(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

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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. a compound that can ing lanthanide-catalyzed cis-1,4-polydienes that give undergo a chemical reaction to form a non-coordinating reduced cold flow, improved processability, and reduced hys anion, may be employed in lieu of a halogen-containing com teresis. pound. In one embodiment, where the alkylating agent includes an organoaluminum hydride compound, the halo SUMMARY OF THE INVENTION 45 gen-containing compound may be a tinhalideas disclosed in U.S. Pat. No. 7,008,899, which is incorporated herein by In one or more embodiments, the present invention reference. In these or other embodiments, other organome includes a method for preparing a functionalized polymer, the tallic compounds, Lewis bases, and/or catalyst modifiers, method comprising the steps of (i) polymerizing conjugated may be employed in addition to the ingredients or compo diene monomer by employing a lanthanide-based catalyst to 50 nents set forth above. For example, in one embodiment, a form a reactive polymer, and (ii) reacting the reactive polymer nickel-containing compound may be employed as a molecu with a nitro compound. lar weight regulator as disclosed in U.S. Pat. No. 6,699,813, In one or more embodiments, the present invention further which is incorporated herein by reference. includes a functionalized polymer prepared by a method Various lanthanide compounds or mixtures thereof can be comprising the steps of (i) polymerizing conjugated diene 55 employed. In one or more embodiments, these compounds monomer by employing a lanthanide-based catalyst to form a may be soluble in hydrocarbon Solvents such as aromatic reactive polymer, and (ii) reacting the reactive polymer with hydrocarbons, aliphatic hydrocarbons, or cycloaliphatic a nitro compound. hydrocarbons. In other embodiments, hydrocarbon-insoluble lanthanide compounds, which can be suspended in the poly BRIEF DESCRIPTION OF THE DRAWINGS 60 merization medium to form the catalytically active species, are also useful. FIG. 1 is a graph showing cold-flow gauge (mm) as a Lanthanide compounds may include at least one atom of function of polymer Mooney (ML at 100° C.) for two lanthanum, neodymium, cerium, praseodymium, prome unmodified polymers and three modified polymers prepared thium, Samarium, europium, gadolinium, terbium, dyspro in accordance with the present invention. 65 sium, holmium, erbium, thulium, ytterbium, lutetium, and FIG. 2 is a graph showing compound Mooney (ML at didymium. Didymium may include a commercial mixture of 130°C.) as a function of polymer Mooney (ML at 100° C.) rare-earth elements obtained from monazite sand. US 7,732,534 B2 3 4 The lanthanide atom in the lanthanide compounds can be in neodymium octadecylphosphinate, neodymium oleylphos various oxidation states including but not limited to the 0, +2, phinate, neodymium phenylphosphinate, neodymium +3, and +4 oxidation states. Lanthanide compounds include, (p-nonylphenyl)phosphinate, neodymium dibutylphosphi but are not limited to, lanthanide carboxylates, lanthanide nate, neodymium dipentylphosphinate, neodymium dihexy organophosphates, lanthanide organophosphonates, lan lphosphinate, neodymium diheptylphosphinate, neodymium thanide organophosphinates, lanthanide carbamates, lan dioctylphosphinate, neodymium bis(1-methylheptyl)phos thanide dithiocarbamates, lanthanide Xanthates, lanthanide phinate, neodymium bis(2-ethylhexyl)phosphinate, neody 3-diketonates, lanthanidealkoxides oraryloxides, lanthanide mium didecylphosphinate, neodymium didodecylphosphi halides, lanthanide pseudo-halides, lanthanide oxyhalides, nate, neodymium dioctadecylphosphinate, neodymium and organolanthanide compounds. 10 dioleylphosphinate, neodymium diphenylphosphinate, Without wishing to limit the practice of the present inven neodymium bis(p-nonylphenyl)phosphinate, neodymium tion, further discussion will focus on neodymium com butyl(2-ethylhexyl)phosphinate, neodymium (1-methylhep pounds, although those skilled in the art will be able to select tyl) (2-ethylhexyl)phosphinate, and neodymium (2-ethyl similar compounds that are based upon other lanthanide met hexyl) (p-nonylphenyl)phosphinate. als. 15 Neodymium carbamates include neodymium dimethylcar Neodymium carboxylates include neodymium formate, bamate, neodymium diethylcarbamate, neodymium diiso neodymium acetate, neodymium acrylate, neodymium meth propylcarbamate, neodymium dibutylcarbamate, and neody acrylate, neodymium Valerate, neodymium gluconate, mium dibenzylcarbamate. neodymium citrate, neodymium fumarate, neodymium lac Neodymium dithiocarbamates include neodymium dim tate, neodymium maleate, neodymium oxalate, neodymium ethyldithiocarbamate, neodymium diethyldithiocarbamate, 2-ethylhexanoate, neodymium neodecanoate (a.k.a. neody neodymium diisopropyldithiocarbamate, neodymium dibu mium versatate), neodymium naphthenate, neodymium tyldithiocarbamate, and neodymium dibenzyldithiocarbam Stearate, neodymium oleate, neodymium benzoate, and ate. neodymium picolinate. Neodymium Xanthates include neodynium methylxan Neodymium organophosphates include neodymium dibu 25 thate, neodymium ethylxanthate, neodymium isopropylxan tyl phosphate, neodymium dipentyl phosphate, neodymium thate, neodymium butylxanthate, and neodymium benzylx dihexyl phosphate, neodymium diheptyl phosphate, neody anthate. mium dioctyl phosphate, neodymium bis(1-methylheptyl) Neodymium B-diketonates include neodymium acetylac phosphate, neodymium bis(2-ethylhexyl) phosphate, neody etonate, neodymium trifluoroacetylacetonate, neodymium mium didecyl phosphate, neodymium didodecyl phosphate, 30 hexafluoroacetylacetonate, neodynium benzoylacetonate, neodymium