was carried out at this temperature for 1 hour to obtain 32g of polypropylene. By measurement, it was confirmed that the complex activity was 10.7X 10⁴And the obtained polypropylene had a melting point (Tm) of 154.4 ℃, a Melt Flow Rate (MFR) of 0.08, and a weight average molecular weight (Mw) of 8.4X 10⁵And a Q value (Mw/Mn) of 3.8.

Example 10

(1) Chemical treatment of clay minerals

22.20g of commercial montmorillonite ("KUNIPIA F" manufactured by KUNIMINE INDUSTRIES CO., LTD.) was dispersed in a solution prepared by dissolving 15.96g of magnesium sulfate in 134ml of desalted water. The obtained dispersion was heated to 86 ℃ while stirring, thereby obtaining a wet cake. Next, the wet cake thus obtained was dispersed in a solution prepared by dissolving 23.38g of sulfuric acid and 29.16g of magnesium sulfate in 69.24ml of desalted water, and then treated under reflux for 2 hours. The dispersion is then filtered, and the filter cake is separated therefrom. The obtained filter cake was washed with water until the pH of the filtrate reached 6. The resulting product was dried at 100 ℃ for 3 hours, powdered in a porcelain mortar, and separated by sieving to give granules having a particle size of not more than 105 μm. The pellets were dried at 200 ℃ under reduced pressure for 2 hours to obtain component (B).

(2) Production of solid catalyst component and prepolymerization of propylene

0.8796g of component (B) obtained in the above (1) was charged into a 100ml flask under a nitrogen atmosphere. Also, 3.5ml of a toluene solution containing 0.50mmol/ml triethylaluminum was added to the flask, and the mixture was then stirred at room temperature for 45 minutes. Subsequently, the mixture is filtered to separate a solid component therefrom. The solid component thus separated was washed with toluene until the washing efficiency reached 1/100. Thereafter, the solid component was mixed with 15ml of toluene to prepare a toluene slurry.

Separately, 0.6ml of a toluene solution of triisobutylaluminum (0.50mmol/ml) and 19.1ml of a toluene solution of racemic dimethylsilylenebis {1, 1' - (2-methyl-4-phenyl-4-hydroazulenyl) } hafnium dichloride (1.5. mu. mol/ml) obtained in example 9(1) were added to the flask, and stirred at room temperature to obtain a solution. The solution thus obtained is mixed with the toluene slurry prepared above to form a slurry containing the solid catalyst component.

40ml of toluene and then 36ml of the slurry containing the solid catalyst component prepared above were charged at room temperature and under a nitrogen atmosphere in a 2-liter stirred autoclave. While the temperature of the autoclave was kept at 24 ℃, 104ml of propylene was charged into the autoclave and subjected to prepolymerization for 3 minutes to obtain a prepolymerization catalyst slurry. The amount of the polymer obtained by the prepolymerization was 2.98g/g of the solid catalyst component. The concentration of the solid catalyst component in the obtained prepolymerization catalyst slurry was 12.5 mg/ml.

(3) Block copolymerization of propylene

0.40mmol of triisobutylaluminum, the prepolymerization catalyst slurry obtained in the above (2) containing 50.0mg of the solid catalyst component, 200ml of hydrogen and 1,500ml of liquid propylene were charged into a 2-liter stirring autoclave. The contents of the autoclave were then heated to 75 ℃ to allow polymerization of the propylene to proceed for 45 minutes. Then, unreacted propylene was discharged to terminate the polymerization reaction of propylene, thereby obtaining 289g of polypropylene. By measurement, it was confirmed that the catalyst activity was 5780 and the complex activity was 2.4X 10⁵And the obtained polypropylene had a melting point (Tm) of 151.8 ℃ and a Melt Flow Rate (MFR) of 14.2.

After 17g of the polypropylene obtained had been discharged from the autoclaveWhile keeping the autoclave contents at 60 ℃, propylene and then ethylene were supplied to the autoclave until the propylene and ethylene pressures in the autoclave reached 10kgf/cm, respectively²G and 20kgf/cm²G is up to. The propylene and ethylene thus supplied were subjected to polymerization for 80 minutes while introducing a mixed gas of ethylene and propylene having a partial pressure of propylene of 49.97% to maintain the internal pressure of the autoclave at 20kgf/cm²G. Then, a mixed gas of ethylene and propylene was discharged to terminate the polymerization reaction, thereby obtaining 46g of an ethylene/propylene rubber component. By measurement, it was confirmed that the catalyst activity was 978 and the complex activity was 4.0X 10⁴And the content of the rubber component in the obtained block copolymer was 14.5% by weight, and the Melt Flow Rate (MFR) was 7.0.

Example 11

(1) Synthesis of dimethylgermylidenebis {1, 1' - (2-methyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride:

1.5g of 2-methylazulene were dissolved in 38ml of n-hexane. 9.8ml of a cyclohexane/diethyl ether solution of phenyllithium (1.08M equiv.) are added dropwise to the n-hexane solution at 3 ℃ to 5 ℃. After stirring at room temperature for 1 hour, the obtained solution was cooled to 0 ℃, and then 38ml of tetrahydrofuran was added. In addition, 0.02ml of 1-methylimidazole and 0.61ml of dimethyl germanium dichloride were added dropwise to the solution. After stirring at 0 ℃ for 20 minutes, the temperature of the reaction solution was raised to room temperature, followed by stirring at room temperature for 3.5 hours. The reaction solution was mixed with a saturated aqueous solution of ammonium chloride and extracted with n-hexane. The extract was separated into an aqueous phase and an organic phase. The organic phase was washed with saturated brine and dried over magnesium sulfate. The dried product was stirred under reduced pressure to remove the solvent remaining therein. 2.9g of the concentrated residue thus obtained was purified by column chromatography to obtain 2.4g of an amorphous solid product.

2.4g of the amorphous solid product thus obtained are dissolved in 30ml of diethyl ether. 5.6ml of a hexane solution of n-butyllithium (1.59M) was added dropwise to the ether solution at-78 ℃. After stirring at this temperature for 10 minutes, the temperature of the solution was gradually raised to room temperature. After further stirring at room temperature for 2 hours, the solution was allowed to stand overnight. The reaction solution was stirred under reduced pressure to remove the solvent, and then mixed with 20ml of toluene and 0.5ml of diethyl ether. After cooling to-78 ℃, the reaction solution was mixed with 1.0g of zirconium tetrachloride, and the reaction temperature was then gradually raised to room temperature, followed by stirring at room temperature for a total of 5 hours. The obtained reaction solution was filtered through celite to separate a solid component therefrom. The solid component thus obtained was washed twice with 5ml of toluene and then extracted with dichloromethane. The extract was stirred under reduced pressure to remove the solvent, thereby obtaining 0.93g of a racemic and meso mixture of dimethylgermylidebis {1, 1' - (2-methyl-4-phenyl-4-hydroazulenyl) zirconium dichloride (the ratio of the rac to the meso is about 6: 4) (yield 30%).

Of the racemic and meso mixtures obtained above¹Chemical shifts of H-NMR were as follows:

300MHz，CDCl₃(ppm)1.14(s, meso SiMe), 1.18(s, meso SiMe), 1.20(s, meso SiMe), 2.16(s, 2-Me), 4.98-5.00(m, -CH ═ 5.06-5.08(m, -CH ═) 5.83-5.94(m, -CH ═) 6.06-6.3(m, -CH ═) 6.67(s, -CH ═) 6.71(s, -CH ═) 7.2-7.5(m, aromatic ring)

(2) Chemical treatment of clay minerals and preparation of solid catalyst component

10g of montmorillonite ("KUNIPIA F" manufactured by KUNIMINE INDUSTRIES CO., LTD.) was dispersed in dilute sulfuric acid consisting of 10g of sulfuric acid and 90ml of desalted water. The resulting dispersion was heated to its boiling point and then stirred at this temperature for 6 hours. Then, the recovered montmorillonite was sufficiently washed with desalted water, and dried at 200 ℃ for 2 hours after predrying to obtain a chemically treated clay mineral. 200mg of the chemically treated montmorillonite was added to 0.8ml of a toluene solution of triethylaluminum (0.5 mol/L). The mixture was stirred at room temperature for 1 hour and then washed with toluene to obtain a montmorillonite/toluene slurry containing 20mg/ml of montmorillonite.

(3) Polymerization of propylene

0.5mmol (calculated as Al atom) of triisobutylaluminum (produced by TOSOH AKZO CORP.) was addedInto a 2 liter stirred autoclave. Separately, 2.1mg of the above-prepared racemic and meso mixture of dimethylgermylidene bis {1, 1' - (2-methyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride obtained in (1) above was diluted with 1.1ml of toluene. The diluted racemic and meso mixtures were added to a catalyst feeder equipped with a safety diaphragm. Further, 100mg of the triethylaluminum-treated montmorillonite obtained in the above (2) and 0.3mmol (in terms of Al atom) of triisobutylaluminum were charged into the autoclave. Then, 1,500ml of propylene was added to the autoclave, and then the safety diaphragm of the catalyst feeder was broken at room temperature. The contents of the autoclave were heated to 80 ℃ and polymerization of propylene was carried out at this temperature for 1 hour, thereby obtaining 69g of polypropylene. Through measurement, it was confirmed that the catalyst activity was 690 and the complex activity was 3.3X 10⁵. Furthermore, it has been confirmed that polypropylene insoluble in boiling heptane has a melting point (Tm) of 147.9 ℃, a Melt Flow Rate (MFR) of 7.3 and a weight average molecular weight (Mw) of 2.4X 10⁵And a Q value (Mw/Mn) of 2.4.

Example 12

(1) Synthesis of dimethylsilylenebis [1, 1' - { 2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl } ] zirconium dichloride.

(a) Synthesis of racemic and meso mixtures:

11.7ml of a pentane solution containing 19.2mmol of t-butyllithium (1.64M) was added dropwise at-78 ℃ to a solution prepared by dissolving 1.84g (9.6mmol) of 1-bromo-4-chlorobenzene in a mixed solvent composed of 10ml of n-hexane and 10ml of diethyl ether. The resulting solution was stirred at-5 ℃ for 1.5 hours, then 1.2g (8.6mmol) of 2-methylazulene was added to the obtained solution. The obtained reaction solution was stirred for 1.5 hours while the temperature thereof was elevated to room temperature.

