JPH11240909A - New transition metal compound, catalyst component for alpha-olefin polymerization and production of alpha-olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound which can become a catalyst component for α-olefin polymerization capable of providing an olefin polymer having high molecular weight and high melting point and capable of carrying out extrusion molding and injection molding. SOLUTION: This compound is represented by the formula [R<1> , R<2> , R<4> and R<5> are each H, a 1-10C hydrocarbon, etc.; R<3> and R<6> are each a 3-10C divalent hydrocarbon forming a condensed ring to bound two 5-membered rings; R<7> and R<8> are each a 1-20C hydrocarbon, a 1-20C halogenated hydrocarbon or the like; (m) and (n) are each 0-20; Q is a 1-20C divalent hydrocarbon binding two 5-membered rings, silylene or the like; M is a transition metal of IV to VI group], e.g. dimethylsilylenebis 1,1'-[2-methyl-4-(4-chlorophenyl)-4 hydroazulenyl]}zirconium chloride. The compound of the formula is obtained by reacting an alkyllithium compound or an aryllithium compound with an azulene compound in an inert solvent to produce a lithium.salt of dihydroazulenyl compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel transition metal compound, a catalyst component for α-olefin polymerization comprising the transition metal compound, and a method for producing an α-olefin polymer using the same. Specifically, the present invention
The present invention relates to a highly active polymerization catalyst component and a polymerization catalyst capable of producing a high molecular weight and high melting point α-olefin polymer, and a method for producing an α-olefin polymer using the catalyst.

[0002]

2. Description of the Related Art A so-called Kaminski catalyst known as a homogeneous catalyst for olefin polymerization has a high polymerization activity and can produce a polymer having a sharp molecular weight distribution.

As a transition metal compound used for producing an isotactic polyolefin with a Kaminsky catalyst, ethylene bis (indenyl) zirconium dichloride or ethylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride is used. It is known (for example, JP-A-61-130314). However, in the case of using such a catalyst, there is a problem that the molecular weight of the obtained polyolefin is generally small, and when low-temperature polymerization is performed to increase the molecular weight, the polymerization activity of the catalyst is reduced.

Further, for the purpose of producing a high-molecular-weight polyolefin, a method has been proposed in which a hafnium compound is used instead of the above-mentioned zirconium compound (Journa).
l of Molecular Catalysis, 56 (1989), 237
247). However, this method has a problem that the polymerization activity of the catalyst is low.

Further, dimethylsilylenebis-substituted cyclopentadienyl zirconium dichloride and the like have been proposed (JP-A-1-301704, Polymer Preprints, Jap.
an39 (1990), 1614-1616, JP-A-3-1
No. 2406), dimethylsilylenebis (indenyl) zirconium dichloride and the like have been proposed (Japanese Patent Application Laid-Open No. 63-295007, Japanese Patent Application Laid-Open No. 1-275609).
No.). The use of these compounds makes it possible to produce a polymer having a high stereoregularity and a high melting point in relatively low-temperature polymerization, but the stereoregularity and melting point of the polymer obtained under high-temperature polymerization conditions that are economical. And low molecular weight. On the other hand, a catalyst comprising a transition metal compound in which a halogen atom is introduced into a substituent on an atom bridging a ligand and a co-catalyst has been proposed (Japanese Patent Application Laid-Open No. 4-366106). However, such a catalyst has a problem that the molecular weight and stereoregularity of the produced polymer are lower than those of the above-mentioned similar catalysts containing no halogen atom.

[0006] Further, there is known a compound in which a substituent is added to an indenyl group which is a part of a ligand to improve the isotacticity and molecular weight of polypropylene (for example, Japanese Patent Application Laid-open No. 4-268307
JP-A-6-157661). Furthermore, transition metal compounds in which the sub-ring including two adjacent carbon atoms of the conjugated five-membered ring is a ring having a number of members other than the six-membered ring are also known (for example, JP-A-4-275294, JP-A-6-275294). −
239914, JP-A-8-59724).

However, these compounds have insufficient catalytic performance under high-temperature polymerization conditions, which are economical, and the catalyst systems of these compounds are often soluble in the reaction medium. Therefore, the resulting polymer has extremely poor particle properties such as an irregular particle shape, a low bulk density, and a large amount of fine powder. Therefore, when applied to slurry polymerization, gas phase polymerization, and the like, there are many problems in the production process, such as difficulty in continuous stable operation.

On the other hand, in order to solve the above-mentioned problems, a catalyst in which a transition metal compound and / or organoaluminum is supported on an inorganic oxide (for example, silica, alumina or the like) or an organic substance has been proposed (for example, Japanese Patent Application Laid-Open No. H11-157556). Kaisho 61-
Nos. 108610, 60-135408, 61-296008, JP-A-3-74412, and 3-74415). However, polymers obtained with these catalysts contain many fine powders and coarse particles, and are not sufficient in terms of particle properties such as low bulk density, and further have low polymerization activity per solid component. In addition, there are problems such as a lower molecular weight and stereoregularity as compared with a system using no carrier.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in consideration of the above circumstances, and has as its object to produce a high-molecular-weight, high-melting-point olefin polymer which can be extruded or injection-molded in a high yield. An object of the present invention is to provide a novel transition metal compound which can be a catalyst component for α-olefin polymerization that can be obtained. Another object of the present invention is to provide an α-olefin polymerization catalyst component comprising the above transition metal compound. Another object of the present invention is to provide α
-To provide an olefin polymerization catalyst and a method for producing an α-olefin polymer using the same. Still another object of the present invention is to provide a novel catalyst component which has a small decrease in performance when the catalyst component is used by being supported on a carrier in order to improve process applicability.

[0010]

That is, the first aspect of the present invention is as follows.
The gist of the present invention resides in a novel transition metal compound represented by the following general formula (Ia).

[0011]

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In the general formula (Ia), R ¹ , R ² , R ⁴ , R
⁵ independently represents 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. R
³ and R ⁶ each independently represent a saturated or unsaturated divalent hydrocarbon group having 3 to 10 carbon atoms which forms a condensed ring with the five-membered ring to which it is bonded. However, R ³ and R ⁶
Has at least one carbon number of 5 to 8, and R ³ or R ⁶
Forming a condensed ring consisting of a 7- to 10-membered ring having an unsaturated bond derived therefrom. R ⁷ and R ⁸ are each 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 is shown. Where R ⁷
And at least one of R ⁸ is a halogenated hydrocarbon group having 1 to 20 carbon atoms. m and n are each independently 0
Represents an integer of up to 20. However, m and n do not become 0 at the same time. When m or n is 2 or more, R
⁷ or R ⁸ may be linked to each other to form a new ring structure. Q is a group having 1 carbon atom connecting two 5-membered rings;
A divalent hydrocarbon group having from 20 to 20, a silylene group which may have a hydrocarbon group having from 1 to 20 carbon atoms, an oligosilylene group,
Shows any of the germylene groups. X and Y are each 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, 1-20 carbon atoms
Oxygen-containing hydrocarbon group, amino group or C1-20
And M represents a transition metal belonging to Groups 4 to 6 of the periodic table.

A second gist of the present invention is that the following general formula (I)
b) a novel transition metal compound.

[0014]

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In the general formula (Ib), R ¹ , R ² , R ⁴ , R ⁵ ,
Q, X, Y, and M have the same meanings as in the above formula (Ia), and R ⁹ , R ¹⁰ , R ¹¹ , R ¹² ,
R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a carbon group having 1 to 20 carbon atoms.
Represents a halogenated hydrocarbon group. Ar represents an aryl group which may have a substituent. However, the condition is that a halogenated hydrocarbon group having 1 to 20 carbon atoms is bonded to at least one of the two 7-membered rings.

The third gist of the present invention resides in the general formula (I)
a) or a transition metal compound represented by the general formula (Ib).

A fourth gist of the present invention resides in an α-olefin polymerization catalyst comprising the following essential components (A) and (B) and an optional component (C).

[0018]

TABLE 1 Component (A): transition metal compound represented by general formula (Ia) or general formula (Ib) Component (B): aluminum oxy compound, which reacts with component (A) to cationize component (A) Ionic compound or Lewis acid capable of being converted to component (C): fine particle carrier

A fifth aspect of the present invention resides in an α-olefin polymerization catalyst comprising the following essential components (A) and (D) and an optional component (E).

[0020]

TABLE 2 Component (A): transition metal compound represented by general formula (Ia) or general formula (Ib) Component (D): ion-exchange layered compound or inorganic silicate excluding silicate Component (E): Organic aluminum compounds

A sixth aspect of the present invention resides in a method for producing an α-olefin polymer, which comprises contacting any one of the above-mentioned catalysts with an α-olefin to carry out polymerization or copolymerization. .

[0022]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
First, the first transition metal compound of the present invention will be described. The first transition metal compound of the present invention has the following general formula (I)
a).

[0023]

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The first transition metal compound of the present invention comprises a five-membered ring ligand having substituents R ¹ , R ² and R ³ , a substituent R ⁴ ,
The compound (a) and the compound (b) which are asymmetric with respect to the plane containing M, X and Y in terms of relative position via the group Q with the five-membered ring ligand having R ⁵ and R ⁶ )including.

However, in order to produce an α-olefin polymer having a high molecular weight and a high melting point, in order to produce the above-mentioned compound (a), in other words, two compounds opposed to each other across a plane containing M, X and Y It is preferable to use a compound whose five-membered ring ligand is not in a mirror image of the entity with respect to the plane.

In the general formula (Ia), R ¹ , R ² , R ⁴ , R
⁵ each independently represents 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 hydrocarbon group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl and n-butyl. Alkyl groups such as pentyl, n-hexyl, cyclopropyl, cyclopentyl, cyclohexyl and methylcyclohexyl; alkenyl groups such as vinyl, propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl; and aryls such as trans-styryl Alkenyl group, phenyl, tolyl, dimethylphenyl, ethylphenyl, trimethylphenyl,
And aryl groups such as 1-naphthyl and 2-naphthyl.

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

In the above-mentioned halogenated hydrocarbon group having 1 to 18 carbon atoms, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. And
When the halogen atom is, for example, a fluorine atom, the halogenated hydrocarbon group is a compound in which a fluorine atom is substituted at an arbitrary position of the hydrocarbon group. Specifically, 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- , P-fluorophenyl, o-, m-, p-chlorophenyl, o-, m-, p-bromophenyl, 2,4
-, 3,5-, 2,6-, 2,5-difluorophenyl,
2,4-, 3,5-, 2,6-, 2,5-dichlorophenyl, 2,4,6-trifluorophenyl, 2,4,6-trichlorophenyl, pentafluorophenyl, pentachlorophenyl, 4-fluoro Naphthyl, 4-chloronaphthyl, 2,4-difluoronaphthyl, heptafluoro-1
-Naphthyl, heptachloro-1-naphthyl, o-, m-,
p-trifluoromethylphenyl, o-, m-, p-trichloromethylphenyl, 2,4-, 3,5-, 2,6-, 2,
5-bis (trifluoromethyl) phenyl, 2,4-,
3,5-, 2,6-, 2,5-bis (trichloromethyl)
Examples include phenyl, 2,4,6-tris (trifluoromethyl) phenyl, 4-trifluoromethylnaphthyl, 4-trichloromethylnaphthyl, and 2,4-bis (trifluoromethyl) naphthyl group.

Among them, R ¹ and R ⁴ are preferably a hydrocarbon group having 1 to 7 carbon atoms such as methyl, ethyl, propyl, butyl and benzyl, and R ² and R ⁵ are preferably hydrogen atoms. .

In the general formula (Ia), R ³ and R ⁶ each independently represent a saturated or unsaturated divalent having 3 to 10 carbon atoms which forms a condensed ring with the five-membered ring to which it is bonded. Represents a hydrocarbon group. Therefore, the condensed ring is a 5- to 12-membered ring. However, at least one of R ³ and R ⁶ has 5 carbon atoms.
8 to 7 having an unsaturated bond derived from R ³ or R ^6.
It is an essential condition to form a condensed ring composed of a 10-membered ring. In this case, it is preferable that both of the condensed rings are 7 to 10-membered rings.

Specific examples of the above R ³ and R ⁶ include divalent saturated hydrocarbon groups such as trimethylene, tetramethylene, pentamethylene, hexamethylene and heptamethylene, propenylene, 2-butenylene, and 1,3-butadienylene. , 1-pentenylene, 2-pentenylene, 1,3-pentadienylene, 1,4-pentadienylene, 1-hexenylene, 2-hexenylene, 3-hexenylene,
3-hexadienylene, 1,4-hexadienylene, 1,
5-hexadienylene, 2,4-hexadienylene, 2,
Examples thereof include divalent unsaturated hydrocarbon groups such as 5-hexadienylene and 1,3,5-hexatrienylene. Among these, a pentamethylene group, a 1,3-pentadienylene group, a 1,4-pentadienylene group or a 1,3,5-hexatrienylene group is preferable, and a 1,3-pentadienylene group or a 1,4-pentadienylene group is preferable. Particularly preferred.

