USOO6169208B1 (12) United States Patent (10) Patent No.: US 6,169,208 B1 Lee (45) Date of Patent: Jan. 2, 2001 (54) PROCESS FOR PRODUCING A MAGNESIUM Goldberg et al., “Synthesis of Sodium Tetrakis(3,5-DI(Tri DITETRAKIS(ARYL)BORATE AND fluoromethyl)Phenyl Borate”, Zhurnal organicheskoi PRODUCTS THEREFROM Khimi, 1989, vol. 25, No. 5, pp. 1099–1102 (translation thereof), pp. 989-991. (75) Inventor: John Y. Lee, Baton Rouge, LA (US) Golden et al., “Lithium-Mediated Organofluorine Hydrogen Bonding: Structure of Lithium Tetreakis(3,5-bis(trifluorom (73) Assignee: Albemarle Corporation, Richmond, ethyl)phenyl)borate Tetrahydrate”, Inorg. Chem. vol. 33, VA (US) 1994, pp. 5374–5375. Hayashi et al., “A Novel Chiral Super-Lewis Acidic Cata (*) Notice: Under 35 U.S.C. 154(b), the term of this lyst for Enantioselective Synthesis”, J. Am. Chem. Soc., patent shall be extended for 0 days. 1996, vol. 118, No. 23, pp. 5502–5503. Hughes et al., “Synthesis and Structure of the Thallium(I) (21) Appl. No.: 09/453,606 Salt of the Tetrakis {3,5-bis(trifluoromethyl)phenylborate Anion”, Inorg. Chem. vol. 36, 1997, pp. 1726–1727. (22) Filed: Dec. 3, 1999 Jia et al., “Cationic Metallocene Polymerization Catalysts (51) Int. Cl." ........................................................ C07F 5/02 Based on Tetrakis(pentafluorophenyl)borate and Its Deriva (52) U.S. Cl. ...................................................... 568/6; 568/1 tives. Probing the Limits of Anion “Noncoordination” via a (58) Field of Search ............................................... 568/1, 6 Synthetic, Solution Dynamic, Structural, and Catalytic Ole fin Polymerization Study', Organometallics, 1997, vol. 16, (56) References Cited p. 842-857. Jia et al., “Protected (Fluoroaryl)borates as Effective Coun U.S. PATENT DOCUMENTS teranions for Cationic Metallocene Polymerization Cata 4,808.282 2/1989 Gregory .............................. 204/58.5 lysts”, Organometallics, vol. 14, 1995 pp. 3135-3137. 5,070,161 12/1991 Nakano et al. ... 526/193 Chem. Abstract #17030, Line H, Myl, et al., “Preparation of 5,078.974 1/1992 Ashby et al. .. ... 422/187 Sodium Tetraphenylborate”, Benzene Derivatives, 10-E 5,096,936 3/1992 Seko et al. ............................. 522/31 Benzene derivatives, 1959, 1 page. 5,189,222 2/1993 Ashby et al. .. ... 568/1 5,223,591 6/1993 Nyander et al. ... ... 526/204 Nesmeyanov et al., “Synthesis of Sodium Tetraphenylbo 5,340,898 8/1994 Cavezzan et al. ..................... 528/19 ron”, IZV. Akad. Nauk SSSR, Otd. Khim. Nauk, 1955, pp. 5,399,781 3/1995 Doellein ............ ... 568/6 187. (Translation pp. 167). 5,468,902 11/1995 Castellanos et al. .................... 568/6 Nishida et al., “Tetrakis(3,5-bis(trifluoromethyl)phenylbo 5,473,036 12/1995 Piotrowski et al. ..................... 528/4 rate. Highly Lipophilic Stable Anionic Agent for Solven 5,488,169 1/1996 Ikeda et al. ........ ... 568/3 t-extraction of Cations”, Bull Chem. Soc. Jpn., vol. 57, No. 5,493,056 2/1996 Ikeda et al. ... ... 568/6 9, 1984, pp. 2600–2604. 5,510,536 4/1996 Ikeda et al. .... ... 568/6 5,514,728 5/1996 Lamanna et al. ...................... 522/31 (List continued on next page.) 5,600,003 2/1997 Baur et al. ............................... 568/1 5,670,682 9/1997 Sangokoya ..... 556/181 Primary Examiner Jean F Vollano 5,693,867 12/1997 Bauer et al. ... ... 