Catalysts for polymerization of xcex1-olefin, composed of a transition metal compound, an inorganic silicate or an ion exchangeable layer compound other than silicate, and optionally an organoaluminum compound, are described. The transition metal compound is represented by formula (I):

The present invention relates to catalysts for polymerization of xcex1-olefin, a process for producing xcex1-olefin polymers, novel transition metal compounds and catalyst components for polymerization of xcex1-olefin.
As catalysts for polymerization of xcex1-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 afore-mentioned catalysts are soluble in reaction solvent, the obtained polymer has extremely poor properties in which the polymer has irregular particle shape, has low bulk density and includes a large amount of fine powder therein. Therefore, in the case where these catalysts are applied toga slurry polymerization or a gas-phase polymerization of xcex1-olefin, there have been caused various problems concerning the production of polymers, for example, it has been difficult to conduct safe operations continuously, for the production of polymers.
On the other hand, in order to solve the afore-mentioned problems, there have been proposed catalysts obtained by supporting one or both of a transition metal compound and an organoaluminum on an inorganic oxide such as silica or alumina or an organic substance (Japanese Patent Applications Laid-Open (KOKAI) Nos. 61-108610, 60-135408, 61-296008, 3-74412 and 3-74415, etc.).
However, polymers obtained by using such catalysts have contained a large amount of fine particles or coarse particles, and deteriorated in particle properties such as low bulk density. Further, there arises problems in which the catalysts have a low catalytic activity for the polymerization based on unit weight of solid components thereof, and the obtained polymers have disadvantages such as lower molecular weight or lower stereo regularity as compared to those obtained by using catalysts not supported on a carrier.
The present invention has been attained for solving the afore-mentioned problems in the prior arts.
It is an object of the present invention to provide catalysts for polymerization of xcex1-olefins, capable of producing xcex1-olefin polymers which are free from poor in properties caused by supporting the catalyst on a carrier such as low molecular weight or low stereo regularity, and which can show not only a narrow composition distribution but also excellent transparency and mechanical strength, and to a process for producing the xcex1-olefin polymer by using the said catalyst.
It is another object of the present invention to provide novel transition metal compounds and catalyst components (catalytically active components) for polymerization of xcex1-olefin.
As a result of the present inventors"" earnest studies, it has been found that by using a catalyst comprising a specific transition metal compound and either a specific ion exchangeable layer compound or an inorganic silicate, the above-mentioned objects can be readily achieved.
In a first aspect of the present invention, there is provided a catalyst for polymerization of xcex1-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):
xe2x80x83wherein A1 and A2 are independently a conjugate 5-membered ring ligand with the proviso that A1 and A2 may be the same or different in a molecule, and at least one of A1 and A2 forms a 7- to 10-membered condensed ring including adjacent two carbon atoms of the conjugate 5-membered ring, which condensed ring is formed by joining two adjacent substituent groups on the conjugate 5-membered ring; Q is a bridging group of the two conjugate 5-membered rings of A1 and A2 at optional positions of the 5-membered rings; M is a metal atom selected from the group consisting of elements belonging to Group 4-6 of the Periodic Table; and 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 polymerization of xcex1-olefin, which comprises:
an essential component (A) of a transition metal compound,
an essential component (D) of an aluminumoxy compound, an ionic compound capable of reacting with the component (A) so as to convert the component (A) to a cation, or a Lewis acid, and
an optional component (E) of a fine particle carrier,
said component (A) being represented by the following general formula (II), (III), (IV), (V) or (VI) included in the above general formula (I).

wherein R1, R2, R4 and R5 are independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms or halogenated hydrocarbon group having 1 to 18 carbon atoms; R3 and R6 are independently a saturated or unsaturated divalent hydrocarbon group having 3 to 10 carbon atoms, which forms a condensed ring in cooperation with each of 5-membered rings to which R3 and R6 are respectively bonded, with the proviso that at least one of R3 and R6 has 5 to 8 carbon atoms and forms a 7- to 10-membered condensed ring having at least one unsaturated bond derived from R3 or R6; R7 and R8 are independently 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 at least one of R7 and R8 is the halogenated hydrocarbon group having 1 to 20 carbon atoms; m and n are independently an integer of 0 to 20 with the proviso that m and n are not 0 at the same time; Q is a bridging group of the 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 an oligosilylene group which may have a hydrocarbon group or halogenated hydrocarbon group having 1 to 20 carbon atoms or a germylene group which may have a hydrocarbon group or 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; and M is a transition metal selected from the group consisting of elements belonging to Group 4-6 of the Periodic Table.

wherein R1, R2, R4, R5, Q, X, and M have the same meanings as defined in the above general formula (II); R9, R10, R11, R12, R13, R14, R15 and R16 are independently a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms; and Ar is an aryl group which may be substituted, with the proviso that at least one of the two 7-membered rings is bonded to the halogenated hydrocarbon group having 1 to 20 carbon atoms.

wherein R1 and R4 are independently 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; R2 and R5 are independently 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; R3 and R6 are independently a saturated or unsaturated divalent hydrocarbon group having 3 to 10 carbon atoms and forms a condensed ring in cooperation with 5-membered rings to which R3 and R6 are respectively bonded, with the proviso that at least one of R3 and R6 has 5 to 10 carbon atoms and forms a 7- to 10-membered condensed ring having at least one unsaturated bond derived from R3 or R6; R7 and R8 are independently 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 with the proviso that m and n are not 0 at the same time, and when m or n is an integer of not less than 2, the R7 or the R8 may be bonded to each other to form a ring; Q is a bridging group of the 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 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; 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; and M is a transition metal selected from the group consisting of elements belonging to Group 4-6 of the Periodic Table.

wherein R1 and R4 are independently 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; R2 and R5 are independently 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.; R3 and R6 are independently a saturated or unsaturated divalent hydrocarbon group having 3 to 10 carbon atoms and forms a condensed ring in cooperation with 5-membered rings to which R3 and R6 are respectively bonded, with the proviso that at least one of R3 and R6 has 5 to 10 carbon atoms and forms a 7- to 10-membered condensed ring having at least one unsaturated bond derived from R3 or R6; R7 and R8 are independently 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 with the proviso that m and n are not 0 at the same time, and when m or n is an integer of not less than 2, the R7 or the R8 may be bonded to each other to form a ring; Q is a bridging group of the 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 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; 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; and M is a transition metal selected from the group consisting of elements belonging to Group 4-6 of the Periodic Table.

wherein R1, R2, R4 and R5 are independently 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; R3 and R6 are independently a saturated or unsaturated divalent hydrocarbon group having 3 to 10 carbon atoms and forms a condensed ring in cooperation with 5-membered rings to which R3 and R6 are respectively bonded, with the proviso that at least one of R3 and R6 has 5 to 8 carbon atoms and forms a 7- to 10-membered condensed ring having at least one unsaturated bond derived from R3 or R6; R7 and R8 are independently 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 a divalent unsaturated hydrocarbon group having 3 to 12 carbon atoms and forms a ring in cooperation with the Q to which A is bonded; Ra is a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atom; m and n are independently an integer of 0 to 20 with the proviso that m and n are not 0 at the same time, that when m or n is an integer of not less than 2, the R7 or the R8 may be bonded to each other to form a ring; 1 is an integer of 0 to 22, when 1 is an integer of not less than 2, the Ra may 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; and M is a transition metal selected from the group consisting of elements belonging to Group 4-6 of the Periodic Table.
In a third aspect of the present invention, there is provided a process for producing an xcex1-olefin polymer, comprising bringing an xcex1-olefin into contact with any of the catalysts defined in the afore-mentioned first and second aspects to conduct the polymerization or copolymerization of the xcex1-olefin.
In a fourth aspect of the present invention, there is provided a novel transition metal compound represented by the afore-mentioned general formula (II).
In a fifth aspect of the present invention, there is provided a novel transition metal compound represented by the afore-mentioned general formula (III).
In a sixth aspect of the present invention, there is provided a novel transition metal compound represented by the afore-mentioned general formula (IV).
In a seventh aspect of the present invention, there is provided a novel transition metal compound represented by the afore-mentioned general formula (V).
In an eighth aspect of the present invention, there is provided a novel transition metal compound represented by the afore-mentioned general formula (VI).
In a ninth aspect of the present invention, there is provided a catalyst component for polymerization of xcex1-olefin which comprises a transition metal compound represented by the afore-mentioned general formula (II).
In a tenth aspect of the present invention, there is provided a catalyst component for polymerization of xcex1-olefin which comprises a transition metal compound represented by the afore-mentioned general formula (III).
In an eleventh aspect of the present invention, there is provided a catalyst component for polymerization of xcex1-olefin which comprises a transition metal compound represented by the afore-mentioned general formula (IV).
In a twelfth aspect of the present invention, there is provided a catalyst component for polymerization of xcex1-olefin which comprises a transition metal compound represented by the afore-mentioned general formula (V).
In a thirteenth aspect of the present invention, there is provided a catalyst component for polymerization of xcex1-olefin which comprises a transition metal compound represented by the afore-mentioned general formula (VI).
The present invention is described in detail below.
The catalyst for polymerization of xcex1-olefin according to the present invention comprises a specific transition metal compound (component A) as an essential component.
First, the component A of transition metal compound is explained below. In the present invention, as the transition metal compound, there can be used those compounds represented by the general formula (I):
In the afore-mentioned general formula (I), A1 and A2 are conjugate 5-membered ring ligands with the proviso that A1 and A2 may be the same-or different in a molecule and at least one of A1 and A2 forms a 7- to 10-membered condensed ring including adjacent two carbon atoms of the conjugate 5-membered ring, which condensed ring is formed by joining two adjacent substituent groups on the conjugate 5-membered ring. Further, the conjugate 5-membered ring ligands represented by A1 and A2 may have substituent groups bonded to carbon atoms other than those bonded to the group Q.
An typical example of the above conjugate 5-membered ring ligands is a cyclopentadienyl group. The cyclopentadienyl group may be an unsubstituted one, i.e., xe2x80x9cC5H4xe2x80x94xe2x80x9d having four hydrogen atoms, or may be substituted ones in which one or more of the hydrogen atoms are substituted by any substituent groups, as described above.
Examples of the substituent groups are hydrocarbon groups having 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms. Specific examples of the hydrocarbon groups may include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a phenyl group, a naphthyl group, a butenyl group, a butadienyl group, a triphenylcarbyl group or the like.
The afore-mentioned hydrocarbon groups may be monovalent groups bonded to the cyclopentadienyl group. Further, the two hydrocarbon substituent groups may be bonded with each other at end positions thereof to form a condensed ring. Typical examples of the cyclopentadienyl groups having the condensed ring may include indene, fluorene, azulene or derivatives thereof. Incidentally, in the present invention, the transition metal compounds used are required to have at least one 7- to 10-membered ring as the condensed ring, as described in detail hereinafter.
As the substituent groups other than the afore-mentioned hydrocarbon groups, there can be exemplified hydrocarbon groups containing silicon, oxygen, nitrogen, phosphorus, boron, sulfur or the like. Typical examples of the hydrocarbon residues may include a methoxy group, an ethoxy group, a phenoxy group, a furyl group, a trimethylsilyl group, a diethylamino group, a diphenylamino group, a pyrazolyl group, an indolyl group, a carbazolyl group, a dimethylphosphino group, a diphenylphosphino group, a diphenylboron group, a dimethoxyboron group, a thienyl group or the like.
As other substituent groups, there can be exemplified halogen, halogen-containing hydrocarbons or the like. Typical examples of the other substituent groups may include a chlorine atom, a bromine atom, a fluorine atom, a trichloromethyl group, a thrifluoromethyl group, a fluorophenyl group, a pentafluorophenyl group or the like.
Meanwhile, in the transition metal compounds used in the present invention, at least one of the conjugate 5-membered ring ligands A1 and A2 has a 7- to 10-membered condensed ring including adjacent two carbon atoms thereof and the condensed ring is formed by joining two adjacent substituent groups on the conjugate 5-membered ring. That is, at least one of A1 and A2 must form a 7- to 10-membered condensed ring which includes adjacent two carbon atoms of the conjugate 5-membered ring ligand.
Examples of the afore-mentioned ligands which constitute at least one of A1 and A2, may include a hydroazulenyl group, a methylhydroazulenyl group, an ethylhydroazulenyl group, a dimethylhydroazulenyl group, a methylethylhydroazulenyl group, a methylisopropylhydroazulenyl group, a methylphenylisopropylhydroazulenyl group, various hydrogenated azulenyl groups, a bicyclo-[6.3.0]-undecanyl group, a methyl-bicyclo-[6.3.0]-undecanyl group, an ethyl-bicyclo-[6.3.0]-undecanyl group, a phenyl-bicyclo-[6.3.0]-undecanyl group, a methylphenyl-bicyclo-[6.3.0]-undecanyl group, an ethylphenyl-bicyclo-[6.3.0]-undecanyl group, a methyldiphenyl-bicyclo-[6.3.0]-undecanyl group, a methyl-bicyclo-[6.3.0]-undecadienyl group, a methylphenyl-bicyclo-[6.3.0]-undecadienyl group, an ethylphenyl-bicyclo-[6.3.0]-undecadienyl group, a methylisopropyl-bicyclo-[6.3.0]-undecadienyl group, a bicyclo-[7.3.0]-dodecanyl group or derivatives thereof, a bicyclo-[7.3.0]-dodecadienyl group or derivatives thereof, a bicyclo-[8.3.0]-tridecanyl group or derivatives thereof, a bicyclo-[8.3.0]-tridecadienyl group or derivatives thereof, or the like.
The afore-mentioned groups may further have substituent groups such as hydrocarbon groups, hydrocarbon groups containing silicon, oxygen, nitrogen, phosphorus, boron, sulfur or the like, halogens or halogen-containing hydrocarbons, etc., as described hereinbefore.
The Q is a bridging group of the two conjugate 5-membered rings of A1 and A2 at optional positions of the 5-membered rings. That is, the Q is a divalent bonding group and acts to cross-link the two conjugate 5-membered rings with each other. The kinds of bonding groups Q are not particularly restricted. Examples of the bonding groups Q may include (a) divalent hydrocarbon or halogenated hydrocarbon groups having usually 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more specifically, unsaturated divalent hydrocarbon groups such as alkylene groups, cycloalkylene groups, arylene groups, haloalkylene groups or halocycloalkylene groups; (b) silylene groups or oligosilylene groups; (c) silylene groups or oligosilylene groups substituted with hydrocarbon or halogenated hydrocarbon groups having usually 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms; (d) germylene groups; (e) germylene groups substituted with hydrocarbon or halogenated hydrocarbon groups having usually 1 to 20 carbon atoms; or the like. Among them, alkylene groups, cycloalkylene groups, arylene groups, silylene groups substituted with hydrocarbon groups or germylene groups substituted with hydrocarbon groups are preferred.
The M represents a transition metal atom selected from the group consisting of elements belonging to Group 4-6 of the Periodic Table. Among them, Group 4 transition metals such as titanium, zirconium or hafnium are preferred, and zirconium or hafnium is more preferred.
The X and Y represent 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 afore-mentioned hydrocarbon groups may have usually 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms. Specific examples of the preferred X and Y may include a hydrogen atom, a chlorine atom, a methyl group, an isobutyl group, a phenyl group, a dimethyl amino group, a diethyl amino group or the like.
Some groups of the transition metal compounds represented by the aforementioned general formula (I), i.e., the transition metal compounds represented by the below-mentioned general formula (II), (III), (IV), (V) and (VI) are novel compounds.
The novel transition metal compounds classified into the first group is explained below. The transition metal compounds of the first group is represented by the general formula (II):
The novel transition metal compound represented by the general formula (II) involves compounds (a) in which the 5-membered ring ligand having substituent groups R1, R2 and R3 and the 5-membered ring ligand having substituent groups R4, R5 and R6 are asymmetrical with respect to a plane containing M, X and Y when viewed as to the relative positions thereof through the group Q, and compounds (b) in which the 5-membered ring ligand having substituent groups R1, R2 and R3 and the 5-membered ring ligand having substituent groups R4, R5 and R6 are symmetrical with respect to a plane containing M, X and Y when viewed as to the relative positions thereof through the group Q.
