Process for preparation of polyolefins via degenerative...

Details Process for preparation of polyolefins via degenerative... Process for preparation of polyolefins via degenerative...

2007-01-29

2009-06-02

Jagannathan, Vasu (Department: 1796)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S161000, C526S172000, C526S943000, C526S941000, C526S134000, C526S348200, C526S348300, C526S348500, C526S348600, C526S348000, C526S336000, C526S339000, C526S340200, C526S340300, C526S079000, C526S087000

Reexamination Certificate

active

07541412

ABSTRACT:
Disclosed is 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 the first monomer for a time sufficient to form the polyolefin. The method allows for the use of a minimum amount of activating co-catalyst, and allows for the production of stereoregular and non-stereoregular polyolefins. The use of configurationally stable metallocene pre-catalysts allows for the production of monomodal isotactic polyolefins having narrow polydispersity. The use of configurationally unstable metallocene pre-catalysts allows for the production of monomodal atactic polyolefins having narrow polydispersity. The method of the present invention optionally further comprises contacting the polyolefin with a second amount of said co-catalyst; adding a second olefin monomer; polymerizing said second olefin monomer to form a block-polyolefin composition. Also disclosed are monomodal diblock copolymer compositions made according to the present invention.

REFERENCES:
patent: 3175999 (1965-03-01), Natta et al.
patent: 3903017 (1975-09-01), Ziegler et al.
patent: 4335225 (1982-06-01), Collette et al.
patent: 4522982 (1985-06-01), Ewen
patent: 4530914 (1985-07-01), Ewen et al.
patent: 5162466 (1992-11-01), Karol et al.
patent: 5214173 (1993-05-01), Jordan et al.
patent: 5317036 (1994-05-01), Brady, III et al.
patent: 5318935 (1994-06-01), Canich et al.
patent: 5391629 (1995-02-01), Turner et al.
patent: 5527752 (1996-06-01), Reichle et al.
patent: 5594080 (1997-01-01), Waymouth et al.
patent: 5674795 (1997-10-01), Wasserman et al.
patent: 5681908 (1997-10-01), Mehra et al.
patent: 5726332 (1998-03-01), Eisch et al.
patent: 5756614 (1998-05-01), Chien et al.
patent: 5866659 (1999-02-01), Chung et al.
patent: 5912202 (1999-06-01), Oskam et al.
patent: 5969070 (1999-10-01), Waymouth et al.
patent: 6063105 (2000-05-01), Totakura
patent: 6211311 (2001-04-01), Wang et al.
patent: 6429274 (2002-08-01), Siedle et al.
patent: 6448358 (2002-09-01), Siedle et al.
patent: 6541583 (2003-04-01), Meverden et al.
patent: 6579998 (2003-06-01), Sita et al.
patent: 6737487 (2004-05-01), Meverden
patent: 6777476 (2004-08-01), Jeong et al.
patent: 7053157 (2006-05-01), Sita et al.
patent: 7183364 (2007-02-01), Sita
patent: 2004/0186253 (2004-09-01), Sita
patent: 0 416 815 (1991-03-01), None
patent: WO 96/08519 (1996-03-01), None
patent: WO 98/30606 (1998-07-01), None
patent: WO 01/30858 (2001-05-01), None
patent: WO 03/008459 (2003-01-01), None
patent: WO 2006/102106 (2006-09-01), None
patent: WO 2006/102119 (2006-09-01), None
Cannizzo et al. Macromolecules, 1988, 21, 1961-1967.
Epshteyn et al. J. Am. Chem. Soc., 2006, 128, 16052-16053.
U.S. Appl. No. 11/886,536, Sita et al., International filing date of Mar. 17, 2006, now published as WO 06/102119 A2.
U.S. Appl. No. 11/886,535, Sita et al., International filing date of Mar. 17, 2006, now published as WO 06/102106 A1.
Andresen, A., et al., “Halogen-Free Soluble Ziegler Catalysts for the Polymerization of Ethylene. Control of Molecular Weight by Choice of Temperature,”Angew. Chem. Int. Ed. Engl. 15: 630-632, VCH Verlagsgesellschaft (1976).
Asakura, T., et al., “Carbon-13 NMR Spectral Assignment of Five Polyolefins Determined from the Chemical Shift Calculation and the Polymerization Mechanism,”Macromolecules 24:2334-2340, American Chemical Society (1991).
Babu, G. N., et al., “Microstructure of Poly(1-hexene) Produced by ansa-Zirconocenium Catalysis,” Macromolecules 27:3383-3388, American Chemical Society (1994).
