USO08017695B2 (12) United States Patent (10) Patent No.: US 8,017,695 B2 Luo et al. (45) Date of Patent: *Sep. 13, 2011 (54) METHOD FOR PRODUCING 7,294,680 B2 11/2007 Sone et al. A 7,351,776 B2 4/2008 Tartamella et al. FUNCTIONALIZED CIS-1,4-POLYDIENES 7,825,201 B2 * 1 1/2010 Luo et al. ...................... 526,137 HAVING HIGH CIS-14-LINKAGE CONTENT 2005/0197474 A1 9, 2005 Tartamella et al. AND HIGH FUNCTIONALITY 2006/0004131 A1 1/2006 Ozawa et al. 2006, OO25539 A1 2/2006 Ozawa et al. (76) Inventors: Steven Luo, Copley, OH (US); Junko 299;Eg, A. 239; y s al. Kurazumi, Kodaira (JP); YoichiO O Ozawa, 2007/0276122 A1 11/2007 LuoO. ca. Kodaira (JP). Timothy L. Tartamella, 2008/0051552 A1 2/2008 Luo et al. Silver Lake, OH (US); Mark Smale, 2008/O146745 A1 6/2008 Luo et al. Hudson, OH (US); Kevin McCauley, 2009/0292043 A1 11/2009 KuraZumi et al. Coventry Township, OH (US) FOREIGN PATENT DOCUMENTS (*) Notice: Subject to any disclaimer, the term of this EP O713885 A1 5, 1996 patent is extended or adjusted under 35 s 6. Al Lice U.S.C. 154(b) by 388 days. JP 05-051406 A 3, 1993 This patent is Subject to a terminal dis- E. E. A 3. claimer. JP 11-035633 A 2, 1999 WO WO 2006112450 A1 10, 2006 (21)21) Appl. NoNo.: 11/964,8489 OTHER PUBLICATIONS (22) Filed: Dec. 27, 2007 D.J. Wilson, Journal of Polymer Science, Part A. Polymer Chemistry, O O 1995, vol. 33, pp. 2505-2513. (65) Prior Publication Data R. P. Quirk, A. M. Kells, Polymer International, 2000, vol. 49, pp. 751-756. US 2008/O182954 A1 Jul. 31, 2008 U.S. Appl. No. 1 1/890,590, Luo et al., “Process for Producing O O Functionalized Polymers'. Related U.S. Application Data European Official Communication and Extended Search Report. (60) Provisional application No. 60/877,535, filed on Dec. European Search Report, Application No. EP 07255064 dated Jun. 28, 2006. 26, 2009. * cited by examiner (51) Int. Cl. CSF 8/00 (2006.01) Primary Examiner — Fred MTeskin CSF 4/52 (2006.01) (74) Attorney, Agent, or Firm — Meredith E. Hooker; Arthur B6OC5/OO (2006.01) M. Reginelli (52) U.S. Cl. .................. 525/333.1: 525/105:525/332.3; 525/332.8: 525/333.2; 525/137; 525/144; (57) ABSTRACT 58) Field of Classi i. h 64; 525/902; s This invention relates to a method for producing functional (58) Field o as Star 164,525/106 332 3. ized cis-1,4-polydienes having a combination of a high cis 525/332 8 333 333 2, 105 152/450 1.4-linkage content and a high functionality, the resulting • Yls • us - - - polymers and the Vulcanized products containing the poly See application file for complete search history. mers. The functionalized cis-1,4-polydienes of the present (56) References Cited invention are produced by a method comprising the steps of (1) preparing a reactive polymer by polymerizing conjugated U.S. PATENT DOCUMENTS diene monomer with a lanthanide-based catalyst in the pres ence of less than 20% by weight of organic solvent based on 4,906,706 A 3, 1990 Hattori et al. 4,990,573 A 2, 1991 Andreussi et al. the total weight of monomer, organic solvent, and resulting 5,064,910 A 11, 1991 Hattori et al. polymer, where the lanthanide-based catalyst is the combina 5,567,784. A 10, 1996 Wieder et al. tion of or reaction product of (a) a lanthanide compound, (b) 5,844,050 A 12/1998 Fukahori et al. an aluminoxane, (c) an organoaluminum compound other 6,699,813 B2 3, 2004 Luo et al. 6,838,526 B1 1/2005 Sone et al. than an aluminoxane, and (d) a halogen-containing com 6,897,270 B2 5, 2005 Ozawa et al. pound; and (2) contacting the reactive polymer with a func 6,977.281 B1 12/2005 Ozawa et al. tionalizing agent. 6,992,147 B1 1/2006 Ozawa et al. 7,094,849 B2 8, 2006 Luo et al. 39 Claims, No Drawings US 8,017,695 B2 1. 2 METHOD FOR PRODUCING erally have a lower functionality as compared to other func FUNCTIONALIZED CIS-1,4-POLYDIENES tionalized polymers that are produced by anionic polymer HAVING HIGH CIS-14-LINKAGE CONTENT ization methods. AND HIGH FUNCTIONALITY Therefore, there is a need to develop a method for produc ing functionalized cis-1,4-polydienes that have a combina This invention claims the benefit of U.S. Provisional Patent tion of a high cis-1,4-linkage content and a high functionality. Application Ser. No. 60/877,535, filed on Dec. 28, 2006, which is incorporated herein by reference. BRIEF SUMMARY OF THE INVENTION FIELD OF THE INVENTION 10 In one embodiment, the present invention provides a func tionalized cis-1,4-polydiene having a cis-1.4-linkage content This invention relates to methods for producing cis-1,4- of greater than or equal to 95% and a functionality of greater polydienes having a combination of a high cis-1,4-linkage than or equal to 75%, where the functionality is defined as the content and a high percentage of reactive polymerchains. The percentage of polymer chains comprising at least one func 15 tional group versus the total polymer chains in the polymer methods employ a