The reaction solution was then cooled to 0 ℃ and mixed with 15. mu.l (0.19mmol) of 1-methylimidazole and then with 0.52ml (4.3mmol) of dimethyldichlorosilane. After the reaction solution was stirred at room temperature for 1.5 hours, dilute hydrochloric acid was added to terminate the reaction. The reaction solution was separated into an organic phase and an aqueous phase, and the organic phase was concentrated under reduced pressure. After dichloromethane was added to the concentrated organic phase, the mixture was dried over magnesium sulfate and stirred under reduced pressure to remove the solvent. The product thus obtained was purified by silica gel column chromatography (mixed solvent: dichloromethane and n-hexane), whereby 2.1g of an amorphous solid product was obtained.

Next, 1.27g of the thus obtained amorphous solid product was dissolved in 15ml of diethyl ether. 2.8ml of an n-hexane solution (1.66M) containing 4.5mmol of n-butyllithium was added dropwise to the ether solution at-78 ℃. After the end of the dropwise addition, the reaction solution was stirred for 12 hours while its temperature was gradually raised to room temperature. After the reaction solution was stirred under reduced pressure to remove the solvent, 5ml of a mixed solvent of toluene and diethyl ether (40: 1) was added thereto. After cooling to-78 ℃, the reaction solution was mixed with 0.53g (2.3mmol) of zirconium tetrachloride, the temperature of which was immediately raised to room temperature, and then stirred at room temperature for 4 hours. The obtained reaction solution was filtered through celite to separate a solid component therefrom. The solid component thus obtained was washed with 3ml of toluene to recover a solid reaction product. The recovered solid reaction product was extracted with dichloromethane. The extract was stirred under reduced pressure to remove the solvent, thereby obtaining 906mg of a racemic and meso mixture of dimethylsilylenebis [ {1, 1' - (2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl } ] zirconium dichloride (yield: 56%).

Of the racemic and meso mixtures obtained above¹Chemical shifts of H-NMR were as follows:

300MHz，C₆D₆(ppm)0.45(s，meso SiMe)，0.50(s，racemic SiMe)，0.57(s，meso SiMe)，1.88(s，meso 2-Me)，1.96(s，racemic 2-Me)，5.17(br s，racemic4-H)，5.22(br s，meso 4-H)，5.6-6.1(m，-CH＝)，6.65-6.8(m，-CH＝)，7.1-7.40(m，-CH＝)

(b) purification of racemic compound:

900mg of the racemic and meso mixture produced above were dissolved in 20ml of dichloromethane and irradiated by light for 40 minutes using a 100W high-pressure mercury vapor lamp to increase the percentage of racemic compounds in the mixture. Insoluble components are then removed from the solution by filtration, and the recovered filtrate is then concentrated, dried and solidified. Subsequently, the solid component thus obtained was mixed with 22ml of toluene with stirring, and then kept, and then the supernatant liquid was removed. The purification operation was repeated 4 times, and the solid residue obtained was dried to obtain 275mg of a racemic compound of dimethylsilylenebis [ {1, 1' - (2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl) } zirconium dichloride.

Process for producing racemic compound obtained above¹Chemical shifts of H-NMR were as follows:

300MHz，CDCl₃(ppm)0.95(s，6H，SiMe)，2.13(s，6H，2-Me)，4.82-4.85(br d，2H)，5.70-5.78(m，2H)，5.83-5.92(m，4H)，6.03-6.12(m，2H)，6.70(d，J＝12Hz，2H)，7.1-7.35(m，8H，-CH＝)

(2) polymerization of propylene using methylaluminoxane as cocatalyst

4mmol (calculated as Al atom) of methylaluminoxane ("MMAO" manufactured by TOSOH AKZO CORP. and 0.29mg of the racemic compound obtained above were charged into a 2-liter stirring autoclave. Further, 1,500ml of propylene was charged into the autoclave. The contents of the autoclave were heated to 70 ℃ to perform polymerization of propylene for 1 hour, thereby obtaining 72g of polypropylene. Through measurement, the complex activity is confirmed to be 24.9 multiplied by 10⁴The obtained polypropylene has a melting point (Tm) of 150.4 ℃ and a Melt Flow Rate (MFR)Is 1.1, and has a weight average molecular weight (Mw) of 3.6X 10⁵And a Q value (Mw/Mn) of 3.0.

Example 13

< polymerization of propylene Using Clay mineral as cocatalyst >

(1) Chemical treatment of clay minerals and preparation of solid catalyst component

The same procedure as defined in example 11(2) was carried out to obtain a montmorillonite/toluene slurry containing 33mg/ml of montmorillonite.

(2) Polymerization of propylene

0.25mmol (in terms of Al atom) of triisobutylaluminum (produced by TOSOH AKZO CORP.) was charged into a 1-liter stirring autoclave. Separately, 1.09mg of the compound prepared in example 12(1)The racemic compound obtained in (1.1) was diluted with 1.1ml of toluene and then added to a catalyst feeder equipped with a safety diaphragm. Further, the slurry prepared above containing 50mg of montmorillonite and 0.15mmol (in terms of Al atom) of triisobutylaluminum was charged into a pressure autoclave. Then, 700ml of propylene was added to the autoclave, and then the safety diaphragm of the catalyst feeder was broken at room temperature. The contents of the autoclave were heated to 80 ℃ and polymerization of propylene was carried out at this temperature for 1 hour, thereby obtaining 131.3g of polypropylene. By measurement, it was confirmed that the catalyst activity was 3,000 and the complex activity was 13.5X 10⁴The obtained polypropylene had a melting point (Tm) of 149.2 ℃, a Melt Flow Rate (MFR) of 5.8 and a weight average molecular weight (Mw) of 2.4X 10⁵And a Q value (Mw/Mn) of 2.5.

Example 14

(1) Synthesis of dimethylsilylenebis [1, 1' - { 2-methyl-4- (4-trifluoromethylphenyl) -4-hydroazulenyl) zirconium dichloride

The same procedures as defined in example 12(1) (a) were carried out except for using 1.35g of 1-bromo-4-trifluoromethylbenzene in place of 1.15g of 1-bromo-4-chlorobenzene in example 12(1) (a), to obtain 1.16g of an amorphous solid product.

The same procedures as defined in example 12(1) (a) were carried out using the amorphous solid product produced above, 2.2ml of a n-hexane solution of n-butyllithium (1.66M) and 0.42g (1.8mmol) of zirconium tetrachloride, to thereby obtain 0.36g of a yellow solid product. As¹As a result of H-NMR analysis, the yellow solid product was confirmed to be a racemic and meso mixture of dimethylsilylenebis [1, 1' - { 2-methyl-4- (4-trifluoromethylphenyl) -4-hydroazulenyl) zirconium dichloride. The yield of the product was 15%.

(2) Polymerization of propylene using methylaluminoxane as cocatalyst

4mmol (calculated as Al atom) of methylaluminoxane (produced by TOSOH AKZO CORP., Ltd.)"MMAO") and 0.6mg of the racemic and meso compounds obtained above were charged to a 2 liter stirred autoclave. Further, 1,500ml of propylene was charged into the autoclave. Inside of the pressure kettleAfter the contents were heated to 70 ℃, polymerization of propylene was carried out at this temperature for 1 hour, thereby obtaining 50g of polypropylene. The activity of the complex was confirmed to be 8.3X 10 by measurement⁴The obtained polypropylene had a melting point (Tm) of 153.2 ℃ and a Melt Flow Rate (MFR) of 1.0.

Example 15

(1) Synthesis of dimethylsilylenebis [1, 1' - { 2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl } ] zirconium dichloride:

(a) synthesis of racemic and meso mixtures:

10ml of a pentane solution containing 16.4mmol of t-butyllithium (1.64M) was added dropwise at-78 ℃ to a solution prepared by dissolving 0.90ml (8.2mmol) of 1-bromo-4-fluorobenzene in a mixed solvent composed of 10ml of n-hexane and 10ml of diethyl ether. The resulting solution was stirred at-78 ℃ for 15 minutes and then at-10 ℃ for 45 minutes. The solution was then combined with 1.05g (7.37mmol) 2-methylazulene and the components were reacted with each other. The resulting reaction solution was stirred for 1 hour while the temperature thereof was elevated to room temperature. Then, the reaction solution was cooled to 0 ℃ and mixed with 10ml of tetrahydrofuran. In addition, the reaction solution was mixed with 16. mu.l (0.20mmol) of 1-methylimidazole and 0.45ml (3.7mmol) of dimethyldichlorosilane. After the reaction solution was stirred at room temperature for 1 hour, dilute hydrochloric acid was added to terminate the reaction. The reaction solution was separated into an organic phase and an aqueous phase, and the organic phase thus separated was concentrated under reduced pressure and dried over magnesium sulfate. The dried product was stirred under reduced pressure to remove the solvent remaining therein. The product thus obtained was purified by silica gel column chromatography (mixed solvent: dichloromethane and n-hexane), whereby 2.1g of an amorphous solid product was obtained.

Next, 1.55g of the thus-obtained amorphous solid product was dissolved in 15ml of diethyl ether. 3.5ml of an n-hexane solution (1.66M) containing 5.8mmol of n-butyllithium was added dropwise to the ether solution at-78 ℃. After the end of the dropwise addition, the reaction solution was stirred for 12 hours while its temperature was gradually raised to room temperature. After the reaction solution was stirred under reduced pressure to remove the solvent, 6ml of a mixed solvent of toluene and diethyl ether (40: 1) was added thereto. After cooling to-78 ℃, the reaction solution was further mixed with 0.68g (2.9mmol) of zirconium tetrachloride, the temperature of which was immediately raised to room temperature, and then stirred at room temperature for 4 hours. The obtained reaction solution was mixed with 30ml of dichloromethane and filtered through celite (celite). To the obtained filtrate, 25ml of n-hexane was added, thereby obtaining 1.0g of a racemic and meso mixture of dimethylsilylenebis [1, 1' - { 2-methyl-4- (4-fluorophenyl) -4-hydroazulenyl } ] zirconium dichloride as a precipitated product (yield: 50%).

