Transition metal compound, catalyst for olefin...

Details Transition metal compound, catalyst for olefin... Transition metal compound, catalyst for olefin...

1997-09-29

2002-01-15

Wu, David W. (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C502S103000, C502S117000, C556S053000, C526S134000, C526S161000, C526S943000

Reexamination Certificate

active

06339135

ABSTRACT:

TECHNICAL FIELD
The present invention relates to a transition metal compound, a double crosslinking type biscyclopenta-dienyl derivative and bisindenyl derivative for use in the transition metal compound, its preparation process, a catalyst for olefin polymerization using the transition metal compound, an olefin polymer obtained by the use of this catalyst, and a process for preparing the olefin polymer. More specifically, the present invention relates to a novel double crosslinking type transition metal compound useful as a component of a catalyst for olefin polymerization, a specific double crosslinking type biscyclopentadienyl derivative and bisindenyl derivative useful as a ligand of this transition metal compound, a process for efficiently preparing the double crosslinking type bisindenyl derivative, a catalyst for polymerization which has a high activity and an excellent copolymerizability and which contains the transition metal compound and which is capable of forming an olefin polymer having a uniform composition and a narrow molecular weight distribution, an olefin homopolymer and an olefin copolymer obtained by the use of this catalyst for polymerization, and a process for efficiently preparing the olefin polymer.
BACKGROUND ART
Heretofore, as highly active soluble catalysts for olefin polymerization, catalysts comprising a combination of a transition metal compound and an aluminoxane are known (Japanese Patent Application Laid-open Nos. 19309/1983 and 217209/1985). Furthermore, it has been reported that cationic species are useful as active species of the soluble catalyst for olefin polymerization [J. Am. Chem. Soc., Vol. 81, p. 81 (1959), Vol. 82, p. 1953 (1960), and Vol. 107, p. 7219 (1985)]. In addition, examples where each of these active species is isolated and is applied to the olefin polymerization have been described in J. Am. Chem. Soc., Vol. 108, p. 7410 (1986), Japanese PCT Patent Application Laid-open No. 502636/1989, Japanese Patent Application Laid-open No. 139504/1991, EP-A-O 468651 and the like. Other examples where this active species is used together with an organic aluminum compound have been described in Japanese Patent Application Laid-open No. 207704/1991, WO 92-1723 and the like. Moreover, an example of a catalyst for olefin polymerization which comprises a transition metal compound having a ligand containing an —SO
3
R group and an organic aluminum oxycompound has been described in EP-A-O No. 519746 and the like.
However, these catalysts do not always satisfy a catalytic activity for olefin polymerization, copolymerizability, and the composition uniformity and the molecular weight distribution of an obtained polymer.
On the other hand, with regard to double cross-linking type metallocene complexes, “Organometallics”, Vol. 12, p. 1931 (1993) has described a polymerization example of propylene in the presence of a dimethylsilylene double crosslinking type metallocene complex, but in order to obtain isotactic polypropylene by the utilization of this polymerization technique, the separation of a meso form of the metallocene complex from a racemic form thereof is required, and the heat stability of a catalyst itself is also poor.
Furthermore, the double crosslinking type metallocene complexes containing an ethylene crosslinking group has been suggested in “Organometallics”, Vol. 13, p. 3868-3872 (1994), but in this case, a cyclopentadienyl group which can be used as a ligand does not have any substituent other than a crosslinking agent. Additionally, in its synthetic route, any product having a substituted cyclopentadienyl structure such as an indenyl group cannot be obtained.
DISCLOSURE OF THE INVENTION
The present invention has been intended under such circumstances, and an object of the present invention is to provide (1) a novel double crosslinking type transition metal compound (a double crosslinking type metallocene complex) useful as a component of a catalyst for olefin polymerization, (2) a double crosslinking type biscyclopentadienyl derivative and bisindenyl derivative usable as a ligand of this transition metal compound, (3) a process for efficiently preparing the double crosslinking type bisindenyl derivative, (4) a catalyst for polymerization which has a high activity and an excellent copolymerizability and which is capable of forming an olefin polymer having a uniform composition and a narrow molecular weight distribution, and (5) a process for efficiently preparing a catalyst by which a highly steric regular olefin polymer can be produced without requiring the division between a racemic form and a meso form.
The present inventors have intensively researched to achieve the above-mentioned object, and as a result, it has been found that a novel double crosslinking type transition metal compound having a specific structure is useful as a catalytic component for olefin polymerization; a specific double crosslinking type biscyclopentadienyl and bisindenyl derivative is useful as a ligand of the above-mentioned transition metal compound; and the double crosslinking type bisindenyl derivative can efficiently be prepared by a specific process.
Furthermore, the present inventors have found that a polymerization catalyst, which comprises the double crosslinking type transition metal compound, an activation cocatalyst, for example, a compound capable of reacting with the transition metal compound or its derivative to form an ionic complex, and if necessary, an organic aluminum compound, has a high activity and an excellent copolymerizability and can efficiently provide an olefin homopolymer or copolymer having a uniform composition and a narrow molecular weight distribution.
In consequence, the present invention has been completed on the above-mentioned findings.
That is to say, according to the present invention, there can be provided
(1) a transition metal compound represented by the general formula (I)
 wherein N is a metallic element in the groups 3 to 10 or a lanthanoide series of the periodic table; E
1
and E
2
are each a ligand selected from the group consisting of a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a heterocyclopentadienyl group, a substituted heterocyclopentadienyl group, an amido group, a phosphide group, a hydrocarbon group and a silicon-containing group, and they form a crosslinking structure via A
1
and A
2
, and they may be the same or different; X is a &sgr;-bonding ligand, and when a plurality of Xs are present, these plural Xs may be the same or different, and each X may crosslink with another X, E
1
, E
2
or Y; Y is a Lewis base, and when a plurality of Ys are present, these plural Ys may be the same or different, and each Y may crosslink with another Y, E
1
, E
2
or X; A
1
and A
2
are each a cross-linking group comprising a hydrocarbon group of one or more carbon atoms, and they may be the same or different; q is an integer of 1 to 5 [(the valence of M)−2]; and r is an integer of 0 to 3,
(2) a double crosslinking type biscyclopentadienyl derivative represented by the general formula (V)
 wherein A
1
and A
2
are as defined above; R
1
to R
6
are each a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group or a hetero-atom-containing group, but at least one of R
1
to R
6
is not a hydrogen atom, and they may be the same or different, and the adjacent groups of R
1
to R
6
may bond to each other to form a ring structure; and the positions of double bonds are not limited to the above,
(3) a double crosslinking type bisindenyl derivative represented by the general formula (VII)
 wherein A
1
and A
2
are as defined above; R
7
to R
10
are each a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group or a hetero-atom-containing group, and they may be the same or different, and the a

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