In order to produce xcex1-olefin polymers having a high molecular weight and a high melting point, the afore-mentioned compounds (a), i.e., the compounds in which the two 5-membered ring ligands do not have a relationship of real and mirror images with respect to the plane containing M, X and Y, can be preferably used. Also, in case of use of the novel transition metal compound represented by the following general formulae (III), (IV), (V) and (VI).
In the general formula (II), R1, R2, R4 and R5 are independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a silicon-containing hydrocarbon group having 1 to 18 carbon atoms or halogenated hydrocarbon group having 1 to 18 carbon atoms, as described above.
Specific examples of the afore-mentioned hydrocarbon group having 1 to 10 carbon atoms may include alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclopentyl, cyclohexyl or methylcyclohexyl; alkenyl groups such as vinyl, propenyl or cyclohexenyl; aralkyl groups such as benzyl, phenylethyl or phenylpropyl; aryl-alkenyl groups such as trans-styryl; aryl groups such as phenyl, tolyl, dimethylphenyl, ethylphenyl, trimethylphenyl, 1-naphthyl or 2-naphthyl; or the like.
Specific examples of the afore-mentioned silicon-containing hydrocarbon atom having 1 to 18 carbon atoms may include trialkylsilyl groups such as trimethylsilyl, triethylsilyl or t-butyldimethylsilyl; triarylsilyl groups such as triphenylsilyl; (alkyl)(aryl)silyl groups such as dimethylphenylsilyl; alkylsilylalkyl groups such as bis(trimethylsilyl)methyl; or the like.
As the afore-mentioned halogen atoms contained in the halogenated hydrocarbon groups having 1 to 18 carbon atoms, there can be used a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. In the case where the halogen atom contained in the halogenated hydrocarbon group is, for example, a fluorine atom, the fluorine atom can be bonded to optional position(s) of the hydrocarbon group. Specific examples of the halogenated hydrocarbon groups may include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, 2,2,2-trifluoromethyl, 2,2,1,1-tetrafluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluoropropyl, nonafluorobutyl, trifluorovinyl, 1,1-difluorobenzyl, 1,1,2,2-tetrafluorophenylethyl, o-, m- or p-fluorophenyl, o-, m- or p-chlorophenyl, o-, m- or p-bromophenyl, 2,4-, 3,5-, 2,6- or 2,5-difluorophenyl, 2,4-, 3,5-, 2,6- or 2,5-dichlorophenyl, 2,4,6-trifluorophenyl, 2,4,6-trichlorophenyl, pentafluorophenyl, pentachlorophenyl, 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 or the like.
Among them, as the R1 and R4, hydrocarbon groups having 1 to 7 carbon atoms such as methyl, ethyl, propyl, butyl or benzyl are preferred, and as the R2 and R5, a hydrogen atom is preferred.
In the general formula (II), R3 and R6 are independently a saturated or unsaturated divalent hydrocarbon group having 3 to 10 carbon atoms and forms a condensed ring in cooperation with the 5-membered ring to which the R3 or R6 is bonded. The condensed ring formed by the R3 or R6 may be a 5- to 12-membered ring. However, it is essentially required that at least one of the R3 and R6 has 5 to 8 carbon atoms and forms a 7- to 10-membered condensed ring having at least one unsaturated bond derived from the R3 or R6. In this case, it is preferred that both of the condensed rings are 7- to 10-membered rings.
Specific examples of the R3 and R6 may include divalent saturated hydrocarbon groups such as trimethylene, tetramethylene, pentamethylene, hexamethylene or heptamethylene; divalent unsaturated hydrocarbon groups such as propenylene, 2-butenylene, 1,3-butadienylene, 1-pentenylene, 2-pentenylene, 1,3-pentadienylene, 1,4-pentadienylene, 1-hexenylene, 2-hexenylene, 3-hexenylene, 1,3-hexadienylene, 1,4-hexadienylene, 1,5-hexadienylene, 2,4-hexadienylene, 2,5-hexadienylene or 1,3,5-hexatrienylene; or the like. Among them, pentamethylene, 1,3-pentadienylene, 1,4-pentadienylene or 1,3,5-hexatrienylene are preferred, and 1,3-pentadienylene or 1,4-pentadienylene are especially preferred.
In the general formula (II), R7 and R8 are independently 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, it is required that at least one of the R7 and R8 is the halogenated hydrocarbon group having 1 to 20 carbon atoms.
Specific examples of the afore-mentioned hydrocarbon group having 1 to 20 carbon atoms may include alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclopentyl, cyclohexyl or methylcyclohexyl; alkenyl groups such as vinyl, propenyl or cyclohexenyl; aralkyl groups such as benzyl, phenylethyl or phenylpropyl; arylalkenyl groups such as trans-styryl; aryl groups such as phenyl, tolyl, dimethylphenyl, ethylphenyl, trimethylphenyl, 1-naphthyl, 2-naphthyl, acenaphthyl, phenanthryl or anthryl; or the like. Among them, alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl or cyclopropyl, and aryl groups having 6 to 20 carbon atoms such as phenyl, tolyl, dimethylphenyl, ethylphenyl, trimethylphenyl, 1-naphthyl or 2-naphthyl are preferred.
As the afore-mentioned halogen atoms contained in the halogenated hydrocarbon groups having 1 to 20 carbon atoms, there can be used a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. In the case where the halogen atom contained in the halogenated hydrocarbon group is, for example, a fluorine atom, the fluorine atom can be bonded to optional position(s) of the hydrocarbon group. Specific examples of the halogenated hydrocarbon groups may include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, 2,2,2-trifluoroethyl, 2,2,1,1-tetrafluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluoropropyl, nonafluorobutyl, trifluorovinyl, 1,1-difluorobenzyl, 1,1,2,2-tetrafluorophenylethyl, -o-, m- or p-fluorophenyl, o-, m- or p-chlorophenyl, o-, m- or p-bromophenyl, 2,4-, 3,5-, 2,6- or 2,5-difluorophenyl, 2,4-, 3,5-, 2,6- or 2,5-dichlorophenyl, 2,4,6-trifluorophenyl, 2,4,6-trichlorophenyl, pentafluorophenyl, pentachlorophenyl, 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 or the like. Among them, fluorinated hydrocarbon groups or chlorinated hydrocarbon groups are preferred, and o-, m- or p-fluorophenyl, o-, m- or p-chlorophenyl or o-, m- or p-trifluoromethylphenyl are especially preferred.
Specific examples of the afore-mentioned oxygen-containing hydrocarbon groups having 1 to 20 carbon atoms may include alkoxy groups such as methoxy, ethoxy, propoxy, cyclopropoxy or butoxy; aryloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy or naphthoxy; arylalkoxy groups such as phenylmethoxy or naphthylmethoxy; oxygen-containing heterocyclic groups such as furyl group; or the like.
Specific examples of the afore-mentioned nitrogen-containing hydrocarbon groups having 1 to 20 carbon atoms may include alkylamino groups such as methylamino, dimethylamino, ethylamino or diethylamino; arylamino groups such as phenylamino or diphenylamino; (alkyl)(aryl)amino groups such as (methyl)(phenyl) amino; nitrogen-containing heterocyclic groups such as pyrazolyl or indolyl; or the like.
In the general formula (II), m and n are independently an integer of 0 to 20, preferably 1 to 5. If m and/or n are an integer of 2 to 20, a plurality of the R7 or R8 may be the same or different. The integers m and n are not zero at the same time. That is, it is essential that the divalent groups R3 and/or R6 have the afore-mentioned substituent groups R7 or R8, and the substituent groups R7 and/or R8 are the halogenated hydrocarbon groups having 1 to 20 carbon atoms. In addition, when the integer m or n is not less than 2, the R7 or the R8 may be bonded to each other to form an additional ring. The substituent group R7 or R8 may be bonded to any position of R3 or R6, but it is preferred that the substituent groups R7 or R8 is bonded to the carbon atoms of R3 or R6, adjacent to the 5-membered ring (the carbon at xcex1-position).
In the general formula (II), Q is a bridging group of the two 5-membered rings, and is a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene or an oligosilylene group which may have a hydrocarbon or halogenated hydrocarbon group having 1 to 20 carbon atoms or a germylene group which may have a hydrocarbon group or halogenated hydrocarbon group having 1 to 20 carbon atoms. When silylene group or germylene group has two hydrocarbon or halogenated hydrocarbon groups, those groups may be bonded to each other to form a ring.
Specific examples of the group Q may include alkylene groups such as methylene, methylmethylene, dimethylmethylene, 1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene or 1,4-cyclohexylene; arylalkylene groups such as (methyl)(phenyl)methylene or diphenylmethylene; silylene groups; alkylsilylene groups such as methylsilylene, dimethylsilylene, diethylsilylene, di(n-propyl)silylene, di(i-propyl)silylene or di(cyclohexyl)silylene; (alkyl)(aryl)silylene groups such as methylphenylsilylene or methyltolylsilylene; arylsilylene groups such as diphenylsilylene; haloalkylsilylene groups such as di(chloromethyl)silylene or di(2-chloroethyl)silylene; (alkyl)(haloalkyl)silylene groups such as methyl(4-chlorophenyl)silylene; di(haloalkyl)silylene groups such as di(4-chlorophenyl)silylene or bis(3,5-dichlorophenyl)silylene; germylene groups; alkyl germylene groups obtained by substituting germanium for a silicon atom of the afore-mentioned silylene groups having the C1 to C20 hydrocarbon groups; alkyl aryl germylene groups or aryl germylene groups; or the like. Among them, the silylene groups having the C1 to C20 hydrocarbon groups or the germylene groups having the C1 to C20 hydrocarbon groups are preferred, and the alkylsilylene groups, the alkyl arylsilylene groups or the arylsilylene groups are especially preferred.
In the general formula (II), X and Y represent independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, 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 afore-mentioned halogen atoms, there can be used a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. As the afore-mentioned hydrocarbon groups having 1 to 20 carbon atoms and the halogenated hydrocarbon group having 1 to 20 carbon atoms, there can be exemplified the same hydrocarbon groups and halogenated hydrocarbon groups as defined above with respect to the R7 and R8.
Specific examples of the afore-mentioned silicon-containing hydrocarbon groups may include trialkylsilylmethyl groups such as trimethylsilylmethyl or triethylsilylmethyl; di(alkyl) (aryl)silyl methyl groups such as dimethylphenylsilylmethyl, diethylphenylsilylmethyl, dimethyltolylsilylmethyl; or the like.
Specific examples of the afore-mentioned oxygen-containing hydrocarbon groups having 1 to 20 carbon atoms may include alkoxy groups such as methoxy, ethoxy, propoxy, cyclopropoxy or butoxy; aryloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy or naphthoxy; arylalkoxy groups such as phenylmethoxy or naphthylmethoxy; or the like.
Specific examples of the afore-mentioned nitrogen-containing hydrocarbon groups having 1 to 20 carbon atoms may include alkylamino groups such as methylamino, dimethylamino, ethylamino or diethylamino; arylamino groups such as phenylamino or diphenylamino; (alkyl) (aryl) amino groups such as (methyl)(phenyl) amino; or the like.
In the general formula (II), the 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, the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms or the nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms are more preferred. Further, the especially preferred X and Y are a chlorine atom, a methyl group, an i-butyl 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 Group 4-6 of the Periodic Table. Among them, Group 4 transition metals such as titanium, zirconium or hafnium are preferred. Further, zirconium or hafnium are more preferred.
The novel transition metal compounds represented by the general formula (II) can be produced by optional methods according to the kinds of substituent groups or bonding manners thereof. Typically, the transition metal compounds can be produced through the following reaction scheme. Incidentally, xe2x80x9cH2Raxe2x80x9d and xe2x80x9cH2Rbxe2x80x9d in the reaction scheme have the following chemical formulae: xe2x80x83H2Ra+n-C4H9Lixe2x86x92HRaLi+C4H10
H2Rb+n-C4H9Lixe2x86x92HRbLi+C4H10
HRaLi+HRbLi+QCl2xe2x86x92HRaxe2x80x94Qxe2x80x94HRb+2LiCl
HRaxe2x80x94Qxe2x80x94HRb+2(n-C4H9Li)xe2x86x92LiRaxe2x80x94Qxe2x80x94LiRb+2C4H10
LiRaxe2x80x94Qxe2x80x94LiRb+ZrCl4xe2x86x92(Raxe2x80x94Qxe2x80x94Rb)ZrCl2+2LiCl2
In addition, the metal salts of the cyclopentadienyl compounds such as the afore-mentioned HRaLi and HRbLi may be produced by addition reaction of alkyl groups or aryl groups, for example, as described in European Patent No. 697418. More specifically, an alkyl lithium compound or an aryl lithium compound is reacted with an azulene derivative in an inert solvent to produce a lithium salt of a dihydroazulenyl derivative. As the alkyl lithium compounds, there can be used methyl lithium, i-propyl lithium, n-butyl lithium, t-butyl lithium or the like. As the aryl lithium compounds, there can be used phenyl lithium, p-chlorophenyl lithium, p-fluorophenyl lithium, p-trifluoromethylphenyl lithium, naphthyl lithium or the like. In addition, as the inert solvents, there can be used hexane, benzene, toluene, diethyl ether, tetrahydrofuran or mixed solvents thereof.
Next, the novel transition metal compounds classified into the second group are explained below. The transition metal compounds of the second group are specific compounds among those belonging to the first group, which are represented by the general formula (III):
In the general formula (III), R1, R2, R4, R5, Q, X, Y and M have the same meanings as defined in the above general formula (II), and R9, R10, R11, R12, R13, R14, R15 and R16 bonding to 7-membered ring are independently a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms. The Ar represents an aryl group. However, it is required that at least one of the two 7-membered rings is substituted with the halogenated hydrocarbon group having 1 to 20 carbon atoms. As the hydrocarbon groups having 1 to 20 carbon atoms or the halogenated hydrocarbon groups having 1 to 20 carbon atoms, there can be exemplified the same hydrocarbon groups and halogenated hydrocarbon groups as defined above with respect to the general formula (II). Specific examples of the aryl groups may include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group or the like. These aryl groups may be substituted by 1 to 5 halogen atoms or halogenated hydrocarbon groups.
Next, the novel transition metal compounds classified into the third group are explained below. The transition metal compounds of the third group are represented by the general formula (IV):
In the general formula (IV), R1 and R4 are independently 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 afore-mentioned hydrocarbon groups having 1 to 6 carbon atoms may include alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclopentyl or cyclohexyl; alkenyl groups such as vinyl, propenyl or cyclohexenyl; a phenyl group; or the like.
Examples of the afore-mentioned silicon-containing hydrocarbon groups having 1 to 7 carbon atoms may include trialkylsilyl groups such as trimethylsilyl, triethylsilyl or t-butyldimethylsilyl; alkylsilylalkyl groups such as bis(trimethylsilyl)methyl; or the like.
As the halogen atom in the afore-mentioned halogenated hydrocarbon groups having 1 to 6 carbon atoms, there may be used the same atoms as described with respect to the general formula (II). In case where the halogen atom contained in the halogenated hydrocarbon group is, for example, a fluorine atom, the afore-mentioned halogenated hydrocarbon groups is that substituted with fluorine atom at optional position(s) thereof. Specific examples of the halogenated hydrocarbon groups may include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, 2,2,2-trifluoroethyl, 2,2,1,1-tetrafluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluoropropyl, nonafluorobutyl, trifluorovinyl, o-, m- or p-fluorophenyl, o-, m- or p-chlorophenyl, o-, m- or p-bromophenyl, 2,4-, 3,5-, 2,6- or 2,5-difluorophenyl, 2,4-, 3,5-, 2,6- or 2,5-dichlorophenyl, 2,4,6-trifluorophenyl, 2,4,6-trichlorophenyl, pentafluorophenyl, pentachlorophenyl, or the like.
Among them, as the R1 and R4, the hydrocarbon groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl or butyl are preferred.
In the general formula (IV), R2 and R5 are independently 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. Specific examples of the substituents R2 and R5 may be the same as those described in the general formula (II).
