JP2001048894A - NEW TRANSITION METAL COMPOUND, OLEFIN POLYMERIZATION CATALYST COMPONENT AND PRODUCTION OF alpha-OLEFIN POLYMER - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new transition metal compound useful as a catalyst component for the polymerization of an α-olefin for producing an olefin polymer having high molecular weight and high melting point and moldable by extrusion molding, etc., in high production yield. SOLUTION: The transition metal compound is expressed by formula I [R1, R2, R4 and R5 are each H, a 1-6C hydrocarbon group or the like; R3 and R6 are each a 3-10C bivalent hydrocarbon group; R41 and R42 are each a 1-20C hydrocarbon group or the like; R7 and R8 are each a group of formula II (R10 and R11 are each H, a 1-6C hydrocarbon group or the like; R12 is a 3-10C bivalent hydrocarbon group; R13 is a halogen or the like; (l) is 0-20; R9 is a group other than H); (j), (k), (m) and (n) are each a non-negative integer satisfying the formulas 0<=j+m<=20 and 0<=k+n<=20; Q is a 1-20C bivalent hydrocarbon group or the like; X and Y are each H, a halogen or the like; and M is a transition metal of group 4-6 of the periodic table]. An example of the compound of formula I is the compound of formula III producible by producing 2-bromo-4- chloronaphthalene from 1-amino-4-chloronaphthalene, adding n-butyl lithium and 2-ethylazulene and then adding and reacting hafnium tetrachloride.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel transition metal compound, an α-olefin polymerization catalyst component comprising the transition metal compound, an α-olefin polymerization catalyst containing the same, and an α-olefin polymerization using the same. The present invention relates to a method for producing a united product. More specifically, 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. is there.

[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 transition metal compounds used for producing isotactic polyolefins by Kaminsky catalyst, ethylene bis (indenyl) zirconium dichloride and ethylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride are known. (For example,
No. 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 (Jou).
rnal of Molecular Catalysts
is, 56 (1989), 237-247). However, this method has a problem that the polymerization activity of the catalyst is low. Furthermore, dimethylsilylenebis-substituted cyclopentadienyl zirconium dichloride and the like have been proposed (JP-A-1-301704, Polymer).
Preprints, Japan 39 (199
0), 1614-1616, JP-A-3-12406), dimethylsilylenebis (indenyl) zirconium dichloride and the like have been proposed (JP-A-63-295).
007, JP-A-1-275609). 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.

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 the molecular weight of polypropylene (see, for example, Japanese Patent Application Laid-Open No. HEI 9-163191). 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, etc.) 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.

[0007]

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.

[0008]

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).

[0009]

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(In the general formula (Ia), R ¹ , R ² , R ⁴ ,
R ⁵ is each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a silicon-containing hydrocarbon group having 1 to 7 carbon atoms, or a halogenated hydrocarbon group having 1 to 6 carbon atoms: R ³ , R ^3
6 , each independently represents a saturated or unsaturated divalent hydrocarbon group having 3 to 10 carbon atoms: R ⁴¹ and R ⁴² are each independently a hydrocarbon group having 1 to 20 carbon atoms or a carbon number having 1 to 20 carbon atoms; 1 to 20 halogenated hydrocarbon groups: R ⁷ and R ⁸ are each independently a group represented by the following general formula (Ib):

[0011]

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(In the general formula (Ib), R ¹⁰ and R ¹¹ are
Each independently represent a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a halogenated hydrocarbon group of a silicon-containing hydrocarbon group or a 1 to 6 carbon atoms having 1 to 7 carbon atoms: R ¹² is 3 carbon
10 saturated or unsaturated divalent hydrocarbon groups: R
¹³ is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
A halogenated hydrocarbon group having 1 to 20 carbon atoms, 1 to 2 carbon atoms
0 is a silicon-containing hydrocarbon group, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms: l is an integer of 0 to 20 (when l is 2 or more, R ¹³
They may be bonded at any position to form a ring structure. ): R ⁹ represents a group other than hydrogen. J, k, m and n are 0 ≦ j + m ≦ 20 and 0 ≦ k
A non-negative integer satisfying the relationship + n ≦ 20 (provided that m and n are not simultaneously 0 and j or k is 2 or more, R ⁴¹ or R ⁴² is bonded at an arbitrary position to form a ring May form a 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, Or a germylene group: 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, or a halogenated group having 1 to 20 carbon atoms. M is a hydrocarbon group, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms: M represents a transition metal belonging to Groups 4 to 6 of the periodic table. A second aspect of the present invention resides in a novel transition metal compound represented by the following general formula (Ic).

[0013]

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(In the general formula (Ic), R ¹ , R ² , R ⁴ ,
R ⁵ , R ⁷ , R ⁸ , Q, M, X and Y are represented by the general formula (Ia)
Has the same meaning as in R ¹⁴ , R ¹⁵ ,
^{R 16, R 1 7, R} 18, R 19, R 20, R 21 are,
Each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms. The third aspect of the present invention resides in a novel transition metal compound represented by the following general formula (Id).

[0015]

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(In the general formula (Id), R ¹ , R ² , R ⁴ ,
R ⁵ , R ⁷ , R ⁸ , Q, M, X and Y are represented by the general formula (Ia)
Has the same meaning as in R ²² , R ²³ ,
^{R 24, R 2 5, R} 26, R 27, R 28, R 29, R
^{30, R 31, R 32,} R 33, R 3 4, R 35, R
³⁶ and R ³⁷ 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. )

A fourth gist of the present invention resides in the general formula (I)
a) or a catalyst component for olefin polymerization characterized by comprising a transition metal compound represented by (Ic) or (Id). A fifth gist of the present invention is that the following component (A)
And (B) and an optional component (C).
-Present in olefin polymerization catalysts; Component (A): transition metal compound represented by the above general formula (Ia) or (Ic) or (Id) Component (B): an aluminum oxy compound, which reacts with component (A) to cationize component (A) Selected from the group consisting of ionic compounds or Lewis acids capable of being converted to a component (C): fine particle carrier

According to a sixth aspect of the present invention, there is provided an α-type composition comprising the following components (A) and (D) and an optional component (E).
It is present in olefin polymerization catalysts. Component (A): transition metal compound represented by the above general formula (Ia), (Ic), or (Id) Component (D): selected from the group consisting of ion-exchange layered compounds other than silicates or inorganic silicates Component (E): organoaluminum compound A seventh aspect of the present invention is to provide an α-olefin characterized by performing polymerization or copolymerization by bringing any of the above-mentioned catalysts into contact with an α-olefin. The present invention relates to a method for producing a polymer.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
First, the transition metal compound of the present invention will be described. The transition metal compound of the present invention is represented by the following general formula (Ia).

[0020]

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The transition metal compound of the present invention has a substituent R ¹ ,
A five-membered ring ligand having R ² and R ³ and substituents R ⁴ , R
Compound (a) which is asymmetric with respect to a plane containing M, X and Y, and compound (b) which is symmetric with respect to a plane containing M, X and Y, in terms of relative position via Q and ⁵ and R ⁶
including. However, in order to produce an α-olefin polymer having a high molecular weight and a high melting point, the above-mentioned compound (a), that is, two 5-membered ring arrangements opposed to each other across a plane including M, X and Y It is preferred to use compounds whose ligands are not mirror images 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 6 carbon atoms, a silicon-containing hydrocarbon group having 1 to 7 carbon atoms, or a halogenated hydrocarbon group having 1 to 6 carbon atoms. Specific examples of the hydrocarbon group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-
Butyl, s-butyl, t-butyl, n-pentyl, n-
Examples include an alkyl group such as hexyl, cyclopropyl, cyclopentyl, and cyclohexyl; an alkenyl group such as vinyl, propenyl and cyclohexenyl; and a phenyl group.

Specific examples of the silicon-containing hydrocarbon group having 1 to 7 carbon atoms include trialkylsilyl groups such as trimethylsilyl, triethylsilyl and t-butyldimethylsilyl, and alkylsilylalkyl groups such as bis (trimethylsilyl) methyl. And the like.

In the halogenated hydrocarbon group having 1 to 6 carbon atoms, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. 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. As a specific example,
Fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, 2,2,2-trifluoroethyl,
2,2,1,1-tetrafluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluoropropyl, nonafluorobutyl, trifluorovinyl, 2-,
3-, 4-fluorophenyl, 2-, 3-, 4-chlorophenyl, 2-, 3-, 4-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 and the like can be mentioned. (Note that, in the present specification, some of the substituents and the like exemplified as examples are omitted. For example, the above-mentioned “2,3,4-fluorophenyl” is replaced with “2- It means that three compounds of "fluorophenyl", "3-fluorophenyl", and "4-fluorophenyl" were mentioned.
As another abbreviation, "2,4-, 3,5-,
"2,6-, 2,5-difluorophenyl" is defined as "2,4
-Difluorophenyl "," 3,5-difluorophenyl "," 2,6-difluorophenyl ", and" 2,5-difluorophenyl ". )

In these, R ¹ and R ⁴ are:
Hydrocarbon groups having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, and butyl, are preferred, 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. In this case, it is preferable that both of the condensed rings are 6- to 10-membered rings.