dioctadecyl phosphate, neodymium dioleyl and neodymium 2.2.6,6-tetramethyl-3,5-heptanedionate. phosphate, neodymium diphenyl phosphate, neodymium bis Neodymium alkoxides or aryloxides include neodymium (p-nonylphenyl) phosphate, neodymium butyl (2-ethylhexyl) methoxide, neodymium ethoxide, neodymium isopropoxide, phosphate, neodymium (1-methylheptyl) (2-ethylhexyl) neodymium 2-ethylhexoxide, neodymium phenoxide, phosphate, and neodymium (2-ethylhexyl) (p-nonylphenyl) 35 neodymium nonylphenoxide, and neodymium naphthoxide. phosphate. Neodymium halides include neodymium fluoride, neody Neodymium organophosphonates include neodymium mium chloride, neodymium bromide, and neodymium butyl phosphonate, neodymium pentyl phosphonate, neody iodide. Suitable neodymium pseudo-halides include neody mium hexyl phosphonate, neodymium heptyl phosphonate, mium cyanide, neodymium cyanate, neodymium thiocyan neodymium octyl phosphonate, neodymium (1-methylhep 40 ate, neodymium azide, and neodymium ferrocyanide. Suit tyl) phosphonate, neodymium (2-ethylhexyl) phosphonate, able neodymium oxyhalides include neodymium neodymium decyl phosphonate, neodymium dodecyl phos oxyfluoride, neodymium oxychloride, and neodymium oxy phonate, neodymium octadecyl phosphonate, neodymium bromide. Where neodymium halides, neodymium oxyha oleyl phosphonate, neodymium phenyl phosphonate, neody lides, or other neodymium compounds containing labile halo mium (p-nonylphenyl) phosphonate, neodymium butyl 45 gen atoms are employed, the neodymium-containing butylphosphonate, neodymium pentyl pentylphosphonate, compound can also serve as the halogen-containing com neodymium hexyl hexylphosphonate, neodymium heptyl pound. A Lewis base such as tetrahydrofuran (THF) may be heptylphosphonate, neodymium octyl octylphosphonate, employed as an aid for solubilizing this class of neodymium neodymium (1-methylheptyl) (1-methylheptyl)phosphonate, compounds in inert organic solvents. neodymium (2-ethylhexyl) (2-ethylhexyl)phosphonate, 50 The term organolanthanide compound may refer to any neodymium decyl decylphosphonate, neodymium dodecyl lanthanide compound containing at least one lanthanide-car dodecylphosphonate, neodymium octadecyl octadecylphos bon bond. These compounds are predominantly, though not phonate, neodymium oleyl oleylphosphonate, neodymium exclusively, those containing cyclopentadienyl (Cp), Substi phenyl phenylphosphonate, neodymium (p-nonylphenyl) tuted cyclopentadienyl, allyl, and Substituted allyl ligands. (p-nonylphenyl)phosphonate, neodymium butyl (2-ethyl 55 Suitable organolanthanide compounds include Cp Ln, hexyl)phosphonate, neodymium (2-ethylhexyl) butylphos Cp LinR, Cpl.nCl, Cpl.nCl, Cpl n(cyclooctatetraene), phonate, neodymium (1-methylheptyl) (2-ethylhexyl)phos (C5Me5)LinR, LinRs, Ln(allyl), and Ln(allyl)C1, where Ln phonate, neodymium (2-ethylhexyl) (1-methylheptyl) represents a lanthanide atom, and R represents a hydrocarbyl phosphonate, neodymium (2-ethylhexyl) (p-nonylphenyl) group. phosphonate, and neodymium (p-nonylphenyl) 60 Various alkylating agents, or mixtures thereof, can be used. (2-ethylhexyl)phosphonate. Alkylating agents, which may also be referred to as hydro Neodymium organophosphinates include neodymium carbylating agents, include organometallic compounds that butylphosphinate, neodymium pentylphosphinate, neody can transfer hydrocarbyl groups to another metal. Typically, mium hexylphosphinate, neodymium heptylphosphinate, these agents include organometallic compounds of electrop neodymium octylphosphinate, neodymium (1-methylheptyl) 65 ositive metals such as Groups 1, 2, and 3 metals (Groups IA, phosphinate, neodymium (2-ethylhexyl)phosphinate, neody IIA, and IIIA metals). In one or more embodiments, alkylat mium decylphosphinate, neodymium dodecylphosphinate, ing agents include organoaluminum and organomagnesium US 7,732,534 B2 5 6 compounds. Where the alkylating agent includes a labile chloride, dibenzylaluminum chloride, phenylethylaluminum halogen atom, the alkylating agent may also serve as the chloride, phenyl-n-propylaluminum chloride, phenylisopro halogen-containing compound. pylaluminum chloride, phenyl-n-butylaluminum chloride, The term “organoaluminum compound may refer to any phenylisobutylaluminum chloride, phenyl-n-octylaluminum aluminum compound containing at least one aluminum-car chloride, p-tolylethylaluminum chloride, p-tolyl-n-propyla bon bond. In one or more embodiments, organoaluminum luminum chloride, p-tolylisopropylaluminum chloride, compounds may be soluble in a hydrocarbon solvent. p-tolyl-n-butylaluminum chloride, p-tolylisobutylaluminum In one or more embodiments, organoaluminum com chloride, p-tolyl-n-octylaluminum chloride, benzylethylalu pounds include those represented by the formula AlRX, minum chloride, benzyl-n-propylaluminum chloride, benzyl where each R, which may be the same or different, is a 10 isopropylaluminum chloride, benzyl-n-butylaluminum chlo mono-valent organic group that is attached to the aluminum ride, benzylisobutylaluminum chloride, and benzyl-n- atom via a carbon atom, where each X, which may be the octylaluminum chloride. same or different, is a hydrogen atom, a halogen atom, a Hydrocarbylaluminum dichloride include ethylaluminum carboxylate group, an alkoxide group, or an aryloxide group, dichloride, n-propylaluminum dichloride, isopropylalumi and where n is an integer of 1 to 3. In one or more embodi 15 num dichloride, n-butylaluminum dichloride, isobutylalumi ments, each R may be a hydrocarbyl group Such as, but not num dichloride, and n-octylaluminum dichloride. limited to, alkyl, cycloalkyl, Substituted cycloalkyl, alkenyl, Other organoaluminum compounds include dimethylalu cycloalkenyl, Substituted cycloalkenyl, aryl, Substituted aryl, minum hexanoate, diethylaluminum