Metallocene complexes and method of preparing the same

Details Metallocene complexes and method of preparing the same Metallocene complexes and method of preparing the same

1999-09-09

2001-10-16

Nazario-Gonzalez, Porfirio (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heavy metal containing

C556S136000, C556S137000, C556S140000, C556S146000, C502S152000, C526S160000, C526S943000

Reexamination Certificate

active

06303805

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to metallocene complexes. More specifically, the present invention relates to new metallocene complexes with high selectivity and activity, which are prepared by reacting a transition metal complex of Group IIIB-VIII of the Periodic Table, having at least one cycloalkanedienyl group, with a compound having at least two functional groups.
BACKGROUND OF THE INVENTION
A binuclear metallocene complex bridged by a functional group shows excellent properties as a catalyst (M. A. Mansour et al. at
J. Am. Chem. Soc.
1998, 120, 1329-1330; and J. C. Vickery et al.
Angew. Chem. Int. Ed. Engl.
1997. 36, 1179-1181). Also, it was found that a dimeric palladium compound bridged by a functional group has excellent activity than a palladium acetate compound in the Heck reaction (G. Dyker at Journal of Organometallic Chemistry 1998. 555 141-143).
U.S. Pat. No. 5,233,093 discloses an improved allyl alcohol hydroformylation process and a catalyst therefor. The process employes a catalyst system comprising a Group VIII metal carbonyl complex catalyst, a trisubstituted phosphine, a neutral Group VIII(a) metal complex co-catalyst, and optionally, a diphosphinoalkane. The bimetallic catalyst systems give high selectivity.
U.S. Pat. No. 5,567,847 discloses a process for the production of amines by the catalytic disproportionation of a feedstock containing a primary amine to produce a reaction product containing a secondary amine. The patent resides in the use of a bimetallic catalyst comprising nickel or cobalt in combination with rhodium, palladium, ruthenium or platinum.
Korean Patent Application No.
98-21032
discloses new catalysts having at least two cycloalkanedienyl groups, which are synthesized by bridging metallocene moleculars with an ancillary ligand having at least two functional groups. The catalysts have higher activity than conventional catalysts.
The present inventors have developed a method of preparing new metallocene complexes with high activity, such as bimetallic complex, trimetallic complex, tetrametallic complex, etc. The method of preparing the metallocene catalysts comprises reacting a compound having at least two functional groups with a metal compound of Group IIIB-VIII of the Periodic Table having at least one cycloalkanedienyl group.
OBJECTS OF THE INVENTION
An object of the present invention is to provide metallocene complexes in which two metallocene complexes are bridged with an ancillary ligand, which are prepared by reacting a compound having at least two functional groups with transition metal complexes of Group IIIB-VIII having at least one cycloalkanedienyl group.
Another object of the present invention is to provide metallocene complexes having high selectivity and activity.
A further object of the present invention is to provide metallocene complexes with high activity which are capable of preparing polyolefin or polystyrene having good stereoregularity, high melting temperature and good molecular weight distribution.
A further object of the present invention is to provide metallocene complexes with high activity which are capable of preparing a large amount of polyolefin or polystyrene by using small amount of a co-catalyst.
A further object of the present invention is to provide methods of reparing the metallocene complexes above and methods of polymerizing olefin or styrene by using the metallocene complexes.
These and other objects and advantages of this invention will be apparent from the ensuing disclosure and appended claims.
SUMMARY OF THE INVENTION
