Emulsion process for improved large spherical polypropylene catalysts
View Patent ↗Disclosed are spherical magnesium-based catalyst supports and methods of using the same in a Ziegler-Natta catalyst system for the polymerization of an olefin. The spherical magnesium-based catalyst supports are made by reacting a magnesium halide, a haloalkylepoxide, and a phosphate acid ester in an organic solvent that does not have to contain substantial amounts of toluene.
1. A solid titanium catalyst component for the production of a polyolefin, comprising:
a titanium compound;
a magnesium-based support;
the solid titanium catalyst component having a substantially spherical shape and a median diameter from about 5 to about 150 μm (on a 50% by volume basis); and
the solid titanium catalyst component made by a process comprising contacting a non-reducible magnesium compound, an alkylepoxide, a Lewis base, and an organic solvent to form an intermediate; wherein the organic solvent contains up to 25% toluene and at least one non-aromatic alkane-based solvent, wherein the intermediate forms at least two phases subsequent to the addition of a titanium halide: one phase comprising magnesium compounds and a second organic solvent phase, followed by forming an emulsion of the two phases;
then raising the emulsion to a greater temperature to solidify the magnesium phase to form the solid titanium catalyst component and separating the solidified solid titanium catalyst component having a substantially spherical shape.
2. The solid titanium catalyst component of claim 1 , wherein a polymer surfactant is added when raising the temperature to a greater temperature to solidify the magnesium phase.
3. The solid titanium catalyst component of claim 1 , wherein the solid titanium catalyst component further comprises an internal electron donor.
4. The solid titanium catalyst component of claim 1 , wherein the alkylepoxide is epichlorohydrin and the Lewis base is tributyl phosphate acid ester.
5. The solid titanium catalyst component of claim 1 , wherein the sphericalness, f, of the solid titanium catalyst component is greater than about 0.8.
6. The solid titanium catalyst component of claim 1 , wherein the particle size span of the magnesium-based support is from about 0.25 to about 1.75 when the particle size span is determined by subtracting the D10 size from the D90 size, then dividing by the D50 size.
7. A method of making a solid titanium catalyst component for the production of a polyolefin, comprising:
contacting a non-reducible magnesium compound, an alkylepoxide, a Lewis base, and an organic solvent to form an intermediate; wherein the organic solvent contains up to 25% toluene and at least one non-aromatic alkane-based solvent wherein the intermediate forms at least two phases subsequent to the addition of a titanium halide: one phase comprising at least one magnesium compound and a second organic solvent phase followed by forming an emulsion of the two phases;
then raising the emulsion to a greater temperature to solidify the magnesium phase to form a solid titanium catalyst component and separating the solid titanium catalyst component having a substantially spherical shape.
8. The method of claim 7 , further comprising controlling the size of the solid titanium catalyst component separated from the emulsion by adjusting the temperature of the addition of the titanium halide and adding a surfactant when raising the temperature to a greater temperature to solidify the magnesium phase.
9. The method of claim 7 , further comprising:
agitating the emulsion at an energy; and
controlling the size of the solid titanium catalyst component separated from the emulsion by adjusting the energy of agitation.
10. The method of claim 7 , wherein the sphericalness, f, of the solid titanium catalyst component is greater than about 0.8.
11. The method of claim 7 , wherein the non-aromatic alkane based organic solvent is selected from the group consisting of pentane, hexane, heptane, octane, and cyclohexane.
12. The method of claim 7 , wherein the Lewis base comprises a trialkyl phosphate acid ester.
13. The method of claim 7 , wherein the Lewis base comprises a tributyl phosphate acid ester.
14. The method of claim 7 , wherein the non-reducible magnesium compound is MgCl 2 , the haloalkylepoxide is epichlorohydrin, the Lewis base is tributyl phosphate acid ester, and the non-aromatic alkane based organic solvent is hexane.
15. The method of claim 7 , wherein the surfactant comprises a polymer surfactant.
16. The method of claim 7 , wherein contact between the non-reducible magnesium compound and the haloalkylepoxide forms an intermediate species having a magnesium atom bonded to a haloalkoxide moiety.
17. The method of claim 7 , wherein the temperature of the addition of the titanium halide is from about −10 to about 10° C. and the temperature of addition of surfactant is from about 15 to about 30° C.
18. The method of claim 7 , further comprising heating the phase-separated mixture to a temperature to solidify the magnesium-based catalyst support, wherein the temperature of the addition of the titanium halide is from about −10 to about 10° C., the temperature of addition of surfactant is from about 15 to about 30° C., and the temperature to solidify the magnesium phase to form a solid titanium catalyst component is from about 35 to about 50° C.
19. The method of claim 7 , wherein the particle size span of the solid titanium catalyst component is from about 0.25 to about 1.75 when the particle size span is determined by subtracting the D10 size from the D90 size, then dividing by the D50 size.
20. The method of claim 7 , further comprising combining the solid titanium catalyst component with an internal electron donor.
21. The method of claim 20 , wherein the internal electron donor comprises a phthalate ester.
22. The method of claim 20 , wherein the internal electron donor comprises a Lewis base.
23. A catalyst system for the polymerization of an olefin, comprising:
a solid titanium catalyst component having a substantially spherical shape and a median diameter from about 5 to about 150 μm (on a 50% by volume basis), the solid titanium catalyst component comprising a titanium halide compound and a magnesium-based support, the solid titanium catalyst component made by process comprising contacting a non-reducible magnesium compound, an alkylepoxide, a Lewis base, and an organic solvent to form an intermediate, wherein the organic solvent contains up to 25% toluene and at least one non-aromatic alkane-based solvent wherein the intermediate forms at least two phases subsequent to the addition of a titanium halide: one phase comprising magnesium compounds and a second organic solvent phase, followed by forming an emulsion of the two phases, then raising the emulsion to a greater temperature to solidify the magnesium phase to form the solid titanium catalyst component and separating the solid titanium catalyst component having a substantially spherical shape; and
an organoaluminum compound having at least one aluminum-carbon bond, and
an external electron donor.