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

1994-11-22

1996-06-18

Gibson, Sharon

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

Synthetic resins

Polymers from only ethylenic monomers or processes of...

526127, 526150, 502102, 502103, 502114, 502117, C08F 444, C08F 402, B01J 3100

Patent

active

055278680

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 subgroup III, IV or V of the Periodic Table of Elements or a metal of the lanthanide group, -cycloalkyl, C.sub.6 -C.sub.15 -aryl, alkylaryl of 7 to 15 carbon atoms or --OR.sup.15, arylalkyl, fluoroalkyl or fluoroaryl, each having 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the aryl radical, each C.sub.3 -C.sub.10 -cycloalkyl which in turn may carry C.sub.1 -C.sub.10 -alkyl as substituent, or are each 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 are each Si(R.sup.16).sub.3, -C.sub.10 -cycloalkyl, Ge(R.sup.17).sub.2 or Sn(R.sup.17).sub.2, -C.sub.10 -cycloalkyl, alkylaryl or Si(R.sup.18).sub.3 and -C.sub.10 -cycloalkyl or alkylaryl, III ##STR4## where R.sup.19 is C.sub.1 -C.sub.4 -alkyl and m is an integer from 5 to 30.
The invention furthermore relates to the use of such 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 patent literature, for example EP-A 69 951, describes many examples of unbridged, achiral metallocene complexes in conjunction with alumoxanes as catalysts for the polymerization of olefins. Stereoselective polymerizations are not possible with these systems. Furthermore, the introduction of chiral substituents in the cyclopentadienyl ring does not induce stereoselectivity in the polymerization of alk-1-enes with alumoxane as cocatalyst.
Makromol. Chem., Macromol. Symp. 48/49 (1991), 253-295 discloses that metallocene complexes which have a bridge between the cyclopentadienyl rings are suitable for stereospecific polymerizations of alk-1-enes. However, the synthesis of such compounds is expensive.
It is an object of the present invention to provide novel catalyst systems which are suitable for the uniform homopolymerization and in particular copolymerization of alkenes, give polymers having narrow molecular weight and comonomer distributions and are capable of stereoselectively polymerizing prochiral olefins.
We have found that this object is achieved by the catalyst systems defined at the outset and intended for the preparation of polyalk-1-enes. We have also found the use of such 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 active components contained in the novel catalyst systems include one or more complexes of the general formula I: ##STR5##
M is a metal of subgroup III, IV or V of the Periodic Table of Elements or a metal of the lanthanide group, preferably a metal of 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.3 -C.sub.10 -cycloalkyl, preferably C.sub.5 - or C.sub.6 -cycloalkyl, C.sub.6 -C.sub.15 -aryl, preferably phenyl, alkylaryl of 7 to 15 carbon atom, preferably benzyl, or a group --OR.sup.15, where R.sup.15 is C.sub.1 -C.sub.10 -alkyl, C.sub.6 -C.sub.15 -aryl, alkylaryl, arylalkyl, fluoroalkyl or fluoroaryl, each having 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.14, independently of one another, are each preferably hydrogen, C.sub.1 -C.sub.10 -alkyl, preferably C.sub.1 -C.sub.4 -alkyl, C.sub.3 -C.sub.10 -cycloalkyl, preferably C.sub.5 - or C.sub.6 -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, preferably benzyl. It is also possible for two adjacent radicals, ie. R.sup.1 and R.sup.2, R.sup.2 and R.sup.3, R.sup.5 and R.sup.6 or R.sup.6 and R.sup.7 and R.sup.8 and R.sup.9, R.sup.9 and R.sup.10,

REFERENCES:
patent: 5329033 (1994-07-01), Spalech et al.
Makromol. Chem., Macromol. Symp 48/49 (1991) 253-295, Ewen et al.
J. Organometal. Chem. 369 (1989), 359-370--Wiesenfeldt et al.

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