Barner-Kowollik, C., et al., “Modeling the Reversible Addition-Fragmentation Chain Transfer Process in Cumyl Dithiobenzoate-Mediated Styrene Homopolymerizations: Assessing Rate Coefficients for the Addition-Fragmentation Equilibrium,”J. Polymer Sci.: Part A: Polymer Chem. 39:1353-1365, John Wiley & Sons, Inc. (Published online Mar. 14, 2001).
Baumann, R., et al., “Synthesis of Titanium and Zirconium Complexes That Contain the Tridentate Diamido Ligand, [((t-Bu-d6)N-o-C6H4)2O]2−([NON]2−) and the Living Polymerization of 1-Hexene by Activated [NON]ZrMe2,” J. Am. Chem. Soc. 119: 3830-3831, American Chemical Society (1997).
Bochmann, M., and Lancaster, S.J., “Monomer-Dimer Equilibria in Homo- and Heterodinuclear Cationic Alkylzirconium Complexes and Their Role in Polymerization Catalysis,”Angew. Chem. Int. Ed. 33:1634-1637, VCH Verlagsgesellschaft (1994).
Bravakis, A.M., et al., “Synthesis of Elastomeric Poly(propylene) Using Unsymmetrical Zirconocene Catalysts: Marked Reactivity Differences of ‘Rac’- and ‘Meso’-like Diastereomers,”Macromolecules 31:1000-1009, American Chemical Society (1998).
Brintzinger, H.H., et al., “Stereospecific Olefin Polymerization with Chiral Metallocene Catalysts,”Angew. Chem. Int. Ed. Engl. 34:1143-1170, VCH Verlagsgesellschaft (1995).
Britovsek, G.J.P. et al., “The Search for New-Generation Olefin Polymerization Catalysts: Life beyond Metallocenes,”Angew. Chem. Int. Ed. 38:428-447, Wiley-VCH (1999).
Chen, Y.-X., et al., “Organo-Lewis Acids As Cocatalysts in Cationic Metallocene Polymerization Catalysis. Unusual Characteristics of Sterically Encumbered Tris(perfluorobiphenyl)borane,”J. Am. Chem. Soc. 118:12451-12452, American Chemical Society (1996).
Chernega, A. N., et al., “Mono-η-cyclopentadienyl-benzamidinato Compounds of Titanium, Zirconium and Hafnium,”J. Chem. Soc. Chem. Commun., pp. 1415-1417, Royal Society of Chemistry (1993).
Coates, G.W., and Waymouth, R.M., “Oscillating Stereocontrol: A Strategy for the Synthesis of Thermoplastic Elastomeric Polypropylene,”Science 267:217-219, American Association for the Advancement of Science (1995).
Coates, G.W., et al., “Catalysts For The Living Insertion Polymerization of Alkenes: Access to New Polyolefin Architectures Using Ziegler-Natta Chemistry,”Angew. Chem. Int. Ed. 41:2237-2257, Wiley-VCH (2002).
Coughlin, E.B., et al., “Iso-Specific Ziegler-Natta Polymerization of .alpha.-Olefins with a Single-Component Organoyttrium Catalyst,”J. Am. Chem. Soc. 114:7606-7607, American Chemical Society (1992).
De Rosa, C., et al., “Mechanical Properties and Elastic Behavior of High-Molecular-Weight Poorly Syndiotactic Polypropylene,”Macromolecules 36:7607-7617, American Chemical Society (Published Online Sep. 12, 2003).
Ewen, J. A., “Mechanisms of Stereochemical Control in Propylene Polymerizations with Soluble Group 4B Metallocene/Methylalumoxane Catalysts,”J. Am. Chem. Soc. 106:6355-6364, American Chemical Society (1984).
Ewen, J. A., “Symmetry rules and reaction mechanisms of Ziegler-Natta catalysts,”J. Mol. Cat. A: Chem. 128:103-109, Elsevier (1998).
Hawker, C.J., “‘Living’ Free Radical Polymerization: A Unique Technique for the Preparation of Controlled Macromolecular Architectures,”Acc. Chem. Res. 30:373-382, American Chemical Society (1997).
Hlatky, G.G., et al., “Ionic, Base-Free Zirconocene Catalysts for Ethylene Polymerization,”J. Am. Chem. Soc. 111:2728-2729, American Chemical Society (1989).
Jayaratne, K.C., and Sita, L.R., “Direct Methyl Group Exchange between Cationic Zirconium Ziegler-Natta Initiators and Their Living Polymers: Ramifications for the Production of Stereoblock Polyolefins,”J. Am. Chem. Soc. 123:10754-10755, American Chemical Society (2001).
Jayaratne, K.C., and Sita, L.R., “Stereospecific Living Ziegler-Natta Polymerization of 1-Hexene,”J. Am. Chem. Soc. 122:958-959, American Chemical Society (2000).
Jayaratne, K.C., et al., “Living Ziegler-Natta Cyclopolymerization of Nonconjugated Dienes: New Classes of Microphase-Separated Polyolefin Block Copolymers via a Tandem Polymerization/Cyclopolymerization Strategy,”J. Am. Chem. Soc. 122:10490-10491, American Chemical Society

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