octoate, diisobutylalu aralkyl, alkaryl, allyl, and alkynyl groups. These hydrocarbyl minum 2-ethylhexanoate, dimethylaluminum neodecanoate, groups may contain heteroatoms such as, but not limited to, diethylaluminum Stearate, diisobutylaluminum oleate, nitrogen, oxygen, boron, silicon, Sulfur, and phosphorus methylaluminum bis(hexanoate), ethylaluminum bis(oc atOmS. toate), isobutylaluminum bis(2-ethylhexanoate), methylalu Organoaluminum compounds include, but are not limited minum bis(neodecanoate), ethylaluminum bis(Stearate), to, trihydrocarbylaluminum, dihydrocarbylaluminum isobutylaluminum bis(oleate), dimethylaluminum methox hydride, hydrocarbylaluminum dihydride, dihydrocarbylalu 25 ide, diethylaluminum methoxide, diisobutylaluminum meth minum carboxylate, hydrocarbylaluminum bis(carboxylate), oxide, dimethylaluminum ethoxide, diethylaluminum ethox dihydrocarbylaluminum alkoxide, hydrocarbylaluminum ide, diisobutylaluminum ethoxide, dimethylaluminum dialkoxide, dihydrocarbylaluminum halide, hydrocarbylalu phenoxide, diethylaluminum phenoxide, diisobutylalumi minum dihalide, dihydrocarbylaluminum aryloxide, and num phenoxide, methylaluminum dimethoxide, ethylalumi hydrocarbylaluminum diaryloxide compounds. 30 num dimethoxide, isobutylaluminum dimethoxide, methyla Trihydrocarbylaluminum compounds include trimethyla luminum diethoxide, ethylaluminum diethoxide, luminum, triethylaluminum, triisobutylaluminum, tri-n-pro isobutylaluminum diethoxide, methylaluminum diphenox pylaluminum, triisopropylaluminum, tri-n-butylaluminum, ide, ethylaluminum diphenoxide, isobutylaluminum diphe tri-t-butylaluminum, tri-n-pentylaluminum, trineopentylalu noxide, and the like, and mixtures thereof. minum, tri-n-hexylaluminum, tri-n-octylaluminum, tris(2- 35 Another class of organoaluminum compounds includes ethylhexyl)aluminum, tricyclohexylaluminum, tris(1-meth aluminoxanes. Aluminoxanes include oligomeric linear alu ylcyclopentyl)aluminum, triphenylaluminum, tri-p- minoxanes that can be represented by the general formula: tolylaluminum, tris(2,6-dimethylphenyl)aluminum, tribenzylaluminum, diethylphenylaluminum, diethyl-p-toly laluminum, diethylbenzylaluminum, ethyldiphenylalumi 40 R1 R1 num, ethyldi-p-tolylaluminum, and ethyldibenzylaluminum. Dihydrocarbylaluminum hydride compounds include Al-o-Al-o- diethylaluminum hydride, di-n-propylaluminum hydride, RI R1 R diisopropylaluminum hydride, di-n-butylaluminum hydride, disobutylaluminum hydride, di-n-octylaluminum hydride, 45 diphenylaluminum hydride, di-p-tolylaluminum hydride, and oligomeric cyclic aluminoxanes that can be represented dibenzylaluminum hydride, phenylethylaluminum hydride, by the general formula: phenyl-n-propylaluminum hydride, phenylisopropylalumi num hydride, phenyl-n-butylaluminum hydride, phenyl isobutylaluminum hydride, phenyl-n-octylaluminum 50 hydride, p-tolylethylaluminum hydride, p-tolyl-n-propylalu minum hydride, p-tolylisopropylaluminum hydride, p-tolyl ... .y n-butylaluminum hydride, p-tolylisobutylaluminum hydride, RI p-tolyl-n-octylaluminum hydride, benzylethylaluminum hydride, benzyl-n-propylaluminum hydride, benzylisopro 55 pylaluminum hydride, benzyl-n-butylaluminum hydride, where X may be an integer of 1 to about 100, and in other benzylisobutylaluminum hydride, and benzyl-n-octylalumi embodiments about 10 to about 50: y may be an integer of 2 num hydride. to about 100, and in other embodiments about 3 to about 20: Hydrocarbylaluminum dihydrides include ethylaluminum and where each R', which may be the same or different, may dihydride, n-propylaluminum dihydride, isopropylaluminum 60 be a mono-valent organic group that is attached to the alumi dihydride, n-butylaluminum dihydride, isobutylaluminum num atom via a carbon atom. In one or more embodiments, dihydride, and n-octylaluminum dihydride. each R' is a hydrocarbyl group such as, but not limited to, Dihydrocarbylaluminum chloride compounds include alkyl, cycloalkyl, Substituted cycloalkyl, alkenyl, cycloalk diethylaluminum chloride, di-n-propylaluminum chloride, enyl, Substituted cycloalkenyl, aryl, Substituted aryl, aralkyl, diisopropylaluminum chloride, di-n-butylaluminum chlo 65 alkaryl, allyl, and alkynyl groups. These hydrocarbyl groups ride, diisobutylaluminum chloride, di-n-octylaluminum may contain heteroatoms such as, but not limited to, nitrogen, chloride, diphenylaluminum chloride, di-p-tolylaluminum oxygen, boron, silicon, Sulfur, and phosphorus atoms. It US 7,732,534 B2 7 8 should be noted that the number of moles of the aluminoxane aryl, allyl, Substituted aryl, aralkyl, alkaryl, and alkynyl as used in this application refers to the number of moles of the groups. These hydrocarbyl groups may contain heteroatoms aluminum atoms rather than the number of moles of the Such as, but not limited to, nitrogen, oxygen, boron, silicon, oligomeric aluminoxane molecules. This convention is com Sulfur, and phosphorus atoms. In one or more embodiments, monly employed in the art of catalysis utilizing aluminox X is a carboxylate group, an alkoxide group, or an aryloxide aS. group. Aluminoxanes can be prepared by reacting trihydrocarby Exemplary types of organomagnesium compounds that laluminum compounds with water. This reaction can be per can be represented by the formula RMgX include, but are not formed according to known methods, such as (1) a method in limited to, hydrocarbylmagnesium hydride, hydrocarbyl which the trihydrocarbylaluminum compound may be dis 10 magnesium halide, hydrocarbylmagnesium carboxylate, Solved in an organic solvent and then contacted with water, hydrocarbylmagnesium alkoxide, hydrocarbylmagnesium (2) a method in which the trihydrocarbylaluminum com aryloxide, and mixtures thereof. pound may be reacted with water of crystallization contained Specific examples of organomagnesium