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

In the general formula (Ia), R ⁴¹ and R ⁴² each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, and n -Hexyl, cyclopropyl, cyclopentyl, cyclohexyl, alkyl groups such as methylcyclohexyl, vinyl,
Alkenyl groups such as propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl; arylalkenyl groups such as trans-styryl; phenyl, tolyl, dimethylphenyl, ethylphenyl, trimethylphenyl, 1-naphthyl, 2- And aryl groups such as naphthyl, acenaphthyl, phenanthryl and anthryl.

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. Specific examples thereof include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, 2,2,2-trifluoroethyl,
2,2,1,1-tetrafluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluoropropyl, nonafluorobutyl, trifluorovinyl, 1,1
-Difluorobenzyl, 1,1,2,2-tetrafluorophenylethyl, 2-, 3-, 4-fluorophenyl, 2-, 3-, 4-chlorophenyl, 2-, 3-, 4
-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-fluoronaphthyl, 4-chloronaphthyl, 2,4-
Difluoronaphthyl, heptafluoro-1-naphthyl,
Heptachloro-1-naphthyl, 2-, 3-, 4-trifluoromethylphenyl, 2-, 3-, 4-trichloromethylphenyl, 2,4-, 3,5-, 2,6-, 2,5
-Bis (trifluoromethyl) phenyl, 2,4-,
3,5-, 2,6-, 2,5-bis (trichloromethyl) phenyl, 2,4,6-tris (trifluoromethyl) phenyl, 4-trifluoromethylnaphthyl, 4-
Examples include a trichloromethylnaphthyl group and a 2,4-bis (trifluoromethyl) naphthyl group.

In the general formula (Ia), R ⁷ and R ⁸ are each independently represented by the following general formula (Ib).

[0031]

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In the general formula (Ib), R ¹⁰ and R ¹¹ are each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a silicon-containing hydrocarbon group having 1 to 7 carbon atoms or a carbon atom having 1 carbon atom. And represents 6 to 6 halogenated hydrocarbon groups. The above carbon number 1
As specific examples of the hydrocarbon groups of to 6, methyl, ethyl,
alkyl groups such as n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclopentyl, cyclohexyl, vinyl, propenyl, cyclohexenyl, etc. And a phenyl group.

Specific examples of the silicon-containing hydrocarbon group having 1 to 7 carbon atoms include trialkylsilyl groups such as trimethylsilyl, triethylsilyl and t-butyldimethylsilyl, and alkylsilylalkyl groups such as bis (trimethylsilyl) methyl. And the like.

In the halogenated hydrocarbon group having 1 to 6 carbon atoms, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. 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. As a specific example,
Fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, 2,2,2-trifluoroethyl,
2,2,1,1-tetrafluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluoropropyl, nonafluorobutyl, trifluorovinyl, 2-,
3-, 4-fluorophenyl, 2-, 3-, 4-chlorophenyl, 2-, 3-, 4-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 and the like can be mentioned.

Among them, hydrogen atom, methyl group, ethyl group, propyl group, i-propyl, n-butyl, i-
Alkyl group such as butyl group, silicon-containing hydrocarbon group such as trimethylsilyl and triethylsilyl, or fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, etc. Is more preferable, a hydrogen atom or an alkyl group such as a methyl group, an ethyl group, a propyl group and an i-propyl group is more preferable, and a hydrogen atom is particularly preferable.

[0036] Specific examples of the above ^{R 12} is trimethylene, tetramethylene, pentamethylene, divalent saturated hydrocarbon group of hexamethylene etc., propenylene, 2-butenylene, 1,3-butadienylene, 1-pentenylene,
2-pentenylene, 1,3-pentadienylene, 1,4
-Pentadienylene, 1-hexenylene, 2-hexenylene, 3-hexenylene, 1,3-hexadienylene,
Examples thereof include divalent unsaturated hydrocarbon groups such as 1,4-hexadienylene, 1,5-hexadienylene, 2,4-hexadienylene, 2,5-hexadienylene, and 1,3,5-hexatrienylene. Of these, trimethylene, tetramethylene, propenylene, 1,3
-Butadienylene group, pentamethylene group, 1,3-pentadienylene group, 1,4-pentadienylene group or 1,3,5-hexatrienylene group is preferred, and trimethylene group, tetramethylene group, propenylene group, 1,3
-Butadienylene group is more preferable, and tetramethylene group or 1,3-butadienylene group is particularly preferable.

R ¹³ is a halogen atom, having 1 carbon atom.
To 20 hydrocarbon groups, halogenated hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing hydrocarbon groups having 1 to 20 carbon atoms, oxygen-containing hydrocarbon groups having 1 to 20 carbon atoms or 1 to 20 carbon atoms
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.

Specific examples of the 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,
And aryl groups such as dimethylphenyl, ethylphenyl, trimethylphenyl, 1-naphthyl, 2-naphthyl, acenaphthyl, phenanthryl and anthryl.

In the above-mentioned 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. Specific examples thereof include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, 2,2,2-trifluoroethyl,
2,2,1,1-tetrafluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluoropropyl, nonafluorobutyl, trifluorovinyl, 1,1
-Difluorobenzyl, 1,1,2,2-tetrafluorophenylethyl, 2-, 3-, 4-fluorophenyl, 2-, 3-, 4-chlorophenyl, 2-, 3-, 4
-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-fluoronaphthyl, 4-chloronaphthyl, 2,4-
Difluoronaphthyl, heptafluoro-1-naphthyl,
Heptachloro-1-naphthyl, 2-, 3-, 4-trifluoromethylphenyl, 2-, 3-, 4-trichloromethylphenyl, 2,4-, 3,5-, 2,6-, 2,5
-Bis (trifluoromethyl) phenyl, 2,4-,
3,5-, 2,6-, 2,5-bis (trichloromethyl) phenyl, 2,4,6-tris (trifluoromethyl) phenyl, 4-trifluoromethylnaphthyl, 4-
Examples include a trichloromethylnaphthyl group and a 2,4-bis (trifluoromethyl) naphthyl group.

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.

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.

In the general formula (Ib), 1 represents an integer of 0 to 20, particularly preferably 0 to 8. When 1 is an integer of 2 or more, the groups R ¹³ may be the same or different from each other. When l is 2 or more, each of R ¹³
They may be connected to each other to form a new ring structure.

In the general formula (Ib), R ⁹ represents a group other than hydrogen, and includes a halogen atom, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms, and a group having 1 to 20 carbon atoms.
A silicon-containing hydrocarbon group, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms or a nitrogen-containing 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.

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. Specific examples thereof include fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, 2,2,2-trifluoroethyl,
2,2,1,1-tetrafluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluoropropyl, nonafluorobutyl, trifluorovinyl, 1,1
-Difluorobenzyl, 1,1,2,2-tetrafluorophenylethyl, 2-, 3-, 4-fluorophenyl, 2-, 3-, 4-chlorophenyl, 2-, 3-, 4
-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-fluoronaphthyl, 4-chloronaphthyl, 2,4-
Difluoronaphthyl, heptafluoro-1-naphthyl,
Heptachloro-1-naphthyl, 2-, 3-, 4-trifluoromethylphenyl, 2-, 3-, 4-trichloromethylphenyl, 2,4-, 3,5-, 2,6-, 2,5
-Bis (trifluoromethyl) phenyl, 2,4-,
3,5-, 2,6-, 2,5-bis (trichloromethyl) phenyl, 2,4,6-tris (trifluoromethyl) phenyl, 4-trifluoromethylnaphthyl, 4-
Examples include a trichloromethylnaphthyl group and a 2,4-bis (trifluoromethyl) naphthyl group.

Specific examples of the 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,
And aryl groups such as dimethylphenyl, ethylphenyl, trimethylphenyl, 1-naphthyl, 2-naphthyl, acenaphthyl, phenanthryl and anthryl.

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.

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.

