Process for producing polyolefin elastomer employing a metallocene catalyst

• US 6,225,426 B1
• Filed: 04/10/1996
• Issued: 05/01/2001
• Est. Priority Date: 04/10/1996
• Status: Expired due to Term

• Current Assignee: Lion Copolymer Geismar, LLC (East West Copolymer LLC)
• Original Assignee: Uniroyal Chemical Company Inc (Lanxess AG)
• Inventors: Gillis, Daniel J., Karpeles, Richard
• Primary Examiner(s): Wu, David W.
• Assistant Examiner(s): CHOI, LING SIU
• Application Number:
  US08/630,650
• Time in Patent Office: 1,847 Days
• Field of Search: 526/160, 526/132, 526/133, 526/943, 526/352, 526/348, 526/159, 526/131, 502/152
• 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 2/06 Organic solvent
• CPC Class Codes: C08F 210/06 Propene
• 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 210/18 with non-conjugated dienes, e.g. EPT rubbers
• CPC Class Codes: C08F 236/00 Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds C08F232/00 takes precedence
• CPC Class Codes: C08F 2500/01 High molecular weight, e.g. >800,000 Da.
• CPC Class Codes: C08F 2500/03 Narrow molecular weight distribution, i.e. Mw/Mn < 3
• CPC Class Codes: C08F 2500/17 Viscosity
• CPC Class Codes: C08F 2500/21 Rubbery or elastomeric properties
• CPC Class Codes: C08F 2500/25 Cycloolefine
• 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 4/6592 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
• CPC Class Codes: C08F 4/65927 two cyclopentadienyl rings being mutually bridged
• CPC Class Codes: F16G 5/04 made of rubber F16G5/02 takes precedence consisting of several parts F16G5/16
• CPC Class Codes: Y10S 526/904 Monomer polymerized in presence of transition metal containing catalyst at least part of which is supported on a polymer, e.g. prepolymerized catalysts
• CPC Class Codes: Y10S 526/943 Polymerization with metallocene catalysts

Abstract

A liquid phase polymerization process is provided for producing a polyolefin elastomer, e.g., one derived from ethylene, another α-olefin such as propylene and optionally, a diene, employing a metallocene catalyst. The process comprises contacting monomer under liquid phase polymerization conditions with a catalyst composition obtained by combining (a) a metallocene procatalyst, preferably one containing a bridging group possessing at least two bulky groups, and (b) a cocatalyst such as aluminoxane, preferably a cation-generating cocatalyst, in partial or total replacement of aluminoxane.

Claims

1. A process for the liquid phase polymerization of ethylene, at least one other α

-olefin and, optionally, at least one diene monomer to provide an elastomer, the process comprising polymerizing the monomer under liquid phase elastomer-forming polymerization conditions in the presence of a catalytically effective amount of catalyst comprising the product obtained by combining a metallocene procatalyst with a cocatalyst, the metallocene procatalyst being at least one compound of general formulae (I) and/or (II);

2. The process of claim 1 wherein in metallocene procatalyst (I), bridging group R³ possesses the structure

in which groups R⁴ and R⁵ each, independently, is, or contains, a cyclic group of from 6 to about 20 carbon atoms, from 0 to 3 heteroatoms and hydrogen as the remaining atoms.

3. The process of claim 2 wherein in metallocene procatalyst (I), the cyclic group is a cycloalkyl, heterocycloalkyl, cycloalkenyl, heterocycloalkenyl, aryl, heteroaryl, alkaryl, allylheteroaryl, aralkyl or heteroaralkyl group.

4. The process of claim 3 wherein in metallocene procatalyst (I), ligand (Cp¹R_m¹) is unsubstituted cyclopentadienyl, ligand (Cp²R_p²) is substituted or unsubstituted indenyl or fluorenyl, M¹ is zirconium, R⁴ and R⁵ each is phenyl and each ligand X is chlorine.

5. The process of claim 1 wherein in metallocene procatalyst (II), n and r are both 1, the valence of M is 4, ligand X is halogen and s is 2.

6. The process of claim 1 wherein in the different cation-generating cocatalyst, the first component is an aluminum compound, the second component is a borane compound and the third component is a metal borate compound.

7. The process of claim 6 wherein the aluminum compound is a trialkylaluminum or dialkylaluminum hydride, the borane compound is a tris(haloaryl)borane and the metal borate compound is an alkali metal-, alkaline earth metal-, or transition metal-tetrakis(haloaryl)borate.

8. The process of claim 7 wherein the aluminum compound is a trialkylaluminum, the borane compound is a tris(halophenyl)borane and the metal borate compound is an alkali metal tetrakis(halophenyl)borate.

