Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Organic compound containing
Reexamination Certificate
1999-04-20
2001-09-04
Bell, Mark L. (Department: 1755)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Organic compound containing
C502S103000, C502S104000, C502S111000, C502S113000, C502S117000, C502S118000, C502S119000, C502S120000, C502S121000, C502S122000, C502S123000, C502S128000, C502S150000, C502S155000, C502S156000, C502S157000, C502S167000, C502S168000, C502S172000, C526S943000
Reexamination Certificate
active
06284701
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to new metallocene catalysts for use in preparation of olefin polymers or co-polymers. More specifically, the present invention relates to methods of preparing the metallocene catalysts and methods of preparing olefin polymers such as mono-polymers of ethylene or &agr;-olefin, ethylene/&agr;-olefin co-polymers, propylene/&agr;-olefin co-polymers, etc using the metallocene catalysts.
BACKGROUND OF THE INVENTION
Metallocene catalysts have high activities and are capable of preparing resin with enhanced physical properties in comparison with the resin polymerized by using Ziegler-Natta catalysts. The metallocene catalysts are compounds of Group IV transition metals of the Periodic Table such as titanium, zirconium, hafnium, etc., and have a coordinated structure with a metal compound and ligands composed of one or two groups of cyclopentadienyl, indenyl, fluorenyl or their derivatives. The metallocene catalysts are usually employed with a co-catalyst. And the co-catalyst is normally an alkylaluminoxane such as methylaluminoxane prepared by reacting an alkylaluminium compound with H
2
O, unlike the co-catalyst employed with the Ziegler-Natta catalysts.
U.S. Pat. No. 3,740,384 discloses a process for polymerization of mono-olefins by contacting the olefin with a catalyst composition containing an organomettallic zirconium complex selected from hydrocarbyl complexes of zirconium in which the valence or co-ordination requirements of the metal are satisfied by alkyl, alkenyl, or arylalkyl groups which may be partially replaced by other monovalent ligands, using the catalyst composition of 1,1,3,3-tetraphenylsiloxane-1,3-diol. The organometallic zirconium compounds contain allyl, ethylbenzyl, methylene or naphthyl ligands.
EP Publication No. 423 872 A2 discloses a reaction product (for example, Cp
2
ZrR
2
, R=alkyl or halogen) of a silicon of siloxane diol and a dicyclopentadienyl zirconium as a catalyst for ethylene polymerization.
The inventors of the present invention have discovered that the metallocene catalyst prepared by reacting a diol (or diamine, alkyl dimagnesium halide, aryl dimagnesium halide) compound with a cyclopentadienyl zirconium halide has a higher activity in preparation of olefin polymers than conventional catalysts, and that the metallocene catalysts are capable of using less amount of a co-catalyst such as an alkylaluminoxane than conventional catalysts when they are employed in preparation of olefin polymers.
Accordingly, the present inventors have developed new metallocene catalysts for use in preparation of olefin polymers, and methods of preparing the metallocene catalysts and methods of preparing olefin polymers such as mono-polymers of ethylene or &agr;-olefin, ethylene/&agr;-olefin co-polymers, propylene/&agr;-olefin co-polymers, etc using the metallocene catalysts.
OBJECTS OF THE INVENTION
An object of the present invention is to provide metallocene catalysts having a high activity to prepare polyolefins with enhanced physical properties in comparison with the polyolefins prepared by using Ziegler-Natta catalysts.
Another object of the present invention is to provide metallocene catalysts which are capable of using less amount of a co-catalyst such as an alkylaluminoxane than conventional catalysts when they are employed in preparation of olefin polymers.
A further object of the present invention is to provide a method of preparing the metallocene catalysts according to the present invention.
A further object of the present invention is to provide a method of preparing olefin polymers such as mono-polymers of ethylene or &agr;-olefin, ethylene/&agr;-olefin co-polymers, propylene/&agr;-olefin co-polymers, etc using the metallocene catalysts.
