JP2002212218A - Polymerization catalyst for olefin polymer and method of producing olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst system which can be simply and industrially synthesized, has a high ability to copolymerized ethylene with other olefins, or ethylene with a styrene compound, and has high polymerization activity, and a method of producing an olefin polymer. SOLUTION: The catalyst system for copolymerization comprises a combination of a titanium complex having a specified structure with an activator having a specified structure. The catalyst system is used for the method of producing a copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel olefin polymerization catalyst comprising a transition metal component and an activator and a method for producing an olefin polymer using a novel complex catalyst.

[0002]

2. Description of the Related Art There has been proposed a so-called metallocene catalyst comprising a transition metal compound belonging to Group 4 of the periodic table having a group having a cyclopentadiene-type anion skeleton as a ligand and an aluminoxane compound. For example, JP-A-4-12283 discloses a transition metal compound (Cp) ₂ MRX (4) represented by the following formula (4) (where Cp is a cyclopentadienyl group, and R is a carbon atom having 1 carbon atom).
To 6 alkyl groups or halogens, M represents zirconium or titanium, and X represents halogen. ) And an aluminoxane compound represented by the following formula (5) or (6): (R) ₂ AlO [—Al (R) O—] _n Al (R) ₂ (5) [—Al (R) O—] _{n + 2} (6) (wherein R is a methyl group or an ethyl group, and n is an integer of 4 to 20). A method of polymerizing an olefin in the presence of a catalyst is described.

Further, Japanese Patent Publication No. 5-80493 discloses that
In the presence of a catalyst composed of a zirconium hydride compound and an aluminoxane compound having a group having a conjugated π electron as a ligand, ethylene or propylene is polymerized, or ethylene and an α-olefin having 3 to 10 carbon atoms and an α-olefin having 5 to 5 carbon atoms are used.
By copolymerizing 20 non-conjugated polyenes, the molecular weight distribution (weight average molecular weight / number average molecular weight) is 1.97 to
A method for preparing 2.15 (co) polymers is described.

[0004] In addition to these general metallocene catalysts, metallocene compounds having a cross-linked structure by silicon atoms or the like (JP-A-60-35007, JP-A-3-1705)
No. 2406) and a constrained geometric polymerization catalyst (so-called CG
C, Japanese Unexamined Patent Publication (Kokai) No. 3-163088) and the like, a method of copolymerizing ethylene and an α-olefin is known.

However, each of these catalysts has several problems. Generally, in a metallocene catalyst,
There is a problem that the synthesis of the transition metal compound used is complicated and technically difficult. In particular, in the synthesis of a compound having two groups having a cyclopentadienyl skeleton as a ligand (a metallocene compound in a narrow sense), the synthesis route is 2
It is complicated with many steps of 5 or more.

A second problem with metallocene catalysts is that it is difficult to achieve both polymerization activity and copolymerizability. For example, an ethylene-bridged bisindenyl complex, which is a typical metallocene catalyst, has high polymerization activity, but low α-olefin copolymerizability, and the content of α-olefin is limited to about 50% by weight.

On the other hand, a complex system having a constrained geometric shape is α-
Although the olefin has high copolymerizability, it has low polymerization activity and requires a large amount of organometallic components.

[0008]

DISCLOSURE OF THE INVENTION The present invention is to find a catalyst system which can be synthesized more easily for industrial use, has a high copolymerizability of ethylene and olefins or ethylene and styrenes, and has a high polymerization activity. It was made for the purpose of.

[0009]

According to the present invention, a transition metal complex having a specific structure is much easier to synthesize than a conventional complex, and a transition metal complex (A) having a specific structure and an active substance having a specific structure are used. By combination with the agent (B),
This is based on the surprising fact that it has a much higher polymerization activity compared to conventional metallocene catalyst systems while maintaining high polymerizability.

That is, the present invention relates to a transition metal component (A)
And a catalyst suitable for producing an olefin polymer comprising the activator (B), wherein the transition metal component (A) is represented by the following formula (1):

[0011]

Embedded image

(In the formula, X and Y may be the same or different, and each represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aryl group, an allyloxy group, or a halogen. R ¹ To R ⁷ may be the same or different, and are each composed of hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aryl group, an allyloxy group, or a substituted silyl group represented by the following formula (2). _{^{. -Si- (R 8) 3 (}} 2) ( wherein, R ⁸ is hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aryl group, selected from the group consisting of aryloxy group.) R ¹ to R Out of ⁵ , arbitrary two or three may be bonded to form a ring, and the ring includes those having an aromatic property including a conjugated double bond, and n represents an integer of 0 to 5. )) The activator (B) is an alkyl It relates olefin polymer-body polymerization catalyst which is a Miniumuokishi compound or a boron compound.

Further, in a catalyst suitable for producing an olefin polymer comprising a transition metal component (A) and an activator (B), the transition metal component (A) is represented by the following formula (3):

[0014]

Embedded image

(In the formula, X and Y may be the same or different and each represents hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aryl group, an allyloxy group or a halogen. R ⁹ To R ¹² may be the same or different, and are each composed of an alkyl group, an alkoxy group, an aryl group or an allyloxy group having 1 to 20 carbon atoms, and when there are a plurality of R ⁹ , any two or three And the two may combine to form a ring, and the ring includes those having an aromatic property including a conjugated double bond.
¹³ is an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aryl group, an allyloxy group, or a substituted silyl group represented by the following formula (2). —Si— (R ⁸ ) ₃ (2) (wherein, R ⁸ is selected from the group consisting of hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aryl group, and an allyloxy group.) M is 1 to 3 And n represents an integer of 0 to 3, respectively. ) The polymerization catalyst characterized in that the activator (B) is an alkylaluminumoxy compound or a boron compound.