In the general formula (Ia), R ⁷ and R ⁸ are each independently a hydrocarbon group having 1 to 20 carbon atoms,
A halogenated hydrocarbon group of 20; 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, at least one of R ⁷ and R ⁸ has 1 carbon atom.
To 20 halogenated hydrocarbon groups.

Specific examples of the above-mentioned hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl and n-butyl. Alkyl groups such as pentyl, n-hexyl, cyclopropyl, cyclopentyl, cyclohexyl and methylcyclohexyl; alkenyl groups such as vinyl, propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl; and aryls such as trans-styryl Alkenyl group, phenyl, tolyl, dimethylphenyl, ethylphenyl, trimethylphenyl,
And aryl groups such as 1-naphthyl, 2-naphthyl, acenaphthyl, phenanthryl and anthryl. Among these, alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, cyclopropyl, phenyl, tolyl, Dimethylphenyl, ethylphenyl,
An aryl group having 6 to 20 carbon atoms such as trimethylphenyl, 1-naphthyl and 2-naphthyl is preferred.

In the halogenated hydrocarbon group having 1 to 20 carbon atoms, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. And
When the halogen atom is, for example, a fluorine atom, the halogenated hydrocarbon group is a compound in which a fluorine atom is substituted at an arbitrary position of the hydrocarbon group. Specifically, 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- , P-fluorophenyl, o-, m-, p-chlorophenyl, o-, m-, p-bromophenyl, 2,4
-, 3,5-, 2,6-, 2,5-difluorophenyl,
2,4-, 3,5-, 2,6-, 2,5-dichlorophenyl, 2,4,6-trifluorophenyl, 2,4,6-trichlorophenyl, pentafluorophenyl, pentachlorophenyl, 4-fluoro Naphthyl, 4-chloronaphthyl, 2,4-difluoronaphthyl, heptafluoro-1
-Naphthyl, heptachloro-1-naphthyl, o-, m-,
p-trifluoromethylphenyl, o-, m-, p-trichloromethylphenyl, 2,4-, 3,5-, 2,6-, 2,
5-bis (trifluoromethyl) phenyl, 2,4-,
3,5-, 2,6-, 2,5-bis (trichloromethyl)
Examples include phenyl, 2,4,6-tris (trifluoromethyl) phenyl, 4-trifluoromethylnaphthyl, 4-trichloromethylnaphthyl, and 2,4-bis (trifluoromethyl) naphthyl group. Among these, a fluorinated hydrocarbon group or a chlorinated hydrocarbon group is preferable,
Particularly preferred are o-, m-, p-fluorophenyl, o-, m-, p-chlorophenyl, o-, m- or p-trifluoromethylphenyl.

Specific examples of the oxygen-containing hydrocarbon group having 1 to 20 carbon atoms include alkoxy groups such as methoxy, ethoxy, propoxy, cyclopropoxy and butoxy, and allyloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy. Aryloxy groups such as phenylmethoxy and naphthylmethoxy, and oxygen-containing heterocyclic groups such as a furyl group.

Specific examples of the nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms include methylamino, dimethylamino,
Alkylamino groups such as ethylamino and diethylamino,
Arylamino groups such as phenylamino and diphenylamino; (alkyl) groups such as (methyl) (phenyl) amino
And nitrogen-containing heterocyclic groups such as (aryl) amino groups, pyrazolyl and indolyl.

Specific examples of the above-mentioned sulfur-containing hydrocarbon group having 1 to 20 carbon atoms include a substituent in which oxygen of the oxygen-containing compound is replaced with sulfur.

In the general formula (Ia), m and n each independently represent an integer of 0 to 20. m and n are preferably 1 to 5. When m and / or n is an integer of 2 to 20, a plurality of groups R ⁷ (R ⁸ ) may be the same or different. However, m and n do not become 0 at the same time.
That is, the divalent group R ³ and / or R ⁶ has the substituent R ⁷ or R ⁸ as described above, and further, R ⁷ and / or R ⁸
Is an essential condition that it is a halogenated hydrocarbon group having 1 to 20 carbon atoms as described above. When m or n is 2 or more, R ^{7 and} R ⁸ may be connected to each other to form a new ring structure. The bonding position of R ⁷ and R ⁸ to R ³ and R ⁶ is not particularly limited,
It is preferably a carbon (carbon at the α-position) adjacent to each 5-membered ring.

In the general formula (Ia), Q represents a divalent hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms, which bonds two five-membered rings. Good silylene group,
Indicates either an oligosilylene group or a germylene group. When two hydrocarbon groups or halogenated hydrocarbon groups are present on the silylene group, oligosilylene group or germylene group, they may be bonded to each other to form a ring structure.

Specific examples of the above Q include methylene, methylmethylene, dimethylmethylene, 1,2-ethylene, 1,3
An alkylene group such as trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene, 1,4-cyclohexylene;
Arylalkylene groups such as (methyl) (phenyl) methylene and diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene and the like An alkylsilylene group of
(Alkyl) (aryl) silylene groups such as methylphenylsilylene and methyl (tolyl) silylene; arylsilylene groups such as diphenylsilylene; alkyl oligosilylene groups such as tetramethyldisilylene; germylene groups; An alkylgermylene group in which silicon of a silylene group having a hydrocarbon group of 20 to 20 is replaced with germanium; an (alkyl) (aryl) germylene group; an arylgermylene group. Among these, a silylene group having a hydrocarbon group having 1 to 20 carbon atoms or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms is preferable, and an alkylsilylene group, an (alkyl) (aryl) silylene group or An arylsilylene group is particularly preferred.

In the general formula (Ia), X and Y each independently represent 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, 1 to 2 carbon atoms
0 oxygen-containing hydrocarbon group, amino group or 1-2 carbon atoms
And 0 represents a nitrogen-containing hydrocarbon group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The above-mentioned hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, Examples of the oxygen-containing hydrocarbon group having 1 to 20 carbon atoms and the nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms include the same groups as those described above for R ⁷ and R ⁸ .

Specific examples of the silicon-containing hydrocarbon group having 1 to 20 carbon atoms include trialkylsilylmethyl groups such as trimethylsilylmethyl and triethylsilylmethyl.
Examples thereof include di (alkyl) (aryl) silylmethyl groups such as dimethylphenylsilylmethyl, diethylphenylsilylmethyl, and dimethyltolylsilylmethyl.

X and Y in the general formula (Ia) 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.
A halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms is more preferable, and a chlorine atom, a methyl group, an i-butyl group, a phenyl group, a dimethylamino group or a diethylamino group is particularly preferable. preferable.

In the general formula (Ia), M represents a transition metal belonging to Groups 4 to 6 of the periodic table, preferably a transition metal belonging to Group 4 such as titanium, zirconium and hafnium, more preferably zirconium or hafnium.

The transition metal compound represented by the general formula (Ia) can be synthesized by any method suitable for the substituent or the bonding mode. A typical synthetic route is as shown in the following reaction formula. In the reaction formula, H ₂ R _a
And H ₂ R _b each have the following structure.

[0048]

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[0049]

Embedded image_TwoR_a+ N-C_FourH₉Li → HR_aLi + C_FourH_Ten H_TwoR_b+ N-C_FourH₉Li → H R_bLi + C_FourH_Ten H R_aLi + H R_bLi + QCl_Two→ H R_a−Q−H R_b+ 2LiC
lH R_a−Q−H R_b+ 2n-C_FourH₉Li → LiR_a-Q-LiR_b+ 2C
_FourH_Ten LiR_a-Q-LiR_b+ ZrCl_Four→ (R_a−Q−R_b) ZrCl_Two+
2LiCl

The above-mentioned metal salts of cyclopentadienyl compounds such as HR _a Li and HR _b Li can be produced by, for example,
As described in European Patent No. 679418, it may be synthesized by a method involving an addition reaction of an alkyl group or an aryl group. Specifically, an alkyllithium compound or an aryllithium compound is reacted with an azulene compound in an inert solvent to generate a lithium salt of a dihydroazulenyl compound. As the alkyllithium compound, methyllithium, i-propyllithium, n-butyllithium, t-butyllithium or the like is used. As the aryllithium compound, phenyllithium, p-chlorophenyllithium, p-fluorophenyllithium, p-fluorophenyllithium or the like is used. Trifluoromethylphenyl lithium, naphthyl lithium and the like are used. As the inert solvent, hexane, benzene, toluene, diethyl ether, tetrahydrofuran, a mixed solvent thereof or the like is used.

Next, the second transition metal compound of the present invention will be described. This compound is a compound in which the transition metal compound represented by the general formula (Ia) is specified, and is represented by the following general formula (Ib).

[0052]

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In the general formula (Ib), R ¹ , R ² , R ⁴ , R ⁵ ,
Q, X, Y, and M have the same meanings as in the above formula (Ia), and R ⁹ , R ¹⁰ , R ¹¹ , R ¹² ,
R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a carbon group having 1 to 20 carbon atoms.
Represents a halogenated hydrocarbon group. Ar represents an optionally substituted aryl group. However, the condition is that a halogenated hydrocarbon group having 1 to 20 carbon atoms is bonded to at least one of the two 7-membered rings. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms or the halogenated hydrocarbon group having 1 to 20 carbon atoms include the same hydrocarbon group or halogenated hydrocarbon group as in the general formula (Ia).
Specific examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group. These aryl groups may be substituted with 1 to 5 halogen atoms or halogenated hydrocarbon groups.

Specific examples of the transition metal compound of the present invention include the following compounds. Although these compounds are simply referred to by their chemical names only, their steric structures mean both the compounds having asymmetry and the compounds having symmetry according to the present invention. First, to understand the nomenclature of the following compounds, the structural formula of zirconium dichloride described in the following (1) is shown below. This zirconium dichloride is derived from a compound before complexation having a 1,4-dihydroazulene skeleton, and is named dimethylmethylenebis [1,1 ′-{2-methyl-4- (4-fluorophenyl)- 1,4-dihydroazulenyl}] zirconium dichloride

[0055]

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[0056]

[Table 3] (1) Dimethylmethylenebis [1,1 '-{2-methyl-4 "
-(4-fluorophenyl) -4-hydroazulenyl}] zirconium dichloride (2) dimethylmethylenebis [1,1 '-{2-methyl-4
-(4-chlorophenyl) -4-hydroazulenyl}]
Zirconium dichloride (3) dimethylmethylenebis [1,1 '-{2-methyl-4
-(4-trifluoromethylphenyl) -4-hydroazulenyl} zirconium dichloride (4) ethylenebis [1,1 '-{2-methyl-4- (4-
(Fluorophenyl) -4-hydroazulenyl} zirconium dichloride (5) ethylenebis [1,1 '-{2-methyl-4- (4-
Chlorophenyl) -4-hydroazulenyl}] zirconium dichloride

[0057]

(4) Ethylenebis [1,1 ′-{2-methyl-4- (4-
(Trifluoromethylphenyl) -4-hydroazulenyl} zirconium dichloride (7) trimethylenebis [1,1 '-{2-methyl-4-
(4-Fluorophenyl) -4-hydroazulenyl}]
Zirconium dichloride (8) Trimethylene bis [1,1 '-{2-methyl-4-
(4-chlorophenyl) -4-hydroazulenyl} zirconium dichloride (9) trimethylenebis [1,1 '-{2-methyl-4-
(4-trifluoromethylphenyl) -4-hydroazulenyl}] zirconium dichloride (10) dimethylsilylenebis {1,1 ′-(2-methyl-
4-trifluoromethyl-4-hydroazulenylzirconium dichloride

[0058]

[Table 5] (11) Dimethylsilylenebis [1,1 '-{2-methyl-
4- (2-fluorophenyl) -4-hydroazulenyl}] zirconium dichloride (12) dimethylsilylenebis [1,1 '-{2-methyl-
4- (3-fluorophenyl) -4-hydroazulenyl}] zirconium dichloride (13) dimethylsilylenebis [1,1 '-{2-methyl-
4- (4-fluorophenyl) -4-hydroazulenyl}] zirconium dichloride (14) dimethylsilylenebis [1,1 '-{2-ethyl-
4- (4-fluorophenyl) -4-hydroazulenyl}] zirconium dichloride (15) dimethylsilylenebis [1,1 '-{2-methyl-
4- (2-chlorophenyl) -4-hydroazulenyl}] zirconium dichloride

[0059]

[Table 6] (16) Dimethylsilylene bis [1,1 '-{2-methyl-
4- (3-chlorophenyl) -4-hydroazulenyl} zirconium dichloride (17) dimethylsilylenebis [1,1 '-{2-methyl-
4- (4-chlorophenyl) -4-hydroazulenyl}] zirconium dichloride (18) dimethylsilylenebis [1,1 '-{2-ethyl-
4- (4-chlorophenyl) -4-hydroazulenyl}] zirconium dichloride (19) dimethylsilylenebis [1,1 '-{2-methyl-
4- (2-trifluoromethylphenyl) -4-hydroazulenyl}] zirconium dichloride (20) dimethylsilylenebis [1,1 '-{2-methyl-
4- (3-trifluoromethylphenyl) -4-hydroazulenyl}] zirconium dichloride

[0060]

