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(12) United States Patent (10) Patent No.: US 7,732,534 B2 Luo Et Al

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(12) United States Patent (10) Patent No.: US 7,732,534 B2 Luo Et Al US007732534B2 (12) United States Patent (10) Patent No.: US 7,732,534 B2 Luo et al. (45) Date of Patent: Jun. 8, 2010 (54) POLYMERS FUNCTIONALIZED WITH 6,172,160 B1 1/2001 Nakamura et al. NITRO COMPOUNDS 6, 194505 B1 2/2001 Sone et al. .................. 524/432 6, 197,888 B1 3/2001 Luo ........................... 525,247 (75) Inventors: Steven Luo, Copley, OH (US); Ryuji Nakagawa, Tokyo (JP) 6.255.416 B1 7/2001 Sone et al. .................. 526,153 6.271,315 B1* 8/2001 Kiessling et al. ......... 525,326.1 (73) Assignee: Bridgestone Corporation (JP) 6,291,591 B1 9/2001 Luo ........................... 525, 191 6,303,692 B1 10/2001 Luo ........................... 525, 191 (*) Notice: Subject to any disclaimer, the term of this 6,699,813 B2 3/2004 Luo et al. ................... 502,119 patent is extended or adjusted under 35 6,759,497 B2 7/2004 Grun et al. U.S.C. 154(b) by 526 days. 6,838,526 B1 1/2005 Sone et al. (21) Appl. No.: 11/710,845 6,897,270 B2 5/2005 Ozawa et al. ................. 526,88 6,977.281 B1* 12/2005 Ozawa et al. ............... 525/377 (22) Filed: Feb. 26, 2007 6,992,147 B1 1/2006 Ozawa et al. ............... 525,342 7,008,899 B2 3/2006 Luo et al. ................... 502,131 Prior Publication Data (65) 7,094,849 B2 8/2006 Luo et al. ................... 526, 164 US 2008/OO51552 A1 Feb. 28, 2008 7,351,776 B2 4/2008 Tartamella et al. Related U.S. Application Data 2004/O147694 A1 7/2004 Sone et al. .................. 526, 164 2006, OOO4131 A1 1/2006 Ozawa et al. ............... 525,342 (63) Continuation-in-part of application No. 1 1/512,037, 2006, OO25539 A1 2/2006 Ozawa et al. ............... 525/377 filed on Aug. 28, 2006. 2006, OO30677 A1 2/2006 Ozawa et al. ............... 525,342 (51) Int. C. 2007/O1497.17 A1 6/2007 Luo et al. CSF 36/00 (2006.01) CSF 8/00 (2006.01) CSF 8/30 (2006.01) COSG 75/00 (2006.01) FOREIGN PATENT DOCUMENTS C08G 59/00 (2006.01) C08G 73/00 (2006.01) DE 138 070 10, 1979 (52) U.S. Cl. ................. 525/331.9; 525/326.1, 525/377; EP O 767 179 4f1997 528/378: 528/405:528/422 EP 0 713885 5, 1998 (58) Field of Classification Search ................. 502/117; EP O 863. 165 9, 1998 525/331.9, 377,326.1, 528/378, 405, 442 EP O 894 825 2, 1999 See application file for complete search history. EP O920886 6, 1999 (56) References Cited U.S. PATENT DOCUMENTS (Continued) 1,223,396 A 4, 1917 Karlsson 2,227,957 A 1/1941 Brasse OTHER PUBLICATIONS 3,297,667 A 1/1967 Von Dohlen et al. ....... 260,82.1 3,541,063 A 11, 1970 Throckmorton et al. .... 260.82.1 “Chemical Modification of Neodymium High cis-1,4-Polybutadiene 3,794,604 A 2, 1974 Throckmorton et al. ..... 252/431 with Styreneoxide” by Hattorietal., J. Elastomers and Plastics, Issue 4,185,042 A 1/1980 Verkouw .................... 525/332 23, 135, 1991. 4,461,883. A 7, 1984 Takeuchi et al. ............ 526,139 4,751.275 A 6, 1988 Witte et al. ................. 526,139 (Continued) 4,791,174 A 12/1988 Bronstert et al. 4,906,706 A 3, 1990 Hattori et al. ... ... 525,343 Primary Examiner Ling-Siu Choi 4,990,573 A 2, 1991 Andreussi et al. ... 525/332.3 Assistant Examiner—Monique Peets 5,064,910 A 11, 1991 Hattori et al. ... ... 525/359.1 (74) Attorney, Agent, or Firm Meredith E. Hooker; Arthur 5,066,729 A 1 1/1991 Stayer et al. ... 525/332 Reginelli 5,109,907 A 5/1992 Stayer et al. ... 152,654 5,227,431 A 7, 1993 Lawson et al. .............. 525/237 5,310,798 A 5/1994 Lawson et al. .............. 525,102 (57) ABSTRACT 5,508,333 A 4, 1996 Shimizu ... 524/424 5,567,784. A 10, 1996 Wieder et al. ............... 526, 164 5,844,050 A 12, 1998 Fukahori et al. ............ 525/351 A method for preparing a functionalized polymer, the method 5,866,171 A 2, 1999 Kata ... 425/46 comprising the steps of (i) polymerizing conjugated diene 5,866,650 A 2, 1999 Lawson et al. .............. 524/572 5,876,527 A 3, 1999 Tsuruta et al. .............. 152/541 monomer by employing a lanthanide-based catalyst to form a 5,916,961 A 6/1999 Hergenrother et al. ...... 524/572 reactive polymer, and (ii) reacting the reactive polymer with 5,931,211 A 8, 1999 Tamura ............ ... 152,209.5 a nitro compound. 5,971,046 A 10, 1999 Koch et al. ... ... 152.152.1 6,117,927 A 9/2000 Toba et al. .................. 