Further, the polymer in the present invention includes a copolymer, and the present invention uses a polymerization catalyst of any one of the aforementioned transition metal components (A) and an activator (B). The present invention relates to a method for producing an ethylene polymer, and a method for producing an olefin-based polymer such as a copolymer of ethylene and olefins and a copolymer of ethylene and styrenes.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a polymerization catalyst for an olefin polymer according to the present invention and a method for producing an olefin polymer using the catalyst will be described in detail.

Regarding the transition metal component (A) of the present invention,
In the case of formula (1), X and Y in the formula may be the same or different, and include hydrogen, carbon number 1 to
It consists of any one of 20 alkyl groups, alkoxy groups, aryl groups, allyloxy groups or halogens. R ^{1 to} R ⁷ may be the same or different from each other,
Or 20 of any one of an alkyl group, an alkoxy group, an aryl group, an allyloxy group and a substituted silyl group represented by the following formula (2). —Si— (R ⁸ ) ₃ (2) (wherein, R ⁸ is selected from the group consisting of hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aryl group, and an allyloxy group.) R ^{1 to} R ⁵ Of these, arbitrary two or three may be bonded to form a ring, and the ring includes those having an aromatic property including a conjugated double bond. n represents the integer of 0-5.

When the transition metal component (A) of the present invention is represented by the above formula (3), it is particularly suitable for copolymerizing ethylene with bulky monomers such as styrene or cyclic olefins. In the formula, X and Y may be the same or different, and each is composed of hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aryl group, an allyloxy group or a halogen. R ⁹ to R ¹² may be the same or different and each represents an alkyl group, an alkoxy group having 1 to 20 carbon atoms, consists either of an aryl or aryloxy group, if R ⁹ has a plurality, any two Alternatively, three may be bonded to form a ring, and the ring includes those having an aromatic property including a conjugated double bond. R
¹³ is an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aryl group, an allyloxy group, or a substituted silyl group represented by the following formula (2). —Si— (R ⁸ ) ₃ (2) (wherein, R ⁸ is selected from the group consisting of hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aryl group, and an allyloxy group.) M is 1 to 3 And n represents an integer of 0 to 3, respectively.

