Process for producing polyolefin elastomer employing a metallocene catalyst

• US 6,060,572 A
• Filed: 12/15/1997
• Issued: 05/09/2000
• 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 (Lanxess AG)
• Inventors: Gillis, Daniel J., Karpeles, Richard
• Primary Examiner(s): Wu, David W.
• Assistant Examiner(s): CHOI, LING SIU
• Application Number:
  US08/990,364
• Time in Patent Office: 876 Days
• Field of Search: 526/127, 526/160, 526/132, 526/335, 526/336, 526/904, 526/943
• US Class Current: 526/335
• 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 on total replacement of aluminoxane.

Claims

1. An elastomer obtained from the liquid phase polymerization of ethylene, at least one other α

-olefin and, optionally, it least one diene monomer to provide an elastomer, the process comprising polymerizing the monomer under liquid phase 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);

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

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

wherein Cp¹ of ligand (Cp¹ R¹_m) and Cp² of ligand (Cp² R² p) 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 0 to 5, p is 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 fused to the cyclopentadienyl ring, the fused ring containing from 4 to about 20 carbon atoms, R³ is a bridging group bridging Cp¹ and Cp², n is 0 or 1, Y 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 or halocarbyl-substituted organometalloid group containing up to about 20 carbon atoms, q is equal to the valence of M minus 2, r has the value of n and s is equal to the valence of M minus 1 the valence of M minus 2, r has the value of n and s is equal to the valence of M minus 1 when r is 0 and is equal to the valence of M minus 2 when r is 1, the cocatalyst being an aluminoxane or a different 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 an 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 anionic metal-containing third component having at least one aryl group possessing at least one electron-withdrawing constituent alone or in combination with a metalloid-containing third component having at least one aryl group possessing at least one electron-withdrawing constituent, provided, that when the metallocene procatalyst is one of formula (I) and the cocatalyst is entirely an aluminoxane, or combination of aluminoxane and added trialkylaluminum, ligand (Cp¹ R¹_m) is different from ligand (Cp² R²_p), bridging group R³ contains at least two bulky groups and n is 1 and when the procatalyst is entirely one of formula (II), the cocatalyst comprises said different cation-generating cocatalyst.

2. The elastomer of claim 1 wherein in metallocene procatalyst (I), bridging group R³ possesses the structure ##STR8## 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 elastomer of claim 2 wherein in metallocene procatalyst (I), the cyclic group is a cycloalkyl, heterocycloalkyl, cycloalkenyl, heterocycloalkenyl, aryl, heteroaryl, alkaryl, alkylheteroaryl, aralkyl or heteroaralkyl group.

4. The elastomer of claim 3 wherein in metallocene procatalyst (I), ligand (Cp¹ R_m¹ is unsubstituted cyclopentadienyl, ligand (Cp² R_p²) is substituted or unsubstituted indenyl or fluorenyl, M is zirconium, R⁴ and R⁵ each is phenyl and each ligand X is chlorine.

5. The elastomer 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 elastomer 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 elastomer 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 elastomer 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 elastomer 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, triisobutyl-aluminum, 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.

10. The elastomer 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 elastomer 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 elastomer 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 elastomer 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 elastomer 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 elastomer 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 elastomer 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 elastomer 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 elastomer 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 elastomer of claim 1 wherein the α

-olefin contains from 3 to about 20 carbon atoms.

20. The elastomer of claim 19 wherein the α

-olefin is propylene.

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

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

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

24. The elastomer of claim 1 possessing an M_w of from about 200,000 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 1.25 to about 10, a T_g of below about -25°

C. and a tan δ

of from about 0.3 to about 7.

25. The elastomer of claim 24 possessing an M_w of from about 275,000 to about 1,750,000, an ML₁₊₄ at 125°

C. of from about 15 to about 175, an M_w /M_n of from about 1.25 to about 8.5, a T_g of about -30°

C. and a tan δ

of from about 0.35 to about 6.

26. The elastomer of claim 25 possessing an M_w of from about 300,000 to about 1,500,000, an ML₁₊₄ at 125°

C. of from about 20 to about 150, an M_w /M_n of from about 2.0 to about 7.5, a T_g below about -35°

C. and a tan 6 of from about 0.4 to about 5.