[Table 7] (21) Dimethylsilylenebis [1,1 '-{2-methyl-
4- (4-trifluoromethylphenyl) -4-hydroazulenyl}] zirconium dichloride (22) dimethylsilylenebis [1,1 '-{2-ethyl-
4- (4-trifluoromethylphenyl) -4-hydroazulenyl}] zirconium dichloride (23) dimethylsilylenebis [1,1 '-{2-methyl-
4- (2,4-difluorophenyl) -4-hydroazulenyl}] zirconium dichloride (24) dimethylsilylenebis [1,1 '-{2-methyl-
4- (2,5-difluorophenyl) -4-hydroazulenyl}] zirconium dichloride (25) dimethylsilylenebis [1,1 '-{2-methyl-
4- (2,6-difluorophenyl) -4-hydroazulenyl}] zirconium dichloride

[0061]

[Table 8] (26) Dimethylsilylenebis [1,1 '-{2-methyl-
4- (3,5-difluorophenyl) -4-hydroazulenyl}] zirconium dichloride (27) dimethylsilylenebis [1,1 '-{2-methyl-
4- (2,4,6-trifluorophenyl) -4-hydroazulenyl}] zirconium dichloride (28) dimethylsilylene [1- {2-methyl-4- (4-
Fluorophenyl) -4-hydroazulenyl}] [1-
{2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl}] zirconium dichloride (29) dimethylsilylenebis [1,1 '-{2-methyl-
4- (4-fluorophenyl) -6-isopropyl-4
-Hydroazulenyl}] zirconium dichloride (30) dimethylsilylenebis [1,1 '-{2,8-dimethyl-4- (4-fluorophenyl) -4-hydroazulenyl}] zirconium dichloride

[0062]

(Table 9) (31) Dimethylsilylenebis [1,1 ′-{2-methyl-
4- (4-chlorophenyl) -6-isopropyl-4-
Hydroazulenyl}] zirconium dichloride (32) dimethylsilylenebis [1,1 '-{2-methyl-
4- (4-chlorophenyl) -7-isopropyl-4-
Hydroazulenyl}] zirconium dichloride (33) dimethylsilylenebis [1,1 '-{2,8-dimethyl-4- (4-chlorophenyl) -4-hydroazulenyl}] zirconium dichloride (34) dimethylsilylenebis [1,1' -｛2-methyl-
4- (4-trifluoromethylphenyl) -6-isopropyl-4-hydroazulenyl}] zirconium dichloride (35) dimethylsilylenebis [1,1 '-{2-methyl-
4- (4-trifluoromethylphenyl) -7-isopropyl-4-hydroazulenyl}] zirconium dichloride

[0063]

[Table 10] (36) Dimethylsilylenebis [1,1 '-{2-methyl-
4- (4-fluorophenyl) -7-isopropyl-4-
Hydroazulenyl}] zirconium dichloride (37) dimethylsilylenebis [1,1 '-{2-ethyl-
4- (4-chlorophenyl) -7-isopropyl-4-
Hydroazulenyl}] zirconium dichloride (38) dimethylsilylenebis [1,1 '-{2-ethyl-
4- (4-fluorophenyl) -7-isopropyl-4-
Hydroazulenyl}] zirconium dichloride (39) dimethylsilylenebis [1,1 '-{2-ethyl-
4- (4-trifluoromethylphenyl) -7-isopropyl-4-hydroazulenyl}] zirconium dichloride (40) dimethylsilylenebis [1,1 '-{2-ethyl-
4- (4-chlorophenyl) -7-phenyl-4-hydroazulenyl}] zirconium dichloride

[0064]

(Table 11) (41) Dimethylsilylenebis [1,1 ′-{2-ethyl-
4- (4-fluorophenyl) -7-phenyl-4-hydroazulenyl} zirconium dichloride (42) dimethylsilylenebis [1,1 '-{2-ethyl-
4- (4-trifluoromethylphenyl) -7-phenyl-4-hydroazulenyl}] zirconium dichloride (43) diphenylsilylenebis [1,1 '-{2-ethyl-4- (4-chlorophenyl) -7-isopropyl -4
-Hydroazulenyl}] zirconium dichloride (44) diphenylsilylenebis [1,1 '-{2-ethyl-4- (4-fluorophenyl) -7-isopropyl-4
-Hydroazulenyl}] zirconium dichloride (45) diphenylsilylenebis [1,1 ′-{2-ethyl-4- (4-trifluoromethylphenyl) -7-isopropyl-4-hydroazulenyl}] zirconium dichloride

[0065]

[Table 12] (46) (Methyl) (phenyl) silylenebis [1,1′-
{2-Ethyl-4- (4-chlorophenyl) -7-isopropyl-4-hydroazulenyl}] zirconium dichloride (47) (methyl) (phenyl) silylenebis [1,1′-
{2-Ethyl-4- (4-fluorophenyl) -7-isopropyl-4-hydroazulenyl}] zirconium dichloride (48) (methyl) (phenyl) silylenebis [1,1′-
｛2-ethyl-4- (4-trifluoromethylphenyl)
-7-isopropyl-4-hydroazulenyl}] zirconium dichloride (49) dimethylsilylene [1- {2-ethyl-4- (4-
Chlorophenyl) -7-isopropyl-4-hydroazulenyl}] {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride (50) dimethylsilylene [1- {2-ethyl-4- (4-
Fluorophenyl) -7-isopropyl-4-hydroazulenyl}] {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride

[0066]

Table 13 (51) Dimethylsilylene [1- {2-ethyl-4- (4-
Trifluoromethylphenyl) -7-isopropyl-4-
Hydroazulenyl}] {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride (52) dimethylsilylene [1- {2-ethyl-4- (4-
Chlorophenyl) -7-isopropyl-4-hydroazulenyl}] {1- (2-methyl-4-phenylindenyl)} zirconium dichloride (53) dimethylsilylene [1- {2-ethyl-4- (4-
Fluorophenyl) -7-isopropyl-4-hydroazulenyl}] {1- (2-methyl-4-phenylindenyl)} zirconium dichloride (54) dimethylsilylene [1- {2-ethyl-4- (4-
Trifluoromethylphenyl) -7-isopropyl-4-
Hydroazulenyl}] {1- (2-methyl-4-phenylindenyl)} zirconium dichloride (55) dimethylsilylenebis [1,1 ′-{2-benzyl-4- (4-chlorophenyl) -4-hydroazulenyl}] Zirconium dichloride

[0067]

(56) Dimethylsilylenebis [1,1 ′-{2-benzyl-4- (4-fluorophenyl) -4-hydroazulenyl}] zirconium dichloride (57) Dimethylsilylenebis [1,1′-} 2-benzyl-4- (4-chlorophenyl) -7-isopropyl-4
-Hydroazulenyl}] zirconium dichloride (58) dimethylsilylenebis [1,1 '-{2-benzyl-4- (4-fluorophenyl) -7-isopropyl-4
-Hydroazulenyl}] zirconium dichloride (59) diphenylsilylenebis [1,1 '-{2-benzyl-4- (4-chlorophenyl) -4-hydroazulenyl}] zirconium dichloride (60) diphenylsilylenebis [1,1'- {2-benzyl-4- (4-fluorophenyl) -4-hydroazulenyl}] zirconium dichloride

[0068]

Table 15 (61) (Methyl) (phenyl) silylenebis [1,1′-
{2-benzyl-4- (4-chlorophenyl) -4-hydroazulenyl}] zirconium dichloride (62) (methyl) (phenyl) silylenebis [1,1′-
{2-benzyl-4- (4-fluorophenyl) -4-hydroazulenyl}] zirconium dichloride (63) dimethylsilylene [1- {2-benzyl-4- (4
-Chlorophenyl) -4-hydroazulenyl}] {1-
(2-methyl-4,5-benzoindenyl)} zirconium dichloride (64) dimethylsilylene [1- {2-benzyl-4- (4
-Fluorophenyl) -4-hydroazulenyl}] {1-
(2-methyl-4,5-benzoindenyl)} zirconium dichloride (65) dimethylsilylene [1- {2-benzyl-4- (4
-Chlorophenyl) -4-hydroazulenyl}] {1-
(2-methyl-4-phenylindenyl) zirconium dichloride

[0069]

Table 16 (66) Dimethylsilylene [1- {2-benzyl-4- (4
-Fluorophenyl) -4-hydroazulenyl}] {1-
(2-methyl-4-phenylindenyl) {zirconium dichloride (67) dimethylsilylenebis [1,1 ′-{2,8-dimethyl-4- (4-trifluoromethylphenyl) -4-hydroazulenyl}] zirconium Dichloride (68) dimethylsilylenebis [1,1 '-{2-methyl-
4- (4-fluoro-1-naphthyl) -4-hydroazulenyl}] zirconium dichloride (69) dimethylsilylenebis [1,1 '-{2-methyl-
4- (4-fluoro-2-naphthyl) -4-hydroazulenyl}] zirconium dichloride (70) (methyl) (phenyl) silylenebis [1,1′-
{2-methyl-4- (4-fluorophenyl) -4-hydroazulenyl}] zirconium dichloride

[0070]

[Table 17] (71) (Methyl) (phenyl) silylenebis [1,1′-
{2-Methyl-4- (4-chlorophenyl) -4-hydroazulenyl}] zirconium dichloride (72) (methyl) (phenyl) silylenebis [1,1′-
{2-methyl-4- (4-trifluoromethylphenyl) -4-hydroazulenyl}] zirconium dichloride (73) diphenylsilylenebis [1,1 '-{2-methyl-4- (4-fluorophenyl) -4 -Hydroazulenyl}] zirconium dichloride (74) diphenylsilylenebis [1,1 '-{2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl}] zirconium dichloride (75) diphenylsilylenebis [1,1'- {2-methyl-4- (4-trifluoromethylphenyl) -4-hydroazulenyl}] zirconium dichloride

[0071]

(76) Dimethylgermylene bis [1,1 ′-{2-methyl-4- (4-fluorophenyl) -4-hydroazulenyl}] zirconium dichloride (77) Dimethylgermylene bis [1,1 ′ -{2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl}] zirconium dichloride (78) dimethylgermylene bis [1,1 '-{2-methyl-4- (4-trifluoromethylphenyl)- 4-hydroazulenyl}] zirconium dichloride (79) dimethylsilylene [1- {2-methyl-4- (4-
Fluorophenyl) -4-hydroazulenyl}] {1-
(2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride (80) dimethylsilylene [1- {2-ethyl-4- (4-
Fluorophenyl) -4-dihydroazulenyl}] {1
-(2-ethyl-4-phenyl-4-hydroazulenyl) zirconium dichloride

[0072]

[Table 19] (81) Dimethylsilylene [1- {2-methyl-4- (4-
Chlorophenyl) -4-hydroazulenyl}] {1-
(2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride (82) dimethylsilylene [1- {2-methyl-4- (4-
Trifluoromethylphenyl) -4-hydroazulenyl}] {1- (2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride (83) dimethylsilylene [1- {2-methyl-4- (4-
Fluorophenyl) -4-hydroazulenyl}] {1-
(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl)} zirconium dichloride (84) dimethylsilylene [1- {2-methyl-4- (4-
Fluorophenyl) -4-hydroazulenyl}] {1-
(2-methyl-4- (4-fluorophenyl) -4,5,
6,7,8-Pentahydroazulenyl) zirconium dichloride (85) dimethylsilylene [1- {2-ethyl-4- (4-
Fluorophenyl) -4-hydroazulenyl}] {1-
(2-ethyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl) zirconium dichloride

[0073]

[Table 20] (86) Dimethylsilylene [1- {2-methyl-4- (4-
Chlorophenyl) -4-hydroazulenyl}] {1-
(2-methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl) zirconium dichloride (87) dimethylsilylene [1- {2-methyl-4- (4-
Trifluoromethylphenyl) -4-hydroazulenyl {] {1- (2-methyl-4-phenyl-4,5,6,
7,8-pentahydroazulenyl) zirconium dichloride (88) dimethylsilylene [1- {2-methyl-4- (4-
Fluorophenyl) -4-hydroazulenyl}] {1-
(2-methyl-4-phenylindenyl)} zirconium dichloride (89) dimethylsilylene [1- {2-ethyl-4- (4-
Fluorophenyl) -4-hydroazulenyl}] {1-
(2-ethyl-4-phenylindenyl)} zirconium dichloride (90) dimethylsilylene [1- {2-methyl-4- (4-
Chlorophenyl) -4-hydroazulenyl}] {1-
(2-methyl-4-phenylindenyl) zirconium dichloride

[0074]

Table 21 (91) Dimethylsilylene [1- {2-methyl-4- (4-
Trifluoromethylphenyl) -4-hydroazulenyl}] {1- (2-methyl-4-phenylindenyl)} zirconium dichloride (92) dimethylsilylene [1- {2-methyl-4- (4-
Trifluoromethylphenyl) -4-hydroazulenyl}] {1- (2-methyl-4,5-benzoindenyl)} zirconium dichloride (93) dimethylsilylene [1- {2-methyl-4- (4-
Fluorophenyl) -4-hydroazulenyl}] {1-
(2-methyl-4,5-benzoindenyl)} zirconium dichloride (94) dimethylsilylene [1- {2-methyl-4- (4-
Chlorophenyl) -4-hydroazulenyl}] {1-
(2-methyl-4,5-benzoindenyl)} zirconium dichloride (95) dimethylsilylene [1- {2-methyl-4- (4-
Fluorophenyl) indenyl {1- (2-methyl-
4-phenyl-4-hydroazulenyl) zirconium dichloride

