Metallocene catalyst composition and process for activating a metallocene procatalyst

• US 6,147,025 A
• Filed: 12/15/1997
• Issued: 11/14/2000
• 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
• Inventors: Gillis, Daniel J., Karpeles, Richard
• Primary Examiner(s): Wood, Elizabeth D.
• Application Number:
  US08/990,922
• Time in Patent Office: 1,065 Days
• Field of Search: 502/118, 502/128, 502/129, 502/131, 502/134
• US Class Current: 502/128
• 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 metallocene catalyst is provided which comprises the product obtained by combining (a) a metallocene procatalyst, preferably one containing a bridging group possessing at least two bulky groups, and (b) a cation-generating cocatalyst. A process for activating a metallocene procatalyst is also provided which comprises combining the metallocene procatalyst with the components of a cation-generating cocatalyst.

Claims

1. A catalyst comprising the product obtained by combining a metallocene procatalyst with a cation-generating cocatalyst, the metallocene procatalyst being one or more compounds of general formulae (I) and/or (II):

space="preserve" listing-type="equation">(Cp.sup.1 R.sub.m.sup.1)R.sub.n.sup.3 (Cp.sup.2 R.sub.p.sup.2)MX.sub.q (I)

space="preserve" listing-type="equation">(Cp.sup.1 R.sub.m.sup.1)R.sub.n.sup.3 E.sub.n MX.sub.s (II)

wherein Cp¹ of ligand (Cp¹ R_m¹) and Cp² of ligand (Cp² R_p²) are the same or different cyclopentadienyl rings, R¹ and R² each is, independently, halogen or a hydrocarbyl, halocarbyl, hydrocarbyl-substituted organometalloid or halocarbyl-substituted organometalloid group containing up to about 20 carbon atoms, m is an integer from 0 to 5, p is an integer from 0 to 5 and two R¹ and/or R² substituents on adjacent carbon atoms of the cyclopentadienyl ring associated therewith can be joined together to form a ring containing from 4 to about 20 carbon atoms, R³ is a bridging group bridging Cp¹ and Cp², n is 0 or 1, E is a heteroatom-containing ligand in which the heteroatom is coordinated to M, M is a transition metal having a valence of from 3 to 6, each X is a non-cyclopentadienyl ligand and is, independently, halogen or a hydrocarbyl, oxyhydrocarbyl, halocarbyl, hydrocarbyl-substituted organometalloid, oxyhydrocarbyl-substituted organometalloid or halocarbyl-substituted organometalloid group containing up to about 20 carbon atoms, q is equal to the valence of M minus 2, and s is equal to the valence of M minus 1 when n is 0 and is equal to the valence of M minus 2 when n is 1, the cation-generating cocatalyst comprising;

a metal- and/or metalloid-containing first component capable of exchanging at least one X ligand in the metallocene procatalyst up to the total number thereof with, independently, a hydrogen atom or a carbohydryl group containing up to about 20 carbon atoms or oxycarbohydryl 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 ionic metal-containing third component having at least one aryl group possessing at least one electron-withdrawing substituent, alone or in combination with a metalloid-containing third component having at least one aryl group possessing at least one electron-withdrawing substituent.

2. The catalyst of claim 1 where in metallocene procatalyst (I), bridging group R³ possesses the structure ##STR8## in which bulky groups R⁴ and R⁵ each, independently, is, or contains, a cyclohydrocarbyl group containing up to about 20 carbon atoms and from 0 to 3 heteroatoms.

3. The catalyst of claim 2 wherein the cyclohydrocarbyl group is a cycloalkyl, heterocycloalkyl, cycloalkenyl, heterocycloalkenyl, aryl, heteroaryl, alkaryl, alkylheteroaryl, aralkyl or heteroaralkyl group.

4. The catalyst of claim 3 wherein ligand (Cp¹ R_m¹) is unsubstituted cyclopentadienyl, ligand (Cp² R_p ²) is indenyl or fluorenyl, M is zirconium, R⁴ and R⁵ is each phenyl and each X is chlorine.

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

6. The catalyst of claim 1 wherein in the cation-generating cocatalyst, the first component is at least one aluminum compound, the second component is at least one borane compound and the third component is at least one metal borate compound.