particular lanthanide-based catalyst sys product. tem. The polydienes can be functionalized to produce poly In another embodiment, the present invention provides a mers having a high degree of functionality. Also, certain method for preparing a reactive cis-1,4-polydiene, the lanthanide-based catalyst systems can be employed to pro method comprising the step of polymerizing conjugated duce polymers having a narrow molecular weight distribu diene monomer with a lanthanide-based catalyst in the pres tion. ence of less than about 20% by weight of organic solvent based on the total weight of monomer, organic solvent, and BACKGROUND OF THE INVENTION resulting polymer, where the lanthanide-based catalyst is the combination of or reaction product of (a) a lanthanide com Functionalized polymers can be prepared by anionic poly 25 pound, (b) an aluminoxane, (c) an organoaluminum com merization methods, e.g., by initiating polymerization of 1,3- pound other than an aluminoxane, and (d) a halogen-contain butadiene with a functionalized initiator and/or by reacting a ing compound. living anionic polymer with a functionalizing agent. The In another embodiment, the present invention provides a functionalized polymers made by anionic polymerization method for producing a functionalized cis-1,4-polidiene, the methods can have a high functionality, resulting in polymers 30 method comprising the steps of: (1) preparing a reactive poly that have a greater affinity toward carbon black or silica fillers merby polymerizing conjugated diene monomer with a lan than non-functionalized polymers. Therefore, the rubber Vul thanide-based catalyst in the presence of less than 20% by canizates made from the functionalized polymers give lower weight of organic solvent based on the total weight of mono hysteresis loss than those made from non-functionalized mer, organic solvent, and resulting polymer, where the lan polymers. Unfortunately, Stereoregular polymers such as cis 35 thanide-based catalyst is the combination of or reaction prod uct of (a) a lanthanide compound, (b) an aluminoxane, (c) an 1,4-polydienes, which are often required for the manufacture organoaluminum compound other than an aluminoxane, and of certain tire components, cannot be obtained by anionic (d) a halogen-containing compound; and (2) contacting the polymerization methods because these methods do not pro reactive polymer with a functionalizing agent; wherein the videstrict control over the polymer microstructure such as the 40 resulting functionalized polymer has a cis-1.4-linkage con cis-1.4-linkage content of a polydiene polymer. tent of greater than or equal to about 95% and a functionality Coordination catalysts (also known as Ziegler-Natta cata of greater than or equal to about 75%, where the functionality lysts). Such as lanthanide-based catalysts comprising a lan is defined as the percentage of polymer chains comprising at thanide compound, an alkylating agent, and a halogen-con least one functional group versus the total polymer chains in taining compound, are often highly stereoselective. These 45 the polymer product. catalysts can produce conjugated diene polymers having high In yet another embodiment, the present invention provides cis-1.4-linkage contents. The resulting cis-1,4-polydienes are a functionalized cis-1,4-polydiene produced by a method particularly Suitable for use in tire components such as side comprising the steps of: (1) preparing a reactive polymer by walls and treads. Nevertheless, the use of coordination cata polymerizing conjugated diene monomer with a lanthanide lysts in polymerization limits the ability to functionalize the 50 based catalyst in the presence of less than about 20% by resulting polymers because coordination catalysts operate by weight of organic solvent based on the total weight of mono rather complex chemical mechanisms that involve the inter mer, organic solvent, and resulting polymer, where the lan action among several catalyst components and often involve thanide-based catalyst is the combination of or reaction prod self-termination reactions. As a result, it is difficult to prepare uct of (a) a lanthanide compound, (b) an aluminoxane, (c) an highly functionalized polymers under ordinary conditions by 55 organoaluminum compound other than an aluminoxane, and using coordination catalysts. (d) a halogen-containing compound; and (2) contacting the Cis-1,4-polydienes that are prepared via Solution polymer reactive polymer with a functionalizing agent; wherein the ization processes catalyzed with lanthanide-based catalysts resulting polymer has a cis-1,4-linkage content of greater are known to display some degree of pseudo-living charac than or equal to about 95% and a functionality of greater than teristics, such that Some of the polymer chains possess reac 60 or equal to about 75%, where the functionality is defined as tive chain ends.