Of the racemic and meso mixtures obtained above¹Chemical shifts of H-NMR were as follows:

300MHz，C₆D₆(ppm)0.45(s，meso SiMe)，0.51(s，racemic SiMe)，0.58(s，meso SiMe)，1.89(s，meso 2-Me)，1.97(s，racemic 2-Me)，5.20(br s，racemic4-H)，5.28(br s，meso 4-H)，5.6-6.2(m，-CH＝)，6.75-7.4(m，-CH＝)

(b) purification of racemic compound:

subsequently, 333mg of the racemic and meso mixture produced above were suspended in 20ml of dichloromethane and irradiated using a 100W high pressure mercury vapor lamp for 10 minutes to increase the percentage of racemic compounds in the mixture. Insoluble components are then removed from the solution by filtration, and the recovered filtrate is then concentrated, dried and solidified. Subsequently, the solid component thus obtained was mixed with 4ml of toluene under stirring, and then kept, and then the supernatant liquid was removed. This purification operation was repeated 3 times, and the solid residue obtained was washed twice with hexane and then dried to obtain 115mg of a racemic compound of dimethylsilylenebis [1, 1' - { 2-methyl-4- (4-fluorophenyl) -4-hydroazulenyl } ] zirconium dichloride.

Process for producing racemic compound obtained above¹Chemical shifts of H-NMR were as follows:

300MHz，CDCl₃(ppm)0.95(s，6H，Si-Me)，2.14(s，6H，2-Me)，4.84(br，2H，4-H)，5.72-5.90(m，6H)，6.05-6.10(m，2H)，6.72(d，J＝12Hz，2H)，6.95-7.05(m，4H，-CH＝)，7.32-7.40(m，4H，-CH＝)

(2) polymerization of propylene using methylaluminoxane as cocatalyst

By carrying out the same operation procedure as defined in example 12(2) except for using the racemic compound obtained in the above item (1) in place of the racemic compound obtained in example 12(1), 30g of polypropylene was obtained. The activity of the complex was found to be 10.3X 10 by measurement⁴The obtained polypropylene had a melting point (Tm) of 149.7 ℃, a Melt Flow Rate (MFR) of 1.3 and a weight average molecular weight (Mw) of 3.4X 10⁵And a Q value (Mw/Mn) of 2.3.

Example 16

< polymerization of propylene Using Clay mineral as cocatalyst >

The same operational procedures as defined in example 13(2) were carried out, except that 1.035mg of the racemic compound obtained in example 15 was used instead of the racemic compound obtained in example 13(1), to obtain 154g of polypropylene. As a result of measurement, it was confirmed that the catalyst activity was 3080 and the complex activity was 14.2X 10⁴The obtained polypropylene had a melting point (Tm) of 148.0 ℃, a Melt Flow Rate (MFR) of 6.9 and a weight average molecular weight (Mw) of 2.2X 10⁵And a Q value (Mw/Mn) of 2.4.

Example 17

(1) Synthesis of dimethylsilylenebis [1, 1' - { 2-methyl-4- (3-chlorophenyl) -4-hydroazulenyl } ] hafnium dichloride.

(a) Synthesis of racemic and meso mixtures:

18.7ml of a pentane solution containing 30.65mmol of t-butyllithium (1.64M) was added dropwise at-78 ℃ to a solution prepared by dissolving 1.8ml (15.32mmol) of 1-bromo-3-chlorobenzene in a mixed solvent composed of 20ml of n-hexane and 20ml of diethyl ether. The resulting solution was stirred at-5 ℃ for 1 hour and then combined with 1.96g (13.79mmol) of 2-methylazulene to react the components with each other. The obtained reaction solution was stirred for 1.25 hours while the temperature thereof was elevated to room temperature. Then, the reaction solution was cooled to 0 ℃ and mixed with 20ml of tetrahydrofuran and 30. mu.l (0.38mmol) of 1-methylimidazole, and then mixed with 0.84ml (6.9mmol) of dimethyldichlorosilane. After the reaction solution was stirred at room temperature for 1.5 hours, dilute hydrochloric acid was added to terminate the reaction. The reaction solution was separated into an organic phase and an aqueous phase, and the organic phase was concentrated under reduced pressure. After dichloromethane was added to the concentrated organic phase, the mixture was dried over magnesium sulfate and stirred under reduced pressure to remove the solvent, thereby obtaining an amorphous crude reaction product.

The amorphous crude solid product thus obtained was then dissolved in 20ml of dry diethyl ether. 8.6ml of an n-hexane solution (1.6M) containing 13.8mmol of n-butyllithium was added dropwise to the ether solution at-78 ℃. After the end of the dropwise addition, the reaction solution was stirred for 12 hours while its temperature was gradually raised to room temperature. After the reaction solution was stirred under reduced pressure to remove the solvent, 15ml of a mixed solvent of toluene and diethyl ether (40: 1) was added thereto. After cooling to-78 deg.C, the reaction solution was mixed with 2.2g (6.9mmol) of hafnium tetrachloride, the temperature of which was immediately raised to room temperature, followed by stirring at room temperature for 5 hours. The obtained reaction solution was filtered through celite to separate a solid component therefrom. The solid component thus obtained was washed with 5ml of toluene and 4ml of hexane to recover a solid reaction product. The recovered solid reaction product was extracted with 40ml of dichloromethane. The extract was stirred under reduced pressure to remove the solvent, thereby obtaining 571mg of a racemic and meso mixture of dimethylsilylenebis [1, 1' - { 2-methyl-4- (3-chlorophenyl) -4-hydroazulenyl } ] hafnium dichloride (yield: 10%).

(b) Purification of racemic compound:

571mg of the racemic and meso mixture produced above were dissolved in 15ml of dichloromethane and irradiated by light using a 100W high pressure mercury vapor lamp for 15 minutes to increase the percentage of racemic compounds in the mixture. Insoluble components were then removed from the solution by filtration, and the recovered filtrate was then concentrated, dried and solidified. Subsequently, the solid component thus obtained was mixed with 5ml of toluene with stirring, and then the resulting reaction mixture was filtered from a glass cullet. The obtained solid residue was washed with 3ml of toluene and 4ml of hexane and then dried under reduced pressure, thereby obtaining 290mg of a racemic compound of dimethylsilylenebis [1, 1' - { 2-methyl-4- (3-chlorophenyl) -4-hydroazulenyl } ] hafnium dichloride.

Process for producing racemic compound obtained above¹Chemical shifts of H-NMR were as follows:

300MHz，CDCl₃(ppm)0.95(s, 6H, SiMe), 2.22(s, 6H, 2-Me), 4.93-4.97(br d, 2H), 5.70-5.90(m, 6H), 5.97-6.05(m, 2H), 6.75(d, 2H), 7.15-7.27(m, 6H, aromatic), 7.33(s, 2H, aromatic)

(2) Polymerization of propylene using clay minerals as co-catalyst

By carrying out the same operation procedure as defined in example 13(2) except for using 1.22mg of the racemic compound obtained in the above item (1) in place of the racemic compound obtained in example 12(1), 110g of polypropylene was obtained. The activity of the complex was confirmed to be 9.0X 10 by measurement⁴The catalyst activity was 2200, and the obtained polypropylene had a melting point (Tm) of 152.4 ℃ and a Melt Flow Rate (MFR) of 0.5.

Example 18

(1) Synthesis of dimethylsilylenebis [1, 1' - { 2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl } ] hafnium dichloride:

29ml of a pentane solution containing 47.0mmol of t-butyllithium (1.64M) was added dropwise at-78 ℃ to a solution prepared by dissolving 4.5g (23.53mmol) of 1-bromo-4-chlorobenzene in a mixed solvent composed of 30ml of n-hexane and 30ml of diethyl ether. The resulting solution was stirred at-5 ℃ for 1.5 h, then combined with 3.0g (21.2mmol) of 2-methylazulene to react the components with each other. The obtained reaction solution was stirred for 1 hour while the temperature thereof was elevated to room temperature.

The reaction solution was then cooled to-5 ℃ and mixed with 40. mu.l (0.47mmol) of 1-methylimidazole and then with 1.28ml (10.59mmol) of dimethyldichlorosilane. After the reaction solution was stirred at room temperature for 1.5 hours, dilute hydrochloric acid was added to terminate the reaction. The reaction solution was separated into an organic phase and an aqueous phase, and the organic phase was concentrated under reduced pressure. After the solvent was removed, the product thus obtained was purified by silica gel column chromatography (mixed solvent: methylene chloride and n-hexane) to obtain 2.74g of an amorphous solid product.

The reaction product thus obtained was then dissolved in 20ml of dry diethyl ether. 6.3ml of an n-hexane solution (1.54M) containing 9.72mmol of n-butyllithium was added dropwise to the ether solution at-78 ℃. After the end of the dropwise addition, the reaction solution was stirred for 12 hours while its temperature was gradually raised to room temperature. Thereafter, the reaction solution was stirred under reduced pressure to remove the solvent, and then mixed with 15ml of a mixed solvent (40: 1) of dry toluene and dry diethyl ether. After cooling to-78 deg.C, the reaction solution was mixed with 1.56g (4.86mmol) of hafnium tetrachloride, the temperature of which was immediately raised to room temperature, followed by stirring at room temperature for 4 hours. The obtained reaction solution was filtered through celite to separate a solid component therefrom. The solid component thus obtained was extracted with 90ml of dichloromethane. The extract was subjected to distillation to remove the solvent, whereby 320mg of a racemic compound of dimethylsilylenebis [1, 1' - { 2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl } ] hafnium dichloride was obtained (yield: 7%).

Process for producing racemic compound obtained above¹Chemical shifts of H-NMR were as follows:

300MHz，CDCl₃(ppm) Δ 0.95(s, 6H, SiMe), 2.21(s, 6H, 2-Me), 4.92-4.96(br d, 2H), 5.70-6.15(m, 8H), 6.78(d, 2H), 7.28(s, 8H, aromatic)

(2) Polymerization of propylene using methylaluminoxane as cocatalyst

< polymerization of internal olefin >

4mmol (in terms of Al atom) of methylaluminoxane ("MMAO" produced by TOSOH AKZO CORP. RTM.) and a solution containing 0.65mg of dimethylsilylenebis [1, 1' - { 2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl } obtained in (1) above]A toluene solution of a racemic compound of hafnium dichloride was charged into a 2 liter stirred autoclave. Further, 1,500ml of propylene was charged into the autoclave. After the contents of the autoclave were heated to 70 ℃, polymerization of propylene was carried out at this temperature for 1 hour, thereby obtaining 8g of polypropylene. The activity of the complex was confirmed to be 1.23X 10 by measurement⁴The obtained polypropylene had a melting point (Tm) of 154.4 ℃ and a Melt Flow Rate (MFR) of 0.07. The weight average molecular weight (Mw) is 14X 10⁵And a Q value (Mw/Mn) of 4.0.

