USOO8609574B2 (12) United States Patent (10) Patent No.: US 8,609,574 B2 Rhodes et al. (45) Date of Patent: Dec. 17, 2013 (54) INSITU OLEFIN POLYMERIZATION 7,456,329 B2 11/2008 Wu et al. CATALYST SYSTEM 7,459,510 B2 12/2008 Lin et al. 2005/0090383 A1* 4/2005 Thiele et al. .................. 502f152 2006/0287544 A1 12/2006 Amoroso et al. (75) Inventors: Larry F. Rhodes, Silver Lake, OH (US); 2008/0125555 A1 5/2008 Matsunaga et al. Luis Francisco Martin, Zaragoza (ES); Andrew Bell, Lakewood, OH (US) FOREIGN PATENT DOCUMENTS (73) Assignee: Promerus LLC, Brecksville, OH (US) WO 2006.004376 1, 2006 (*) Notice: Subject to any disclaimer, the term of this OTHER PUBLICATIONS patent is extended or adjusted under 35 I.C. Appleby, “The Hazards of M-Trifluoromethyl U.S.C. 154(b) by 287 days. phenylmagnesium Bromide Preparation.” Chemistry & Industry, London, United Kingdom, Issue 4, 1971. (21) Appl. No.: 12/428,936 Yoshiharu Inoue, “Useful Synthetic Routes to Pure exo-5-Vinyl-2- norbornene and endo-5-Vinyl-2-norbornene.” The Chemical Society (22) Filed: Apr. 23, 2009 of Japan, vol. 6, No. 5, 1987. Eric J. Moore, et al., “Metal Fluoride Stability.” Chemical & Engi (65) Prior Publication Data neering News, vol. 75, Issue 11, 1997. Terunobu Maeda, et al., “Rearrangement of 5-Vinyl-2-norbornene to US 2009/027O247 A1 Oct. 29, 2009 3a,4,7,7a-Tetrahydroindene.” Nippon Kagaku Kaishi, No. 8, 1974. Shaw-Tao Lin, et al. “Synthesis of (n^6-Arene)NIR2 and CoR2 O O (R=o-Bound Halosilanes and Haloarenes) by (Aliyl) 2Ni/HR Reac Related U.S. Application Data tions and Combined Metal Trifluoroacetate/Grignard Reagent Meth (60) Provisional application No. 61/047,812, filed on Apr. ods.” Organometallics, vol. 4, 1985. 25, 2008. Daniel L. Reger, et al, Sodium Tetrakis(3,5- s bis(trifluoromethyl)phenyl)borate, NaB(3.5-(CF3)2C6H3)4].” (51) Int. Cl. Inorganic Synthesis, vol. 34, 2004. CSF 4/80 (2006.01) stational Search Report for PCT/US09/41613 Mailed Jun. 11, (52) U.S. Cl. Written Opinion for PCT/US09/41613 Mailed Jun. 11, 2009. USPC ........... 502/152: 502/159; 502/169; 526/171; 526/281; 526/282; 526/284 * cited by examiner (58) Field of Classification Search USPC .......... 502/151, 150, 155; 526/171,281, 282, Primary Examiner — Melvin C Mayes 526,284 Assistant Examiner — Colette Nguyen See application file for complete search history. (74) Attorney, Agent, or Firm — Turocy & Watson, LLP (56) References Cited (57) ABSTRACT U.S. PATENT DOCUMENTS Embodiments in accordance with the present invention encompass methods of forming in situ olefin polymerization 5,362.423 A 11/1994 Ikeda et al. catalyst systems, catalysts encompassed by Such systems and 5,600,004 A * 2/1997 Diefenbach ....................... 568, 1 polymers made using Such systems. For Such in situ olefin 5,891,963 A 4/1999 Brookhart et al. 6,136,499 A 10, 2000 Goodall et al. polymerization catalyst systems, a hydrocarbyl magnesium 6,174.975 B1 1/2001 Johnson et al. halide is generally contacted with a halohydrocarbyl com 6,232,417 B1 5, 2001 Rhodes et al. pound to form a halohydrocarbyl Grignard and Such Grignard 6,455,650 B1* 9/2002 Lipian et al. .................. 526,171 is generally contacted with a Group 10 metal compound to 6,613,915 B1 9, 2003 Johnson et al. form an olefin polymerization catalyst which is contacted 6,660,677 B1 12/2003 Mackenzie et al. 6,825.307 B2 11/2004 Goodall with one or more olefin monomers to form a polymer there 7,022,790 B2 4/2006 Elce et al. from. 7,098,165 B2 * 8/2006 Weiss ............................ 502,150 7,259,214 B2 8, 2007 Bazan et al. 20 Claims, 14 Drawing Sheets U.S. Patent Dec. 17, 2013 Sheet 1 of 14 US 8,609,574 B2 wa-wavelligates saxxxxx ~~)— U.S. Patent Dec. 17, 2013 Sheet 3 of 14 US 8,609.574 B2 o —s . 