Process for the preparation of solid catalyst

1. A process for the preparation of a solid olefin polymerization catalyst or a solid olefin polymerization catalyst component, the process comprising the steps of:

(a) forming a liquid/liquid emulsion of:

(i) a first organic liquid comprising at least one olefin polymerization catalyst component, and

(ii) an optionally halogenated hydrocarbon liquid immiscible therewith;

wherein the liquid/liquid emulsion comprises a dispersed phase and a continuous phase,

wherein the first organic liquid forms the dispersed phase and the optionally halogenated hydrocarbon liquid forms the continuous phase of the liquid/liquid emulsion, and

wherein the dispersed phase forms droplets in the continuous phase; and

(b) transforming the droplets of the dispersed phase to solid particulate particles comprising the at least one olefin polymerization catalyst component, wherein the liquid/liquid emulsion is stabilized with a solid particulate stabilizer.

2. The process according to claim 1 , wherein the optionally halogenated hydrocarbon liquid comprises a fluorinated hydrocarbon solvent.

3. The process according to claim 2 , wherein the fluorinated hydrocarbon solvent comprises a semi or perfluorinated hydrocarbon, or a hydrocarbon wherein the majority of the —C—H units are replaced with —C—F units.

4. The process according to claim 3 , wherein the fluorinated hydrocarbon solvent comprises a perfluorohydrocarbon.

5. The process as claimed in claim 1 , wherein transforming the droplets of the dispersed phase to solid particulate particles is effected by a temperature change.

6. A process for the preparation of a solid catalyst system (CS), the process comprising the steps of:

(i) preparing a liquid clathrate (LC) by mixing an aluminoxane (A), an aromatic compound (AC), and a polarity modifier (PM);

(ii) mixing the liquid clathrate (LC) with an organometallic compound (C) to obtain a liquid mixture (MI);

(iii) contacting the liquid mixture (MI) with a hydrocarbon liquid immiscible with the liquid mixture (MI), in the presence of a solid particulate stabilizer to form a liquid/liquid emulsion system, which comprises the liquid mixture (MI) dispersed in the hydrocarbon liquid;

(iv) precipitating the solid catalyst system (CS) out of the liquid/liquid emulsion system by adding a saturated aliphatic compound to the liquid/liquid emulsion system; and

(v) optionally recovering the solid catalyst system (CS), wherein the solid catalyst system (CS) comprises solid particles.

7. The process as claimed in claim 6 , wherein the liquid mixture (MI) is contacted with the solid particulate stabilizer to form a catalyst mixture (CM), and the liquid/liquid emulsion is formed by contacting the catalyst mixture (CM) with the hydrocarbon liquid, which is immiscible with the catalyst mixture (CM).

8. The process according to claim 6 , wherein the organometallic compound (C) comprises a transition metal and the mol-ratio between the aluminum (Al) of the aluminoxane (A) and the transition metal (M) of the organometallic compound (C), [(Al)/(M)], is in the range of 50 to 600.

9. The process according to claim 6 , wherein the polarity modifier (PM) is an organo-silicon compound (OS).

10. The process as claimed in claim 9 , wherein the organo-silicon compound (OS) is selected from the group consisting of octamethyltrisiloxane, decamethyltetrasiloxane, octamethylcyclotetrasiloxane, methoxytrimethylsilane, tetraethoxysilane, and 1,1,1,3,5,5,5-heptamethyl-3-phenyltrisiloxane.

11. The process according to claim 6 , wherein

(a) the aromatic compound (AC) is toluene; or

(b) the saturated aliphatic compound is selected from the group consisting of n-pentane, n-hexane, n-heptane, n-octane, and mixtures thereof; or

(c) the aromatic compound (AC) is toluene and the saturated aliphatic compound is selected from the group consisting of n-pentane, n-hexane, n-heptane, n-octane, and mixtures thereof.