Example 19

Polymerization of propylene

The same procedures as those conducted in example 6(2) were conducted except that dimethylsilylenebis [1, 1' - { 2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl } obtained in example 18(1)]As component (A), a racemic compound of hafnium dichloride was used to obtain 146g of polypropylene. The catalyst activity was found to be 2900 and the complex activity was found to be 12.0X 10 by measurement⁴The obtained polypropylene had a melting point (Tm) of 150.6 ℃, a Melt Flow Rate (MFR) of 0.4 and a weight average molecular weight (Mw) of 5.6X 10⁵And a Q value (Mw/Mn) of 3.1.

Example 20

(1) Chemical treatment and granulation of clay minerals

3kg of commercial montmorillonite ("KUNPAF", manufactured by KUNINE INDUSTRUESCO., LTD.) was ground to a fine powder by a vibratory ball mill and dispersed in 16 liters of a 3% aqueous sulfuric acid solution. The dispersion was mixed with 2.1kg of magnesium sulfate and then stirred at 90 ℃ for 3 hours. Thereafter, the dispersion was filtered to separate a solid component therefrom. The solid component thus obtained was washed with water to adjust its pH to not less than 5. Continuously, after the solid content of the obtained slurry was adjusted to 15%, the slurry was sprayed by means of a spray dryer to granulate the solid component. The particles thus obtained have a spherical shape.

Then, 10.0g of the chemically treated montmorillonite obtained above was added to a 200ml flask and heated and dehydrated under reduced pressure at 300 ℃ for 2 hours to obtain component (B).

(2) Preparation of solid catalyst component and prepolymerization of propylene

400ml of heptane were charged into a 1 l stirred autoclave and maintained at 40 ℃.

Separately, 10g of component (B) obtained in (1) above was dispersed in 40.2ml of toluene. The dispersion was mixed with 79.8ml of a diluted toluene solution containing triethylaluminum in an amount corresponding to 60 mmol. After allowing the components to contact for 1 hour at room temperature, the supernatant was removed from the mixture, and the solid residue was washed with toluene and then charged into the autoclave.

Next, 48.g ml of a solution containing dimethylsilylenebis [1, 1' - { 2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl } obtained in example 18(1) in an amount corresponding to 0.10mmol]The hafnium dichloride solution in toluene is added to the autoclave. Further, 4.96ml of a dilute toluene solution containing triisobutylaluminum in an amount corresponding to 4mmol was dropped into the autoclave, and propylene was then added thereto to initiate polymerization reaction of propylene (prepolymerization). The polymerization of propylene was continued for 15 minutes while maintaining the pressure of propylene in the autoclave at 5kgf/cm²G. After the polymerization reaction was completed, the polymerized slurry was discharged from the autoclave, and the supernatant was removed to obtain a solid residue. The solid residue was dried at 40 ℃ and under reduced pressure for 3 hours, thereby obtaining a dried catalyst. The amount of the polymer obtained by the prepolymerization was 3.1g/g of the component (B).

(3) Polymerization of propylene

0.4g of triisobutylaluminum and 1.5 liters of propylene were charged into a 3 liter stirring autoclave. 30mg of the dried catalyst obtained in the above item (2) (the same amount as component (B) except for the prepolymerized product) was added under reduced pressure to the autoclave while keeping the contents of the autoclave at 30 ℃. Subsequently, the contents of the autoclave were heated to 75 ℃ and polymerization of propylene was carried out at this temperature for 1 hour, and after the polymerization was completed, unreacted propylene was discharged to recover the produced polypropylene. The results are shown in Table 3.

Examples 21 and 22

< polymerization of propylene >

The same procedures as defined in examples 20(1) - (3) were carried out except that, after the dry catalyst was added in example 20(3), hydrogen was introduced into the autoclave in the amount shown in Table 3. The results are shown in Table 3.

Example 23

< polymerization of propylene >

The same procedures as defined in examples 20(1) - (3) were conducted, except that the amount of the dry catalyst charged into the autoclave of example 20(3) was changed to 15mg (the same amounts as the components, except for the prepolymerization product). The results are shown in Table 3.

Example 24

< random copolymerization of propylene and ethylene >

The same procedures as defined in examples 20(1) - (3) were conducted, except that the amount of the dry catalyst charged in the autoclave of example 20(3) was changed to 15mg (the same amounts as the components except for the prepolymerization product), and 1.5 liters of propylene and 45g of ethylene were introduced into the autoclave. The results are shown in Table 3.

Examples 25 to 27

The same procedures as defined in (1) - (3) of example 20 were carried out, except that the conditions of example 20 were changed as follows. The results are shown in Table 3.

(1) Preparation of solid catalyst component and prepolymerization of propylene

A dry catalyst was prepared under the same conditions as defined in example 20(2) except that the compounds shown in table 3 were used as component (a).

(2) Polymerization of propylene

Polymerization of propylene was conducted under the same conditions as defined in example 20(3) except that 50mg of each of the dried catalysts obtained in (1) above was used (in the same amount as component (B) except for the prepolymerized product).

Comparative example 3

(1) Preparation of solid catalyst component and prepolymerization of propylene

A dry catalyst was prepared under the same conditions as defined in example 20(2) except that 10g of dimethylsilylenebis {1, 1' - (2-methyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride was used as compound (A) and 10g of methylaluminoxane supported on a silica support (MAO/SiO manufactured by Witco Co., Ltd.)₂The Al atomic content: 23%) was used as the compound (B) in place of the chemically treated clay mineral. The amount of polymer obtained from the prepolymerization was 2.8 g/g MAO/SiO₂。

(2) Polymerization of propylene

The same procedure as defined in example 20(3) was conducted, except that the catalyst component prepared in the above item (1) was used in place of the catalyst used in example 20 (3). The results are shown in Table 3.

TABLE 3

	Components (A)	The catalyst used is solid Amount of body (mg)	A component (C): three different types Butyl aluminium (mg)	Of the hydrogen supplied Volume (ml)	Of ethylene supplied Quantity (g)
						Ex.20	a	30	400	0	0
Ex.21	a	30	400	42.5	0
						Ex.22	a	30	400	136	0
Ex.23	a	15	400	0	0
						Ex.24	a	15	400	0	45
Ex.25	b	50	400	0	0
						Ex.26	c	50	400	0	0
Ex.27	d	50	400	0	0
						Comp. Ex.3	d	50	400	0	0

Note: a: dimethylsilylenebis [1, 1' - { 2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl }]Hafnium dichloride;

b: dimethylsilylenebis [1, 1' - { 2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl } ] zirconium dichloride;

c: dimethylsilylenebis {1, 1' - (2-methyl-4-phenyl-4-hydroazulenyl) ] hafnium dichloride;

d: dimethylsilylenebis {1, 1' - (2-methyl-4-phenyl-4-hydroazulenyl) ] zirconium dichloride;

TABLE 3 continuation

	Catalyst activity	Complex activity	Melting Point (. degree.C.)	MFR(g/10min)
					Example 20	1900	23.4	153.1	0.19
Example 21	5600	68.9	153.7	1.87
					Example 22	9400	115.7	155.0	16.1
Example 23	1600	19.7	154.0	0.076
					Example 24	9700	119.4	127.7	0.038
Example 25	1430	19.7	149.3	4.6
					Example 26	3100	41.7	150.9	0.84
Example 27	2020	30.8	147.7	6.2
					Comparative example 3	710	10.8	146.7	7.6

TABLE 3 continuation

	Mw (×105)	Q (Mw/Mn)	Bulk Density (g/ml)
				Example 20	-	-	0.38
Example 21	-	-	0.38
				Example 22	-	-	0.41
Example 23	-	-	0.39
				Example 24	-	-	0.38
Example 25	3.2	3.4	0.48
				Example 26	5.8	3.9	0.48
Example 27	2.8	3.0	0.47
				Comparative example 3	2.5	2.8	0.37

Example 28

(1) Synthesis of dimethylsilylenebis {1, 1' - (2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl } ] zirconium dichloride:

4.9ml of a cyclohexane/diethyl ether solution (1.08M) containing 5.2mmol of phenyllithium were added dropwise at 0 ℃ to 20ml of a hexane solution containing 0.97g (5.2mmol) of 2-methyl-5-isopropylazulene. The resulting solution was stirred for 1 hour while allowing the temperature to gradually rise to room temperature. After this time, the reaction mixture was cooled to 0 ℃ and mixed with 20ml of tetrahydrofuran and 12. mu.l (0.15mmol) of dimethylaminopyridine and then with 0.34g (2.6mmol) of dichlorodimethylsilane. After the reaction solution was stirred at room temperature for 2 hours, dilute hydrochloric acid was added thereto to terminate the reaction. The reaction solution was separated into an organic phase and an aqueous phase, the organic phase was extracted with hexane, dried over magnesium sulfate and stirred under reduced pressure to remove the solvent. The obtained product was purified by silica gel column chromatography (mixed solvent: dichloromethane and n-hexane), whereby 1.4g of the reaction product was obtained as a dark green powder.

Next, 1.4g of the reaction product thus obtained was dissolved in 15ml of diethyl ether. 3.2ml of an n-hexane solution (1.54M) containing 4.9mmol of n-butyllithium was added dropwise to the ether solution at-78 ℃. After the end of the dropwise addition, the reaction solution was stirred for 2 hours while its temperature was gradually raised to 0 ℃. After the reaction solution was stirred under reduced pressure to remove the solvent, 23ml of a mixed solvent of toluene and diethyl ether (20: 1) was added thereto. After cooling to-78 deg.C, the reaction solution was further mixed with 0.57g (2.4mmol) of zirconium tetrachloride, the temperature of which was immediately raised to 0 deg.C, and then stirred at 0 deg.C for 1 hour. Further, the temperature of the reaction solution was raised to room temperature and stirred at room temperature for 6 hours. The obtained reaction solution was filtered through celite, and a solid component was separated. The solid component thus separated was washed with 3ml of toluene to recover a solid product. The recovered solid product was extracted with dichloromethane. The extract was stirred under reduced pressure to remove the solvent, thereby obtaining 0.11g of a racemic and meso mixture of dimethylsilylenebis {1, 1' - { 2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl } ] zirconium dichloride (yield: 6%).