In the general formula (IV), R3 is a saturated or unsaturated divalent hydrocarbon group having 3 to 10 carbon atoms and forms a condensed ring in cooperation with a 5-membered ring to which R3 is bonded. Accordingly, the condensed ring formed by the R3 is a 5- to 12-membered ring. Specific examples of the R3 may include divalent saturated hydrocarbon groups such as trimethylene, tetramethylene, pentamethylene or hexamethylene; divalent unsaturated hydrocarbon groups such as propenylene, 2-butenylene, 1,3-butadienylene, 1-pentenylene, 2-pentenylene, 1,3-pentadienylene, 1,4-pentadienylene, 1-hexenylene, 2-hexenylene, 3-hexenylene, 1,3-hexadienylene, 1,4-hexadienylene, 1,5-hexadienylene, 2,4-hexadienylene, 2,5-hexadienylene or 1,3,5-hexatrienylene; or the like. Among them, pentamethylene, 1,3-pentadienylene, 1,4-pentadienylene or 1,3,5-hexatrienylene are preferred. Further, pentamethylene, 1,3-pentadienylene or 1,4-pentadienylene are more preferred. Still further, 1,3-pentadienylene or 1,4-pentadienylene are especially preferred.
That is, it is preferred that the R3 is a C5 divalent saturated or unsaturated hydrocarbon group forms a condensed ring in cooperation with the 5-membered ring to which the R3 is bonded. It is more preferred that the R3 is pentadienylene.
In the general formula (IV), R6 is a saturated or unsaturated divalent hydrocarbon group having 5 to 8 carbon atoms and forms a condensed ring in cooperation with a 5-membered ring to which R6 is bonded. Accordingly, the condensed ring formed by the R6 is a 7- to 10-membered ring. Specific examples of the R6 may include divalent saturated hydrocarbon groups such as pentamethylene, hexamethylene or heptamethylene; divalent unsaturated hydrocarbon groups such as 1-pentenylene, 2-pentenylene, 1,3-pentadienylene, 1,4-pentadienylene, 1-hexenylene, 2-hexenylene, 3-hexenylene, 1,3-hexadienylene, 1,4-hexadienylene, 1,5-hexadienylene, 2,4-hexadienylene, 2,5-hexadienylene or 1,3,5-hexatrienylene; or the like. Among them, pentamethylene, 1,3-pentadienylene, 1,4-pentadienylene or 1,3,5-hexatrienylene are preferred. Further, pentamethylene, 1,3-pentadienylene or 1,4-pentadienylene are more preferred. Still further, 1,3-pentadienylene or 1,4-pentadienylene are especially preferred.
That is, it is preferred that the R6 is a C5 divalent saturated or unsaturated hydrocarbon group forms a condensed ring in cooperation with the 5-membered ring to which the R6 is bonded. It is more preferred that the R6 is pentadienylene.
In the general formula (IV), R7 and R8 are independently 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 R8 is present at a xcex2- or remoter position on R6 with respect to the 5-membered ring. As the R7 and R8 of the general formula (IV), there may be used the same groups as those described in general formula (II) except for the halogenated hydrocarbon groups.
In the general formula (IV), m is 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, the R7 or the R8 may be bonded to each other to form a ring. The m and n are preferably an integer of 1 to 5, more preferably 2 to 5. In the case where the m and/or n are an integer of not less than 2, a plurality of R7 (or a plurality of R8) may be the same or different. The position of R3 to which the R7 is bonded or the position of R6 to which the R8 is bonded is not particularly restricted except for the afore-mentioned definitions concerning the bonding position of the R8, but it is preferred that the R7 or the R8 is bonded to a carbon atom of the R3 or R6 adjacent to the 5-membered ring (i.e., carbon atom of xcex1-position).
In the general formula (IV), Q is a bridging group of the two 5-membered rings, and represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene 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. As the Q of the general formula (IV), there may be used the same groups as those described in general formula (II).
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. As the X and Y of the general formula (IV), there may be used the same groups as those described in general formula (II).
In the general formula (IV), M is a transition metal selected from the group consisting of elements belonging to Group 4-6 of the Periodic Table. As the M of the general formula (IV), there may be used the same transition metals as those described in general formula (II).
The novel transition metal compounds represented by the general formula (IV) can be produced by the same production method as used for the transition metal compound represented by the general formula (II).
Next, the novel transition metal compounds classified into the fourth group are explained below. The transition metal compounds of the fourth group are represented by the general formula (V):
In the general formula (V), R1 and R4 are independently 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. Specific examples of the aforementioned R1 and R4 may include alkyl groups such as n-heptyl, 1,1,2,2-tetramethylpropyl, n-octyl, s-octyl, n-nonyl or cyclohexylmethyl; alkenyl groups such as 1-heptenyl, 2-heptenyl or cyclohexenylmethyl; aralkyl groups such as benzyl, 1-phenylethyl or 2-phenylethyl; aryl groups such as o-, m- or p-tolyl or 2,5-dimethylphenyl; or the like.
Specific examples of the afore-mentioned silicon-containing hydrocarbon group having 8 to 18 carbon atoms may include trialkylsilyl groups such as tripropylsilyl. tri-n-butylsilyl or tri-t-butylsilyl; (alkyl)(aryl) silyl groups such as dimethylphenylsilyl or methyldiphenylsilyl; alkylsilyl alkyl groups such as tris(trimethylsilyl)methyl; or the like.
As the halogen atom in the afore-mentioned halogenated hydrocarbon groups having 7 to 12 carbon atoms, there may be used the same atoms as described with respect to the general formula (II). In case where the halogen atom contained in the halogenated hydrocarbon group is, for example, a fluorine atom, the afore-mentioned halogenated hydrocarbon groups is that substituted with fluorine atom at optional position thereof. Specific examples of the halogenated hydrocarbon groups may include 1,1-difluorobenzyl, 1,1,2,2-tetrafluorophenylethyl, 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 or the like.
Among them, as R1 and R4, the hydrocarbon groups such as n-heptyl, benzyl or 1-phenylethyl are preferred. Further, the aralkyl groups such as benzyl or 1-phenylethyl are more preferred.
In the general formula (V), R2 and R5 are independently 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. As the R2 and R5 of the general formula (V), there may be used the same groups as described in the general formula (II).
In the general formula (V), R3 and R5 are independently a saturated or unsaturated divalent hydrocarbon group having 3 to 10 carbon atoms and forms a condensed ring in cooperation with 5-membered rings to which R3 and R6 are respectively bonded, with the proviso that at least one of R3 and R6 has 5 to 10 carbon atoms and forms a 7- to 10-membered condensed ring having at least one unsaturated bond derived from R3 or R6. As the R3 and R6 of the general formula (V), there may be used the same groups as described in the general formula (II).
In the general formula (V), R7 and R8 are independently 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. As the R7 and R8 of the general formula (V), there may be used the same groups as described in the general formula (II) except for halogenated hydrocarbon groups.
In the general formula (V), m and n are independently an integer of 0 to 20, preferably 1 to 5. In the case where the 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 zero at the same time. In addition, when the m or n is an integer of not less than 2, R7 or R8 may be bonded to each other to form a ring. The substituent group R7 or R8 may be bonded to any position of R3 or R6, but it is preferred that the R7 or the R8 is bonded to a carbon atom of R3 or R6 adjacent to the 5-membered ring (i.e., carbon atom of xcex1-position).
In the general formula (V), Q is a bridging group of the two 5-membered rings, and represents a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene 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. As the Q of the general formula (V), there may be used the same groups as described for that of the general formula (II).
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. As the X and Y of the general formula (V), there may be used the same groups as described for those of the general formula (II).
In the general formula (V), M is a transition metal selected from the group consisting of elements belonging to Group 4-6 of the Periodic Table. As the M of the general formula (V), there may be used the same transition metals as described for that of the general formula (II).
The novel transition metal compounds represented by the general formula (V) can be produced by the same production method as used for the transition metal compound represented by the general formula (II).
Next, the novel transition metal compounds classified into the fifth group are explained below. The transition metal compounds of the fifth group are represented by the general formula (VI):
In the general formula (VI), R1, R2, R4 and R5 are independently 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. As the R1, R2, R4 and R5 of the general formula (VI), there may be used the same groups as described for those of the general formula (II).
In the general formula (VI), R3 and R6 are independently a saturated or unsaturated divalent hydrocarbon group having 3 to 10 carbon atoms and forms a condensed ring in cooperation with 5-membered rings to which R3 and R6 are respectively bonded, with the proviso that at least one of R3 and R6 has 5 to 8 carbon atoms and forms a 7- to 10-membered condensed ring having at least one unsaturated bond derived from R3 or R6. As the R3 and R6 of the general formula (VI), there may be used the same groups as described for those of the general formula (II) except for halogenated hydrocarbon groups.
In the general formula (VI), R7 and R8 are independently 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. As the R7 and R8 of the general formula (VI), there may be used the same groups as described for those of the general formula (II).
In the general formula (VI), Q is a silicon atom, a germanium atom or a tin atom. Among them, a silicon atom and a germanium atom are preferred.
In the general formula (VI), A is a divalent unsaturated hydrocarbon group having 3 to 12 carbon atoms and forms a ring in cooperation with the Q to which A is bonded. Specific examples of such unsaturated hydrocarbon groups may include divalent unsaturated hydrocarbon groups such as propenylene, butenylene, butadienylene, pentenylene, pentadienylene, hexenylene, hexadienylene, hexatrienylene or the like. Among them, divalent hydrocarbon groups having 3 to 5 carbon atoms such as propenylene, butenylene, butadienylene, pentenylene or pentadienylene are preferred. Further, butadienylene is more preferred.
In the general formula (VI), Ra is a saturated or unsaturated hydrocarbon group having 1 to 10 carbon atom. Specific examples of such unsaturated hydrocarbon groups may include alkyl groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, cyclopropyl or cyclopentyl; alkenyl groups such as vinyl, propenyl, butenyl, butadienyl, hexenyl or hexadienyl; aralkyl groups such as benzyl, phenylethyl or phenylpropyl; arylalkenyl groups such as trans-styryl; aryl groups such as phenyl, tolyl, dimethylphenyl, ethylphenyl, trimethylphenyl, 1-naphthyl or 2-naphthyl; or the like. Among them, methyl, ethyl, n-propyl, i-propyl, propenyl or butenyl are preferred.
In the general formula (VI), m and n are independently an integer of 0 to 20. The m and n are preferably an integer of 1 to 5. In the case where the m and/or n are 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 zero at the same time. In addition, when the m or n is an integer of not less than 2, R7 or R8 may be bonded to each other to form a ring. The position of R3 to which the R7 is bonded or the position of R6 to which the R8 is bonded is not particularly restricted, but it is preferred that the R7 or the R8 is bonded to a carbon atom of R3 or R6 adjacent to the 5-membered ring (carbon atom of xcex1-position). The 1 is an integer of 0 to 22, preferably an integer of 1 to 10, more preferably an integer of 1 to 4. When the 1 is an integer of 2 to 22, a plurality of Ra may be the same or different. Further, when the 1 is an integer of not less than 2, the Ra may 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. As the X and Y of the general formula (VI), there may be used the same groups as described for those of the general formula (II).
In the general formula (VI), M is a transition metal selected from the group consisting of elements belonging to Group 4-6 of the Periodic Table. As the M of the general formula (VI), there may be used the same transition metals as described for that of the general formula (II).
The novel transition metal compounds represented by the general formula (VI) can be produced by the same production method as used for the transition metal compound represented by the general formula (II). In this case, in the reaction scheme exemplified for the transition metal compound represented by the general formula (II), the QCl2 is represented by the following general formula:
Specific examples of the transition metal compounds according to the present invention may include the below-mentioned compounds. Incidentally, although these compounds are indicated below merely by chemical names thereof, it is intended that each involves both compounds having symmetrical and asymmetrical stereo structures as mentioned above. First, for better understanding of nomenclatures of these transition metal compounds, the structural formula of zirconium chloride compound (1) is represented below. It should be noted that the zirconium chloride compound is also named as xe2x80x9cmethylene bis{1,1xe2x80x2-(2-methyl-4-phenyl-1,4-dihydroazulenyl)} zirconium dichloride, if the nomenclature derived from a compound before complexing thereof which has a skeleton of 1,4-dihydroazulene is considered.

