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
1998-09-23
2001-08-21
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...
C502S103000, C502S152000, C526S160000, C556S053000
Reexamination Certificate
active
06277778
ABSTRACT:
The present invention relates to novel metallocene catalyst systems for homo- and copolymerization of olefins, especially propylene, ethylene and higher alpha-olefins, in the presence of a cocatalyst, such as methylaluminoxane (MAO). Especially the invention relates to metallocenes with heteroatom substituted indenyl and indenyl derivative ligands, a method for their preparation, and their use in polymerization of olefins, especially propylene and ethylene.
Chiral C-
2
symmetric bis(indenyl)ansa-metallocenes are precursors to highly active catalysts for stereoselective polymerization of alpha-olefins. The performance characteristics of these systems are different, the variations being induced by size and position of the substituents. E.g., dimethylsilylene bridged 2,2′-dimethyl-4,4′-diaryl substituted bis(indenyl)zirconocenes developed by Brintzinger and co-workers (Organometallics 1994, 13, 964) and Spaleck et al. (Organometallics 1994, 13, 954), produce isotactic polypropylenes with catalyst activities and polymer properties comparable to those obtained with heterogeneous Ziegler-Natta catalysts.
The area of electronically altered bis(indenyl)metallocenes has remained relatively unexplored. Previously, it has been reported that halogen or alkoxy substitution in the six-membered rings of indenes reduces the activity of the catalyst system and the molecular weight of the produced polymer (Consiglio et al, Organometallics 1990, 9, 3098; Collins et al., Organometallics 1992, 11, 2115). Bis(indenyl) zirconocenes with 2-amino functionalized ligands have been reported recentily by several groups (Luttikhedde et a/., Organometallics 1996, 15, 3092; Plenio and Burth, J. Organomet Chem. 1996, 519, 269; Brintzinger et al., J. Organomet. Chem. 1996, 520, 63). The bridged complexes show somewhat lower catalytic activities compared with their unsubstituted bis(indenyl)zirconocene analogues.
The present invention concerns novel metallocene complexes (I) with an oxygen atom directly bonded to the 2-position of a pentahapto indenyl moiety, e.g., racemic [ethylenebis(2-(tert-butyldimethylsiloxy)indenyl)]zirconium dichloride, and their application in polymerization of olefins. These complexes (I), in combination with MAO or other activators, form highly active catalyst systems for homo- and copolymerization of olefins. E.g., the I/MAO catalyst systems polymerizes propylene to highly isotactic polypropylene. The propylene and ethylene polymerization activities of these (I)/MAO systems exceeds those of several conventional ansa-metallocene/MAO catalyst systems, such as dimethylsilylenebis(4,5,6,7-tetrahydroindenyl)zirconium dichloride/MAO, under similar polymerization conditions. The novel catalyst systems are very stable and retain their high activities at exceptionally low [A1]:[Zr1] ratios.
According to the invention a new catalyst precursor is obtained, in which a siloxy substitution in the 2-position of 5-membered ring of an indenyl-type compound has been carried out. Thereby it is possible to produce metallocene compounds, in which an oxygen atom is directly bonded to the 2-position of a penta-hapto indenyl moiety.
Thus the catalyst precursor according to the invention concerns an indenyl compound having the formula (I):
(IndY)
m
MR
n
B
o
(I)
wherein: each IndY is the same or different and is one of a mono- or polysubstituted, fused or non-fused, homo- or heterocyclic indenyl ligand, dihydroindenyl ligand or tetrahydroindenyl ligand, which ligand is substituted at the 2-position of its indenyl structure by the group Y, which group Y has the following structure (II):
wherein D is one of silicon or germanium, R
3
, R
3′
and R
4
are the same or different and are one of a hydrogen atom, a C
1
-C
10
hydrocarbyl group or a C
1
-C
10
hydrocarbyloxy group, or at least two of R
3
, R
3′
and R
4
form together a C
2
-C
20
ring structure; M is a transition metal of group 4 of the Periodic Table and is bound to the ligand IndY in at least an &eegr;
5
bonding mode; each R is the same or different and is one of a hydrogen atom, a halogen atom, a C
1
-C
10
hydrocarbyl group, a C
1
-C
10
hydrocarbyloxy group, a tri-hydrocarbyl silyl group or two R form together a C
2
-C
20
ring structure; B is a bridge atom or group between two IndY ligands or between one IndY ligand and the transition metal M; m is 1 or 2; o is 0 or 1; and n is 4−m when there is no bridge B or B is a bridge atom or group between two IndY ligands, or n is 4−m−o when B is a bridge atom or group between one IndY ligand and the transition metal M.
