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(12) Patent Application Publication (10) Pub. No.: US 2010/0113717 A1 Voskoboynikov Et Al

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(12) Patent Application Publication (10) Pub. No.: US 2010/0113717 A1 Voskoboynikov Et Al US 20100113717A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2010/0113717 A1 Voskoboynikov et al. (43) Pub. Date: May 6, 2010 (54) PROCESS FOR PRODUCING SUBSTITUTED Publication Classification METALLOCENE COMPOUNDS FOR OLEFIN POLYMERIZATION (51) Int. Cl. CSF 4/6 (2006.01) (76) Inventors: Alexander Z. Voskoboynikov, C07F 1700 (2006.01) Moscow (RU); Alexey N. Ryabov, BOI 3L/2 (2006.01) Moscow (RU); Catalina L. Coker, BOI 3/4 (2006.01) Baytown, TX (US); Jo Ann M. (52) U.S. Cl. ........... 526/126; 556/11: 502/152: 502/117; Canich, Houston, TX (US) 556/53; 549/3: 502/155; 526/154 Correspondence Address: ExxonMobil Chemical Company (57) ABSTRACT Law Technology P.O. Box 21.49 Baytown, TX 77522-2149 (US) A process for producing a Substituted metallocene compound comprises reacting a first compound with a transfer-agent, (21) Appl. No.: 12/641,123 wherein the first compound comprises a complex of a transi tion metal atom selected from Group 3, 4, 5 or 6 of the (22) Filed: Dec. 17, 2009 Periodic Table of Elements, or a lanthanide metal atom, or actinide metal atom and at least one monocyclic or polycyclic Related U.S. Application Data ligand that is pi-bonded to M and is substituted with at least one halogen or Sulfonate Substituent and the transfer-agent (62) Division of application No. 1 1/302,997, filed on Dec. comprises a hydrocarbyl, Substituted hydrocarbyl, halocar 14, 2005. byl, substituted halocarbyl, silylcarbyl, or germylcarbyl radi (60) Provisional application No. 60/636,662, filed on Dec. cal capable of replacing said at least one halogen or Sulfonate 16, 2004. Substituent of said first compound under reaction conditions. US 2010/01 13717 A1 May 6, 2010 PROCESS FOR PRODUCING SUBSTITUTED synthesis or modification, and, then, metallocene preparation METALLOCENE COMPOUNDS FOR OLEFIN starting from each ligand synthesized. POLYMERIZATION 0008 For example, U.S. Pat. No. 5,840,644 describes cer tain metallocenes containing aryl-substituted indenyl deriva CROSS REFERENCE TO RELATED tives as ligands, which are said to provide propylene polymers APPLICATIONS having high isotacticity, narrow molecular weight distribu tion and very high molecular weight. However, synthesis of 0001. This application is a divisional of U.S. Ser. No. these compounds involves initial assembly of each aryl-Sub 11/302,997, filed Dec. 12, 2005 which claims priority from stituted indene ligand from a Substituted diphenyl compound U.S. Provisional Patent Application No. 60/636,662, filed on and then reaction of the ligand with MC1. Thus Example A Dec. 16, 2004. discloses synthesis of rac-dimethylsilylbis(2-methyl-4-phe nyl-indenyl)Zirconium dichloride by reaction of 2-phenyl FIELD benzyl bromide with diethylmethyl malonate and then KOH to produce 2-(2-phenylbenzyl)propionic acid, followed by 0002 This invention relates to a process for producing cyclization of the 2-(2-phenylbenzyl)propionic acid to pro Substituted metallocene compounds for use in olefin poly duce 2-methyl-4-phenylindan-1-one and reduction of the merization and to a process to polymerize olefins using Such 2-methyl-4-phenylindan-1-one to produce 2-methyl-7-phe Substituted metallocene compounds. nylindene. The 2-methyl-7-phenylindene is then reacted with dimethyldichlorosilane to produce dimethylbis(2-methyl-4- BACKGROUND phenylindenyl)silane, which is then reacted with butyllithium and zirconium tetrachloride to produce the desired bridged 0003 Various processes and catalysts exist for the metallocene. homopolymerization or copolymerization of olefins. For 0009. According to the present invention, a novel method many applications, it is desirable for a polyolefin to have a of producing Substituted metallocene complexes of early high weight average molecular weight while having a rela transition metals has been developed in which halogen Sub tively narrow molecular weight distribution. A high weight stituents on existing metallocene compounds are directly average molecular weight, when accompanied by a narrow replaced with other groups, such as hydrocarbyl groups. In molecular weight distribution, typically provides a polyolefin this way, a single base synthesis of a given halogen-substi with high strength properties. tuted metallocene compound can be used to generate a large 0004 Traditional Ziegler-Natta catalysts systems com number of final metallocene products with varying ligand prise a transition metal compound co-catalyzed by an alumi substituents. num alkyl and are typically capable of producing polyolefins 0010 Modification of the coordinated ligands of late tran having a high molecular weight, but with a broad molecular sition