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
1999-08-13
2001-07-10
Wu, David W. (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...
C502S103000, C502S104000, C502S118000, C502S123000, C502S125000, C502S122000
Reexamination Certificate
active
06258744
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a catalyst system based on fulvene cyclopentadienyl metal complexes, to a method of producing said catalyst system and a process for the polymerization and copolymerization of olefins and/or dienes using such catalyst systems.
BACKGROUND OF THE INVENTION
Since the discovery of ferrocene, metal complexes with cyclopentadienyl ligands have been intensively investigated. The use of biscyclopentadienyl-metal complexes (metallocenes), in admixture with activating co-catalysts, preferably alumoxanes, for the polymerization of olefins and diolefins has long been known (e.g., EP-A 69,951, 129,368, 351,392, 485,821, 485,823). Metallocenes have proved to be highly effective, specific catalysts for the polymerization of olefins. In combination with co-catalysts, metal complexes with only one cyclopentadienyl ligand (semi-sandwich complexes) are also suitable as specific polymerization catalysts (U.S. Pat. No. 5,132,380, EP 416,815, WO 91/04257, WO 96/13529). There is therefore a multiplicity of new metallocene catalysts or semi-sandwich catalysts for the polymerization of olefinic compounds which have been developed in recent years in order to increase catalyst activity and selectivity and to control the microstructure, molecular weights and molecular weight distribution thereof. Metal complexes with cyclopentadienyl ligands, particularly chiral ansa-metallocenes, have also been described as hydrogenation catalysts, e.g., for olefins or imines (J. Am. Chem. Soc. 1993,115,12569. J. Am. Chem. Soc. 1994,116, 8952-8965). Chiral metallocenes are also used as catalysts in asymmetric synthesis, e.g. for asymmetric Diels-Alder reactions (J. Chem. Soc. Chem. Commun. 1995, 1181).
However, relatively little is known about metal complexes with fulvene ligands.
According to Bercaw et al., JACS (1972), 94, 1219, the fulvene complex (&eegr;
6
-2,3,4,5-tetra-methylcyclopentadienyl-1-methylene)(&eegr;
5
-pentamethylcyclopentadienyl)titanium-methyl is formed by the thermolysis of bis(&eegr;
5
-pentamethylcyclopentadienyl)-titaniumdimethyl. T. J. Marks et al., JACS (1988), 110, 7701 have described the thermolysis of pentamethylcyclopentadienyl complexes of zirconium and hafnium. The fulvene complex (&eegr;
6
-2,3,4,5-tetramethylcyclopentadienyl-1-methylene)(&eegr;
5
-pentamethylcyclopentadienyl)zirconiumphenyl is formed by the thermolysis of bis(&eegr;
5
-penta-methylcyclopentadienyl)zirconiumdiphenyl.
Metal fulvene complexes and a method of producing them were described in a previous Application (German Patent Application 19 756 742.8). Metal fulvene complexes which cannot be obtained by a thermal method can be obtained in high yield by the reaction of a fulvene compound with a suitable transition metal complex in the presence of a reducing agent. The direct introduction of the fulvene ligand provides access to a multiplicity of new fulvene metal complexes. In combination with co-catalysts, specific polymerization catalysts can be produced, the catalytic activity of which is comparable with the activity of catalysts based on metallocenes.
A method for the thermal production of metal fulvene complexes and their use as polymerization catalysts in combination with co-catalysts are described in the prior Application DE 19 732 804.0. In combination with co-catalysts, specific polymerization catalysts can be produced, the catalytic activity of which is comparable with the activity of catalysts based on metallocenes. One disadvantage is that metal fulvene complexes are extremely sensitive to air and moisture. Metal fulvene complexes therefore have to be produced and stored under inert gas conditions.
Little is known about the reaction behavior of metal fulvene complexes. The reaction of aldehydes and ketones with the complex compound (&eegr;
6
-cyclopentadienyl-1-methylene)(&eegr;
5
-methylcyclopenta-dienyl)phenyltitanium is described in Z. Naturforsch. 44 b, 1989, 1593-1598. The reaction of (&eegr;
6
-2,3,4,5-tetramethylcyclo-pentadienyl-1-methylene)(&eegr;
5
-pentamethylcyclopentadienyl)titanium chloride with acetophenone is described in Organometallics, 1991, 10, 1637-1639. The reaction of isonitriles with pentamethylcyclopentadienyl-tetramethylfulvene complexes of titanium and zirconium is described in Organometallics 1991, 10, 2665-2671. On their own, however, the reaction products described above exhibit no activity for the polymerization of olefinic compounds.
