Transition metal compound, ligand system, catalyst system...

Details Transition metal compound, ligand system, catalyst system... Transition metal compound, ligand system, catalyst system...

2000-07-11

2003-09-30

Nazario-Gonzalez, Porfirio (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heavy metal containing

C556S001000, C556S012000, C556S043000, C556S053000, C556S058000, C526S160000, C526S943000, C502S103000, C502S117000

Reexamination Certificate

active

06627764

ABSTRACT:

The present invention relates to ligand systems, transition metal compounds, catalyst systems and their use in the polymerization of olefins.
Metallocenes can, if desired in combination with one or more cocatalysts, be used as catalyst components for the polymerization and copolymerization of olefins. In particular, halogen-containing metallocenes which can be converted, for example, by an aluminoxane into a polymerization-active cationic metallocene complex are used as catalyst precursors (EP-A-129368).
The preparation of metallocenes is known per se (U.S. Pat. No. 4,752,597; U.S. Pat. No. 5,017,714; EP-A-320762; EP-A-416815; EP-A-537686; EP-A-669340; H. H. Brintzinger et al.; Angew. Chem., 107 (1995), 1255; H. H. Brintzinger et al., J. Organomet. Chem. 232 (1982), 233). They can be prepared, for example, by reacting cyclopentadienyl-metal compounds with halides of transition metals such as titanium, zirconium and hafnium.
A route which can be used for preparing isotactic polypropylene having a low molar mass is the addition of comparatively large amounts of hydrogen during the polymerization. This leads to processes which are difficult to control in engineering terms and to greatly increased costs.
It would therefore be desirable to have a cationic metallocene catalyst system in unsupported or supported form which gives the desired low molar masses of isotactic polypropylene in the presence of only small amounts of added hydrogen and also gives unaltered high activities and melting points.
Isotactic polypropylene having a low molar mass is of particular interest for film products.
EP-A-659757 and Spaleck et al., J. Mol. Catal. A: Chemical 1998, 128, 279-287, describe metallocene compounds which contain two differently substituted indenyl ligands. It is found that metallocene compounds in which there is no substituent in the 2 position on one of the indenyl substituents give isotactic polypropylene having low molar masses of 100,000-300,000 g/mol. However, a critical disadvantage of the compounds described there is that the polymerization activities in a heterogeneous polymerization are drastically reduced compared to a homogeneous polymerization. This leads to limited commercial utilization.
It is an object of the present invention to find metallocenes which, after conversion into the polymerization-active species, avoid the disadvantages of the prior art and display, in particular, a markedly increased polymerization activity with a heterogeneous polymerization procedure.
We have found that this object is achieved by metallocenes, in particular those which have specific substitutions on the indenyl ligand.
The present invention provides compounds of the formula (I),
where
M
1
is a metal of transition group III, IV, V or VI of the Periodic Table of the Elements, in particular Ti, Zr or Hf,
R
7
are identical or different and are each a hydrogen atom or Si(R
12
)
3
, where R
12
are identical or different and are each a hydrogen atom or a C
1
-C
40
-group such as C
1
-C
20
-alkyl, C
1
-C
10
-fluoroalkyl, C
1
-C
10
-alkoxy, C
6
-C
20
-aryl, C
6
-C
10
-fluoroaryl, C
6
-C
10
-aryloxy, C
2
-C
10
-alkenyl, C
7
-C
40
-arylalkyl, C
7
-C
40
-alkylaryl or C
8
-C
40
-arylalkenyl, or R
7
is a C
1
-C
30
-group such as C
1
-C
25
-alkyl, e.g. methyl, ethyl, tert-butyl, n-hexyl, cyclohexyl or octyl, C
2
-C
25
-alkenyl, C
3
-C
15
-alkylalkenyl, C
6
-C
24
-aryl, C
5
-C
24
-heteroaryl, C
7
-C
30
-arylalkyl, C
7
-C
30
-alkylaryl, fluorinated C
1
-C
25
-alkyl, fluorinated C
6
-C
24
-aryl, fluorinated C
7
-C
30
-arylalkyl, fluorinated C
7
-C
30
-alkylaryl or C
1
-C
12
-alkoxy, or two or more radicals R
7
can be joined to one another so that the radicals R
7
and the atoms of the cyclopentadienyl ring which connect them form a C
4
-C
24
ring system which may in turn be substituted,
R
8
are identical or different and are each a hydrogen atom or Si(R
12
)
3
, where R
12
are identical or different and are each a hydrogen atom or a C
1
-C
40