Of the racemic and meso mixtures obtained above¹Chemical shifts of H-NMR were as follows:

300MHz，C₆D₆(ppm)0.55(s，meso SiMe)，0.57(s，racemic SiMe)，0.60(s，meso SiMe)，1.00(d，iPr-Me)，1.12(d，iPr-Me)，1.88(s，2-Me)，1.90(s，2-Me)，3.1(m，iPr-CH)，5.26(br s，4-H)，5.28(br s，4-H)，5.7-5.9(m，-CH＝)，7.0-7.5(m，-CH＝)

(2) polymerization of propylene using methylaluminoxane as cocatalyst

4mmol (calculated as Al atom) of methylaluminoxane ("MMAO" manufactured by TOSOH AKZO CORP. RTM.) was charged into a 2-liter stirring autoclave. Separately, 0.3mg of the racemic and meso mixture produced above was diluted with toluene and then added to the catalyst feeder equipped with a safety diaphragm. 1,500ml of propylene was added to the autoclave and the safety diaphragm of the catalyst feeder was broken at room temperature. After the contents of the autoclave were heated to 70 ℃, polymerization of propylene was carried out at this temperature for 1 hour, thereby obtaining 32g of polypropylene. The activity of the complex was confirmed to be 1.1X 10 by measurement⁵The obtained polypropylene had a melting point (Tm) of 152.6 ℃, a Melt Flow Rate (MFR) of 1.4 and a weight average molecular weight (Mw) of 3.6X 10⁵And a Q value (Mw/Mn) of 3.5.

Example 29

< polymerization of α -olefin Using Clay mineral as cocatalyst >

(1) Chemical treatment of clay minerals and preparation of solid catalyst component

The same procedure as defined in example 11(2) was carried out to obtain a montmorillonite/toluene slurry having a montmorillonite content of 33 mg/ml.

(2) Polymerization of propylene

0.5mmol (in terms of Al atom) of triisobutylaluminum (produced by TOSOH AKZO CORP.) was charged into a 2-liter stirring autoclave. Separately, 1.8mg of the racemic and meso mixture obtained in example 28(1)Diluted with toluene and then added to the catalyst feeder equipped with a safety diaphragm. Furthermore, the above preparation of a mixture containing 100mg of montmorillonite and 0.3mmol (in terms of Al atom) of triisobutylaluminum was carried outIs added to the catalyst feeder. Thereafter, 1,500ml of propylene was added to the autoclave, and the safety diaphragm of the catalyst feeder was broken at room temperature. After the contents of the autoclave were heated to 80 ℃, polymerization of propylene was carried out at this temperature for 1 hour, thereby obtaining 37g of polypropylene. As a result of measurement, it was confirmed that the catalyst activity was 370 and the complex activity was 2.1X 10⁴The obtained polypropylene had a melting point (Tm) of 146.0 ℃, a Melt Flow Rate (MFR) of 143, and a weight average molecular weight (Mw) of 1.4X 10⁵And a Q value (Mw/Mn) of 2.2.

Example 30

(1) Synthesis of dimethylsilylenebis {1, 1' - (2-ethyl-4-phenyl-7-isopropyl-4-hydroazulenyl } ] zirconium dichloride:

7.2ml of a cyclohexane/diethyl ether solution (1.08M) containing 7.8mmol of phenyllithium were added dropwise at 0 ℃ to 20ml of a hexane solution containing 1.54g (7.8mmol) of 2-ethyl-5-isopropylazulene. The resulting solution was stirred for 1 hour while allowing the temperature to gradually rise to room temperature. After this time, the reaction mixture was cooled to 0 ℃ and mixed with 20ml of tetrahydrofuran and 12. mu.l (0.15mmol) of dimethylaminopyridine and then with 0.50g (3.9mmol) of dichlorodimethylsilane. After the reaction solution was stirred at room temperature for 2 hours, dilute hydrochloric acid was added thereto to terminate the reaction. The reaction solution was separated into an organic phase and an aqueous phase, and the organic phase was extracted with hexane, dried over magnesium sulfate and stirred under reduced pressure to remove the solvent, thereby obtaining 2.5g of the reaction product in the form of dark green powder.

Next, 2.5g of the reaction product thus obtained was dissolved in 30ml of diethyl ether. 4.9ml of an n-hexane solution (1.59M) containing 7.8mmol of n-butyllithium was added dropwise to the ether solution at-78 ℃. After the end of the dropwise addition, the reaction solution was stirred for 4 hours while its temperature was gradually raised to room temperature. After the reaction solution was stirred under reduced pressure to remove the solvent, 20ml of a mixed solvent of toluene and diethyl ether (20: 1) was added thereto. After cooling to-78 ℃, the reaction solution was mixed with 0.91g (3.9mmol) of zirconium tetrachloride, the temperature of which was immediately raised to 0 ℃, and then stirred at 0 ℃ for 1 hour. Further, the temperature of the reaction solution was raised to room temperature and stirred at room temperature for 11 hours. The obtained reaction solution was filtered through celite, and a solid component was separated. The solid component thus separated was washed with 3ml of toluene to recover a solid product. The recovered solid product was extracted with dichloromethane. The extract was stirred under reduced pressure to remove the solvent, thereby obtaining 0.4g of a racemic and meso mixture of dimethylsilylenebis [1, 1' - { 2-ethyl-4-phenyl-7-isopropyl-4-hydroazulenyl } ] zirconium dichloride (yield: 7%).

Of the racemic and meso mixtures obtained above¹Chemical shifts of H-NMR were as follows:

300MHz，C₆D₆(ppm)0.58(s，meso SiMe)，0.60(s，racemic SiMe)，0.62(s，meso SiMe)，1.1(d，iPr-Me，Et-Me)，1.92(q，Et-CH₂)，1.98(q，Et-CH₂)，3.2(m，iPr-CH)，5.26(br s，4-H)，5.29(br s，4-H)，5.7-5.9(m，-CH＝)，7.0-7.5(m，-CH＝)

(2) polymerization of propylene using methylaluminoxane as cocatalyst

4mmol (calculated as Al atom) of methylaluminoxane ("MMAO" manufactured by TOSOH AKZO CORP. RTM.) was charged into a 2-liter stirring autoclave. Separately, 0.3mg of the racemic and meso mixture produced above was diluted with toluene and then added to the catalyst feeder equipped with a safety diaphragm. Then, 1,500ml of propylene was added to the autoclave, and the safety diaphragm of the catalyst feeder was broken at room temperature. After the contents of the autoclave were heated to 70 ℃, polymerization of propylene was carried out at this temperature for 1 hour, thereby obtaining 52g of polypropylene. The activity of the complex was confirmed to be 1.7X 10 by measurement⁵The obtained polypropylene had a melting point (Tm) of 155.5 ℃, a melt flow rate (MER) of 0.2 and a weight average molecular weight (Mw) of 5.3X 10⁵And a Q value (Mw/Mn) of 3.8.

Example 31

< polymerization of propylene Using Clay mineral as cocatalyst >

0.25mmol (in terms of Al atom) of triisobutylaluminum (produced by TOSOH AKZO CORP.) was charged into a 1-liter stirring autoclave. Separately, 0.8mg of the racemic and meso mixture obtained in example 30(1) was diluted with toluene and then added to a catalyst feeder equipped with a safety diaphragm. Further, 50mg of triethylaluminum-treated montmorillonite obtained in example 29(1) and 0.15mmol (in terms of Al atom) of triisobutylaluminum were fed to the catalyst feeder. Then, 700ml of propylene was added to the autoclave, and the safety diaphragm of the catalyst feeder was broken at room temperature. After the contents of the autoclave were heated to 80 ℃, polymerization of propylene was carried out at this temperature for 1 hour, thereby obtaining 4g of polypropylene. As a result of measurement, it was confirmed that the catalyst activity was 76 and the complex activity was 5.0X 10³The polypropylene obtained had a melting point (Tm) of 148.4 ℃ and a weight-average molecular weight (Mw) of 1.5X 10⁵And a Q value (Mw/Mn) of 2.8.

Example 32

(1) Synthesis of dimethylsilylenebis {1, 1' - (2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl } ] zirconium dichloride as component (A)

(a) 2-tosyl-4-isopropyltropolone

10.2g (62.3mmol) of hinokitiol were dissolved in 20ml of pyridine. To the solution prepared above, 20ml of a pyridine solution containing 12.1g (63.5mmol) of tosyl chloride was added at room temperature. The resulting reaction solution was extracted with toluene. The organic phase of the extraction was dried over magnesium sulfate, and then the solvent contained therein was removed under reduced pressure to obtain 20.7g of a mixture of 2-tosyl-4-isopropyltropolone and 2-tosyl-6-isopropyltropolone.

(b) Synthesis of 1-methoxycarbonyl-6-isopropylcycloheptatrien-2-one

A solution of sodium methoxide prepared from 100ml of methanol and 2.1g (94.3mmol) of sodium is added at 0 ℃ to 100ml of a solution of methanol containing 17.6g (55.5mmol) of the mixture obtained in (a) above and 10.8ml (94.3mmol) of dimethyl malonate. The mixed solution was stirred at 0 ℃ for 1 hour and then at room temperature overnight. After removing the solvent contained therein under reduced pressure, the mixed solution was mixed with water, followed by extraction with a mixed solvent composed of hexane and ethyl acetate. The organic phase of the extraction was dried over magnesium sulfate, and the solvent was removed under reduced pressure, whereby 12.2g of a crude product of 1-methoxycarbonyl-6-isopropylcycloheptatrien-2-one was obtained.

(c) Synthesis of 1-methoxycarbonyl-2-methyl-6-isopropylazulene

600ml of acetone and 200ml of diethylamine were added to 12.2g of the crude 1-methoxycarbonyl-6-isopropylcycloheptatrien-2-one obtained above. The mixture was refluxed intermittently for 15 hours while being heated. Then, the solvent contained in the mixture was removed under reduced pressure. The obtained crude product was purified by column chromatography using a mixed solvent composed of hexane and ethyl acetate (5: 1) as an eluent, to obtain 3.93g of 1-methoxycarbonyl-2-methyl-6-isopropylazulene.

(d) Synthesis of 2-methyl-6-isopropyl azulene

70ml of phosphoric acid were added to 3.93g (16.2mmol) of 1-methoxycarbonyl-2-methyl-6-isopropylazulene and the mixture was heated at 100 ℃ for 1 hour. The resulting reaction solution was added to 300ml of an aqueous solution containing 30g of sodium hydroxide, followed by extraction with hexane. The organic phase of the extraction was dried over magnesium sulfate and the solvent contained therein was removed under reduced pressure. The crude product obtained was filtered through silica gel. Further, the solvent contained in the filtered solid component was removed, whereby 2.23g of 2-methyl-6-isopropylazulene was obtained (yield: 75%).