[0075]

Table 22 (96) Dimethylsilylene [1- {2-ethyl-4- (4-
Fluorophenyl) indenyl {1- (2-ethyl-
4-phenyl-4-hydroazulenyl) zirconium dichloride (97) dimethylsilylene [1- {2-methyl-4- (4-
Chlorophenyl) indenyl {1- (2-methyl-4)
-Phenyl-4-hydroazulenyl) zirconium dichloride (98) dimethylsilylene [1- {2-methyl-4- (4-
Trifluoromethylphenyl) indenyl {1- (2
-Methyl-4-phenyl-4-hydroazulenyl) zirconium dichloride (99) dimethylsilylene [1- {2-methyl-4- (4-
Trifluoromethylphenyl) indenyl}] [1-
{2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl}] zirconium dichloride (100) dimethylsilylenebis [1,1 '-{2-methyl-
4- (4-fluorophenyl) cyclopentacyclooctenyl}] zirconium dichloride

[0076]

[Table 23] (101) Dimethylsilylenebis [1,1 ′-{2-ethyl-
4- (4-chlorophenyl) cyclopentacyclooctenyl}] zirconium dichloride (102) dimethylsilylenebis [1,1 '-{2-methyl-
5- (4-trifluoromethylphenyl) cyclopentacyclooctenyl}] zirconium dichloride

In the above compound, one or both of the chlorine atoms forming the X and Y moieties in the general formula (Ia) or (Ib) are a hydrogen atom, a fluorine atom, a bromine atom, an iodine atom, a methyl Compounds substituted for a group, a phenyl group, a fluorophenyl group, a benzyl group, a methoxy group, a dimethylamino group, a diethylamino group, etc. can also be exemplified. Further, compounds in which the central metal (M) of the compounds exemplified above is replaced with titanium, hafnium, tantalum, niobium, vanadium, tungsten, molybdenum or the like instead of zirconium can also be exemplified.
Of these, zirconium, titanium or hafnium group 4 transition metal compounds are preferred, with zirconium or hafnium being particularly preferred.

Next, the α-olefin polymerization catalysts (1) and (2) of the present invention will be described. Each of these catalysts contains the above-mentioned transition metal compound of the present invention as an essential component (A).

First, the α-olefin polymerization catalyst (1) of the present invention will be described. This catalyst is an essential component (B)
As an optional component (C), an aluminum oxy compound, an ionic compound or a Lewis acid capable of converting the component (A) into a cation by reacting with the component (A). Some of the above-mentioned Lewis acids can be understood as ionic compounds capable of reacting with the component (A) to convert the component (A) into a cation. Therefore, compounds belonging to both the above-mentioned Lewis acids and ionic compounds are understood to belong to either one.

The above aluminum oxy compound is specifically represented by the following general formula (II), (III) or (IV)
The compound represented by these is mentioned.

[0081]

Embedded image

In each of the above formulas, R ⁹ represents a hydrogen atom or a hydrocarbon residue, preferably a hydrocarbon residue having 1 to 10 carbon atoms, more preferably a hydrocarbon residue having 1 to 6 carbon atoms. A plurality of R ⁹ may be the same or different. Also,
p represents an integer of 0 to 40, preferably 2 to 30.

The compounds represented by the general formulas (II) and (III) are compounds also called alumoxanes and are obtained by reacting one kind of trialkylaluminum or two or more kinds of trialkylaluminums with water. Specifically, (a) methylalumoxane, ethylalumoxane, propylalumoxane, butylalumoxane, isobutylalumoxane obtained from one type of trialkylaluminum and water, (b) two types of trialkylaluminum and Examples thereof include methylethylalumoxane, methylbutylalumoxane, and methylisobutylalumoxane obtained from water. Of these, methylalumoxane or methylisobutylalumoxane is preferred.

The above-mentioned alumoxanes can be used in combination of two or more in each group and between each group. The alumoxane can be prepared under various known conditions. Specifically, the following method can be exemplified.

[0085]

Table 24 (a) Method of directly reacting trialkylaluminum with water in the presence of a suitable organic solvent such as toluene, benzene, ether, etc. (b) Salt hydrate having trialkylaluminum and water of crystallization, for example, sulfuric acid Method of reacting copper and aluminum sulfate hydrate (c) Method of reacting trialkylaluminum with water impregnated in silica gel and the like (d) Mixing trimethylaluminum and triisobutylaluminum, then toluene, benzene By direct reaction with water in the presence of a suitable organic solvent such as water, ether, etc.

[0086]

(E) a salt hydrate having a mixture of trimethylaluminum and triisobutylaluminum and water of crystallization, for example,
(F) A method of heating and reacting a hydrate with copper sulfate and aluminum sulfate (f) A method of impregnating water into silica gel or the like, treating with triisobutylaluminum, and further treating with trimethylaluminum (g) Methylalumoxane and isobutyl A method of synthesizing alumoxane by a known method, mixing a predetermined amount of these two components and reacting by heating (h) Salt having crystallization water such as copper sulfate pentahydrate in an aromatic hydrocarbon solvent such as benzene or toluene And adding trimethylaluminum to react under a temperature condition of about -40 to 40 ° C.

The amount of water used in the reaction is usually 0.5 to 1.5 in molar ratio to trimethylaluminum.
The methylalumoxane obtained by the above method is a linear or cyclic organoaluminum polymer.

The compound represented by the general formula (IV) may be a compound of the following formula: It can be obtained by a 1: 1 (molar ratio) reaction. In the general formula (V), R ¹⁰ represents a hydrocarbon residue having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms or a halogenated hydrocarbon group.

[0089]

Embedded image R ¹⁰ B (OH) ₂ (V)

[0090]

[Table 26] Specifically, the following reaction products can be exemplified. (A) Trimethylaluminum and methylboronic acid 2:
(B) 2: 1 reaction product of triisobutylaluminum and methylboronic acid (c) 1: 1: 1 reaction product of trimethylaluminum, triisobutylaluminum and methylboronic acid (d) 2: 2 reaction of trimethylaluminum and methylboronic acid
1 Reactant (e) Triethylaluminum and butylboronic acid 2:
1 reactant

The ionic compound capable of converting the component (A) into a cation by reacting with the component (A) includes a compound represented by the general formula (VI).

[0092]

Embedded image (K) e ⁺ [Z] e ^- (VI)

In the general formula (VI), K is a cation component, for example, carbonium cation, tropylium cation, ammonium cation, oxonium cation,
Examples include a sulfonium cation and a phosphonium cation. In addition, metal cations and organic metal cations that are easily reduced by themselves are also included.

Specific examples of the above cation include triphenylcarbonium, diphenylcarbonium, cycloheptatrienium, indenium, triethylammonium, tripropylammonium, tributylammonium, N, N-dimethylanilinium, 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 and the like.

In the above general formula (VI), Z is an anion component, which is a component (generally a non-coordinating component) which becomes a counter anion to the converted cation species of component (A). As Z, for example, an organic boron compound anion,
Organic aluminum compound anion, organic gallium compound anion, organic phosphorus compound anion, organic arsenic compound anion, organic antimony compound anion, and the like,
Specific examples include the following anions.

[0096]

Table 27 (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, etc. (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, etc.

[0097]

[Table 28] (c) Tetraphenylgallium, tetrakis (3,4,5)
-Trifluorophenyl) gallium, tetrakis ｛3,
5-bis (trifluoromethyl) phenyl @ gallium,
Tetrakis {3,5-di (t-butyl) phenyl} gallium, tetrakis (pentafluorophenyl) gallium, etc. (d) tetraphenyl phosphorus, tetrakis (pentafluorophenyl) phosphorus, etc. (e) tetraphenyl arsenic, tetrakis (pentafluoro) (F) tetraphenylantimony, tetrakis (pentafluorophenyl) antimony, etc. (g) decaborate, undecaborate, carbadodecaborate, decachlorodecaborate, etc.

Examples of the Lewis acid, particularly the Lewis acid capable of converting the component (A) into a cation, include various organic boron compounds, metal halide compounds, solid acids, and the like. Is mentioned.

[0099]

(A) Organic boron compounds such as triphenylboron, tris (3,5-difluorophenyl) boron and tris (pentafluorophenyl) boron (b) 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 hydroxide, magnesium bromide hydroxide, magnesium chloride alkoxide, magnesium bromide alkoxide, etc. Metal halide compounds (c) Solid acids such as alumina and silica-alumina

The α-olefin polymerization catalyst of the present invention (1)
In the above, the fine particle carrier as the optional component (C) is a fine particle carrier made of an inorganic or organic compound and usually having a particle size of 5 μ to 5 mm, preferably 10 μ to 2 mm.

Examples of the inorganic carrier include, for example, SiO 2
₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , Zn
Oxides such as O, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ ,
SiO ₂ —TiO ₂ , SiO ₂ —Cr ₂ O ₃ , SiO ₂ —Al
Complex oxides such as ₂ O ₃ —MgO are exemplified.

Examples of the organic carrier include (co) polymers of α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene, styrene, divinylbenzene and the like. And a fine particle carrier of a porous polymer comprising a (co) polymer of an aromatic unsaturated hydrocarbon. These specific surface areas are usually 20 to
1000 m ² / g, preferably 50~700m ² / g, pore volume is usually 0.1 cm ² / g or more, preferably 0.3 cm ² / g, more preferably 0.8 cm ² / g or more is there.

The catalyst for polymerization of α-olefin of the present invention (1)
Is an optional component other than the fine particle carrier, for example, H
₂ O, active hydrogen-containing compounds such as methanol, ethanol and butanol; electron-donating compounds such as ethers, esters and amines; alkoxy such as phenyl borate, dimethylmethoxyaluminum, phenyl phosphite, tetraethoxysilane and diphenyldimethoxysilane Compounds can be included.

The optional components other than those described above include tri-lower alkyl aluminum such as trimethyl aluminum, triethyl aluminum and triisobutyl aluminum, halogen-containing alkyl aluminum such as diethyl aluminum chloride, diisobutyl aluminum chloride and methyl aluminum sesquichloride, and diethyl aluminum. Alkyl aluminum hydrides such as hydrides,
Alkoxy-containing alkylaluminums such as diethylaluminum ethoxide and dimethylaluminum butoxide; and aryloxy-containing alkylaluminums such as diethylaluminum phenoxide are exemplified.

The α-olefin polymerization catalyst of the present invention (1)
In the above, an aluminum oxy compound, an ionic compound capable of converting the component (A) into a cation by reacting with the component (A) or a Lewis acid is used alone as the component (B), and these are used alone. The three components can be used in appropriate combination. Further, the lower alkyl aluminum, halogen-containing alkyl aluminum,
One or more of alkylaluminum hydride, alkoxy-containing alkylaluminum, and aryloxy-containing alkylaluminum are optional components, but may be used in combination with an aluminum oxy compound, an ionic compound or a Lewis acid to form an α-olefin polymerization catalyst ( It is preferable to include it in 1).

The α-olefin polymerization catalyst of the present invention (1)
Can be prepared by contacting the above components (A) and (B) in the presence or absence of a monomer to be polymerized inside and outside a polymerization tank. That is, the components (A) and (B) and, if necessary, the component (C) and the like may be separately introduced into the polymerization vessel, or the components (A) and (B) may be brought into contact with the polymerization vessel after being brought into contact in advance. May be introduced.
Alternatively, the mixture of the components (A) and (B) may be impregnated with the component (C) and then introduced into the polymerization tank.

The above components may be contacted with each other in an inert gas such as nitrogen or an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene, or xylene. The contact temperature ranges from -20 ° C to the boiling point of the solvent, in particular,
Temperatures in the range from room temperature to the boiling point of the solvent are preferred. The catalyst thus prepared may be used without washing after preparation, or may be used after washing. Furthermore, after the preparation, the components may be used in combination as needed.

The components (A) and (B) and the component (C)
Can be preliminarily polymerized in the presence of a monomer to be polymerized to partially polymerize the α-olefin. That is, before polymerization, ethylene,
Preliminary polymerization of olefins such as propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane, styrene, etc., was carried out if necessary. The prepolymerized product can also be used as a catalyst. This prepolymerization is
The reaction is preferably performed under mild conditions in an inert solvent, and is preferably performed so as to generate usually 0.01 to 1000 g, preferably 0.1 to 100 g of polymer per 1 g of the solid catalyst.

