Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Organic compound containing
Reexamination Certificate
2000-01-18
2001-07-03
Bell, Mark L. (Department: 1755)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Organic compound containing
C502S155000, C502S118000, C502S128000, C502S202000, C526S132000, C526S133000, C526S134000
Reexamination Certificate
active
06255246
ABSTRACT:
BACKGROUND OF THE INVENTION
This invention relates to cocatalysts or activators useful with metallocene catalysts, particularly with metallocene catalysts used to make olefin polymers.
Metallocene catalysts are well known, especially for polymerization of olefins. The term “metallocene catalysts” is used to mean organometallic compounds having a rare earth or transition metal in coordination with members of at least one five-membered carbon (preferably cyclopentadienyl) ring.
It is generally recognized that cocatalysts or activators are useful with metallocene catalysts, especially in polymerization of olefins. Known activating cocatalysts include e.g. polymeric or oligomeric alumoxanes, especially methylalumoxane, triisobutyl aluminum modified methylalumoxane, or diisobutylalumoxane; strong Lewis acids (the term “strong Lewis acid” as used herein is defined as trihydrocarbyl substituted Group 13 compounds, especially tri(hydrocarbyl)aluminum- or tri(hydrocarbyl)boron compounds and halogenated derivatives thereof, having from 1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group, more especially perfluorinated tri(aryl)boron compounds, and most especially tris(pentafluorophenyl)borane); amine, phosphine, aliphatic alcohol and mercaptan adducts of halogenated tri(C
1-10
hydrocarbyl)boron compounds, especially such adducts of perfluorinated tri(aryl)boron compounds; nonpolymeric, ionic, compatible, noncoordinating, activating compounds (including the use of such compounds under oxidizing conditions); and combinations of the foregoing activating cocatalysts and techniques. Preferred species include tris(pentafluorophenyl)borane and the ionic activators containing the anion tetrakis (pentafluorophenyl)borate. These compounds are effective but require several pentafluorophenyl groups per molecule which are difficult to obtain or synthesize and are, therefore, quite expensive. Ionic activators react irreversibly with metallocenes and therefore may be preferred over the neutral strong Lewis acid activators, which may react reversibly with a metallocene. However, a commercial drawback of these ionic activators is their poor solubility in the polymerization medium, i.e., hydrocarbon solvents.
It would be desirable to have activators or cocatalysts which retain good solubility in hydrocarbon solvents and are preferably less likely to result in reversible reactions and/or which are less expensive, that is use less of the difficult to obtain pentafluorophenyl group.
Boratabenzenes are known and have been used as ligands but are not used as cocatalysts, activators or counterions for metallocene catalysts.
The boratabenzenes are anionic species which are boron containing analogues to benzene. They are previously known in the art having been described by G. Herberich, et al., in Organometallics, 14,1, 471-480 (1995). They may be prepared by reaction of stannocyclohexadiene and a borontrihalide followed by substitution with a hydrocarbyl group.
SUMMARY OF THE INVENTION
It has now been found that cocatalysts or activators comprising hydroboratabenzenes or boratabenzene anions, preferably as the neutral 1,4-dihydroboratabenzene, are useful in polymerization of olefins using metallocene catalysts. Boratabenzene cocatalysts advantageously involve fewer pentafluorophenyl groups than preferred trispentafluorophenyl borane and salts containing tetrakis(pentafluorophenyl) borates, respectively. Furthermore, 1,4-dihydroboratabenzenes are advantageously involved in less reversible reactions with metallocenes.
The present invention includes a process of polymerizing olefins using metallocene catalysts in the presence of at least one activator comprising a 1,4-dihydroboratabenzene or boratabenzene (collectively boratabenzene cocatalysts) as well as a process for polymerizing olefins using at least one metallocene catalyst wherein the catalyst is activated by at least one activator comprising a boratabenzene.
Further, the invention includes a composition of matter comprising at least one metallocene catalyst and at least one cocatalyst comprising a boratabenzene and compositions of matter comprising the resulting cationic metallocene catalysts and anionic boratabenzene counterions preferably which arise from the reaction of metallocenes in the +4 oxidation state with a cocatalyst comprising a boratabenzene.
Additionally, the invention includes perfluorophenyl hydroboratabenzenes of Formula 1 wherein R′ is a pentafluorobenzene group, especially 1-pentafluorophenyl-1,4-dihydroboratabenzene [C
5
H
6
B—C
6
F
5
] and the anion thereof, [C
5
H
5
B—C
6
F
5
]
−
.