(e) Synthesis of bis {1, 1' - (2-methyl-4-phenyl-6-isopropyldihydroazulenyl) } dimethylsilane

An ether/cyclohexane solution (1.0N) containing 12.1mmol of phenyllithium was added dropwise to 40ml of a hexane solution containing 2.08g (11.3mmol) of the above-produced 2-methyl-6-isopropylazulene at 0 ℃. The mixed solution was stirred at room temperature for 2 hours and then mixed with 30ml of tetrahydrofuran at-10 ℃. Further, 0.68ml (5.64mmol) of dichlorodimethylsilane was added to the mixed solution at-30 ℃ followed by stirring at room temperature for 1 hour and at 45 ℃ for 2 hours. After the mixed solution was left at room temperature overnight, an aqueous ammonium chloride solution was added to the obtained reaction solution. After the reaction solution was separated into an aqueous phase and an organic phase, the separated organic phase was dried over magnesium sulfate, and the solvent was removed under reduced pressure. The obtained crude product was purified by column chromatography using a mixed solvent composed of hexane and dichloromethane (10: 1 to 5: 1) as an eluent, to obtain 1.23g of bis {1, 1' - (2-methyl-4-phenyl-6-isopropyl-1, 4-dihydroazulenyl) } dimethylsilane (yield: 38%).

(f) Synthesis of dimethylsilylenebis {1, 1' - (2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl } ] zirconium dichloride

A hexane solution containing 4.55mmol (1.63N) of N-butyllithium was added to a 20ml ether solution containing 1.2g (2.07mmol) of bis {1, 1' - (2-methyl-4-phenyl-6-isopropyl-1, 4-dihydroazulenyl) } dimethylsilane produced above at-78 ℃. After the mixed solution was stirred at room temperature overnight, the solvent contained in the obtained product was removed. The resulting product was again washed with hexane, dried and solidified. The solid product obtained was mixed with 20ml of toluene and 0.5ml of diethyl ether to form a solution. 434mg (1.89mmol) of zirconium tetrachloride were added to the solution at-70 ℃.

The temperature of the obtained reaction solution was gradually raised to room temperature and stirred at room temperature overnight. The reaction solution was then filtered through celite, and the solvent contained in the separated solid component was removed under reduced pressure. The solid component was again dissolved in 1ml of dichloromethane and then mixed with 10ml of hexane. No precipitate formed at this point. The obtained solution was dried and solidified under reduced pressure, thereby obtaining 1.36g of dimethylsilylenebis {1, 1' - { 2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl } ] zirconium dichloride.

(2) Polymerization of propylene

The same procedures as defined in example 1(4) were carried out except for using dimethylsilylenebis {1, 1' - { 2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl } produced above]Zirconium dichloride is used as component (a)A) 120g of polypropylene was obtained. The catalyst activity was 1200 and the complex activity was 11.6X 10 as measured⁴The obtained polypropylene had a melting point (Tm) of 148.5 ℃, a Melt Flow Rate (MFR) of 8.8 and a weight average molecular weight (Mw) of 2.4X 10⁵And a Q value (Mw/Mn) of 2.8.

Example 33

< polymerization of propylene Using Methylaluminoxane as a cocatalyst >

4mmo1 (calculated as Al atom) of methylaluminoxane ("MMAO" manufactured by TOSOH AKZO CORP. RTM.) and 1mg of dimethylsilylenebis {1, 1' - { 2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl } manufactured in example 32(1)]Zirconium dichloride was diluted with toluene and then charged into a 2 liter stirred autoclave. Then, 1,500ml of propylene was charged into the autoclave. The contents of the autoclave were heated to 70 deg.CAfter that, polymerization reaction of propylene was carried out at this temperature for 1 hour, thereby obtaining 70.4g of polypropylene. The activity of the complex was confirmed to be 7.0X 10 by measurement⁴The obtained polypropylene had a melting point (Tm) of 149.8 ℃, a Melt Flow Rate (MFR) of 7.9 and a weight average molecular weight (Mw) of 2.6X 10⁵And a Q value (Mw/Mn) of 2.8.

Example 34

(1) Synthesis of dimethylsilylenebis {1, 1' - (2-benzyl-4-phenyl-4-hydroazulenyl } ] zirconium dichloride:

7.2ml of a cyclohexane/diethyl ether solution (1.08M) containing 7.8mmol of phenyllithium were added dropwise at-5 ℃ to 35ml of a hexane solution containing 1.7g (7.8mmol) of 2-benzylazulene. The resulting solution was stirred for 2 hours while allowing the temperature to gradually rise to room temperature. Thereafter, the reaction mixture is cooled to 0 ℃ and mixed with 35ml of tetrahydrofuran and 0.016g of 1-methylimidazole and then with 0.5g (3.9mmol) of dichlorodimethylsilane. After the reaction solution was stirred at room temperature for 1 hour, dilute hydrochloric acid was added thereto to terminate the reaction. The reaction solution was separated into an organic phase and an aqueous phase, the organic phase was extracted with diethyl ether, dried over magnesium sulfate and stirred under reduced pressure to remove the solvent, and the obtained product was purified by silica gel column chromatography (mixed solvent: dichloromethane and n-hexane) to obtain 1.5g of the reaction product in the form of dark green powder.

Next, 1.5g of the reaction product thus obtained was dissolved in 10ml of diethyl ether. 2.9ml of an n-hexane solution (1.59M) containing 46.4mmol of n-butyllithium was added dropwise to the ether solution at-78 ℃. After the end of the dropwise addition, the reaction solution was stirred for 4 hours while its temperature was gradually raised to room temperature. After the reaction solution was stirred under reduced pressure to remove the solvent, 15ml of a mixed solvent of toluene and diethyl ether (40: 1) was added thereto. After cooling to-78 ℃, the reaction solution was mixed with 0.54g (2.32mmol) of zirconium tetrachloride, the temperature of which was immediately raised to room temperature, and then stirred at room temperature for 12 hours. The obtained reaction solution was filtered through celite (celite) in a nitrogen stream, and a solid component was separated. The solid component thus separated was washed with toluene, and stirred under reduced pressure to remove the solvent, thereby obtaining 1.4g of a racemic and meso mixture of dimethylsilylenebis {1, 1' - (2-benzyl-4-phenyl-4-hydroazulenyl) } zirconium dichloride (yield: 74%).

Of the racemic and meso mixtures obtained above¹Chemical shifts of H-NMR were as follows:

300MHz，C₆D₆(ppm)0.83(s, meso SiMe), 0.92(s, racemic SiMe), 1.05(meso SiMe), 3.75(d, racemic benzyl CH)₂) 3.90(d, meso benzyl CH)₂) 4.04(d, racemic and meso benzyl CH)₂)，4.99(d，racemic 4-H)，5.06(d，meso4-H)，5.08-6.2(m，-CH＝)，6.8-7.6(m，-CH＝)

(2) Polymerization of propylene using methylaluminoxane as cocatalyst

2mmol (calculated as Al atom) of methylaluminoxane ("MMAO" manufactured by TOSOH AKZO CORP. RTM.) was charged into a 1-liter stirring autoclave. Separately, 0.32mg of the racemic and meso mixture produced above was diluted with toluene and then added to the catalyst feeder equipped with a safety diaphragm. Then, 700ml of propylene was added to the autoclave, and the safety diaphragm of the catalyst feeder was broken at room temperature. After the contents of the autoclave have been heated to 70 ℃ the polymerization of propylene is carried out at this temperatureIt was allowed to stand for 1 hour, thereby obtaining 10g of polypropylene. The activity of the complex was confirmed to be 3.1X 10 by measurement⁴The obtained polypropylene had a melting point (Tm) of 156.6 ℃, a Melt Flow Rate (MFR) of 400 and a weight average molecular weight (Mw) of 0.8X 10⁵And a Q value (Mw/Mn) of 3.2.

Example 35

< polymerization of propylene Using Clay mineral as cocatalyst >

(1) Chemical treatment of clay minerals and preparation of solid catalyst component

The same procedure as defined in example 11(2) was carried out to obtain a montmorillonite/toluene slurry having a montmorillonite content of 33 mg/ml.

(2) Polymerization of propylene

0.25mmol (in terms of Al atom) of triisobutylaluminum (produced by TOSOH AKZO CORP.) was charged into a 1-liter stirring autoclave. Separately, 2.4mg of the racemic and meso mixture obtained in example 34(1) were diluted with toluene and then added to a catalyst feeder equipped with a safety diaphragm. Further, the above-produced toluene slurry containing 50mg of montmorillonite and 0.15mmol (in terms of Al atom) of triisobutylaluminum were fed to the catalyst feeder. Then, 700ml of propylene was added to the autoclave, and the safety diaphragm of the catalyst feeder was broken at room temperature. After the contents of the autoclave were heated to 80 ℃, polymerization of propylene was carried out at this temperature for 1 hour, thereby obtaining 0.8g of polypropylene. As a result of measurement, it was confirmed that the catalyst activity was 16, the complex activity was 300, and the obtained polypropylene had a melting point (Tm) of 152.4 ℃ and a weight average molecular weight (Mw) of 0.5X 10⁵And a Q value (Mw/Mn) of 2.5.

Example 36

(1) Synthesis of dimethylsilylenebis {1, 1' - (2-benzyl-4-phenyl-7-isopropyl-4-hydroazulenyl } ] zirconium dichloride:

5.5ml of a cyclohexane/diethyl ether solution (1.08M) containing 5.9mmol of phenyllithium were added dropwise at 0 ℃ to 20ml of a hexane solution containing 1.54g (5.9mmol) of 2-benzyl-5-isopropylazulene. The resulting solution was stirred for 1.5 hours while allowing the temperature to gradually rise to room temperature. After this time, the reaction mixture was cooled to 0 ℃ and mixed with 20ml of tetrahydrofuran and 11. mu.l (0.14mmol) of dimethylaminopyridine and then with 0.36g (3.0mmol) of dichlorodimethylsilane. After the reaction solution was stirred for 3.5 hours while the temperature thereof was gradually increased to 10 ℃, dilute hydrochloric acid was added thereto to terminate the reaction. The reaction solution was separated into an organic phase and an aqueous phase, the organic phase was extracted with hexane, dried over magnesium sulfate and stirred under reduced pressure to remove the solvent. The obtained product was purified by silica gel column chromatography (mixed solvent: dichloromethane and n-hexane) to obtain 1.7g of the reaction product in the form of dark green powder.

