Transition metal compound, catalyst, its production and its...

Details Transition metal compound, catalyst, its production and its... Transition metal compound, catalyst, its production and its...

2000-02-29

2002-10-01

Bell, Mark L. (Department: 1755)

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

Organic compounds

Heavy metal containing

C502S103000, C502S117000, C502S152000, C502S155000, C502S156000

Reexamination Certificate

active

06458982

ABSTRACT:

The present invention relates to transition metal compounds, catalyst systems, a process for producing them 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.
Crystalline, amorphous and elastic polypropylene are known. Crystalline polypropylene usually has a dominant isotactic or syndiotactic content. In contrast, amorphous polypropylene has predominantly atactic structural elements. (U.S. Pat. No. 3,112,300 and U.S. Pat. No. 3,112,301). The preparation of elastomeric polypropylene is described in U.S. Pat. No. 3,175,199, where it is isolated from a polymer mixture of isotactic and atactic polypropylene. The elastomeric properties of this polypropylene are caused by alternating isotactic and atactic block sequences.
Metallocene catalysts are able to give, depending on the geometry of the metallocene, atactic, isotactic or syndiotactic polypropylene. It is primarily the two stereoisomers (rac isomer and meso isomer), which are usually formed in equal proportions in the synthesis, which are responsible for this. The meso form gives atactic polypropylene and its polymerization activity is usually lower than that of the rac form which gives isotactic or, depending on the substitution pattern, also syndiotactic polypropylene (J. Am. Chem. Soc. 1984, 106, 6355-6364).
Metallocenes which give polypropylene having elastomeric properties are described by Chien et al. (J. Polymer Science, Part A: Polymer Chemistry , 1992, 30, 2601-2617), and by Babu et al. (Macromolecules, 1992, 25, 6980-6987) and Dong et al. (Macromolecules, 1992, 25, 1242-1253). However, these metallocenes have low activities and give low molar masses of M
w
=200,000.
A first breakthrough was achieved by Waymouth et al. (U.S. Pat. No. 5,994,080) who used unbridged indenyl systems which bear an aromatic ring system such as phenyl and substituted phenyl rings in position 2 on the indenyl ring. These systems have the ability to isomerize between chiral and achiral arrangements by rotation of the indenyl system during chain growth. This results in an atactic-isotactic stereoblock polypropylene having elastomeric properties.
Although these metallocenes have a higher activity than the systems described up to then, these activities are not sufficient for cost-effective industrial use. It is therefore desirable to develop metallocene catalysts for the preparation of polypropylene having elastomeric properties, which catalysts have a significantly higher activity than the previously known systems.
It is an object of the present invention to find metallocenes which, after conversion into the polymerization-active species, display the abovementioned polymerization properties.
We have found that this object is achieved by metallocenes which have specific heteroaromatics in position 2 or 3 of the indenyl system.
The present invention provides compounds of the formula (I),
where
M
1
is a metal of group 3, 4, 5 or 6 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
16
)
3
, where R
16
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
4
-C
24
-heteroaryl, C
4
-C
24
-alkylheteroaryl, 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
16
)
3
, where R
16
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
1
can be identical or different and are each a hydrogen atom, a C
2
-C
10
-hydrocarbon group such as C
1
-C
10
-alkyl or C
6
-C
10
-aryl, a halogen atom, or OR
17
, SR
17
, OSi(R
17
)
3
, Si(R
17
)
3
, P(R
17
)
2
or N(R
17
)
2
, where R
17
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.
Preference is given to unbridged metallocene compounds of the formula (I), in particular those in which 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, 3 position, 4 position, 2,4,5 positions, 2,4,6 positions, 3,4,6 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, C
4
-C
24
-heteroaryl, C
4
-C
24
-alkylheteroaryl, where two or more substituents of the indenyl ring may together form a ring system.
Particular preference is given to unbridged metallocene compounds of the formula (II),
where
M is Ti, Zr or Hf, particularly preferably zirconium,
R
3
and R
5
or R
4
and 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, n-hexyl, cyclohexyl or octyl, C
2
-C
10
-alkenyl, C
3
-C
15
-alkylalkenyl, C
6
-C
18
-aryl, C
4
-C
24
-heteroaryl, C
4
-C
24
-alkylheteroaryl, 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, particularly preferably C
4
-C
24
-heteroaryl, C
4
-C
24
-alkylheteroaryl such as
 where R
10
, R
11
, R
12
, R
13
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, n-hexyl, cyclohexyl or octyl, C
2
-C
10
-alkenyl, C
3
-C
15
-alkylalkenyl, C
6
-C
18
-aryl, C
4
-C
24
-heteroaryl, C
4
-C
24
-alkylheteroaryl, C
7
-C
20
-arylalkyl, C
7
-C
20
-alky

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