Among these, a fluorine atom, a chlorine atom,
Halogen atom such as bromine atom, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, 2,
2,2-trifluoroethyl, 2,2,1,1-tetrafluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluoropropyl, nonafluorobutyl, 2-, 3-, 4-fluorophenyl, 2-, 3-,
4-chlorophenyl, 2-, 3-, 4-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-fluoronaphthyl, 4-chloronaphthyl, 2,4-difluoronaphthyl, heptafluoro-1- Naphthyl, heptachloro-1
-Naphthyl, 2-, 3-, 4-trifluoromethylphenyl, 2-, 3-, 4-trichloromethylphenyl,
2,4-, 3,5-, 2,6-, 2,5-bis (trifluoromethyl) phenyl, 2,4-, 3,-, 2,6
-, 2,5-bis (trichloromethyl) phenyl, 2,
4,6-tris (trifluoromethyl) phenyl, 4-
Halogenated hydrocarbon groups such as trifluoromethylnaphthyl, 4-trichloromethylnaphthyl, 2,4-bis (trifluoromethyl) naphthyl, methyl, ethyl, n-propyl, i-propyl, cyclohexyl, phenylethyl, phenyl, tolyl And hydrocarbon groups such as dimethylphenyl, ethylphenyl, trimethylphenyl, 1-naphthyl and 2-naphthyl. Furthermore, a fluorine atom, a chlorine atom, trifluoromethyl, chloromethyl,
-, 4-fluorophenyl, 2-, 3-, 4-chlorophenyl, 2,4,6-trifluorophenyl, 2,4
6-trichlorophenyl, pentafluorophenyl, pentachlorophenyl, 2-, 3-, 4-trifluoromethylphenyl, 2-, 3-, 4-trichloromethylphenyl, methyl, ethyl, n-propyl, i-propyl,
Cyclohexyl, phenyl, tolyl and the like are particularly preferred.

In the general formula (Ia), j, k, m and n are
It is a non-negative integer satisfying the relationship of 0 ≦ j + m ≦ 20 and 0 ≦ k + n ≦ 20. When j, m, k and / or n is an integer of 2 or more, a plurality of groups R ⁷ and / or R ⁴¹ (R
⁸ and / or R ⁴² ) may be the same or different from each other. When j and / or k are 2 or more, R ⁴¹ and / or R ⁴² may be connected to each other to form a new ring structure. R ^{3 of} R ⁷ and R ⁸
And the bonding position to R ⁶ is not particularly limited, but is preferably a carbon (carbon at the α-position) adjacent to each of the five-membered rings.

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 are present on the above-mentioned 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-trimethylene, 1,4-tetramethylene, 1,
Alkylene groups such as 2-cyclohexylene and 1,4-cyclohexylene; arylalkylene groups such as (methyl) (phenyl) methylene and diphenylmethylene; silylene groups; methylsilylene, dimethylsilylene, diethylsilylene, di (n- Alkyl silylene groups such as propyl) silylene, di (i-propyl) silylene and di (cyclohexyl) silylene; (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene and methyl (tolyl) silylene; aryl such as diphenylsilylene A silylene group;
Alkyl oligosilylene group such as tetramethyldisilylene; germylene group; alkylgermylene group in which silicon of the above-mentioned divalent silylene group having a hydrocarbon group having 1 to 20 carbon atoms is replaced with germanium; (alkyl) (aryl) Germylene group; and 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 halogenated hydrocarbon group having 1 to 20 carbon atoms,
C1-C20 silicon-containing hydrocarbon group, C1-C2
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.

Specific examples of the 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,
And aryl groups such as dimethylphenyl, ethylphenyl, trimethylphenyl, 1-naphthyl, 2-naphthyl, acenaphthyl, phenanthryl and anthryl.

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.

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, 2,2,2
1,1-tetrafluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluoropropyl, nonafluorobutyl, trifluorovinyl, 1,1-difluorobenzyl, 1,1,2,2-tetrafluorophenylethyl, 2- , 3-, 4-fluorophenyl, 2
-, 3-, 4-chlorophenyl, 2-, 3-, 4-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-fluoronaphthyl, 4-chloronaphthyl, 2,4-difluoronaphthyl, hepta Fluoro-1-naphthyl, heptachloro-1-naphthyl, 2-, 3-, 4-trifluoromethylphenyl, 2-, 3-, 4-trichloromethylphenyl, 2,4-, 3,5-, 2,6 -, 2,5-bis (trifluoromethyl) phenyl, 2,4-, 3,5-,
2,6-, 2,5-bis (trichloromethyl) phenyl, 2,4,6-tris (trifluoromethyl) phenyl, 4-trifluoromethylnaphthyl, 4-trichloromethylnaphthyl, 2,4-bis (tri Fluoromethyl)
And a naphthyl group.

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 are a hydrogen atom, a halogen atom, a carbon number of 1 to
20 hydrocarbon groups and nitrogen-containing hydrocarbon groups having 1 to 20 carbon atoms are preferable, and halogen atoms, hydrocarbon groups having 1 to 20 carbon atoms and nitrogen-containing hydrocarbon groups having 1 to 20 carbon atoms are more preferable, and chlorine atoms , A methyl group, an i-butyl group, a phenyl group, a benzyl group, a dimethylamino group or a diethylamino group.

In the general formula (Ia), M is the fourth to sixth periodic table.
It represents a Group 4 transition metal, preferably a Group 4 transition metal of titanium, zirconium and hafnium, more preferably zirconium or hafnium. The transition metal compound of the present invention can be synthesized by any method suitable for the type of substituent or bond. A typical synthetic route is as shown in the following reaction formula. Note that H in the reaction formula
₂ R ^a and _H 2 ^{R b} respectively show the following such a structure.

[0061]

Embedded image (R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ ,
R ⁴¹ , R ⁴² , and j, k, m, n are represented by the general formula (Ia)
As defined in. )

H₂R^a+ N-C₄H₉Li → HR^aLi
+ C₄H₁₀  H₂R^b+ N-C₄H₉Li → HR^bLi + C₄H₁₀  HR^aLi + HR^bLi + QCl₂→ HR^a-Q-HR
^b+ 2LiCl HR^a-Q-HR^b+ 2n-C₄H₉Li → LiR^a−
Q-LiR^b+ 2C₄H ₁₀  LiR^a-Q-LiR^b+ HfCl₄→ R^a-Q-
R^b) HfCl₂+ 2LiCl

The metal salt of a cyclopentadienyl compound such as HR ^a Li and HR ^b Li is formed by, for example, adding an aryl group or the like as described in European Patent No. 679418. You may synthesize | combine by the method as accompanying. Specifically, an aryllithium compound and an azulene compound are reacted in an inert solvent to generate a lithium salt of a dihydroazulenyl compound. As the aryllithium compound, phenyllithium, naphthyllithium, fluoronaphthyllithium, biphenylyllithium, fluorobiphenylyllithium 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 represented by the following general formula (Ic).

[0065]

Embedded image

In the general formula (Ic), R ¹ , R ² , R ⁴ , R
⁵ , R ⁷ , R ⁸ , Q, M, X, and Y represent the same meaning as described above. R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R
¹⁹ , R ²⁰ and R ²¹ 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. R ¹⁴ , R ¹⁵ , R
It is preferable that all of R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ are hydrogen atoms. Next, the third transition metal compound of the present invention will be described. This compound is represented by the following general formula (Id).

[0067]

Embedded image

In the general formula (Id), R ¹ , R ² , R ⁴ , R
⁵ , R ⁷ , R ⁸ , Q, M, X, and Y represent the same meaning as described above. R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R
²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R
³³ , R ³⁴ , R ³⁵ , R ³⁶ , and R ³⁷ 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. R ²² ,
R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R
^{29, R 30, R 31,} R 32, R 33, R 34, R
³⁵ , R ³⁶ and R ³⁷ are preferably all hydrogen atoms.

Specific examples of the transition metal compound of the present invention are shown in the following table. In addition, the three-dimensional structure means both the compound having asymmetry and the compound having symmetry in the present invention. In order to understand the structure of the compound, (15)
The structural formulas and names of hafnium dichloride described in the above are shown below.
The compound of this structural formula is referred to as dichloro {1,1′-dimethylsilylenebis [2-methyl-4- (4-chloro-2-naphthyl) -4H-azulenyl]} hafnium.

[0070]

Embedded image

In the table, the general formula (Ia ') of the compound is shown below.

[0072]

Embedded image

Azu, Ind, Az used in the table
u-H, Ind-H, Naph, Naph-H show the following structures. The description of R ^{9 to} R ¹³ in the table is the description of the general formula (Ib).