(1) methylene bis{1,1xe2x80x2-(2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(2) methylene bis{1,1xe2x80x2-(4-hydroazulenyl)} zirconium dichloride;
(3) methylene bis{1,1xe2x80x2-(2-methyl-4-hydroazulenyl)} zirconium dichloride;
(4) methylene bis{1,1xe2x80x2-(2,4-dimethyl-4-hydroazulenyl)} zirconium dichloride;
(5) methylene bis{1,1xe2x80x2-2-ethyl-4-hydroazulenyl)} zirconium dichloride;
(6) methylene bis{1,1xe2x80x2-(2-ethyl-4-methyl-4-hydroazulenyl)} zirconium dichloride;
(7) methylene bis{1,1xe2x80x2-(2-ethyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(8) methylene bis{1,1xe2x80x2-(2,4,4-trimethyazulenyl)} zirconium dichloride;
(9) methylene bis{1,1xe2x80x2-(2-methyl-4,5,6,7,8-pentahydroazulenyl)} zirconium dichloride;
(10) methylene bis{1,1xe2x80x2-(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)} zirconium dichloride;
(11) methylene bis{1,1xe2x80x2-(4-methyl-4-hydroazulenyl)} zirconium dichloride;
(12) methylene bis{1,1xe2x80x2-(4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(13) methylene bis{1,1xe2x80x2-(4-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(14) methylene bis{1,1xe2x80x2-(4-naphthyl-4-hydroazulenyl)} zirconium dichloride;
(15) methylene bis{1,1xe2x80x2-(2-phenyl-4-hydroazulenyl)} zirconium dichloride;
(16) methylene bis{1,1xe2x80x2-(2-benzyl-4-hydroazulenyl)} zirconium dichloride;
(17) methylene bis{1,1xe2x80x2-(2-styryl-4-hydroazulenyl)} zirconium dichloride;
(18) methylene bis{1,1xe2x80x2-(2-t-butyl-4-hydroazulenyl)} zirconium dichloride;
(19) methylene bis{1,1xe2x80x2-cyclopentacyclooctenyl) zirconium dichloride;
(20) methylene bis{1,1xe2x80x2-(4-methylcyclopentacyclooctenyl)} zirconium dichloride;
(21) methylene bis{1,1xe2x80x2-(4-ethylcyclopentacyclooctenyl)} zirconium dichloride;
(22) methylene bis{1,1xe2x80x2-(4-phenylcyclopentacyclooctenyl)} zirconium dichloride;
(23) methylene bis{1,1xe2x80x2-(2-ethyl-4-phenylcyclopentacyclooctenyl)} zirconium dichloride;
(24) methylene bis{1,1xe2x80x2-(4-methyl-4,5,6,7,8,9-hexahydrocyclopentacyclooctenyl)} zirconium dichloride;
(25) methylene bis(9-bicyclo[8.3.0]trideca-2-methylpentaenyl) zirconium dichloride;
(26) methylene bis(9-bicyclo[8.3.0]trideca-2,12-dimethylpentaenyl) zirconium dichloride;
(27) methylene bis (9-bicyclo[8 3.0]trideca-2,12-dimethyloctahydropentaenyl) zirconium dichloride;
(28) methylene bis(9-bicyclo[8.3.0]trideca-2-phenyl,12-ethylpentaenyl) zirconium dichloride;
(29) ethylene bis{1,1xe2x80x2-(4-hydroazulenyl)} zirconium dichloride;
(30) ethylene bis{1,1xe2x80x2-(2-methyl-4-hydroazulenyl)} zirconium dichloride;
(31) ethylene bis{1,1xe2x80x2-(2,4-dimethyl-4-hydroazulenyl)} zirconium dichloride;
(32) ethylene bis{1,1xe2x80x2-(2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(33) ethylene bis{1,1xe2x80x2-(2-ethyl-4-hydroazulenyl)} zirconium dichloride;
(34) ethylene bis{1,1xe2x80x2-(2-ethyl-4-methyl-4-hydroazulenyl)} zirconium dichloride;
(35) ethylene bis{1,1xe2x80x2-(2-ethyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(36) ethylene bis{1,1xe2x80x2-(2,4,4-trimethylazulenyl} zirconium dichloride;
(37) ethylene bis{1,1xe2x80x2-(2-methyl-4,5,6,7,8-pentahydroazulenyl)} zirconium dichloride;
(38) ethylene bis{1,1xe2x80x2-(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)} zirconium dichloride;
(39) ethylene bis{1,1xe2x80x2-(4-methyl-4-hydroazulenyl)} zirconium dichloride;
(40) ethylene bis{1,1xe2x80x2-(4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(41) ethylene bis{1,1xe2x80x2-(4-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(42) ethylene bis{1,1xe2x80x2-(4-naphthyl-4-hydroazulenyl)} zirconium dichloride;
(43) ethylene bis{1,1xe2x80x2-(2-phenyl-4-hydroazulenyl)} zirconium dichloride;
(44) ethylene bis{1,1xe2x80x2-(2-benzyl-4-hydroazulenyl)} zirconium dichloride;
(45) ethylene bis{1,1xe2x80x2-(2-styryl-4-hydroazulenyl)} zirconium dichloride;
(46) ethylene bis{1,1xe2x80x2-(2-t-butyl-4-hydroazulenyl)} zirconium dichloride;
(47) ethylene bis(1,1xe2x80x2-cyclopentacyclooctenyl) zirconium dichloride;
(48) ethylene bis{1,1xe2x80x2-(4-methylcyclopentacyclooctenyl)} zirconium dichloride;
(49) ethylene bis{1,1xe2x80x2-(4-ethylcyclopentacyclooctenyl)} zirconium dichloride;
(50) ethylene bis{1,1xe2x80x2-(4-phenylcyclopentacyclooctenyl)} zirconium dichloride;
(51) ethylene bis{1,1xe2x80x2-(2-ethyl-4-phenylcyclopentacyclooctenyl)} zirconium dichloride;
(52) ethylene bis{1,1xe2x80x2-(4-methyl-4,5,6,7,8,9-hexahydrocyclopentacyclooctenyl)} zirconium dichloride;
(53) ethylene bis(9-bicyclo[8.3.0]trideca-2-methylpentaenyl) zirconium dichloride;
(54) ethylene bis(9-bicyclo[8.3.0]trideca-2,12-dimethylpentaenyl) zirconium dichloride,
(55) ethylene bis(9-bicyclo[8.3.0]trideca-2,12-dimethyloctahydropentaenyl) zirconium dichloride;
(56) ethylene bis(9-bicyclo[8.3.0]trideca-2-phenyl,12-ethylpentaenyl) 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-benzoindenyl)}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-t-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)} zircorium dichloride;
(69) ethylene {1-(2-propyl-4-phenylindenyl)}{1-(4-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(70) ethylene {1-(2-t-butylindenyl)}{1-(4-naphthyl-4-hydroazulenyl)} zirconium dichloride;
(71) dimethylmethylene bis{1,1xe2x80x2-(4-hydroazulenyl)} zirconium dichloride;
(72) dimethylmethylene bis{1,1xe2x80x2-(2-methyl-4-hydroazulenyl)} zirconium dichloride;
(73) dimethylmethylene bis{1,1xe2x80x2-(2,4-dimethyl-4-hydroazulenyl)} zirconium dichloride;
(74) dimethylmethylene bis{1,1xe2x80x2-(2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(75) dimethylmethylene bis{1,1xe2x80x2-(2-ethyl-4-hydroazulenyl)} zirconium dichloride;
(76) dimethylmethylene bis{1,1xe2x80x2-(2-ethyl-4-methyl-4-hydroazulenyl)} zirconium dichloride;
(77) dimethylmethylene bis{1,1xe2x80x2-(2-ethyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(78) dimethylmethylene bis{1,1xe2x80x2-(2,4,4-trimethylazulenyl)} zirconium dichloride;
(79) dimethylmethylene bis{1,1xe2x80x2-(2-methyl-4,5,6,7,8-pentahydroazulenyl)} zirconium dichloride;
(80) dimethylmethylene bis{1,1xe2x80x2-(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)} zirconium dichloride;
(81) dimethylmethylene bis{1,1xe2x80x2-(4-methyl-4-hydroazulenyl)} zirconium dichloride;
(82) dimethylmethylene bis{1,1xe2x80x2-(4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(83) dimethylmethylene bis{1,1xe2x80x2-(4-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(84) dimethylmethylene bis{1,1xe2x80x2-(4-naphthyl-4-hydroazulenyl)} zirconium dichloride;
(85) dimethylmethylene bis{1,1xe2x80x2-(2-phenyl-4-hydroazulenyl)} zirconium dichloride;
(86) dimethylmethylene bis{1,1xe2x80x2-(2-benzyl-4-hydroazulenyl)} zirconium dichloride;
(87) dimethylmethylene bis{1,1xe2x80x2-(2-styryl-4-hydroazulenyl)} zirconium dichloride;
(88) dimethylmethylene bis{1,1xe2x80x2-(2-t-butyl-4-hydroazulenyl)} zirconium dichloride;
(89) dimethylmethylene bis(1,1xe2x80x2-cyclopentacyclooctenyl) zirconium dichloride;
(90) dimethylmethylene bis{1,1xe2x80x2-(4-methylcyclopentacyclooctenyl)} zirconium dichloride;
(91) dimethylmethylene bis{1,1xe2x80x2-(4-ethylcyclopentacyclooctenyl)} zirconium dichloride;
(92) dimethylmethylene bis{1,1xe2x80x2-(4-phenylcyclopentacyclooctenyl)} zirconium dichloride;
(93) dimethylmethylene bis{1,1xe2x80x2-(2-ethyl-4-phenylcyclopentacyclooctenyl)} zirconium dichloride;
(94) dimethylmethylene bis{1,1xe2x80x2-(4-methyl-4,5,6,7,8,9-hexahydrocyclopentacyclooctenyl)} zirconium dichloride;
(95) dimethylmethylene bis(9-bicyclo[8.3.0]trideca-2-methyl pentaenyl) zirconium dichloride;
(96) dimethylmethylene bis(9-bicyclo[8.3.0]trideca-2,12-dimethylpentaenyl) zirconium dichloride;
(97) dimethylmethylene bis(9-bicyclo[8.3.0]trideca-2,12-dimethyloctahydropentaenyl) zirconium dichloride;
(98) dimethylmethylene bis(9-bicyclo[8.3.0]trideca-2-phenyl, 12-ethylpentaenyl) 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-benzoindenyl)}{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)} zirconium dichloride;
(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-t-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-t-butylindenyl)}{1-(4-naphthyl-4-hydroazulenyl)} zirconium dichloride;
(113) 2,3-butylene bis{1,1xe2x80x2-(2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(114) dimethylsilylene bis{1,1xe2x80x2-(4-hydroazulenyl)} zirconium dichloride;
(115) dimethylsilylene bis{1,1xe2x80x2-(2-methyl-4-hydroazulenyl)} zirconium dichloride;
(116) dimethylsilylene bis{1,1xe2x80x2-(2,4-dimethyl-4-hydroazulenyl)} zirconium dichloride;
(117) dimethylsilylene bis{1,1xe2x80x2-(2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(118) dimethylsilylene bis{1,1xe2x80x2-(2-ethyl-4-hydroazulenyl)} zirconium dichloride;
(119) dimethylsilylene bis{1,1xe2x80x2-(2-ethyl-4-methyl-4-hydroazulenyl)} zirconium dichloride;
(120) dimethylsilylene bis{1,1xe2x80x2-(2-ethyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(121) dimethylsilylene bis{1,1xe2x80x2-(2,4,4-trimethylazulenyl)} zirconium dichloride;
(122) dimethylsilylene bis{1,1xe2x80x2-(2-methyl-4,5,6,7,8-pentahydroazulenyl)} zirconium dichloride;
(123) dimethylsilylene bis{1,1xe2x80x2-(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)} zirconium dichloride;
(124) dimethylsilylene bis{1,1xe2x80x2-(4-methyl-4-hydroazulenyl)} zirconium dichloride;
(125) dimethylsilylene bis{1,1xe2x80x2-(4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(126) dimethylsilylene bis{1,1xe2x80x2-(4-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(127) dimethylsilylene bis{1,1xe2x80x2-(4-naphthyl-4-hydroazulenyl)} zirconium dichloride;
(128) dimethylsilylene bis{1,1xe2x80x2-(2-phenyl-4-hydroazulenyl)} zirconium dichloride;
(129) dimethylsilylene bis{1,1xe2x80x2-(2-benzyl-4-hydroazulenyl)} zirconium dichloride;
(130) dimethylsilylene bis{1,1xe2x80x2-(2-styryl-4-hydroazulenyl)} zirconium dichloride;
(131) dimethylsilylene bis{1,1xe2x80x2-(2-t-butyl-4-hydroazulenyl)} zirconium dichloride;
(132) dimethylsilylene bis(1,1xe2x80x2-cyclopentacyclooctenyl) zirconium dichloride;
(133) dimethylsilylene bis{1,1xe2x80x2-(4-methylcyclopentacyclooctenyl)} zirconium dichloride;
(134) dimethylsilylene bis{1,1xe2x80x2-(4-ethylcyclopentacyclooctenyl)} zirconium dichloride;
(135) dimethylsilylene bis{1,1xe2x80x2-(4-phenylcyclopentacyclooctenyl)} zirconium dichloride;
(136) dimethylsilylene bis{1,1xe2x80x2-(2-ethyl-4-phenylcyclopentacyclooctenyl)} zirconium dichloride;
(137) dimethylsilylene bis{1,1xe2x80x2-(4-methyl-4,5,6,7,8,9-hexahydrocyclopentacyclooctenyl)} zirconium dichloride;
(138) dimethylsilylene bis(9-bicyclo[8.3.0]trideca-2-methylpentaenyl) zirconium dichloride;
(139) dimethylsilylene bis(9-bicyclo[8.3.0]trideca-2,12-dimethylpentaenyl) zirconium dichloride;
(140) dimethylsilylene bis(9-bicyclo[8.3.0]trideca-2,12-dimethyloctahydropentaenyl) zirconium dichloride;
(141) dimethylsilylene bis(9-bicyclo[8.3.0]trideca-2-phenyl, 12-ethylpentaenyl) 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-benzoindenyl)}{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;
(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-t-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) dimethylsilylene {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-t-butylindenyl)}{1-(4-naphthyl-4-hydroazulenyl)} zirconium dichloride;
(156) (methyl)(phenyl)silylene bis{1,1xe2x80x2-(4-hydroazulenyl)} zirconium dichloride;
(157) (methyl)(phenyl)silylene bis{1,1xe2x80x2-(2-methyl-4-hydroazulenyl)} zirconium dichloride;
(158) (methyl)(phenyl)silylene bis{1,1xe2x80x2-(2,4-dimethyl-4-hydroazulenyl)} zirconium dichloride;
(159) (methyl)(phenyl)silylene bis{1,1xe2x80x2-(2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(160) (methyl)(phenyl)silylene bis{1,1xe2x80x2-(2-ethyl-4-hydroazulenyl)} zirconium dichloride;
(161) (methyl)(phenyl)silylene bis{1,1xe2x80x2-(2-ethyl-4-methyl-4-hydroazulenyl)} zirconium dichloride;
(162) (methyl)(phenyl)silylene bis{1,1xe2x80x2-(2-ethyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(163) (methyl)(phenyl)silylene bis{1,1xe2x80x2-(2,4,4-trimethylazulenyl)} zirconium dichloride;
(164) (methyl)(phenyl)silylene bis{1,1xe2x80x2-(2-methyl-4,5,6,7,8-pentahydroazulenyl)} zirconium dichloride;
(165) (methyl)(phenyl)silylene bis{1,1xe2x80x2-(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)} zirconium dichloride;
(166) diphenylsilylene bis{1,1xe2x80x2-(4-hydroazulenyl)} zirconium dichloride;
(167) diphenylsilylene bis{1,1xe2x80x2-(2-methyl-4-hydroazulenyl)} zirconium dichloride;
(168) diphenylsilylene bis{1,1xe2x80x2-(2,4-dimethyl-4-hydroazulenyl)} zirconium dichloride;
(169) diphenylsilylene bis{1,1xe2x80x2-(2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(170) diphenylsilylene bis{1,1xe2x80x2-(2-ethyl-4-hydroazulenyl)} zirconium dichloride;
(171) diphenylsilylene bis{1,1xe2x80x2-(2-ethyl-4-methyl-4-hydroazulenyl)} zirconium dichloride;
(172) diphenylsilylene bis{1,1xe2x80x2-(2-ethyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(173) diphenylsilylene bis{1,1xe2x80x2-(2,4,4-trimethylzulenyl)} zirconium dichloride;
(174) diphenylsilylene bis{1,1xe2x80x2-(2-methyl-4,5,6,7,8-pentahydroazulenyl)} zirconium dichloride;
(175) diphenylsilylene bis{1,1xe2x80x2-(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)} zirconium dichloride;
(176) tetramethyldisilylene bis{1,1xe2x80x2-(4-hydroazulenyl)} zirconium dichloride;
(177) tetramethyldisilylene bis{1,1xe2x80x2-(2-methyl-4-hydroazulenyl)} zirconium dichloride;
(178) tetramethyldisilylene bis{1,1xe2x80x2-(2,4-dimethyl-4-hydroazulenyl)} zirconium dichloride;
(179) tetramethyldisilylene bis{1,1xe2x80x2-(2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(180) tetramethyldisilylene bis{1,1xe2x80x2-(2-ethyl-4-hydroazulenyl)} zirconium dichloride;
(181) tetramethyldisilylene bis{1,1xe2x80x2-(2-ethyl-4-methyl-4-hydroazulenyl)} zirconium dichloride;
(182) tetramethyldisilylene bis{1,1xe2x80x2-(2-ethyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(183) tetramethyldisilylene bis{1,1xe2x80x2-(2,4,4-trimethylazulenyl)} zirconium dichloride;
(184) tetramethyldisilylene bis{1,1xe2x80x2-(2-methyl-4,5,6,7,8-pentahydroazulenyl)} zirconium dichloride;
(185) tetramethyldisilylene bis{1,1xe2x80x2-(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)} zirconium dichloride;
(186) dimethylgermylene bis{1,1xe2x80x2-(4-hydroazulenyl)} zirconium dichloride;
(187) dimethylgermylene bis{1,1xe2x80x2-(2-methyl-4-hydroazulenyl)} zirconium dichloride;
(188) dimethylgermylene bis{1,1xe2x80x2-(2,4-dimethyl-4-hydroazulenyl)} zirconium dichloride;
(189) dimethylgermylene bis{1,1xe2x80x2-(2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(190) dimethylgermylene bis{1,1xe2x80x2-(2-ethyl-4-hydroazulenyl)} zirconium dichloride;
(191) dimethylgermylene bis{1,1xe2x80x2-(2-ethyl-4-methyl-4-hydroazulenyl)} zirconium dichloride;
(192) dimethylgermylene bis{1,1xe2x80x2-(2-ethyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(193) dimethylgermylene bis{1,1xe2x80x2-(2,4,4-trimethylazulenyl)} zirconium dichloride;
(194) dimethylgermylene bis{1,1xe2x80x2-(2-methyl-4,5,6,7,8-pentahydroazulenyl)} zirconium dichloride;
(195) dimethylgermylene bis{1,1xe2x80x2-(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)} zirconium dichloride;
(196) dimethylsilylene bis{1,1xe2x80x2-(2-trifluoromethyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(197) dimethylsilylene bis{1,1xe2x80x2-(2-ethyl-4-indolyl-4-hydroazulenyl)} zirconium dichloride;
(198) dimethylsilylene bis{1,1xe2x80x2-(2-ethyl-4-phenoxy-4-hydroazulenyl)} zirconium dichloride;
(199) dimethylsilylene bis{1,1xe2x80x2-(2-fluoro-4-pyrazolyl-4-hydroazulenyl)} zirconium dichloride;
(200) silacyclohexylidene bis{1,1xe2x80x2-(2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(201) cyclohexylidene bis{1,1xe2x80x2-(2-methyl-4-furyl-4-hydroazulenyl)} zirconium dichloride.
