Polymer-containing catalyst systems

Details Polymer-containing catalyst systems Polymer-containing catalyst systems

1997-08-22

1998-12-08

Teskin, Fred

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

Synthetic resins

Mixing of two or more solid polymers; mixing of solid...

525 3303, 5253323, 5253333, 525360, 526170, 526171, 526183, 526190, 526943, 502109, 502152, C08F 842

Patent

active

058470557

DESCRIPTION:

BRIEF SUMMARY
The present invention relates to catalyst systems of the formula I -C.sub.10 -alkoxy, C.sub.6 -C.sub.15 -aryl or a compound of the formula II ##STR2## where R.sup.1 to R.sup.5 are hydrogen, C.sub.1 -C.sub.10 -alkyl which may bear from 1 to 5 halogen substituents, 5- to 7-membered cycloalkyl which may in turn bear C.sub.1 -C.sub.6 -alkyl groups as substituents, C.sub.6 -C.sub.15 -aryl or arylalkyl, where two adjacent radicals may also together form a cyclic group having from 4 to 15 carbon atoms, or halogen, C.sub.1 -C.sub.10 -alkoxy, NR.sup.6 R.sup.7 or Si(R.sup.6).sub.3, -C.sub.10 -cycloalkyl, Elements, mixtures
The present invention further relates to a process for preparing such catalyst systems and also their use for preparing polymers of vinylaromatic compounds.
Catalyst systems containing transition metals as active catalyst center are widely used in industry for preparing polymers.
Thus, D. S. Breslow, N. R. Newburg, J. Am. Chem. Soc. 81 (1959), pp. 81-86 discloses homogeneous Ziegler-Natta catalysts.
EP-A 416 815 describes metallocenes in which two aromatic ligands are bridged via carbon or silyl groups.
Furthermore, DE-A 43 03 647 discloses donor-containing catalyst systems.
These known catalyst systems can also be in supported form. Disadvantages of the known systems are that the mass transfer to and through the support is limited, that the selectivity is too low for some applications and that only a relatively small proportion of the metal centers present is catalytically active.
It is an object of the present invention to provide new catalyst systems which do not have the disadvantages mentioned, which can, in particular, be readily separated from the polymer formed and which can be easily activated.
We have found that this object is achieved by the catalyst systems defined in the introduction.
The present invention also provides a process for preparing such catalyst systems and provides for their use for preparing polymers of vinylaromatic compounds.
Among the novel catalyst systems of the formula I particular methyl or ethyl, C.sub.1 -C.sub.4 -alkoxy or particularly preferably a compound of the formula II ##STR3##
Among the compounds of the formula II, preference is given to those in which R.sup.1 to R.sup.5 are hydrogen, C.sub.1 -C.sub.4 -alkyl, in particular methyl, C.sub.6 -C.sub.15 -aryl, in particular phenyl and biphenyl, or where two adjacent radicals together form a cyclic group having from 4 to 15 carbon atoms, in which case X is, for example, indenyl, benzindenyl or fluorenyl, each of which may in turn be substituted by alkyl radicals.
X is particularly preferably pentamethylcyclopentadienyl.
If X is a compound of the formula II, the catalyst systems of the present invention are semisandwich complexes.
The metal M is preferably an element of transition groups IV to VI of the Periodic Table, in particular an element of transition group IV, viz. titanium, zirconium or hafnium, preferably titanium.
Z.sup.1 to Z.sup.3 are polymers of vinylaromatic compounds, dienes such as butadiene or isoprene, acrylates preferably having from 1 to 6 carbon atoms in the ester radical, in particular butyl acrylate, or their mixtures so that Z.sup.1 to Z.sup.3 are then copolymers.
Z.sup.1 to Z.sup.3 are preferably polymers of vinylaromatic compounds of the formula III ##STR4## where the substituents have the following meanings: R.sup.8 is hydrogen or C.sub.1 -C.sub.4 -alkyl, -C.sub.12 -alkyl, C.sub.6 -C.sub.18 -aryl, halogen or two adjacent radicals together form a cyclic group having from 4 to 15 carbon atoms.
Preference is given to vinylaromatic compounds of the formula III, in which phenyl or two adjacent radicals together form a cyclic group having from 4 to 15 carbon atoms, giving, for example, naphthalene derivatives or anthracene derivatives as compounds of the formula III.
Examples of such preferred compounds are:
Styrene, p-methylstyrene, p-chlorostyrene, 2,4-dimethylstyrene, 4-vinylbiphenyl, 2-vinylnaphthalene or 9-vinylanthracene.
Particularly preferred vinylaromatic compounds are styrene and p

REFERENCES:
patent: 3396155 (1968-08-01), Delbouille et al.
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patent: 4290918 (1981-09-01), Bayer et al.
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patent: 4725568 (1988-02-01), Parker et al.
patent: 5492978 (1996-02-01), Peifer et al.
Anionic polymerization:, Morton, Academic PRess (1983).
Breslow et al., J.A.M. Chem. Soc., (1959) 81 S. 81-86 Beilstein 5, 1922, S. 367/474/485.

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