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
1999-03-09
2002-04-16
Wood, Elizabeth D. (Department: 1755)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Plural component system comprising a - group i to iv metal...
C502S103000, C502S114000, C502S152000
Reexamination Certificate
active
06372681
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a catalyst for olefin polymer production comprising a metallocene compound, a reaction product of topotactic reduction by electron transfer, and an organoaluminum compound, and a process for producing an olefin polymer employing the catalyst.
The present invention relates also to a catalyst for olefin polymer production comprising a metallocene compound, a product of a topotactic reduction reaction by electron transfer, an organoaluminum compound, an organoalkaline earth metal compound or an organozinc compound, and a process for producing an olefin polymer employing the catalyst.
2. Description of the Related Art
A catalyst composed of a metallocene compound and an organoaluminum compound, and another catalyst composed of a metallocene compound, an organoaluminum compound, and an organomagnesium compound are disclosed as the catalyst for producing an olefin polymer (JP-A-3-197513, and JP-A-3-290408). However, these catalysts are not satisfactory in the catalyst activity.
Active catalysts for olefin polymer production are disclosed which are composed of a metallocene compound and a methylaluminoxane (JP-A-58-19309, and JP-A-60-35007). These catalyst employs a large amount of expensive aluminoxane to produce a polymer having industrially useful properties, which causes problems of high catalyst cost and residual aluminum.
Highly active olefin polymerization catalysts not containing the methylaluminoxane are disclosed which comprises a metallocene compound, a boron compound, and an organoaluminum compound (Kohyo 1-501950, and Kohyo 1-502036). However, the boron compound for this catalyst is disadvantageously complicated and expensive.
SUMMARY OF THE INVENTION
The present invention intends to solve the above technical problems, and to provide a catalyst for olefin polymer production with high catalyst activity without using an expensive catalyst component. The present invention also provides a process for producing an olefin polymer with the catalyst.
The olefin polymerization catalyst of the present invention comprises [A] a metallocene compound containing a transition metal selected from Groups 3, 4, 5, and 6 of Periodic Table, [B] a reaction product of topotactic reduction with electron transfer, and [C] an organoaluminum compound.
The olefin polymerization catalyst of another embodiment of the present invention comprises [A] a metallocene compound containing a transition metal selected from Groups 3, 4, 5, and 6 of Periodic Table, [B] a reaction product of topotactic reduction by electron transfer, [C] an organoaluminum compound, and [D] an organoalkaline earth metal compound or an organozinc compound.
The process for producing an olefin polymer of the present invention uses the above catalyst.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The topotactic reduction with electron transfer in the present invention is a reaction, as defined by R. Schöllhorn: Angew. Chem. Int. Ed. Eng., 19, 983-1003 (1980), in which a host compound is reduced by electrons and guest are introduced into vacant lattice sites of the host compound to balance the electric charges without change of the structure and composition of the host compound by the reaction. This reaction is represented by General Formula (35) below:
xE
+
+xe
−
+□[Q]→(E
+
)
x
[Q]
x−
(35)
where [Q] is the host compound, □ is a vacant lattice site of [Q], e
−
is an electron, x is a number of reduction, and E
+
is a monovalent guest cation.
The component [B] in the present invention is a reaction product of the above electron-transferring topotactic reduction, and is represented by General Formula (36):
E
n+
(k
)
(L
2
)
h
[Q]
k−
(36)
where [Q] is a host compound, k is a number of reduction, E
n+
is an n-valent guest cation, L
2
is a Lewis base, and h is a number of the Lewis base.
The host compound [Q] includes host compounds of three-dimensional structure, host compounds of two-dimensional structure, host compounds of one-dimensional structure, and host compounds of a molecular solid.