compounds that in, for example, metal salts, or water adsorbed in inorganic or may be represented by the formula RMgX include methyl organic compounds, and (3) a method in which the trihydro 15 magnesium hydride, ethylmagnesium hydride, butylmagne carbylaluminum compound may be reacted with water in the sium hydride, hexylmagnesium hydride, phenylmagnesium presence of the monomer or monomer Solution that is to be hydride, benzylmagnesium hydride, methylmagnesium chlo polymerized. ride, ethylmagnesium chloride, butylmagnesium chloride, Aluminoxane compounds include methylaluminoxane hexylmagnesium chloride, phenylmagnesium chloride, ben (MAO), modified methylaluminoxane (MMAO), ethylalumi Zylmagnesium chloride, methylmagnesium bromide, ethyl noxane, n-propylaluminoxane, isopropylaluminoxane, buty magnesium bromide, butylmagnesium bromide, hexylmag laluminoxane, isobutylaluminoxane, n-pentylaluminoxane, nesium bromide, phenylmagnesium bromide, neopentylaluminoxane, n-hexylaluminoxane, n-octylalumi benzylmagnesium bromide, methylmagnesium hexanoate, noxane, 2-ethylhexylaluminoxane, cyclohexylaluminoxane, ethylmagnesium hexanoate, butylmagnesium hexanoate, 1-methylcyclopentylaluminoxane, phenylaluminoxane, 2.6- 25 hexylmagnesium hexanoate, phenylmagnesium hexanoate, dimethylphenylaluminoxane, and the like, and mixtures benzylmagnesium hexanoate, methylmagnesium ethoxide, thereof. Modified methylaluminoxane can be formed by sub ethylmagnesium ethoxide, butylmagnesium ethoxide, hexy stituting about 20-80% of the methyl groups of methylalumi lmagnesium ethoxide, phenylmagnesium ethoxide, benzyl noxane with C to C2 hydrocarbyl groups, preferably with magnesium ethoxide, methylmagnesium phenoxide, ethyl isobutyl groups, by using techniques knownto those skilled in 30 magnesium phenoxide, butylmagnesium phenoxide, the art. hexylmagnesium phenoxide, phenylmagnesium phenoxide, Aluminoxanes can be used alone or in combination with benzylmagnesium phenoxide, and the like, and mixtures other organoaluminum compounds. In one embodiment, thereof. methyl aluminoxane and at least one other organoaluminum Various halogen-containing compounds, or mixtures compound (e.g., AlRX) such as diisobutylaluminum 35 thereof, that contain one or more labile halogenatoms can be hydride are employed in combination. employed. Examples of halogen atoms include, but are not The term organomagnesium compound may refer to any limited to, fluorine, chlorine, bromine, and iodine. A combi magnesium compound that contains at least one magnesium nation of two or more halogen-containing compounds having carbon bond. Organomagnesium compounds may be soluble different halogen atoms can also be utilized. In one or more in a hydrocarbon Solvent. One class of organomagnesium 40 embodiments, the halogen-containing compounds may be compounds that can be utilized may be represented by the soluble in a hydrocarbon solvent. In other embodiments, formula MgR, where each R, which may be the same or hydrocarbon-insoluble halogen-containing compounds, different, is a mono-valent organic group, with the proviso which can be suspended in the polymerization medium to that the group is attached to the magnesium atom via a carbon form the catalytically active species, may be useful. atom. In one or more embodiments, each R may be a hydro 45 Suitable types of halogen-containing compounds include, carbyl group, and the resulting organomagnesium com but are not limited to, elemental halogens, mixed halogens, pounds are dihydrocarbylmagnesium compounds. Examples hydrogen halides, organic halides, inorganic halides, metallic of the hydrocarbyl groups include, but are not limited to, halides, organometallic halides, and mixtures thereof. alkyl, cycloalkyl, Substituted cycloalkyl, alkenyl, cycloalk Elemental halogens include fluorine, chlorine, bromine, enyl, Substituted cycloalkenyl, aryl, allyl, Substituted aryl, 50 and iodine. Mixed halogens include iodine monochloride, aralkyl, alkaryl, and alkynyl groups. These hydrocarbyl iodine monobromide, iodine trichloride, and iodine pen groups may contain heteroatoms such as, but are not limited tafluoride. to, nitrogen, oxygen, silicon, Sulfur, and phosphorus atom. Hydrogen halides include hydrogen fluoride, hydrogen Examples of Suitable dihydrocarbylmagnesium com chloride, hydrogen bromide, and hydrogen iodide. pounds include diethylmagnesium, di-n-propylmagnesium, 55 Organic halides include t-butyl chloride, t-butyl bromides, diisopropylmagnesium, dibutylmagnesium, dihexylmagne allyl chloride, allyl bromide, benzyl chloride, benzyl bro sium, diphenylmagnesium, dibenzylmagnesium, and mix mide, chloro-di-phenylmethane, bromo-di-phenylmethane, tures thereof. triphenylmethyl chloride, triphenylmethyl bromide, ben Another class of organomagnesium compounds that can be Zylidene chloride, benzylidene bromide, methyltrichlorosi utilized include those that may be represented by the formula 60 lane, phenyltrichlorosilane, dimethyldichlorosilane, diphe RMgX, where R is a mono-valent organic group, with the nyldichlorosilane, trimethylchlorosilane, benzoyl chloride, proviso that the group is attached to the magnesium atom via benzoyl bromide, propionyl chloride, propionyl bromide, a carbon atom, and X is a hydrogen atom, a halogen atom, a methyl chloroformate, and methyl bromoformate. carboxylate group, an alkoxide group, or an aryloxide group. Inorganic halides include phosphorus trichloride, phos In one or more embodiments, R may be a hydrocarbyl group 65 phorus tribromide, phosphorus pentachloride, phosphorus Such as, but not limited to, alkyl, cycloalkyl, Substituted oxychloride, phosphorus oxybromide, boron trifluoride, cycloalkyl, alkenyl, cycloalkenyl, Substituted cycloalkenyl, borontrichloride, borontribromide, silicon tetrafluoride, sili US 