-group such as C
1
-C
20
-alkyl, C
1
-C
10
-fluoroalkyl, C
1
-C
10
-alkoxy, C
6
-C
14
-aryl, C
6
-C
10
-fluoroaryl, C
6
-C
10
-aryloxy, C
2
-C
10
-alkenyl, C
7
-C
40
-arylalkyl, C
7
-C
40
-alkylaryl or C
8
-C
40
-arylalkenyl, or R
8
is a C
1
-C
30
-group such as C
1
-C
25
-alkyl, e.g. methyl, ethyl, tert-butyl, cyclohexyl or octyl, C
2
-C
25
-alkenyl, C
3
-C
15
-alkylalkenyl, C
6
-C
24
-aryl, C
5
-C
24
-heteroaryl which together with the cyclopentadienyl ring form azapentalenes, thiopentalenes or phosphapentalenes, C
7
-C
30
-arylalkyl, C
7
-C
30
-alkylaryl, fluorinated C
1
-C
25
-alkyl, fluorinated C
6
-C
24
-aryl, fluorinated C
7
-C
30
-arylalkyl, fluorinated C
7
-C
30
-alkylaryl or C
1
-C
12
-alkoxy, or two or more radicals R
8
can be joined to one another so that the radicals R
8
and the atoms of the cyclopentadienyl ring which connect them form a C
4
-C
24
ring system which may in turn be substituted,
l is 5 when v=0, and 1 is 4 when v=1,
m is 5 when v=0, and m is 4 when v=1,
L
1
can be identical or different and are each a hydrogen atom, a C
1
-C
10
-hydrocarbon group such as C
1
-C
10
-alkyl or C
6
-C
10
-aryl, a halogen atom, or OR
9
, SR
9
, OSiR
3
9
, SiR
3
9
, PR
2
9
or NR
2
9
, where R
9
is a halogen atom, a C
1
-C
10
-alkyl group, a halogenated C
1
-C
10
-alkyl group, a C
6
-C
20
-aryl group or a halogenated C
6
-C
20
-aryl group, or L
1
is a toluenesulfonyl, trifluoroacetyl, trifluoroacetoxyl, trifluoromethanesulfonyl, nonafluorobutanesulfonyl or 2,2,2-trifluoroethanesulfonyl group,
o is an integer from 1 to 4, preferably 2.
Z is a bridging structural element between the two cyclopentadienyl rings and v is 0 or 1.
Examples of Z are MR
10
R
11
groups, where M is carbon or silicon and R
10
and R
11
are identical or different and are each a C
1
-C
20
-hydrocarbon-containing group such as C
1
-C
10
-alkyl, C
6
-C
14
-aryl, trialkylthionyl, in particular trimethylsilyl, triarylsilyl or an alkylarylsilyl group. Particularly preferred groups Z are Si(Me)
2
, Si(Ph)
2
, Si(MeEt), Si(PhMe), Si(PhEt), Si(Et)
2
, where Ph is substituted or unsubstituted phenyl and Et is ethyl. It is also possible for Z together with one or more radicals R
7
and/or R
8
to form a monocyclic or polycyclic ring system. In the abovementioned radicals, Ph is substituted or unsubstituted phenyl, Et is ethyl and Me is methyl.
Preference is given to bridged metallocene compounds of the formula (I), in particular those in which v is 1 and one or both cyclopentadienyl rings are substituted so that they form an indenyl ring. The indenyl ring is preferably substituted, particularly in the 2 position, 4 position, 2,4,5 positions, 2,4,6 positions, 2,4,7 positions or 2,4,5,6 positions, by C
1
-C
20
-groups such as C
1
-C
18
-alkyl or C
6
-C
18
-aryl, where two or more substituents of the indenyl ring may together form a ring system.
Particular preference is given to bridged metallocene compounds of the formula (II),
where
M is Ti, Zr or Hf, particularly preferably zirconium,
R
3
is a hydrogen atom, a C
1
-C
20
-group, preferably C
1
-C
18
-alkyl such as methyl, ethyl, n-butyl, n-hexyl, cyclohexyl or octyl, C
2
-C
10
-alkenyl, C
3
-C
15
-alkylalkenyl, C
6
-C
18
-aryl, C
5
-C
18
-heteroaryl, C
7
-C
20
-arylalkyl, C
7
-C
20
-alkylaryl, fluorinated C
1
-C
12
-alkyl, fluorinated C
6
-C
18
-aryl, fluorinated C
7
-C
20
-arylalkyl or fluorinated C
7
-C
20
-alkylaryl,
R
5
is a hydrogen atom,
R
6
are identical or different and are each a hydrogen atom, a C
1
-C
20
-group, preferably C
1
-C
18
-alkyl such as methyl, ethyl, n-butyl, cyclohexyl or octyl, C
2
-C
10
-alkenyl, C
3
-C
15
-alkylalkenyl, C
6
-C
18
-aryl, C
5
-C
18
-heteroaryl, C
7
-C
20
-arylalkyl, C
7
-C
20
-alkylaryl, fluorinated C
1
-C
12
-alkyl, fluorinated C
6
-C
18
-aryl, fluorinated C
7
-C
20
-arylalkyl or fluorinated C
7
-C
20
-alkylaryl,
R
20
, R
21
are identical or different and are each a hydrogen atom, a halogen atom or a C
1
-C
20
-group, preferably a linear or branched C
1
-C
18
-alkyl group such as methyl, ethyl, tert-butyl, cyclohexyl or octyl, C
2
-C
10
-alkenyl, C
3
-C
15
-a

Affiliated with

Also associated with

Rating

Transition metal compound, ligand system, catalyst system... does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Transition metal compound, ligand system, catalyst system..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Transition metal compound, ligand system, catalyst system... will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-3002188