The amounts of components (A) and (B) used are arbitrary. For example, in the case of solvent polymerization, the amount of component (A) used is
The transition metal atom is usually in the range of 10 ^-7 to 102 mmol / L, preferably 10 ^-4 to ¹ mmol / L. In the case of an aluminum oxy compound, the molar ratio of Al / transition metal is
Usually 10 to 10 ^5, preferably one hundred to two × 10 ^4, more preferably in the range of 100 to 10 ^4. On the other hand, when an ionic compound or Lewis acid is used as the component (B), the molar ratio thereof to the transition metal is usually 0.1%.
To 1,000, preferably 0.5 to 100, and more preferably 1 to 50.

Next, the α-olefin polymerization catalyst (2) of the present invention will be described. This catalyst comprises an essential component (D)
Contains an ion-exchange layered compound other than silicate or an inorganic silicate, and contains an organic aluminum compound as an optional component (E).

The above-mentioned ion-exchangeable layered compound includes:
Hexagonal close packing type, antimony type, CdCl_TwoType,
CdI_TwoIon crystallinity with layered crystal structure such as mold
And specific examples thereof include α-Zr (H
AsO_Four)_Two・ H_TwoO, α-Zr (HPO_Four)_Two, Α-Zr
(KPO_Four)_Two・ 3H_TwoO, α-Ti (HPO_Four) _Two, Α-
Ti (HAsO_Four)_Two・ H_TwoO, α-Sn (HPO_Four)_Two・
H_TwoO, γ-Zr (HPO_Four)_Two, Γ-Ti (HP
O_Four)_Two, Γ-Ti (NH_FourPO_Four)_Two・ H_TwoPolyvalent metals such as O
And crystalline acid salts thereof.

The above-mentioned ion-exchange layered compound may be used after being subjected to a salt treatment and / or an acid treatment, if necessary. In the state where neither salt treatment nor acid treatment has been performed, the ion-exchangeable layered compound except silicate is a compound having a crystal structure in which surfaces formed by ionic bonds and the like are stacked in parallel with weak bonding force to each other, Exchange of contained ions is possible.

Examples of the above inorganic silicate include clay, clay mineral, zeolite, and diatomaceous earth. They are,
Synthetic products may be used, or naturally occurring minerals may be used. Specific examples of clays and clay minerals include the allophane group such as allophane, the kaolin group such as dickite, nacrite, kaolinite, and anoxite; the halloysite group such as metahaloysite and halloysite; Stone tribe, montmorillonite, sauconite, beidellite,
Non-tronite, saponite, smectites such as hectorite, vermiculite minerals such as vermiculite,
Examples include mica minerals such as illite, sericite and chlorite, attapulgite, sepiolite, palygorskite, bentonite, Kibushi clay, gairome clay, hissingelite, pyrophyllite, and ryokudeite group. These may form a mixed layer. Examples of the artificially synthesized product include synthetic mica, synthetic hectorite, synthetic saponite, and synthetic teniolite.

Among the above inorganic silicates, kaolin family,
Halosite family, serpentine family, smectite, vermiculite mineral, mica mineral, synthetic mica, synthetic hectorite, synthetic saponite or synthetic teniolite are preferred, and smectite, vermiculite mineral, synthetic mica, synthetic hectorite, synthetic saponite or synthetic teniolite are further preferred. preferable. These may be used as they are without any particular treatment, or may be used after having been subjected to treatments such as ball milling and sieving. Further, they may be used alone or as a mixture of two or more.

The acid strength of the above-mentioned inorganic silicate can be changed by a salt treatment and / or an acid treatment, if necessary. In the salt treatment, the surface area and the interlayer distance can be changed by forming an ion complex, a molecular complex, an organic derivative, and the like. That is, by using the ion exchange property and replacing the exchangeable ions between the layers with another large bulky ion, a layered material in which the layers are expanded can be obtained.

The ion-exchangeable layered compound and the inorganic silicate may be used without any treatment. However, the exchangeable metal cation contained in the ion-exchangeable metal cation is combined with the cation dissociated from the following salts and / or acids. Replacement is preferred.

The salts used for the above ion exchange are 1 to
At least one element selected from the group consisting of Group 14 atoms
Is a compound containing a cation containing a proton, preferably
Is at least selected from the group consisting of atoms of groups 1 to 14
A cation containing one type of atom, a halogen atom, an inorganic acid,
At least one element selected from the group consisting of
Consisting of an anion derived from an atom or an atomic group
And more preferably a compound consisting of atoms of groups 2 to 14.
Cation containing at least one atom selected from the group consisting of
And Cl, Br, I, F, PO_Four, SO_Four, NO_Three, C
O_Three, C_TwoO_Four, ClO _Four, OOCCH_Three, CH_ThreeCOCHC
OCH_Three, OCI_Two, O (NO_Three)_Two, O (ClO_Four)_Two, O
(SO_Four), OH, O_TwoCl_Two, OCI_Three, OOCH and O
OCCH_TwoCH_ThreeAt least one member selected from the group consisting of
And a compound comprising: In addition, these salts
May be used in combination of two or more.

The acid used for the above-mentioned ion exchange is preferably selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid and oxalic acid, and two or more of them may be used simultaneously. As a method of combining the salt treatment and the acid treatment, a method of performing an acid treatment after performing the salt treatment, a method of performing the salt treatment after performing the acid treatment, a method of simultaneously performing the salt treatment and the acid treatment,
There is a method of performing salt treatment and acid treatment at the same time after performing salt treatment. In addition, the acid treatment has an effect of removing ions on the surface and ion exchange, and has a crystal structure of Al, Fe, M
It has the effect of eluting some cations such as g and Li.

The conditions for treatment with salts and acids are not particularly limited. However, usually the salt and acid concentrations are at 0.
It is preferable that the treatment is carried out under conditions of 1 to 30% by weight, a treatment temperature of room temperature to the boiling point of the solvent used, a treatment time of 5 minutes to 24 hours, and elution of at least a part of the compound to be treated. In addition, salts and acids are generally used in an aqueous solution.

In the case of performing the salt treatment and / or the acid treatment, the shape may be controlled by pulverization or granulation before, during, or after the treatment. Further, other chemical treatments such as an alkali treatment, an organic compound treatment, and an organic metal treatment may be used in combination. As the component (B) thus obtained, a pore volume having a radius of 20 ° or more measured by a mercury intrusion method is 0.1 c.
It is preferably c / g or more, particularly preferably 0.3 to 5 cc / g. Such a component (B), when treated in an aqueous solution, contains adsorbed water and interlayer water. Here, the adsorbed water is
The water adsorbed on the surface of the ion-exchange layered compound or the inorganic silicate or the crystal fracture surface, and the interlayer water is water existing between the layers of the crystal.

In the present invention, component (D) is preferably used after removing the adsorbed water and interlayer water as described above. Dehydration method is not particularly limited, heat dehydration,
Methods such as heat dehydration under gas flow, heat dehydration under reduced pressure, and azeotropic dehydration with an organic solvent are used. The heating temperature is
The temperature range is such that adsorbed water and interlayer water do not remain,
Usually, the temperature is 100 ° C. or higher, preferably 150 ° C. or higher, but high temperature conditions that cause structural destruction are not preferable. The heating time is at least 0.5 hour, preferably at least 1 hour. At that time, the weight loss of the component (D) after dehydration and drying is preferably 3% by weight or less as a value when sucked for 2 hours at a temperature of 200 ° C. and a pressure of 1 mmHg. In the present invention, when the component (D) whose weight loss is adjusted to 3% by weight or less is used, the same weight loss can be obtained even when the component (A) and the optional component (E) described below come into contact with each other. It is preferable to handle so that the state is maintained.

The α-olefin polymerization catalyst of the present invention (2)
In the formula, an example of the organoaluminum compound as the optional component (E) is represented by the following general formula (VII).

[0123]

Embedded image AlR _a P _3-a (VII)

In the general formula (VII), R represents a hydrocarbon group having 1 to 20 carbon atoms, P represents hydrogen, a halogen, an alkoxy group or a siloxy group, and a represents a number greater than 0 and 3 or less. Specific examples of the organoaluminum compound represented by the general formula (VII) include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum; halogens such as diethylaluminum monochloride and diethylaluminum monomethoxide. Or an alkoxy-containing alkyl aluminum. Of these, trialkylaluminum is preferred. In the α-olefin polymerization catalyst (2) of the present invention, as the component (E), in addition to the organoaluminum compound represented by the general formula (VII), aluminoxanes such as methylaluminoxane may be used. Further, the above-mentioned organoaluminum compounds and aluminoxanes can be used in combination.

The α-olefin polymerization catalyst of the present invention (2)
Can be prepared by the same method as in the case of the α-olefin polymerization catalyst (1). At this time, the contact method of the essential component (A) and the component (D) with the optional component (E) is as follows.
Although not particularly limited, the following methods can be exemplified. In addition, this contact may be performed not only at the time of catalyst preparation but also at the time of prepolymerization with olefin or at the time of polymerization of olefin.

[0126]

[Table 30] (1) Method of contacting component (A) with component (D) (2) Method of adding component (E) after contacting component (A) with component (D) (3) Method of adding component (D) after contacting component (A) with component (E) (4) Method of adding component (A) after contacting component (D) with component (E) ( 5) The components (A), (D) and (E) are brought into contact simultaneously.

At the time of or after the contact of each of the above components, a solid such as a polymer such as polyethylene or polypropylene, or an inorganic oxide such as silica or alumina may coexist or may be brought into contact.

The above components may be brought into contact with each other in an inert gas such as nitrogen or an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene and xylene. The contact is carried out at a temperature between -20 ° C and the boiling point of the solvent, particularly preferably at a temperature between room temperature and the boiling point of the solvent.

The amounts of the components used are as follows.
That is, the amount of the component (A) is usually 10 ^{−4 to} 10 mmol, preferably 10 ^{−3 to 5} mmol per 1 g of the component (D),
Component (E) is usually 0.01 to 10 ⁴ mmol, preferably from 0.1 to 100 mmol. The atomic ratio of the transition metal in the component (A) to the aluminum in the component (E) is usually 1: 0.01 to 10 ⁶ , preferably 1: 0.1 to 10 ⁵ . The catalyst thus prepared may be used without washing after preparation, or may be used after washing. Further, if necessary, the component (E) may be newly used in combination. That is, when the catalyst is prepared using the components (A) and / or (D) and the component (E), the component (E) may be further added to the reaction system separately from the preparation of the catalyst. Good. At this time, the amount of the component (E) used is 1: 0 to 10 ⁴ , preferably 1: 1, as an atomic ratio of the aluminum in the component (E) to the transition metal in the component (A).
It is selected to be 1 to 10 ³ .

Next, the method for producing the α-olefin polymer according to the present invention will be described. In the present invention, polymerization or copolymerization is carried out by bringing the above-mentioned catalyst of the present invention into contact with an α-olefin. The α-olefin polymerization catalyst (1) or (2) of the present invention is applicable not only to solvent polymerization using a solvent but also to liquid phase solventless polymerization, gas phase polymerization, and melt polymerization substantially using no solvent. Also applies. The polymerization method is
Either continuous polymerization or batch polymerization may be used.

Solvents for the solvent polymerization include hexane, heptane, pentane, cyclohexane, benzene,
Independent saturated or aliphatic hydrocarbons, such as toluene, alone or in mixtures are used. The polymerization temperature is usually -78 to 250C, preferably -20 to 100C. Olefin pressure of the reaction system is not particularly limited, is preferably 2,000 kgf / cm ² G from atmospheric pressure, more preferably in the range from normal pressure 50kgf / cm ² G.
Further, for example, the molecular weight can be adjusted by known means such as selection of temperature and pressure or introduction of hydrogen.

As the starting α-olefin, an α-olefin having usually 2 to 20, preferably 2 to 10 carbon atoms is used. Specific examples thereof include ethylene, propylene, 1-butene and 4-methyl-olefin. 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-
Tetradecene, 1-hexadecene, 1-octadecene,
1-eicosene and the like. The catalyst of the present invention is suitably used for the polymerization of α-olefins having 3 to 10 carbon atoms, particularly propylene, for the purpose of stereoregular polymerization.

The catalyst of the present invention is also applicable to copolymerization of the above-mentioned α-olefins or α-olefins with other monomers. Other monomers copolymerizable with the α-olefin include, for example, butadiene, 1,4-
Hexadiene, 1,5-hexadiene, 7-methyl-1,
Conjugated and non-conjugated dienes such as 6-octadiene, 1,8-nonadiene and 1,9-decadiene, and cyclic olefins such as cyclopropene, cyclobutene, cyclopentene, norbornene and dicyclopentadiene. In polymerization, so-called multi-stage polymerization in which the conditions are changed in multiple stages, for example, so-called block copolymerization in which propylene is polymerized in the first stage and ethylene and propylene are copolymerized in the second stage is also possible.

By using the transition metal compound of the present invention as a catalyst component for the polymerization of α-olefins, the resulting polymer has a high melting point, a high molecular weight and a low MFR, as shown in the examples below. Is achieved. Although the reason is not clear, it can be presumed as follows.