7,732,534 B2 10 con tetrachloride, silicon tetrabromide, silicon tetraiodide, In those embodiments where both an aluminoxane and at arsenic trichloride, arsenic tribromide, arsenic triiodide, sele least one other organoaluminum agent are employed as alky nium tetrachloride, selenium tetrabromide, tellurium tetra lating agents, the molar ratio of the aluminoxane to the lan chloride, tellurium tetrabromide, and tellurium tetraiodide. thanide compound (aluminoxane/Ln) can be varied from Metallic halides include tintetrachloride, tintetrabromide, about 5:1 to about 1,000:1, in other embodiments from about aluminum trichloride, aluminum tribromide, antimony 10:1 to about 700:1, and in other embodiments from about trichloride, antimony pentachloride, antimony tribromide, 20:1 to about 500:1; and the molar ratio of the at least one aluminum triiodide, aluminum trifluoride, gallium trichlo other organoaluminum compound to the lanthanide com ride, gallium tribromide, gallium triiodide, gallium trifluo pound (Al/Ln) can be varied from about 1:1 to about 200:1, in ride, indium trichloride, indium tribromide, indium triiodide, 10 other embodiments from about 2:1 to about 150:1, and in indium trifluoride, titanium tetrachloride, titanium tetrabro other embodiments from about 5:1 to about 100:1. mide, titanium tetraiodide, Zinc dichloride, Zinc dibromide, The molar ratio of the halogen-containing compound to the Zinc diiodide, and zinc difluoride. lanthanide compound is best described in terms of the ratio of Organometallic halides include dimethylaluminum chlo the moles of halogen atoms in the halogen-containing com ride, diethylaluminum chloride, dimethylaluminum bromide, 15 pound to the moles of lanthanide atoms in the lanthanide diethylaluminum bromide, dimethylaluminum fluoride, compound (halogen/Ln). In one or more embodiments, the diethylaluminum fluoride, methylaluminum dichloride, ethy halogen/Ln molar ratio can be varied from about 0.5:1 to laluminum dichloride, methylaluminum dibromide, ethylalu about 20:1, in other embodiments from about 1:1 to about minum dibromide, methylaluminum difluoride, ethylalumi 10:1, and in other embodiments from about 2:1 to about 6:1. num difluoride, methylaluminum sesquichloride, In yet another embodiment, the molar ratio of the non ethylaluminum sesquichloride, isobutylaluminum ses coordinating anion or non-coordinating anion precursor to quichloride, methylmagnesium chloride, methylmagnesium the lanthanide compound (An/Ln) may be from about 0.5:1 to bromide, methylmagnesium iodide, ethylmagnesium chlo about 20:1, in other embodiments from about 0.75:1 to about ride, ethylmagnesium bromide, butylmagnesium chloride, 10:1, and in other embodiments from about 1:1 to about 6:1. butylmagnesium bromide, phenylmagnesium chloride, phe 25 The catalyst composition may be formed by combining or nylmagnesium bromide, benzylmagnesium chloride, trim mixing the catalyst ingredients. Although an active catalyst ethyltin chloride, trimethyltin bromide, triethyltin chloride, species is believed to result from this combination, the degree triethyltin bromide, di-t-butyltin dichloride, di-t-butyltin of interaction or reaction between the various ingredients or dibromide, dibutyltin dichloride, dibutyltin dibromide, tribu components is not known with any great degree of certainty. tyltin chloride, and tributyltin bromide. 30 Therefore, the term “catalyst composition' has been Compounds containing non-coordinating anions are employed to encompass a simple mixture of the ingredients, known in the art. In general, non-coordinating anions are a complex of the various ingredients that is caused by physi sterically bulky anions that do not form coordinate bonds cal or chemical forces of attraction, a chemical reaction prod with, for example, the active center of a catalyst System, due uct of the ingredients, or a combination of the foregoing. to steric hindrance. Exemplary non-coordinating anions 35 The catalyst composition of this invention can be formed include tetraarylborate anions, and fluorinated tetraarylborate by various methods. anions. Compounds containing a non-coordinating anion also In one embodiment, the catalyst composition may be contain a counter cation Such as a carbonium, ammonium, or formed in situ by adding the catalyst ingredients to a solution phosphonium cation. Exemplary counter cations include tri containing monomerand solvent, or simply bulk monomer, in arylcarbonium cations and N,N-dialkylanilinium cations. 40 either a stepwise or simultaneous manner. In one embodi Examples of compounds containing a non-coordinating ment, the alkylating agent can be added first, followed by the anion and a counter cation include triphenylcarbonium tet lanthanide compound, and then followed by the halogen rakis(pentafluorophenyl)borate, N,N-dimethylanilinium tet containing compound, if used, or by the compound contain rakis(pentafluorophenyl)borate, triphenylcarbonium tetrakis ing a non-coordinating anion or the non-coordinating anion 45 precursor. 