In the above formulas (1), (2) and (3), specific examples of the alkyl, alkoxy, aryl and alkyloxy and aryl moieties of X, Y and R ^{1 to} R ¹³ are methyl. , Ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, sec-butyl, n-pentyl, isopentyl, 1-methylbutyl, 2-methylbutyl, 1,2-dimethylpropyl, neopentyl, n-hexyl, isohexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl,
1,1-dimethylbutyl, 2,2-dimethylbutyl,
3,3-dimethylbutyl, 1,2-dimethylbutyl,
1,3-dimethylbutyl, 1,1-ethylmethylpropyl, 1-ethylbutyl, 2-ethylbutyl, cyclohexyl, n-heptyl, isoheptyl, 4-methylhexyl, 3-methylhexyl, 2-methylhexyl, 1-methylhexyl , 1,1-dimethylpentyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl, 4,4-
Dimethylpentyl, 1,2-dimethylpentyl, 1,3
-Dimethylpentyl, 1,4-dimethylpentyl, 1-
Ethylpentyl, 1-propylbutyl, 2-ethylpentyl, 3-ethylpentyl, 1,1-ethylmethylbutyl, 1,1-diethylpropyl, 2,3-dimethylpentyl, 2,4-dimethylpentyl, 3,4 -Dimethylpentyl, 1, -ethyl-2-methylbutyl, 1-ethyl-3-methylbutyl, 4-methylcyclohexyl, 3-
Methylcyclohexyl, cycloheptyl, 1,1,2-
Trimethylbutyl, 1,1,3-trimethylbutyl,
2,2,1-trimethylbutyl, 2,2,3-trimethylbutyl, 3,3,1-trimethylbutyl, 3,3,2
-Trimethylbutyl, 1,1,2,2-tetramethylpropyl, n-octyl, 1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, isooctyl, 1-ethylhexyl , 2-ethylhexyl, 3-ethylhexyl, 4
-Ethylhexyl, 1,1-dimethylhexyl, 2,2
-Dimethylhexyl, 3,3-dimethylhexyl, 4,
4-dimethylhexyl, 5,5-dimethylhexyl,
1,2-dimethylhexyl, 1,3-dimethylhexyl, 1,4-dimethylhexyl, 1,5-dimethylhexyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, 3,4-dimethylhexyl, , 5-dimethylhexyl, 3,5-dimethylhexyl, 1,1-methylethylpentyl, 1-ethyl-2-methylpentyl, 1
-Ethyl-3-methylpentyl, 1-ethyl-4-methylpentyl, 2-ethyl-1-methylpentyl, 2,2
-Ethylmethylpentyl, 3,3-ethylmethylpentyl, 2-ethyl-3-methylpentyl, 2-ethyl-4
-Methylpentyl, 3-ethyl-4-methylpentyl,
3-ethyl-2-methylpentyl, 1,1-diethylbutyl, 2,2-diethylbutyl, 1,2-diethylbutyl, 1,1-methylpropylbutyl, 2-methyl-1-
Propylbutyl, 3-methyl-1-propylbutyl, 4-
Ethylcyclohexyl, 3-ethylcyclohexyl,
3,4-dimethylcyclohexyl, 1,1,2-trimethylpentyl, 1,1,3-trimethylpentyl, 1,
1,4-trimethylpentyl, 2,2,1-trimethylpentyl, 2,2,3-trimethylpentyl, 2,2
4-trimethylpentyl, 3,3,1-trimethylpentyl, 3,3,2-trimethylpentyl, 3,3,4-
Trimethylpentyl, 1,2,3-trimethylpentyl, 1,2,4-trimethylpentyl, 1,3,4-trimethylpentyl, 1,2,3-trimethylpentyl,
1,2,4-trimethylpentyl, 1,3,4-trimethylpentyl, 1,1,2,2-tetramethylbutyl,
1,1,3,3-tetramethylbutyl, 1,1,2,3
-Tetramethylbutyl, 2,2,1,3-tetramethylbutyl, 1-ethyl-1,2-dimethylbutyl, 2-ethyl-1,2-dimethylbutyl, 1-ethyl-2,3-
Dimethylbutyl, n-nonyl, isononyl, 1-methyloctyl, 2-methyloctyl, 3-methyloctyl,
4-methyloctyl, 5-methyloctyl, 6-methyloctyl, 1-ethylheptyl, 2-ethylheptyl,
3-ethylheptyl, 4-ethylheptyl, 5-ethylheptyl, 1,1-dimethylheptyl, 2,2-dimethylheptyl, 3,3-dimethylheptyl, 4,4-dimethylheptyl, 5,5-dimethylheptyl, 6,6-dimethylheptyl, 1,2-dimethylheptyl, 1,3-
Dimethylheptyl, 1,4-dimethylheptyl, 1,5
-Dimethylheptyl, 1,6-dimethylheptyl, 2,
3-dimethylheptyl, 2,4-dimethylheptyl,
2,5-dimethylheptyl, 2,6-dimethylheptyl, 3,4-dimethylheptyl, 3,5-dimethylheptyl, 3,6-dimethylheptyl, 4,5-dimethylheptyl, 4,6-dimethylheptyl, 5 , 6-dimethylheptyl, 1,1,2-trimethylhexyl, 1,1,
3-trimethylhexyl, 1,1,4-trimethylhexyl, 1,1,5-trimethylhexyl, 2,2,1-
Trimethylhexyl, 2,2,3-trimethylhexyl, 2,2,4-trimethylhexyl, 2,2,5-trimethylhexyl, 3,3,1-trimethylhexyl,
3,3,2-trimethylhexyl, 3,3,4-trimethylhexyl, 3,3,5-trimethylhexyl, 4,
4,1-trimethylhexyl, 4,4,2-trimethylhexyl, 4,4,3-trimethylhexyl, 4,4
5-trimethylhexyl, 5,5,1-trimethylhexyl, 5,5,2-trimethylhexyl, 5,5,3-
Trimethylhexyl, 5,5,4-trimethylhexyl, 1,2,3-trimethylhexyl, 2,3,4-trimethylhexyl, 3,4,5-trimethylhexyl,
1,3,4-trimethylhexyl, 1,4,5-trimethylhexyl, 2,4,5-trimethylhexyl, 1,
2,5-trimethylhexyl, 1,2,4-trimethylhexyl, 1,1-ethylmethylhexyl, 2,2-ethylmethylhexyl, 3,3-ethylmethylhexyl,
4,4-ethylmethylhexyl, 5,5-ethylmethylhexyl, 1-ethyl-2-methylhexyl, 1-ethyl-3-methylhexyl, 1-ethyl-4-methylhexyl, 1-ethyl-5-methyl Hexyl, 2-ethyl-
1-methylhexyl, 3-ethyl-1-methylhexyl, 3-ethyl-2-methylhexyl, 1,1-diethylpentyl, 2,2-diethylpentyl, 3,3-diethylpentyl, 1,2-diethylpentyl , 1,3-diethylpentyl, 2,3-diethylpentyl, 1,1-
Methylpropylpentyl, 2,2-methylpropylpentyl, 1-methyl-2-propylpentyl, n-decyl, isodecyl, 1-methylnonyl, 2-methylnonyl, 3-methylnonyl, 4-methylnonyl, 5-methylnonyl, 6-methylnonyl , 7-methylnonyl, 1-ethyloctyl, 2-ethyloctyl, 3-ethyloctyl, 4-ethyloctyl, 5-ethyloctyl, 6-ethyloctyl, 1,1-dimethyloctyl, 2,2-dimethyloctyl, , 3-dimethyloctyl, 4,4-
Dimethyloctyl, 5,5-dimethyloctyl, 6,6
-Dimethyloctyl, 7,7-dimethyloctyl, 1,
2-dimethyloctyl, 1,3-dimethyloctyl,
1,4-dimethyloctyl, 1,5-dimethyloctyl, 1,6-dimethyloctyl, 1,7-dimethyloctyl, 2,3-dimethyloctyl, 2,4-dimethyloctyl, 2,5-dimethyloctyl, , 6-dimethyloctyl, 2,7-dimethyloctyl, 3,4-dimethyloctyl, 3,5-dimethyloctyl, 3,6-dimethyloctyl, 3,7-dimethyloctyl, 4,5-dimethyloctyl, 4, 6-dimethyloctyl, 4,7-
Dimethyloctyl, 5,6-dimethyloctyl, 5,7
-Dimethyloctyl, n-undecyl, n-dodecyl,
Phenyl, benzyl, p-tolyl, m-tolyl, xylyl, mesityl, 2,6-dimethylphenyl, 2,4
6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,4,6-trimethoxyphenyl, 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, naphthyl, 2-methoxyphenyl, 2-isopropoxy Phenyl, 2-tert-butoxyphenyl, 2,6-di-tert-butylphenyl, 2-methylphenyl, 2-isopropylphenyl, 2-tert-butylphenyl, 2-methyl-6-isopropylphenyl, 2-methyl-6 Tertiary butyl phenyl and the like can be mentioned.