SUMMARY OF THE INVENTION
The object of the present invention was to identify a catalyst system, which, at least in part, avoids the disadvantages described above. In particular, the object was to identify stable catalysts which can be synthesized in a simple manner and which are easy to handle industrially, and which can be activated without problems for the polymerization of olefinic compounds in particular.
Surprisingly, it has now been found that catalyst systems based on fulvene cyclopentadienyl metal complexes, in combination with unsaturated compounds which contain one or more hetero atoms, are particularly suitable for the achievement of the stated object.
The present invention relates to a catalyst system which can be produced by the reaction of
a) a fulvene cyclopentadienyl metal complex of formula (I):
wherein
M is a metal of the group comprising titanium, zirconium and hafnium,
A denotes a cyclopentadienyl of formula C
5
H
q
R
7
5−q
, where q represents 0, 1, 2, 3, 4 or 5, an idenyl of formula C
9
H
7−r
R
7
r
, where r represents 0, 1, 2, 3, 4, 5, 6 or 7, or a fluorenyl of formula C
13
H
9−p
R
7
p
, where p represents 0, 1, 2, 3, 4, 5, 6, 7 or 8,
X denotes a hydrogen atom, a C
1
to C
10
alkyl group, a C
1
to C
10
alkoxy group, a C
6
to C
10
aryl group, a C
6
to C
10
aryloxy group, a C
2
to C
10
alkenyl group, a C
7
to C
40
arylalkyl group, a C
7
to C
40
alkylaryl group, a C
8
to C
40
arylalkenyl group, a halogen atom or an amide of formula NR
7
2
,
R
1
, R
2
, R
3
, R
4
, R
5
, and R
6
are the same or different and represent hydrogen, a halogen, a cyano group, a C
1
to C
20
alkyl group, a C
1
to C
10
fluoroalkyl group, a C
6
to C
10
fluoroaryl group, a C
1
to C
10
alkoxy group, a C
6
to C
20
aryl group, a C
6
to C
10
aryloxy group, a C
2
to C
10
alkenyl group, a C
7
to C
40
arylalkyl group, a C
7
to C
40
alkylaryl group, a C
8
to C
40
arylalkenyl group, a C
2
to C
10
alkynyl group, a silyl group substituted by C
1
-C
10
hydrocaarbon radicals, a sulphide group substituted by a C
1
-C
10
hydrocarbon radical, or an amino group which is optionally substituted by C
1
-C
20
hydrocarbon radicals, or
R
1
, R
2
, R
3
, R
4
, R
5
, and R
6
each form one or more aliphatic or aromatic ring systems together with the atoms which bond them, which ring systems may contain one or more hetero atoms (O, N, S) and comprise 5 to 10 carbon atoms,
R
7
represents hydrogen, a C
1
to C
20
alkyl group, a C
6
to C
20
aryl group, a C
7
to C
40
arylalkyl group, a C
7
to C
40
alkylaryl group, a silyl group which is substituted by C
1
-C
10
hydrocarbon radicals, or an amino group which is optionally substituted a silyl group which is substituted by C
1
-C
10
hydrocarbon radicals, or an amino group which is optionally substituted by C
1
-C
20
hydrocarbon radicals,
b) an unsaturated compound of formula (II):
R
8
a
R
9
b
CY (II),
wherein
R
8
and R
9
are the same or different, and denote a hydrogen atom, a halogen atom, a hydroxy group, a C
1
to C
10
alkyl group, a C
1
to C
10
alkoxy group, a C
6
to C
10
aryl group which is optionally substituted by halogen atoms, a C
6
to C
10
aryloxy group, a C
2
alkylaryl group, a C
8
to C
40
arylalkenyl group, an amino group which is optionally substituted by C
1
-C
20
hydrocarbon radicals, or an imino group which is optionally substituted by C
1
-C
20
hydrocarbon radicals,
Y denotes a nitrogen atom, an oxygen atom, a sulphur atom or a group of formula NR
10
, wherein R
10
has the same meaning as R
8
and R
9
, and
a and b represent the numbers 0 or 1,
and subsequent reaction of the
Becke Sigurd
Beckhaus Rüdiger
Heinrichs Jürgen
Bayer Aktiengesellschaft
Cheung Noland J.
Gil Joseph C.
Lu Caixia
Wu David W.
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