Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2000-05-22
2002-07-30
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...
C526S127000, C526S943000, C556S053000, C502S152000
Reexamination Certificate
active
06426395
ABSTRACT:
TECNICAL FIELD
The present invention relates to &mgr;-oxo-bis-metallocene complex compounds and catalysts using same for the polymerization of olefins as well as polymerization processes. In particular, the present invention is featured by using as the metallocene complex compounds those having cyclopentadienyl rings, especially a bridged cyclopentadienyl ligand.
BACKGROUND ART
It is known that a variety of metallocene complex compounds are proposed as a component for the polymerization of olefins and that various olefin polymers can be produced by selecting the sort of metallocene complex compounds. Especially in the polymerization of propylene, it is publicly known that any of the atactic polypropylene, isotactic polypropylene and syndiotactic polypropylene can be produced. (Makromol. Chem., Rapid. Commun. 1983, 4,417-421; Angew. Chem., Int. Engl. 1985, 24, 507-508; J. Am. Chem. Soc. 1988, 110, 6255-6256; etc.) Purification of metallocene complex compounds is usually carried out by washing, extraction with a solvent, recrystallization and the like means. However, a considerable amount of metallocene complex compounds remain in a residue after purification, e.g. in washing liquids and a mother liquid of recrystallization, and the metallocene complex compounds cannot be recovered in some cases so that it incurs economical disadvantage.
Depending on the positions of substituents at the time of synthesis, metallocene complexes may permit the existence of stereoisomers. In the event a mixture of complex isomers formed on synthesis is straightforwardly used for polymerization of olefins where different olefin polymers are produced according to the different nature of the isomers, the resultant polymer will become a mixture of two different polymers. In case a uniform polymer is to be produced, therefore, the mixture of polymers has to be separated. For obtaining a highly pure isomeric form, however, repeating of the separation operations was necessary so that efficiency of the production was extremely low.
In Japanese Laid-open Patent Appln. No. Hei. 10-67793, there is disclosed that a method of changing the racemic/meso ratio wherein unnecessary isomer is decomposed with a decomposing agent such as acidic hydrogen atom or a reactive halogen atom. This method pertains to changing of the racemic/meso ratio by decomposing either one of the isomers, and more precisely, the racemic form is decomposed with ethylene-bis(4,7-dimethylindenyl)zirconium dichloride to obtain the pure meso form. As the other isomer is decomposed, however, this decomposed isomer cannot be used as catalyst component so that this method is regarded economically less interested.
A number of references are known concerning &mgr;-oxo-bis-metallocene complex compounds having non-bridged cyclopentadienyl ligans, for example, Inorganic Chemistry 15, No. 9, 1976 disclosing that dimethylhafnocene is brought into contact with water in the air to form &mgr;-oxo-bis(methylhafnocene) and Comprehensive Organometallic Chemistry 4, 1982, 527-528 disclosing a &mgr;-oxo-complex compound containing a briged ligand.
In addition, Japanese laid-open Patent Appln. No. Hei. 7-233211 discloses a catalyst for the polymerization of olefins which contains a &mgr;-oxo-complex combining metals of two nuclear complexes bridging Cp.
TECHNICAL PROBLEMS OF THE INVENTION
It is an object of the present invention to provide a novel &mgr;-oxo-bis-metallocene complex compound excellent in crystallinity and separability and capable of being used as a catalyst component for the polymerization of olefins.
It is another object of the present invention to provide a catalyst for the polymerization of olefins which comprises the aforesaid novel &mgr;-oxo-bis-metallocene complex compound.
It is still another object of the present invention to provide a process for polymerizing olefins by the aid of the above catalyst.
As a result of extensive research made to attain the aforesaid objects, it has now been found that &mgr;-oxo-bis-metallocene complex compounds having an M—O—M bond are excellent in crystallinity and easily capable of being isolated from a reaction liquid at the time of synthesis and can be employed as a catalyst component for the polymerization of olefins. The present invention has been accomplished on the basis of the above finding.
