Catalytic patterns containing metal complexes with an adamantane

Details Catalytic patterns containing metal complexes with an adamantane Catalytic patterns containing metal complexes with an adamantane

1999-04-14

2000-10-03

Teskin, Fred

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

Synthetic resins

Polymers from only ethylenic monomers or processes of...

526126, 526131, 526133, 526134, 526153, 526160, 526161, 526346, 526347, 502103, 502117, 502152, 502154, 556 52, C08F 478, C08F 4642, C08F 1204

Patent

active

061274968

DESCRIPTION:

BRIEF SUMMARY
The present invention relates to catalyst systems comprising as active constituents ##STR2## where the substituents have the following meanings: M is a metal of transition group III, IV, V or VI of the Periodic Table of the Elements or a metal of the lanthanide series, or VI of the Periodic Table of the Elements, C.sub.1 -C.sub.10 -alkoxy, C.sub.1 -C.sub.10 -alkylthio or dialkylamido having from 1 to 4 carbon atoms in each alkyl radical,
The present invention further relates to the use of such catalyst systems for polymerizing olefinically unsaturated compounds, a process for preparing polymers of vinylaromatic compounds with the aid of these catalyst systems and also the polymers obtainable in this way.
Metallocene complexes are known as constituents of catalyst complexes for polymerizing olefinically unsaturated compounds. For example, WO 95706071 describes heterofunctional compounds containing cyclopentadienyl radicals. However, this class of compounds is not able to effectively suppress chain transfer by .beta.-hydride elimination, which leads to premature stopping of the polymerization and thereby to limited molecular weights.
DE-A 44 20 783 discloses heterofunctional, cyclopentadienyl-free compounds which, however, have an open catalyst structure and are therefore not stereoselective or favor chain transfer by .beta.-hydride elimination.
It is an object of the present invention to provide novel catalyst systems which can be used for polymerizing vinylaromatic compounds and in the process effectively suppress .beta.-hydride elimination and are stereoselective. In addition, the polymers formed should have a high molecular weight and a high proportion of syndiotactic structure.
We have found that this object is achieved by the catalyst systems defined at the outset.
We have also found the use of such catalyst systems for polymerizing olefinically unsaturated compounds, a process for preparing polymers of vinylaromatic compounds with the aid of these catalyst systems and the polymers obtainable in this way.
The catalyst systems of the present invention comprise, as component A), metal complexes of the formula I.
Among the metal complexes of the formula I, preference is given to those in which the substituents have the following meanings: Elements, preferably a metal of transition group IV, i.e. titanium, zirconium or hafnium, in particular titanium, C.sub.1 -C.sub.10 -alkoxy, dialkylamido, alkylaryl, arylalkyl, haloalkyl or haloaryl each having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, or fluorine, chlorine, bromine or iodine, preferably C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy or chlorine, in particular methyl, isobutyl, methoxy, isopropoxy or chlorine, Periodic Table of the Elements, preferably N, P, O or S as anion, preferably hydrogen, methyl, ethyl, n-propyl or cyclohexyl, -C.sub.10 -cycloalkyl, C.sub.6 -C.sub.20 -aryl, alkylaryl, arylalkyl, haloalkyl or haloaryl each having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, or fluorine, chlorine, bromine or iodine, or two adjacent radicals may together form a cyclic group having from 4 to 5 carbon atoms, or Si(R.sup.12).sub.3 where C.sub.6 -C.sub.15 -aryl, particular
Examples of particularly preferred metal complexes of the formula I are: diisopropoxide diisopropoxide diisopropoxide
Mixtures of various metal complexes can also be used.
The metal complexes 1,3-dimethylamido-5,5-dimethylcyclohexanetitanium dichloride, 1,3-dimethylamido-5,5-dimethylcyclohexanedimethyltitanium and 1,3-di(isopropylamido)-2,5,5-trimethylcyclohexanetitanium dichloride are particularly preferred.
The metal complexes of the formula I can be prepared by the following methods:
A compound of the formula II ##STR3## is metallated.
This is preferably done by reacting a compound of the formula II with hydrides, carboorganic compounds, nitrogen-organic compounds or organosilicon compounds of alkali metals or alkaline earth metals and then treating the product with haloge

REFERENCES:
patent: 4794096 (1988-12-01), Ewen
patent: 5502133 (1996-03-01), Ishihara et al.
patent: 5707913 (1998-01-01), Schlund et al.
Beilsteins Handbuch der Org. chem. 1922, 367/474/485.

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