Olefin polymerization process employing metallocene catalyst provided by cocatalyst activation of a metallocene procatalyst

• US 6,225,427 B1
• Filed: 10/15/1998
• Issued: 05/01/2001
• Est. Priority Date: 10/15/1998
• Status: Expired due to Term

• Current Assignee: Lion Copolymer Geismar, LLC (East West Copolymer LLC)
• Original Assignee: Uniroyal Chemical Company Inc
• Inventors: Burton, Willie C., Feng, Xu Wu, Gillis, Daniel
• Primary Examiner(s): TESKIN, FRED M
• Application Number:
  US09/173,396
• Time in Patent Office: 929 Days
• Field of Search: 502/152, 502/154, 502/155, 502/123, 502/124, 502/128, 502/129, 502/132, 526/132, 526/133, 526/160, 526/165, 526/127, 526/152, 526/153, 526/156, 526/336, 526/348
• US Class Current: 526/160
• 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 210/06 Propene
• CPC Class Codes: C08F 210/16 Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• CPC Class Codes: C08F 210/18 with non-conjugated dienes, e.g. EPT rubbers
• CPC Class Codes: C08F 2500/03 Narrow molecular weight distribution, i.e. Mw/Mn < 3
• CPC Class Codes: C08F 4/65908 in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
• CPC Class Codes: C08F 4/65912 in combination with an organoaluminium compound
• CPC Class Codes: C08F 4/65916 supported on a carrier, e.g. silica, MgCl2, polymer
• CPC Class Codes: C08F 4/6592 containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
• CPC Class Codes: C08F 4/65922 containing at least two cyclopentadienyl rings, fused or not

Abstract

A polyolefin elastomer possessing a unique combination of properties, i.e., high molecular weight (M_w), high Mooney viscosity (ML₁₊₄ at 125° C.), low polydispersity index (M_w/M_n) and low glass transition temperature (T_g), is obtained by a polymerization process employing a particular type of a metallocene catalyst. The polyolefin elastomer is useful for manufacturing a variety of products including rubber articles such as hoses, belts and moldings, polymer blends containing one or more other hydrocarbon polymers and lubricating oils in which the elastomer functions as a viscosity modifier. Also disclosed is a cocatalyst for activating the metallocene procatalyst employing a specific molar ratio of the components of the cocatalyst to the transition metal of the procatalyst.

Claims

1. A process for the polymerization or copolymerization of at least one α

-olefin and, optionally, at least one diene monomer, to obtain an elastomer, the process comprising polymerizing the at least one α

-olefin in the presence of a catalytically effective amount of catalyst comprising the product obtained by combining a metallocene procatalyst containing a transition metal with a cocatalyst, the cocatalyst comprising at least one organometallic or organometalloid first component containing at least one compound of the general formula

2. The process of claim 1 wherein the metallocene procatalyst is selected from the group consisting of zirconocene dichloride, dimethylbis(indenyl) zirconium, racemic-ethylenebis(indenyl) zirconium dichloride, dimethylsilyl bis(cyclopentadienyl) zirconium dichloride, dimethylsilyl(tetramethylcyclopentadienyl)(tert-butylamido) titanium dichloride, diphenylmethylene (cyclopentadienyl-9-fluorenyl)zirconium dichloride and diphenylsilyl(cyclopentadienyl-9-fluorenyl)zirconium dichloride.

3. The process of claim 1 wherein in the cocatalyst, the first component is selected from the group consisting of alkylaluminum alkoxide, siloxalane, dimeric aluminoxane and oligomeric aluminoxane.

4. The process of claim 3 wherein the alkylaluminum alkoxide is diisobutylaluminum-tert-butoxide.

5. The process of claim 3 wherein the siloxalane is diethylaluminum trimethylsiloxane.

6. The process of claim 3 wherein the dimeric aluminoxane is tetraisobutylaluminoxane.

7. The process of claim 3 wherein the oligomeric aluminoxane is methylaluminoxane.

8. The process of claim 1 wherein in the cocatalyst, the second component is selected from the group consisting of perfluoroarylborane compounds and salts thereof.

9. The process of claim 8 wherein the perfluoroarylborane compound is tris(pentafluorophenyl)-borane.

10. The process of claim 8 wherein the salt of the perfluoroarylborane compound is selected form the group consisting of dimethylanilinium tetrakis (pentafluorophenyl)borate, trityl tetrakis (pentafluorophenyl)borate and lithium tetrakis (pentafluorophenyl)borate.

11. The process of claim 1 wherein in the cocatalyst, the first component is selected from the group consisting of diisobutylaluminum-tert-butoxide, tetraisobutylaluminoxane and methylaluminoxane and the second component is selected from the group consisting of dimethylanilinium tetrakis (pentafluorophenyl)borate, trityl tetrakis (pentafluorophenyl) borate and lithium tetrakis (pentafluorophenyl)borate.