[0074]

Embedded image

[0075]

[Table 1]

[0076]

[Table 2]

[0077]

[Table 3]

[0078]

[Table 4]

[0079]

[Table 5]

[0080]

[Table 6]

[0081]

[Table 7]

[0082]

[Table 8]

[0083]

[Table 9]

[0084]

[Table 10]

[0085]

[Table 11]

[0086]

[Table 12]

[0087]

[Table 13]

[0088]

[Table 14]

[0089]

[Table 15]

[0090]

[Table 16]

In the compounds as described above, one or both of the two chlorine atoms corresponding to the X and Y moieties in the general formula (I) are hydrogen, fluorine, bromine, iodine, methyl, methyl, Phenyl group, fluorophenyl group,
Compounds replacing benzyl, methoxy, dimethylamino, diethylamino and the like can also be mentioned. The central metal (M) of the compound exemplified above is titanium, zirconium, tantalum,
Compounds in place of niobium, vanadium, tungsten, molybdenum and the like can also be exemplified. Among these,
Group 4 transition metal compounds such as zirconium, titanium and hafnium 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. These catalysts
In any case, the transition metal compound of the present invention described above is used as the component (A).
Included as First, as component (B) in addition to component (A),
The α-amino acid compound according to the present invention, comprising an aluminum oxy compound, an ionic compound capable of reacting with the component (A) to convert the component (A) into a cation, or a Lewis acid, and a fine particle carrier as an optional component (C). Olefin polymerization catalyst (1)
Will be described. 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 belong to either one. Specific examples of the aluminum oxy compound include compounds represented by the following general formulas (II), (III) and (IV).

[0093]

Embedded image

In each of the above formulas, R ³⁸ represents a hydrogen atom or a hydrocarbon residue, preferably a hydrocarbon residue having 1 to 10 carbon atoms, particularly preferably a hydrocarbon residue having 1 to 6 carbon atoms. The plurality of R ³⁸ may be the same or different. 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,
It is obtained by reacting one kind of trialkylaluminum or two or more kinds of trialkylaluminum with water.
Specifically, (a) methylalumoxane, ethylalumoxane, propylalumoxane, butylalumoxane, obtained from one kind of trialkylaluminum and water,
Examples thereof include isobutylalumoxane, (b) methylethylalumoxane, methylbutylalumoxane, and methylisobutylalumoxane obtained from two kinds of trialkylaluminums and 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. (A) A method in which a trialkylaluminum is directly reacted with water in the presence of a suitable organic solvent such as toluene, benzene, or ether. (B) A method of reacting a trialkylaluminum with a salt hydrate having water of crystallization, for example, a hydrate of copper sulfate or aluminum sulfate. (C) A method of reacting trialkylaluminum with water impregnated in silica gel or the like. (D) A method in which trimethylaluminum and triisobutylaluminum are mixed and then directly reacted with water in the presence of a suitable organic solvent such as toluene, benzene, or ether.

(E) A method in which a mixture of trimethylaluminum and triisobutylaluminum is heated and reacted with a salt hydrate having water of crystallization, for example, a hydrate of copper sulfate or aluminum sulfate. (F) A method in which silica gel or the like is impregnated with water, treated with triisobutylaluminum, and then additionally treated with trimethylaluminum. (G) A method in which methylalumoxane and isobutylalumoxane are synthesized by a known method, and a predetermined amount of these two components is mixed and reacted by heating. (H) A method in which a salt having water of crystallization such as copper sulfate pentahydrate and trimethylaluminum are added to an aromatic hydrocarbon solvent such as benzene and toluene and reacted at a temperature 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 general formula (I
The compound represented by V) is a compound of one kind of trialkylaluminum or two or more kinds of trialkylaluminum and an alkylboronic acid represented by the following general formula (V):
It can be obtained by a reaction of 1 to 1: 1 (molar ratio).
In the general formula (V), R ³⁹ represents a hydrocarbon residue having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms or a halogenated hydrocarbon group. R ³⁹ B (OH) ₂ (V)

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). [K] ^{e +} [Z] ^e- (VI)

In the general formula (VI), K is a cation component, and examples thereof include a carbonium cation, a tropylium cation, an ammonium cation, an oxonium cation, 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 ions, ferrocenium ions and the like can be mentioned.

In the above general formula (VI), Z is an anion component, which is a component (generally a non-coordinating component) that 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.

(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.

(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) phosphorous, etc. (e) Tetraphenyl arsenic, tetrakis (pentafluorophenyl) arsenic, etc. (f) Tetraphenylantimony, tetrakis (G) decaborate, undecaborate, carbadodecaborate, decachlorodecaborate, etc. Lewis acids, especially Lewis acids capable of converting component (A) into cations, include various organic boron compounds. Examples thereof include compounds, metal halide compounds, and solid acids, and specific examples thereof include the following compounds.

(A) Triphenylboron, tris (3,
Organic boron compounds such as 5-difluorophenyl) boron and tris (pentafluorophenyl) boron (b) aluminum chloride, aluminum bromide, aluminum iodide, magnesium chloride, magnesium bromide, magnesium iodide, magnesium chloride bromide, chloride Metal halide compounds such as magnesium iodide, magnesium bromide iodide, magnesium chloride hydride, magnesium chloride hydroxide, magnesium bromide hydroxide, magnesium chloride alkoxide, magnesium bromide alkoxide, etc. (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 composed of an inorganic or organic compound and having a particle size of usually 5 μm to 5 mm, preferably 10 μm to 2 mm. As the above-mentioned inorganic carrier, for example, SiO ₂ , A
l 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 , Si
A composite oxide such as O ₂ —Al ₂ O ₃ —MgO is 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.

The α-olefin polymerization catalyst 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; and alkoxy such as phenyl borate, dimethylmethoxyaluminum, phenyl phosphite, tetraethoxysilane, and diphenyldimethoxysilane. Compounds can be included.

The optional components other than the 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 and 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
As the transition metal atom, usually ¹⁰ -7 ^~10 2 mmo / L
, Preferably in the range of 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 100 to 2
× 10 ^4, more preferably is in the range of 100 to 10 ^4. On the other hand, when an ionic compound or a Lewis acid is used as the component (B), the molar ratio thereof to the transition metal is usually 0.1 to 1000, preferably 0.5 to 10
0, more preferably 1 to 50.

Next, the α-olefin polymerization catalyst (2) of the present invention containing, as the component (D), an ion-exchange layered compound or an inorganic silicate other than silicate, and an organic aluminum compound as the optional component (E). ) Will be described. Examples of the ion-exchangeable layered compound include an ionic crystalline compound having a layered crystal structure such as a hexagonal close-packed type, an antimony type, a CdCl ₂ type, and a CdI ₂ type. Zr (HAsO ₄ ) ₂・
H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr (KP
_{O 4) 3 · 3H 2 O} , α-Ti (HPO 4) 2, α-T
i (HAsO ₄ ) ₂ .H ₂ O, α-Sn (HPO ₄ ) ₂
・ H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (HPO
₄ ) ₂ , crystalline acidic salts of polyvalent metals such as γ-Ti (NH ₄ PO ₄ ) ₂ .H ₂ O.

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.

Ion-exchangeable layered compound and inorganic silicate
May be used untreated, but may be replaced
Functional metal cations from the following salts and / or acids:
It is preferable to perform ion exchange with the dissociated cation. Up
Salts used for the ion exchange described above,
Cation containing at least one atom selected from the group consisting of
And preferably a compound containing 1 to 14 groups.
Contains at least one atom selected from the group consisting of
A cation and a halogen atom, an inorganic acid or an organic acid.
At least one atom or group of atoms selected from the group
A compound comprising an anion derived from the
Is preferably selected from the group consisting of group 2-14 atoms
A cation containing at least one atom, Cl, Br,
I, F, PO₄, SO₄, NO₃, CO₃, C₂O₄,
ClO₄, OOCCH₃, CH₃COCHCOCH₃,
OCI₂, O (NO₃) ₂, O (ClO₄)₂, O (S
O₄), OH, O₂Cl₂ , OCI₃, OOCH and
OOCCH₂CH₃At least selected from the group consisting of
It is a compound consisting of a kind of anion. Also these
Two or more salts may be used simultaneously.

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.
1 to 30% by weight, the treatment temperature is in the range of room temperature to the boiling point of the solvent to be used, and the treatment time is preferably selected from the conditions of 5 minutes to 24 hours. . 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 (D) 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 (D) contains adsorbed water and interlayer water when treated in an aqueous solution. 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, the component (D) is preferably used after removing the above-mentioned adsorbed water and interlayer water. 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 (D) comes into contact with the essential component (A) and the optional component (E) described below. 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). ^{_{AlR 40 a P 3-a (}} VII)

In the general formula (VII), R ⁴⁰ has 1 to 1 carbon atoms.
20 represents a hydrocarbon group, 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 trimethylaluminum,
Triethyl aluminum, tripropyl aluminum,
Examples thereof include halogen or alkoxy-containing alkyl aluminum such as trialkyl aluminum such as triisobutyl aluminum, diethyl aluminum monochloride, and diethyl aluminum monomethoxide. 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 method of contacting the component (A) and the component (D) with the optional component (E) is not particularly limited, but the following methods can be exemplified.

