Bimetal catalyst for the (co) polymerization of α-olefins

• US 6,723,809 B1
• Filed: 01/18/2002
• Issued: 04/20/2004
• Est. Priority Date: 03/25/1999
• Status: Expired due to Term

• Current Assignee: Polimeri Europa SPA (Eni Petroleum Company Incorporated)
• Original Assignee: Polimeri Europa SPA (Eni Petroleum Company Incorporated)
• Inventors: Menconi, Francesco, Conti, Giuseppe, Zanellato, Alberto, Moalli, Angelo
• Primary Examiner(s): CHOI, LING SIU
• Application Number:
  US09/926,214
• Time in Patent Office: 823 Days
• Field of Search: 526/348, 526/142, 526/123.1, 526/124.3, 502/103, 502/113, 502/115, 502/120
• US Class Current: 526/124.3
• CPC Class Codes: C08F 10/00 Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 210/14 Monomers containing five or more carbon atoms
• CPC Class Codes: C08F 210/16 Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• CPC Class Codes: C08F 2500/12 Melt flow index or melt flow ratio
• CPC Class Codes: C08F 4/651 Pretreating with non-metals or metal-free compounds
• CPC Class Codes: C08F 4/6557 and metals of C08F4/64 or compounds thereof

Abstract

Bimetal catalyst for the (co)polymerization of α-olefins comprising a co-catalyst consisting of a hydride or an organometallic compound of an element of groups 1, 2 or 13 of the periodic table, and a solid component consisting of at least 95% by weight of titanium, magnesium, hafnium, aluminum, chlorine and R—COO carboxylate groups, wherein R is an aliphatic, cycloaliphatic or aromatic hydrocarbon, containing from 1 to 30 carbon atoms, wherein at least 80% of the titanium is in oxidation state +3, and at least 1% of said titanium in oxidation state +3 has a tetrahedral coordination geometry. Said catalyst allows the production of olefinic polymers, particular polyethylene, with a high molecular weight by means of solution polymerization processes at temperatures exceeding 200° C.

Claims

1. A solid component of catalyst for the (co)polymerization of α

-olefins, comprising at least 95% by weight, based on the total weight of the solid component of catalyst, of titanium, magnesium, aluminum, chlorine, carboxylate (R—

COO⁻

) and at least one metal selected from the group consisting of hafnium and zirconium, in the following molar ratios;

2. The solid component according to claim 1, characterized by the following molar ratios:

3. The solid component of catalyst according to claim 1, wherein M is hafnium.

4. The solid component of catalyst according to claim 1, wherein at least 90% of the titanium is in oxidation state +3, and from 2 to 10% of said titanium has a tetrahedral coordination geometry.

5. The solid component of catalyst according to claim 1, wherein the number of carbon atoms of the radical R of said carboxylate ranges from 6 to 15.

6. The solid component of catalyst according to claim 1, wherein the titanium content does not exceed 10% by weight.

20. The solid component of catalyst according to claim 1, comprising from 98 to 100%, by weight, based on the total weight of the solid component of catalyst, of titanium, magnesium, aluminum, chlorine, carboxylate (R—

COO⁻

) and at least one metal selected from the group consisting of hafnium and zirconium.

21. A catalyst for the (co)polymerization of α

-olefins, comprising a co-catalyst consisting of a hydride or an organometallic compound of a metal of groups 1, 2 or 13 of the periodic table, and a solid component, in contact with each other, wherein said solid component comprises the solid component of catalyst according to claim 1.

22. The catalyst according to the claim 21, wherein said co-catalyst is selected from aluminum trialkyls which contain from 1 to 10 carbon atoms in the alkyl portion.

23. The catalyst according to claim 22, wherein the atomic ratio between the aluminum in the co-catalyst and the titanium in the solid component of catalyst ranges from 2:

1 to 500;

1.

24. A process for the (co)polymerization of α

-olefins, comprising polymerizing at least one α

-olefin, either continuously or batchwise, in one or more steps, at low (0.1-1.0 MPa), medium (1.0-10 MPa) or high (10-150 MPa) pressure, at temperatures ranging from 20 to 300°

C., optionally in the presence of an inert diluent, in the presence of a catalyst, wherein the latter is a catalyst according to claim 21.

25. The (co)polymerization process according to claim 24, wherein at least one α

-olefin is ethylene.

26. The (co)polymerization process according to claim 24, wherein ethylene is polymerized to give linear polyethylene, or copolymerized with α

-olefins having from 3 to 10 carbon atoms.

27. The (co)polymerization process according to claim 24, wherein said polymerization process is carried out in a solution of an inert solvent, at temperatures ranging from 130 to 300°

C. and at pressures ranging from 1 to 25 MPa.

28. The (co)polymerization process according to claim 24, wherein said inert solvent is selected from aliphatic or cycloaliphatic hydrocarbons having from 6 to 10 carbon atoms.

29. The (co)polymerization process according to claim 24, wherein the polymerization temperature ranges from 150 to 230°

C.

32. The catalyst according to claim 21, wherein said co-catalyst is selected from aluminum trialkyls which contain from 2 to 6 carbon atoms in the alkyl portion.

33. The catalyst according to claim 22, wherein the atomic ratio between the aluminum in the co-catalyst and the titanium in the solid component of catalyst ranges from 5:

1 to 200;

1.

34. The catalyst according to claim 32, wherein the atomic ratio between the aluminum in the co-catalyst and the titanium in the solid component of catalyst ranges from 2:

1 to 500;

1.

35. The catalyst according to claim 32, wherein the atomic ratio between the aluminum in the co-catalyst and the titanium in the solid component of catalyst ranges from 5:

1 to 200;

1.