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U.S. Patent US 8,609,574 B2 U.S. Patent Dec. 17, 2013 US 8,609,574 B2 10000et|0000Zr —0000II -|00000 £ ----|00006 --------+00008 |1–100004 U.S. Patent Dec. 17, 2013 Sheet 14 of 14 US 8,609,574 B2 b3.pueu??us) Old•^AAJ-{}- starriverseverworweviewers...w o 00006 00008 0000). 00009 00009 US 8,609,574 B2 1. 2 INSITU OLEFN POLYMERIZATION BRIEF DESCRIPTION OF THE DRAWINGS CATALYST SYSTEM Embodiments of the invention are described below with reference to the following accompanying drawings. CROSS-REFERENCE TO RELATED FIG. 1 shows a 'F NMR spectrum of (m-toluene)Ni APPLICATIONS (CFS) in a mixture of toluene and thfas described in Com parative Example 1. This application claims the benefit of priority to Provi FIG. 2 shows a 'F NMR spectrum of (m-toluene)Ni sional Application Ser. No. 61/047,812 filedon Apr. 25, 2008, (CFS) in the same solvent mixture as Catalyst Example 1 which is incorporated herein by reference. 10 (cyclohexane/EtOAc/thf) as described in Comparative Example 2. TECHNICAL FIELD FIG.3 shows a 'F NMR spectrum of the Group 10 metal catalyst of Catalyst Example 1. FIG. 4 depicts a 'F NMR spectrum of a Group 10 metal Described herein are Group 10 metal containing cycloole 15 catalyst made in the manner of Catalyst Example 2. fin polymerization catalysts, methods of making the polymer FIG. 5 depicts a 'F NMR spectrum of a Group 10 metal ization catalysts, and methods of polymerizing cycloolefins catalyst made in the manner of Catalyst Example 3. using the polymerization catalysts. FIG. 6 shows a 'F NMR spectrum of a Group 10 catalyst made in the manner of Catalyst Example 4. BACKGROUND FIG. 7 shows a 'F NMR spectrum of a Group 10 catalyst made in the manner of Catalyst Example 5. Cycloolefin polymers such as norbornene polymers are FIG. 8 shows a drawing of a molecular structure for Ni valuable as insulating materials in the electronics field due to catalyst isolated from the Group 10 metal catalyst of Catalyst excellent dielectric properties and low water absorption prop 25 Example 6. erties. Of the cycloolefin polymers, cycloolefin addition poly FIG.9 depicts a 'F NMR spectrum of a Group 10 metal catalyst made in the manner of Catalyst Example 6. mers typified by norbornene addition polymers are generally FIG. 10 shows a drawing of a molecular structure for Suitable for use as various kinds of moldings, sealing mate inactive Nispecies isolated from the Group 10 metal catalyst rials for electronic parts, and insulating materials, owing to 30 of Catalyst Example 7. various properties such as low moisture-absorption and FIG. 11 depicts a 'F NMR spectrum of an inactive Ni excellent dielectric properties. species isolated from the Group 10 metal catalyst of Catalyst Cycloolefin polymers in general and norbornene-type Example 7. polymers in particular can be made using nickel catalysts. For FIG. 12 depicts a 'F NMR spectrum of a Group 10 metal example, U.S. Pat. No. 6,136,499 describes the use of E.Ni 35 catalyst made in the manner of Catalyst Example 8. (C.F.) (where n=1 or 2 and where E is a neutral electron FIG. 13 is a graph showing the effect of equivalents of donor ligand). Where E is toluene, such catalyst is made by halohydrocarbyl Grignard versus Mw and yield for a result the reaction of suitable starting materials such nickel(II) tri ant copolymer in the manner of Synthesis Example 5. fluoroacetate and CFMgBr (Brezinski and Klabunde in FIG. 14 is a graph showing the effect of equivalents of Organometallics, 1983, 2, 1116). Such nickel catalysts are 40 halohydrocarbyl Grignard versus Mw and PD for a resultant made using fluorinated aryl Grignard reagents. copolymer in the manner of Synthesis Example 5. However, handling of fluorinated Grignard reagents raises DETAILED DESCRIPTION safety concerns. There have been reports of explosions asso ciated with fluorinated aryl magnesium halides (See, a) 45 The in situ olefin polymerization catalyst system in accor Appleby, Chem.