That is, since the substituents R ⁷ and R ⁸ in the transition metal compound of the present invention form a condensed ring in which R ³ and R ⁶ to which they are bonded have 7 or more members, R ³ or R It occupies a configuration with a certain angle from the plane of the fused ring formed with R ⁶ . Moreover, the substituents R ⁷ and R ⁸
Have halogen atoms that are sterically bulkier than hydrogen atoms, but these halogen atoms form moderate steric hindrances and shapes that cannot be achieved with hydrocarbons alone. as a result,
It is presumed that the action of regulating the direction of polymer chain growth and the direction of coordination of the monomer is enhanced, the tacticity of the resulting polymer is improved, and a polymer having a high melting point is obtained.

In addition, a central metal (for example, zirconium,
It is estimated that the chain transfer reaction is suppressed and the molecular weight of the obtained polymer is increased by the electronic action of the halogen atom on hafnium and the like and the three-dimensional structure as described above. Further, 7-1 formed by R ³ or R ⁶
Due to the double bond present in the 0-membered ring, the movement of the substituent R ⁷ or R ⁸ is suppressed, and the ligand structure becomes firm. Therefore, even when the polymerization temperature is increased, the growth direction of the polymer chain and the The effects of the substituents R ⁷ and R ⁸ that regulate the coordination direction do not decrease, and as a result, a high molecular weight polymer having excellent stereoregularity can be obtained.

[0137]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. In the following examples, the catalyst synthesis step and the polymerization step were all performed under a purified nitrogen atmosphere, and the solvent was dehydrated with MS-4A, and then deaerated by bubbling with purified nitrogen before use. The activity per solid catalyst component is defined as the catalytic activity (unit: g-
The activity per complex component was expressed as a complex activity (unit: g-polymer / g-complex).

(1) Measurement of MFR: To 6 g of the polymer, 6 g of an acetone solution (0.6% by weight) of a heat stabilizer (BHT) was added. Next, after drying the above-mentioned polymer, it was filled in a melt indexer (230 ° C.) and left under a condition of a load of 2.16 kg for 5 minutes. Thereafter, the amount of the polymer extruded was measured, converted into the amount per 10 minutes, and the MFR was calculated.
Value.

(2) Measurement of molecular weight distribution: weight average molecular weight (Mw) and number average molecular weight (Mn) obtained by GPC
(Mw / Mn = Q value). As the GPC device, “150CV type” manufactured by Waters was used. The solvent used was ortho-dichlorobenzene, and the measurement temperature was 13
5 ° C.

(3) Measurement of melting point: DSC (“TA2000” manufactured by DuPont) was used at 20 ° C./min at 10 ° C./min.
The temperature was determined by measuring the temperature at the second time after the temperature was raised and lowered to 00 ° C. once.

Example 1 (1) Synthesis of dimethylsilylenebis [1,1 '-{2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl}] zirconium dichloride: (a) Synthesis of racemic / meso mixture A solution of 1.84 g (9.6 mmol) of 1-bromo-4-chlorobenzene in n-hexane (10 ml) and diethyl ether (10 ml) at −78 ° C. in pentane solution of t-butyllithium (1.64 M) 11. 0.7 ml (19.2 mmol) was added dropwise. After stirring the obtained solution at -5 ° C for 1.5 hours, 1.2 g (8.6 mmol) of 2-methylazulene was added to the solution.
l) was added to carry out the reaction. The reaction solution was stirred for 1.5 hours while gradually returning to room temperature. Thereafter, the reaction solution was cooled to 0 ° C., and 15 μl of 1-methylimidazole was added.
(0.19 mmol) and then 0.52 ml (4.3 mmol) of dichlorodimethylsilane.
After stirring the reaction solution at room temperature for 1.5 hours, dilute hydrochloric acid was added to stop the reaction, the separated organic phase was concentrated under reduced pressure, dichloromethane was added, and the mixture was dried over magnesium sulfate. After evaporating the solvent under reduced pressure, the residue was purified by silica gel column chromatography to obtain an amorphous solid 2.1.
g was obtained.

Next, 1.27 g of the above reaction product was dissolved in 15 ml of diethyl ether.
1. n-hexane solution of butyllithium (1.66 M)
8 ml (4.5 mmol) were added dropwise. After completion of the dropwise addition, the reaction solution was stirred for 12 hours while gradually returning to room temperature.
After distilling off the solvent under reduced pressure, 5 ml of a mixed solvent of toluene and diethyl ether (40: 1) was added, and the mixture was cooled to -78 ° C, and 0.53 g of zirconium tetrachloride (2.3 g) was added thereto.
mmol) was added. Then, immediately return to room temperature,
The reaction was performed with stirring at room temperature for 4 hours. The obtained reaction solution was filtered over celite, and the solid separated by filtration was mixed with 3 ml of toluene.
And washed. The collected solid was extracted with dichloromethane, the solvent was distilled off from the extract, and racemic dimethylsilylenebis [1,1 ′-{2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl}] zirconium dichloride was obtained. -906 mg (56% yield) of a meso mixture was obtained.

¹ H-NMR of the above racemic / meso mixture
Were as follows. 300MHz, C ₆
D ₆ (ppm) 0.45 (s, meso-form SiMe), 0.50
(S, racemic SiMe), 0.57 (s, meso SiM)
e) 1.88 (s, meso-form 2-Me), 1.96 (s,
Racemic 2-Me), 5.17 (brs, racemic 4-
H), 5.22 (brs, meso-form 4-H), 5.6
6.1 (m, -CH =), 6.65-6.8 (m, -CH
=), 7.1-7.40 (m, -CH =)

(B) Purification of racemic form: Further, 900 mg of the above-mentioned racemic-meso mixture was dissolved in 20 ml of dichloromethane, and the mixture was irradiated with a high-pressure mercury lamp of 100 W for 40 minutes to increase the ratio of the racemic form. Filter out,
The collected filtrate was concentrated to dryness. Then, the obtained solid component was stirred with 22 ml of toluene, and after standing, the supernatant was removed. This purification operation was repeated four times. The remaining solid component was dried, and dimethylsilylenebis [1,1′-
{2-Methyl-4- (4-chlorophenyl) -4-hydroazulenyl}] racemic zirconium dichloride 27
5 mg were obtained.

The ¹ H-NMR chemical shifts of the above racemate were as follows. 300 MHz, CDCl ₃ (pp
m) 0.95 (s, 6H, SiMe), 2.13 (s, 6
H, 2-Me), 4.82-4.85 (br d, 2
H) 5.70-5.78 (m, 2H), 5.83-
5.92 (m, 4H), 6.03-6.12 (m, 2
H), 6.70 (d, J = 12 Hz, 2H), 7.1-7.
35 (m, 8H, -CH =)

(2) Polymerization of propylene using methylalumoxane as a co-catalyst: In a 2-liter stirred autoclave, methylalumoxane ("MM" manufactured by Tosoh Akzo Co., Ltd.) was added.
(AO)) 4 mmol (in terms of Al atom) and 0.29 mg of the above-mentioned racemate were added, and 1500 ml of propylene was introduced. The temperature was raised to 70 ° C., and the polymerization operation was performed for 1 hour, to obtain 72 g of polypropylene. Complex activity is 24.9 × 10 ⁴
Met. Tm of polypropylene is 150.4 ° C, MF
R was 1.1, Mw was 3.6 × 10 ⁵ , and Q was 3.0.

Example 2 <Polymerization of propylene using clay mineral as co-catalyst> (1) Chemical treatment of clay mineral and preparation of solid catalyst component:
10 g of montmorillonite ("Kunipia F" manufactured by Kunimine Industries) in dilute sulfuric acid consisting of 10 g of sulfuric acid and 90 ml of demineralized water
Was dispersed, heated to the boiling point, and then stirred for 6 hours. Thereafter, the collected montmorillonite was sufficiently washed with demineralized water, preliminarily dried, and then dried at 200 ° C. for 2 hours to obtain a chemically treated clay mineral. To 200 mg of the chemically treated montmorillonite, 0.8 ml of a toluene solution of triethylaluminum having a concentration of 0.5 mol / l was added, and the mixture was stirred at room temperature for 1 hour. Then, it was washed with toluene to obtain a montmorillonite-toluene slurry of 33 mg / ml.

(2) Polymerization: 0.25 mmol (in terms of Al atom) of triisobutylaluminum (manufactured by Tosoh Akzo) was introduced into a 1 L internal volume stirred autoclave. on the other hand,
1.09 mg of the racemate obtained in Example 1 (1) was diluted with toluene and introduced into a catalyst feeder with a rupture disk.
The above toluene slurry containing 50 mg of montmorillonite and 0.015 mmol (in terms of Al atom) of triisobutylaluminum were introduced. Thereafter, 700 ml of propylene was introduced into the autoclave, and the rupture plate was cut at room temperature.
The temperature was raised to 0 ° C., and the polymerization operation was performed for 1 hour to obtain 131.3 g of polypropylene. The catalyst activity was 3000 and the complex activity was 13.5 × 10 ⁴ . Tm of polypropylene is 1
49.2 ° C., MFR 5.8, Mw 2.4 × 10 ⁵ ,
Q was 2.5.

Example 3 (1) Synthesis of dimethylsilylenebis [1,1 '-{2-methyl-4- (4-trifluoromethylphenyl) -4-hydroazulenyl}] zirconium dichloride: Example 1 (1) In (a), except that 1.35 g of 1-bromo-4-trifluoromethylbenzene was used instead of 1.15 g of 1-bromo-4-chlorobenzene,
By operating in the same manner as in Example 1 (1) (a), 1.16 g of an amorphous solid was obtained.

As in Example 1 (b), using 2.2 ml of the above amorphous solid and n-hexane solution of n-butyllithium (1.66M) and 0.42 g (1.8 mmol) of zirconium tetrachloride. To yellow solid 0.
36 g were obtained. This was identified as a racemic / meso mixture of dimethylsilylenebis [1,1 ′-{2-methyl-4- (4-trifluoromethylphenyl) -4-hydroazulenyl}] zirconium dichloride based on 1 H-NMR. The yield was 15%.

(2) Polymerization of propylene using methylalumoxane as a co-catalyst: In a 2-liter stirred autoclave, methylalumoxane ("MM" manufactured by Tosoh Akzo Co., Ltd.) was added.
AO ”) 4 mmol (in terms of Al atom) and 0.6 mg of the above-mentioned racemic / meso mixture are added, and 1500 ml of propylene is added.
Was introduced. The temperature was raised to 70 ° C., and the polymerization operation was performed for 1 hour, to obtain 50 g of polypropylene. Complex activity is 8.3 ×
It was 10 ⁴ . Tm of polypropylene is 153.2
° C and MFR were 1.0.

Example 4 (1) Synthesis of dimethylsilylenebis [1,1 ′-{2-methyl-4- (4-fluorophenyl) -4-hydroazulenyl}] zirconium dichloride: (a) Preparation of racemic / meso mixture Synthesis; 1-bromo-4-fluorobenzene 0.90 ml (8.2 mmol) of n
-Hexane (10 ml) and diethyl ether (10 m
10 ml (16.4 mmol) of a pentane solution of t-butyllithium (1.64 M) was added dropwise to the solution with 1) at -78 ° C. The resulting solution was stirred at -78 ° C for 15 minutes and then at -10 ° C for 45 minutes. Thereafter, 1.05 g (7.37 mmol) of 2-methylazulene was added to this solution to carry out a reaction. The reaction solution was stirred for 1 hour while gradually returning to room temperature. Thereafter, the reaction solution was cooled to 0 ° C., and 10 ml of tetrahydrofuran was added.
16 μl of 1-methylimidazole (0.20 mmol)
And 0.45 ml of dichlorodimethylsilane (3.7 mmol
l) was added. After stirring the reaction solution at room temperature for 1 hour, dilute hydrochloric acid was added to stop the reaction, and the separated organic phase was concentrated under reduced pressure and dried over magnesium sulfate. After evaporating the solvent under reduced pressure, the residue was purified by silica gel column chromatography to obtain 2.1 g of an amorphous solid.

Next, 1.55 g of the above reaction product was dissolved in 15 ml of diethyl ether.
2. n-hexane solution of butyllithium (1.66 M)
5 ml (5.8 mmol) were added dropwise. After completion of the dropwise addition, the reaction solution was stirred for 12 hours while gradually returning to room temperature.
After distilling off the solvent under reduced pressure, 6 ml of a mixed solvent of toluene and diethyl ether (40: 1) was added, the mixture was cooled to -78 ° C, and further 0.68 g of zirconium tetrachloride (2.9)
mmol) was added. Then, immediately return to room temperature,
The reaction was performed with stirring for 4 hours. 30 ml of dichloromethane was added to the obtained reaction solution, and the mixture was stirred and filtered over celite. 25 ml of n-hexane was added to the filtrate, and dimethylsilylenebis [1,1 ′-{2-methyl-4-ethyl-4-
(4-Fluorophenyl) -4-hydroazulenyl}]
1.0 g of a racemic / meso mixture of zirconium dichloride was filtered off. The yield was 50%.

