Solid component of catalyst for the (co)polymerization of ethylene

• US 5,188,997 A
• Filed: 09/05/1991
• Issued: 02/23/1993
• Est. Priority Date: 09/07/1990
• Status: Expired due to Term

• Current Assignee: ECP ENICHEM POLIMERI S.R.1.
• Original Assignee: ECP Enichem Polimeri S.r.l.
• Inventors: Invernizzi, Renzo, Luciani, Luciano, Borghi, Italo, Pondrelli, Maddalena
• Primary Examiner(s): Garvin, Patrick P.
• Application Number:
  US07/755,063
• Time in Patent Office: 537 Days
• Field of Search: 502/107, 502/111, 502/113, 502/119, 502/120
• US Class Current: 502/107
• CPC Class Codes: C08F 10/02 Ethene
• CPC Class Codes: C08F 4/6365 and magnesium or compounds thereof

Abstract

A solid component of a catalyst for the (co)polymerization of ethylene is composed of a silica carrier and a catalytically active part which includes titanium, magnesium, chlorine and also alkoxy groups, and is obtained: by suspending an activated silica in an ethanolic solution of magnesium chloride; by contact of the suspension with an alkoxy or halogen alkoxyde of titanium and with a silicon halide; by eliminating the ethanol from the resulting suspension in order to recover a solid matter; and by making this solid react with an aluminum alkyl chloride.

Claims

1. A proccess for the preparation of a solid component of a catalyst for the polymerization of ethylene and the copolymerization of ethylene with alfa-olefins, composed of 50-90% by wt. of a carrier of silica particles and 50-10% by wt. of a catalytically active part comprising titanium, magnesium, chlorine and alkoxy groups, comprising the following steps:

(a) a solution of magnesium chloride in ethanol is prepared;

(b) activated silica particles are impregnated with the solution prepared under (a) by suspending the silica particles in the solution;

(c) at least one titanium compound chosen from alkoxides and halogen alkoxides of titanium and a silicon halide are added to the suspension prepared in (b), with an atomic ratio between the magnesium, in the magnesium chloride, and the titanium ranging from 2.0/1 to 12.1/1 and the ratio between the silicon atoms and alkoxy groups in the alkoxide or halogen alkoxide of titanium ranging from 01./1 to 4.0/1;

(d) the ethanol is eliminated from the suspension obtained in (c) by evaporation to recover a solid;

(e) the solid obtained in (d) is reacted with an alkyl aluminum chloride, with an atomic ratio between the chlorine atoms in the alkyl aluminum chloride and the alkoxy groups in the alkoxide or halogen alkoxide of titanium, ranging from 0.5/1 to 7.0/1; and

(f) the solid component of the catalyst is recovered.

2. A process according to claim 1, characterized by the fact that an ethanol solution with a concentration of magnesium chloride ranging from 1 to 15% by weight, is prepared in step (a).

3. A process according to claim 1, characterized by the fact that in step (b) a microspheroidal silica is impregnated, having a particle size ranging from 10 to 100 μ

m, a SiO₂ content of >

90% by weight, a surface area ranging from 250 to 400 m² g, volume of the pores ranging from 1.3 to 1.8 ml/g and average diameter of the pores ranging from 20 to 30 μ

m, this silica being activated by heating in an inert atmosphere, at a temperature ranging from approximately 100°

C. to approximately 650°

C., over a period from 1 to 20 hours, or by putting the silica in contact with an organometallic compound selected from the group consisting of magnesium alkyl and an aluminum alkyl, operating at room temperature or at higher temperatures.

4. A process according to claim 3, characterized by the fact that in step (b) from 10 to 20 parts by weight of silica for every 100 parts by volume of the ethanol solution of magnesium chloride are suspended and contact is maintained at a temperature which is brought from 20°

-25°

C. to approximately 50°

-65°

C., over a period of from 0.5 to 2.0 hours.

5. A process according to claim 1, characterized by the fact that the titanium compounds used in step (c) are selected from the group consisting of alkoxides and chloroalkoxides of titanium containing from 1 to 4 carbon atoms in the alkoxide portion thereof.

6. A process according to claim 5, characterized by the fact that a mixture of titanium tetrachloride and a titanium tetraalkoxide, is used, with a molar ratio between them of approx. 1/3.

7. A process according to claim 1, characterized by the fact that the silicon halide in stage (c) is selected from the group consisting of silicon tetrahalides and halogen silanes.

8. A process according to claim 1, characterized by the fact that step (c) of the procedure is carried out with an atomic ratio between the magnesium and titanium of from 3.5/1 to 8.5/1 and with a ratio between the silicon atoms and alkoxy groups ranging from 0.5/1 to 2.0/1.