Other objects and advantages of this invention will be apparent from the ensuing disclosure and appended claims.
SUMMARY OF THE INVENTION
The new metallocene catalysts according to the present invention are prepared by reacting a metallocene compound with a compound having at least two functional groups. The metallocene compound is a transition metal compound, which is coordinated with a main ligand such as cyclopentadienyl group, and an ancillary ligand. The functional groups in the compound are selected from the group consisting of a hydroxyl group, an alkyl or aryl magnesium halide, a thiol group, a primary amine group, a secondary amine group, a primary phosphorous group, a secondary phosphorous group, etc.
The metallocene catalysts of the present invention can be also prepared by reacting a metallocene compound with the dianion compound produced by reacting an alkali metal compound with a compound having those functional groups.
The metallocene catalysts according to the present invention have a structure in which an ancillary ligand of a metallocene compound is bonded to the functional groups of a compound having at least two functional groups. A structure of the metallocene catalysts can be varied with the type of a metallocene compound and a compound having at least two functional groups, and the molar ratio of each reactant.
The metallocene catalysts are employed with a co-catalyst for olefin polymerization. The co-catalyst is an organometallic compound, or a mixture of non-coordinated Lewis acid and alkylaluminium as it is well known in the art.
DETAILED DESCRIPTION OF THE INVENTION
The metallocene catalysts according to the present invention are prepared by reacting a metallocene compound with a compound having at least two functional groups. The metallocene catalyst is a transition metal compound, which is coordinated with a main ligand such as cyclopentadienyl group and an ancillary ligand. The functional groups in the compound having at least two functional groups are selected from the group consisting of a hydroxyl group, an alkyl or aryl magnesium halide, a thiol group, a primary amine group, a secondary amine group, a primary phosphorous group, a secondary phosphorous group, etc. The metallocene catalysts of the present invention can be also prepared by reacting a metallocene compound with a dianion compound produced by reacting an alkali metal compound with a compound having those functional groups.
The metallocene catalysts according to the present invention have a structure in which an ancillary ligand of a metallocene compound is bonded to the functional groups of a compound having at least two functional groups. A structure of the metallocene catalysts can be varied with the type of a metallocene compound and a compound having at least two functional groups, and the molar ratio of each reactant.
The metallocene catalysts are employed with a co-catalyst for olefin polymerization. The co-catalyst is an organometallic compound, or a mixture of non-coordinated Lewis acid and alkylaluminium, which is well known in the art. The organometallic compound is usually an alkylaluminoxane, an inorganic compound supported alkylaluminoxane or an organoaluminium compound.
A monomer such as olefin and/or &agr;-olefin is polymerized by using the catalyst system consisting of the metallocene catalysts of the present invention and a co-catalyst. The monomer is mono-polymerized or co-polymerized to prepare olefin polymer or copolymer.
The metallocene catalysts of the present invention are prepared by reacting the metallocene compound represented by the following general formula (A) or (B) with the compound having at least two functional groups represented by the following general formula (C), (D), (E) or (F), and having a structure in which an ancillary ligand of the metallocene compound is bonded to the functional groups of the compound having at least two functional groups:
(C
n
R
1
m
)
2
MX
2
or (C
n
R
1
m
)R
2
(C
n
R
1
m
)MX
2
(A)
(C
n
R
1
m
)E(R
1
m
)J(R
1
m
)MX
2
(B)
wherein M in the formulae (A) and (B) represents a transition metal of Group IV, V or VI of the Periodic Table, preferably of Group IV such as titanium, zirconium, hafnium, etc;
(C
n
R
1
m
) is a substituted cyclopentadienyl group, a substituted indenyl grou
Chang Seok
Jung Won-Cheol
Lyu Yi-yeol
Yoon Keun-Byoung
Bell Mark L.
DiVerdi Michael J.
Samsung General Chemicals Co. Ltd.
Woodcock Washburn Kurtz Mackiewicz & Norris LLP
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