¹ H-NMR of the above racemic / meso mixture
Were as follows. 300MHz, C ₆
D ₆ (ppm) 0.45 (s, meso-form SiMe), 0.51
(S, racemic SiMe), 0.58 (s, meso SiM)
e) 1.89 (s, meso form 2-Me), 1.97 (s,
Racemic 2-Me), 5.20 (brs, racemic 4-
H), 5.28 (brs, meso-form 4-H), 5.6
6.2 (m, -CH =), 6.75-7.4 (m, -CH
=)

(B) Purification of the racemic form; Then, the racemic-meso mixture 3 obtained above was added to 20 ml of dichloromethane.
33 mg was suspended, and the ratio of the racemate was increased by irradiating with a 100-w high-pressure mercury lamp for 10 minutes. Thereafter, the insoluble matter was separated by filtration, and the collected filtrate was concentrated to dryness. Next, the obtained solid component was stirred with 4 ml of toluene, and after standing, the supernatant was removed. Such a purification operation was repeated three times, and the remaining solid component was washed twice with hexane and then dried, and dimethylsilylenebis [1,1 ′-{2-methyl-
115 mg of racemic 4- (4-fluorophenyl) -4-hydroazulenyl}] zirconium dichloride was obtained.

The ¹ H-NMR chemical shifts of the above racemate were as follows. 300MHz, CDCl ₃ (ppm)
0.95 (s, 6H, Si-Me), 2.14 (s, 6
H, 2-Me), 4.84 (br, 2H, 4-H), 5.7
2-5.90 (m, 6H), 6.05-6.10 (m, 2
H), 6.72 (d, J = 12 Hz, 2H), 6.95-
7.05 (m, 4H, -CH =), 7.32-7.40
(M, 4H, -CH =)

(2) Polymerization of propylene with methylalumoxane as a cocatalyst:
In place of the racemate obtained in (1), the above racemate 0.2
Except for using 9 mg, the same operation as in Example 1 (2) was carried out to obtain 30 g of polypropylene. Complex activity is 10.3
× 10 ⁴ . Tm of polypropylene is 149.7
° C, MFR is 1.3, Mw is 3.4 × 10 ⁵ , Q is 2.
It was 3.

Example 5 <Polymerization of propylene using clay mineral as co-catalyst> Example 2
In (2), instead of the racemate obtained in Example 1 (1), 1.035 mg of the racemate obtained in Example 3 (1)
154 g of polypropylene was obtained by performing the same operation as in (2) of Example 2 except for using. Catalyst activity is 308
0 and the complex activity was 14.2 × 10 ⁴ . The Tm of the polypropylene was 148.0 ° C., the MFR was 6.9, the Mw was 2.2 × 10 ⁵ , and the Q was 2.4.

Example 6 (1) Synthesis of dimethylsilylenebis [1,1 '-{2-methyl-4- (3-chlorophenyl) -4-hydroazulenyl}] hafnium dichloride: (a) Synthesis of racemic / meso mixture 1.8 ml (15.32 mmol) of 1-bromo-3-chlorobenzene in 20 ml of normal hexane and 20 ml of diethyl ether
18.7 ml (30.65 mmol) of a solution of t-butyllithium in pentane (1.64 M) at −78 ° C.
l) was added dropwise. After stirring the obtained solution at -5 ° C for 1 hour, 1.96 g of 2-methylazulene (13.
(79 mmol) was added to carry out the reaction. The reaction solution was stirred for 1.25 hours while gradually returning to room temperature. Thereafter, the reaction solution was cooled to 0 ° C, and tetrahydrofuran (20 mL) and 30 µl of 1-methylimidazole (0.
38 mmol) and then 0.84 ml (6.9 mmol) of dichlorodimethylsilane. After stirring the reaction solution at room temperature for 1.5 hours, dilute hydrochloric acid was added to stop the reaction, the separated organic phase was concentrated under reduced pressure, dichloromethane was added, and the mixture was dried over magnesium sulfate. After distilling off the solvent under reduced pressure, an amorphous crude product was obtained.

Next, the above reaction product was dissolved in 20 ml of dry diethyl ether, and 8.6 ml of an n-hexane solution of n-butyllithium (1.6 M) was added at -78 ° C.
(13.8 mmol) was added dropwise. After completion of the dropwise addition, the reaction solution was stirred for 12 hours while gradually returning to room temperature. After distilling off the solvent under reduced pressure, 15 ml of a mixed solvent of toluene and diethyl ether (40: 1) was added and the mixture was cooled to −78 ° C., and 2.2 g of hafnium tetrachloride (6.9 mmol) was added thereto.
l) was added. Thereafter, the temperature was immediately returned to room temperature, and the reaction was performed with stirring for 5 hours. The obtained reaction solution was filtered on celite, and the solid separated by filtration was mixed with 5 ml of toluene and 4 ml of hexane.
Washed with ml and collected. The collected solid was extracted with 40 ml of dichloromethane, the solvent was distilled off from the extract, and dimethylsilylenebis [1,1 ′-{2-methyl-4- (3-
Chlorophenyl) -4-hydroazulenyl {] hafnium dichloride racemic / meso mixture (571 mg, yield 1)
0%).

(B) Purification of the racemic form: Further, 571 mg of the above-mentioned racemic-meso mixture was dissolved in 15 ml of dichloromethane, and the mixture was irradiated with a high-pressure mercury lamp of 100 W for 15 minutes to increase the ratio of the racemic form. The mixture was separated by filtration, and the collected filtrate was concentrated to dryness. Next, the obtained solid component was stirred with 5 ml of toluene, and filtered with a frit. The remaining solid components were dissolved in toluene 3 ml and hexane 4 m
and dried under reduced pressure to obtain 290 mg of dimethylsilylenebis [1,1 ′-{2-methyl-4- (3-chlorophenyl) -4-hydroazulenyl}] hafnium dichloride.

The ¹ H-NMR chemical shifts of the above racemate were as follows. 300 MHz, CDCl ₃ (pp
m) 0.95 (s, 6H, SiMe), 2.22 (s, 6
H, 2-Me), 4.93-4.97 (br d, 2
H) 5.70-5.90 (m, 6H), 5.97-6.
05 (m, 2H), 6.75 (d, 2H), 7.15-
7.27 (m, 6H, arom), 7.33 (s, 2H, arom)

(2) Polymerization of propylene with clay mineral as cocatalyst: In Example 2 (2), the racemic compound 1 obtained in the above (1) was used instead of the racemic product obtained in the example 1 (1). .
Except that 22 mg was used, the same operation as in Example 2 (2) was performed to obtain 110 g of polypropylene. The complex activity was 9.0 × 10 ⁴ and the catalyst activity was 2200. The Tm of the polypropylene was 152.4 ° C., and the MFR was 0.5.

Example 7 (1) Synthesis of dimethylsilylenebis [1,1 '-{2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl}] hafnium dichloride: 1-bromo-4-
4.5 g (23.53 mmol) of n-chlorobenzene
Hexane (30 ml) and diethyl ether (30 ml)
29 ml (47.0 mmol) of a pentane solution of t-butyllithium (1.64M) was added dropwise to the solution of -78 ° C. After stirring the obtained solution at -5 ° C for 1.5 hours, 3.0 g (21.2 mmol) of 2-methylazulene was added to the solution.
Was added to carry out the reaction. The reaction solution was stirred for 1 hour while gradually returning to room temperature. After that, the reaction solution is
C. and cooled to 40 μl of 1-methylimidazole (0.4
7 mmol) and 1.28 ml (10.59 mmol) of dichlorodimethylsilane. After stirring the reaction solution at room temperature for 1.5 hours, the reaction was stopped by adding dilute hydrochloric acid, the separated organic phase was concentrated under reduced pressure, the solvent was distilled off, and the residue was purified by silica gel column chromatography to obtain an amorphous phase. 2.74 g of a solid was obtained.

Next, the above reaction product was dissolved in 20 ml of dry diethyl ether, and 6.3 ml of an n-hexane solution (1.54 M) of n-butyllithium was added at −78 ° C.
(9.72 mmol) was added dropwise. After completion of the dropwise addition, the reaction solution was stirred for 12 hours while gradually returning to room temperature. After distilling off the solvent under reduced pressure, 15 ml of a mixed solvent of dry toluene and dry diethyl ether (40: 1) was added, and -7 was added.
Cool to 8 ° C and add 1.56 g of hafnium tetrachloride
(4.86 mmol) was added. Thereafter, the temperature was immediately returned to room temperature, and the mixture was stirred for 4 hours to carry out a reaction. The obtained reaction solution was filtered over celite, and the filtered solid was extracted with dichloromethane (90 ml), and the solvent was distilled off from the extract.
Dimethylsilylenebis [1,1 '-{2-methyl-4-
320 mg of racemic (4-chlorophenyl) -4-hydroazulenyl}] hafnium dichloride (7% yield)
I got

The ¹ H-NMR chemical shifts of the above racemate were as follows. 300MHz, CDCl
₃ (ppm) δ 0.95 (s, 6H, SiMe ₂ ), 2.21
(S, 6H, 2-Me), 4.92-4.96 (br d,
2H), 5.70-6.15 (m, 8H), 6.78
(D, 2H), 7.28 (s, 8H, arom)

(2) Polymerization of propylene using methylalumoxane as a co-catalyst: In a 2-liter stirred autoclave, methylalumoxane (manufactured by Tosoh Akzo), 4 mm
ol (in terms of Al atom) and racemic dimethylsilylenebis [1,1 ′-{2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl}] hafnium dichloride obtained in the above (1) (0.65 mg) )), And 1500 ml of propylene were introduced. 1 at 70 ° C
Polymerization was carried out for a time to obtain 8 g of polypropylene. The complex activity was 1.23 × 10 ⁴ . Tm of polypropylene is 154.4 ° C., MFR is 0.07, Mw is 14 × 1
0 ⁵ and Q were 4.0.

Example 8 <Polymerization of propylene using clay mineral as co-catalyst> (1) Chemical treatment of clay mineral and preparation of solid catalyst component:
By the same operation as in Example 2 (1), a montmorillonite-toluene slurry of 20 mg / ml was obtained.

(2) Polymerization: Triisobutylaluminum (0.045 mmol) and montmorillonite (50 mg) were placed in a 1 L stirred autoclave at room temperature under a nitrogen stream.
The above toluene slurry containing liquid propylene 700
ml was introduced. Further, Example 7 was used as the component (A).
Dimethylsilylene bis [1,1 ′-{2} obtained in (1)
-Methyl-4- (4-chlorophenyl) -4-hydroazulenyl}] racemic 1.5 µ of hafnium dichloride
mol was dissolved in toluene and pressurized with high-pressure argon, and the autoclave was heated to 80 ° C. and polymerized for 1 hour to obtain 146 g of polypropylene. The catalytic activity is 29
00, the complex activity was 12.0 × 10 ⁴ . The Tm of the polypropylene was 150.6 ° C., the MFR was 0.4, the Mw was 5.6 × 10 ⁵ , and the Q was 3.1.

Example 9 (1) Chemical treatment and granulation of clay mineral: 3 kg of commercially available montmorillonite (“Kunipia F” manufactured by Kunimine Kogyo Co., Ltd.) was pulverized by a vibration mill, dispersed in 16 L of a 3% aqueous sulfuric acid solution, and treated with magnesium sulfate. After adding 2.1 kg, 90 ° C
For 3 hours. Thereafter, the solid was filtered off and washed with water, p
H was adjusted to 5 or more. Next, a slurry having a solid content of 15% was prepared, and spray granulation was performed using a spray drier. The shape of the particles thus obtained was spherical. 10.0 g of the chemically treated montmorillonite obtained above was placed in a 200 ml flask, and subjected to heat dehydration treatment at 300 ° C. for 2 hours under reduced pressure to obtain a component (B).

(2) Preparation of solid catalyst component and prepolymerization treatment: Heptane 400 was placed in a 1 L stirred autoclave.
Then, the temperature was adjusted to 40 ° C. On the other hand, 10 g of the component (B) obtained in the above (1) was dispersed in 40.2 ml of toluene,
79.8 ml of triethylaluminum toluene dilution
(Equivalent to 60 mmol) was added, and the mixture was brought into contact at room temperature for 1 hour. Then, the supernatant was taken out, and the solid portion was washed with toluene and introduced into the above autoclave. Then, Example 7
Dimethylsilylene bis {1,1 ′-(2-) obtained in (1)
48. Toluene solution of methyl-4- (4-chlorophenyl) -4-hydroazulenyl) hafnium dichloride
8 ml (corresponding to 0.10 mmol) were introduced, and 4.96 ml of a diisobutylaluminum toluene dilution was further added.
(Equivalent to 4 mmol) was added dropwise, and propylene was fed to initiate polymerization. Propylene pressure is 5 kgf / cm ²
G was maintained for 15 minutes. After the completion of the polymerization, the polymerization slurry was extracted, the supernatant was removed, and the resultant was dried under reduced pressure at 40 ° C. for 3 hours to obtain a dried catalyst. The prepolymerization amount was 3.1 g per 1 g of the component (B).