524/261 21 Claims, 3 Drawing Sheets US 7,732,534 B2 Page 2 FOREIGN PATENT DOCUMENTS OTHER PUBLICATIONS EP O 957 115 11, 1999 "Functionalization with Styreneoxide” by Hattorietal. Polym. Adv. Techol. Issue 4, 450 1993. EP 1 O99 711 11, 1999 Z. Shen, J. Ouyang, F. Wang, Z. Hu, F.Yu, and B. Qian, Journal of GB 835752 7, 1956 Polymer Science: Polymer Chemistry Edition, 1980, vol. 18, pp. JP 05-051406 A 2, 1993 3345-3357 JP O5-59103. A 9, 1993 H.L. Hsieh, H.C.Yeh, Rubber Chemistry and Technology, 1985, vol. 58, pp. 117-145. JP 10-306113 A 11, 1998 D.J. Wilson, Journal of Polymer Science, Part A. Polymer Chemistry, JP 11-035633 A 9, 1999 1995, vol. 33, pp. 2505-2513. WO 95/04090 9, 1995 R.P. Quirk, A.M. Kells, Poymer International, 2002 vol. 49, pp. WO O1,34659 11, 2000 751-756. WO O2,38615 11, 2000 * cited by examiner U.S. Patent Jun. 8, 2010 Sheet 1 of 3 US 7,732,534 B2 9400),qeTWnauuÁIod I?In3?? (uu 8 eulu) efinef Awo-poo 0997O?79€.0€GZ US 7,732,534 B2 1. 2 POLYMERS FUNCTIONALIZED WITH for two unmodified polymers and three modified polymers NITRO COMPOUNDS prepared in accordance with the present invention. FIG.3 is a graph showingtan 8 (3% strain, 15 Hz, at 50° C.) This application is a continuation-in-part application of as a function of compound Mooney (ML at 130°C.) for U.S. patent application Ser. No. 1 1/512,037, filed on Aug. 28, 5 two unmodified polymers and three modified polymers pre 2006, which is incorporated herein by reference. pared according to the present invention. FIELD OF THE INVENTION DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS One or more embodiments of the present invention relates 10 to functionalized polymers and methods for their manufac According to one or more embodiments of the present ture. invention, conjugated diene monomer can be polymerized with a lanthanide-based catalyst system to form a pseudo BACKGROUND OF THE INVENTION living polymer, and this polymer can then be functionalized 15 by reaction with a nitro compound. The resultant functional Lanthanide-based catalyst systems that comprise a lan ized polymer is characterized by advantageous cold flow thanide compound, an alkylating agent, and a halogen Source resistance, as well as improved processability, and it provides are known to be useful for producing conjugated diene poly rubber Vulcanizates characterized by lower hysteresis as mers having high cis-1,4-linkage contents. The resulting cis compared to those prepared from unmodified polymer. 1,4-polydienes have a linear backbone, which is believed to Examples of conjugated diene monomer include 1,3-buta provide better tensile properties, higher abrasion resistance, diene, isoprene, 1,3-pentadiene, 1.3-hexadiene, 2,3-dim lower hysteresis loss, and better fatigue resistance than those ethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2-methyl-1,3- of analogous polymers prepared with other catalyst systems pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3- Such as titanium-, cobalt-, and nickel-based catalyst systems. pentadiene, and 2.4-hexadiene. Mixtures of two or more Therefore, cis-1,4-polydienes made with lanthanide-based 25 conjugated dienes may also be utilized in copolymerization. catalyst systems are particularly suitable for use in tire com Practice of one or more embodiments of the present inven ponents such as sidewall and tread. tion is not limited by the selection of any particular lan However, due to the linear backbone structure, one disad thanide-based catalyst. In one or more embodiments, the Vantage of cis-1,4-polydienes prepared with lanthanide catalyst composition may include a lanthanide compound, an based catalyst systems is that the polymers exhibit relatively 30 alkylating agent, and a halogen-containing compound that high cold flow, which can cause problems during storage and includes one or more labile halogen atoms. Where the lan transport. The high cold flow also hinders the use of automatic thanide compound and/or alkylating agent include one or feeding equipment in rubber compound mixing facilities. more labile halogen atoms, the catalyst need not include a Another disadvantage of cis-1,4-polydienes prepared with separate halogen-containing compound; e.g., the catalyst lanthanide-based catalyst systems is that they give relatively 35 may simply include a halogenated lanthanide compound and high compound Mooney viscosity, which can adversely an alkylating agent. In certain embodiments, the alkylating affect the processability and scorch safety of the rubber com agent may include both an aluminoxane and at least one other pounds. Furthermore, in the art of making tires, it is desirable organoaluminum compound. In yet other embodiments, a to employ elastomers that give reduced hysteresis. compound containing a non-coordinating anion, or a non Therefore, there is a need to develop a method for produc 40 coordinating anion precursor, i.e.
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