7. The catalyst 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-, transition metal- or metal tetrakis,(haloaryl)borate.

8. The catalyst 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 catalyst of claim 6 wherein the aluminum compound is selected from the group consisting 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 and di(n-butyl)aluminum ethoxide, the borane compound is selected from the group consisting of tris(pentafluoro-phenyl)borane, tris(methoxyphenyl)borane, tris(trifluoromethylphenyl)borane, tris(3,5-di[trifluoromethyl]phenyl) borane, tris(tetrafluoroxylyl)borane and tris(tetrafluoro-o-tolyl)borane and the metal borate compound is selected from the group consisting 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 and tin tetrakis (pentafluorophenyl)borate.

10. The catalyst of claim 1 wherein the metallocene procatalyst is combined with the components of the cation-generating cocatalyst in any order thereof in the presence of an alpha-olefin.

11. In a catalyst comprising the product obtained by combining a metallocene procatalyst possessing at least one non-cyclopentadienyl ligand X coordinated to a transition metal having a valence of from 3 to 6 with an aluminoxane cocatalyst, the improvement comprising substituting part or all of the aluminoxane cocatalyst with a cation-generating cocatalyst comprising:

a metal- and/or metalloid-containing first component capable of exchanging one or more ligands X up to the fill 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 ionic metal-containing third component having at least one aryl group possessing at least one electron-withdrawing substituent, alone or in combination with a metalloid-containing third component having at least one aryl group possessing at least one electron-withdrawing substituent.

12. The catalyst of claim 11 wherein in the cation-generating cocatalyst, the first component is at least one aluminum compound, the second component is at least one borane compound and the third component is at least one metal borate compound.

13. The catalyst of claim 12 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-, transition metal- or metal tetrakis (haloaryl) borate.

14. The catalyst of claim 13 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.

15. The catalyst of claim 12 wherein the aluminum compound is selected from the group consisting of trimethylaluminum, triethylaluminum, tri(n-propyl)aluminium, 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 and di(n-butyl)aluminum ethoxide, the borane compound is selected from the group consisting of tris(pentafluoro-phenyl)borane, tris(methoxyphenyl)borane, tris(trifluoromethylphenyl)borane, tris(3,5-di[trifluoromethyl]phenyl) borane, tris(tetrafluoroxylyl)borane and tris(tetrafluoro-o-tolyl)borane and the metal borate compound is selected from the group consisting 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 and tin tetrakis (pentafluorophenyl)borate.

16. The catalyst of claim 11 wherein the metallocene procatalyst is combined with the components of the cation-generating cocatalyst in any order thereof in the presence of an alpha-olefin.

17. A process for the activation of a metallocene procatalyst with a cation-generating cocatalyst, the metallocene procatalyst being at least one compound of general formulae (I) and/or (II):

space="preserve" listing-type="equation">(Cp.sup.1 R.sub.m.sup.1)R.sub.n.sup.3 (Cp.sup.2 R.sub.p.sup.2)MX.sub.q (I)

space="preserve" listing-type="equation">(Cp.sup.1 R.sub.m.sup.1)R.sub.n.sup.3 E.sub.n MX.sub.s (II)

wherein Cp¹ of ligand (Cp¹ R_m¹) and Cp² of ligand (Cp² R_p²) are the same or different cyclopentadienyl rings, R¹ and R² each is, independently, halogen or a hydrocarbyl, halocarbyl, hydrocarbyl-substituted organometalloid or halocarbyl-substituted organometalloid group containing up to about 20 carbon atoms, m is an integer from 0 to 5, p is an integer from 0 to 5 and two R¹ and/or R² substituents on adjacent carbon atoms of the cyclopentadienyl ring associated therewith can be joined together to form a ring containing from 4 to about 20 carbon atoms, R³ is a bridging group bridging Cp¹ and Cp², n is 0 or 1, E is a heteroatom-containing group in which the heteroatom is coordinated to M, M is a transition metal having a valence of from 3 to 6, each X is a non-cyclopentadienyl ligand and is, independently, halogen or a hydrocarbyl, oxyhydrocarbyl, halocarbyl, hydrocarbyl-substituted organometalloid, oxyhydrocarbyl-substituted organometalloid or halocarbyl-substituted organometalloid group containing up to about 20 carbon atoms, q is equal to the valence of M minus 2, and s is equal to the valence of M minus 1 when n is 0 and is equal to the valence of M minus 2 when n is 1, the cation-generating cocatalyst comprising;