(1) A method of bringing component (A) into contact with component (D). (2) A method of adding an optional component (E) after bringing the component (A) into contact with the component (D). (3) A method of bringing the component (A) into contact with the optional component (E) and then adding the component (D). (4) A method of adding the component (A) after bringing the component (D) into contact with the optional component (E). (5) A method in which the components (A), (D), and (E) are simultaneously contacted.

This contact may be performed not only at the time of preparing the catalyst but also at the time of prepolymerization with olefin or at the time of polymerization of olefin. During or after the contact of each of the above components, a polymer such as polyethylene or polypropylene, or a solid of an inorganic oxide such as silica or alumina may coexist or may be brought into contact.

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 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 above components are as follows. That is, the amount of the component (A) is usually 10 g / g of the component (D).
^{-4 to} 10 mmol, preferably 10 ^{-3 to 5} mmol
And component (E) is usually 0.01 to 10 ⁴ mmol
1, preferably 0.1 to 100 mmol. Also,
Aluminum atomic ratio in the transition metal component of component (A) (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 optional component (E) may be newly used in combination. On this occasion,
The amount of optional component (E) used will be 1: 0 to 10 ⁴ , preferably 1: 1 to 10 ⁴ , in atomic ratio of aluminum in optional component (E) to transition metal in component (A). Is chosen like this.

Next, a 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, α-olefins having usually 2 to 20, preferably 2 to 10 carbon atoms are 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 the above-mentioned α-olefins or copolymerization of α-olefins with other monomers. Other monomers copolymerizable with the α-olefin include, for example, butadiene, 1,4-
Hexadiene, 1,5-hexadiene, 7-methyl-
1,6-octadiene, 1,8-nonadiene, 1,9-
Conjugated and non-conjugated dienes such as 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-olefin, effects such as an increase in the melting point of the obtained polymer can be achieved, as shown in Examples described later. Although the reason is not clear, it can be presumed as follows. That is, the R ⁹ substituent of the substituents R ⁷ and / or R ⁸ in the transition metal compound of the present invention becomes sterically bulky as compared with the unsubstituted one, and forms an appropriate steric hindrance and shape. As a result, the action of regulating the growth direction of the polymer chain and the coordination direction of the monomer is enhanced, and the ratio of erroneous insertion of the monomer is sharply reduced,
As a result, it is estimated that a polymer having a high melting point can be obtained.

[0136]

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) MFR measurement: 6 g of an acetone solution (0.6% by weight) of a heat stabilizer (BHT) was added to 6 g of the polymer. 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: ratio (Mw / Mw) of weight average molecular weight (Mw) and number average molecular weight (Mn) obtained by GPC
Mn = Q value). GPC device is Water
rs Co., Ltd. "150CV type" was used. Ortho-dichlorobenzene was used as the solvent, and the measurement temperature was 135 ° C. (3) Measurement of melting point: DSC (TA200 manufactured by DuPont)
"Type 0"), the temperature was raised and lowered from 20 to 200 [deg.] C. once at 10 [deg.] C./min. (4) Measurement of the amount of 2,1-insertion and 1,3-insertion of propylene that causes position irregularity in propylene polymerization: the following partial structure (VIII) containing 2,1-insertion of propylene that is positionally irregular And 1,3- of propylene
The following partial structure (IX) including the insertion is shown below.

[0138]

Embedded image

It is considered that such a partial structure is caused by positional irregularities generated during the polymerization of the propylene polymer. The propylene monomer is usually a 1,2-insertion in which the methylene side is bonded to the catalyst center metal side, but is rarely a 2,1-insertion.
-Insertion or 1,3-insertion. 2,1-
The monomer polymerized by the insertion forms a regiorandom unit represented by the above partial structure (VIII) in the polymer chain. Further, the monomer polymerized by the 1,3-insertion forms a position irregular unit represented by the partial structure (IX) in the polymer chain. First, the polymer sample
^{A 13} C-NMR measurement is performed. The method is as follows.
100 to 5 in a 10 mmφ NMR measurement sample tube
A sample of 00 mg was completely dissolved in a solvent obtained by adding about 0.5 ml of deuterated benzene as a lock solvent to about 2.0 ml of o-dichlorobenzene, and measured at 130 ° C. by a complete proton decoupling method. The measurement conditions were flip angle 60 °, repetition 5 seconds, 10,000 to 200
00 times. . Then, 2,
The 1-insertion and 1,3-insertion amounts are determined.

[0140]

(Equation 1)

A, A, A, A, A, A, A, A
, A and A are 42.3 ppm and 35.
9ppm, 38.6ppm, 30.6ppm, 36.0p
pm, 31.5 ppm, 31.0 ppm, 37.2 pp
m, the area of 27.4 ppm, and the partial structure (VII
The abundance ratio of carbon shown in I) and (IX) is shown.

Example 1 Synthesis of 2-bromo-4-chloronaphthalene: (1) Synthesis of 1-amino-3-bromo-4-chloronaphthalene 1-amino-4-chloronaphthalene (12.87 g, 7
2.4 mmol) in chloroform (86 ml) solution,
A solution of bromine (11.58 g, 72.4 mmol) in chloroform (45 ml) was added dropwise with stirring at room temperature for 1 hour. After dropping, chloroform (70 m
l) In addition, the mixture was further stirred at room temperature for 1 hour. After filtration, the precipitate was washed with chloroform (20 ml), and the washed precipitate was dried under reduced pressure at 50 ° C. for 2 hours. After the dried precipitate was dissolved in ethanol (200 ml), NaHCO
In addition ₃ saturated water (500 ml), and stirred for 5 minutes. After collecting the precipitate, an organic substance was extracted with chloroform (500 ml). The extract was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain a crude product. Further, the crude product was recrystallized by adding high-temperature hexane to obtain 1-
Amino-3-bromo-4-chloronaphthalene (15.6
2g, 84.1%). ¹ H-NMR (300 MHz, CDCl ₃ ) δ 4.5
0 to 4.80 (br, 2H), 7.54 to 7.61
(M, 3H), 7.82 (d, J = 9.0 Hz, 1
H), 8.21 (d, J = 9.9 Hz, 1H).

(2) Synthesis of 2-bromo-4-chloronaphthalene 1-amino-3-bromo-4-chloronaphthalene (1
0.00g, 40.0mmol) with glacial acetic acid (166m
l) and water (33 ml) were added and the suspension was cooled to 8 ° C. While maintaining the temperature of the suspension at 15 ° C. or lower, concentrated sulfuric acid (47 ml) was slowly added dropwise. After dropping, sodium nitrite (3.67 g, 53.2 mmol)
A solution of l) in water (10 ml) was slowly added dropwise while keeping the temperature of the suspension below 10 ° C. After completion of the dropwise addition, the mixture was further stirred for 1 hour while maintaining the temperature at 8 ° C. The suspension solution was heated to 65 ° C. with copper monoxide (8.30 g, 5
8.0 mmol) in methanol (330 ml). Thereafter, the suspension was slowly cooled to room temperature, water (330 ml) was added thereto, and hexane (500
ml). The extracted solution was NaHCO ₃ saturated water and N
After washing with aCl saturated water, drying over magnesium sulfate and distilling off the solvent under reduced pressure, a crude product was obtained. Further, the crude product was purified using a silica gel column (developing solvent: hexane) to obtain 2-bromo-4-chloronaphthalene (8.63 g, 89.3%). ¹ H-NMR (300 MHz, CDCl ₃ ) δ 7.5
4 to 7.69 (m, 3H), 7.82 (d, J = 6.9)
Hz, 1H), 7.94 (s, 1H), 8.22 (d,
J = 6.6 Hz, 1H).

(3) Synthesis of racemic dichloro {1,1′-dimethylsilylenebis [2-ethyl-4- (4-chloro-2-naphthyl) -4H-azulenyl]} hafnium: 2-bromo-4 -Chloronaphthalene (2.50 g,
10.30 mmol) in diethyl ether (7.5 m).
l) and hexane (50 ml) in a mixed solvent.
Butyl lithium solution in hexane (6.8 ml, 10.4
mmol, 1.53N) was added dropwise at 19 ° C. At 20 ° C
The mixture was stirred for 1.0 hour, 2-ethylazulene (1.47 g, 9.41 mmol) was added to the solution at 5 ° C, and the mixture was stirred at room temperature for 1.0 hour. On the way, diethyl ether (5.0
ml) was added. After standing, the supernatant solution was removed, and the precipitate was washed with hexane (20 ml). Hexane (25 ml) was added thereto, cooled to 0 ° C., and tetrahydrofuran (25 ml) was added. N-methylimidazole (30
μl) and dimethyldichlorosilane (0.51 ml, 4.
20 mmol) and stirred at 0 ° C. for 1.5 hours. Thereafter, a saturated aqueous solution of ammonium chloride (50 ml) was added, and the mixture was separated. The organic phase was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. As a crude product, dimethylsilylenebis [2-ethyl-4- ( 4-chloro-2-naphthyl) -1,4-dihydroazulene] (3.11 g) was obtained.