By mono- or polysubstituted is meant that, in addition to said substituent Y, there may optionally be other substituents at the rings at said ligand IndY.
By fused or non-fused is meant that any ring at said ligand IndY may be fused or non-fused, i.e. have at least two atoms in common, with at least one further ring.
By homo- and heterocyclic is meant that any ring of said ligand IndY may have only carbon ring atoms (homo- or isocyclic) or may have other ring atoms than carbon (heterocyclic).
Preturately the indenyl compound according to formula (I) has the following formula (III)
where
M is a metal selected from zirconium, titanium or hafnium,
D is an element selected from silicon (Si) or germanium (Ge),
B is abridge comprising at least one of —(CH
2
)
n
—, —Si(R
3
)
2
— or —Ge(R
3
)
2
—,
R
1
and R
2
are the same or different groups selected from a hydrogen atom, a C
1
-C
10
alkyl group, C
1
-C
10
alkoxy group, C
6
-C
10
aryl group, C
6
-C
10
aryloxy group, C
2
-C
10
alkenyl group, C
2
-C
10
arylalkyl group, C
2
-C
10
alkylaryl group, C
8
-C
40
arylalkenyl group or a halogen atom, preferably a C
1
-C
10
alkyl group and/or a halogen atom.
R
3′
, R
3
-R
6
are same or different groups selected from hydrogen, C
1
-C
10
alkyl group, C
1
-C
10
alkoxy group, C
6
-C
10
aryl group, C
6
-C
10
aryloxy group, C
2
-C
10
alkenyl group, C
2
-C
10
arylalkyl group, C
2
-C
10
alkylaryl group, C
8
-C
40
arylalkenyl group and a halogen atom. R
3
and R
3′
groups can also be connected to each other to form a ring structure and R
4
may also be part of a ring structure.
Preferably M
1
is zirconium.
R
1
and R
2
are preferably the same and most preferably they are halogen atoms, for example chlorine atoms.
R
3
is preferably C
1
-C
10
alkyl or aryl group and most preferably it is methyl group. R
4
is likewise preferably C
1
-C
10
alkyl or aryl group, for example tert-butyl group, t-hexyl group or cyclohexyl group.
Most preferably D is Si, B is —CH
2
CH
2
—, R
1
=R
2
and is chlorine, R
3
is CH
3
and R
5
-R
6
is aromatic or fused aromatic or alkyl or hydrogen.
The invention also relates to 2-trihydrocarbyl and 2-trihydrokarbyloxy siloxyindene and germyloxyindene compounds having the general formula:
wherein: D is one of silicon and germanium; R
3
, R
3′
and R
4
are the same or different and are one of a hydrogen atom, a C
1
-C
10
hydrocarbyl group or a C
1
-C
10
hydrocarbyloxy group, or at least two of R
3
, R
3′
and R
4
form together a C
2
-C
20
ring structure; R
7
is a four-atom chain forming an unsubstituted or substituted, further non-fused or further fused, homocyclic (=isocyclic) or heterocyclic, unsaturated or saturated, aliphatic or aromatic six-membered ring; and R
8
, R
9
and R
10
are the same or different and are one of a hydrogen atom, a C
1
-C
10
hydrocarbyl group, a C
1
-C
10
hydrocarbyloxy group, a tri-C
1
-C
10
hydrocarbyl silyl group or a tri-C
1
-C
10
hydrocarbyloxy silyl group, or one of R
8
and R
9
may be a bridge atom or group B to a cyclopentadienyl, fluorenyl or indenyl group. Preferably, they have the formula:
wherein: R
3′
, R
3
-R
6
are the same or different and are one of a hydrogen atom, a C
1
-C
10
alkyl group, a C
1
-C
10
alkoxy group, a C
6
-C
10
aryl group, a C
2
-C
10
alkenyl group, a C
7
-C
22
arylalkyl group, a C
7
-C
22
alkylaryl group, a C
8
-C
23
arylalkenyl group or a halogen atom, or at l
Leino Reko
Luttikhedde Hendrik
Nasman Jan
Wilen Carl-Erik
Bell Mark L.
Birch & Stewart Kolasch & Birch, LLP
Borealis A/S
DiVerdi Michael J.
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