DISCLOSURE OF THE INVENTION
According to the present invention, there is provided a &mgr;-oxo-bis-metallocene complex compound represented by the formula (1):
wherein M stands for a transition metal belonging to Group III, IV, V, VI, Lantanoid or Actinoid of the Periodic Table, n stands for an integer of 1 or 2, Y stands for carbon, silicon, germanium or tin, X's may be the same or different and each independently stands for a halogen atom, a halogenoid atomic group, a hydrocarbon group having 1-20 carbon atoms which may contain a silicon, germanium, oxygen, sulfur, or nitrogen, or a monocyclic or polycyclic heteroaromatic group which may contain a hetero atom or atoms selected from the group consisting of oxygen atoms, sulfur atoms and nitrogen atoms in the 5-membered or 6-membered ring or rings thereof and which may be substituted on the ring or rings thereof by other substituents, R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 may be the same or different and each stands for hydrogen, an alkyl group having 1-20 carbon atoms, a cycloalkyl group having 3-20 carbon atoms, an alkenyl group with 2-20 carbon atoms, an aryl group having 6-20 carbon atoms, an alkylaryl group having 7-20 carbon atoms, or an aralkyl group having 7-20 carbon atoms with the proviso that these groups may contain a silicon, germanium, oxygen, sulfur, or- nitrogen, or a monocyclic or polycyclic heteroaromatic group which may contain a hetero atom or atoms selected from the group consisting of oxygen atoms, sulfur atoms and nitrogen atoms in the 5-membered or 6-membered ring or rings thereof and which may be substituted on the ring or rings by other substituents with the proviso that the adjacent substituents on the cyclopentadienyl groups may form together a cyclic structure having 5-8 carbon atoms and the cyclic structure may be an aromatic ring, that R9 and R10 may form together with Y a cyclic structure having 4-8 carbon atoms and which may contain oxygen, sulfur and nitrogen, and that R1-R8 are not hydrogen at the same time.
According to the present invention, there is also provided the aforesaid &mgr;-oxo-bis-metallocene complex compound wherein R2, R3, R6 and R7 in the above formula (1) are not hydrogen at the same time.
According to the present invention, there is further provided the aforesaid &mgr;-oxo-bis-metallocene complex compound wherein M and Y in the above formula (1) each stands for titanium, zirconium or hafnium and for carbon, silicon or germanium, respectively.
According to the present invention, there is still another provided a &mgr;-oxo-bis-metallocene complex compound represented by the formula (2):
wherein M stands for titanium, zirconium, or hafnium, n stands for an integer of 1 or 2, Y stands for carbon, silicon, or germanium, X's may be the same or different and: each independently stands for a halogen atom, a halogenoid atomic group, a hydrocarbon group hang 1-20 carbon atoms which may contain silicon, germanium, oxygen, sulfur or nitrogen, or a monocyclic heteroaromatic group which may contain a hetero atom or atoms selected. from the group consisting of oxygen atoms, sulfur atoms and nitrogen atoms in the 5-membered or 6-membered ring or rings. thereof and which may be substituted on the ring or rings thereof by other substituents, R1, R2, R4, R5, R7 and R8 may be the same or different and each stands for hydrogen, an alkyl group having 1-20 carbon atoms, a cycloalkyl group having 3-20 carbon atoms, an alkenyl group with 2-20 carbon atoms, an aryl group having 6-20 carbon atoms, an alkylaryl group having 7-20 carbon atoms, or an aralkyl group having 7-20 carbon atoms with the proviso that these groups may contain silicon, germanium, oxygen, sulfur, or nitrogen, or a monocyclic or polycyclic heteroaromat
Harada Masato
Koyama Mina
Mitani Seiki
Nakano Masato
Saito Jun
Chisso Corporation
Harlan R.
Leydig , Voit & Mayer, Ltd.
Wu David W.
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