Next, the reaction product (3.0) obtained above was obtained.
9 g, 4.21 mmol) in diethyl ether (44 m
l) and dissolved in n-butyllithium at -70 ° C.
Solution (5.5 ml, 8.41 mmol, 1.53 mol)
1 / l) was added dropwise, the temperature was gradually raised, and the mixture was stirred at room temperature for 2 hours.
Was. The solvent was distilled off, and toluene (99 ml) and diethyl ether were added.
-Tel (11 ml) was added. Cool to -70 ° C, tetrasalt
Hafnium bromide (1.375 g, 4.29 mmol) was added.
Then, the temperature was gradually raised and the mixture was stirred at room temperature overnight. The resulting slurry
-Concentrate the solution to one-third and filter using celite
Then, the mixture was washed with toluene (15 ml), and the filtrate was concentrated.
Wash the crude product 5 times with diethyl ether (10 ml)
Then, dichloro {1,1′-dimethylsilylenebis [2-
Ethyl-4- (4-chloro-2-naphthyl) -4H-a
Zurenyl] racemic hafnium (1.20 g, yield
27%).¹ H-NMR (300 MHz, CDCl₃) Δ 1.0
0 (s, 6H, SiMe ₂), 1.00 (t, J = 7.
8Hz, 6H, 2-CH₃CH₂), 2.40-2.5
9 (m, 2H, 2-CH₃CHH), 2.59-2.7.
5 (m, 2H, 2-CH₃CHH), 5.22 (d, J
= 4.2 Hz, 2H, 4-H), 5.83 to 5.93.
(M, 6H), 6.04 to 6.08 (m, 2H), 6.
80 (d, J = 12 Hz, 2H), 7.50 to 7.60
(M, 4H, arom), 7.59 (d, J = 1.5H)
z, 2H, arom), 7.73 (d, J = 0.6H)
z, 2H, arom), 7.81 to 7.84 (m, 2
H, arom), 8.22-8.25 (m, 2H, ar)
om).

(4) Polymerization of propylene using methylalumoxane as a co-catalyst: In a 2-liter stirred autoclave, methylalumoxane (MMA manufactured by Tosoh Akzo Co., Ltd.) was used.
O ") (8.0 mmol) in terms of Al atom).
On the other hand, the above racemate (1.5 mg) was diluted with toluene and introduced into a catalyst feeder with a rupturable plate. Then, after introducing propylene (1500 ml) into the autoclave, the rupture plate was cut at room temperature, the temperature was raised to 70 ° C., and the polymerization operation was performed for 1 hour to obtain polypropylene (42 g). The complex activity was 2.8 × 10 ⁵ . The Tm of the polypropylene was 159.4 ° C., and the MFR was 0.09.

Example 2 <Polymerization of α-olefin using clay mineral as cocatalyst> (1) Chemical treatment of clay mineral: dilute sulfuric acid consisting of sulfuric acid (10 g) and demineralized water (90 ml) was added to montmorillonite (10
g) (Kunimine Industries “Kunipia F”) is dispersed,
After the temperature was raised to the boiling point, the mixture was 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 this chemically treated montmorillonite (200 mg) was added a toluene solution (1.0 ml) of triethylaluminum having a concentration (0.4 mol / l), and the mixture was stirred at room temperature for 1 hour. Thereafter, the resultant was washed with toluene, and a montmorillonite-toluene slurry (33 mg /
ml).

(2) Polymerization: Triisobutylaluminum (manufactured by Tosoh Akzo) (0.25 mmol) (in terms of Al atom) was introduced into a 1 L stirred autoclave. On the other hand, Example 1 was applied to the catalyst feeder with a rupture disk.
The racemate (1.41 mg) obtained in (3) was diluted with toluene and introduced, and the above slurry containing montmorillonite (50 mg) and triisobutylaluminum (0.015 mmol) (in terms of Al atom) were further introduced. .
Thereafter, propylene (700 ml) was introduced into the autoclave, and the rupture plate was cut at room temperature.
Polymerization was carried out for an hour to obtain polypropylene (116 g).
The catalyst activity was 2,300 and the complex activity was 8.2 × 10 ⁴ . The Tm of the polypropylene was 157.4 ° C., the MFR was 0.49, the Mw was 5.0 × 10 ⁵ , and the Q was 2.9. According to NMR analysis of the polymer, 2,1-insertion was 0.30% and 1,3-insertion was 0.11%.

Example 3 (1) Dichloro {1,1′-dimethylsilylenebis [2-
Methyl-4- (4-chloro-2-naphthyl) -4H-a
[Zulenyl]｝ A mixture of racemic-meso isomers of hafnium
Composition: 2-bromo-4-chloronaphthalene (2.50 g,
10.30 mmol) in diethyl ether (2.5 m
l) and hexane (50 ml) in a mixed solvent.
Butyllithium solution in hexane (6.72 ml, 10.
4mmol, 1.53N) was added dropwise at 10-18 ° C.
Stir at 20 ° C for 20 minutes and add 2-methyl
Add azulene (1.35 g, 9.52 mmol) and add water
The bath bath was removed and the mixture was stirred at room temperature for 30 minutes. Settle the supernatant
After removing the liquid, hexane (20 ml) was added, and the mixture was stirred and allowed to stand.
Then, the supernatant was removed. Repeat the same operation once more
Hexane (15 ml) and tetrahydrofuran
(15 ml) was added. After the above reaction solution was brought to 0 ° C.,
N-methylimidazole (19 μl) and dimethyldichloro
Rosilane (0.58 ml, 4.76 mmol) was added,
The mixture was stirred for 1.5 hours while gradually returning to room temperature. After this,
A saturated aqueous solution of ammonium chloride (50 ml) was added and the layers were separated.
After that, the organic phase is dried over magnesium sulfate, and the solvent is removed under reduced pressure.
After distillation, dimethylsilylenebis
[2-methyl-4- (4-chloro-2-naphthyl)-
1,4-dihydroazulene] was obtained. Then, above
The obtained reaction product was added to diethyl ether (11 ml).
Dissolved and n-butyl lithium in hexane at -60 ° C
(6.22 ml, 9.52 mmol, 1.53 N) in drops
After stirring at -70 ° C for 10 minutes, gradually raise the temperature to room temperature.
For 5 hours. At room temperature, toluene (80
ml). Cool to -65 ° C, hafnium tetrachloride
(1.525 g, 4.76 mmol), and then added at -65 ° C.
After stirring for 20 minutes, the temperature was gradually raised and the mixture was stirred at room temperature overnight.
After concentrating the obtained slurry solution to one third,
The mixture was filtered using a filter and washed with toluene (15 ml).
The liquid was concentrated. The crude product is treated with diethyl ether,
Mixed solvent of ether and methylene chloride (5: 1), hexa
Washing with dichloromethane repeatedly gives dichloro '1,1'-dimethyl
Rusilylenebis [2-methyl-4- (4-chloro-2-
Naphthyl) -4H-azulenyl] racemic hafnium
Mixture of isomer-meso form (racemic form: meso form = 80: 20,
2.07 g, 47% yield).¹ H-NMR (300 MHz, CDCl₃) Δ 1.0
0 (s, 3H, SiMe ₂ Meso body), 1.03 (s,
6H, SiMe₂ Racemic), 1.07 (s, 3H,
SiMe₂ Meso form), 2.26 (s, 6H, 2-CH
₃), 5.22 (d, J = 3 Hz, 2H, 4-H race)
5.35 (d, J = 3 Hz, 2H, 4-H
So-body), 5.91 (m, 6H), 6.05-6.1
(M, 2H), 6.81 (d, J = 11 Hz, 2H, 8
-H racemic), 6.88 (d, J = 11 Hz, 2
H, 8-H meso form), 7.5 to 7.9 (m, 10H,
arom), 8.2 to 8.5 (m, 2H, arom).

