Compounds containing boron and aluminium

Details Compounds containing boron and aluminium Compounds containing boron and aluminium

2000-01-27

2002-07-09

Wu, David W. (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S178000, C526S151000, C526S348000, C526S943000, C502S132000, C502S202000, C502S117000, C502S102000, C502S103000

Reexamination Certificate

active

06417302

ABSTRACT:

The present invention relates to a chemical compound which, in combination with a metallocene, can form a catalyst system which can advantageously be employed for the polymerization of olefins. The use of an aluminoxane, such as methylaluminoxane (MAO), as cocatalyst is unnecessary in this polymerization, and yet high catalyst activity is still achieved.
The role of cationic complexes in Ziegler-Natta polymerization using metallocenes is generally recognized (H. H. Brintzinger, D. Fischer, R. Mülhaupt, R. Rieger, R. Waymouth, Angew. Chem. 1995, 107, 1255-1283). As the most effective cocatalyst hitherto, MAO has the disadvantage of being employed in a large excess, which results in a high aluminum content in the polymer. The preparation of cationic alkyl complexes gives access to MAO-free catalysts of comparable activity, where the cocatalyst can be employed in a virtually stoichiometric amount.
The synthesis of “cation-similar” metallocene polymerization catalysts is described in J. Am. Chem. Soc. 1991, 113, 3623. This synthesis involves alkyl abstraction from an alkyl metallocene compound by means of trispentafluorophenylborane. EP 427 697 claims this synthetic principle and a corresponding catalyst system consisting of a neutral metallocene species (for example CP
2
ZrMe
2
), a Lewis acid (for example B(C
6
F
5
)
3
) and alkylaluminum compounds. A process for the preparation of salts of the general form LMX
+
XA
−
by the above-described principle is claimed in EP 520 732.
Disadvantages of known alternative cocatalyst systems are their high sensitivity to catalyst poisons and the problem of leaching on supporting of the catalyst systems.
The object of the present invention was to provide a chemical compound which avoids the disadvantages of the prior art and nevertheless facilitates high polymerization activities.
The present invention thus relates to a novel chemical compound and to a process for the preparation of this chemical compound. It furthermore relates to a catalyst system comprising at least one metallocene and at least one chemical compound according to the invention as cocatalyst. The catalyst system may additionally comprise further organometallic components and be immobilized on a support material. Furthermore, a process for the preparation of polyolefins is described.
The object is achieved by a chemical compound of the formula A
in which R
1
are identical or different and are a hydrogen atom, a halogen atom, a boron-free C
1
-C
40
-hydrocarbon-containing group, such as C
1
-C
20
-alkyl, C
1
-C
20
-haloalkyl, C
1
-C
10
-alkoxy, C
6
-C
20
-aryl, C
6
-C
20
-haloaryl, C
6
-C
20
-aryloxy, C
7
-C
40
-arylalkyl, C
7
-C
40
-haloarylalkyl, C
7
-C
40
-alkylaryl or C
7
-C
40
-haloalkylaryl, or R
1
can be an OSiR
3
3
group, in which R
3
are identical or different and are a hydrogen atom, a halogen atom, a C
1
-C
40
-hydrocarbon-containing group, such as C
1
-C
20
-alkyl, C
1
-C
20
-haloalkyl, C
1
-C
10
-alkoxy, C
6
-C
20
-aryl, C
6
-C
20
-haloaryl, C
6
-C
20
-aryloxy, C
7
-C
40
-arylalkyl, C
7
-C
40
-haloarylalkyl, C
7
-C
40
-alkylaryl or C
7
-C
40
-haloalkylaryl, or R
1
can be a CH(SiR
4
3
)
2
group in which R
4
may be identical or different and are a hydrogen atom, a halogen atom, a C
1
-C
40
-hydrocarbon-containing group, such as C
1
-C
20
-alkyl, C
1
-C
20
-haloalkyl, C
1
-C
10
-alkoxy, C
6
-C
20
-aryl, C
6
-C
20
-haloaryl, C
6
-C
20
-aryloxy, C
7
-C
40
-arylalkyl, C
7
-C
40
-haloarylalkyl, C
7
-C
40
-alkylaryl or C
7
-C
40
-halo-alkylaryl,
X is identical or different and is an element from group VIa of the Periodic Table of the Elements or is an NR group, where R is hydrogen or a C
1
-C
20
-hydrocarbon radical, such as C
1
-C
20
-alkyl or C
1
-C
20
-aryl,
R
a
and R
b
may be identical or different and are a hydrogen atom, a halogen atom, a boron-free C
1
-C
40
-hydrocarbon-containing group, such as C
