Claims
- 1. A method of producing a polyolefin composition comprising contacting a metallocene pre-catalyst with a substoichiometric amount of a co-catalyst; adding a first olefin monomer; and polymerizing said first monomer for a time sufficient to form said polyolefin.
- 2. The method of claim 1, wherein said metallocene pre-catalyst has the formula:
- 3. The method of claim 2, wherein:
said optional substituents on phenyl are amino, hydroxy, alkoxy, amide, aryl, alkyl, halo, ketone, ester, —SO3H, aldehyde, carboxylic acid, cyano, nitro and ammonium.
- 4. The method of claim 2, wherein said metallocene pre-catalyst is 1,2,3,4,5-pentamethylcyclopentadienyl dimethyl zirconium (N-ethyl-N-tbutyl-2-methyl)amidinate or 1,2,3,4,5-pentamethylcyclopentadienyl chloro isobutyl zirconium (N-ethyl-N-tbutyl-2-methyl)amidinate.
- 5. The method of claim 1, wherein said co-catalyst has one of the formulae:
- 6. The method of claim 5, wherein said co-catalyst is [PhNMe2H][B(C6F5)4] or Si(CH2CH3)3[B(C6F5)4].
- 7. The method of claim 1, wherein said metallocene pre-catalyst and said co-catalyst are contacted in a metallocene catalyst:co-catalyst ratio of about 1:1-100:1.
- 8. The method of claim 7, wherein said metallocene pre-catalyst and said co-catalyst are contacted in a metallocene catalyst:co-catalyst ratio of about 2:1.
- 9. The method of claim 1, wherein said co-catalyst is added in an amount of about 1-5 mole % of said precatalyst.
- 10. The method of claim 1, wherein said metallocene pre-catalyst is contacted with a substoichiometric amount of a co-catalyst in an inert solvent.
- 11. The method of claim 10, wherein said solvent is chlorobenzene, dichlorobenzene, isopentane, hexane, cyclohexane, heptane, benzene, toluene, trifluorotoluene, pentane, octane, isooctane or dichloromethane.
- 12. The method of claim 1, wherein said metallocene pre-catalyst and said co-catalyst are contacted at a temperature of about −20° C. to about 10° C.
- 13. The method of claim 1, wherein said first olefin and second olefin are independently ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, styrene, alpha-methyl styrene, butadiene, isoprene, acrylonitrile, methyl acrylate, methyl methacrylate, vinyl acetate, vinyl chloride, vinyl fluoride, vinylidene chloride, N-vinyl pyrrolidone, 3-methylbutene, 3-methyl-1-pentene, vinylcyclohexane, vinylcyclobutane, vinylcyclopentane, vinylcyclooctane, 1-decene, enantiomerically pure β-citronellene, 3,5,5-trimethyl-1-hexene or 4-methyl-1-pentene.
- 14. The method of claim 1, wherein said first olefin monomer is a non-conjugated diene having the formula:
- 15. The method of claim 1, wherein said first olefin monomer is 1,4-pentadiene, 1,5-hexadiene, 5-vinyl-2-norbomene, 1,7-octadiene, vinylcyclohexene, dicyclopentadiene, butadiene, isobutylene, isoprene or ethylidene norbomene.
- 16. The method of claim 1, wherein said metallocene pre-catalyst and said first olefin monomer are added in a metallocene catalyst:first monomer ratio of about 1:10-1:10,000.
- 17. The method of claim 16, wherein said ratio is about 1:10.
- 18. The method of claim 16, wherein said ratio is about 1:100.
- 19. The method of claim 16, wherein said ratio is about 1:1000.
- 20. The method of claim 1, further comprising contacting said polyolefin with a second amount of said co-catalyst; adding a second olefin monomer; and polymerizing said second olefin monomer to form a block-polyolefin composition.
- 21. The method of claim 20, wherein said second amount of co-catalyst is about a stoichiometric amount or more of said metallocene catalyst.
- 22. The method of claim 20, wherein said second amount is a metallocene pre-catalyst:co-catalyst ratio of about 0.5:1-2:1.
- 23. The method of claim 20, wherein said metallocene pre-catalyst and said second olefin monomer are added in a metallocene catalyst:second monomer ratio of about 1:10-1:10,000.
- 24. The method of claim 23, wherein said ratio is about 1:10.
- 25. The method of claim 23, wherein said ratio is about 1:100.
- 26. The method of claim 23, wherein said ratio is about 1:1000.
- 27. The method of claim 20, wherein said first olefin and second olefin are independently ethene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, styrene, alpha-methyl styrene, butadiene, isoprene, acrylonitrile, methyl acrylate, methyl methacrylate, vinyl acetate, vinyl chloride, vinyl fluoride, vinylidene chloride, N-vinyl pyrrolidone, 3-methylbutene, 3-methyl-1-pentene, vinylcyclohexane, vinylcyclobutane, vinylcyclopentane, vinylcyclooctane, 1-decene, enantiomerically pure β-citronellene, 3,5,5-trimethyl-1-hexene or 4-methyl-1-pentene.
- 28. The method of claim 20, wherein said first olefin monomer is a non-conjugated diene having the formula:
- 29. The method of claim 27, wherein said first olefin and said second olefin are the same.
- 30. The method of claim 20, wherein said polyolefin is an atactic living polyolefin.
- 31. The method of claim 20, wherein said block-polyolefin composition comprises a diblock copolymer having the formula: atactic-poly(first olefin)-b-isotactic-poly(second olefin).
- 32. The method of claim 31, wherein said atactic-poly(first olefin) block has degree of polymerization about equal to said isotactic-poly(second olefin) block.
- 33. The method of claim 31, wherein said diblock copolymer composition has polydispersity about 1.02-1.1.
- 34. The method of claim 33, wherein said polydispersity is about 1.05.
- 35. The method of claim 31, wherein said diblock copolymer is monomodal.
- 36. A monomodal diblock copolymer composition with narrow polydispersity made according to the method of claim 19.
- 37. The method of claim 1, wherein said polyolefin is an isotactic polyolefin having polydispersity index of about 1.02-1.1.
Government Interests
[0001] Part of the work performed during development of this invention utilized U.S. Government funds. The work was partly funded by the National Science Foundation Grant CHE-0092493. The U.S. Government has certain rights in this invention.
Provisional Applications (1)
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Number |
Date |
Country |
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60435432 |
Dec 2002 |
US |