Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Plural component system comprising a - group i to iv metal...
Reexamination Certificate
1998-11-02
2001-01-09
Wu, David W. (Department: 1713)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Plural component system comprising a - group i to iv metal...
C556S042000, C556S043000, C556S052000, C556S053000, C556S012000, C556S022000, C556S023000, C556S011000, C502S152000, C502S155000
Reexamination Certificate
active
06171994
ABSTRACT:
DESCRIPTION
1. Technical Field
The present invention relates to a transition metal ompound, a compound which can be used as its material, a process for preparing each of these compounds, 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 multiple-crosslinking type transition metal compound (multiple crosslinking metallocene complex) useful as a component of a catalyst for olefin polymerization, a bisindenyl derivative usable as a ligand of this transition metal compound, its precursor, a process for efficiently preparing each of the transition metal compound and its precursor, 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 each of these olefin polymers.
2. 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 and EP-A-O 468651. 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 and WO 92-1723. 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.
However, these catalysts do not always satisfy a catalytic activity for olefin polymerization, copolymerizability, and the uniformity and molecular weight distribution of an obtained polymer.
On the other hand, a transition metal compound having a bicyclopentadienyl group, i.e., a metallocene complex is particularly highly active and is known to be useful as a highly steric regular catalyst. This metallocene complex can be classified into a non-crosslinking type, a single crosslinking type and a multiple crosslinking type on the basis of the crosslinking structure of two cyclopentadienyl groups, but most of the conventional metallocene complexes are of the non-crosslinking type and the single crosslinking type.
Examples of the non-crosslinking type metallocene complex have been disclosed or reported in U.S. Pat. No. 5,200,537, Japanese Patent Application Laid-open Nos. 222177/1988, 222178/1988, 222179/1988, 301704/1989 and the like, and examples of the single crosslinking type metallocene complex have been disclosed or reported in Japanese Patent Application Laid-open Nos. 131488/1990 and 41303/1992, “Angew. Chem. Int. Ed. Engl.”, Vol. 24, Vol. 6, p. 507 (1985) and the like.
On the contrary, with regard to the multiple crosslinking type (double crosslinking type) metallocene complexes, their synthetic examples are limited, and they are described only in WO 93-20113 and “Organometallics”, Vol. 12, p. 1931 (1993). In addition, these publications have described a polymerization example of propylene in the presence of a dimethylsilylene double crosslinking type metallocene complex, but the heat stability of this catalyst itself is poor. Since this metallocene complex has a specific crosslinking structure, the isomerization of a meso form into a racemic form occurs during the preparation of the complex, and therefore the desired complex cannot always be obtained.
On the other hand, “Organometallics”, Vol. 12, p. 5012 (1993) has described a preparation process of a bisindenyl derivative in which the crosslinking is made at the 2-position, but this process is not practical, because its synthetic route is intricate.
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 multiple crosslinking type transition metal compound (multiple crosslinking metallocene complex) useful as a component of a catalyst for olefin polymerization, (2) a multiple crosslinking type bisindenyl derivative usable as a ligand of this transition metal compound, (3) a process for efficiently preparing the transition metal compound of the above-mentioned (1), (4) a bisindenyl derivative usable as a precursor of the multiple crosslinking type bisindenyl derivative of the above-mentioned (2), (5) a process for efficiently preparing the bisindenyl derivative of the above-mentioned (4), (6) 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, (7) an olefin homopolymer or copolymer having a uniform composition and a narrow molecular weight distribution obtained by the use of this catalyst for polymerization, and (8) a process for efficiently preparing the olefin homopolymer or copolymer.
Thus, the present inventors have intensively researched to achieve the above-mentioned object, and as a result, it has been found that a novel multiple crosslinking type transition metal compound having a specific structure is useful as a catalytic component for olefin polymerization; a specific multiple crosslinking type bisindenyl derivative is useful as a ligand of the above-mentioned transition metal compound; and the transition metal compound can efficiently be prepared by a specific process.
In addition, the present inventors have also found that a bisindenyl derivative, which can be used as a precursor of the multiple crosslinking type bisindenyl derivative useful as the ligand of the above-mentioned transition metal compound, can efficiently be prepared by a specific process.
Furthermore, the present inventors have found that a polymerization catalyst, which comprises the multiple 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 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 M 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 &sgr;-bonding or a &pgr;-bonding ligand, and they form a cross-linking structure via (A
1
)
p
, (A
2
)
p
, . . . (A
n
)
p
and (D)
s
, 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
, A
2
, . . . A
n
are each a crosslinking group, and they may be the same or different, but at least one of them comprises a crosslinked structure c
Okamoto Takuji
Tani Noriyuki
Watanabe Masami
Yabunouchi Nobuhiro
Yokota Kiyohiko
Choi Ling-Siu
Idemitsu Kosan Co. Ltd.
Oblon & Spivak, McClelland, Maier & Neustadt P.C.
Wu David W.
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