As a specific metal complex represented by the above formula (1) or (3), for example, CpTiCl ₂ [N (SiMe ₃ ) (2,6-M
e ₂ C ₆ H ₃ )], Cp * TiCl ₂ [N (SiMe ₃ ) (2,6-Me ₂ C ₆ H ₃ )], MeCpTiC
l ₂ [N (SiMe ₃ ) (2,6-Me ₂ C ₆ H ₃ )], 1,3-Me ₂ CpTiCl ₂ [N (SiMe ₃ )
(2,6-Me ₂ C ₆ H ₃ )], 1,2,3-Me ₃ CpTiCl ₂ [N (SiMe ₃ ) (2,6-Me ₂ C
₆ H ₃ )], 1,2,4-Me ₃ CpTiCl ₂ [N (SiMe ₃ ) (2,6-Me ₂ C ₆ H ₃ )], nB
uCpTiCl ₂ [N (SiMe ₃ ) (2,6-Me ₂ C ₆ H ₃ )], 1,3-nBu ₂ CpTiCl ₂ [N
(SiMe ₃ ) (2,6-Me ₂ C ₆ H ₃ )], tBuCpTiCl ₂ [N (SiMe ₃ ) (2,6-Me ₂
C ₆ H ₃ )], 1,3-tBu ₂ CpTiCl ₂ [N (SiMe ₃ ) (2,6-Me ₂ C ₆ H ₃ )], Cp
TiCl ₂ [N (SiMe ₃ ) (2,6-iPr ₂ C ₆ H ₃ )], Cp * TiCl ₂ [N (SiMe ₃ )
(2,6-iPr ₂ C ₆ H ₃ )], MeCpTiCl ₂ [N (SiMe ₃ ) (2,6-iPr ₂ C
₆ H ₃ )], 1,3-Me ₂ CpTiCl ₂ [N (SiMe ₃ ) (2,6-iPr ₂ C ₆ H ₃ )], 1,
2,3-Me ₃ CpTiCl ₂ [N (SiMe ₃ ) (2,6-iPr ₂ C ₆ H ₃ )], 1,2,4-Me ₃ C
pTiCl ₂ [N (SiMe ₃ ) (2,6-iPr ₂ C ₆ H ₃ )], nBuCpTiCl ₂ [N (SiM
e ₃ ) (2,6-iPr ₂ C ₆ H ₃ )], 1,3-nBu ₂ CpTiCl ₂ [N (SiMe ₃ ) (2,6-i
Pr ₂ C ₆ H ₃ )], tBuCpTiCl ₂ [N (SiMe ₃ ) (2,6-iPr ₂ C ₆ H ₃ )], 1,3
-tBu ₂ CpTiCl ₂ [N (SiMe ₃ ) (2,6-iPr ₂ C ₆ H ₃ )], CpTiCl ₂ [N (Si
Me ₃ ) (2,6-Me ₂ C ₆ H ₃ )], Cp * TiCl ₂ [N (SiMe ₃ ) (2,6-Me ₂ C
₆ H ₃ )], MeCpTiCl ₂ [N (SiMe ₃ ) (2,6-Me ₂ C ₆ H ₃ )], 1,3-Me ₂ Cp
TiCl ₂ [N (SiMe ₃ ) (2,6-Me ₂ C ₆ H ₃ )], 1,2,3-Me ₃ CpTiCl ₂ [N (S
iMe ₃ ) (2,6-Me ₂ C ₆ H ₃ )], 1,2,4-Me ₃ CpTiCl ₂ [N (SiMe ₃ ) (2,6
-Me ₂ C ₆ H ₃ )], nBuCpTiCl ₂ [N (SiMe ₃ ) (2,6-Me ₂ C ₆ H ₃ )], 1,3
-nBu ₂ CpTiCl ₂ [N (SiMe ₃ ) (2,6-Me ₂ C ₆ H ₃ )], tBuCpTiCl ₂ [N
(SiMe ₃ ) (2,6-Me ₂ C ₆ H ₃ )], 1,3-tBu ₂ CpTiCl ₂ [N (SiMe ₃ ) (2,
6-Me ₂ C ₆ H ₃ )], CpTiCl ₂ [N (Me) (2,6-iPr ₂ C ₆ H ₃ )], Cp * TiCl
₂ [N (Me) (2,6-iPr ₂ C ₆ H ₃ )], MeCpTiCl ₂ [N (Me) (2,6-iPr ₂ C ₆
H ₃ )], 1,3-Me ₂ CpTiCl ₂ [N (Me) (2,6-iPr ₂ C ₆ H ₃ )], 1,2,3-M
e ₃ CpTiCl ₂ [N (Me) (2,6-iPr ₂ C ₆ H ₃ )], 1,2,4-Me ₃ CpTiCl ₂ [N
(Me) (2,6-iPr ₂ C ₆ H ₃ )], nBuCpTiCl ₂ [N (Me) (2,6-iPr ₂ C
₆ H ₃ )], 1,3-nBu ₂ CpTiCl ₂ [N (Me) (2,6-iPr ₂ C ₆ H ₃ )], tBuCp
TiCl ₂ [N (Me) (2,6-iPr ₂ C ₆ H ₃ )], 1,3-tBu ₂ CpTiCl ₂ [N (Me)
(2,6-iPr ₂ C ₆ H ₃ )], CpTiCl ₂ [N (Et) (2,6-Me ₂ C ₆ H ₃ )], Cp * T
iCl ₂ [N (Et) (2,6-Me ₂ C ₆ H ₃ )], MeCpTiCl ₂ [N (Et) (2,6-Me ₂ C
₆ H ₃ )], 1,3-Me ₂ CpTiCl ₂ [N (Et) (2,6-Me ₂ C ₆ H ₃ )], 1,2,3-M
e ₃ CpTiCl ₂ [N (Et) (2,6-Me ₂ C ₆ H ₃ )], 1,2,4-Me ₃ CpTiCl ₂ [N
(Et) (2,6-Me ₂ C ₆ H ₃ )], nBuCpTiCl ₂ [N (Et) (2,6-Me ₂ C
₆ H ₃ )], 1,3-nBu ₂ CpTiCl ₂ [N (Et) (2,6-Me ₂ C ₆ H ₃ )], tBuCpT
iCl ₂ [N (Et) (2,6-Me ₂ C ₆ H ₃ )], 1,3-tBu ₂ CpTiCl ₂ [N (Et) (2,