9. A process according to claim 1, characterized by the fact that a compound of zirconium or hafnium selected from the group consisting of zirconium and hafnium halides, alkoxides and halogen alkoxides is added in step (c), in such quantities as to provide an atomic ratio between the titanium and zirconium or hafnium of from 0.5/1 to 2.0/1.

10. A process according to claim 1, characterized by the fact that the operating temperature in step (c) ranges from room temperature to about 100°

C., over a period ranging from 0.5 to 3 hours.

11. A process according to claim 1, characterized by the fact that in step (d) of the procedure, the ethanol is eliminated by means of evaporation carried out at either atmospheric pressure or at a reduced pressure and the solid is dried for 0.5 to 2 hours at a temperature of about 120°

C., under a pressure of 5-10 mm Hg.

12. A process according to claim 1, characterized by the fact that in stage (e) of the procedure, the solid is reacted with an alkyl aluminium chloride, with an atomic ratio between the chlorine atoms in the alkyl aluminium chloride and the alkoxy groups of the alkoxide or halogen alkoxide of titanium, ranging from 0.5/1 to 7.0/1, operating in an inert hydrocarbon liquid, at a temperature ranging from 10°

to 100°

C., over a period ranging from 10 minutes to 24 hours.

13. A process according to claim 12, characterized by the fact that the aluminum chloride alkyl is selected from the group consisting of diethyl aluminum chloride, ethyl aluminum sesquichloride, diisobutyl aluminum chloride and isobutyl aluminum dichloride, operating at a temperature ranging from 20°

to 90°

C., for a period of from 10 minutes to 1 hour.

14. Solid component of catalyst obtained according to the process described in claim 1 with 50 to 90% by weight of silica and from 50-10% by weight of a catalytically active part including titanium, magnesium and chorine, and also alkoxy groups, with the following atomic ratios:

Mg/Ti from 2.0/1 to 12.0/1;

Cl/Ti from 10/1 to 40/1, alkoxy groups/Ti from 0/1 to 20/1, and with a titanium content ranging from 0.5 to 5.0% by weight, with respect to the weight of the solid component.

15. Solid component of catalyst, according to claim 14, with from 55 to 80% by weight of silica and from 45 to 20% of a catalytically active part, including titanium, magnesium, chlorine and alkoxy groups, with the following atomic ratios:

Mg/Ti from 3.5/1 to 8.5/1;

Cl/Ti from 12/1 to 36/1, alkoxy groups/Ti from 2/1 to 10/1 and with a titanium content ranging from 0.8 to 2.0% by weight, with respect to the weight of the above solid component.

16. Solid component of catalyst according to claim 14 or 15, with the addition of either zirconium or hafnium, with an atomic ratio between the titanium and zirconium or hafnium ranging from 0.5/1 to 2.0/1.

17. Catalyst for the polymerization of ethylene or for the polymerization of ethylene with alfa-olefins, composed of the solid component of catalyst according to claims 14 or 15 and of an organometallic compound of aluminium chosen from aluminium trialkyls and aluminium alkyl chlorides, containing from 1 to 5, carbon atoms in the alkyl section, with an atomic ratio between the aluminium, in the organometallic compound of aluminium and titanium, in the solid component of catalyst, ranging from 20:

1 to 250;

1.

18. A process according to claim 3, wherein the silica is activated by putting the silica in contact with an organometallic compound selected from the group consisting of magnesium butyl, butyl octyl magnesium and aluminum triethyl, operating at about 60°

C.

19. A process according to claim 5, wherein the alkoxides and chloroalkoxides of titanium are selected from the group consisting of titanium tetra-n-propylate, titanium tetra-n-butylate, titanium tetra-i-propylate, titanium tetra-i-butylate and the corresponding titanium mono- or di-chloroalkoxides.

20. A process according to claim 7, wherein the silicon halide is selected from the group consisting of silicon tetrachloride, trichlorosilane, vinyl trichlorosilane, and chloroethyl trichlorosilane.

21. A process according to claim 9, wherein the compound of zirconium or hafnium is selected from the group consisting of zirconium and hafnium tetrachlorides and chloralkoxides.

22. A process according to claim 10, wherein step (c) is carried out at about 60°

C. for a period of about 1 hour.

23. A catalyst according to claim 17, wherein said organometalic compound of aluminum chosen from aluminum trialkyls and aluminum alkyl chlorides contains 2-4 carbon atoms in the alkyl section, with an atomic ratio between the aluminum, in the organometallic compound of aluminum and titanium, in the solid component of catalyst, ranging from 100:

1-200;

1.