Metallocene catalyst components supported on activating supports
AssigneeTotal Petrochemicals Research Feluy
InventorFloran Prades
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Abstract
The present invention discloses a catalyst system consisting of a mono- or di-fluorinated metallocene catalyst component of formula and a fluorinated activating support.
Claims15
An active catalyst system consisting of
- a) a metallocene catalyst component of formula
- R″s(CpRm)(CpR′n)MQF (I)
- or R″s(CpRm)XMQF (II)
- wherein Cp is a cyclopentadienyl group, R and R′ are each independently selected from hydrogen or hydrocarbyl having from 1 to 20 carbon atoms and two consecutive substituents can be linked together to form a ring, M is a metal group 4 of the Periodic Table, R″ is an optional bridge between the two cyclopentadienyl groups or between one cyclopentadienyl group and X, s being 0 when the bridge is absent and 1 when it is present, Q is selected from halogen, hydrogen, alkyl, cycloalkyl or alkoxy having at most 8 carbon atoms, and X is an heteroatom selected from groups 15 or 16 of the Periodic Table, preferably N, P or O, and
- b) a fluorinated activating support.
The catalyst system of any one of the preceding claims wherein Q is F.
The catalyst system of any one of the preceding claims wherein the metallocene catalyst component is selected from ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium difluoride, ethylenebis(indenyl)zirconium difluoride, isopropylidene(cyclopentadienyl-fluorenyl)zirconium difluoride, isopropylidenebis(3-tert-butyl-cyclopentadienyl)zirconium difluoride, dimethylsilyl(3-tert-butyl-cyclopentadienyl-fluorenyl)zirconium difluoride and dimethylsilyl-bisindenyl-zirconium difluoride.
The catalyst system of any one of the preceding claims wherein the activating support is prepared by the steps of:
- a) providing a support prepared from one or more porous mineral oxides;
- b) optionally heating the support under inert gas;
- c) functionalising the support with a solution containing an alkylating agent;
- d) heating the functionalised support of step c) under an inert gas and then under oxygen;
- e) fluorinating the support with a solution containing a fluorinating agent;
- f) retrieving an active fluorinated support.
The catalyst system of any one of the preceding claims wherein the functionalising and fluorinating agent is Al (R″)2F wherein the R″ groups are the same or different and are alkyl groups having from 1 to 20 carbon atoms.
The catalyst system of any one of the preceding claims wherein the number of aluminium atoms present in the support per nm2 is of from 0.25 to 10 Al/nm2 and the number of fluor atoms present in the support per nm2 is of from 0.25 to 20 F/nm2.
A process for preparing the catalyst system of any one of the preceding claims that comprises the steps of:
- a) providing a functionalised and fluorinated support;
- b) subjecting the support of step a) to a thermal treatment under inert gas;
- c) subjecting the support of step b) to a thermal treatment under oxygen;
- d) dissolving a metallocene catalyst component, optionally pre-alkylated in an organic solvent;
- e) optionally, providing an alkylating agent;
- f) impregnating the solution of step d) and the optional alkylating agent of step e) onto the support either simultaneously or in any order;
- g) retrieving an active supported catalyst system.
Dependencies are inferred from the claim text.