6-Me ₂ C ₆ H ₃ )], CpTiCl ₂ [N (Et) (2,6-iPr ₂ C ₆ H ₃ )], Cp * TiCl
₂ [N (Et) (2,6-iPr ₂ C ₆ H ₃ )], MeCpTiCl ₂ [N (Et) (2,6-iPr ₂ C ₆
H ₃ )], 1,3-Me ₂ CpTiCl ₂ [N (Et) (2,6-iPr ₂ C ₆ H ₃ )], 1,2,3-M
e ₃ CpTiCl ₂ [N (Et) (2,6-iPr ₂ C ₆ H ₃ )], 1,2,4-Me ₃ CpTiCl ₂ [N
(Et) (2,6-iPr ₂ C ₆ H ₃ )], nBuCpTiCl ₂ (N (Et) (2,6-iPr ₂ C
₆ H ₃ )], 1,3-nBu ₂ CpTiCl ₂ [N (Et) (2,6-iPr ₂ C ₆ H ₃ )], tBuCp
TiCl ₂ [N (Et) (2,6-iPr ₂ C ₆ H ₃ )], 1,3-tBu ₂ CpTiCl ₂ [N (Et)
(2,6-iPr ₂ C ₆ H ₃ )], CpTiCl ₂ [N (iPr) (2,6-Me ₂ C ₆ H ₃ )], Cp *
TiCl ₂ [N (iPr) (2,6-Me ₂ C ₆ H ₃ )], MeCpTiCl ₂ [N (iPr) (2,6-M
e ₂ C ₆ H ₃ )], 1,3-Me ₂ CpTiCl ₂ [N (iPr) (2,6-Me ₂ C ₆ H ₃ )], 1,
2,3-Me ₃ CpTiCl ₂ [N (iPr) (2,6-Me ₂ C ₆ H ₃ )], 1,2,4-Me ₃ CpTi
Cl ₂ [N (iPr) (2,6-Me ₂ C ₆ H ₃ )], nBuCpTiCl ₂ [N (iPr) (2,6-Me
₂ C ₆ H ₃ )], 1,3-nBu ₂ CpTiCl ₂ [N (iPr) (2,6-Me ₂ C ₆ H ₃ )], tBu
CpTiCl ₂ [N (iPr) (2,6-Me ₂ C ₆ H ₃ )], 1,3-tBu ₂ CpTiCl ₂ [N (iP
r) (2,6-Me ₂ C ₆ H ₃ )], CpTiCl ₂ [N (iPr) (2,6-iPr ₂ C ₆ H ₃ )], C
p * TiCl ₂ [N (iPr) (2,6-iPr ₂ C ₆ H ₃ )], MeCpTiCl ₂ [N (iPr) (2,
6-iPr ₂ C ₆ H ₃ )], 1,3-Me ₂ CpTiCl ₂ [N (iPr) (2,6-iPr ₂ C
₆ H ₃ )], 1,2,3-Me ₃ CpTiCl ₂ [N (iPr) (2,6-iPr ₂ C ₆ H ₃ )], 1,
2,4-Me ₃ CpTiCl ₂ [N (iPr) (2,6-iPr ₂ C ₆ H ₃ )], nBuCpTiCl ₂ [N
(iPr) (2,6-iPr ₂ C ₆ H ₃ )], 1,3-nBu ₂ CpTiCl ₂ (N (iPr) (2,6-i
Pr ₂ C ₆ H ₃ )], tBuCpTiCl ₂ [N (iPr) (2,6-iPr ₂ C ₆ H ₃ )], 1,3-t
Bu ₂ CpTiCl ₂ [N (iPr) (2,6-iPr ₂ C ₆ H ₃ )], CpTiCl ₂ [N (tBu)
(2,6-Me ₂ C ₆ H ₃ )], Cp * TiCl ₂ [N (tBu) (2,6-Me ₂ C ₆ H ₃ )], MeC
pTiCl ₂ [N (tBu) (2,6-Me ₂ C ₆ H ₃ )], 1,3-Me ₂ CpTiCl ₂ [N (tBu)
(2,6-Me ₂ C ₆ H ₃ )], 1,2,3-Me ₃ CpTiCl ₂ (N (tBu) (2,6-Me ₂ C ₆ H
₃ )], 1,2,4-Me ₃ CpTiCl ₂ [N (tBu) (2,6-Me ₂ C ₆ H ₃ )], nBuCpT
iCl ₂ [N (tBu) (2,6-Me ₂ C ₆ H ₃ )], 1,3-nBu ₂ CpTiCl ₂ [N (tBu)
(2,6-Me ₂ C ₆ H ₃ )], tBuCpTiCl ₂ [N (tBu) (2,6-Me ₂ C ₆ H ₃ )],
1,3-tBu ₂ CpTiCl ₂ [N (tBu) (2,6-Me ₂ C ₆ H ₃ )], CpTiCl ₂ [N (tB
u) (2,6-iPr ₂ C ₆ H ₃ )], Cp * TiCl ₂ [N (tBu) (2,6-iPr ₂ C
₆ H ₃ )], MeCpTiCl ₂ [N (tBu) (2,6-iPr ₂ C ₆ H ₃ )], 1,3-Me ₂ CpT
iCl ₂ [N (tBu) (2,6-iPr ₂ C ₆ H ₃ )], 1,2,3-Me ₃ CpTiCl ₂ [N (tB
u) (2,6-iPr ₂ C ₆ H ₃ )], 1,2,4-Me ₃ CpTiCl ₂ (N (tBu) (2,6-iPr
₂ C ₆ H ₃ )], nBuCpTiCl ₂ [N (tBu) (2,6-iPr ₂ C ₆ H ₃ )], 1,3-nBu
₂ CpTiCl ₂ [N (tBu) (2,6-iPr ₂ C ₆ H ₃ )], tBuCpTiCl ₂ [N (tBu)
(2,6-iPr ₂ C ₆ H ₃ )], 1,3-tBu ₂ CpTiCl ₂ [N (tBu) (2,6-iPr ₂ C ₆
H ₃ )] (wherein Cp is a cyclopentadienyl group,
* Represents a pentamethylcyclopentadienyl group, respectively. ) Can be exemplified. These may be used alone or in combination.