3,5-bis(trifluoromethyl)phenylborate, and N,N- In another embodiment, the catalyst ingredients may be dimethylanilinium tetrakis3.5-bis(trifluoromethyl)phenyl pre-mixed outside the polymerization system at an appropri borate. ate temperature, which may be from about -20°C. to about Non-coordinating anion precursors include compounds 80°C., and the resulting catalyst composition may be aged for that can form a non-coordinating anion under reaction con 50 a period of time ranging from a few minutes to a few days and ditions. Exemplary non-coordinating anion precursors then added to the monomer Solution. include triarylboron compounds, BR, where R is a strong In yet another embodiment, the catalyst composition may electron-withdrawing aryl group Such as a pentafluorophenyl be pre-formed in the presence of at least one conjugated diene or 3.5-bis(trifluoromethyl)phenyl group. monomer. That is, the catalyst ingredients may be pre-mixed The foregoing catalyst compositions may have high cata 55 in the presence of a small amount of conjugated diene mono lytic activity for polymerizing conjugated dienes into Ste meratan appropriate temperature, which may be from about reospecific polydienes over a wide range of catalyst concen -20° C. to about 80° C. The amount of conjugated diene trations and catalyst ingredient ratios. It is believed that the monomer that may be used for pre-forming the catalyst can catalyst ingredients may interact to form an active catalyst range from about 1 to about 500 moles per mole, in other species. It is also believed that the optimum concentration for 60 embodiments from about 5 to about 250 moles per mole, and any one catalyst ingredient may be dependent upon the con in other embodiments from about 10 to about 100 moles per centrations of the other catalyst ingredients. mole of the lanthanide compound. The resulting catalyst In one or more embodiments, the molar ratio of the alky composition may be aged for a period of time ranging from a lating agent to the lanthanide compound (alkylating agent/ few minutes to a few days and then added to the remainder of Ln) can be varied from about 1:1 to about 1,000:1, in other 65 the conjugated diene monomer that is to be polymerized. embodiments from about 2:1 to about 500:1, and in other And in yet another embodiment, the catalyst composition embodiments from about 5:1 to about 200:1. may beformed by using a two-stage procedure. The first stage US 7,732,534 B2 11 12 may involve combining the alkylating agent with the lan in preparing the catalyst composition. An organic solvent that thanide compound in the absence of conjugated diene mono is inert with respect to the catalyst composition employed to mer or in the presence of a small amount of conjugated diene catalyze the polymerization may be selected. Exemplary monomer at an appropriate temperature, which may be from hydrocarbon solvents have been set forth above. When a about -20° C. to about 80°C. In the second stage, the fore Solvent is employed, the concentration of the monomer to be going reaction mixture and the halogen-containing com polymerized may not be limited to a special range. In one or pound, non-coordinating anion, or non-coordinating anion more embodiments, however, the concentration of the mono precursor can be charged in either a stepwise or simultaneous merpresent in the polymerization medium at the beginning of manner to the remainder of the conjugated diene monomer the polymerization can be in a range of from about 3% to that is to be polymerized. 10 about 80% by weight, in other embodiments from about 5% When a solution of the catalyst composition or one or more to about 50% by weight, and in other embodiments from of the catalyst ingredients is prepared outside the polymer about 10% to about 30% by weight. ization system as set forth in the foregoing methods, an The polymerization of conjugated dienes may also be car organic solvent or carrier may be employed. The organic ried out by means of bulk polymerization, which refers to a Solvent may serve to dissolve the catalyst composition or 15 polymerization environment where Substantially no solvents ingredients, or the solvent may simply serve as a carrier in are employed. The bulk polymerization can be conducted which the catalyst composition or ingredients may be sus either in a condensed liquid phase or in a gas phase. pended. The organic solvent may be inert to the catalyst The polymerization of conjugated dienes may be carried composition. Useful solvents include hydrocarbon solvents out as a batch process, a continuous process, or a semi Such as aromatic hydrocarbons, aliphatic hydrocarbons, and continuous process. In the semi-continuous process, mono cycloaliphatic hydrocarbons. Non-limiting examples of aro mer may be intermittently charged as needed to replace that matic hydrocarbon solvents include benzene, toluene, monomer already polymerized. In any case, the polymeriza Xylenes, ethylbenzene, diethylbenzene, mesitylene, and the tion may be conducted under anaerobic conditions by using like. Non-limiting examples of aliphatic hydrocarbon Sol an inert protective gas Such as nitrogen, argon or helium, with vents include n-pentane, n-hexane, n-heptane, n-octane, 25 moderate to vigorous agitation. The polymerization tempera n-nonane, n-decane, isopentane, isohexanes, isopentanes, ture may vary widely from a low temperature, such as -10°C. isooctanes, 2,2-dimethylbutane, petroleum ether, kerosene, or below, to a high temperature such as 100° C. or above. In petroleum spirits, and the like. And, non-limiting examples of one embodiment, the polymerization temperature may be cycloaliphatic hydrocarbon solvents include cyclopentane, from about 20°C. to about 90° C. The heat of polymerization cyclohexane, methylcyclopentane, methylcyclohexane, and 30 may be removed by external cooling (e.g., with a thermally the like. Commercial mixtures of the above hydrocarbons controlled reactor jacket), internal cooling (e.g., by evapora may also be used. tion and condensation of the monomer or the solvent through The production of polymer can be accomplished by poly the use of a reflux condenser connected to the reactor), or a merizing conjugated diene monomer in the presence of a combination of the methods. Although the polymerization catalytically effective amount of the foregoing catalyst com 35 pressure employed may vary widely, a pressure range of from position. The total catalyst concentration to be employed in about 1 atmosphere to about 10 atmospheres may be main the polymerization mass may depend on