Organic compounds -- part of the class 532-570 series – Organic compounds – Heavy metal containing
Reexamination Certificate
2002-05-10
2004-08-03
Wu, David W. (Department: 1713)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heavy metal containing
C556S051000, C502S103000, C502S118000, C526S160000, C526S170000, C526S943000, C526S351000
Reexamination Certificate
active
06770772
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a transition metal compound, an olefin polymerization catalyst, the olefin polymer obtained by using the said catalyst, and its production method. More specifically, the present invention relates to a transition metal compound which is highly efficient for production, useful and novel double cross-linked metallocene complex, the olefin polymerization catalyst containing above transition metal compound for efficiently providing a homogeneous, highly stereoregular olefin homopolymer or copolymer having narrow molecular weight distribution, above described olefin based polymer and its production method.
BACKGROUND ARTS
Heretofore, a combination of transition metal compound and aluminoxane is known as highly active and soluble type olefin polymerization catalyst [Japanese Patent Application Laid-Open S58-19309 (1983), Japanese Patent Application Laid-Open S60-217209 (1985)]. It was also reported that cationic ingredient was useful as an active ingredient for soluble type olefin polymerization catalyst [Journal of the American Chemical Society (J. Am. Chem. Soc.) Vol.81, p.81 (1959), Vol.82, p. 1953 (1960), Vol.107, p.7219 (1985)]. Examples of isolating this active ingredient for application of olefin polymerization were described in Journal of the American Chemical Society (J. Am. Chem. Soc.) Vol.108, p. 7410 (1986), Japanese Patent Application Laid-Open H1-502636, H3-139504, European Patent Laid-Open 468651, and examples of using this active ingredient together with organic aluminum compound were described in Japanese Patent Application Laid-Open H3-207704 (1991), International Patent Laid-Open 92-1723.
However, those catalysts were not quite satisfactory with respect to the catalyst activity for olefin polymerization, copolymerization characteristics or homogeneity of polymer composition and molecular weight distribution. On the other hand, the catalyst for providing isotactic polypropylene has C
2
axis of symmetry such as Me
2
Si (2,3,5-Me
3
C
5
H)(2′,4′,5′-Me
3
C
5
H) ZrCl
2
in the molecule, structurally having two stereoisomers of racemi form and meso form, and it was necessary to separate racemic form to completely remove meso form to obtain a homogeneous isotactic polypropylene having narrow molecular weight distribution. This resulted in a high cost of production.
On the other hand, as single cross-linked metallocene complex is thermally weak and tends to change property of active site due to heat of polymerization, multi cross-linked type (double cross-linked type) metallocene complex is under study. However, only a few examples of synthesis of multi cross-linked type metallocene complex were reported such as in the International Patent Laid-Open 93-20113, and Organometallics Vol.12, p.1931 (1993), Organometallics Vol.13, p.3868 (1994), Organometallics Vol.17, p.5528 (1998). Although its behavior as polymerization catalyst was reported in Organometallics Vol.12, p.5528 (1998), separation of meso form and racemic form of the metallocene complex was necessary for obtaining isotactic polypropylene, and the obtained molecular weight of the polypropylene was low.
Catalysts for production of polypropylene using multi cross-linked metallocene complex were also disclosed in the International Patent Laid-Open 99-67303, and the Japanese Patent Application Laid-Open 2000-256411, solving above problems. However, melting point of the obtained polymer is low, and no polymer having a good balance between molecular weight and stereoregularity was obtained.
All the references cited above are related to symmetrical metallocene complex having two ring-structured ligands of the same structure coordinated around the center metal. For example, in the above described International Patent Laid-Open 99-67303, as well as in the Japanese Patent Application Laid-Open 2000-256411, double cross-linked metallocene complex having two indenyl rings with substituting group in the tertiary position was disclosed, but the yield of the ligand was low.
DISCLOSURE OF THE INVENTION
With such background as described above, the object of the present invention is to provide a transition metal compound which is highly efficient for production and useful novel double cross-linked metallocene complex, a highly active polymerization catalyst for giving a high molecular weight and homogeneous olefin based polymer with narrow molecular weight distribution, and an olefin based homopolymer or copolymer having high molecular weight, homogeneous composition, narrow molecular weight dictribution, high stereoregularity and high melting point, prepared by using above catalyst.
The inventors of the present invention, as the result of their intensive study for achieving above described object, have found that a transition metal compound of a novel asymmetrical type double cross-linked metallocene complex with a specified structure was useful as a component of olefin polymerization catalyst, and that the polymerization catalyst comprising above transition metal compound and an activating co-catalyst has high activity, and efficiently provide olefin based polymer and copolymer with high molecular weight, homogeneous composition and narrow molecular weight distribution. The present invention has been completed based on such findings.
Namely, the present invention provides
(1) a transition metal compound represented by the general formula (I),
[wherein, M represents a metal element in the groups 3 to 10 group of the periodic table or in the lanthanide series, X represents a &sgr; bonding ligand bonded to M, if X is plural, X may be the same or different, or cross-linked with indenyl ring or Y.
Y represents a Lewis base, if Y is plural, Y may be the same or different, or may be cross-linked with indenyl ring or X. A represents a cross-linking group, p is an integer of 1 to 20, q is an integer of 1 to 5 and represents [(valence of M)−2], r is an integer of 0 to 3. R
1
represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen containing hydrocarbon group having 1 to 20 carbon atoms, a silicon containing group or a hetero-atom containing group. Each of R
2
to R
9
represents respectively hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen containing hydrocarbon group having 1 to 20 carbon atoms, a silicon containing group or a hetero-atom containing group, they may be the same or different with each other, or may form a ring with neighboring group.]
(2) (A) Olefin polymerization catalyst comprising a transition metal compound represented by above general formula (I) and an activating co-catalyst as the main components,
(3) Olefin based polymer obtained by using above olefin polymerization catalyst, and
(4) Production method of above olefin based polymer characterized by homo polymerizing olefins, or co-polymerizing other olefins and/or other monomer, under the presence of above olefin polymerization catalyst.
PREFERRED EMBODIMENTS OF THE INVENTION
Transition metal compound of the present invention is a novel double cross-linked type metallocene complex represented by the general formula (I).
In the general formula (I), R
1
represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen containing hydrocarbon group having 1 to 20 carbon atoms, a silicon containing group or a hetero-atom containing group; R
2
to R
9
represents hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen containing hydrocarbon group having 1 to 20 carbon atoms, a silicon containing group or a hetero-atom containing group. R
1
is preferably a hydrocarbon group having 1 to 20 carbon atoms or a silicon containing group.
Examples of hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group and octyl group; alkenyl groups such as vinyl group, propenyl group, cyclohexenyl group; arylalkyl groups such as benzyl gr
Kashiwamura Takashi
Minami Yutaka
Okamoto Takuji
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