Olefin polymerization catalysts are of great use in industry. Hence there is interest in finding new catalyst systems that increase the commercial usefulness of the catalyst and allow the production of polymers having improved properties.
Catalysts for olefin polymerization are often based on metallocenes as catalyst precursors, which are generally activated either with an alumoxane or with an activator containing a non-coordinating anion.
Cyclopropyl cyclopentadiene is reported in “Chemistry of Polyhalocyclo-pentadienes and related compounds: XVII Reaction of Hexachlorocyclopentadiene with unsaturated compounds,” Reimschneider, R. et al, Univ Berlin-Dahlem, Monatshefte Fuer Chemie (1960).
2-Cyclopropyl indene is disclosed in: 1) “Nickle Catalyzed Carboannulation Reaction of o-Bromobenzyl Zinc Bromide with Unsaturated Compounds,” Deng, Ruixue, et al. Department of Chemistry, School of Science, Tianjin University, Tianjin, People's Republic of China, Organic Letters (2007) 9(25) pp. 5207-5210; and 2) “Are Perpendicular Alkene Triplets Just 1,2 Biradicals? Studies with the Cyclopropylcarbinyl Clock,” Caldwell, Richard A. et al. Program in Chemistry, The University of Texas, Dallas, Richardson, Tex., USA, Journals of the American Chemical Society (1994) 116(6), pp. 2271-2275.
1 and 3-cyclopropyl indene are disclosed in reference to the photolysis of 2-cyclopropyl indene (and have not been prepared in large scale) in Upper Excited State Photochemistry: Solution and Gas Phase Photochemistry and Photophysics of 2- and 3-Cyclopropylindene; Waugh, Tim; Morrison, Harry; Department of Chemistry, Purdue University, West Lafayette, Ind., USA; Journal of the American Chemical Society (1999), 121(13), pp. 3083-3092.
Cyclopropyl substituted fluorenyls are disclosed in “Transformations of arylcyclopropanes under the action of dinitrogen tetroxide,” Mochalov, S. S.; Ku/min, Ya. I.; Fedotov, A. N.; Trofimova, E. V.; Gazzaeva, R. A.; Shabarov, Yu. S.; Zefirov, N. S., Russian Journal of Organic Chemistry (Translation of Zhurnal Organicheskoi Khimii), (1998), 34(9), pp. 1322-1330, MAIK Nauka/Interperiodica Publishing.
2-cyclopropylfluorene is disclosed in the abstract of “Reaction of 2-cyclopropylfluorene with mercury acetate,” Shabarov, Yu. S.; Bandaev, S. G.; Sychkova, L. D., Vestnik Moskovskogo Universiteta, Seriya 2: Khimiya, (1976), 17(5), pp. 620-621.
Nitration of 2-cyclopropylbiphenyl is disclosed in “Nitration of biphenylcyclopropanes,” Mochalov, S. S.; Novokreshchennykh, V. D.; Shabarov, Yu. S., Zhurnal Organicheskoi Khimii, (1976), 12(5), pp. 1008-1014.
Other references of interest include: 1) “An efficient three-step synthesis of cyclopenta[b]pyrans via 2-donor-substituted Fischer ethenylcarbenechromium complexes,” de Meijere, Armin; Schirmer, Heiko; Stein, Frank; Funke, Frank; Duetsch, Michael; Wu, Yao-Ting; Noltemeyer, Mathias; Belgardt, Thomas; Knieriem, Burkhard, Chemistry—A European Journal (2005), 11(14), pp. 4132-4148; 2) “Novel Pi Systems Possessing Cyclopropenylidene Moiety,” Yoshida, Zenichi, Pure and Applied Chemistry (1982), 54(5), pp. 1059-74; 3) JP 55010596 B (1980); 4) “An efficient three-step synthesis of cyclopenta[b]pyrans via 2-donor-substituted Fischer ethenylcarbene-chromium complexes,” de Meijere, Armin; Schirmer, Heiko; Stein, Frank; Funke, Frank; Duetsch, Michael; Wu, Yao-Ting; Noltemeyer, Mathias; Belgardt, Thomas; Knieriem, Burkhard, Chemistry—A European Journal (2005), 11(14), pp. 4132-4148; and 5) “Novel Pi Systems Possessing Cyclopropenylidene Moiety,” Yoshida, Zenichi, Pure and Applied Chemistry (1982), 54(5), pp. 1059-74.
U.S. Pat. No. 7,829,495 discloses alkyl substituted metallocenes having a “ . . . C3 or greater hydrocarbyl . . . substitutent bonded to either the LA or LB ring through a primary carbon atom . . . preferably an n-alkyl substituent . . . ” (see column 4, lines 9-12). Further, in the Examples section, (n-propylcyclopentadienyl)(tetramethylcyclopentadienyl)zirconium dichloride combined with methylalumoxane and Davision™ 948 silica is used for ethylene hexene polymerization; bis(n-propyl cyclopentadienyl) zirconium dichloride combined with methylalumoxane and Davision™ 948 silica is used for ethylene hexene polymerization; and dimethylsilyl(flourenyl)(n-propyl cyclopentadienyl) zirconium dichloride combined with methylalumoxane and Davision silica is used for ethylene hexene polymerization.
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There is still a need in the art for new and improved catalyst systems for the polymerization of olefins, in order to achieve specific polymer properties, such as high melting point, high molecular weights, to increase conversion or comonomer incorporation, or to alter comonomer distribution without deteriorating the resulting polymer's properties.
It is therefore an object of the present invention to novel catalyst compounds, catalysts systems comprising such compounds, and processes for the polymerization of olefins using such compounds and systems.