the interplay of tained. various factors such as the purity of the ingredients, the poly The polymers prepared by employing the lanthanide-based merization temperature, the polymerization rate and conver catalyst compositions of one or more embodiments of the sion desired, the molecular weight desired, and many other 40 present invention may include reactive chain ends before the factors. Accordingly, a specific total catalyst concentration polymerization mixture is quenched. These reactive poly cannot be definitively set forth except to say that catalytically mers, which may be referred to as pseudo-living polymers, effective amounts of the respective catalyst ingredients can be can be reacted with nitro compounds or mixtures thereof to used. In one or more embodiments, the amount of the lan form functionalized polymers. thanide compound used can be varied from about 0.01 to 45 Nitro compounds include those compound containing at about 2 mmol, in other embodiments from about 0.02 to about least one nitro group (i.e., NO). In one or more embodi 1 mmol, and in other embodiments from about 0.05 to about ments, nitro compounds include organic nitro compounds 0.5 mmol per 100 g of conjugated diene monomer. that may be defined by the formula R NO, where R The polymerization can be carried out in an organic solvent includes a monovalent organic group. Monovalent organic as the diluent. In one embodiment, a solution polymerization 50 groups may includehydrocarbyl groups or Substituted hydro system can be employed, which is a system where the mono carbyl groups such as, but not limited to alkyl, cycloalkyl, mer to be polymerized and the polymer formed are soluble in Substituted cycloalkyl, alkenyl, cycloalkenyl, Substituted the polymerization medium. Alternatively, a precipitation cycloalkenyl, aryl, allyl, Substituted aryl, aralkyl, alkaryl, and polymerization system may be employed by choosing a sol alkynyl groups. These hydrocarbyl groups may contain het vent in which the polymer formed is insoluble. In both cases, 55 eroatoms such as, but not limited to, nitrogen, oxygen, sili the monomerto be polymerized may be in a condensed phase. con, tin, Sulfur, boron, and phosphorous atoms. In certain Also, the catalyst ingredients may be solubilized or Sus embodiments, the monovalent organic group may contain pended within the organic solvent. In these or other embodi one or more nitro groups attached thereto. As a result, the ments, the catalyst ingredients or components are unsup organic nitro compounds may contain two or more nitro ported or not impregnated onto a catalyst Support. In other 60 groups. embodiments, the catalyst ingredients or components may be In certain embodiments, the monovalent organic group Supported. may be an aliphatic group, a cycloaliphatic group, an aro In performing these polymerizations, an amount of organic matic group, or a heterocyclic group. Accordingly, the corre Solvent in addition to the amount of organic solvent that may sponding nitro compound may be referred to as an aliphatic, be used in preparing the catalyst composition may be added to 65 cycloaliphatic, aromatic, or heterocyclic nitro compound. In the polymerization system. The additional organic Solvent these or other embodiments, the monovalent organic group may be the same as or different from the organic solvent used may contain multiple types of groups. For example, the US 7,732,534 B2 13 14 monovalent organic group may be an aromatic group having dinitrodiphenyl ether, 2.7-dinitrofluorene, 2,7-dinitro-9- a heteroaromatic substituent. Although other forms of fluorenone, ethyl 3,5-dinitrobenzoate, 2,4- nomenclature may be employed, these types of nitro com dinitrobenzaldehyde, 2,6-dinitrobenzaldehyde, 3,5- pounds may be categorized according to the group adjacent to dinitroacetophenone, 3,5-dinitrobenzoyl chloride, 1.5- the nitro group. For example, 1-(4-nitrophenyl)-2-pyrrolidi 5 dinitroanthraquinone, 1,8-dinitroanthraquinone, 2,4- none may be categorized as an aromatic nitro compound dinitrobenzenesulfonyl chloride, 2,4-dinitrobenzonitrile, because the nitro group is directly attached to a phenyl group 3,5-dinitrobenzonitrile, 3,5-dinitrophenyl isocyanate, 3.8- having a heterocyclic Substituent (i.e., 1-pyrrodinonyl). dinitrophenanthridine, 1-(2,4-dinitrophenylsulfanyl)aziri Representative examples of aliphatic nitro compounds dine, 1-(2,4-dinitrophenylsulfanyl)dodecane, 3,6-dinitro-9- include nitromethane, nitroethane, 1-nitropropane, 2-nitro 10 ethylcarbazole, and mixtures thereof. propane, 1-nitrobutane, 1-nitropentane, 1-nitrohexane, 5-ni Representative examples of heterocyclic nitro compounds tro-1-pentene, 1-(dimethylamino)-2-nitroethylene, 2-(2-ni include 5-nitro-2-thiophenecarboxaldehyde, 5-nitroquino trovinyl)furan, 2-(2-nitrovinyl)thiophene, trans-B- line, 6-nitroquinoline, 7-nitroquinoline, 8-nitroquinoline, nitrostyrene, and mixtures thereof. 5-nitroisoquinoline, 6-nitroisoquinoline, 7-nitroisoquino Representative examples of aliphatic di-nitro compounds 15 line, 8-nitroisoquinoline, 3-nitro-2,6-lutidine, 4-nitro-2,3-lu include 2,3-dimethyl-2,3-dinitrobutane, 1,3-dinitro-2-ethyl tidine-N-oxide, 8-nitroquinaldine, 5-nitro-2-furaldehyde, 2-methylpropane, 1,4-dinitro-1,1,4,4-tetrabromobutane, 1,4- 1-nitropyrazole, 2-nitropyridine, 3-nitropyridine, 4-nitropy dinitro-1,1,4,4-tetrachlorobutane, 2,3-dimethyl-2,3-dinitro ridine, 2-nitrofuran, 2-nitrothiophene, 4-nitropyridine N-ox 1,4-diphenylbutane, and mixtures thereof. ide, 4-nitro-2-picoline N-oxide, 4-nitroquinoline 1-oxide, Representative examples of cycloaliphatic nitro com and mixtures thereof. pounds include 1-nitro-1-cyclohexene, 2-nitrocyclohex Representative examples of heterocyclic di-nitro com anone, 2-nitrocyclododecanone, nitrocyclopentane, nitrocy pounds include 