complexes, particularly, ferrocene derivatives, has been weight distribution. described (see Hassan, J.; Sevignon, M. Gozzi, C.; Schulz, 0005 More recently metallocene catalyst systems have E.; Lemaire, M. Chem. Rev. 2002, 102, 1359, and references been developed wherein the transition metal compound has therein). However, no similar transformations of early tran one or more cyclopentadienyl, indenyl or fluorenyl ring sition metal complexes, which include highly polarized and ligands (typically two). Metallocene catalyst systems, when reactive metal-ligand bonds, have been described so far. 0011 Scarce examples of transformations of the coordi activated with cocatalysts, such as alumoxane, are effective to nated cyclopentadienyl ligands of Group 4 metal complexes polymerize monomers to polyolefins having not only a high resulting in no modification of the nearest coordination poly weight average molecular weight but also a narrow molecular hedron have been described, e.g. H/D exchange in m-cyclo weight distribution. pentadienyls (Larsonneur, A.-M.; Choukroun, R., Jaud, J. 0006 Certain metallocenes containing substituted, Organometallics 1993, 12, 3216); Pd/C or PtC), catalyzed bridged indenyl derivatives are noted for their ability to pro hydrogenation of m-indenyls giving m-tetrahydroindenyls duce isotactic propylene polymers having high isotacticity (Wild, F. R. W. P. Zsolnai, L.; Huttner, G.; Brintzinger, H. H. and narrow molecular weight distribution. Considerable J. Organomet. Chem. 1982. 232, 233. Schäfer, A.; Karl, E.; effort has been made towards obtaining metallocene-pro Zsolani, L.; Huttner, G.; Brintzinger, H. H. J. Organomet. duced propylene polymers having ever-higher molecular Chem. 1987,328,87. Bandy, J. A.; Green, M. L. H.; Gardiner, weight and melting point, while maintaining Suitable catalyst I. M.; Prout, K. J. Chem. Soc., Dalton Trans. 1991, 2207. activity. Researchers currently theorize that there is a direct Rheingold, A. L.; Robinson, N. P.; Whelan, J.; Bosnich, B. relationship between the way in which a metallocene is sub Organometallics 1992, 11, 1869. Hollis, T. K.; Rheingold, A. stituted, and the molecular structure of the resulting polymer. L.; Robinson, N. P.; Whelan, J.; Bosnich, B. Organometallics For the substituted, bridged indenyl type metallocenes, it is 1992, 11, 2812); hydroboration of allyl- and vinyl-m-cyclo believed that the type and arrangement of substituents on the pentadienyl complexes (Erker, G.; Nolfe, R.; Aul, R.; Wilker, indenyl groups, as well as the type of bridge connecting the S.: Kriger, C.; Noe, R. J. Am. Chem. Soc. 1991, 113, 7594. indenyl groups, determines such polymer attributes as Erker, G.; Aul, R. Chem. Ber: 1991, 124, 1301); intramolecu molecular weight and melting point. lar photochemical 2+2 cycloaddition of vinyl-m-cyclopen 0007. There is, therefore, significant interest in producing tadienyl complexes (Erker, G.; Wilker, S.; Kriger, C.; Nolte, metallocene compounds with a variety of Substituents on the M. Organometallics 1993, 12, 2140); Ru-catalyzed metathe arenyl ligands. However, current methods for producing Sub sis of bis(allyl-m-cyclopentadienyl)Zirconium and -hafnium stituted metallocene compounds, and especially Group 4 dichlorides (Ogasawara, M.; Nagano, T.; Hayashi, T. J. Am. metallocene compounds, involve synthesis of each individual Chem. Soc. 2002, 124,9068). ligand family and then reaction with a simple metal deriva tive, such as MC1 and M(N(CH)), where M-Ti, Zr, or Hf, SUMMARY using transmetallation and amine elimination reactions, 0012. In one aspect, the invention resides in a process respectively. This methodology requires preliminary ligand producing a Substituted transition metal compound, the pro US 2010/01 13717 A1 May 6, 2010 cess comprising contacting: (a) a transition metal compound ated, linear or branched alicyclic hydrocarbyl substituent; or comprising at least one ligand having a halogen or Sulfonate a C-Coo Substituted or unsubstituted Saturated hydrocarbyl substituent directly bonded to any sp carbonatomat a bond radical; able ring position of said ligand, with (b), a transfer-agent t is the coordination number of the heteroatom T where “t-1- capable of replacing the halogen or Sulfonate Substituent of y’ indicates the number of R" substituents bonded to T; and the ligand with a hydrocarbyl, substituted hydrocarbyl, halo each X is, independently, a univalent anionic ligand, or two X carbyl, substituted halocarbyl, silylcarbyl, or germylcarbyl are joined and bound to the metal atom to form a metallocycle Substituent, and (c) a coupling-catalyst. ring, or two X are joined to form a chelating ligand, a diene 0013. In a further aspect, the invention resides in a process ligand, or an alkylidene ligand; producing a substituted metallocene compound, the process provided that Z is substituted with at least one halogen or comprising: sulfonate
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