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
2000-05-31
2002-12-03
Bell, Mark L. (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...
C502S117000, C502S152000, C502S155000, C502S156000, C526S134000, C526S161000, C526S169200, C526S172000
Reexamination Certificate
active
06489261
ABSTRACT:
The invention relates to a catalyst composition comprising a reduced transition metal complex and a cocatalyst.
Catalyst compositions comprising a reduced transition metal complex and a cocatalyst are known from WO-A-96/13529.
In this patent application the reduced transition metal complex of the catalyst composition is represented by the following formula (I):
wherein the symbols have the following meanings:
M a reduced transition metal selected from group 4, 5 or 6 of the Periodic Table of Elements;
X a multidentate monoanionic ligand represented by the formula: (Ar—R
t
—)
s
Y(—R
t
—DR′
n
)
q
;
Y a cyclopentadienyl, amido (—NR′—), or phosphido group (—PR′—), which is bonded to the reduced transition metal M;
R at least one member selected from the group consisting of (i) a connecting group between the Y group and the DR′
n
group and (ii) a connecting group between the Y group and the Ar group, wherein when the ligand X contains more than one R group, the R groups can be identical to or different from each other;
D an electron-donating hetero atom selected from group 15 or 16 of the Periodic Table of Elements;
R′ a substituent selected from the group consisting of a hydrogen, hydrocarbon radical and hetero atom-containing moiety, except that R′ cannot be hydrogen when R′ is directly bonded to the electron-donating hetero atom D, wherein when the multidentate monoanionic ligand X contains more than one substituent R′, the substituents R′ can be identical or different from each other;
Ar an electron-donating aryl group;
L a monoanionic ligand bonded to the reduced transition metal M, wherein at least one L is an electron-donating ligand bonded to M via a metal-carbon bond, and wherein this ligand L is not methyl or benzyl;
K a neutral or anionic ligand bonded to the reduced transition metal M, wherein when the transition metal complex contains more than one ligand K, the ligands K can be identical or different from each other;
m is the number of K ligands, wherein when the K ligand is an anionic ligand m is 0 for M
3+
, m is 1 for M
4+
, and m is 2 for M
5+
, and when K is a neutral ligand m increases by one for each neutral K ligand;
n the number of the R′ groups bonded to the electron-donating hetero atom D, wherein when D is selected from group 15 of the Periodic Table of Elements n is 2, and when D is selected from group 16 of the Periodic Table of Elements n is 1;
q,s q and s are the number of (—R
t
—DR′
n
) groups and (Ar—R
t
) groups bonded to group Y, respectively, wherein q+s is an integer not less than 1; and
t the number of R groups connecting each of (i) the Y and Ar groups and (ii) the Y and DR′
n
, groups, wherein t is selected independently as 0 or 1.
It has now surprisingly been found that when at least one of the monoanionic ligands L in the reduced transition metal complex is bonded to the reduced transition metal M via a covalent metal-carbon bond and additionally this L is capable to non-covalently interact with the metal via one or more functional groups the catalyst composition is more active during olefin polymerisation. A further advantage of the catalyst composition according to the invention is that the reduced transition metal complex is more stable, and can often be obtained as a solid. Therefore the transition metal complex is easier obtained in a pure form and is easier to handle when it is used for olefin polymerisation. When a catalyst composition that is used for olefin polymerization is more active, more polymer per unit of time is produced when using a fixed amount of this catalyst. This is very advantageous in olefin polymerization because polyolefins are produced in large amounts.
Various components of the transition metal complex are discussed below in more detail.
(a) The Transition Metal (M)
The transition metal in the complex is selected from groups 4-6 of the Periodic Table of Elements. As referred to herein, all references to the Periodic Table of Elements mean the version set forth in the new IUPAC notation found on the inside of the cover of the Handbook of Chemistry and Physics, 70th edition, 1989/1990, the complete disclosure of which is incorporated herein by reference.
The transition metal is present in reduced form in the complex, which means that the transition metal is in a reduced oxidation state. As referred to herein, “reduced oxidation state” means an oxidation state which is greater than zero but lower than the highest possible oxidation state of the metal (for example, the reduced oxidation state is at most M
3+
for a transition metal of group 4, at most M
4+
for a transition metal of group 5 and at most M
5+
for a transition metal of group 6).
(b) The X Ligand
The X ligand is a multidentate monoanionic ligand represented by the formula: (Ar—R
t
—)
s
Y(—R
t
—DR′
n
)
q
.
As referred to herein, a multidentate monoanionic ligand is bonded with a covalent bond to the reduced transition metal (M) at one site (the anionic site, Y) and is bonded either (i) with a coordinate bond to the transition metal at one other site (bidentate) or (ii) with a plurality of coordinate bonds at several other sites (tridentate, tetradentate, etc.). Such coordinate bonding can take place, for example, via the D heteroatom or Ar group(s). Examples of tridentate monoanionic ligands include, without limitation, Y—R
t
—DR′
n−1
—R
t
—DR′
n
and Y(—R—DR′
n
)
2
. It is noted, however, that heteroatom(s) or aryl substituent(s) can be present on the Y group without coordinately bonding to the reduced transition metal M, so long as at least one coordinate bond is formed between an electron-donating group D or an electron donating Ar group and the reduced transition metal M.
R represents a connecting or bridging group between the DR′
n
and Y, and/or between the electron-donating aryl (Ar) group and Y. Since R is optional, “t” can be zero. The R group is discussed below in paragraph (d) in more detail.
(c) The Y Group
The Y group of the multidentate monoanionic ligand (X) is preferably a cyclopentadienyl, amido (—NR′—), or phosphido (—PR′—) group.
Most preferably, the Y group is a cyclopentadienyl ligand (Cp group). As referred to herein, the term cyclopentadienyl group encompasses substituted cyclopentadienyl groups such as indenyl, fluorenyl, and benzoindenyl groups, and other polycyclic aromatics containing at least one 5-member dienyl ring, so long as at least one of the substituents of the Cp group is an R
t
—DR′
n
group or R
t
—Ar group that replaces one of the hydrogens bonded to the five-member ring of the Cp group via an exocyclic substitution.
Examples of a multidentate monoanionic ligand with a Cp group as the Y group (or ligand) include the following (with the (—R
t
—DR′
n
) or (Ar—R
t
—) substituent on the ring):
The Y group can also be a hetero cyclopentadienyl group. As referred to herein, a hetero cyclopentadienyl group means a hetero ligand derived from a cyclopentadienyl group, but in which at least one of the atoms defining the five-member ring structure of the cyclopentadienyl is replaced with a hetero atom via an endocyclic substitution. The hetero Cp group also includes at least one R
t
—DR′
n
group or R
t
—Ar group that replaces one of the hydrogens bonded to the five-member ring of the Cp group via an exocyclic substitution. As with the Cp group, as referred to herein the hetero Cp group encompasses indenyl, fluorenyl, and benzoindenyl groups, and other polycyclic aromatics containing at least one 5-member dienyl ring, so long as at least one of the substituents of the hetero Cp group is an R
t
—DR′
n
group or R
t
—Ar group that replaces one of the hydrogens bonded to the five-member ring of the hetero Cp group via an exocyclic substitution.
The hetero atom can be selected from group 14, 15 or 16 of the Periodic Table of Elements. If there is more than one hetero atom present in the five-member ring, these hetero atoms can be either the same or di
Gruter Gerardus J. M.
Herklots Marc
Kranenburg Mirko
Bell Mark L.
DSM N.V.
Pasterczyk J.
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