7. A process for the preparation of a solid component of catalyst for the (co)polymerization of α

-olefins, comprising at least 95% by weight, based on the total weight of the solid component of catalyst, of titanium, magnesium, aluminum, chlorine, carboxylate (R—

COO⁻

) and at least one metal selected from the group consisting of hafnium and zirconium, in the following molar ratios;

8. The process according to claim 7, wherein said metal M is hafnium and said R group of the R—

COOH carboxylic acid comprises from 6 to 15 carbon atoms.

9. The process according to claim 7, wherein said inert organic liquid used for preparing the mixture of step (i) is selected from aliphatic, cycloaliphatic and aromatic hydrocarbons.

10. The process according to claim 7, wherein at least two compounds selected from those of magnesium, hafnium and zirconium in step (i) are insoluble in said inert organic liquid and form a suspension therein.

11. The process according to claim 7, wherein at least 50% by weight of the compounds of step (i) is insoluble in the preselected inert organic liquid.

12. The process according to claim 7, wherein said compounds in step (i) are mixed with the inert organic liquid with an overall concentration of the soluble and insoluble metals ranging from 0.05 to 2.0 moles/1.

13. The process according to claim 7, wherein the magnesium and the at least one metal selected from hafnium and zirconium, are introduced into the mixture of step (i) as chlorides in the form of granular solids or in powder form.

14. The process according to claim 7, wherein the dissolution temperature in step (ii) ranges from 70 to 120°

C.

15. The process according to claim 7, wherein said step (ii) is carried out so that there are no significant exchanges of matter with the outside.

16. The process according to claim 7, wherein, in step (iii), “

n”

of said alkyl aluminum chloride having formula (II), is a decimal number ranging from 0.9 to 2.1.

17. The process according to claim 7, wherein the quantity of said alkyl aluminum chloride used in said step (iii) ranges from 1.1 to 2.0 times the minimum quantity predetermined by means of the equation:

18. The process according to claim 7, wherein, in step (iii), the alkyl aluminum chloride is added to the solution of step (ii) operating at values ranging from room temperature (20-25°

C.) to a temperature of about 60°

C., and the mixture obtained is heated and maintained at a temperature ranging from 50 to 100°

C., for a time ranging from 45 to 180 minutes.

19. A solid component of catalyst for the (co)polymerization of α

-olefins, comprising at least 95% by weight, based on the total weight of the solid component of catalyst, of titanium, magnesium, aluminum, chlorine, carboxylate (R—

COO⁻

) and at least one metal selected from the group consisting of hafnium and zirconium, in the following molar ratios;

30. The solid component of catalyst according to claim 19, comprising from 98 to 100%, by weight, based on the total weight of the solid component of catalyst, of titanium, magnesium, aluminum, chlorine, carboxylate (R—

COO⁻

) and at least one metal selected from the group consisting of hafnium and zirconium.

31. A catalyst for the (co)polymerization of α

-olefins, comprising a co-catalyst consisting of a hydride or an organometallic compound of a metal of groups 1, 2 or 13 of the periodic table, and a solid component, in contact with each other, wherein said solid component comprises the solid component of catalyst according to claim 19.

36. The catalyst according to claim 31, wherein said co-catalyst is selected from aluminum trialkyls which contain from 1 to 10 carbon atoms in the alkyl portion.

37. The catalyst according to claim 31, wherein said co-catalyst is selected from aluminum trialkyls which contain from 2 to 6 carbon atoms in the alkyl portion.

38. The catalyst according to claim 36, wherein the atomic ratio between the aluminum in the co-catalyst and the titanium in the solid component of catalyst ranges from 2:

1 to 500;

1.

39. The catalyst according to claim 36, wherein the atomic ratio between the aluminum in the co-catalyst and the titanium in the solid component of catalyst ranges from 5:

1 to 200;

1.

40. The catalyst according to claim 37, wherein the atomic ratio between the aluminum in the co-catalyst and the titanium in the solid component of catalyst ranges from 2:

1 to 500;

1.

41. The catalyst according to claim 37, wherein the atomic ratio between the aluminum in the co-catalyst and the titanium in the solid component of catalyst ranges from 5:

1 to 200;

1.

42. A process for the (co)polymerization of α

-olefins, comprising polymerizing at least one α

-olefin, either continuously or batchwise, in one or more steps, at low (0.1-1.0 MPa), medium (1.0-10 MPa) or high (10-150 MPa) pressure, at temperatures ranging from 20 to 300°

C., optionally in the presence of an inert diluent, in the presence of a catalyst according to claim 31.

43. The (co)polymerization process according to claim 42, wherein at least one α

-olefin is ethylene.

44. The (co)polymerization process according to claim 42, wherein ethylene is polymerized to give linear polyethylene, or copolymerized with α

-olefins having from 3 to 10 carbon atoms.

45. The (co)polymerization process according to claim 42, wherein said polymerization process is carried out in a solution of an inert solvent, at temperatures ranging from 130 to 300°

C. and at pressures ranging from 1 to 25 MPa.

46. The (co)polymerization process according to claim 42, wherein said inert solvent is selected from aliphatic or cycloaliphatic hydrocarbons having from 6 to 10 carbon atoms.

47. The (co)polymerization process according to claim 42, wherein the polymerization temperature ranges from 150 to 230°

C.

48. The process according to claim 7 wherein the quantity of alkyl aluminum chloride is at least sufficient to make from 80 to 100% of the titanium present in the solution of said step (ii) precipitate into the form of a solid compound.

49. The process according to claim 7 wherein said solid component of catalyst for the (co)polymerization of α

-olefins, comprises 98 to 100% by weight, based on the total weight of the solid component of catalyst of titanium, magnesium, aluminum, chlorine, carboxylate (R—

COO⁻

) and at least one metal selected from the group consisting of hafnium and zirconium.