The alkyl aluminum oxy compound of the activator (B) is represented by the following general formulas (7), (8) and (9)
And at least one compound of the organoaluminum oxy compounds represented by (10).

[0023]

Embedded image (In the formula, R ^{14 to} R ¹⁶ may be the same or different, each represents a hydrocarbon group having 1 to 8 carbon atoms, and n represents an integer of 1 to 50.)

[0024]

Embedded image (In the formula, R ^{17 to} R ¹⁹ may be the same or different, and each represents a hydrocarbon group having 1 to 8 carbon atoms, and n represents an integer of 1 to 50.)

[0025]

Embedded image (Wherein, R ²⁰ is a hydrocarbon group having 1 to 8 carbon atoms, and n is 1 to 5
Represents an integer up to 0. )

[0026]

Embedded image (In the formula, R ^{21 to} R ²⁴ may be the same or different, each represents a hydrocarbon group having 1 to 8 carbon atoms, and n represents an integer of 1 to 50.)

Specific examples of the alkylaluminumoxy compound include methylaluminoxane (hereinafter abbreviated as MAO), ethylaluminoxane, propylaluminoxane, butylaluminoxane, isobutylaluminoxane, methylethylaluminoxane, methylbutylaluminoxane, methylisobutylaluminoxane and the like. Particularly, methylaluminoxane, isobutylaluminoxane, and methylisobutylaluminoxane can be preferably used.

Examples of the organoboron compound of the activator (B) include at least one of the organoboron compounds represented by the following general formulas (11) and (12). (BR ²⁵ R ²⁶ R ²⁷ ) _n (11) (wherein, R ^{25 to} R ²⁷ may be the same or different, and include a hydrocarbon containing a halogenated aryl group or halogenated aryloxy group having 1 to 14 carbon atoms.) Group, n represents an integer from 1 to 4.) A (BR ²⁸ R ²⁹ R ³⁰ R ³¹ ) _n (12) (wherein A is a quaternary amine or a quaternary ammonium salt or a carbocation or a valence of +1) R ^{28 to} R ³¹ may be the same or different, and a hydrocarbon group containing a halogenated aryl group or a halogenated allyloxy group having 1 to 14 carbon atoms, and n represents 1 to 4 Represents an integer.)

Specific examples of the hydrocarbon groups of the above formulas (11) and (12) include phenyl, benzyl, p-tolyl, m
-Tolyl, xylyl, mesityl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,4,6-trimethoxyphenyl, 2,6-diisopropylphenyl, 2,4 , 6-triisopropylphenyl, naphthyl, o-isopropoxyphenyl, pentafluorophenyl, pentafluorobenzyl, tetrafluorophenyl, tetrafluorotolyl and the like.

Specific examples of A in the above formula (12) include pyridinium, 2,4-dinitro-N, N-diethylanilinium, p-nitroanilinium, 2,5-dichloroaniline, p-nitro- N, N-dimethylanilinium, quinolinium, N, N-dimethylanilinium,
Methyldiphenylammonium, N, N-diethylanilinium, 8-chloroquinolinium, trimethylammonium, tripropylammonium, triethylammonium, tributylammonium, triphenylphosphonium, ammonium, triphenylmethyl, sodium, lithium, potassium, cesium, Calcium, magnesium and the like.

Specific examples of these organic boron compounds include trimethylammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, and triphenylphosphonium tetrakis (pentafluorophenyl).
Borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate and the like. Most preferred is triphenylcarbenium tetrakis (pentafluorophenyl) borate.

The catalyst suitable for use in the present invention comprises the transition metal compound (A) and the alkylaluminum oxy compound or organoboron compound (B) in any order and in any suitable Manufactured by combining in a manner. A preferable catalyst composition ratio (molar ratio) of the component (A) and the component (B) is (A) :( B) =
1: 0.01 to 1: 10000. Catalyst preparation may be performed in advance by mixing in a suitable solvent under an inert gas atmosphere such as nitrogen or argon,
The components (A) and (B) may be separately poured into a reactor where a monomer coexists, and then prepared in the reactor. Suitable solvents for preparing the catalyst include hydrocarbon solvents such as alkane such as hexane and cyclohexane, and aromatic solvents such as toluene, benzene and ethylbenzene. Further, it is preferable to remove water and the like in these solvents in the pretreatment. The optimum temperature for preparing the catalyst is from -20 ° C to 150 ° C.

The olefins that can be polymerized or copolymerized using the catalyst of the present invention include, for example, ethylene and
To 30 α-olefins. The catalyst of the present invention is particularly suitable for producing a copolymer of ethylene and olefins or ethylene and styrene.