Additional components in the compositions of the invention include trialkylaluminum and/or methylalumoxanes or derivatives, thereof, e.g. triisopropylaluminum modified methylaluminumoxane. Also included in the invention are reaction products of the compositions of the invention especially those formed under reaction (polymerization) conditions.
REFERENCES:
patent: 4381386 (1983-04-01), Ritter et al.
patent: 5089536 (1992-02-01), Palazzotto
patent: 5198401 (1993-03-01), Turner et al.
patent: 5278119 (1994-01-01), Turner et al.
patent: 5372682 (1994-12-01), Devore et al.
patent: 5374696 (1994-12-01), Rosen et al.
patent: 5425872 (1995-06-01), Devore et al.
patent: 5457171 (1995-10-01), Langhauser et al.
patent: 5470993 (1995-11-01), Devore et al.
patent: 5486632 (1996-01-01), Devore et al.
patent: 5494874 (1996-02-01), Rosen et al.
patent: 5554775 (1996-09-01), Krishnamurti et al.
patent: 5565534 (1996-10-01), Aulbach et al.
patent: 5756611 (1998-05-01), Etherton et al.
patent: 5902866 (1999-05-01), Nagy et al.
patent: 6034027 (2000-03-01), Krishnamurti et al.
patent: 6107421 (2000-08-01), Timmers et al.
patent: 6114270 (2000-09-01), Krishnamurti et al.
patent: 478913 B1 (1988-01-01), None
patent: WO 97/01566 (1997-01-01), None
G. Bazan et al., J. Am. Chem. Soc., vol. 118, No. 9, pp. 2291-2292 Mar. 1996.*
G. Herberich et al., Chem. Ber., vol. 115, pp. 3315-3127 1982.*
K. Gustafsson, Acta Chem. Scandinavia B, vol. 32, No. 10, pp. 765-768 1978.*
G. Herberich et al., Chem. Ber. vol. 112, pp. 607-624 1979.*
U. Koelle, J. Organomet. Chem., vol. 152, pp. 225-228 May 1978.*
C. W. Allen and D. E. Palmer, “The Borabenzene Anion and Its Transition Metal Complexes”, vol.55, No. 8, pp. 497-500 (1978).
D. A. Hoic et al., “A Boron Analogue of Benzene: Synthesis, Structrure, and Reactivity of 1-H-Boratabenzene”,Journal of American Chemical Society, vol. 117, No. 32, pp. 8480-8481 (1995).
G. E. Herberich et al., “Borabenzene Derivatives. 221Synthesis of Boratabenzene Salts from 2,4-Pentadienylboranes. Structure of [NMe3Ph][C5H5BMe]”,Organometallics,vol. 14, pp.471-480 (1995).
“Boron Ring Systems as Ligands to Metls”,Comprehensive Organo-Metallic Chemistry, vol. 1, pp. 392-410.
A. J. Ashe, III and P. Shu, “The 1-Phenylborabenzene Anion”,Journal of the American Chemical Society, vol. 93, No. 7. pp. 1804-1805 (1971).
CHEMICAL ABSTRACT 142:146958u, Bazan et al., “Aminoboratabenzene Deriativesof Zirconium: A New Class of Olefin Polymerization Cataysts”,Journal of American Chemical Society, vol. 118, No. 9, 2291-2292 (1996).
CHEMICAL ABSTRACT 125:58576H, S. Qiao et al., “Nucleophilic Aromatic Substitution Reactions of Borabenzene-Trimethyphosphine: A Versatile Route to 1-Substituted Boratabenzenes”,Journal of American Chemical Society, vol. 118, No. 26, pp. 6329-6330 (1996).
CHEMICAL ABSTRACT 125:222129, D. A. Hoic et al., “Diphenylphoshidoboratabenzene: An Anionic Analog of Triphenylphosphine”,Journal of American Chemical Society, vol. 118, No. 34, pp. 8176-8177 (1996).
CHEMICAL ABSTRACT 119:180866u, G. E. Herbrich et al., “Borabenzene derivatives, 21 2,4-Pentadienylboranes as key intermediates of a novel route to boracyclohexadienes and boratabenzenes, Structure of [Li(TMPDA)](C8H4BNMe2)”,Organometallics, vol. 12, No.8 pp. 2891-2893 (1993).
CHEMICAL ABSTRACT 125:10902j, G. E. Herberich et al., “Borabenzene Derivatives 23. New Synthetic Entry into Borabenzene Chemistry via Doubly Kaliated Pen
Devore David D.
Neithamer David R.
Timmers Francis J.
Bell Mark L.
Pasterczyk J.
The Dow Chemical Company
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