Next, 1.7g of the reaction product thus obtained was dissolved in 20ml of diethyl ether. 2.9ml of an n-hexane solution (1.59M) containing 4.7mmol of n-butyllithium was added dropwise to the ether solution at-5 ℃. After the end of the dropwise addition, the reaction solution was stirred for 3 hours while its temperature was gradually raised to 10 ℃. After the reaction solution was stirred under reduced pressure to remove the solvent, 12ml of a mixed solvent of toluene and diethyl ether (20: 1) was added thereto. After cooling to-78 ℃, the reaction solution was mixed with 0.55g (2.4mmol) of zirconium tetrachloride. Thereafter, the reaction solution was stirred for 4 hours while gradually raising the temperature to room temperature, and then stirred at room temperature for 11 hours. The obtained reaction solution was filtered through celite (celite) in a nitrogen stream, and a solid component was separated. The solid component thus obtained was washed with 3ml of toluene to recover a solid product. The solid product thus recovered was extracted with methylene chloride, and the extract was then stirred under reduced pressure to remove the solvent, thereby obtaining 0.23g of a racemic and meso mixture of dimethylsilylenebis {1, 1' - (2-benzyl-4-phenyl-7-isopropyl-4-hydroazulenyl) } zirconium dichloride (yield: 11%).

Of the racemic and meso mixtures obtained above¹Chemical shifts of H-NMR were as follows:

300MHz，CDCl₃(ppm)0.86(s，meso SiMe)，0.90(s，racemic SiMe)，0.96(s，meso SiMe)，1.07(d，iPr-Me)，1.16(d，iPr-Me)，2.5(m，iPr-CH)，3.7-4.0(m，2-CH₂)，4.85-5.00(m，4-H)，5.7-6.1(m，-CH＝)，6.4-7.5(m，-CH＝)

(2) polymerization of propylene using methylaluminoxane as cocatalyst

4mmol (calculated as Al atom) of methylaluminoxane ("MMAO" manufactured by TOSOH AKZO CORP. RTM.) was charged into a 2-liter stirring autoclave. Separately, 0.36mg of the racemic and meso mixture produced above was diluted with toluene and then added to the catalyst feeder equipped with a safety diaphragm. Then, 1,500ml of propylene was added to the autoclave, and the safety diaphragm of the catalyst feeder was broken at room temperature. After the contents of the autoclave were heated to 70 ℃, polymerization of propylene was carried out at this temperature for 1 hour, thereby obtaining 25g of polypropylene. The activity of the complex was confirmed to be 7.0X 10 by measurement⁴The obtained polypropylene had a melting point (Tm) of 156.4 ℃, a Melt Flow Rate (MFR) of 36 and a weight average molecular weight (Mw) of 1.6X 10⁵And a Q value (Mw/Mn) of 3.5.

Example 37

< polymerization of propylene Using Clay mineral as cocatalyst >

0.25mmol (in terms of Al atom) of triisobutylaluminum (produced by TOSOH AKZO CORP.) was charged into a 1-liter stirring autoclave. Separately, 1.8mg of the racemic and meso mixture obtained in example 36(1) was diluted with toluene and then added to a catalyst feeder equipped with a safety diaphragm. Further, 50mg of triethylaluminum-treated montmorillonite obtained in example 35(1) and 0.15mmol (in terms of Al atom) of triisobutylaluminum were fed to the catalyst feeder. Then, 700ml of propylene was added to the autoclave, and the safety diaphragm of the catalyst feeder was broken at room temperature. After the contents of the autoclave were heated to 80 ℃, polymerization of propylene was carried out at this temperature for 1 hour, thereby obtaining 0.5g of polypropylene. By measurement, it was confirmed that the catalyst activity was 1, the complex activity was 37, and the obtained polypropylene had a melting point (Tm) of 147.6 ℃.

Example 38

(1) Synthesis of 9-silafluorene-9.9-diylbis {1, 1' - (2-methyl-4-phenyl-4-hydroazulenyl } ] zirconium dichloride:

5.2ml of a cyclohexane/diethyl ether solution (1.08M) containing 5.6mmol of phenyllithium were added dropwise at-5 ℃ to 10ml of a hexane solution containing 0.8g (5.6mmol) of 2-methylazulene. The resulting solution was stirred for 2 hours while allowing the temperature to gradually rise to room temperature. After this time, the reaction mixture was cooled to 0 ℃ and mixed with 10ml of tetrahydrofuran and 0.017g of dimethylaminopyridine and then with 0.7g (2.8mmol) of 9, 9-dichloro-9-dimethylsilylfluorene. After the reaction solution was stirred at room temperature for 1 hour, dilute hydrochloric acid was added thereto to terminate the reaction. The reaction solution was separated into an organic phase and an aqueous phase, the organic phase was extracted with diethyl ether, dried over magnesium sulfate and stirred under reduced pressure to remove the solvent. The obtained product was purified by silica gel column chromatography (mixed solvent: dichloromethane and n-hexane) to obtain 0.9g of the reaction product in the form of dark green powder.

Next, 0.9g of the reaction product thus obtained was dissolved in 6ml of diethyl ether. 1.98ml of an n-hexane solution (1.47M) containing 2.9mmol of n-butyllithium was added dropwise to the ether solution at-78 ℃. After the end of the dropwise addition, the reaction solution was stirred for 4 hours while its temperature was gradually raised to room temperature. After the reaction solution was stirred under reduced pressure to remove the solvent, 15ml of a mixed solvent of toluene and diethyl ether (40: 1) was added thereto. After cooling to-78 deg.C, the reaction solution was mixed with 0.35g (1.5mmol) of zirconium tetrachloride. Thereafter, the reaction solution was stirred, and the temperature thereof was immediately raised to room temperature, followed by stirring at room temperature for 12 hours. The obtained reaction solution was stirred under reduced pressure to remove the solvent, and then mixed with toluene to form a suspension. The resulting suspension was filtered through celite in a stream of nitrogen and the solid component was separated. The solid component thus obtained was washed with toluene, and then extracted with dichloromethane. Then, the extract was then stirred under reduced pressure to remove the solvent, thereby obtaining 0.25g of a racemic and meso mixture of 9-silafluorene-9.9-diylbis {1, 1' - (2-methyl-4-phenyl-4-hydroazulenyl } ] zirconium dichloride (yield: 22%).

Of the racemic and meso mixtures obtained above¹Chemical shifts of H-NMR were as follows:

300MHz，CDCl₃(ppm)2.40(s，meso 2-Me)，2.44(s，racemic 2-Me)，5.01(br s，racemic 4-H)，5.03(br s，meso 4-H)，5.8-6.2(m，-CH＝)，7.1-7.7(m，-CH＝)，7.9-8.1(m，-CH＝)，8.3-8.5(m，-CH＝)

(2) polymerization of propylene using methylaluminoxane as cocatalyst

2mmol (calculated as Al atom) of methylaluminoxane ("MMAO" manufactured by TOSOH AKZO CORP. RTM.) was charged into a 1-liter stirring autoclave. Separately, 0.1mg of the racemic and meso mixture produced above was diluted with toluene and then added to the catalyst feeder equipped with a safety diaphragm. Then, 700ml of propylene was added to the autoclave, and the safety diaphragm of the catalyst feeder was broken at room temperature. After the contents of the autoclave were heated to 70 ℃, polymerization of propylene was carried out at this temperature for 1 hour, thereby obtaining 20g of polypropylene. Through measurement, the complex activity is confirmed to be 20X 10⁴The polypropylene obtained had a melting point (Tm) of 152.8 ℃ and a Melt Flow Rate (MFR) of 1.3.

Example 39

< polymerization of propylene Using Methylaluminoxane as a cocatalyst >

500ml of toluene was charged into a 1 liter stirring autoclave. Successively, 2.1mmol (in terms of Al atom) of methylaluminoxane ("MMAO" produced by TOSOH AKZO CORP. and 0.3mg of the racemic and meso mixture produced in example 38(1) were diluted with toluene and then charged into the autoclave. Propylene was then introduced into the autoclave. After the contents of the autoclave were heated to 70 ℃, polymerization of propylene was carried out at this temperature for 1 hour while maintaining the pressure of propylene in the autoclave at 5kgf/cm²G, thereby obtaining 4G of polypropylene. The activity of the complex was confirmed to be 1.3X 10 by measurement⁴The polypropylene obtained had a melting point (Tm) of 156.2 ℃.

Example 40

< polymerization of propylene Using Clay mineral as cocatalyst >

(1) Chemical treatment of clay minerals and preparation of solid catalyst component

The same procedure as defined in example 11(2) was carried out to obtain a montmorillonite/toluene slurry having a montmorillonite content of 33 mg/ml.

(2) Polymerization of propylene

0.25mmol (in terms of Al atom) of triisobutylaluminum (produced by TOSOH AKZO CORP.) was charged into a 1-liter stirring autoclave. Separately, 3mg of the racemic and meso mixture obtained in example 38(1) was diluted with toluene and then added to a catalyst feeder equipped with a safety diaphragm. Further, the above-produced toluene slurry containing 50mg of montmorillonite and 0.15mmol (in terms of Al atom) of triisobutylaluminum were fed to the catalyst feeder. Then, 700ml of propylene was added to the autoclave, and the safety diaphragm of the catalyst feeder was broken at room temperature. After the contents of the autoclave were heated to 80 ℃, polymerization of propylene was carried out at this temperature for 1 hour, thereby obtaining 72g of polypropylene. The catalyst activity was confirmed to be 1.4X 10 by measurement³The complex activity is 3.0X 10⁴The obtained polypropylene had a melting point (Tm) of 147.9 ℃ and a Melt Flow Rate (MFR) of 21.3.

Claims (28)

1. A catalyst for the polymerization of α -olefins, comprising:

a transition metal compound as a base component (A),

an essential component (B) of an ion-exchangeable layer compound other than a silicate or an inorganic silicate,

an optional organoaluminum compound component (C),

the component (A) is represented by the following general formula (I):wherein A is¹And A²Independently a conjugated 5-membered ring ligand, with the proviso that A¹And A²May be the same or different in one molecule, and A¹And A²At least one of which forms two vicinities comprising a conjugated 5-membered ringA 7-to 10-membered fused ring of carbon atoms formed by connecting two adjacent substituents on a conjugated 5-membered ring; q is A¹And A²The two conjugated 5-membered rings of (a) are bridging groups at any position of the 5-membered ring; m is a metal atom selected from elements belonging to groups 4-6 of the periodic Table of the elements; x and Y are independently a hydrogen atom, a halogen atom, a hydrocarbon group, an amino group, a halogenated hydrocarbon group, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, a phosphorus-containing hydrocarbon group or a silicon-containing hydrocarbon group.