Specific examples of α-olefins include propylene, 1-butene, 1-hexene, 4-methyl-1-
Penten, 1-heptene, 1-octene, 1-decene and the like can be mentioned.

The olefins that can be polymerized using the catalyst of the present invention include cyclic olefins. The cyclic olefin is not particularly limited, and may have a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, an oxygen atom or a substituent containing a nitrogen atom, and is usually a monocyclic ring having 3 to 12 carbon atoms. Cycloalkenes, monocyclic cycloalkadienes,
And polycyclic cycloalkenes and polycyclic cycloalkadienes. Among the substituents, examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, and n
-An alkyl group having 1 to 20 carbon atoms such as propyl group, isopropyl group, t-butyl group, hexyl group, cyclohexyl group, cyclooctyl group, phenyl group, naphthyl group, benzyl group, p-tolyl group, etc. 6 to 20 aryl groups, alkylaryl groups, arylalkyl groups,
Examples thereof include an alkylidene group having 1 to 20 carbon atoms such as a methylidene group, an ethylidene group and a propylidene group, and an alkenyl group having 2 to 20 carbon atoms such as a vinyl group and an allyl group.

Specific examples of the substituent containing a halogen atom include halogen groups having 1 to 20 carbon atoms, such as halogen groups such as fluorine, chlorine, bromine and iodine, and chloromethyl, bromomethyl and chloroethyl groups. Examples include a substituted alkyl group. Specific examples of the substituent containing an oxygen atom include a methoxy group, an ethoxy group, a propoxy group,
C1-C20 alkoxy groups such as phenoxy groups, methoxycarbonyl groups, ethoxycarbonyl groups, etc.
To 20 alkoxycarbonyl groups.

Specific examples of the substituent containing a nitrogen atom include a C1-C20 alkylamino group such as a dimethylamino group and a diethylamino group, and a cyano group. These substituents are preferably bonded to a carbon atom other than a double-bonded carbon atom.

Specific examples of the monocyclic cycloalkene include, for example, cyclopropene, cyclobutene, cyclopentene, 3,5-dimethylcyclopentene, cyclohexene, 3-chlorocyclohexene, 3-methoxycyclohexene, cyclooctene, cyclododecene and the like. Is mentioned.

Specific examples of the monocyclic cycloalkadienes include, for example, cyclobutadiene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,4-
Cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, 1,3-cycloheptadiene, 1,4-cycloheptadiene, 1,5-cyclooctadiene, 1,7
-Cyclododecadienes and the like.

Specific examples of polycyclic cycloalkenes include, for example, norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, 1-methylnorbornene, and 7-methylnorbornene. Methyl norbornene, 5,5,6-trimethylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene, 5-ethylidene-2-norbornene, 5-vinylnorbornene, 1,2-dihydrodicyclopentadiene, 5-chloronorbornene, , 5-dichloronorbornene, 5-fluoronorbornene, 5,
5,6-trifluoro-6-trifluoromethylnorbornene, 5-methoxynorbornene, 5-dimethylaminonorbornene, 5-cyanonorbornene and the like can be mentioned.

Specific examples of the polycyclic cycloalkadienes include, for example, dicyclopentadiene, norbornadiene, dimethyldicyclopentadiene, 7,7-dimethylnorbornadiene, 1,1-bis (5-bicyclo [2. 2.1] Hept-2-enyl) methane, 1,2-bis (5-bicyclo [2.2.1] hepta-2-enyl) ethane, 1,6-bis (5-bicyclo [2.2. 1] Hept-2-enyl) hexane and the like.

Further, examples of the styrenes which can be polymerized or copolymerized by using the catalyst of the present invention include aromatic vinyl compounds. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o, m,
p-methylstyrene, o, p-dimethylstyrene, ethylstyrenes, isopropylstyrenes, vinyl-substituted or nucleus-substituted alkylstyrenes of butylstyrenes,
Halogenated styrenes can be mentioned.

The polymerization method of the present invention can be carried out in the presence of a monomer and a catalyst, under any of reduced pressure, atmospheric pressure and pressurized conditions, in any of bulk, solution and slurry methods.

The preferred temperature range for carrying out the polymerization is-
30 ° C. to 260 ° C., preferably 0 ° C. to 200 ° C.
It is. In addition, the polymerization may be performed in an atmosphere of an inert gas such as nitrogen or argon, or may be performed in an atmosphere of ethylene, or a mixture of ethylene and / or α-olefins with the above-described inert gas. It does not matter even under the atmosphere. Further, hydrogen may be allowed to coexist in addition to the above gas for controlling the molecular weight. Further, the catalyst component may be supported on a suitable carrier such as alumina, magnesium chloride or silica. Further, a solvent can be used in the polymerization. Suitable solvents for use in the polymerization include hexane, cyclohexane, and other hydrocarbon solvents such as alkanes, and toluene, benzene, and the like.
And aromatic solvents such as ethylbenzene. The preferred amount of catalyst in the polymerization is [(weight of polymer produced) K
g] / [catalyst (A) component 1 mol] = 10 kg / 1 mo
It is an amount that gives a polymer of about 1 to 1,000,000 kg / 1 mol. As a method for separating the polymer after polymerization in the present invention, for example, a method of adding a polar solvent which is a poor solvent such as acetone or an alcohol obtained by mixing an acid or an alkali to the polymerization solution to precipitate and recover the polymer, A method in which the mixture is poured into boiling water with stirring and then recovered by distillation together with the solvent, or a method in which the solvent is distilled off by directly heating the reaction solution can be used.

The polymerization catalyst of the present invention can be easily synthesized industrially, has high copolymerizability of ethylene and olefins or ethylene and styrene, and has high polymerization activity.

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.