1
-C
20
-alkyl, C
1
-C
20
-haloalkyl, C
1
-C
10
-alkoxy, C
6
-C
20
-aryl, C
6
-C
20
-haloaryl, C
6
-C
20
-aryloxy, C
7
-C
40
-arylalkyl, C
7
-C
40
-haloarylalkyl, C
7
-C
40
-alkylaryl or C
7
-C
40
-haloalkylaryl, or R
1
can be an OSiR
3
3
group, in which R
3
are identical or different and are a hydrogen atom, a halogen atom, a C
1
-C
40
-hydrocarbon-containing group, such as C
1
-C
20
-alkyl, C
1
-C
20
-haloalkyl, C
1
-C
10
-alkoxy, C
6
-C
20
-aryl, C
6
-C
20
-haloaryl, C
6
-C
20
-aryloxy, C
7
-C
40
-arylalkyl, C
7
-C
40
-haloarylalkyl, C
7
-C
40
-alkylaryl or C
7
-C
40
-haloalkylaryl,
In addition, R
a
and R
b
can be a boron-containing group, such as, for example, —X—BR
1
2
, in which X is an element from group VIa of the Periodic Table of the Elements or an NR group, where R is hydrogen or a C
1
-C
20
-hydrocarbon radical, such as C
1
-C
20
-alkyl or C
1
-C
20
-aryl, and R
1
are identical or different and are a hydrogen atom, a halogen atom, a boron-free C
1
-C
40
-hydrocarbon-containing group, such as C
1
-C
20
-alkyl, C
1
-C
20
-haloalkyl, C
1
-C
10
-alkoxy, C
6
-C
20
-aryl, C
6
-C
20
-haloaryl, C
6
-C
20
-aryloxy, C
7
-C
40
-arylalkyl, C
7
-C
40
-haloarylalkyl, C
7
-C
40
-alkylaryl or C
7
-C
40
-haloalkylaryl, or R
1
can be an OSiR
3
3
group, in which R
3
are identical or different and are a hydrogen atom, a halogen atom, a C
1
-C
40
-hydrocarbon-containing group, such as C
1
-C
20
-alkyl, C
1
-C
20
-haloalkyl, C
1
-C
10
-alkoxy, C
6
-C
20
-aryl, C
6
-C
20
-haloaryl, C
6
-C
20
-aryloxy, C
7
-C
40
-arylalkyl, C
7
-C
40
-haloarylalkyl, C
7
-C
40
-alkylaryl or C
7
-C
40
-haloalkylaryl, or R
1
can be a CH(SiR
4
3
)
2
group, in which R
4
are identical or different and are a hydrogen atom, a halogen atom, a C
1
-C
40
-hydrocarbon-containing group, such as C
1
-C
20
-alkyl, C
1
-C
20
-haloalkyl, C
1
-C
10
-alkoxy, C
6
-C
20
-aryl, C
6
-C
20
-haloaryl, C
6
-C
20
-aryloxy, C
7
-C
40
-arylalkyl, C
7
-C
40
-haloarylalkyl, C
7
-C
40
-alkylaryl or C
7
-C
40
-haloalkylaryl, and k is an integer from 1 to 100.
The compound of the formula A according to the invention can form dimers, trimers or higher oligomers through acid-base interactions, where k can be a natural number from 1 to 100.
Preferred chemical compounds of the formula A conform to the general formulae I, II and III:
in which R
1
are identical or different and are a hydrogen atom, a halogen atom, a boron-free C
1
-C
40
-hydrocarbon-containing group, such as C
1
-C
20
-alkyl, C
1
-C
20
-haloalkyl, C
1
-C
10
-alkoxy, C
6
-C
20
-aryl, C
6
-C
20
-haloaryl, C
6
-C
20
-aryloxy, C
7
-C
40
-arylalkyl, C
7
-C
40
-haloarylalkyl, C
7
-C
40
-alkylaryl or C
7
-C
40
-haloalkylaryl, or R
1
can be an OSiR
3
3
group, in which R
3
are identical or different and are a hydrogen atom, a halogen atom, a C
1
-C
40
-hydrocarbon-containing group, such as C
1
-C
20
-alkyl, C
1
-C
20
-haloalkyl, C
1
-C
10
-alkoxy, C
6
-C
20
-aryl, C
6
-C
20
-haloaryl, C
6
-C
20
-aryloxy, C
7
-C
40
-arylalkyl, C
7
-C
40
-haloarylalkyl, C
7
-C
40
-alkylaryl or C
7
-C
40
-haloalkylaryl, or R
1
can be a CH(SiR
4
3
)
2
group in which R
4
may be identical or different and are a hydrogen atom, a halogen atom, a C
1
-C
40
-hydrocarbon-containing group, such as C
1
-C
20
-alkyl, C
1
-C
20
-haloalkyl, C
1
-C
10
-alkoxy, C
6
-C
20
-aryl, C
6
-C
20
-haloaryl, C
6
-C
20
-aryloxy, C
7
-C
40
-arylalkyl, C
7
-C
40
-haloarylalkyl, C
7
-C
40
-alkylaryl or C
7
-C
40
-halo-lkylaryl,
R
2
may be identical or different and are a hydrogen atom, a halogen atom, a boron-free C
1
-C
40
-hydrocarbon-containing group, such as C
1
-C
20
-alkyl, C
1
-C
20
-haloalkyl, C
1
-C
10
-alkoxy, C
6
-C
20
-aryl, C
6
-C
20
-haloaryl, C
6
-C
20
-aryloxy, C
7
-C
40
-arylalkyl, C
7
-C
40
-haloarylalkyl, C
7
-C
40
-alkylaryl or C
7
-C
40
-haloalkylaryl, or R
2
can be an OSiR
3
3
group, in which R
3
are identical or different and are a hydrogen atom, a halogen atom, a C
1
-C
40
-hydrocarbon-containing group, such as C
1
-C
20
-alkyl, C
1
-C
20
-haloalkyl, C
1
-C
10
-alkoxy, C
6
-C
20
-aryl, C
6
-C
20
-haloaryl, C
6
-C
20
-aryloxy, C
7
-C
40
-aryl-alkyl, C
7
-C
40
-haloarylalkyl, C
7
-C
40
-alkylaryl or C
7
-C
40
-haloalkylaryl.
X is identical or different and is a

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