2. The catalyst according to claim 1, wherein the transition metal compound (A) represented by the general formula (I) has at least one conjugated 5-membered ring ligand A¹And A²Having a 7-membered fused ring.

3. The catalyst according to claim 1, wherein in the formula (I), A is¹And A²Independently a conjugated 5-membered ring ligand; a. the¹And A²Form a 7-to 10-membered fused ring comprising two adjacent carbon atoms of the conjugated 5-membered ring, the fused ring being formed by connecting two adjacent substituents on the conjugated 5-membered ring; the conjugated 5-membered ring and the conjugated 5-membered ring ligand having the fused ring have a substituent which is a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms, a boron-containing hydrocarbon group having 1 to 20 carbon atoms, a sulfur-containing hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, or a halogenated hydrocarbon group having 1 to 20 carbon atoms; q is a bridging group of two conjugated 5-membered rings and is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group which may have 1 to 20 carbon atoms or a methylene of the halogenated hydrocarbon groupGermylene which is silicon-based, or which may have a hydrocarbyl or halohydrocarbyl group of 1 to 20 carbon atoms.

4. The catalyst according to claim 1, wherein the two conjugated 5-membered ring ligands A of the transition metal compound (A) represented by the general formula (I)¹And A²Has a value of 7 toA 10-membered fused ring.

5. The catalyst according to claim 1, wherein M of the transition metal compound (A) represented by the general formula (I) is selected from transition metals belonging to groups 4 to 6 of the periodic Table of the elements.

6. The catalyst according to claim 1, wherein M of the transition metal compound (A) represented by the general formula (I) is zirconium.

7. The catalyst according to claim 1, wherein M of the transition metal compound (A) represented by the general formula (I) is hafnium.

8. The catalyst according to claim 1, wherein the transition metal compound (a) is a compound represented by the following general formula (II):

wherein R is¹、R²、R⁴And R⁵Independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms or a halogenated hydrocarbon group having 1 to 18 carbon atoms; r³And R⁶Independently is a saturated or unsaturated divalent hydrocarbon group of 3 to 10 carbon atoms, and R³And R⁶Respectively to each occurrence of R³And R⁶Form a fused ring together with two 5-membered rings, provided that R³And R⁶At least one of which has from 5 to 8 carbon atoms and forms a compound having at least one group derived from R³Or R⁶7 to 10 membered ring of unsaturated bond(s); r⁷And R⁸Independently a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms or a sulfur-containing hydrocarbon group having 1 to 20 carbon atoms, with the proviso that R⁷And R⁸At least one of which is a compound having 1 to 20Halogenated hydrocarbon groups of carbon atoms; m and n are independently integers from 0 to 20, provided that m and n are not both 0 at the same time; q is a bridging group of two 5-membered rings and is a divalent hydrocarbon radical having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon radical having 1 to 20 carbon atoms, orSilylene group or oligosilylene group having a hydrocarbon group or a halogenated hydrocarbon group of 1 to 20 carbon atoms, or germylene group having a hydrocarbon group or a halogenated hydrocarbon group of 1 to 20 carbon atoms; x and Y are independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms; m is a transition metal selected from elements belonging to groups 4-6 of the periodic Table.

9. The catalyst according to claim 8, wherein R of the transition metal compound represented by the general formula (II)³And R⁶At least one of which is derived from R³Or R⁶A 7-membered ring having an unsaturated bond of (1);

10. the catalyst according to claim 8, wherein R of the transition metal compound represented by the general formula (II)⁷And R⁸At least one of which is a halogenated aryl group or an aryl group substituted with a halogenated hydrocarbon group.

11. The catalyst according to claim 1, wherein the transition metal compound (a) is a compound represented by the following general formula (III):wherein R is¹、R²、R⁴、R⁵Q, X, Y and M have the same meaning as defined in formula (II) above; r⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵And R¹⁶Independently a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms; ar is an aryl group which may be substituted, provided that at least one of the two 7-membered rings is bonded to a halogenated hydrocarbon group having 1 to 20 carbon atoms.

12. The catalyst according to claim 1, wherein the transition metal compound (A) is a transition metal compound represented by the following general formula (IV)A compound represented by:

wherein R is¹And R⁴Independently a hydrocarbyl group having 7 to 12 carbon atoms, a silicon-containing hydrocarbyl group having 8 to 18 carbon atoms, or a halogenated hydrocarbyl group having 7 to 12 carbon atoms; r²And R⁵Independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms, or a halogenated hydrocarbon group having 1 to 18 carbon atoms; r³And R⁶Independently is a saturated or unsaturated divalent hydrocarbon group having 3 to 10 carbon atoms, and R³And R⁶Respectively to each occurrence of R³And R⁶Form a fused ring together with two 5-membered rings, provided that R³And R⁶At least one of which has from 5 to 10 carbon atoms and forms a compound having at least one group derived from R³Or R⁶7 to 10 membered ring of unsaturated bond(s); r⁷And R⁸Independently a hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms or a sulfur-containing hydrocarbon group having 1 to 20 carbon atoms; m and n are independently an integer of 0 to 20, provided that m and n are not 0 at the same time, and when m or n is an integer of not less than 2, R⁷And R⁸May be bonded to each other to form a ring; q is a bridging group of two 5-membered rings and is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a silylene or oligosilylene group which may be substituted with a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms, or a germylene group which may be substituted with a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms; x and Y are independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms; m is a transition metal selected from the group consisting of elements belonging to groups 4 to 6 of the periodic Table of the elements.

13. The catalyst according to claim 1, wherein the transition metal compound (A) is a compound represented by the following general formula (V)：Wherein R is¹And R⁴Independently a hydrocarbyl group having 7 to 12 carbon atoms, a silicon-containing hydrocarbyl group having 8 to 18 carbon atoms, or a halogenated hydrocarbyl group having 7 to 12 carbon atoms; r²And R⁵Independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms, or a halogenated hydrocarbon group having 1 to 18 carbon atoms; r³And R⁶Independently is a saturated or unsaturated divalent hydrocarbon group having 3 to 10 carbon atoms, and R³And R⁶Respectively to each occurrence of R³And R⁶Form a fused ring together with two 5-membered rings, provided that R³And R⁶At least one of which has from 5 to 10 carbon atoms and forms a compound having at least one group derived from R³Or R⁶7 to 10 membered ring of unsaturated bond(s); r⁷And R⁸Independently a hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, or a sulfur-containing hydrocarbon group having 1 to 20 carbon atoms; m and n are independently an integer of 0 to 20, provided that m and n are not 0 at the same time, and when m or n is an integer of not less than 2, R⁷And R⁸May be bonded to each other to form a ring; q is a bridging group of two 5-membered rings and is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a silylene or oligosilylene group which may be substituted with a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms, or a germylene group which may be substituted with a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms; x and Y are independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms; m is selected from the group consisting ofTransition metals of group 4-6 elements.

14. The catalyst according to claim 1, wherein the transition metal compound (A) is a transition metal compound represented by the formulaA compound represented by the general formula (VI):wherein R is¹、R²、R⁴And R⁵Independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms, or a halogenated hydrocarbon group having 1 to 18 carbon atoms; r³And R⁶Independently is a saturated or unsaturated divalent hydrocarbon group having 3 to 10 carbon atoms, and R³And R⁶Respectively to each occurrence of R³And R⁶Form a fused ring together with two 5-membered rings, provided that R³And R⁶At least one of which has from 5 to 8 carbon atoms and forms a compound having at least one group derived from R³Or R⁶7 to 10 membered ring of unsaturated bond(s); r⁷And R⁸Independently a hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, or a sulfur-containing hydrocarbon group having 1 to 20 carbon atoms; q is a silicon atom, a germanium atom or a tin atom; a is an unsaturated hydrocarbon group having 3 to 12 carbon atoms and forms a ring together with Q to which A is attached; r^aIs a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atoms; m and n are independently an integer of 0 to 20, provided that m and n are not 0 at the same time, and when m or n is an integer of not less than 2, R⁷And R⁸May be bonded to each other to form a ring; 1 is an integer of 0 to 22, and when 1 is an integer of not less than 2, R^aMay be bonded to each other to form a ring; x and Y are independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms; m is a transition metal selected from the group consisting of transition metals belonging to groups 4 to 6 of the periodic Table of the elements.

15. The catalyst according to claims 1 to 7, wherein the organoaluminum compound (C) is a compound represented by the following general formula (VII):

AlR_aP_3-a(VII) wherein R is a hydrocarbon having 1 to 20 carbon atomsA group; p is a hydrogen atom, a halogen atom, an alkoxy group or a siloxy group; "a" is a number satisfying 0 < a.ltoreq.3.

16. A catalyst for the polymerization of α -olefins, comprising:

a transition metal compound as a base component (A),

an aluminumoxy compound as an essential component (D), which is an ionic compound capable of reacting with the component (A) to convert the component (A) into a cation or a Lewis acid, and

an optional fine particulate support component (E),

the component (A) is represented by a general formula (II), a general formula (III), a general formula (IV), a general formula (V) or (VI).

17. A process for producing an α -olefin polymer, which comprises contacting a catalyst as defined in claim 1 with a α -olefin to effect polymerization or copolymerization of a α -olefin.

18. A process for producing α -olefin polymer comprising contacting the catalyst defined in claim 16 with α -olefin for the polymerization or copolymerization of α -olefin.

19. A novel transition metal compound represented by the general formula (II).

20. A novel transition metal compound represented by the general formula (III).

21. A novel transition metal compound represented by the general formula (IV).

22. A novel transition metal compound represented by the general formula (V).

23. A novel transition metal compound represented by the general formula (VI).

24. A catalyst component comprising a novel transition metal compound represented by the general formula (II).

25. A catalyst component comprising a novel transition metal compound represented by the general formula (III).

26. A catalyst component comprising a novel transition metal compound represented by the general formula (IV).

27. A catalyst component comprising a novel transition metal compound represented by the general formula (V).

28. A catalyst component comprising a novel transition metal compound represented by the general formula (VI).