(3) Polymerization of propylene: 0.4 g of triisobutylaluminum was placed in a 3 L stirred autoclave.
1.5 L of propylene was introduced, 30 mg of the dry catalyst obtained in the above (2) (provided as the component (B) excluding the prepolymerized amount) was pumped under the condition of 30 ° C., and then the temperature was raised to 75 ° C. Polymerized for 1 hour. After completion of the polymerization, propylene was purged to recover a polymerized polymer. Tables 31 and 32 show the results.
Shown in

Examples 10 and 11 <Polymerization of propylene> The procedure of Example 9 (3) was repeated, except that the amount of hydrogen shown in Table 31 was introduced after the introduction of the dry catalyst.
The operations and polymerization of Example 9 (1) to (3) were performed.
The results are shown in Table 31 and Table 32.

Example 12 <Polymerization of propylene> The procedure of Example 9 (3) was repeated except that the amount of the dry catalyst introduced into the autoclave was changed to 15 mg (as the component (B) excluding the prepolymerized amount). The operations and polymerization of Example 9 (1) to (3) were performed. The results are shown in Table 31 and Table 32.

Example 13 <Random copolymerization of propylene / ethylene> Example 9
In Example (3), the amount of the dried catalyst introduced into the autoclave was changed to 15 mg (however, as the component (B) excluding the prepolymerized amount), and 1.5 L of propylene and 45 g of ethylene were introduced into the autoclave. 9
Each operation and polymerization of (1) to (3) were performed. The results are shown in Table 31 and Table 32.

Example 14 and Comparative Examples 1 and 2 Example 9 was repeated except that the following changes were made.
Each operation and polymerization of (1) to (3) were performed. The results are shown in Table 31 and Table 32. (1) Preparation of solid catalyst component and pre-polymerization treatment: A dried catalyst was prepared under the same conditions as in Example 9 (2) except that in Example 9 (2), component (A) was changed to the compound described in Table 31. I got (2) Polymerization of propylene: Example 9 Example 9 was repeated except that 50 mg of the dried catalyst obtained in (1) was used (but as the component (B) excluding the amount of prepolymerization).
Polymerization was carried out under the same conditions as in (3). Tables 31 and 32 show the results.
Shown in

[0177]

[Table 31]

A: dimethylsilylenebis {1,1′-
(2-methyl-4- (4-chlorophenyl) -4-hydroazulenyl) {hafnium dichloride b: dimethylsilylenebis} 1,1 ′-(2-methyl-
4- (4-chlorophenyl) -4-hydroazulenyl) {zirconium dichloride c: dimethylsilylenebis} 1,1 ′-(2-methyl-
4-phenyl-4-hydroazulenyl) {hafnium dichloride d: dimethylsilylenebis} 1,1 ′-(2-methyl-
4-phenyl-4-hydroazulenyl) zirconium dichloride

[0179]

[Table 32]

Comparative Example 3 (1) Synthesis of dimethylsilylenebis {1,1 ′-(2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride: (a) Synthesis of racemic / meso mixture; 62-207
In 22 ml of hexane was dissolved 2.22 g of 2-methylazulene synthesized according to the method described in JP-A-232, and 15.6 ml (1.0 equivalent) of a solution of phenyllithium in cyclohexane-diethyl ether was added little by little at 0 ° C. .
After the solution was stirred at room temperature for 1 hour, it was cooled to -78 ° C and 30 ml of tetrahydrofuran was added. 0.95 ml of dimethyldichlorosilane was added to this solution, the temperature was returned to room temperature, and the mixture was further heated at 50 ° C. for 1.5 hours. Thereafter, an aqueous solution of ammonium chloride was added to separate the solution, and the organic phase was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The obtained crude product was purified by silica gel column chromatography (hexane-dichloromethane 5: 1) to give dimethylbis {1,1 ′-(2-methyl-4-phenyl-1,4-).
1.48 g of dihydroazulenyl) @silane was obtained.

The dimethylbis {1,1′-
(2-methyl-4-phenyl-1,4-dihydroazulenyl) ア 768 mg of silane in 15 ml of diethyl ether
And 1.98 ml (1.64 mol / L) of a hexane solution of n-butyllithium was added dropwise at −78 ° C., and the mixture was stirred for 12 hours while gradually returning to room temperature. After evaporating the solvent under reduced pressure, the obtained solid was washed with hexane and dried under reduced pressure. 20 ml of a mixed solvent of toluene and diethyl ether (40: 1) was added thereto, 325 mg of zirconium tetrachloride was added at -60 ° C, and the mixture was stirred for 15 hours while gradually returning to room temperature. The obtained solution was concentrated under reduced pressure, reprecipitated by adding hexane, and a racemic / meso mixture of dimethylsilylenebis {1,1 ′-(2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride ( 150 mg of a racemic / meso mixture showing the following spectral data) was obtained.

(B) Purification of racemic compound: 887 mg of the above-mentioned racemic / meso mixture was dissolved in 30 ml of dichloromethane, and introduced into a pyrex glass container having a 100 W high-pressure mercury lamp. Then, the solution was irradiated with light (300 nm to 600 nm) at normal pressure for 30 minutes while stirring to increase the ratio of the racemate, and then dichloromethane was distilled off under reduced pressure. After 7 ml of toluene was added to the obtained yellow solid and stirred, the mixture was allowed to stand to precipitate a yellow solid, and the supernatant was removed. Further, the same washing operation was performed with 4 ml of toluene and 2 m of toluene.
and 3 times with 2 ml of hexane, and the resulting solid was dried under reduced pressure to give dimethylsilylenebis {1,1 ′}.
437 mg of a racemic form of-(2-methyl-4-phenyl-4-hydroazulenyl)} zirconium dichloride was obtained.

<Chemical Shift of ¹ H-NMR of Racemic Form> 300 MHz, C ₆ D ₆ (ppm) δ 0.51 (s, 6H, S
_{i (CH 3) 2),} 1.92 (s, 6H, CH 3), 5.3
0 (br d, 2H), 5.75-5.95 (m, 6
H), 6.13 (s, 2H), 6.68 (d, J = 14H)
z, 2H), 7.05-7.20 (m, 2H, arom), 7.
56 (d, J = 7Hz, 4H)

<Chemical shift in ¹ H-NMR of meso form> 300 MHz, C ₆ D ₆ (ppm) δ 0.44 (s, 6 H, Si
CH ₃ ), 0.59 (s, 6H, SiCH ₃ ), 1.84
_{(S, 6H, CH 3)} , 5.38 (br d, 2H), 5.
75-6.00 (m, 6H), 6.13 (s, 2H),
6.78 (d, J = 14 Hz, 2H), 7.00-7.20
(M, 2H, arom), 7.56 (d, J = 7 Hz, 4H)

(2) Polymerization of propylene using methylalumoxane as a cocatalyst: A methylalumoxane (MMA manufactured by Tosoh Akzo Co., Ltd.) was placed in a 2 L stirred autoclave.
O ") 4 mmol (in terms of Al atom) and 0.26 mg (0.4 µmol) of the racemic product obtained in the above (1) were added, and 1500 ml of propylene was introduced. Raise the temperature to 70 ° C and
The polymerization was carried out for 4 hours to obtain 43.5 g of polypropylene. The complex activity was 16.7 × 10 ⁴ . The Tm of polypropylene is 150.9, the MFR is 1.3, and the Mw is 3.
5 × 10 ⁵ , Q was 2.7.

Comparative Example 4 <Polymerization of propylene using clay mineral as co-catalyst> (1) Chemical treatment of clay mineral: 10 g of sulfuric acid and 90 m of deionized water
Then, 10 g of montmorillonite ("Kunipia F", manufactured by Kunimine Kogyo Co., Ltd.) was dispersed in the diluted sulfuric acid, and the mixture was heated to the boiling point and stirred for 6 hours. After that, the collected montmorillonite was sufficiently washed with demineralized water, and pre-dried.
It dried under reduced pressure at 00 degreeC for 2 hours. To 200 mg of the chemically treated montmorillonite was added 0.8 ml of a toluene solution of triethylaluminum having a concentration of 0.5 mol / ml, and the mixture was stirred at room temperature for 1 hour. Then, it was washed with toluene to obtain a montmorillonite-toluene slurry of 33 mg / ml.

(2) Polymerization: 0.25 mmol (in terms of Al atom) of triisobutylaluminum (manufactured by Tosoh Akzo) was introduced into a 1 L stirred autoclave. on the other hand,
Racemic dimethylsilylenebis {1,1 ′-(2-methyl-4-phenyl-4-)-4- was added to the catalyst feeder with a rupture disk.
Hydroazulenyl) zirconium dichloride 0.98
mg (1.5 μmol) diluted with toluene and introduced. Further, the above toluene slurry containing 50 mg of montmorillonite and 0.015 mmol of triisobutylaluminum (Al
(Atomic conversion) was introduced. Thereafter, 700 ml of propylene was introduced into the autoclave, and the rupture plate was cut at room temperature.
After the temperature was raised to 80 ° C., a polymerization operation was performed for 1 hour, and 205
g of polypropylene was obtained. Complex activity is 21.0 × 10
^{Was 4} . Tm of polypropylene is 148.8 ° C, M
FR was 9.9, Mn was 8.4 × 10 ⁴ , and Q was 2.4.

[0188]

According to the present invention described above, a novel transition metal compound is provided. According to the catalyst of the present invention containing such a transition metal compound, the molecular weight and stereoregularity of the produced polymer are reduced. Without this, an olefin polymer having a high molecular weight and a high melting point, which can be extruded or injection-molded, can be obtained in high yield.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Nao Iwama 1000 Kamoshita-cho, Aoba-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsubishi Chemical Research Laboratory (72) Inventor Taku Kato 1000 Kamoshita-cho, Aoba-ku, Yokohama-shi, Kanagawa Mitsubishi Inside the Yokohama Research Laboratory, Chemical Co., Ltd. (72) Toshihiko Sugano 1000 Kamoshita-cho, Aoba-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsubishi Chemical Research Laboratory (72) Noriyuki Aoshima 1000 Kamoshita-cho, Aoba-ku, Yokohama-shi, Kanagawa Mitsubishi Chemical Research Institute Yokohama Research Laboratory

Claims (8)

[Claims] 1. A novel transition metal compound represented by the following general formula (Ia). Embedded image (In the general formula (Ia), R ¹ , R ² , R ⁴ , and R ⁵ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a silicon-containing hydrocarbon group having 1 to 18 carbon atoms. Or carbon number 1
And 18 represents a halogenated hydrocarbon group. R ³ and R ⁶ each independently represent a saturated or unsaturated divalent hydrocarbon group having 3 to 10 carbon atoms which forms a condensed ring with the five-membered ring to which R ³ and R ⁶ are bonded. However, at least one of R ³ and R ⁶ has 5 to 8 carbon atoms and forms a condensed ring composed of a 7- to 10-membered ring having an unsaturated bond derived from R ³ or R ⁶ . R
⁷ and R ⁸ are each 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, 1
A nitrogen-containing hydrocarbon group having from 20 to 20 or a sulfur-containing hydrocarbon group having from 1 to 20 carbon atoms. However, at least one of R ⁷ and R ⁸ is a halogenated hydrocarbon group having 1 to 20 carbon atoms. m and n each independently represent an integer of 0 to 20. However, m and n do not become 0 at the same time. m
Alternatively, when n is 2 or more, R ^{7 and} R ⁸ may be connected to each other to form a new ring structure. Q
Is a divalent hydrocarbon group having 1 to 20 carbon atoms, a silylene group which may have a hydrocarbon group having 1 to 20 carbon atoms, an oligosilylene group, a germylene group Indicates either. X and Y each independently represent 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, It represents 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 represents a transition metal belonging to Groups 4 to 6 of the periodic table. ) 2. The method according to claim 1, wherein at least one of R ³ and R ⁶ in formula (Ia) forms a condensed ring composed of a 7-membered ring having an unsaturated bond derived from R ³ or R ⁶ . Transition metal compounds. 3. The transition metal compound according to claim 1, wherein at least one of R ⁷ and R ^{8 in} the general formula (Ia) is a halogenated aryl group or a halogenated hydrocarbon group-substituted aryl group. 4. A novel transition metal compound represented by the following general formula (Ib). Embedded image (In the general formula (Ib), R ¹ , R ² , R ⁴ , R ⁵ , Q, X,
Y and M have the same meanings as those in the above formula (Ia), and R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ ,
R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms. Ar represents an aryl group which may have a substituent. However, the condition is that a halogenated hydrocarbon group having 1 to 20 carbon atoms is bonded to at least one of the two 7-membered rings. ) 5. A catalyst component for olefin polymerization, comprising the transition metal compound according to claim 1. Description: 6. An α-olefin polymerization catalyst comprising the following essential components (A) and (B) and an optional component (C). Component (A): the transition metal compound according to any one of claims 1 to 4 Component (B): an aluminum oxy compound, an ion capable of reacting with the component (A) to convert the component (A) into a cation Compound or Lewis acid Component (C): fine particle carrier 7. An α-olefin polymerization catalyst comprising the following essential components (A) and (D) and an optional component (E). Component (A): the transition metal compound according to any one of claims 1 to 4 Component (D): an ion-exchange layered compound or an inorganic silicate excluding silicate Component (E): an organoaluminum compound 8. A method for producing an α-olefin polymer, comprising contacting the catalyst according to claim 6 or 7 with an α-olefin to carry out polymerization or copolymerization.