9. The process of claim 6 wherein the aluminum compound is at least one of trimethylaluminum, triethylaluminum, tri(n-propyl)aluminum, triisopropylaluminum, tri(n-butyl)aluminum, tri(n-propyl)aluminum, triisobutylaluminum, tri(n-hexyl)aluminum, tri(n-octyl) aluminum, dimethyaluminum hydride, diethylaluminum hydride, diisopropylaluminum hydride, di(n-propyl)aluminum hydride, diisobutylaluminum hydride, di(n-butyl)aluminum hydride, dimethylaluminum ethoxide, di(n-propyl)aluminum ethoxide, diisobutylaluminum ethoxide or di(n-butyl)aluminum ethoxide, the borane compound is at least one of tris(pentafluorophenyl)borane, tris(methoxyphenyl)borane, tris(trifluoromethylphenyl)borane, tris(3,5-di[trifluoromethyl]phenyl) borane, tris(tetrafluoroxylyl)borane or tris(tetrafluoro-o-tolyl)borane and the metal borate compound is at least one of lithium tetrakis(trifluoromethylphenyl)borate, lithium tetrakis(pentafluorophenyl)borate, lithium tetrakis(3,5-di[trifluoromethyl]phenyl)borate, sodium tetrakis (pentafluorophenyl)borate, potassium tetrakis(pentafluoro-phenyl)borate, magnesium tetrakis(pentafluorophenyl)borate, titanium tetrakis(pentafluorophenyl)borate or tin tetrakis (pentafluorophenyl)borate.

10. The process of claim 1 wherein the metallocene procatalyst is combined with the components of the different cation-generating cocatalyst in the presence of monomer.

11. The process of claim 2 wherein the metallocene procatalyst is combined with the components of the different cation-generating cocatalyst in the presence of monomer.

12. The process of claim 3 wherein the metallocene procatalyst is combined with the components of the different cation-generating cocatalyst in the presence of monomer.

13. The process of claim 4 wherein the metallocene procatalyst is combined with the components of the different cation-generating cocatalyst in the presence of monomer.

14. The process of claim 5 wherein the metallocene procatalyst is combined with the components of the different cation-generating cocatalyst in the presence of monomer.

15. The process of claim 6 wherein the metallocene procatalyst is combined with the components of the different cation-generating cocatalyst in the presence of monomer.

16. The process of claim 7 wherein the metallocene procatalyst is combined with the components of the different cation-generating cocatalyst in the presence of monomer.

17. The process of claim 8 wherein the metallocene procatalyst is combined with the components of the different cation-generating cocatalyst in the presence of monomer.

18. The process of claim 9 wherein the metallocene procatalyst is combined with the components of the different cation-generating cocatalyst in the presence of monomer.

19. The process of claim 1 wherein the α

-olefin contains from 3 to about 20 carbon atoms.

20. The process of claim 19 wherein the α

-olefin is propylene.

21. The process of claim 20 wherein one diene is a nonbranching diene and another diene is a branching diene.

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

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

24. The process of claim 5 wherein in metallocene procatalyst (II), bridging group R³ possesses the structure

in which groups R⁴ and R⁵ each, independently, is, alkyl from 1 to about 5 carbon atoms or a cyclic group of from about 6 to about 20 carbon atoms.

25. The process of claim 24 wherein in metallocene catalyst (II), ligand (Cp¹R¹_m) is substituted cyclopentadienyl, M is selected from the group consisting of titanium and zirconium, Y is t-butylamide, R⁴ and R⁵ each is methyl and each ligand X is chlorine.

26. A process for the polymerization of olefin to provide a polyolefin, the process comprising polymerizing at least one olefin in the presence of a catalytically effective amount of catalyst comprising the product obtained by combining a metallocene procatalyst with a cocatalyst, the metallocene procatalyst being at least one compound of general formulae (I) and/or (II):

27. The process of claim 26 wherein in the cocatalyst, the first component is an aluminum compound, the second component is a borane compound and the third component is a metal borate compound.

28. The process of claim 27 wherein the aluminum compound is a trialkylaluminum or dialkylaluminum hydride, the borane compound is a tris(haloaryl)borane and the metal borate compound is an alkali metal-, alkaline earth metal-, or transition metal-tetrakis(haloaryl)borate.

29. The process of claim 28 wherein the aluminum compound is a trialkylaluminum, the borane compound is a tris(halophenyl)borane and the metal borate compound is an alkali metal tetrakis(halophenyl)borate.

30. The process of claim 27 wherein the aluminum compound is at least one of trimethylaluminum, triethylaluminum, tri(n-propyl)aluminum, triisopropylaluminum, tri(n-butyl)aluminum, tri(n-propyl)aluminum, triisobutylaluminum, tri(n-hexyl)aluminum, tri(n-octyl)aluminum, dimethyaluminum hydride, diethylaluminum hydride, diisopropylaluminum hydride, di(n-propyl)aluminum hydride, diisobutylaluminum hydride, di(n-butyl)aluminum hydride, dimethylaluminum ethoxide, di(n-propyl)aluminum ethoxide, diisobutylaluminum ethoxide or di(n-butyl)aluminum ethoxide, the borane compound is at least one of tris(pentafluorophenyl)borane, tris(methoxyphenyl)borane, tris(trifluoromethylphenyl)borane, tris(3,5-di[trifluoromethyl]phenyl)borane, tris(tetrafluoroxylyl)borane or tris(tetrafluoro-o-tolyl)borane and the metal borate compound is at least one of lithium tetrakis(pentafluorophenyl)borate, lithium tetrakis(trifluoromethylphenyl)borate, lithium tetrakis (3,5-di[trifluoromethyl]phenyl)borate, sodium tetrakis (pentafluorophenyl)borate, potassium tetrakis(pentafluorophenyl)borate, magnesium tetrakis(pentafluorophenyl)borate, titanium tetrakis(pentafluorophenyl)borate or tin tetrakis (pentafluorophenyl)borate.