The host compounds of three-dimensional structure include hexamolybdenum octasulfide, hexamolybdenum octaselenide, trimolybdenum tetrasulfide, trititanium tetrasulfide, hexatitanium octaselenide, triniobium tetrasulfide, hexavanadium octasulfide, pentavanadium octasulfide, divanadium pentaoxide, tungsten trioxide, titanium dioxide, vanadium dioxide, chromium dioxide, manganese dioxide, tungsten dioxide, ruthenium dioxide, osmium dioxide, and iridium dioxide.
The host compounds of two-dimensional structure include titanium disulfide, zirconium disulfide, hafnium disulfide, vanadium disulfide, niobium disulfide, tantalum disulfide, chromium disulfide, molybdenum disulfide, tungsten disulfide, rhenium disulfide, platinum disulfide, tin disulfide, lead disulfide, titanium diselenide, zirconium diselenide, hafnium diselenide, vanadium diselenide, niobium diselenide, tantalum diselenide, chromium diselenide, molybdenum diselenide, tungsten diselenide, rhenium diselenide, platinum diselenide, tin diselenide, lead diselenide, titanium ditelluride, zirconium ditelluride, hafnium ditelluride, vanadium ditelluride, niobium ditelluride, tantalum ditelluride, chromium ditelluride, molybdenum ditelluride, tungsten ditelluride, rhenium ditelluride, platinum ditelluride, tin ditelluride, lead ditelluride, magnesium phosphorus trisulfide, calcium phosphorus trisulfide, vanadium phosphorus trisulfide, manganese phosphorus trisulfide, iron phosphorus trisulfide, cobalt phosphorus trisulfide, nickel phosphorus trisulfide, palladium phosphorus trisulfide, zinc phosphorus trisulfide, cadmium phosphorus trisulfide, mercury phosphorus trisulfide, tin phosphorus trisulfide, magnesium phosphorus triselenide, calcium phosphorus triselenide, vanadium phosphorus triselenide, manganese phosphorus triselenide, iron phosphorus triselenide, cobalt phosphorus triselenide, nickel phosphorus triselenide, palladium phosphorus triselenide, zinc phosphorus triselenide, cadmium phosphorus triselenide, mercury phosphorus triselenide, tin phosphorus triselenide, chromium phosphorus tetrasulfide, tantalum sulfide carbide, molybdenum trioxide, octadecamolybdenum dopentacontaoxide (18-molubdenum 52-oxide), divanadium pentaoxide gel, iron oxychloride, titanium oxychloride, vanadium oxychloride, chromium oxychloride, aluminum oxychloride, bismuth oxychloride, &agr;-zirconium nitride chloride, &bgr;-zirconium nitride chloride, &agr;-zirconium nitride bromide, &bgr;-zirconium nitride bromide, zirconium nitride iodide, titanium nitride chloride, titanium nitride bromide, titanium nitride iodide, graphite, and polyacene.
The host compounds of one-dimensional structure include titanium trisulfide, niobium triselenide, potassium iron disulfide, polyacetylene, polyaniline, polypyrrole, polythiophene, poly(p-phenylene), poly(triphenylene), polyazulene, polyfluorene, polynaphthalene, polyanthracene, polyfuran, polycarbazole, tetrathiafluvalene-substituted polystyrene, ferrocene-substituted polyethylene, carbazole-substituted polyethylene, and polyoxyphenazine.
The host compounds of a molecular solid include tetracyanoquinodimethane, and tetrathiafluvalene.
The host compound [Q] may be a mixture of two or more of the above host compounds.
The number of reduction, k, is preferably in the range of 0<k≦3, more preferably 0<k≦2 for high catalytic activity for olefin polymerization, but is not especially limited thereto.
The Lewis base or a cyclopentadienyl group, L
2
, may be one capable of coordinating with E
n+
. The Lewis base includes water, amine compounds, nitrogen-containing heterocyclic compounds; ethers such as ethyl ether and n-butyl ether; amides such as formamide, N-methylformamide, N,N-dimethylformamide, and N-methylacetamide; alco
Yamada Satoru
Yano Akihiro
Sughrue & Mion, PLLC
Tosoh Corporation
Wood Elizabeth D.
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