Catalytic system comprising a solid precursor and process...

Details Catalytic system comprising a solid precursor and process... Catalytic system comprising a solid precursor and process...

1998-04-13

2001-04-10

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...

C526S124200, C526S124300, C526S129000, C526S134000, C526S160000, C526S904000, C526S907000, C526S943000, C526S906000, C526S113000, C526S114000, C526S119000

Reexamination Certificate

active

06214948

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to a solid precursor of a catalytic system which may be used for the polymerization of olefins, in particular a solid precursor comprising a metallocene. It also relates to a process for the preparation of this solid precursor, a catalytic system comprising this precursor and a process for the polymerization of olefins in the presence of this catalytic system.
TECHNOLOGY REVIEW
Patent Application EP-426,638 (FINA TECHNOLOGY INC.) discloses a process for the polymerization of olefins in the presence of a metallocene-type catalyst in the ionized state, obtained by mixing a solution of an ionizing agent, such as a solution of triphenylcarbenium tetrakis(pentafluorophenyl)borate in toluene, with a solution of a neutral metallocene which is alkylated and derived from a transition metal (for example a solution of bis(cyclopentadienyl)dimethylzirconium in toluene). These neutral alkylated metallocenes have the disadvantages of being unstable and difficult to prepare and to store. Moreover, these known catalysts are particularly unstable and, during their use for the polymerization of olefins, have an activity which rapidly decreases from the moment of their preparation.
The preparation of these catalysts may be simplified, as described in Patent Application EP-0,500,944-A1 (MITSUI TOATSU CHEMICALS INC.), by selecting among the neutral metallocenes those which are halogenated, by first of all reacting an organoaluminium compound with the neutral halogenated metallocene in an aromatic solvent, and in subsequently ionizing the product thus obtained by means of an ionizing agent. To this end, there are successively introduced into the polymerization reactor: (a) the product of the alkylation reaction between the organoaluminium compound and the neutral halogenated metallocene in an aromatic solvent, (b) the olefin which it is desired to polymerize and (c) the ionizing agent. In this process, the preliminary reaction of alkylation of the neutral halogenated metallocene with the organoaluminium compound in an aromatic solvent is of essential importance for obtaining a catalyst which is stable and active. This known process has the disadvantage of requiring a preliminary treatment of the neutral halogenated metallocene by means of an organoaluminium compound before placing it in contact with the ionizing agent. In addition, since the product of the alkylation reaction of the neutral halogenated metallocene is very unstable, placement of the latter in contact with the ionizing agent must necessarily be carried out in situ in the polymerization reactor.
SUMMARY OF THE INVENTION
The present invention aims to overcome the abovementioned disadvantages by providing a new solid precursor of a catalytic system, the preparation of which is easier and does not require a preliminary treatment of the neutral halogenated metallocene. Another object of the invention is to provide a stable solid precursor which may be prepared beforehand and kept for at least a day (generally longer) before using it for the polymerization of olefins without risk of deactivation. An additional object of the invention is to provide a solid precursor of a catalytic system which makes it possible to obtain olefinic polymers of high average molecular mass, of wide molecular mass distribution and of high apparent specific weight.


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Chemical Abstracts, vol. 117, No. 22, Nov. 30, 1992, Columbus, Ohio, US; abstract No. 213195p, Sugimoto et al “Supported olefin polymerization catalysts” p. 16.

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