568/1 (74) Attorney, Agent, or Firm-Philip M. Pippenger 5,919,983 7/1999 Rosen et al. ............................. 568/3 (57) ABSTRACT FOREIGN PATENT DOCUMENTS A Solution comprising a halomagnesium tetrakis(aryl) 0331496 9/1989 (EP). O913400 5/1999 (EP). borate in a liquid organic medium, wherein the liquid 2727416 5/1996 (FR). organic medium is comprised of one or more liquid dihy 92.95984 11/1997 (JP). drocarbyl ethers, one or more liquid hydrocarbons, one or 92.95985 11/1997 (JP). more liquid halogenated hydrocarbons, or mixtures thereof, 1O-316686 12/1998 (JP). is contacted with water. This produces magnesium 98.07798 2/1998 (WO). ditetrakis(aryl)borate) in the organic phase of a two-phase 9822470 5/1998 (WO). water/liquid organic medium. The magnesium ditetrakis (aryl)borate) can be, but need not be, isolated. A protic OTHER PUBLICATIONS ammonium Salt, an onium Salt, or a triarylmethyl Salt can be Bahr et al., “Trityl Tetrakis(3,5-bis(trifluoromethyl)phe reacted with the magnesium ditetrakis(aryl)borate) to pro nyl)-borate: A New Hybride Abstraction Reagent”, J. Org. duce the corresponding protic ammonium, onium, or triaryl Chem., 1992, vol. 57, No. 20, pp. 5545–5547. methyl tetrakis(aryl)borate. The magnesium ditetrakis Brookhart et al., “I(3,5-(CF)2CH i) BHH(OEt): A (aryl)borate) can instead be reacted with a metal salt to Convenient Reagent for Generation and Stabilization of form a metal tetrakis(aryl)borate. The produced metal Cationic, Highly Electrophilic Organometallic Complexes', tetrakis( aryl)borate can be further reacted with a protic Organometallics, vol. 11, 1992, pp. 3920-3922. ammonium Salt, an onium Salt, or a triarylmethyl Salt to yield Chien et al., “Isospecific Polymerization of Propylene Cata a protic ammonium, onium, or triarylmethyl tetrakis(aryl) lyzed by rac-Ethylenebis(indenyl)methylzirconium”, Cat borate. Certain of these tetrakis(aryl)borates can be con ion Journal Am. Chem. Soc. 1991, vol. 113, pp. 8570–8571. Veniently purified via the formation of a liquid clathrate at Fujiki et al., “Synthesis and Lipophilicities of Tetraarylbo ambient temperatures. rate ions substituted with many Trifluoromethyl Groups', Journal of Fluorine Chemistry, vol. 57, 1992, pp. 307-321. 62 Claims, No Drawings US 6,169,208 B1 Page 2 OTHER PUBLICATIONS Chemical Abstract, # 129:317638z, of WO 9846,647, 1998, Vandeberg et al., “Studies in the Tetraarylborates Part III. p. 831. The Preparation and Reagent Properties of Sodium Tetrak Atwood, Jerry L., Coordination Chemistry of Aluminum, is(p-Trifluoromethylphenyl) Borate and Sodium Tetrak Chapter 6, “Anionic and Cationic Organoaluminum Com is(m-Fluorophenyl) Borate', Analytica Chimica Acta, pounds”, 1993, p. 197-232. Elsevier Publishing Company, Amsterdam, 1969, vol. 44, Chemical Abstract, #214696R, Wakabayshi et al., “Pyri pp. 175-183. dinium and Quinolinium Tetraphenylborate Salts as Agro Chemical Abstract, #15921, line G., Vit, Jaroslav, “Preparing chemical and Industrial Microbicides”, Organometallics, Sodium Tetraaylborates, esp. Sodium Tetraphenylborate”, 1989, vol. 111, p. 611. Organometallic Compounds, vol. 64, 1966, col. 15921, 1 page. Wittig et al., “Uber Komplexbildung mit Triphenyl-bor (III. Chemical Abstract, # 124402W, Wakabayashi et al., “Agro Mitt)", Annalen der Chemie, 1951, vol. 573, pp. 195-209. chemical and Industrial Microbicides Containing Tetraphe Coleman et al., “Air-Stable Liquid Clathrates. 