Organometallic compounds with fused indenyl ligands

Details Organometallic compounds with fused indenyl ligands Organometallic compounds with fused indenyl ligands

2001-01-23

2003-09-02

Harlan, Robert D. (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...

C502S152000, C502S155000, C556S011000, C556S012000, C556S020000, C556S043000, C556S053000, C556S054000, C526S127000, C526S160000, C526S161000, C526S943000

Reexamination Certificate

active

06613713

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to transition metal organometallic compounds with an indenyl ligand attached in position 2 and fused in position 5,6, and also to a process for the production thereof and to the use thereof as catalysts for the (co)polymerization of olefinic and/or diolefinic monomers.
BACKGROUND OF THE INVENTION
In accordance with IUPAC nomenclature, the positions of the ring atoms of indene are designated as follows in the present application:
Stereo-rigid chiral metallocenes having bridged indenyl ligands are known as catalysts for the production of polyolefins. It has been found in this connection that the nature and position of the substituents on the indenyl anion and the nature and position of the bridging have an influence both upon catalyst activity and upon polymer properties. Many indenyl metallocenes are bridged in position 1 (1-indenyl metallocenes).
Bis(1-indenyl) metallocenes substituted in position 2 and/or 4 with indenyl residues bridged in position 1 are of particular significance in the production of highly isotactic polypropylene having elevated crystallinity and an elevated melting point. (EP-A1-485 821, EP-A1-485 823, EP-A2-519 237). Bis(1-indenyl) metallocenes benzo-fused in position 4,5 are also of significance (c.f.
Organometallics
1994, 13, 964-970).
It is also known to use organometallic compounds with only one indenyl anion as catalysts (constrained geometry complexes with 1-indenyl ligands, c.f. U.S. Pat. No. 5,026,798, WO-97/15583-A1).
WO-94/11406-A1 discloses transition metal organometallic compounds which comprise one indenyl and one cyclopentadienyl ligand, wherein the indenyl ligand is substituted in position 2; this substituent may also act as a bridge to the second ligand. The practical Examples show multistage production processes with highly unsatisfactory yields which, in the case of bridged compounds, give rise to 1-cyclopentadienyl-2-(2-indenyl)ethanezirconium chloride, to bis(2-indenyl)methanezirconium chloride or to dimethyl-bis(2-indenyl)silanezirconium dichloride, which still contains impurities.
Organometallics
1993, 12, 5012-5015 describes a multistage synthesis pathway to ethylenebis(2-indenyl)titanium dichloride. Due to the multistage synthesis and the numerous purification operations, the achievable yield is very low. Due to the synthesis pathway, the structural variety of ethylene-bridged ligands is limited.
EP-A-2-941 997 discloses ethylene-bridged bis(2-indenyl)zircono-cenes. These zirconocenes are used for the production of special low molecular weight polyolefins.
EP-A1-940 408 describes silyl-bridged 2-indenyl metallocenes and a process for the production of organometallic compounds with indenyl ligands attached in position 2.
Comparatively little is known about organometallic compounds with indenyl ligands fused in position 5,6 (for example tetrahydroindacenyl ligands). Example 3 of WO-98/09999-A1 discloses the production of a half-sandwich titanium complex with a tetrahydroindacenyl ligand. Availability of the tetrahydroindacenyl titanium complex bridged in position 1 is, however, unsatisfactory (overall yield <1%). WO-98/49212-A1 and WO-98/27103-A1 describe the production of half-sandwich complexes with tetrahydroindacenyl ligands bridged in position 1 and substituted in position 2 and/or 3 and the use thereof as catalysts for polymerizing olefins.
Transition metal complexes with tetrahydroindacenyl ligands bridged in position 2 are not known.
SUMMARY OF THE INVENTION
It has now been found that such organometallic catalysts, the bridging of which begins in position 2 of at least one tetrahydroindacenyl anion, have particular characteristics as polymerization catalysts, in particular producing largely atactic polymers having elevated molecular weights in the (co)polymerization of &agr;-olefins. It was accordingly desirable to find a production process for such catalysts bridged in position 2 of at least one tetrahydroindacenyl anion.