(202) dimethylsilylene bis{1,1xe2x80x2-(2-benzyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)} zirconium dichloride;
(203) dimethylsilylene bis[1,1xe2x80x2-{2-benzyl-4-(4-chlorophenyl)-4,5,6,7,8-pentahydroazulenyl}] zirconium dichloride;
(204) dimethylsilylene bis[1,1xe2x80x2-{2-benzyl-4-(4-fluorophenyl)-4,5,6,7,8-pentahydroazulenyl}] zirconium dichloride; (205) dimethylsilylene bis[1,1xe2x80x2-{2-benzyl-4-(1-naphthyl)-4,5,6,7,8-pentahydroazulenyl}] zirconium dichloride;
(206) dimethylsilylene bis[1,1xe2x80x2-{2-benzyl-4-(2-naphthyl)-4,5,6,7,8-pentahydroazulenyl}] zirconium dichloride;
(207) dimethylsilylene bis{1,1xe2x80x2-(2-benzyl-4-phenyl-7-isopropyl-4,5,6,7,8-pentahydroazulenyl)} zirconium dichloride;
(208) dimethylsilylene bis[1,1xe2x80x2-{2-(1-phenylethyl)-4-phenyl-4,5,6,7,8-pentahydroazulenyl)} zirconium dichloride;
(209) dimethylsilylene bis[1,1xe2x80x2-{2-(1-phenylethyl)-4-phenyl-7-isopropyl-4,5,6,7,8-pentahydroazulenyl)} zirconium dichloride;
(210) 9-silafluorene-9,9-diyl bis{1,1xe2x80x2-(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)} zirconium dichloride;
(211) 1-silaindene-1,1-diyl bis{1,1xe2x80x2-(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)} zirconium dichloride;
(212) tetramethyl-1-silacyclopentadiene-1,1-diyl bis{1,1xe2x80x2-(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)} zirconium dichloride;
(213) 1-silacyclo-3-pentene-1,1-diyl bis{1,1xe2x80x2-(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)} zirconium dichloride;
(214) dimethylmethylene bis[1,1xe2x80x2-{2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl}] zirconium dichloride;
(215) dimethylmethylene bis[1,1xe2x80x2-{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}] zirconium dichloride;
(216) dimethylmethylene bis[1,1xe2x80x2-{2-methyl-4-(4-trifluoro methylphenyl)-4-hydroazulenyl}] zirconium dichloride;
(217) ethylene bis[1,1xe2x80x2-{2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl}] zirconium dichloride;
(218) ethylene bis[1,1xe2x80x2-{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}] zirconium dichloride;
(219) ethylene bis[1,1xe2x80x2-{2-methyl-4-(4-trifluoromethyl phenyl)-4-hydroazulenyl}] zirconium dichloride;
(220) trimethylene bis[1,1xe2x80x2-{2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl}] zirconium dichloride;
(221) trimethylene bis[1,1xe2x80x2-{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}] zirconium dichloride;
(222) trimethylene bis[1,1xe2x80x2-{2-methyl-4-(4-trifluoromethyl phenyl)-4-hydroazulenyl}] zirconium dichloride;
(223) dimethylsilylene bis{1,1xe2x80x2-(2-methyl-4-trifluoromethyl-4-hydroazulenyl}] zirconium dichloride;
(224) dimethylsilylene bis[1,1xe2x80x2-{2-methyl-4-(2-fluorophenyl)-4-hydroazulenyl}] zirconium dichloride;
(225) dimethylsilylene bis[1,1xe2x80x2-{2-methyl-4-(3-fluorophenyl)-4-hydroazulenyl}] zirconium dichloride;
(226) dimethylsilylene bis[1,1xe2x80x2-{2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl}] zirconium dichloride;
(227) dimethylsilylene bis[1,1xe2x80x2-{2-ethyl-4-(4-fluorophenyl)-4-hydroazulenyl}] zirconium dichloride;
(228) dimethylsilylene bis[1,1xe2x80x2-{2-methyl-4-(2-chlorophenyl)-4-hydroazulenyl}] zirconium dichloride;
(229) dimethylsilylene bis[1,1xe2x80x2-{2-methyl-4-(3-chlorophenyl)-4-hydroazulenyl}] zirconium dichloride;
(230) dimethylsilylene bis[1,1xe2x80x2-{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}] zirconium dichloride;
(231) dimethylsilylene bis[1,1xe2x80x2-{2-ethyl-4-(4-chlorophenyl)-4-hydroazulenyl{] zirconium dichloride;
(232) dimethylsilylene bis[1,1xe2x80x2-{2-methyl-4-(2-trifluoromethylphenyl)-4-hydroazulenyl}] zirconium dichloride;
(233) dimethylsilylene bis[1,1xe2x80x2-{2-methyl-4-(3-trifluoromethylphenyl)-4-hydroazulenyl}] zirconium dichloride;
(234) dimethylsilylene bis[1,1xe2x80x2-(2-methyl-4-(4-trifluoromethylphenyl)-4-hydroazulenyl}] zirconium dichloride;
(235) dimethylsilylene bis[1,1xe2x80x2-{2-ethyl-4-(4-trifluoromethylphenyl)-4-hydroazulenyl}] zirconium dichloride;
(236) dimethylsilylene bis[1,1xe2x80x2-{2-methyl-4-(2,4-difluorophenyl)-4-hydroazulenyl}] zirconium dichloride;
(237) dimethylsilylene bis[1,1xe2x80x2-{2-methyl-4-(2,5-difluorophenyl)-4-hydroazulenyl{] zirconium dichloride;
(238) dimethylsilylene bis[1,1xe2x80x2-{2-methyl-4-(2,6-difluorophenyl)-4-hydroazulenyl}] zirconium dichloride;
(239) dimethylsilylene bis[1,1xe2x80x2-{2-methyl-4-(3,5-difluorophenyl)-4-hydroazulenyl}] zirconium dichloride;
(240) dimethylsilylene bis[1,1xe2x80x2-(2-methyl-4-(2,4,6-trifluorophenyl)-4-hydroazulenyl}] zirconium dichloride;
(241) dimethylsilylene [1-{2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl{] [1-{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}] zirconium dichloride;
(242) dimethylsilylene bis[1,1xe2x80x2-{2-methyl-4-(4-fluorophenyl)-6-isopropyl-4-hydroazulenyl}] zirconium dichloride;
(243) dimethylsilylene bis[1,1xe2x80x2-(2,8-dimethyl-4-(4-fluorophenyl)-4-hydroazulenyl}] zirconium dichloride;
(244) dimethylsilylene bis[1,1xe2x80x2-(2-methyl-4-(4-chlorophenyl)-6-isopropyl-4-hydroazulenyl}] zirconium dichloride;
(245) dimethylsilylene bis[1,1xe2x80x2-{2-methyl-4-(4-chlorophenyl)-7-isopropyl-4-hydroazulenyl}] zirconium dichloride;
(246) dimethylsilylene bis[1,1xe2x80x2-{2,8-dimethyl-4-(4-chlorophenyl)-4-hydroazulenyl}] zirconium dichloride;
(247) dimethylsilylene bis[1,1xe2x80x2-{2-methyl-4-(4-trifluoro methylphenyl)-6-isopropyl-4-hydroazulenyl}] zirconium dichloride;
(248) dimethylsilylene bis[1,1xe2x80x2-{2-methyl-4-(4-trifluoro methylphenyl)-7-isopropyl-4-hydroazulenyl}] zirconium dichloride;
(249) dimethylsilylene bis[1,1xe2x80x2-{2-methyl-4-(4-fluorophenyl)-7-isopropyl-4-hydroazulenyl}] zirconium dichloride;
(250) dimethylsilylene bis[1,1xe2x80x2-{2-ethyl-4-(4-chlorophenyl)-7-isopropyl-4-hydroazulenyl}] zirconium dichloride;
(251) dimethylsilylene bis[1,1xe2x80x2-{2-ethyl-4-(4-fluorophenyl)-7-isopropyl-4-hydroazulenyl}] zirconium dichloride;
(252) dimethylsilylene bis[1,1xe2x80x2-{2-ethyl-4-(4-trifluoromethyl phenyl)-7-isopropyl-4-hydroazulenyl}] zirconium dichloride;
(253) dimethylsilylene bis[1,1xe2x80x2-{2-ethyl-4-(4-chlorophenyl)-7-phenyl-4-hydroazulenyl}] zirconium dichloride;
(254) dimethylsilylene bis[1,1xe2x80x2-{2-ethyl-4-(4-fluorophenyl)-7-phenyl-4-hydroazulenyl}] zirconium dichloride;
(255) dimethylsilylene bis[1,1xe2x80x2-{2-ethyl-4-(4-trifluoromethyl phenyl)-7-phenyl-4-hydroazulenyl}] zirconium dichloride;
(256) diphenylsilylene bis[1,1xe2x80x2-(2-ethyl-4-(4-chlorophenyl)-7-isopropyl-4-hydroazulenyl}] zirconium dichloride;
(257) diphenylsilylene bis[1,1xe2x80x2-{2-ethyl-4-(4-fluorophenyl)-7-isopropyl-4-hydroazulenyl}] zirconium dichloride;
(258) diphenylsilylene bis[1,1xe2x80x2-{2-ethyl-4-(4-trifluoromethyl phenyl)-7-isopropyl-4-hydroazulenyl}] zirconium dichloride;
(259) (methyl)(phenyl)silylene bis[1,1xe2x80x2-{2-ethyl-4-(4-chlorophenyl)-7-isopropyl-4-hydroazulenyl}] zirconium dichloride;
(260) (methyl) (phenyl)silylene bis[1,1xe2x80x2-{2-ethyl-4-(4-fluorophenyl)-7-isopropyl-4-hydroazulenyl}] zirconium dichloride;
(261) (methyl)(phenyl)silylene bis[1,1xe2x80x2-{2-ethyl-4-(4-trifluoromethylphenyl)-7-isopropyl-4-hydroazulenyl}] zirconium dichloride;
(262) dimethylsilylene bis[1,1xe2x80x2-{2-ethyl-4-(4-chlorophenyl)-7-isopropyl-4,5,6,7,8-pentahydroazulenyl}] zirconium dichloride;
(263) dimethylsilylene bis[1,1xe2x80x2-{2-ethyl-4-(4-fluorophenyl)-7-isopropyl-4,5,6,7,8-pentahydroazulenyl}] zirconium dichloride;
(264) dimethylsilylene bis[1,1xe2x80x2-(2-ethyl-4-(4-trifluoromethyl phenyl)-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-trifluoromethyl phenyl)-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;
(261) dimethylsilylene bis[1,1xe2x80x2-{2-benzyl-4-(4-chlorophenyl)-4-hydroazulenyl)}] zirconium dichloride;
(272) dimethylsilylene bis[1,1xe2x80x2-{2-benzyl-4-(4-fluorophenyl)-4-hydroazulenyl)} zirconium dichloride;
(273) dimethylsilylene bis[1,1xe2x80x2-{2-benzyl-4-(4-chlorophenyl)-7-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(274) dimethylsilylene bis[1,1xe2x80x2-{2-benzyl-4-(4-fluorophenyl)-7-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(275) diphenylsilylene bis[1,1xe2x80x2-{2-benzyl-4-(4-chlorophenyl)-4-hydroazulenyl)} zirconium dichloride;
(276) diphenylsilylene bis[1,1xe2x80x2-{2-benzyl-4-(4-fluorophenyl)-4-hydroazulenyl)} zirconium dichloride;
(277) (methyl) (phenyl)silylene bis[1,1xe2x80x2-{2-benzyl-4-(4-chlorophenyl)-4-hydroazulenyl)} zirconium dichloride;
(278) (methyl) (phenyl)silylene bis[1,1xe2x80x2-{2-benzyl-4-(4-fluorophenyl)-4-hydroazulenyl)} zirconium dichloride;
(279) dimethylsilylene [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-chlorophenyl)-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 bis[1,1xe2x80x2-{2,8-dimethyl-4-(4-trifluoro methylphenyl)-4-hydroazulenyl}  zirconium dichloride;
(284) dimethylsilylene bis[1,1xe2x80x2-{2-methyl-4-(4-fluoro-1-naphthyl)-4-hydroazulenyl}] zirconium dichloride;
(285) dimethylsilylene bis[1,1xe2x80x2-{2-methyl-4-(4-fluoro-2-naphthyl)-4-hydroazulenyl}] zirconium dichloride;
(286) (methyl)(phenyl)silylene bis[1,1xe2x80x2-{2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl}] zirconium dichloride;
(287) (methyl)(phenyl)silylene bis[1,1xe2x80x2-{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}] zirconium dichloride;
(288) (methyl)(phenyl)silylene bis[1,1xe2x80x2-{2-methyl-4-(4-trifluoromethylphenyl)-4-hydroazulenyl}] zirconium dichloride;
(289) diphenylsilylene bis[1,1xe2x80x2-{2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl}] zirconium dichloride;
(290) diphenylsilylene bis[1,1xe2x80x2-{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}] zirconium dichloride;
(291) diphenylsilylene bis[1,1xe2x80x2-{2-methyl-4-(4-trifluoromethylphenyl)-4-hydroazulenyl}] zirconium dichloride;
(292) dimethylgermylene bis[1,1xe2x80x2-{2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl}] zirconium dichloride;
(293) dimethylgermylene bis[1,1xe2x80x2-{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}] zirconium dichloride;
(294) dimethylgermylene bis[1,1xe2x80x2-{2-methyl-4-(4-trifluoromethylphenyl)-4-hydroazulenyl}] zirconium dichloride;
(295) dimethylsilylene [1-{2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl}] {1-(2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(296) dimethylsilylene [1-{2-ethyl-4-(4-fluorophenyl)-4-dihydroazulenyl}] {1-(2-ethyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(297) dimethylsilylene [1-{2-methyl-4-(4-chlorophenyl)-4-hydroazulenyl}] {1-(2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(298) dimethylsilylene [1-{2-methyl-4-(4-trifluoromethylphenyl)-4-hydroazulenyl}] {1-(2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(299) dimethylsilylene [1-{2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl}] {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}] {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) dimethylsilylene bis[1,1xe2x80x2-{2-methyl-4-(4-fluorophenyl)cyclopentacyclooctenyl} zirconium dichloride;
(318) dimethylsilylene bis[1,1xe2x80x2-{2-ethyl-4-(4-chlorophenyl)cyclopentacyclooctenyl} zirconium dichloride;
(319) dimethylsilylene bis[1,1xe2x80x2-{2-methyl-5-(4-trifluoromethylphenyl)cyclopentacyclooctenyl} zirconium dichloride.
