Catalyst systems for the polymerization of C.sub.2 -C.sub.10 -al

Details Catalyst systems for the polymerization of C.sub.2 -C.sub.10 -al Catalyst systems for the polymerization of C.sub.2 -C.sub.10 -al

1994-06-13

1996-03-05

Delmendo, Romulo H.

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

Synthetic resins

Polymers from only ethylenic monomers or processes of...

526160, 502102, 502103, 502117, C08F 4642

Patent

active

054969026

DESCRIPTION:

BRIEF SUMMARY
The present invention relates to catalyst systems for the polymerization of C.sub.2 -C.sub.10 -alk-1-enes, containing, as active components, ##STR3## where
M is a metal of the subgroup III, IV or V of the Periodic Table of elements or a metal selected from the group consisting of the lanthanides,
X is fluorine, chlorine, bromine, iodine, hydrogen, C.sub.1 -C.sub.10 -alkyl, C.sub.6 -C.sub.15 -aryl or --OR.sup.7,
R.sup.7 is C.sub.1 -C.sub.10 -alkyl, C.sub.6 -C.sub.15 -aryl, alkylaryl, arylalkyl, fluoroalkyl or fluoroaryl, in each case having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical,
n is the valency of M minus two,
R.sup.1 to R.sup.6 are each hydrogen, C.sub.1 -C.sub.10 -alkyl, 5-membered to 7-membered cycloalkyl which in turn may carry C.sub.1 -C.sub.10 -alkyl as a substituent, C.sub.6 -C.sub.15 -aryl or arylalkyl, where two adjacent radicals together may furthermore form a cyclic group of 4 to 15 carbon atoms, or Si(R.sup.8).sub.3,
R.sup.8 is C.sub.1 -C.sub.10 -alkyl, C.sub.6 -C.sub.15 -aryl or C.sub.3 -C.sub.10 -cycloalkyl,
E.sup.1 and E.sup.2 are independent of one another and are each Si(R.sup.9).sub.2, Ge(R.sup.9).sub.2, Sn(R.sup.9).sub.2 or C(R.sup.9).sub.2 -C(R.sup.9).sub.2 and
R.sup.9 is C.sub.1 -C.sub.10 -alkyl, C.sub.3 -C.sub.10 -cycloalkyl or C.sub.6 -C.sub.15 -aryl, and ##STR4## where R.sup.10 is C.sub.1 -C.sub.4 -alkyl and m is an integer of from 5 to 30.
The present invention furthermore relates to a process for the preparation of metallocene complexes of the formula I, the use of a catalyst system for the preparation of polyalk-1-enes, processes for the preparation of polyalk-1-enes with the aid of these catalyst systems and the polyalk-1-enes obtainable thereby.
Metallocene dichlorides having a single dimethylsilyl bridge have already been widely mentioned in the patent literature and, in conjunction with alumoxanes, constitute olefin polymerization catalysts which are defined in molecular terms. Owing to the bridging of the cyclopentadienyl ligands, the ligand skeletons are stereorigid and result in high stereospecificity in the e-olefin polymerization, as disclosed in, for example, EP-A 302 424.
However, precisely at the technically interesting higher temperatures, the ligand skeleton may lose stereo-rigidity, so that the stereospecificity decreases.
It is an object of the present invention to provide catalyst systems which have high stereorigidity and, in conjunction with alumoxanes, possess the high productivities typical for metallocene catalysts.
We have found that this object is achieved by the catalyst systems defined at the outset for the preparation of polyalk-1-enes. We have also found processes for the preparation of metallocene complexes of the formula I, the use of the catalyst systems for the preparation of polyalk-1-enes, processes for the preparation of polyalk-1-enes with the aid of these catalyst systems and the polyalk-1-enes obtainable thereby.
The novel catalyst systems contain, as active components, inter alia one or more complexes of the formula I ##STR5## where M is a metal of the subgroup III, IV or V of the Periodic Table of elements or a metal from the group consisting of lanthanides, preferably a metal of the subgroup IV or V, in particular titanium, zirconium or hafnium. X is halogen, preferably chlorine, hydrogen, C.sub.1 -C.sub.10 -alkyl, preferably linear alkyl of 1 to 4 carbon atoms, in particular methyl or ethyl, C.sub.6 -C.sub.15 -aryl, preferably phenyl, or --OR.sup.7, R.sup.7 being C.sub.1 -C.sub.10 -alkyl, C.sub.6 -C.sub.15 -aryl, alkylaryl, arylalkyl, fluoroalkyl or fluoroaryl having in each case 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical.
R.sup.1 to R.sup.6 independently of one another are each preferably hydrogen, C.sub.1 -C.sub.10 -alkyl, preferably C.sub.1 -C.sub.4 -alkyl, 5-membered to 7-membered cycloalkyl which in turn may carry C.sub.1 -C.sub.10 -alkyl as a substituent, C.sub.6 -C.sub.15 -aryl, preferably phenyl, or arylalkyl. It is also possible for two a

REFERENCES:
patent: 4794096 (1988-12-01), Ewen
Siemeling et al., "Trinuclear Homo-and Heterometallic Complexes of a Doubly Bridged Cyclopentadienyl Ligand," Chemische Beriehte, 125, pp. 31-35 (1992).

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