Example 1 Cp * TiCl ₂ [N (SiMe ₃ ) (2,6-Me ₂ C ₆ H ₃ )] (Synthesis of Metal Complex-1) Cp * TiCl ₃ cooled to −30 ° C. (500 mg, 1.727
mmol) into a toluene solution containing the synthesized lithium amide (N (Li) (SiMe ₃ ) (2,6-Me ₂ C ₆ H ₃ )) (344 mg,
1.727 mmol) was added slowly, and the temperature was gradually raised to room temperature with stirring. Thereafter, the reaction was performed for 12 hours under reflux of toluene. The reaction solution was filtered through celite, and the filtrate was distilled off under reduced pressure. The remaining solid (crude crystal) was dissolved in diethyl ether, hexane was gently added, and the mixture was allowed to stand at −30 ° C., whereby metal complex-1 (602 mg, 1.349 m) was obtained.
mol, yield: 78%). ¹ H NMR (CDCl ₃ ): 7.01 (d, J = 7.6)
Hz, 2H), 6.89 (t, 1H), 2.12 (s,
6H), 1.86 (s, 15H), 0.25 (s, 9
H) ¹³ C NMR (CDCl ₃ ): 155.7, 131.9;
130.2, 128.2, 124.1, 21.3, 1
2.9, 3.7 ppm

Example 2 Polymerization of ethylene White solid MAO (2 mmol in terms of Al, manufactured by Tosoh Akzo: PMAO-S: solvent toluene and AlM) were placed in a 100 ml autoclave in which the inside was degassed under vacuum and replaced with nitrogen.
Using e ₃ except under vacuum. ) Was introduced, and then 28 ml of dehydrated and deoxygenated toluene was added. After maintaining the internal temperature of the autoclave at room temperature and adding 2 ml of a toluene solution containing 2 μmol of metal complex-1 to the autoclave, 0.1 ml of a toluene solution was added.
6 MPa of ethylene gas was introduced to start the polymerization reaction. Polymerization was performed for 10 minutes while maintaining the internal temperature of the autoclave and the ethylene pressure. The catalyst activity is 1080kg-PE
/ Mol-Ti · hour.

Example 3 Polymerization of Ethylene 3 mmol of white solid MAO in terms of Al, metal complex-1
Example 2 except that 1 μmol was used and the polymerization time was 30 minutes.
The experiment was performed in exactly the same way. Catalyst activity is 1010k
g-PE / mol-Ti-hour.

Example 4 Polymerization of Ethylene An experiment was carried out in exactly the same manner as in Example 3 except that 5 mmol of a white solid MAO in terms of Al was used. The catalyst activity is 902 kg-PE / m
ol-Ti · hour.

[0051]

Industrial Applicability The polymerization catalyst of the present invention is an excellent catalyst which can be synthesized more easily in industrial use, has high copolymerizability of ethylene and α-olefins or ethylene and styrene, and has extremely high polymerization activity. Provide system.

Continued on the front page F-term (reference) 4J028 AA01A AB01A AC10A BA00A BA01B BB00A BB01B BC12B BC25B EA01 EB02 EB04 EB05 EB07 EB09 EB10 EB17 EB18 EB21 EC01 EC02 EC03 FA02 GB02 4J128 AA01 EB01 EB01 EB01 EB01 BA01 EB01 EB01 EB01 EB01 EB01 EB01 BA01 EB01 EB01 EB09 EB10 EB17 EB18 EB21 EC01 EC02 EC03 FA02 GB02

Claims (5)

[Claims] 1. A transition metal component (A) and an activator (B)
In a catalyst suitable for producing an olefin-based polymer, the transition metal component (A) is represented by the following formula (1): (In the formula, X and Y may be the same or different, and each comprises hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aryl group, an allyloxy group, or a halogen. R ^{1 to} R ⁷ May be the same or different, and are each composed of hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aryl group, an allyloxy group, or a substituted silyl group represented by the following formula (2). - (. wherein, R ⁸ is hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aryl group, selected from the group consisting of aryloxy _{^{groups) (R 8) 3 (2}} ) of R ¹ to R ⁵ And any two or three of them may be bonded to form a ring, and the ring includes those having an aromatic property including a conjugated double bond, and n represents an integer of 0 to 5.) Agent (B) is an alkyl aluminum oxide Olefin polymer-body polymerization catalyst which is a sheet compound or a boron compound. 2. Transition metal component (A) and activator (B)
In a catalyst suitable for producing an olefin polymer, the transition metal component (A) is represented by the following formula (3): (In the formula, X and Y may be the same or different, and each comprises hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aryl group, an allyloxy group, or a halogen. R ^{9 to} R ¹² May be the same or different, and are each composed of an alkyl group, an alkoxy group, an aryl group or an allyloxy group having 1 to 20 carbon atoms, and when there are a plurality of R ⁹ , any two or three are bonded R ¹³ may include a ring having an aromatic property including a conjugated double bond.
And 20 of any of an alkyl group, an alkoxy group, an aryl group, an allyloxy group and a substituted silyl group represented by the following formula (2). —Si— (R ⁸ ) ₃ (2) (wherein, R ⁸ is selected from the group consisting of hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an aryl group, and an allyloxy group.) M is 1 to 3 And n represents an integer of 0 to 3, respectively. A) a polymerization catalyst for an olefin polymer, wherein the activator (B) is an alkylaluminum oxy compound or a boron compound; 3. A method for producing an olefin polymer, comprising using the polymerization catalyst according to claim 1 or 2. 4. The olefin polymer according to claim 3, wherein the olefin polymer is a copolymer of ethylene and olefins.
The method for producing the olefin polymer described above. 5. The method for producing an olefin polymer according to claim 3, wherein the olefin polymer is a copolymer of ethylene and styrene.