12. The process according to claim 9 , wherein

(a) in step (i), the mixing of the aluminoxane (A), the aromatic compound (AC), and the organo-silicon compound (OS) is accomplished at a temperature in the range of −20 to 70° C.;

(b) in step (ii), the mixing of the liquid clathrate (LC) with the organometallic compound (C) is accomplished at a temperature in the range of 0 to 50° C.

13. The process according to claim 6 , wherein the liquid mixture (MI) is homogeneous.

14. The process according to claim 1 , wherein the at least one olefin polymerization catalyst component comprises an aluminoxane and there is 0.5 to 8.0 wt % of the solid particulate stabilizer based on the weight of the aluminoxane.

15. The process according to claim 1 , wherein the solid olefin polymerization catalyst comprises an organometallic compound (C) of formula (I)

( L ) m R n MX q   (I)

wherein

“M” is a transition metal (M) of group 3 to 10 of the Periodic Table (IUPAC 2007),

each “X” is independently a mono anionic ligand,

each “L” is independently an organic ligand which coordinates to the transition metal “M”,

“R” is a bridging group linking the organic ligands (L),

“m” is 1, 2 or 3,

“n” is 0, 1 or 2,

“q” is 1, 2 or 3, and

m+q is equal to the valency of the transition metal (M).

16. The process according to claim 1 , wherein the solid particulate stabilizer is a nanoparticulate material.

17. The process according to claim 1 , wherein the solid particulate stabilizer is a hydrophobic nanosilica.

18. The process according to claim 6 , further comprising recovering the solid particles of the solid catalyst system, wherein the solid particles have an average size range of 5 to 200 μm.

19. A solid catalyst obtained according to the process of claim 1 .

20. The solid catalyst according to claim 19 , wherein the solid catalyst comprises 0.25 to 4.0 wt % of the solid particulate stabilizer.

21. A process for the preparation of a polymer by polymerizing monomers in the presence of the solid catalyst as defined in claim 19 .

22. A process comprising the steps of:

(A) preparing a solid catalyst according to the process of claim 1 ,

(B) conducting polymerization in the presence of the solid catalyst of claim 1 to obtain a polymer.

23. The process according to claim 4 , wherein the fluorinated hydrocarbon solvent comprises a C3-C30 perfluoroalkane, -alkene or -cycloalkane.

24. The process according to claim 4 , wherein the fluorinated hydrocarbon solvent comprises a C4-C10 perfluoroalkane, -alkene or -cycloalkane.

25. The process according to claim 4 , wherein the fluorinated hydrocarbon solvent comprises perfluorohexane, perfluoroheptane, perfluorooctane, perfluoro(methylcyclohexane), or a mixture thereof.

26. The process according to claim 6 , wherein in step (i) the mol ratio between the polarity modifier (PM) and the aluminum (Al) of the aluminoxane (A), [(PM)/(Al)], is equal to or below 0.1.

27. The process according to claim 6 , wherein in step (iii) the hydrocarbon liquid immicible with the liquid mixture (MI) is an aromatic solvent.

28. The process according to claim 12 , wherein in step (i), the mixing of the aluminoxane (A), the aromatic compound (AC), and the organo-silicon compound (OS) is accomplished at a temperature in the range of 10 to 40° C.

29. The process according to claim 12 , wherein in step (ii), the mixing of the liquid clathrate (LC) with the organometallic compound (C) is accomplished at a temperature in the range of 20 to 30° C.

30. The process according to claim 15 , wherein each “X” is independently a σ ligand.

31. The process according to claim 15 , wherein “m” is 2.

32. The process according to claim 15 , wherein “n” is 1.

33. The process according to claim 15 , wherein “q” is 2.

34. The process according to claim 18 , wherein the solid particles have an average size range of 10 to 100 μm.

35. The process according to claim 21 , wherein the polymer is polypropylene or polyethylene.

36. The process according to claim 22 , wherein the polymer is polypropylene or polyethylene.