a metal- and/or metalloid-containing first component capable of exchanging at least one X ligand in the metallocene procatalyst up to the total number thereof with, independently, a hydrogen atom or a carbohydryl group containing up to about 20 carbon atoms or oxycarbohydryl 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 ionic metal-containing third component having at least one aryl group possessing at least one electron-withdrawing substituent, the process comprising combining the metallocene procatalyst with the components of the cation-generating cocatalyst in any order thereof in the presence of an alpha-olefin, alone or in combination with a metalloid-containing third component having at least one aryl group possessing at least one electron-withdrawing substituent.

18. The process of claim 17 wherein in metallocene procatalyst (I), bridging group R³ possesses the structure ##STR9## in which bulky groups R⁴ and R⁵ each, independently, is, or contains, a cyclohydrocarbyl group containing up to about 20 carbon atoms and from 0 to 3 heteroatoms.

19. The process of claim 18 wherein the cyclohydrocarbyl group is a cycloalkyl, heterocycloalkyl, cycloalkenyl, heterocycloalkenyl, aryl, heteroaryl, alkaryl, alkylheteroaryl, aralkyl or heteroaralkyl group.

20. The process of claim 19 wherein ligand (Cp¹ R_m¹) is unsubstituted cyclopentadienyl, ligand (Cp² R_p²) is indenyl or fluorenyl, M is zirconium, R⁴ and R⁵ each is phenyl and each ligand X is chlorine.

21. The process of claim 17 wherein in metallocene catalyst (II), n is 1, the valence of M is 4, ligand X is halogen and s is 2.

22. The process of claim 17 wherein in the cation-generating cocatalyst, the first component is at least one aluminum compound, the second component is at least one borane compound and the third component is at least one metal borate compound.

23. The process of claim 22 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-, transition metal- or metal tetrakis(haloaryl)borate.

24. The process of claim 23 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.

25. The process of claim 22 wherein the aluminum compound is selected from the group consisting 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 and di(n-butyl)aluminum ethoxide, the borane compound is selected from the group consisting of tris(pentafluoro-phenyl)borane, tris(methoxyphenyl)borane, tris(trifluoromethylphenyl)borane, tris(3,5-di[trifluoromethyl]phenyl) borane, tris(tetrafluoroxylyl)borane and tris(tetrafluoro-o-tolyl)borane and the metal borate compound is selected from the group consisting 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 and tin tetrakis (pentafluorophenyl)borate.

26. In a process for activating a metallocene procatalyst with an aluminoxane cocatalyst to provide a metallocene catalyst, the improvement comprising substituting part or all of the aluminoxane cocatalyst with a cation-generating cocatalyst comprising:

a metal- and/or metalloid-containing first component capable of exchanging one or more non-cyclopentadienyl ligands coordinated to a transition metal having a valence of from 3 to 6 of the metallocene up to the full number of such ligands present 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 ionic metal-containing third component having at least one aryl group possessing at least one electron-withdrawing substituent, alone or in combination with a metalloid-containing third component having at least one aryl group possessing at least one electron-withdrawing substituent.

27. The process of claim 26 the first component is at least one aluminum compound, the second component is at least one borane compound and the third component is at least one 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-, transition metal- or 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 compound is an alkali metal tetrakis(halophenyl)borate.

30. The process of claim 29 wherein the aluminum compound is selected from the group consisting 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 and di(n-butyl)aluminum ethoxide, the borane compound is selected from the group consisting of tris(pentafluoro-phenyl)borane, tris(methoxyphenyl)borane, tris(trifluoromethylphenyl)borane, tris(3,5-di[trifluoromethyl]phenyl) borane, tris(tetrafluoroxylyl)borane and tris(tetrafluoro-o-tolyl)borane and the metal borate compound is selected from the group consisting 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 and tin tetrakis (pentafluorophenyl)borate.

31. The process of claim 26 wherein the metallocene procatalyst is combined with the components of the cation-generating cocatalyst in any order thereof in the presence of an alpha-olefin.