12. The process of claim 1 wherein the molar ratio of the first component of the cocatalyst to the transition metal is from about 10 to about 1,000.

13. The process of claim 1 wherein the molar ratio of the second component of the cocatalyst to the transition metal is from about 0.2 to about 10.

14. The process of claim 1 wherein the metallocene procatalyst is combined with the components of the cocatalyst in any combination or in any order thereof.

15. The process of claim 11 wherein the metallocene procatalyst is combined with the components of the cocatalyst in any combination or in any order thereof.

16. The process of claim 1 wherein the metallocene procatalyst is first combined with at least a portion of the first component of the cocatalyst and thereafter combined with the product comprising the reaction of the second component with the remaining portion of the first component.

17. The process of claim 1 wherein the cocatalyst further comprises a third component.

18. The process of claim 17 wherein the third component is a trialkylaluminum.

19. The process of claim 18 wherein the trialkylaluminum is selected from the group consisting of trimethylaluminum, triethylaluminum, tri(n-propyl)aluminum, triisopropylaluminum, tri(n-butyl)aluminum, triisobutylaluminum tri(n-hexyl)aluminum and tri(n-octyl)aluminum.

20. The process of claim 18 wherein the molar ratio of the third component to the transition metal is from 0 to about 1,000.

21. The process of claim 1 wherein the catalyst further comprises a support material.

22. The process of claim 21 wherein the support material is an inorganic solid porous support.

23. The process of claim 22 wherein the inorganic solid porous support is selected from the group consisting of talc, silica, alumina, silica-alumina and mixtures thereof.

24. The process of claim 1 wherein the α

-olefin contains from 2 to about 20 carbon atoms and the diene, where present, is a conjugated or nonconjugated, acyclic or cyclic, diene.

25. The process of claim 1 wherein the α

-olefin is selected from the group consisting of ethylene and propylene.

26. The process of claim 1 wherein polymerization is carried out under solution polymerization conditions.

27. The process of claim 1 wherein polymerization is carried out under slurry polymerization conditions.

28. The process of claim 1 wherein the elastomer possesses an M_w of from about 70,000 to about 2,000,000, an ML₁₊₄ at 125°

C. of from about 10 to about 200, an M_w/M_n of from about 1.5 to about 10 and a T_g of below about −

40°

C.

29. The process of claim 1 wherein the elastomer possesses an M_w of from about 250,000 to about 1,750,000, an ML₁₊₄ at 125°

C. of from about 15 to about 150, an M_w/M_n of from about 2.0 to about 7.5 and a T_g of about −

40°

C.

30. A process for the improved initiation of polymerization of at least one′

α

-olefin and, optionally, at least one diene monomer, to obtain an elastomer, the process comprising polymerizing the at least one α

-olefin in the presence of a catalytically effective amount of catalyst comprising the product obtained by combining metallocene procatalyst containing a transition metal with a cocatalyst, the cocatalyst comprising at least one organometallic or organometalloid first component containing at least one compound of the general formula

31. The process of claim 30 wherein the metallocene procatalyst is selected from the group consisting of zirconocene dichloride, dimethylbis(indenyl) zirconium, racemic-ethylenebis(indenyl) zirconium dichloride, dimethylsilyl bis(cyclopentadienyl) zirconium dichloride, dimethylsilyl(tetramethylcyclopentadienyl)(tert-butylamido) titanium dichloride, diphenylmethylene (cyclopentadienyl-9-fluorenyl)zirconium dichloride and diphenylsilyl(cyclopentadienyl-9-fluorenyl)zirconium dichloride.

32. The process of claim 30 wherein in the cocatalyst, the first component is selected from the group consisting of alkylaluminum alkoxide, siloxalane, dimeric aluminoxane and oligomeric aluminoxane.

33. The process of claim 30 wherein in the cocatalyst, the second component is selected from the group consisting of perfluoroarylborane compounds and salts thereof.

34. The process of claim 30 wherein in the cocatalyst, the first component is selected from the group consisting of diisobutylaluminum-tert-butoxide, tetraisobutylaluminoxane and methylaluminoxane and the second component is selected from the group consisting of dimethylanilinium tetrakis (pentafluorophenyl)borate, trityl tetrakis (pentafluorophenyl) borate and lithium tetrakis (pentafluorophenyl)borate.

35. The process of claim 30 wherein the metallocene procatalyst is combined with the components of the cocatalyst in any combination or in any order thereof in the absence of olefin.

36. The process of claim 30 wherein the metallocene procatalyst is combined with the components of the cocatalyst in any combination or in any order thereof in the presence of olefin.