31. The process of claim 26 wherein the metallocene procatalyst is combined with the components of the cocatalyst in the presence of olefin.

32. The process of claim 26 wherein the olefin is ethylene, propylene or a mixture of ethylene and propylene.

33. The process of claim 26 wherein in metallocene procatalyst (I), bridging group R³ possesses the structure

in which groups R⁴ and R⁵ each, independently, is, or contains, a cyclic group of from 6 to about 20 carbon atoms, from 0 to 3 heteroatoms and hydrogen as the remaining atoms.

34. The process of claim 33 wherein in metallocene procatalyst (I), the cyclic group is a cycloalkyl, heterocycloalkyl, cycloalkenyl, heterocycloalkenyl, aryl, heteroaryl, alkaryl, alkylheteroaryl, aralkyl or heteroaralkyl group.

35. The process of claim 34 wherein in metallocene procatalyst (I), ligand (Cp¹R_m¹) is unsubstituted cyclopentadienyl, ligand (Cp²R_p²) is substituted or unsubstituted indenyl or fluorenyl, M¹ is zirconium, R⁴ and R⁵ each is phenyl and each ligand X is chlorine.

36. In a process for polymerizing at least one olefin to provide a polyolefin employing, as polymerization catalyst, the product obtained by combining a metallocene procatalyst possessing at least one non-cyclopentadienyl ligand X coordinated to its transition metal with an aluminoxane cocatalyst, wherein the improvement comprises employing a different cation-generating cocatalyst in place of part or all of said aluminoxane cocatalyst, said different cation-generating cocatalyst comprising:

a metal- and/or metalloid-containing first component capable of exchanging one or more ligands X up to the full number thereof with, independently, a hydrogen atom, a carbohydryl group containing up to about 20 carbon atoms or an oxyhydrocarbyl group containing up to 20 carbon atoms;

a neutral metal- and/or metalloid-containing second component having at least one aryl group possessing at least one electron-withdrawing substituent; and

, an anionic metal-containing third component having at least one aryl group possessing at least one electron-withdrawing substituent alone or in combination with an anionic metalloid-containing third component having at least one aryl group possessing at least one electron-withdrawing substituent.

37. The process of claim 36 wherein in the different cation-generating cocatalyst, the first component is an aluminum compound, the second component is a borane compound and the third component is a metal borate compound.

38. The process of claim 37 wherein the aluminum compound is a trialkylaluminum or dialkylaluminum hydride, the borane compound is a tris(haloaryl)borane and the metal borate compound is an alkali metal-, alkaline earth metal-, or transition metal-tetrakis(haloaryl)borate.

39. The process of claim 38 wherein the aluminum compound is a trialkylaluminum, the borane compound is a tris(halophenyl)borane and the metal borate compound is an alkali metal tetrakis(halophenyl)borate.

40. The process of claim 37 wherein the aluminum compound is at least one of trimethylaluminum, triethylaluminum, tri(n-propyl)aluminum, triisopropylaluminum, tri(n-butyl)aluminum, tri(n-propyl)aluminum, triisobutylaluminum, tri(n-hexyl)aluminum, tri(n-octyl)aluminum, dimethyaluminum hydride, diethylaluminum hydride, diisopropylaluminum hydride, di(n-propyl)aluminum hydride, diisobutylaluminum hydride, di(n-butyl)aluminum hydride, dimethylaluminum ethoxide, di(n-propyl)aluminum ethoxide, diisobutylaluminum ethoxide or di(n-butyl)aluminum ethoxide, the borane compound is at least one of tris(pentafluorophenyl)borane, tris(methoxyphenyl)borane, tris(trifluoromethylphenyl)borane, tris(3,5-di[trifluoromethyl]phenyl) borane, tris(tetrafluoroxylyl)borane or tris(tetrafluoro-o-tolyl)borane and the metal borate compound is at least one of lithium tetrakis(pentafluorophenyl)borate, lithium tetrakis(trifluoromethylphenyl)borate, lithium tetrakis (3,5-di[trifluoromethyl]phenyl)borate, sodium tetrakis (pentafluorophenyl)borate, potassium tetrakis(pentafluorophenyl)borate, magnesium tetrakis(pentafluorophenyl)borate, titanium tetrakis(pentafluorophenyl)borate or tin tetrakis (pentafluorophenyl)borate.

41. The process of claim 36 wherein the metallocene procatalyst is combined with the components of the different cation-generating cocatalyst in the presence of olefin.

42. The process of claim 36 wherein the olefin is ethylene, propylene or a mixture of ethylene and propylene.