(2) Polymerization of propylene using methylalumoxane as a co-catalyst: A methylalumoxane (MMA manufactured by Tosoh Akzo Co., Ltd.) was placed in a 1 L stirred autoclave.
O ") (8.0 mmol) (in terms of Al atom). On the other hand, the above-mentioned racemic-
The meso mixture (corresponding to 0.7 mg of the racemate) was introduced after being diluted with toluene. Then, after introducing propylene (700 ml) into the autoclave, the rupture plate was cut at room temperature, the temperature was raised to 70 ° C., and the polymerization operation was performed for 1 hour to obtain polypropylene (9.8 g). Complex activity is 1.3 × 10
It was ⁴ . The obtained polypropylene was extracted with boiling heptane for 3 hours, and dried under reduced pressure at 60 ° C. for 8 hours. Polypropylene has a Tm of 157.3 ° C. and an MFR of 0.01
There were five.

Example 4 <Polymerization of α-olefin using clay mineral as co-catalyst> In Example 2 (2), the racemic product obtained in Example 1 (3) was used instead of Example 3 (1). Example 2 except that the obtained racemic-meso mixture (equivalent to 1.4 mg of racemic body) was used.
The same operation as in (2) was performed to obtain polypropylene (65.1).
g) was obtained. The catalytic activity is 1300, the complex activity is 4.7 ×
10 was ^4. The obtained polypropylene was extracted with boiling heptane for 3 hours, and dried under reduced pressure at 60 ° C. for 8 hours. The Tm of the polypropylene was 155.0 ° C., the MFR was 0.23, the Mw was 6.0 × 10 ⁵ , and the Q was 2.8. According to NMR analysis of the polymer, 2,1-insertion was 0.28% and 1,3-insertion was 0.32%.

Example 5 (1) Dichloro {1,1′-dimethylsilylenebis [2
-Isopropyl-4- (4-chloro-2-naphthyl)-
4H-azulenyl] Synthesis of racemic hafnium: 2
-Bromo-4-chloronaphthalene (3.08 g, 12.
8 mmol) in a mixed solvent of diethyl ether (50 ml) and hexane (2.5 ml), and a hexane solution of n-butyllithium (8.3 ml, 12.8 mmol,
1.54M) was added dropwise at 5 ° C. The mixture was stirred at 20 ° C. for 1 hour, and 2-isopropylazulene (2.0 g,
11.8 mmol) was added at 5 ° C., and the mixture was stirred at room temperature for 2 hours. On the way, diethyl ether (18 ml) was added. After standing, the supernatant solution was removed, and the precipitate was washed with hexane (8 m
Washed 3 times in 1). Hexane (15 ml) and tetrahydrofuran (15 ml) were added thereto, cooled to 0 ° C.
-Methylimidazole (20 µl) and dimethyldichlorosilane (0.64 ml, 5.3 mmol) were added, and the mixture was stirred at room temperature for 1 hour. Thereafter, 1N hydrochloric acid (50 ml) was added, and the mixture was separated. The organic phase was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The crude product obtained is subjected to column chromatography (silica gel, Merck Co., methylene chloride /
n-hexane) to give dimethylsilylenebis [2-
Isopropyl-4- (4-chloro-2-naphthyl)-
1,4-dihydroazulene] (2.4 g, yield 52%)
was gotten.

Next, the reaction product (2.4) obtained above was obtained.
g, 3.3 mmol) in diethyl ether (25 ml)
In n-butyllithium at -70 ° C
Liquid (4.3 ml, 6.6 mmol, 1.54 M) is added dropwise
Then, the temperature was gradually increased, and the mixture was stirred at room temperature for 3 hours. Evaporate the solvent
And toluene (40 ml) and diethyl ether (1 m
l) was added. Cool to -70 ° C, hafnium tetrachloride
(1.06 g, 3.3 mmol) and gradually heated.
Stirred overnight at room temperature. The obtained slurry solution is celite
, And washed with toluene (15 ml).
Was concentrated. The crude product was dissolved in diethyl ether (10 ml)
And washed five times with
Lenbis [2-isopropyl-4- (4-chloro-2-
Naphthyl) -4H-azulenyl] racemic hafnium
(0.47 g, 15% yield) was obtained.¹ H-NMR (300 MHz, CDCl₃) Δ 1.0
6 (s, 6H, SiMe ₂), 1.06 (d, J = 1
3.2 Hz, 12H, 2-CH (CH₃)₂), 3.0
5 to 3.16 (m, 2H, 2-CH (CH₃)₂)),
5.28 (d, J = 5.4 Hz, 2H, 4-H);
82-6.05 (m, 8H), 6.78 (d, J = 12
Hz, 2H), 7.50 to 7.85 (m, 10H, ar
om), 8.22-8.25 (m, 2H, arom).

(2) Polymerization of propylene with methylalumoxane as a cocatalyst: Example 3
Example 3 except that the above racemate (1.16 mg) was used instead of the racemic-meso mixture obtained in (1).
The same operation as in (2) was performed to obtain polypropylene (65 g). The complex activity was 5.6 × 10 ⁴ . Polypropylene has a Tm of 162.0 ° C., an MFR of 20, and an Mw of 1.7.
× 10 ⁵ , Q was 2.6. The polymer NM
By R analysis, 2,1-insertion was below the detection limit,
The insertion was below the detection limit.

Example 6 <Polymerization of α-olefin using clay mineral as co-catalyst> In Example 2 (2), the racemic product obtained in Example 1 (3) was used instead of Example 5 (1). The obtained racemic form (1.45)
mg)) to obtain polypropylene (10 g) in the same manner as in Example 2 (2). The catalytic activity is 2
00, the complex activity was 6.9 × 10 ³ . The Tm of polypropylene is 161.0 ° C., the MFR is 50, and the Mw is 1.
5 × 10 ⁵ , Q was 2.5. Also, the polymer N
According to MR analysis, 2,1-insertion detection limit or less, 1,3-
Insertion was 0.08%.

Example 7 (1) Dichloro {1,1′-dimethylsilylenebis [2
-Ethyl-4- (4-chloro-5,6,7,8-tetra
Hydronaphthyl) -4H-5,6,7,8-tetrahydride
Loazulenyl]｝ Synthesis of hafnium: In Example 1 (3)
Synthesized dichloro '1,1'-dimethylsilylenebis
[2-ethyl-4- (4-chloro-2-naphthyl) -4
H-azulenyl] racemic hafnium (100.3
mg) in dichloromethane (25 ml).
Gold (24 mg) was added. The mixture is placed under hydrogen (5M
Pa) at 30 ° C. for 2 hours. The suspension obtained
Filter through celite and wash with methylene chloride (15 ml)
And the filtrate was concentrated. The crude product was treated with diethyl ether (1
0 ml), and dried under reduced pressure.
1'-dimethylsilylenebis [2-ethyl-4- (4-
Chloro-5,6,7,8-tetrahydronaphthyl) -4
H-5,6,7,8-tetrahydroazulenyl] @hough
Nium (90 mg) was obtained.¹ H-NMR (300 MHz, CDCl₃) Δ 0.9
0 (s, 6H, SiMe ₂), 1.03 (s, 6H, C
H₃CH₃), 1.00 to 2.78 (m, 36H),
4.23 (d, J = 11 Hz, 2H, 4-H), 5.7
0 (s, 2H), 7.15 (s, 2H), 7.18
(S, 2H).

(2) Polymerization of propylene with methylalumoxane as cocatalyst: Example 3
In place of the racemate obtained in (1), the above racemate (0.
Except for using 39 mg), the same operation as in Example 3 (2) was carried out to obtain polypropylene (26 g). The complex activity was 6.7 × 10 ⁴ . Tm of polypropylene is 16
2.7 ° C, MFR was 0.02.

Example 8 <Polymerization of α-olefin using clay mineral as co-catalyst> In Example 2 (2), the racemic product obtained in Example 1 (3) was used instead of Example 7 (1). The obtained racemic form (2.0 m
Except for using g), the same operation as in Example 2 (2) was performed to obtain polypropylene (51 g). Catalytic activity 102
0 and the complex activity was 2.6 × 10 ⁴ . The Tm of the polypropylene was 159.7 ° C., the Mw was 4.3 × 10 ⁵ , the Q value was 3.1, and the MFR was 0.9. According to NMR analysis of the polymer, 2,1-insertion was 0.15%, 1,3
-Insertion was 0.10%.

Comparative Example 1 (1) Dichloro {1,1′-dimethylsilylenebis [2
-Methyl-4-phenyl-4H-azulenyl] {synthesis of racemic hafnium: (a) Synthesis of racemic / meso mixture: 2-methylazulene (3.22 g) was dissolved in hexane (30 ml), and cyclohexane of phenyllithium was dissolved. -Diethyl ether solution (21 ml) was added in small portions at 0 ° C. After stirring this solution at room temperature for 1.5 hours, it was cooled to -78 ° C and tetrahydrofuran (30 ml) was added. 1-Methylimidazole (0.05 mmol) and dimethyldichlorosilane (1.37 ml) were added to the solution, and the mixture was heated to room temperature and reacted for 1 hour. Thereafter, an aqueous ammonium chloride solution was added,
After liquid separation, the organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. As a result, dimethylsilylenebis [2
-Methyl-4-phenyl-1,4-dihydroazulene]
(5.84 g) was obtained.