(320) 9-silafluorene-9,9-diyl bis[1,1xe2x80x2-{2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl}] zirconium dichloride;
(321) 9-silafluorene-9,9-diyl bis[1,1xe2x80x2-{2-methyl-4-(4-trifluoromethylphenyl)-4-hydroazulenyl}] zirconium dichloride;
(322) 1-silaindene-1,1-diyl bis[1,1xe2x80x2-{2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl}] zirconium dichloride;
(323) 1-silaindene-1,1-diyl bis[1,1xe2x80x2-{2-methyl-4-(4-trifluoromethylphenyl)-4-hydroazulenyl}] zirconium dichloride;
(324) tetramethyl-1-silacyclopentadiene-1,1-diyl bis[1,1xe2x80x2-(2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl}] zirconium dichloride;
(325) tetramethyl-1-silacyclopentadiene-1,1-diyl bis[1,1xe2x80x2-{2-methyl-4-(4-trifluoromethylphenyl)-4-hydroazulenyl}] zirconium dichloride;
(326) 1-silacyclo-3-pentene-1,1-diyl bis[1,1xe2x80x2-{2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl}] zirconium dichloride;
(327) 1-silacyclo-3-pentene-1,1-diyl bis[1,1xe2x80x2-{2-methyl-4-(4-trifluoromethylphenyl)-4-hydroazulenyl}] zirconium dichloride;
(328) (4-fluorophenyl)methylsilylene bis[1,1xe2x80x2-{2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl] zirconium dichloride;
(329) (4-chlorophenyl)methylsilylene bis[1,1xe2x80x2-{2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl}] zirconium dichloride;
(330) (chloromethyl)methylsilylene bis[1,1xe2x80x2-{2-methyl-4-(4-trifluoromethylphenyl)-4-hydroazulenyl}] zirconium dichloride;
(331) (4-fluorophenyl)methylsilylene [1-(2-methyl-4-(4-fluorophenyl)-4-hydroazulenyl}] {1-(2-ethyl-4-phenylindenyl)} zirconium dichloride;
(332) dimethylsilylene bis{1,1xe2x80x2-(2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(333) dimethylsilylene bis{1,1xe2x80x2-(2-ethyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(334) dimethylsilylene bis{1,1xe2x80x2-(2-propyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(335) dimethylsilylene bis{1,1xe2x80x2-(2-isopropyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(336) dimethylsilylene bis{1,1xe2x80x2-(2-phenyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(337) dimethylsilylene bis{1,1xe2x80x2-(2-trimethylsilylmethyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(338) dimethylsilylene bis[1,1xe2x80x2-{2-methyl-4-(1-naphthyl)-7-isopropyl-4-hydroazulenyl}] zirconium dichloride;
(339) dimethylsilylene bis[1,1xe2x80x2-{2-methyl-4-(2-naphthyl)-7-isopropyl-4-hydroazulenyl}] zirconium dichloride;
(340) dimethylsilylene bis[1,1xe2x80x2-{2-ethyl-4-(1-naphthyl)-7-isopropyl-4-hydroazulenyl}] zirconium dichloride;
(341) dimethylsilylene bis[1,1xe2x80x2-{2-ethyl1-4-(2-naphthyl)-7-isopropyl-4-hydroazulenyl}] zirconium dichloride;
(342) dimethylsilylene bis{1,1xe2x80x2-(2-ethyl-4-phenyl-7-phenyl-4-hydroazulenyl)} zirconium dichloride;
(343) dimethylsilylene bis[1,1xe2x80x2-{2-ethyl-4-(1-naphthyl)-7-phenyl-4-hydroazulenyl}] zirconium dichloride;
(344) dimethylsilylene bis[1,1xe2x80x2-{2-ethyl-4-(2-naphthyl)-7-phenyl-4-hydroazulenyl}] zirconium dichloride;
(345) diphenylsilylene bis{1,1xe2x80x2-(2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(346) diphenylsilylene bis{1,1xe2x80x2-(2-ethyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(347) diphenylsilylene bis{1,1xe2x80x2-(2-propyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(348) diphenylsilylene bis{1,1xe2x80x2-(2-isopropyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(349) diphenylsilylene bis{1,1xe2x80x2-(2-phenyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(350) diphenylsilylene bis{1,1xe2x80x2-(2-trimethylsilylmethyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(351) diphenylsilylene bis[1,1xe2x80x2-{2-ethyl-4-(1-naphthyl)-7-isopropyl-4-hydroazulenyl}] zirconium dichloride;
(352) diphenylsilylene bis[1,1xe2x80x2-{2-ethyl-4-(2-naphthyl)-7-isopropyl-4-hydroazulenyl}] zirconium dichloride;
(353) (methyl)(phenyl)silylene bis{1,1xe2x80x2-(2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl}] zirconium dichloride;
(354) (methyl)(phenyl)silylene bis{1,1xe2x80x2-(2-ethyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(355) (methyl)(phenyl)silylene bis[1,1xe2x80x2-{2-ethyl-4-(1-naphthyl)-7-isopropyl-4-hydroazulenyl}] zirconium dichloride;
(356) (methyl)(phenyl)silylene bis[1,1xe2x80x2-{2-ethyl-4-(2-naphthyl)-7-isopropyl-4-hydroazulenyl}] zirconium dichloride;
(357) dimethylsilylene bis{1,1xe2x80x2-(2-methyl-4-phenyl-7-isopropyl-4,5,6,7,8-pentahydroazulenyl)} zirconium dichloride;
(358) dimethylsilylene bis{1,1xe2x80x2-(2-ethyl-4-phenyl-7-isopropyl-4,5,6,7,8-pentahydroazulenyl)} zirconium dichloride;
(359) dimethylsilylene bis[1,1xe2x80x2-{2-ethyl-4-(1-naphthyl)-7-isopropyl-4,5,6,7,8-pentahydroazulenyl}] zirconium dichloride;
(360) dimethylsilylene bis[1,1xe2x80x2-{2-ethyl-4-(2-naphthyl)-7-isopropyl-4,5,6,7,8-pentahydroazulenyl}] 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}] {1-(2-methyl-4-phenylindenyl)} zirconium dichloride;
(368) dimethylsilylene [1-{2-ethyl-4-(2-naphthyl)-7-isopropyl-4-hydroazulenyl}] {1-(2-methyl-4-phenylindenyl)} zirconium dichloride;
(369) methylene bis{1,1xe2x80x2-(2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(370) methylene bis{1,1xe2x80x2-(2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(371) methylene bis{1,1xe2x80x2-(2-methyl-6-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(372) methylene bis{1,1xe2x80x2-(2-ethyl-4,7-diisopropyl-4,5,6,7,8-pentahydroazulenyl)} zirconium dichloride;
(373) methylene bis{1,1xe2x80x2-(4,6-dimethylcyclopentacyclooctenyl)} zirconium dichloride;
(374) methylene bis{1,1xe2x80x2-(4-methyl-6-isopropylcyclopentacyclooctenyl)} zirconium dichloride;
(375) methylene bis{1,1xe2x80x2-(2-methyl-5-phenylcyclopentacyclooctenyl)} zirconium dichloride;
(376) ethylene bis{1,1xe2x80x2-(2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(377) ethylene bis{1,1xe2x80x2-(2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(378) ethylene bis{1,1xe2x80x2-(2-methyl-6-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(379) ethylene bis{1,1xe2x80x2-(2-ethyl-4,7-diisopropyl-4,5,6,7,8-pentahydroazulenyl)} zirconium dichloride;
(380) ethylene bis{1,1xe2x80x2-(4,6-dimethylcyclopentacyclooctenyl)} zirconium dichloride;
(381) ethylene bis{1,1xe2x80x2-(4-methyl-6-isopropylcyclopentacyclooctenyl)} zirconium dichloride;
(382) ethylene bis{1,1xe2x80x2-(2-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-benzoindenyl)}{1-(2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(385) dimethylmethylene bis{1,1xe2x80x2-(2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(386) dimethylmethylene bis{1,1xe2x80x2-(2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(387) dimethylmethylene bis{1,1xe2x80x2-(2-methyl-6-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(388) dimethylmethylene bis{1,1xe2x80x2-(2-ethyl-4,7-diisopropyl-4,5,6,7,8-pentahydroazulenyl)} zirconium dichloride;
(389) dimethylmethylene bis{1,1xe2x80x2-(4,6-dimethylcyclopentacyclooctenyl)} zirconium dichloride;
(390) dimethylmethylene bis{1,1xe2x80x2-(4-methyl-6-isopropylcyclopentacyclooctenyl)} zirconium dichloride;
(391) dimethylmethylene bis{1,1xe2x80x2-(2-methyl-5-phenylcyclopentacyclooctenyl)} zirconium dichloride;
(392) dimethylmethylene {(1-(2,4,7-trimethylindenyl)}{1-(2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(393) dimethylmethylene {(1-(2-ethyl-4,5-benzoindenyl)}{1-(2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(394) dimethylsilylene bis{1,1xe2x80x2-(2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(395) dimethylsilylene bis{1,1xe2x80x2-(2-methyl-6-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(396) dimethylsilylene bis{1,1xe2x80x2-(2-ethyl-4,7-diisopropyl-4-hydroazulenyl)} zirconium dichloride;
(397) dimethylsilylene bis{1,1xe2x80x2-(4,6-dimethylcyclopentacyclooctenyl)} zirconium dichloride;
(398) dimethylsilylene bis{1,1xe2x80x2-(4-methyl-6-isopropylcyclopentacyclooctenyl)} zirconium dichloride;
(399) dimethylsilylene bis{1,1xe2x80x2-(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-benzoindenyl)}{1-(2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(402) (methyl)(phenyl)silylene bis{1,1xe2x80x2-(2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(403) (methyl)(phenyl)silylene bis{1,1xe2x80x2-(2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(404) diphenylsilylene bis{1,1xe2x80x2-(2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(405) tetramethyldisilylene bis{1,1xe2x80x2-(2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(406) tetramethyldisilylene bis{1,1xe2x80x2-(2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(407) dimethylgermylene bis{1,1xe2x80x2-(2-methyl-4-phenyl-6-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(408) dimethylgermylene bis{1,1xe2x80x2-(2-methyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(409) dimethylsilylene bis{1,1xe2x80x2-(2-benzyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(410) dimethylsilylene bis{1,1xe2x80x2-(2-heptyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(411) dimethylsilylene bis{1,1xe2x80x2-{2-octyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(412) dimethylsilylene bis[1,1xe2x80x2-{2-(1-phenylethyl)-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(413) dimethylsilylene bis[1,1xe2x80x2-{2-(2-phenylethyl)-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(414) dimethylsilylene bis[1,1xe2x80x2-{2-(1-naphthyl)-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(415) dimethylsilylene bis[1,1xe2x80x2-(2-(2-naphthyl)-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(416) dimethylsilylene bis{1,1xe2x80x2-(2-dimethylphenylsilyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(417) dimethylsilylene bis[1,1xe2x80x2-{2-benzyl-4-(1-naphthyl)-4-hydroazulenyl)} zirconium dichloride;
(418) dimethylsilylene bis[1,1xe2x80x2-{2-benzyl-4-(2-naphthyl)-4-hydroazulenyl)} zirconium dichloride;
(419) dimethylsilylene bis{1,1xe2x80x2-(2-benzyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(420) dimethylsilylene bis{1,1xe2x80x2-(2-heptyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(421) dimethylsilylene bis{1,1xe2x80x2-(2-octyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(422) dimethylsilylene bis[1,1xe2x80x2-{2-(1-phenylethyl)-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(423) dimethylsilylene bis[1,1xe2x80x2-{2-(2-phenylethyl)-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(424) dimethylsilylene bis[1,1xe2x80x2-{2-(1-naphthyl)-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(425) dimethylsilylene bis[1,1xe2x80x2-{2-(2-naphthyl)-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(426) dimethylsilylene bis{1,1xe2x80x2-(2-dimethylphenylsilyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(427) dimethylsilylene bis[1,1xe2x80x2-{2-benzyl-4-(1-naphthyl)-7-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(428) dimethylsilylene bis[1,1xe2x80x2-{2-benzyl-4-(2-naphthyl)-7-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(429) diphenylsilylene bis{1,1xe2x80x2-(2-benzyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(430) diphenylsilylene bis[1,1xe2x80x2-{2-benzyl-4-(1-naphthyl)-4-hydroazulenyl)} zirconium dichloride;
(431) diphenylsilylene bis[1,1xe2x80x2-{2-benzyl-4-(2-naphthyl)-4-hydroazulenyl)} zirconium dichloride;
(432) diphenylsilylene bis{1,1xe2x80x2-(2-benzyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(433) diphenylsilylene bis[1,1xe2x80x2-{2-(1-phenylethyl)-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(434) diphenylsilylene bis[1,1xe2x80x2-{2-(1-phenylethyl)-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(435) (methyl)(phenyl)silylene bis{1,1xe2x80x2-(2-benzyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(436) (methyl)(phenyl)silylene bis[1,1xe2x80x2-{2-benzyl-4-(1-naphthyl)-4-hydroazulenyl)} zirconium dichloride;
(437) (methyl) (phenyl)silylene bis[1,1xe2x80x2-{2-benzyl-4-(2-naphthyl)-4-hydroazulenyl)} zirconium dichloride;
(438) (methyl)(phenyl)silylene bis{1,1xe2x80x2-(2-benzyl-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(439) (methyl)(phenyl)silylene bis[1,1xe2x80x2-{2-(1-phenylethyl)-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(440) (methyl)(phenyl)silylene bis[1,1xe2x80x2-{2-(1-phenylethyl)-4-phenyl-7-isopropyl-4-hydroazulenyl)} zirconium dichloride;
(441) dimethylsilylene {1-(2-benzyl-4-phenyl-4-hydroazulenyl)} {1-(2-methyl-4,5-benzoindenyl)} zirconium dichloride;
(442) dimethylsilylene [1-{2-benzyl-4-(1-naphthyl)-4-hydroazulenyl}] {1-(2-methyl-4,5-benzoindenyl)} zirconium dichloride;
(443) dimethylsilylene [1-{2-benzyl-4-(2-naphthyl)-4-hydroazulenyl)] {1-(2-methyl-4,5-benzoindenyl)} zirconium dichloride;
(444) dimethylsilylene [1-(2-benzyl-4-phenyl-7-isopropyl-4-hydroazulenyl}] {1-(2-methyl-4,5-benzoindenyl)} zirconium dichloride;
(445) dimethylsilylene [1-{2-(1-phenylethyl)-4-phenyl-4-hydroazulenyl}] {1-(2-methyl-4,5-benzoindenyl)} zirconium dichloride;
(446) dimethylsilylene [1-{2-(1-phenylethyl)-4-phenyl-7-isopropyl-4-hydroazulenyl}] {1-(2-methyl -4,5-benzoindenyl)} zirconium dichloride;
(447) dimethylsilylene {1-(2-benzyl-4-phenyl-4-hydroazulenyl}] {1-(2-methyl-4-phenylindenyl)} zirconium dichloride;
(448) dimethylsilylene [1-{2-benzyl-4-(1-naphthyl)-4-hydroazulenyl}] {1-(2-methyl-4-phenylindenyl)} zirconium dichloride;
(449) dimethylsilylene [1-{2-benzyl-4-(2-naphthyl)-4-hydroazulenyl}] {1-(2-methyl-4-phenylindenyl)} zirconium dichloride;
(450) dimethylsilylene [1-{2-benzyl-4-phenyl-7-isopropyl-4-hydroazulenyl}] {1-(2-methyl-4-phenylindenyl)} zirconium dichloride;
(451) dimethylsilylene [1-{2-(1-phenylethyl)-4-phenyl-4-hydroazulenyl}] {1-(2-methyl-4-phenylindenyl)} zirconium dichloride;
(452) dimethylsilylene [1-{2-(1-phenylethyl)-4-phenyl-7-isopropyl-4-hydroazulenyl}] {1-(2-methyl-4-phenylindenyl)} zirconium dichloride;
(453) 9-silafluorene-9,9-diyl bis{1,1xe2x80x2-(2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(454) 9-silafluorene-9,9-diyl bis{1,1xe2x80x2-(2-ethyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(455) 9-silafluorene-9,9-diyl bis{1,1xe2x80x2-(2,8-dimethyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(456) 9-silafluorene-9,9-diyl bis{1,1xe2x80x2-{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-diyl bis{1,1xe2x80x2-(2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(460) 1-silaindene-1,1-diyl bis{1,1xe2x80x2-(2-ethyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(461) 1-silaindene-1,1-diyl bis{1,1xe2x80x2-(2,8-dimethyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(462) 1-silaindene-1,1-diyl bis[1,1xe2x80x2-{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-silacyclopentadiene-1,1-diyl bis(1,1xe2x80x2-(2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(466) tetramethyl-1-silacyclopentadiene-1,1-diyl bis{1,1xe2x80x2-(2-ethyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(467) tetramethyl-1-silacyclopentadiene-1,1-diyl bis{1,1xe2x80x2-(2,8-dimethyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(468) tetramethyl-1-silacyclopentadiene-1,1-diyl bis[1,1xe2x80x2-{2-methyl-4-(1-naphthyl)-4-hydroazulenyl}] zirconium dichloride; (469) tetramethyl-1-silacyclopentadiene-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-silacyclopentadiene-1,1-diyl {1-(2-methyl-4-phenyl-4-hydroazulenyl)} {1-(2-methyl-4-phenylindenyl)} zirconium dichloride;
(471) 1-silacyclo-3-pentene-1,1-diyl bis{1,1xe2x80x2-(2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(472) 1-silacyclo-3-pentene-1,1-diyl bis{1,1xe2x80x2-(2-ethyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(473) 1-silacyclo-3-pentene-1,1-diyl bis{1,1xe2x80x2-(2,8-dimethyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride;
(474) 1-silacyclo-3-pentene-1,1-diyl bis[1,1xe2x80x2-{2-methyl-4-(1-naphthyl)-4-hydroazulenyl}] zirconium dichloride;
(475) 1-silacyclo-3-pentene-1,1-diyl {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-diyl {1-(2-methyl-4-phenyl-4-hydroazulenyl)} {1-(2-methyl-4-phenylindenyl)} zirconium dichloride.