The metallocene complexes according to the present invention are prepared by reacting a transition metal complex of Group IIIB-VIII of the Periodic Table, having at least one cycloalkanedienyl group, with a compound having at least two functional groups. The transition metal complex has at least one main ligand such as a cycloalkanedienyl group and at least one ancillary ligand which are coordinated with a transition metal of Group IIIB-VIII. The functional groups in the compound having at least two functional groups are selected from the group consisting of a hydroxyl group (—OH), a thiol group (—SH), a primary amine group (—NH
2
), a secondary amine group (RNH—), a tertiary amine group (RR′N) a primary phosphorous group (—PH
2
), a secondary phosphorous group (RPH—), a tertiary phosphorous group (RR′P), a thiirane group
Also, the metallocene complexes of the present invention can be prepared by reacting a transition metal complex (a half metallocene complex) with a dianion, a trianion or a tetraanion complex. The dianion, trianion or tetraanion complex is produced by reacting a compound having a hydroxyl group (—OH), a thiol group (—SH), a primary amine group (—NH
2
), a secondary amine group (—NH—), a primary phosphorous group (—PH
2
) or a secondary phosphorous group (RPH—) with an alkali metal compound.
DETAILED DESCRIPTION OF THE INVENTION
The metallocene complexes of the present invention have a structure in which ancillary ligands of a transition metal complex (a half metallocene complex) are bridged with a functional group of a compound having at least two functional groups. The metallocene complexes of the present invention can be prepared in various chemical structures depending on the types of the transition metal complex (half metallocene complex) and the compound having at least two functional groups, and the molar ratio of the reactants.
The metallocene complexes of the present invention are prepared by reacting a transition metal complex represented by the following formula (A) with a compound having two, three or four functional groups represented by the following formula (B), (C) and (D), respectively. The transition metal complex contains at least one cyclopentadienyl group. The metallocene complexes have a structure in which ancillary ligands of a transition metal complex are bridged with a functional group of a compound having at least two functional groups.
 T
1
—Y—R
2
—Y
1
—T
2
  (B)
wherein
M is a transition metal of Group IIIB-VIII of the Periodic Table;
R is a hydrocarbon group of C
1
~C
20
or a hydrocarbon group of C
1
~C
20
containing a halogen, an amine group, a phosphine group or an alkoxy group, and the two adjacent R groups are bonded to a carbon of a hydrocarbon group C
4
~C
20
to form a polycycliccyclopentadienyl group in the transition metal complex;
x is 0, 1, 2, 3 or 4;
B is a covalent bonding group linking (C
5
H
4−x
R
x
) and J
k
, which is selected from the group consisting of dialkyl silicon, alkyl aryl silicon, diaryl silicon, dialkyl germanium, alkyl aryl germanium, diaryl germanium, alkyl phosphine, aryl phosphine, amine, methylene, and ethylene;
J is selected from the group consisting of a cyclopentadienyl group, an alkyl substituted amine group, an aryl substituted amine group, an alkyl substituted phosphine group, an aryl substituted phosphine group, a sulfur atom and an oxygen atom;
k is 0 or 1, and when k is 0, B is a hydrogen atom or a methyl group;
X is selected from the group consisting of a halogen, a triflate, a trifluoroacetate, a hydroxy, an alkyl substituted siloxy, an aryl substituted siloxy, a triphenylphosphine, an alkyl, and an aryl;
a, b, c and d are 0 or 1;
T
1
, T
2
, T
3
and T
4
are selected from the group consisting of H, Na, Li, K, and MgX (magnesium halide);
Y, Y
1
, Y
2
and Y
3
are selected from the group consisting of an oxygen atom, a sulfur atom, an alkyl with or without a double bond or a hetero atom, an aryl with or without a double bond or a hetero atom, a thiirane group
 —Nr
1
and —Pr
2
, wherein r
1
and r
2
are selected from the group consisting of a hydrogen atom, an alkyl group of C
1
~C
10
, a cycloalkyl group of C
1
-C
10
, an alkoxy group of C
1
~C
10
, an aryl group of C
6
~C
20
, an alkylaryl group of C
6
~C
20
and an arylalkyl of C
6
~C
20
;
R
2
is selected from the group consisting of a linear or branched alkyl group of C
1
~C
20
; a cycloalkyl group of C
3
~C
20
; a substituted cycloalkyl group of C
3
~C
20
; an ar

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