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
2002-06-04
2004-04-20
Harlan, Robert (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...
C502S117000, C502S152000, C502S155000, C526S127000, C526S160000, C526S161000, C526S348600, C526S352000, C556S011000, C556S012000, C556S020000, C556S043000, C556S053000, C556S054000
Reexamination Certificate
active
06723676
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to organometallic compounds of transition metals with an indenyl ligand bound in the 2-position and substituted in the 1,3-position, a process for their production, and their use as catalysts for the (co)polymerization of olefinic and/or diolefinic monomers.
BACKGROUND OF THE INVENTION
Corresponding to the IUPAC nomenclature the positions of the ring atoms of indene are identified as follows in the present application:
The production of substituted indenes [Spaleck, W.; Rohrmann, J.; Antberg, M.; EP-A1-0 530 647] is known in the relevant literature, and substituted indenes may be produced for example starting from 1-indanones [Smonou, I.; Ofranopopuolos, M. Synth. Commun. 1990, 20 (9), 1387].
The synthesis of 2-bromoindenes is based on known processes for their production [Billups, W.; J. Org. Chem. 1980, 23, 4638; Porter, H. D.; Suter, C. M. J. Am. Chem. Soc. 1935, 57, 2022; Koelsch, C. J. Org. Chem. 1960, 25, 130; Wei&bgr;, R.; Luft, S.; Monatsh. Chem. 1927, 48, 341].
Stereorigid chiral metallocenes with bridged indenyl ligands are known as catalysts for the production of polyolefins. In this connection, it has been found that the nature and position of the substituents on the indenyl anion and the nature and position of the bridge have an influence on both the catalyst activity and also the polymer properties. Many of the indenyl metallocenes have a bridge in the 1-position (1-indenyl metallocenes).
The bis(1-indenyl)-metallocenes substituted in the 2- and/or 4-position with indenyl residues bridged in the 1-position are particularly important for the production of highly isotactic polypropylene with a high degree of crystallinity and a high melting point. (EP-A1-485 821, EP-A1-485 823, EP-A2-519237). Also important are the bis(1-indenyl)-metallocenes benzanellated in the 4,5-position (see 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, see U.S. Pat. No. 5,026,798, WO-97/15583-A1).
Organometallic compounds of transition metals that contain an indenyl ligand and a cyclopentadienyl ligand are known from WO-94/11406-A1, the indenyl ligand being substituted in the 2-position; this substituent may also be formed as a bridge to the second ligand. The examples of implementation illustrate multistage productions with extremely unsatisfactory yields that lead in the case of bridged compounds to 1-cyclopentadenyl-2-(2-indenyl)-ethane zirconium chloride, to bis-(2-indenyl)-methane zirconium dichloride, or to dimethyl-bis-(2-indenyl)-silane zirconium dichloride, which still contains impurities. A multistage synthesis pathway to ethylene-bis-(2-indenyl) titanium dichloride is described in Organometallics 1993, 12, 5012-5015. On account of the multistage synthesis and the numerous purification operations the achievable yield is very low. On account of the synthesis pathway the structural multiplicity is restricted to ethylene-bridged ligands.
Ethylene-bridged bis(2-indenyl) zirconocenes are disclosed in EP-A2-941 997. These zirconocenes are used for the production of special polyolefins with low molecular weights.
Silyl-bridged 2-indenyl metallocenes and a process for the production of organometallic compounds with an indenyl ligand bonded in the 2-position are described in EP-A1-0 940 408.
Moreover, a process for the production of amorphous polypropylenes using a catalyst system based on monocyclopentadienyl transition metal complexes is described in U.S. Pat. No. 5,504,169. The cyclopentadienyl ring bonded to the transition metal complex is substituted symmetrically with no, two or four substituents.
Transition metal complexes with 1,3-disubstituted indenyl ligands bridged in the 2-position are not known.
It has now been shown that such organometallic catalysts whose bridging attaches at least one 1,3-disubstituted indenyl anion to the 2-position have special properties as polymerization catalysts; they produce in fact predominantly atactic polymers with high molecular weights in the (co)polymerization of &agr;-olefins. It was, therefore, desirable to find a production process for such catalysts bridged in the 2-position by at least one 1,3-disubstituted indenyl anion.
A further object of the invention was to provide a catalyst that is suitable for the synthesis of high molecular weight EPDM.
SUMMARY OF THE INVENTION
The present invention relates to a process for the production of organometallic compounds of transition metals with 2-indenyl ligands substituted in the 1,3-position that correspond to the general formula (I),
wherein
A denotes the benzo system or the tetrahydrocyclohexyl system,
Q
1
, Q
2
are identical or different and, as substituent of the 2-indenyl system substituted in the 1,3-position, denote 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
are identical or different and, as substituent of the 2-indenyl system substituted in the 4,5,6,7-position, denote 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,
M
1
is a transition metal from Group IV, V or VI of the Periodic System of the Elements according to IUPAC 1985,
X denotes an anion,
n is a number from zero to 4 that is determined by the valency and the bonding state of M
1
,
m is a number from zero to 4 that is determined by the number of the radicals Q
3
,
Y is 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
)—, wherein R
1
, R
2
, R
3
and R
4
independently of one another denote hydrogen, halogen, straight-chain 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 and S denotes an electron pair, and the bonding between Z and M
1
is ionic, covalent or co-ordinative, and wherein R
5
, R
6
, R
7
and R
8
independently of one another have the same range of meanings as R
1
to R
4
, and R
5
and R
7
may in addition denote —Si(R
1
R
2
R
3
), and R
6
and R
8
may in addition denote —Si(R
1
R
2
R
3
), —OR
1
, —SR
1
or —N(R
1
R
2
),
characterized in that a halogenated indene substituted in the 1,3-position of the formula (II)
in which Hal
1
denotes Cl, Br or I and Q
1
, Q
2
and Q
3
and m have the above meanings,
is reacted with an elementary metal selected from Groups I, II or XII of the Periodic System according to IUPAC 1985 or a corresponding metal compound in an amount in the range from 1 to 100 moles of elementary metal/metal compound per mole 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
independently of one another denote Cl, Br or I and
Y has the above range of meanings,
in an amount of 1 to 20 moles of (III) per mole of (II), wherein in the case where 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) elementary metal/metal compound, and of (ii) with (III) may also take place simultaneously, and the reaction product of the formula
w
Becke Sigurd
Lang Heinrich
Weiss Thomas
Bayer Aktiengesellschaft
Gil Joseph C.
Harlan Robert
Seng Jennifer R.
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