In addition, as the transition metal compounds according to the present invention, there can also be exemplified those compound in which one or both of two chlorine atoms constituting the groups X and Y in the general formulae (I) to (VI) are substituted by a hydrogen atom, a fluorine atom, bromine atom, an iodine atom, a methyl group, a phenyl group, a fluorophenyl group, a benzyl group, an methoxy group, a dimethylamino group, a diethylamino group, or the like. Further, there can also be exemplified those compounds in which zirconium as the central metal M of each of the above-mentioned compounds, is substituted by titanium, hafnium, tantalum, niobium, vanadium, tungsten, molybdenum or the like. Among them, compounds containing Group 4 transition metals such as zirconium, titanium or hafnium are preferred, and compounds containing zirconium or hafnium are especially preferred.
Next, the catalyst (1) for polymerization of xcex1-olefin according to the first aspect of the present invention is explained below. The catalyst (1) comprises, as essential components, the afore-mentioned transition metal compound (component A) and the specific ion exchangeable layer compound or the inorganic silicate (component B), and as an optional component, the organoaluminum compound (component C).
First, as the component B, the inorganic silicate or the ion exchangeable layer compound except for silicate (hereinafter referred to merely as xe2x80x9cion exchangeable layer compoundxe2x80x9d) is described in detail below.
As the afore-mentioned ion exchangeable layer compounds as the component (B), there can be exemplified ionic crystalline compounds of a hexagonal closest packing type, an antimony type, a CdCl2 type or a CdI2 type, which have a layer crystal structure. Specific examples of the ion exchangeable layer compounds may include crystalline acid salts of polyvalent metals such as xcex1-Zr(HAsO4)2.H2O, xcex1-Zr(HPO4)2, xcex1-Zr(KPO4)2.3H2O, xcex1-Ti (HPO4)2, xcex1-Ti (HAsO4)2.H2O, xcex1-Sn(HPO4)2.H2O, xcex3-Zr(HPO4)2, xcex3-Ti(HPO4)2 or xcex3-Ti(NH4PO4)2xc2x7H2O.
The afore-mentioned ion exchangeable layer compounds may be treated with salts and/or acids, if required. The ion exchangeable layer compounds except for silicates which are treated with neither salts nor acids, have such a crystal structure that layers formed by ionic bond or the like are overlapped in parallel to one another with a weak bonding force therebetween and, therefore, the layers contain ions exchangeable with each other.
As the afore-mentioned inorganic silicates as the component (B), there can be exemplified clays, clay minerals, zeolite, diatomaceous earth or the like. These inorganic silicates may be either synthesized products or naturally outputted minerals. Specific examples of clays or clay minerals may include allophane group clays or clay minerals such as allophane; kaolin group clays or clay minerals such as dickite, nacrite, kaolinite or anauxite, halloysite group clays or clay minerals such as meta-halloysite or halloysite; serpentine group clays or clay minerals such as chrysotile, lizardite or antigorite; smectite group 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; attapulgite; sepiolite; palygorskite; bentonite; gnarl clay; gairome clay hisingerite; pyrophyllite; chlorite groups; or the like. These inorganic silicates may be in the form of mixed layers thereof. In addition, as the synthetic inorganic silicates, there can be exemplified synthetic mica, synthetic hectorite, synthetic saponite, synthetic taeniolite or the like.
Among the afore-mentioned inorganic silicates, kaolin group clays or clay minerals, halloysite group clays or clay minerals, serpentine group clays or clay minerals, smectite group clays or clay minerals, vermiculite minerals, mica minerals, synthetic mica, synthetic hectorite, synthetic saponite or synthetic taeniolite are preferred, and especially preferred inorganic silicates are smectite, vermiculite minerals, synthetic mica, synthetic hectorite, synthetic saponite and synthetic taeniolite. These inorganic silicates may be used in untreated state as they are, or may be used after subjected to treatments such as crushing by a ball mill, screening or the like. Further, these inorganic silicates may be used singly or in the form of a mixture of any two or more thereof.
The afore-mentioned ion exchangeable layer compounds except for silicates and the inorganic silicates as the component (B) can be treated with salts and/or acids to control an acid strength of these solid compounds. Further, when these compounds are treated with salts, ion composites, molecule composites or organic derivatives are formed, so that it becomes possible to appropriately change the surface area and interlayer distance thereof. Specifically, exchangeable ions existing between the respective layers can be replaced with other bulkier ions by the aid of ion exchanging properties of these compounds, thereby obtaining a layer substance having an increased interlayer distance.
If these compounds are not pre-treated as described above, it is preferred that metal cations contained therein are ion-exchanged with cations dissociated from the below-mentioned salts and/or acids.
The salts used for the afore-mentioned ion exchange, may be compounds comprising a cation which contains at least one atom selected from the group consisting of Group 1-14 atoms, preferably compounds comprising a cation which contains at least one atom selected from the group consisting of Group 1-14 atoms and at least one anion derived from an atom or atomic group selected from the group consisting of halogen atoms, inorganic acids and organic acids, more preferably compounds comprising a cation which contains at least one atom selected from the group consisting of Group 2-14 atoms and at least one anion 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, OCl3, OOCH and OOCCH2CH3. These salts may be used singly or in the form of a mixture of any two or more thereof in combination.
The acids used for the aforementioned ion exchange, may be selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid and oxalic acid. These acids may be used singly or in the form of a mixture of any two or more thereof. The salt treatment can be used in combination with the acid treatment. As methods in which the salt treatment and the acid treatment are used in combination, there can be exemplified a method of conducting the acid treatment after the salt treatment, a method of conducting the salt treatment after the acid treatment, a method of conducting the salt and acid treatments simultaneously, and a method of conducting the salt and acid treatments simultaneously after the salt treatment. Incidentally, the acid treatment has such effects, afore-mentioned ion exchange that impurities can be removed from the surface of the component (B), and that a part of cations contained in the crystal structure such as Al, Fe, Mg or Li can be eluted therefrom.
The treating conditions used for the salt or acid treatment are not particularly restricted. However, it is suitable that the concentration of the salt or acid is usually in the range of 0.1 to 30% by weight; the treating temperature is usually from room temperature to a boiling point of solvent used; and the treating time is usually from 5 minutes to 24 hours, such that at least a part of the compound to be treated is solved out. Further, the salts and the acids are usually used in the form of an aqueous solution.
In the afore-mentioned salt and/or acid treatments, the component (B) may be pulverized or granulated before, during or after the salt and/or acid treatments to control the shape thereof. In addition, other chemical treatments such as alkali treatment or treatments by organic substances may be used in combination. The thus-prepared component (B) has preferably a pore volume of usually not less than 0.1 cc/g, more preferably 0.3 to 5 cc/g, when measured with respect to pores having a radius of not less than 20 xc3x85 by a mercury-penetrating method. Such a component (B) generally contains an absorbed water or an interlayer water. Here, the absorbed water means water absorbed on a surface or a crystal fracture face of the ion exchangeable layer compound or the inorganic silicate, and the interlayer water means water existing between the layers.
In accordance with the present invention, it is preferred that the component (B) is used after removal of the afore-mentioned absorbed water or interlayer water. The methods for removing the water, are nor particularly restricted, but there can be used dehydrating methods such as heating, heating in the presence of a flowing gas, heating under a reduced pressure, azeotropy with an organic solvent, or the like. The heating may be conducted at such a temperature that no absorbed water and interlayer water exists in the component (B). The heating temperature is usually not less than 100xc2x0 C., preferably not less than 150xc2x0 C. However, the use of such a high temperature which causes destruction of the crystal structure should be avoided. The heating time is usually not less than 0.5 hour, preferably not less than one hour. The weight loss of the thus-treated component (B) is preferably not more than 3% by weight, when the suction is conducted at a temperature of 200xc2x0 C. under a pressure of 1 mm Hg for 2 hours. In accordance with the present invention, in the case where the component (B) whose weight loss is adjusted to not more than 3% by weight based on the weight of the component (B) is used, it is preferred that the weight loss of the component (B) is also maintained when the component (B) is brought into contact with the essential component (A) and the below-mentioned optional component (C).
Next, the organoaluminum compound (component (C)) is explained in detail below. As the component (C), there can be preferably used organoaluminum compounds represented by the general formula (VII):
AlRaP3-axe2x80x83xe2x80x83(VII)
wherein R is a hydrocarbon group having 1 to 20 carbon atoms; P is a hydrogen atom, a halogen atom, an alkoxy group or a siloxy group; and xe2x80x9caxe2x80x9d is a number satisfying 0 less than axe2x89xa63.
Specific examples of the organoaluminum compounds represented by the afore-mentioned general formula (VII) may include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum or triisobutylaluminum, halogen-containing or alkoxy-containing alkylaluminums such as diethylaluminum monochloride or diethylaluminum monomethoxide, or the like. Among them, trialkylaluminums can be preferably used. Further, in the case of the catalyst (1) for polymerization of xcex1-olefin according to the first aspect of the present invention, aluminoxanes such as methylaluminoxane or the like can also be used as the component (C).
The catalyst (1) for polymerization of xcex1-olefin can be prepared by bringing the essential components (A) and (B) and the optional component (C) in contact with each other. The contacting method is not particularly restricted, but the following methods (i) to (v) can be exemplified. Incidentally, the contact between these components may be performed not only upon the production of the catalyst but also upon pre-polymerization or polymerization of the olefins.
(i) Method of bringing the components (A) and (B) into contact with each other;
(ii) Method of bringing the components (A) and (B) into contact with each other and then adding the component (C) to the mixture;
(iii) Method of bringing the components (A) and (C) into contact with each other and then adding the component (B) to the mixture;
(iv) Method of bringing the components (B) and (C) into contact with each other and then adding the component (A) to the mixture; and
(v) Method of bringing the components (A), (B) and (C) into contact with each other at the same time.
When or after the respective components are brought into contact with each other, polymers such as polyethylene or polypropylene or solid components of inorganic oxides such as silica or alumina may co-exist therein or may be contacted therewith.
In addition, the contact between the respective components can be conducted in an atmosphere of an inert gas such as nitrogen or in the presence of an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene or xylene. Further, the contact is preferably conducted at a temperature of from xe2x88x9220xc2x0 C. to a 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 in the range of 10xe2x88x924 to 10 mmol, preferably 10xe2x88x923 to 5 mmol based on one gram of the component (B). The amount of the component (C) used is usually in the range of 0.01 to 104 mmol, preferably 0.1 to 100 mmol based on one gram of the component (B). In addition, the atomic ratio of the transition metal contained in the component (A) to aluminum contained in the component (C) is usually in the range of 1/0.01 to 1/106, preferably 1/0.1 to 1/105. The thus-prepared catalyst may be used as it is without washing, or may be used after washing. Further, the catalyst can be used in combination with a further component (Cxe2x80x2) which is composed of similar compounds to the component (C), if required. That is, when the components (A) and/or (B) and the component (C) are used to prepare the catalyst, the further component (Cxe2x80x2) may be added to a reaction system separately from that the component (C) used for the preparation of the catalyst. In this case, the amount of the further added component (Cxe2x80x2) can be selected such that the atomic ratio of the transition metal contained in the component (A) to aluminum contained in the further added component (Cxe2x80x2) is 1/0 to 1/104.
Next, the catalyst (2) for polymerization of xcex1-olefin according to the second aspect of the present invention, is explained in detail below. The catalyst (2) may contain, as essential components, (i) a novel transition metal compound represented by the afore-mentioned general formula (II), (III), (IV), (V) or (VI) (component (A)) and (ii) an aluminumoxy compound, an ionic compound capable of reacting with the component (A) to convert the component (A) into a cation or a Lewis acid (component (D)), and as an optional component, (iii) a fine particle carrier (component (E)). Incidentally, some of Lewis acids can act as the ionic compound capable of reacting with the component (A) to convert the component (A) into a cation. Accordingly, if the afore-mentioned compound having the properties of both the Lewis acid and the ionic compound is used, the compound is regarded as belonging to any one thereof.
As the aforementioned aluminumoxy compounds, there can be exemplified those compounds represented by the following general formulae (VIII), (IX) and (X):
In the afore-mentioned general formulae (VIII), (IX) and (X), R9 is a hydrogen atom or a hydrocarbon group having preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, providing that when a plurality of the R9 are present in the same molecule, these R9 may be the same or different; and p is an integer of 0 to 40, preferably 2 to 30.
The compounds represented by the general formulae (VIII) and (IX) are also called xe2x80x9calumoxanexe2x80x9d, 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) compounds obtained by reacting one kind of trialkylaluminum with water, such as methylalumoxane, ethylalumoxane, propylalumoxane, butylalumoxane or isobutylalumoxane, (ii) compounds obtained by reacting two kinds of trialkylaluminum with water, such as methylethylalumoxane, methylbutylalumoxane or methylisobutylalumoxane, or the like. Among them, methylalumoxane and methylisobutylalumoxane are preferred.
The afore-mentioned alumoxanes can be used in combination within each group or between a plurality of groups. The alumoxanes can be prepared under various known conditions. Specifically, the following methods can be used for the production of these alumoxanes:
(a) Method of directly reacting trialkylaluminum with water in the presence of an appropriate organic solvent such as toluene, benzene or ether;
(b) Method of reacting trialkylaluminum with a salt containing crystallization water, e.g., a hydrate of copper sulfate or aluminum sulfate;
(c) Method of reacting trialkylaluminum with a water content impregnated in silica gel or the like;
(d) Method of mixing trimethylaluminum and triisobutylaluminum together, and then directly reacting the mixed trialkylaluminums with water in the presence of an appropriate organic solvent such as toluene, benzene or ether;
(e) Method of mixing trimethylaluminum and triisobutylaluminum together, and then reacting the mixed trialkylaluminums with a salt containing crystallization water, e.g., a hydrate of copper sulfate or aluminum sulfate while heating;
(f) Method of impregnating water into silica gel or the like, and treating the water-impregnated silica gel, etc., with triisobutylaluminum and then with trimethylaluminum;
(g) Method of preparing methylalumoxane and isobutylalumoxane by a known method, and then mixing these two components together at a predetermined ratio to be reacted with each other while heating; and
(h) Method of adding a salt containing crystallization water such as copper sulfate pentahydrate and trimethylaluminum into an aromatic hydrocarbon solvent such as benzene or toluene and reacting these components with each other at a temperature of about xe2x88x9240xc2x0 C. to about 40xc2x0 C.
The molar ratio of water used to the trimethylaluminum is usually in the range of 0.5 to 1.5. Methylalumoxane prepared by the afore-mentioned methods is a linear or cyclic organoaluminum polymer.
The compounds represented by the general formula (X) can be obtained by reacting at least one trialkylaluminum with alkyl boric acid represented by the following general formula (XI) at a molar ratio of 10:1 to 1:1.
R10xe2x80x94Bxe2x80x94(OH)2xe2x80x83xe2x80x83(XI)
wherein R10 is a hydrocarbon group or a halogenated hydrocarbon group both having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.
Specific examples of the compounds represented by the general formula (XI) may include the following reaction products:
(a) Reaction products obtained by reacting trimethylaluminum with methylboric acid at a molar ratio of 2:1;
(b) Reaction products obtained by reacting triisobutylaluminum with methylboric acid at a molar ratio of 2:1;
(c) Reaction products obtained by reacting trimethylaluminum, triisobutylaluminum and methylboric acid with each other at a molar ratio of 1:1:1;
(d) Reaction products obtained by reacting trimethylaluminum with ethylboric acid at a molar ratio of 2:1; and
(e) Reaction products obtained by reacting triethylaluminum with butylboric acid at a molar ratio of 2:1.