Another object was to provide a catalyst which is suitable for synthesizing high molecular weight EPDM.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to a process for the production of transition metal organometallic compounds with 2-indenyl fused in position 5,6 as the first ligand of the formula
in which
Q
1
, Q
2
are identical or different and, as a substituent of the 2-indenyl system fused in position 5,6, mean hydrogen, C
1
-C
4
alkyl, C
6
-C
14
aryl, C
7
-C
10
aralkyl, C
1
-C
4
alkoxy, C
1
-C
4
alkylthio, phenoxy, phenylthio, di-C
1
-C
4
-alkylamino, C
6
-C
14
-aryl-C
1
-C
4
-alkylamino, di-C
6
-C
14
-arylamino, dibenzylamino, tri-C
1
-C
4
-alkylsilyl, di-C
1
-C
4
-alkylboranyl, phenyl-C
1
-C
4
-alkylboranyl, diphenylboranyl, di-C
1
-C
4
-alkylphosphoryl, diphenylphosphoryl or phenyl-C
1
-C
4
-alkylphosphoryl,
Q
3
represents an optionally substituted alkylene residue which, together with the two carbon atoms of the indenyl residue, forms a ring system in position 5 and 6,
M
1
is a transition metal from groups 4, 5 or 6 of the IUPAC 1985 periodic system of elements,
X means an anion,
n is a number from zero to four, which is determined by the valency and bond state of M
1
,
Y represents a bridge from the group of —C(R
1
R
2
)—, —Si(R
1
R
2
)—, —Ge(R
1
R
2
)—, —C(R
1
R
2
)—C(R
3
R
4
)—, —C(R
1
R
2
)—Si(R
3
R
4
)— or —Si(R
1
R
2
)—Si(R
3
R
4
)—, in which R
1
, R
2
, R
3
and R
4
mutually independently mean hydrogen, halogen, linear or branched C
1
-C
10
alkyl, C
5
-C
8
cycloalkyl, C
6
-C
14
aryl or C
7
-C
10
aralkyl and
Z is a second ligand from the group of open-chain and cyclic, optionally anionic &pgr;-systems, —N(R
5
)—, P(R
6
)—, |N(R
5
R
7
), |P(R
6
R
8
)—, —O—, —S—, |OR
5
— or |SR
5
—, wherein the vertical line to the left of the element symbol N, P, O or S means an electron pair and the bond between Z and M
1
is of an ionic, covalent or coordinative nature and in which R
5
, R
6
, R
7
and R
8
mutually independently have the range of meaning of R
1
to R
4
and R
5
and R
7
may additionally mean —Si(R
1
R
2
R
3
) and R
6
and R
8
may additionally mean —Si(R
1
R
2
R
3
), —OR
1
, —SR
1
or —N(R
1
R
2
),
characterized in that a haloindene fused in position 5,6 of the formula
in which Hal
1
denotes Cl, Br or I and Q
1
, Q
2
and Q
3
have the above meaning, is reacted with an elemental metal selected from group 1, 2 or 12 of the IUPAC 1985 periodic system or a corresponding metal compound in a quantity in the range from 1 to 100 mol of elemental metal/metal compound per mol of (II) and with a dihalide of the bridge Y of the formula
Hal
2
-Y-Hal
3
  (III),
in which
Hal
2
and Hal
3
mutually independently mean Cl, Br or I and
Y has the above range of meaning, in a quantity of 1 to 20 mol of (III) per mol of (II), wherein in the event that Y has the meaning —Si(R
1
R
2
)—, —Ge(R
1
R
2
)— or —Si(R
1
R
2
)—Si(R
3
R
4
)—, the reaction of (II) with (i) elemental metal/metal compound and (ii) with (III) may also proceed simultaneously, and the reaction product of the formula
in which Q
1
, Q
2
, Q
3
, Y and Hal
3
have the above meaning,
optionally after the isolation thereof, is reacted with a Z derivative of the formula
ZM
2
p
  (Va)
or
ZR
9
p
  (Vb),
in which
M
2
denotes Li, Na, K or —MgHal
4
, in which Hal
4
has the range of meaning of Hal
2
,
p represents the number one or two,
R
9
represents hydrogen, —Si(R
1
R
2
R
3
) or Sn(R
1
R
2
R
3
) and
Z, R
1
, R
2
and R
3
have the above meaning,
with elimination of a compound of the formula
 M
2
Hal
3
  (VIa)
or
R
9
Hal
3
  (VIb)
in which M
2
, R
9
and Hal
3
have the above meaning,
optionally in the presence of an auxiliary base to yield the 2-indenyl compound of the formula
in which Q
1
, Q
2
, Q
3
, Y and Z have the above meaning, and which may be present as a dianion and in which Z may furthermore bear M
2
, R
9
or an electron pair,
and is then further reacted with a transition metal compound of the formula
M
1
X
q
  (VIII),
in which
M
1
and X have

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