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
2000-12-11
2004-08-17
Choi, Ling-Siu (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...
C502S103000, C502S118000, C502S134000, C502S172000, C526S158000, C526S348000, C526S123100, C526S124300, C423S635000, C423S497000
Reexamination Certificate
active
06777365
ABSTRACT:
TECHNICAL FIELD
The present invention relates to a magnesium compound suitable for a carrier for olefin polymerization catalysts, to an olefin polymerization catalyst comprising it, and to a method for producing olefin polymers. Precisely, the invention relates to a magnesium compound effective in producing olefin polymers having an increased bulk density and a narrowed particle size distribution, not lowering the stereospecificity of the polymers produced and not lowering the polymerization activity in producing the polymers, and also relates to an olefin polymerization catalyst comprising the compound, and to a method for producing such olefin polymers.
BACKGROUND ART
Heretofore widely known in the art is a technique of using a carrier of non-ground magnesium chloride or magnesium alkoxide for olefin polymerization catalysts in homopolymerizing or copolymerizing ethylene or propylene, and this is for improving the catalyst activity and for improving the powder morphology of polymers produced. For example, known are a method of holding a magnesium compound on an inorganic oxide such as silica, for improving the morphology including the particle size and the particle shape of the polymers produced in the presence of it (e.g., Japanese Patent Laid-Open No. 280707/1988); and a method of once dissolving a magnesium compound in a solvent of alcohol or the like followed by re-precipitating it, and using it in producing olefin polymers (e.g., Japanese Patent Laid-Open No. 811/1981). However, the methods are problematic in that their steps are extremely complicated since they indispensably require the step of holding a magnesium compound on a carrier or the step of dissolving a magnesium compound followed by re-precipitating it, and that the properties of the catalysts produced are not stable. On the other hand, another method has been developed, which comprises reacting metal magnesium with alcohol and a specific amount of halogen to prepare a magnesium compound for carrier (e.g., Japanese Patent Laid-Open No. 130107/1992). However, this is still problematic in that the powder morphology (a bulk density, a particle size distribution or the like) of the polymers produced in the presence of it is not all the time satisfactory.
The present invention has been made in consideration of the matters noted above, and its object is to provide a magnesium compound effective in producing olefin polymers having an increased bulk density and a narrowed particle size distribution, not lowering the stereospecificity of the polymers produced and not lowering the polymerization activity in producing the polymers, and also to provide an olefin polymerization catalyst comprising the compound and a method for producing such olefin polymers.
DISCLOSURE OF THE INVENTION
We, the present inventors have assiduously studied in order to attain the object as above, and have found that the object can be attained by an olefin polymerization catalyst that comprises a solid catalyst component prepared by contacting a magnesium compound (this is prepared by reacting a metal magnesium, an alcohol, and at least 0.0001 gram atoms, in terms of the halogen atom relative to one gram atom of magnesium, of a halogen and/or a halogen-containing compound, at a specifically controlled temperature) with titanium and optionally with an electron donor compound, and an organoaluminium compound. On the basis of this finding, we have completed the first aspect of the invention.
Specifically, the first aspect of the invention is to provide a magnesium compound, an olefin polymerization catalyst and a method for producing olefin polymers mentioned below.
1. A magnesium compound obtained by reacting a metal magnesium, an alcohol, and at least 0.0001 gram atoms, in terms magnesium, an alcohol, and at least 0.0001 gram atoms, in terms of the halogen atom relative to one gram atom of magnesium, of a halogen and/or a halogen-containing compound, at 30 to 60° C.
2. The magnesium compound of above 1, wherein the halogen is iodine.
3. The magnesium compound of above 1, wherein the halogen-containing compound is magnesium chloride.
4. A solid magnesium compound substantially comprising a magnesium alkoxide, of which the particle size distribution index (P) represented by the following formula (I-1) is smaller than 4.0, P<4.0:
P=
(
D
90
/D
10
) (I-1)
(wherein D
90
indicates the particle diameter of the compound particles corresponding to the cumulative weight fraction of 90% in the particle size distribution thereof computed from the light transmittance through a suspension of the compound particles in a hydrocarbon; and D
10
indicates the particle diameter of the compound particles corresponding to the cumulative weight fraction of 10% therein.)
5. An olefin polymerization catalyst comprising (A) a solid catalyst component prepared by contacting (a) the magnesium compound of any of above 1 to 4 with (b) a titanium compound of the following general formula (I-3), and (B) an organometallic compound:
Ti(OR)
n
X
4−n
(I-3)
(wherein X indicates a halogen atom; R indicates a hydrocarbon group having from 1 to 10 carbon atoms, and R's may be the same or different; and n indicates an integer of from 0 to 4.)
6. An olefin polymerization catalyst comprising (A) a solid catalyst component prepared by contacting (a) the magnesium compound of any of above 1 to 4, (b) a titanium compound of the following general formula (I-3) and (c) an electron donor compound with each other, (B) an organometallic compound, and (C) a third component of an electron donor compound:
Ti(OR)
n
X
4−n
(I-3)
(wherein X indicates a halogen atom; R indicates a hydrocarbon group having from 1 to 10 carbon atoms, and R's may be the same or different; and n indicates an integer of from 0 to 4.)
7. A method for producing olefin polymers, which comprises polymerizing an olefin in the presence of the olefin polymerization catalyst of above 5 or 6.
We, the present inventors have further found that the object of the invention can be attained by an olefin polymerization catalyst that comprises a solid catalyst component prepared by contacting a specific magnesium compound (this is prepared by reacting a metal magnesium, an alcohol, and at least 0.0005 gram atoms, in terms of the halogen atom relative to one gram atom of magnesium, of a halogen and/or hydrocarbon compound) with titanium and optionally with an electron donor compound, and an organoaluminium compound. On the basis of this finding, we have completed the second aspect of the invention.
Specifically, the second aspect of the invention is to provide a magnesium compound, an olefin polymerization catalyst and a method for producing olefin polymers mentioned below.
1. A magnesium compound obtained by reacting a metal magnesium, an alcohol, and at least 0.0005 gram atoms, in terms of the halogen atom relative to one gram atom of magnesium, of a halogen and/or a halogen-containing compound, in the presence of a saturated hydrocarbon compound.
2. The magnesium compound of above 1, wherein the halogen is iodine.
3. The magnesium compound of above 1, wherein the halogen-containing compound is magnesium chloride.
4. A solid magnesium compound substantially comprising a magnesium alkoxide, of which the particle size distribution index (P) represented by the following formula (II-1) is smaller than 4.0, P<4.0:
P=
(
D
90
/D
10
) (II-1)
(wherein D
90
indicates the particle diameter of the compound particles corresponding to the cumulative weight fraction of 90% in the particle size distribution thereof computed from 90% in the particle size distribution thereof computed from the light transmittance through a suspension of the compound particles in a hydrocarbon; and D
10
indicates the particle diameter of the compound particles corresponding to the cumulative weight fraction of 10% therein.)
5. An olefin polymerization catalyst comprising (A) a solid catalyst component prepared by contacting (a) the magnesium compound of any of above 1 to 4 with (
Funabashi Hideo
Ota Tsuyoshi
Tanase Shohjiroh
Tsuda Takehiro
Choi Ling-Siu
Idemitsu Petrochemical Co. Ltd.
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