Pre-polymerized catalyst components for the polymerization of olefins
View Patent ↗Catalyst components for the preparation of ethylene (co)polymers capable to produce polymers with high bulk density, to avoid the problems of formation of fines and that have a high activity are provided. Said catalyst components are characterized by comprising a non-stereospecific solid catalyst component, comprising a titanium compound and a magnesium dihalide, which is pre-polymerized with an alpha olefin CH 2 ═CHR 1 wherein R is a C1–C8 alkyl group, to such an extent that the amount of the α-olefin pre-polymer is up to 100 g per g of said solid catalyst component.
1. A pre-polymerized catalyst component for the polymerization of ethylene optionally in mixtures with olefins CH 2 ═CHR, wherein R is a C1–C12 alkyl group, comprising a non-stereospecific solid catalyst component, comprising Ti, Mg and a halogen, which is pre-polymerized with an α-olefin CH 2 ═CHR I wherein R 1 is a C1–C8 alkyl group, and the amount of the α-olefin pre-polymer is less than 15 g per g of said solid catalyst component.
2. The pre-polymerized catalyst component according to claim 1 in which the amount of the α-olefin polymer is from 0.8 to 4 g per g of solid catalyst component.
3. The prepolymerized catalyst component according to claim 1 comprising a titanium compound and a magnesium dihalide.
4. The pre-polymerized catalyst component according to claim 1 in which the magnesium dihalide is magnesium dichloride in active form and the titanium compound is selected from the compounds of formula Ti(OR) n−y X y , where R is a C1–C20 hydrocarbon group, X is a halogen, n is the valence of titanium and y is a number between 1 and n.
5. The pre-polymerized catalyst component according to claim 4 in which the titanium compound is chosen from TiCl 4 , TiCl 3 and Ti-tetralcoholates or Ti-chloroalcoholates of formula Ti(OR II ) a Cl n−a where n is the valence of titanium, a is a number comprised between 1 and n, and R II is a C1–C8 alkyl or aryl group.
6. The pre-polymerized catalyst component according to claim 1 in which the solid catalyst component to be pre-polymerized has a surface area, by B.E.T. method, between 20 and 500 m 2 /g, and a total porosity, by B.E.T. method, higher than 0.2 cm 3/ g.
7. The pre-polymerized catalyst component according to claim 1 in which the solid catalyst component to be pre-polymerized has a porosity (Hg method) due to pores with radius up to 10000 Å, of from 0.3 to 1.5 cm 3/ g.
8. The pre-polymerized catalyst component according to claim 1 in which the solid catalyst component is pre-polymerized with an α-olefin selected from propylene, butene-1, hexene, 4-methyl-1-pentene, and octene-1.
9. The pre-polymerized catalyst component according to claim 8 in which the α-olefin is propylene.
10. The pre-polymerized catalyst component according to claim 1 in which the solid catalyst component to be pre-polymerized is obtained by;
(a) reacting a compound MgCl 2 .mROH, wherein 0.3≦m≦1.7 and R is an alkyl, cycloalkyl or aryl radical having 1–12 carbon atoms, with a titanium compound of the formula Ti(OR II ) b X y−b , in which b is comprised between 0 and 0.5, y is the valence of titanium, X is a halogen and R II is a C1–C20 hydrocarbon group;
(b) reacting the product obtained from (a) with an Al-alkyl compound; and
(c) reacting the product obtained from (b) with a titanium compound of the formula Ti(OR II ) n X y−n , in which R II is a C1–C20 hydrocarbon group, X is a halogen, n is the valence of titanium, and y is a number between 1 and n.
11. The pre-polymerized catalyst component according to claim 1 in which the solid catalyst component to be pre-polymerized is obtained by:
(a) thermally dealcoholating adducts MgCl 2 .pEtOH, where p is a number between 2 to 3.5, until forming adducts in which the alcohol content is reduced to values lower than 2 mols per mol of magnesium dihalide;
(b) treating the thermally dealcoholated adduct of step (a) with chemical reagents capable of reacting with the OH groups of the alcohol to dealcoholate the adduct until the alcohol content is reduced to values which are lower than 0.5 mols; and
(c) reacting the chemically dealcoholated adduct of step (b) with a Ti compound of formula Ti(OR II ) n−y X y , where R II is a C1–C20 hydrocarbon group, X is a halogen, n is the valence of titanium and y is a number between 1 and n.
12. The pre-polymerized catalyst component according to claim 1 in which said pre-polymerization is carried out using amounts of an alkyl-Al compound such as to have an Al/Ti molar ratio from 0.001 to 50.
13. The pre-polymerized catalyst component according to claim 12 in which the Al-alkyl compound is a trialkyl aluminum compound.
14. The pre-polymerized catalyst component according to claim 13 in which the trialkyl aluminum compound is chosen from triethylaluminum, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum.
15. A process for the (co)polymerization of ethylene characterized in that it is carried out in the presence of a catalyst comprising (A) a pre-polymerized catalyst component comprising a non-stereospecific solid catalyst component, comprising Ti, Mg and a halogen, which is pre-polymerized with an α-olefin CH 2 ═CHR 1 wherein R I is a C1–C8 alkyl group, and the amount of the α-olefin pre-polymer is less than 15 g per g of said solid catalyst component; and (B) an Al-alkyl compound.
16. The process according to claim 15 in which ethylene is copolymerized with olefins CH 2 ═CHR, wherein R is a C1–C12 alkyl group.
17. The process according to claim 16 in which the olefin is chosen from propylene, butene-1, hexene-1 octene-1 and 4-methyl-1-pentene.
18. The pre-polymerized catalyst component according to claim 11 , wherein in step (a) the alcohol content is reduced to values of from 1.5 to 0.3 mols per mol of magnesium dihalide.
19. The pre-polymerized catalyst component according to claim 12 , wherein the Al/Ti molar ratio is from 0.01 to 10.