In addition, as the ionic compounds capable of reacting with the component (A) to convert the component (A) into a cation, there can be exemplified those compounds represented by the general formula (XII):
[K]e+[Z]exe2x88x92xe2x80x83xe2x80x83(XII)
In the general formula (XII), K represents a cationic component. Examples of the cations may include carbonium cation, tropylium cation, ammonium cation, oxonium cation, sulfonium cation, phosphonium cation or the like. Further, metal cations which tend to be reduced per se, cations of organic metals or the like can also be used.
Specific examples of the afore-mentioned cations may include triphenyl carbonium, diphenyl carbonium, cyclohepta trienium, indenium, triethylammonium, tripropylammonium, tributylammonium, N, N-dimethylammonium, dipropylammonium, dicyclohexylammonium, triphenylphosphonium, trimethylphosphonium, tris(dimethylphenyl)phosphonium, tris(methylphenyl)phosphonium, triphenylsulfonium, triphenyloxonium, triethyloxonium, pyrylium, silver ion, gold ion, platinum ion, copper ion, palladium ion, mercury ion, ferrocenium ion or the like.
In the general formula (XII), Z represents an ionic anion component (generally a non-coordinated component), which constitutes a counter anion against the cation produced by the conversion of the component (A). As the anion Z, there can be exemplified anions of organic boron compounds, anions of organoaluminum compounds, anions of organogallium compounds, anions of organophosphorus compounds, anions of organoarsenic compounds, anions of organoanthimony compounds or the like. Specific examples of these organic compounds are as follows.
(a) tetraphenylboron, tetrakis(3,4,5-trifluorophenyl)boron, tetrakis{3,5-bis(trifluoromethyl)phenyl}boron, tetrakis{3,5-di(t-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(t-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(t-butyl)phenyl)gallium, tetrakis(pentafluoro)phenylgallium, or the like;
(d) tetraphenyl phosphorus, tetrakis (pentafluorophenyl) phosphorus, or the like;
(e) tetraphenyl arsenic, tetrakis(pentafluorophenyl) arsenic, or the like;
(f) tetraphenyl antimony, tetrakis(pentafluorophenyl) antimony, or the like; and
(g) decaborate, undecaborate, carbadodecaborate, decachlorodecaborate, or the like.
Further, as the Lewis acids, especially those capable of converting the component (A) into a cation, there can be exemplified various organoboron compounds, halogenated metal compounds, solid acids or the like. Specific examples of these Lewis acids are as follows:
(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 chloride bromide, magnesium chloride iodide, magnesium bromide iodide, magnesium chloride hydride, magnesium chloride hydroxide, magnesium bromide hydroxide, magnesium chloride alkoxide or magnesium bromide alkoxide; and
(c) solid acids such as alumina or silica-alumina.
In the catalyst (2) for polymerization of xcex1-olefin, the fine particle carrier as the optional component (E) may be composed of an inorganic or organic compound, and in the form of granules or particles having a particle diameter of usually 5 xcexcm to 5 mm, preferably 10 xcexcm to 2 mm.
As the afore-mentioned inorganic carrier, there can be exemplified oxides such as SiO2, Al2O3, MgO, ZrO, TiO2, B2O3 or ZnO; composite oxides such as SiO2xe2x80x94MgO, SiO2xe2x80x94Al2O3, SiO2xe2x80x94TiO2, SiO2xe2x80x94Cr2O3 or SiO2xe2x80x94Al2O3xe2x80x94MgO; or the like.
As the afore-mentioned organic carrier, there can be exemplified fine particles of porous polymers, for example, polymers or copolymers of xcex1-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. These organic carriers have a specific surface area of usually 20 to 1,000 m2/g, preferably 50 to 700 m2/g, and a pore volume of usually not less than 0.1 cm3/g, preferably not less than 0.3 cm3/g, more preferably not less than 0.8 cm3/g.
The catalyst (2) for polymerization of xcex1-olefin may contain, as other optional components than the fine particle carrier, for example, protic compounds such as H2O, methanol, ethanol or butanol; electron donative compounds such as ethers, esters or amines; alkoxy-containing compounds such as phenylborate, dimethylmethoxyaluminum, phenylphosphite, tetraethoxysilane or diphenyldimethosilane; or the like.
As still further optional components other than the afore-mentioned compounds, there can be exemplified tri lower-alkylaluminums such as trimethylaluminum, triethylaluminum or triisobutylaluminum; halogen-containing alkylaluminums such as diethylaluminum chloride, diisobutylaluminum chloride or methylaluminum sesqui-chloride; alkylaluminum hydrides such as diethylaluminum hydride; alkoxy-containing alkylaluminums such as diethylaluminum ethoxide or dimethylaluminum butoxide; aryloxy-containing alkylaluminums such as diethylaluminum phenoxide; or the like.
In the catalyst (2) for polymerization of xcex1-olefin, the aluminum-oxy compound, the ionic compound capable of reacting with the component (A) to convert the component (A) into a cation, and the Lewis acid as the component (D) are used singly or in the form of a mixture of any two or more thereof in combination. Incidentally, it is preferred that as the still further optional components, one or more kinds of the afore-mentioned lower-alkylaluminum, halogen-containing alkylaluminum, alkylaluminum hydride, alkoxy-containing alkylaluminum or aryloxy-containing alkylaluminum are contained in the catalyst (2) for polymerization of xcex1-olefin, together with the aluminum-oxy compound, the ionic compound or the Lewis acid.
The catalyst (2) for polymerization of xcex1-olefin may be prepared by bringing the components (A) and (D) into contact with each other inside or outside of a polymerization vessel and in the presence or absence of a monomer to be polymerized. In this case, the components (A) and (D), and if required, the component (E), etc., may be introduced separately into the polymerization vessel. Alternatively, the components (A) and (D) may be introduced into the polymerization vessel after both the components have been preliminarily brought into contact with each other. Further, after the components (A) and (D) are mixed together and impregnated into the component (E), the mixture may be introduced into the polymerization vessel.
The contact between the respective components can be conducted in 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. In addition, the contact can be conducted at a temperature of from xe2x88x9220xc2x0 C. to a boiling point of the solvent used, preferably from room temperature to the boiling point of the solvent used. The thus-produced catalyst may be used as it is without washing, or may be used after washing. Further, the obtained catalyst may be used in combination with additional components, if required.
Also, when the components (A), (D) and (E) are preliminarily brought into contact with each other, the contact can be performed in the presence of the monomer to be polymerized, i.e., xcex1-olefin to partially polymerize the xcex1-olefin (so-called pre-polymerization). More specifically, before the polymerization, the xcex1-olefin such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkanes or styrene is pre-polymerized and washed, if required. The thus-produced pre-polymerization product can be used as a catalyst. In this case, it is preferred that the pre-polymerization is conducted in the presence of an inert solvent under such a moderate reaction condition that the polymer is produced in an amount of usually 0.01 to 1,000 g, preferably 0.1 to 100 g based on one gram of the solid catalyst.
The amounts of the components (A) and (D) used are optional. For example, in the case of solution polymerization, the amount of the component (A) used is usually in the range of 10xe2x88x927 to 102 mmol/liter (calculated as the transition metal), preferably 10xe2x88x924 to 1 mmol/liter. In the case where the aluminum-oxy compound is used as the component (D), the molar ratio of 1 to the transition metal is usually in the range of 10 to 105, preferably 100 to 2xc3x97104, more preferably 100 to 104. On the other hand, in the case where the ionic compound or the Lewis acid is used as the component (D), the molar ratio of the ionic compound or the 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.
Next, the method for producing an xcex1-olefin polymer according to the present invention, is explained in detail below. In accordance with the present invention, the afore-mentioned catalyst and xcex1-olefin are brought into contact with each other to polymerize or copolymerize the xcex1-olefin. The catalyst for polymerization of xcex1-olefin according to the present invention can be applied to not only a solution polymerization using a solvent, but also a liquid-phase non-solvent polymerization using substantially no solvent, a gas-phase polymerization or a melt polymerization. These polymerizations can be conducted either in a continuous manner or in a batch manner.
As the solvents used for the solution polymerization, there can be exemplified inert saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene or toluene. These solvents can be used singly or in the form of a mixture of any two or more thereof. The polymerization temperature is usually in the range of xe2x88x9278xc2x0 C. to 250xc2x0 C., preferably xe2x88x9220xc2x0 C. to 100xc2x0 C. The olefin pressure in the reaction system is not particularly restricted, but preferably from ordinary pressure to 2,000 kgf /cm2G (Geuge), more preferably from ordinary pressure to 50 kgf/cm2G. Further, the molecular weight of the resultant xcex1-olefin polymer can be controlled by known methods such as appropriate selection of reaction temperature and reaction pressure used or introduction of hydrogen.
As the raw xcex1-olefins, there can be used xcex1-olefins having usually 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms. Specific examples of the xcex1-olefins 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-eicosene or the like. The catalyst according to the present invention can be preferably applied to stereoregulated polymerization of xcex1-olefins having 3 to 10 carbon atoms, especially to the polymerization of propylene.
Further, the catalyst according to the present invention can be applied to not only homopolymerization or copolymerization of the afore-mentioned xcex1-olefins, but also copolymerization of the xcex1-olefins with the other monomers. As the other monomers copolymerizable with the xcex1-olefins, there can be exemplified conjugated dienes or non-conjugated dienes 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 the xcex1-olefins can be performed in multiple stages whose reaction conditions are different from each other, i.e., in a manner of so-called multi-step polymerization, for example, block copolymerization comprising pre-polymerization of propylene and copolymerization of ethylene with the polypropyrene prepared by the said pre-polymerization.
As described above, in accordance with the polymerization method according to the present invention, there can be obtained an xcex1-olefin polymer which has a narrow molecular weight distribution and a narrow composition distribution, is excellent in transparency and mechanical strength and exhibits a good flowability.
Also, in the case where the polymerization of propylene was conducted by using the catalyst according to the present invention, there can be obtained a crystalline polypropylene which can show a high value [mmmm] (e.g., not less than 90%) and a unique regio defect amount: 2,1-inversion of 0.5 to 2.0 mol % and 1,3-insertion of 0.06 to 0.40 mol %. The regio defect amount can be calculated according to the following formula:
2,1-insertion percentage (%)=(Y/X)xc3x971,000xc3x971/5,
1,3-insertion percentage (%)=(Z/X)xc3x971,000xc3x971/5,
X=sum of integrated values from 27 ppm to 48 ppm,
Y=(A{circle around (1)}+A{circle around (2)}+A{circle around (3)}+A{circle around (4)}+A{circle around (5)}+A{circle around (6)})/6,
Z=(A{circle around (7)}+A{circle around (8)}+A{circle around (9)})/6
In the above formulae, A{circle around (1)}, A{circle around (2)}, A{circle around (3)}, A{circle around (4)}, A{circle around (5)}, A{circle around (6)}, A{circle around (7)}, A{circle around (8)} and A{circle around (9)} are areas at 42.3 ppm, 35.9 ppm, 38.6 ppm, 30.6 ppm, 36.0 ppm, 31.5 ppm, 31.0 ppm, 37.2 ppm and 27.4 ppm, respectively, and indicate ratios between quantities of carbon atoms existing at respective positions of the following partial structures (I) and (II):
In addition, in accordance with the present invention, there can be provided novel transition metal compounds. Especially, in the case where the catalyst containing the transition metal compound represented by the general formulae (II)-(VI) according to the present invention is used, the xcex1-olefin polymer which is free from reduction of its molecular weight and deterioration of its stereo regularity, can show a high molecular weight and a high melting point, and therefore, is applicable to extrusion molding or injection molding, can be produced with a high yield. The reason therefor is considered as follows, though not exactly known.
That is, in the novel transition metal compound represented by the general formulae (II) and (III), since the groups R3 and R6 each form a condensed ring having not less than 7 members, the substituent groups R7 and R8 bonded thereto take such a spatial arrangement as inclined at a certain angle relative to a plane of the condensed ring constituted by the 5-membered ring and the R3 or R6. In addition, the substituent groups R7 and R8 contain halogen atom(s) which is spatially bulkier than a hydrogen atom. The halogen atom acts to provide an appropriate steric hindrance and an appropriate configuration which cannot be achieved only by the hydrocarbon. As a result, effects of regulating the direction of growth of polymer chains and the direction of coordination of monomers are enhanced, thereby improving the stereo regularity of the obtained polymers and further increasing the melting point thereof.
Further, it is considered that the halogen atom exerts an electronic effect on centrally located metals, e.g., zirconium or hafnium, and the electronic effect and the afore-mentioned stereostructure can effectively prevent the chain transfer reaction, thereby increasing a molecular weight of the obtained polymer. Furthermore, since the 7- to 10-membered ring formed by the groups R3 or R6 has double bond(s), the movement of the substituent groups R7 and R8 is inhibited and configuration of the ligands is firmly fixed. For this reason, it is considered that even if the polymerization temperature is increased, the substituent groups R7 and R8 do not lose the effects of regulating the direction of growth of polymer chains and the direction of coordination of monomers, thereby obtaining a high-molecular weight polymer having an excellent stereo regularity.
In the novel transition metal compound represented by the general formula (IV), since the substituent group R6 forms a condensed ring having not less than 7 members, the substituent group R8 bonded thereto has such a spatial arrangement as inclined at a certain angle relative to a plane of the condensed ring constituted by the 5-membered ring and the R6. In addition, the substituent group R8 is present at a xcex2- or remoter position on R6 with respect to the 5-membered ring. These conditions allow the transition metal compound to have a spatially bulkier structure, thereby imparting an appropriate steric hindrance and an appropriate configuration thereto. As a result, the same effects as given by the transition metal compound of the general formula (II) can be obtained.
In the novel transition metal compound represented by the general formula (V), since the substituent group R3 and R6 forms a condensed ring having not less than 7 members, the substituent group R7 and R8 bonded thereto has such a spatial arrangement as inclined at a certain angle relative to a plane of the condensed ring constituted by the 5-membered ring and the R3 or R6. In addition, bulkier R1 and R4 are bonded to the 5-membered ring. These conditions allow the transition metal compound to have a spatially bulkier structure, thereby imparting an appropriate steric hindrance and an appropriate configuration thereto. 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), since the groups R3 and R6 each form a condensed ring having not less than 7 members, the substituent groups R7 and R8 bonded thereto have such a spatial arrangement as inclined at a certain angle relative to a plane of the condensed ring constituted by the 5-membered ring and the R3 or R6. In addition, the cyclic substituent group A is bonded to the cross-linking group Q. These conditions allow the transition metal compound to have a spatially bulkier structure, thereby imparting an appropriate steric hindrance and an appropriate configuration thereto. As a result, the same effects as provided by the transition metal compound of the general formula (II) can be obtained. Moreover, since the 7- to 10-membered ring formed by the groups R3 or R6 and the group A contain double bonds therein, the movements of the substituent groups R7, R8 and Ra are inhibited so that configuration of the ligands is firmly fixed. For this reason, it is considered that even if the polymerization temperature is increased, it is possible to obtain a high-molecular weight polymer having an excellent stereo regularity.

Catalysts for polymerization of xcex1-olefins, process for producing xcex1-olefin polymers, novel transition metal compounds and catalyst components for polymerization of xcex1-olefin

Abstract: where A1 and A2 are each independently a conjugated 5-membered ring ligand provided that A1 and A2 may be the same or different in a molecule, and at least one of A1 and A2 forms a 7- to 10-membered condensed ring including two adjacent carbon atoms of the conjugated 5-membered ring, which condensed ring is formed by joining two adjacent substitutent groups on the conjugated 5-membered ring; Q is a bridging group of the two conjugated 5-membered rings of A1 and A2 at optional positions of the 5-membered rings; M is a metal atom selected from elements of Group 4-6 of the Periodic Table; and X and Z are each independently a hydrogen atom, a halogen atom, a hydrocarbon group, and 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.