The dimethylsilylenebis [2
-Methyl-4-phenyl-1,4-dihydroazulene]
Was dissolved in diethyl ether (30 ml), and n-butyllithium in hexane (14.2 ml,
(1.64N) was added dropwise, and the temperature was gradually raised, followed by stirring at room temperature for 12 hours. After evaporating the solvent under reduced pressure, the obtained solid was washed with hexane and dried under reduced pressure. To this, toluene / diethyl ether (40: 1) (80 ml) was added, and hafnium tetrachloride (3.3 g) was added at −60 ° C., and the mixture was gradually heated and stirred at room temperature for 15 hours. The obtained solution is concentrated under reduced pressure,
The obtained solid was washed with toluene, extracted with dichloroethane, and extracted with dichloro {1,1′-dimethylsilylenebis [2-
Methyl-4-phenyl-4H-azulenyl] {hafnium racemic-meso mixture (1.74 g) was obtained.

(B) Purification of the racemic form: The racemic-meso mixture (1.74 mg) obtained above was suspended in dichloromethane (30 ml) and subjected to 40 spectral irradiation using a high-pressure mercury lamp (100 W). The solvent was distilled off from this solution under reduced pressure. Toluene (8 ml) was added to the obtained solid to suspend it, followed by filtration. After washing with hexane (4 ml) and drying under reduced pressure, a racemic form (917 mg) was obtained.

(2) Polymerization of propylene with methylalumoxane as a cocatalyst:
In place of the racemate obtained in (3), the above racemate (0.
Except for using 26 mg), the same operation as in Example 1 (4) was carried out to obtain polypropylene (27.8 g). The complex activity was 1.07 × 10 ⁵ . Tm of polypropylene
Is 154.4 ° C., MFR is 0.08, Mw is 8.4 × 1
0 ⁵ and Q were 3.8. According to NMR analysis of the polymer, 2,1-insertion was 0.48% and 1,3-insertion was 0.18%.

Comparative Example 2 <Polymerization of α-Olefin Using Clay Mineral as Cocatalyst> In Example 2 (2), the racemic product obtained in Example 1 (3) was replaced with Comparative Example 1 (1). The obtained racemic form (0.98
mg)), and the same operation as in Example 2 (2) was performed, to obtain polypropylene (280 g). The catalyst activity was 5,600, and the complex activity was 2.8 × 10 ⁵ . Tm of polypropylene is 152.7 ° C., MFR is 0.8, Mw
Was 4.1 × 10 ⁵ and Q was 2.6. According to NMR analysis of the polymer, 2,1-insertion was 0.46%,
The 1,3-insertion was 0.42%.

[0164]

As described above, the novel transition metal compound of the present invention having a substituent represented by the general formula (Ib), that is, having a substituent in which phenyl has a condensed ring and R ⁹ is other than hydrogen, According to the catalyst of the present invention, the total of erroneous insertions derived from the 2,1-insertion and 1,3-insertion of the polymer was reduced, thereby significantly improving the melting point of the olefin polymer.

[0165]

Embedded image

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masami Kashimoto 1000 Kamoshitacho, Aoba-ku, Yokohama-shi, Kanagawa Prefecture Inside Mitsubishi Chemical Research Institute (72) Inventor Nao Iwama 1000 Kamoshida-cho, Aoba-ku, Yokohama-shi, Kanagawa Mitsubishi F-term in Yokohama Research Laboratory, Chemical Co., Ltd. (reference) 4H049 VN01 VN07 VP02 VQ06 VQ91 VR12 VR22 VR32 VS12 VU13 VW02 4H050 AA01 AA03 AB40 AB49 WB11 WB17 WB21 4J028 AA01A AB00A AB01A AC01A AC08A AC10A ACBBAB ACB BAB ACB BB03B BC12B BC14B BC15B BC16B BC17B BC18B BC24B BC25B BC29B CA15B CA16B CA18B CA19B CA27C CA28C CA29C CA30C CB36B EB02 EB04 EB05 EB07 EB09 EB10 FA02 GA05 GA14 GA19

Claims (12)

[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 6 carbon atoms,
A silicon-containing hydrocarbon group having 1 to 7 carbon atoms or 1 to 7 carbon atoms
6 halogenated hydrocarbon groups: R ³ and R ⁶ are each independently a saturated or unsaturated divalent hydrocarbon group having 3 to 10 carbon atoms: R ⁴¹ and R ⁴² are each independently;
A hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms: R ⁷ and R ⁸ are each independently a group represented by the following formula (Ib): (In the general formula (Ib), R ¹⁰ and R ¹¹ are each independently a hydrogen atom, a hydrocarbon group having 1 to 6 carbon atoms, a silicon-containing hydrocarbon group having 1 to 7 carbon atoms or 1 to 6 carbon atoms. halogenated hydrocarbon ^{group: R 12} is a divalent saturated or unsaturated hydrocarbon group having 3 to 10 carbon ^{atoms: R 13} is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, 1 to carbon atoms 20 halogenated hydrocarbon groups, silicon-containing hydrocarbon groups having 1 to 20 carbon atoms, oxygen-containing hydrocarbon groups having 1 to 20 carbon atoms or nitrogen-containing hydrocarbon groups having 1 to 20 carbon atoms: l is 0 to 20
(When l is 2 or more, R ¹³ may be bonded to an arbitrary position to form a ring structure.): R ⁹ represents a group other than hydrogen. J, k, m and n are 0 ≦ j + m ≦ 20 and 0 ≦ k
A non-negative integer satisfying the relationship + n ≦ 20 (provided that m and n are not simultaneously 0 and j or k is 2 or more, R ⁴¹ or R ⁴² is bonded at an arbitrary position to form a ring May form a 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, Or a germylene group: 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, or a halogenated group having 1 to 20 carbon atoms. M is a hydrocarbon group, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms: M represents a transition metal belonging to Groups 4 to 6 of the periodic table. ) 2. In the general formula (Ia), R ³ and R ⁶
Is a hydrocarbon having 4 or 5 carbon atoms. 3. The method according to claim 1, which is represented by the following general formula (Ic).
Or the transition metal compound according to 2. Embedded image (In the general formula (Ic), R ¹ , R ² , R ⁴ , R ⁵ , R ⁷ ,
R ⁸ , Q, M, X, and Y have the same meaning as described above. R
^{14, R 15, R 16,} R 17, R 18, R 19, R
²⁰ and R ²¹ 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. ) 4. The method according to claim 1, which is represented by the following general formula (Id).
Or the transition metal compound according to 2. Embedded image (In the general formula (Id), R ¹ , R ² , R ⁴ , R ⁵ , R ⁷ ,
R ⁸ , Q, M, X, and Y have the same meaning as described above. R
²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R
²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R
³⁴ , R ³⁵ , R ³⁶ and R ³⁷ are each independently
A hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or 1 carbon atom
And represents 20 to 20 halogenated hydrocarbon groups. ) 5. The transition metal compound according to claim 1, wherein in the general formula (Ib), R ⁹ is a halogen atom. 6. In the general formula (Ib), R ⁹ has 1 to 1 carbon atoms.
The transition metal compound according to any one of claims 1 to 4, which is a halogenated hydrocarbon group of 20. 7. In the formula (Ib), R ⁹ has 1 to 1 carbon atoms.
The transition metal compound according to any one of claims 1 to 4, which has 20 hydrocarbon groups. 8. The transition metal compound according to claim 1, wherein M is a transition metal of Group 4 of the periodic table. 9. An olefin polymerization catalyst component comprising the transition metal compound according to claim 1. Description: 10. An α-olefin polymerization catalyst comprising the following components (A) and (B) and an optional component (C). Component (A): the transition metal compound according to any one of claims 1 to 8 Component (B): an aluminum oxy compound, an ion capable of converting the component (A) into a cation by reacting with the component (A) Selected from the group consisting of hydrophilic compounds or Lewis acids Component (C): fine particle carrier 11. An α-olefin polymerization catalyst comprising the following components (A) and (D) and an optional component (E). Component (A): transition metal compound according to any one of claims 1 to 8 Component (D): selected from the group consisting of ion-exchange layer compounds other than silicate or inorganic silicate Component (E): organic Aluminum compound 12. The catalyst according to claim 10 or 11 and α.
-A method for producing an α-olefin polymer, which comprises contacting with an olefin to carry out polymerization or copolymerization.