1. Crystal nylborates”, 1988, vol. 109, p. 254. Structure of NBuBrand Reactivity of the NBuBr-5 Chemical Abstract, #6607, Line D, Wittig et al., “Complex C.H. Liquid Clathrate”, Journal of Crystallographic and Formation with Triphenylboron. III.'', 1951, vol. 46, 1 page. Spectroscopic Research, vol. 20, No. 2, 1990, pp. 199-201. Chemical Abstract, #85:86471u, Kholkin et al., “Synthesis of Metal Tetraphenylborates by the Exchange Extraction Chem. Abstract, vol. 110, 1989, of JP 63,108,074, 1988, p. Method”, IZV. Sib. Otd. Akad. Nauk., 1976, p. 565. 720, #125211 P. Chemical Abstract, #125: 196680p, of FR 2,727,416, 1996, “Periodic Table of the Elements”, Chem. And Eng. News, p. 20. 1985, pp. 26–27. US 6,169,208 B1 1 2 PROCESS FOR PRODUCING AMAGNESUM organic medium is produced. Each aryl group of the tetrakis DITETRAKIS(ARYL)BORATE AND (aryl)borate has bonded directly to an aromatic ring at least PRODUCTS THEREFROM two fluorine atoms, or at least two perfluorohydrocarbyl groups, or at least one fluorine atom and at least one TECHNICAL FIELD perfluorohydrocarbyl group. The liquid organic medium is comprised of one or more liquid dihydrocarbyl ethers, one This invention relates to a method for making a magne sium ditetrakis(aryl)borate), which can be further reacted or more liquid hydrocarbons, one or more liquid haloge with an organic cation Salt to produce the corresponding nated hydrocarbons, or mixtures thereof. organic cation tetrakis(aryl)borate. When the organic cat The borate anion has four fluorine-containing aryl groups, ion is a protic ammonium cation or a triarylmethyl cation, each of which has bonded directly to an aromatic ring at the tetrakis(aryl)borate salt is useful as a cocatalyst for least two fluorine atoms, or at least two perfluorohydrocar metallocene-catalyzed polymerization. When the organic byl groups, or at least one fluorine atom and at least one cation is an onium cation, the tetrakis(aryl)borate salt is perfluorohydrocarbyl group. It is preferred that at least two useful as an initiator in the crosslinking of polyorganosilox fluorine atoms, or at least two perfluorohydrocarbyl groups 15 are bonded directly to an aromatic ring. Each position on the CS. aromatic ring(s) of the aryl group that is not a fluorine atom BACKGROUND or a perfluorohydrocarbyl group is Substituted by a hydrogen atom, a hydrocarbyl group, an alkoxy group, or a silyl group. It is known that when a halomagnesium Salt of a tetrakis The aryl groups may be the same or different from each (aryl)borate anion is obtained, other magnesium Salts are other; it is preferred that all four aryl groups are the same. usually also present. Often, the removal of these other Another embodiment of this invention is a process which magnesium Salts is necessary because they interfere with the comprises mixing at least a portion of the magnesium intended use of the halomagnesium Salt of the tetrakis(aryl) ditetrakis(aryl)borate produced in the first embodiment in borate anion. Reaction of the halomagnesium tetrakis(aryl) a liquid medium with a Salt Selected from a) a protic borate with an alkali metal Salt to form an alkali metal 25 ammonium salt, b) an onium salt, and c) a triarylmethyl salt, tetrakis(aryl)borate is a separation method that has been wherein the triarylmethyl cation has three aryl groups bound used.