1,4-dinitropiperazine, 2,3-dimethoxy-5,6- clohexane, and mixtures thereof. dinitropyridine, 2-ethoxy-1-methyl-6,8-dinitroquinoline, Representative examples of aromatic nitro compounds 3,5-dinitro-2(1H)-pyridinone, 3,5-dinitro-4(1H)-pyridinone, include nitrobenzene, 2-nitrotoluene, 3-nitrotoluene, 4-nitro 25 and mixtures thereof. toluene, 4-nitrodiphenylmethane, 2-nitrobiphenyl, 3-nitrobi In one or more embodiments, the pseudo-living polymer phenyl, 2-nitromesitylene, 3-nitrostyrene, 1-nitronaphtha and the nitro compound can be reacted by combining or lene, 9-nitroanthracene, 4-nitroaZobenzene, mixing them in the same medium that the pseudo-living poly 2-nitrobenzonitrile, 3-nitrobenzonitrile, 4-nitrobenzonitrile, mer is prepared or stored. For example, where the pseudo 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzalde 30 living polymer is synthesized in solution, the nitro compound hyde, 4-nitroindan, 5-nitropseudocumene, 4-nitrochalcone, can be added to the Solution containing the pseudo-living 6-nitrochromone, 6-nitrochrysene, 2-nitrofluorene, 3-nitrof polymer. In one or more embodiments, the nitro compound luoranthene, 1-nitropyrene, 2-nitro-9-fluorenone, 2-nitro-p- can be reacted with the pseudo-living polymer before the cymene, 2-nitroanisole, 3-nitroanisole, 4-nitroanisole, 4-ni pseudo-living polymer is quenched. In one or more embodi trothioanisole, 2-nitrocinnamaldehyde, 35 ments, the reaction between the nitro compound and the 4-nitrocinnamaldehyde, 4-dimethylamino-2-nitrobenzalde pseudo-living polymer may take place within 30 minutes, in hyde, 2-nitroacetophenone, 3-nitroacetophenone, 4-nitroac other embodiments within 5 minutes, and in other embodi etophenone, 3-nitrobenzophenone, 4-nitrobenzophenone, ments within one minute of reaching the peak polymerization 2-nitrophenyl isocyanate, 2-nitrophenyl isocyanate, 3-nitro temperature resulting from the synthesis of the pseudo-living phenyl isocyanate, 4-nitrophenyl isocyanate, 2-nitrophenyl 40 polymer. In one or more embodiments, the reaction between isothiocyanate, 3-nitrophenyl isothiocyanate, 4-nitrophenyl the pseudo-living polymer and the nitro compound can occur isothiocyanate, N,N-dimethyl-2-nitroaniline, N,N-dimethyl at the peak polymerization temperature. In other embodi 3-nitroaniline, N,N-dimethyl-4-nitroaniline, 3-nitro-1.8- ments, the reaction between the pseudo-living polymer and naphthalic anhydride, 3-nitrophthalic anhydride, 4-nitro the nitro compound can occur after the pseudo-living poly phthalic anhydride, 6-nitrophthalide, 2-nitrophenyl phenyl 45 mers has been stored. In one or more embodiments, the Stor ether, 2-nitrophenyl phenyl Sulfide, 4-nitrophenyl phenyl Sul age of the pseudo-living polymer occurs at room temperature fide, 2-nitrophenyl disulfide, 3-nitrophenyl disulfide, 4-nitro or below under an inert atmosphere. In one or more embodi phenyl disulfide, 2-nitrophenyl phenyl sulfone, 3-nitrophtha ments, the reaction between nitro compound and the pseudo lonitrile, 4-nitrophthalonitrile, 2-nitrophenylacetonitrile, living polymer may take place at a temperature from about 3-nitrophenylacetonitrile, 4-nitrophenylacetonitrile, 2-(4-ni 50 10°C. to about 150°C., and in other embodiments from about trophenyl)propionitrile, 5-(2-nitrophenyl)-2-furonitrile, 20° C. to about 100° C. diethyl (4-nitrobenzyl)phosphonate, 6-nitropiperonal, 1-(2- The amount of the nitro compound that can be reacted with nitrophenyl)piperidine, 1-(4-nitrophenyl)piperidine, 1-(4-ni the pseudo-living polymer may vary depending on the desired trophenyl)-2-pyrrolidinone, 4-(4-nitrobenzyl)pyridine, 5-(2- degree of functionalization. In one or more embodiments, the nitrophenyl)furfural, 5-(3-nitrophenyl)furfural, 5-(4- 55 amount of the nitro compound employed can be described nitrophenyl)furfural, 1-(4-nitrophenyl)-1H-imidazole, 1-(4- with reference to the lanthanide metal of the lanthanide com nitrophenyl)-1H-pyrrole, 4-(4-nitrophenyl)-1,2,3- pound. For example, the molar ratio of the nitro compound to thiadiazole, 4-nitro-2,1,3-benzothiadiazole, the lanthanide metal may be from about 1:1 to about 200:1, in 6-nitrobenzothiazole, 2-(4-nitrophenyl)oxazole, and mix other embodiments from about 5:1 to about 150:1, and in tures thereof. 60 Representative examples of aromatic di-nitro compounds other embodiments from about 10:1 to about 100:1. include 1,2-dinitrobenzene, 1,3-dinitrobenzene, 1,4-dini In one or more embodiments, after the reaction between the trobenzene, 2,3-dinitrotoluene, 2,4-dinitrotoluene, 2,5-dini pseudo-living polymer and nitro compound has been accom trotoluene, 2,6-dinitrotoluene, 3,4-dinitrotoluene, 3,5-dini plished or completed, a quenching agent can be added to the trotoluene, 2,2'-dinitrobiphenyl, 4,4'-dinitrobibenzyl, 1,3- 65 polymerization mixture in order to inactivate any residual dinitronaphthalene, 1,5-dinitronaphthalene, 1,3- reactive polymer chains and the catalyst or catalyst compo dinitropyrene, 1,6-dinitropyrene, 1,8-dinitropyrene, 4,4'- nents. The quenching agent may include a protic compound, US 7,732,534 B2 15 16 which includes, but is not limited to, an alcohol, a carboxylic The rubber compositions may include fillers such as inor acid, an inorganic acid, water, or a mixture thereof. An anti ganic and organic fillers. The organic fillers include carbon oxidant such as 2,6-di-tert-butyl-4-methylphenol may be black and starch. The inorganic fillers may include silica, added along with, before, or after the addition of the quench aluminum hydroxide, magnesium hydroxide, clays (hydrated ing agent. The amount of the antioxidant employed may be in 5 aluminum silicates), and mixtures thereof. the range of 0.2% to 1% by weight of the polymer product. A multitude of rubber curing agents (also called Vulcaniz When the polymerization mixture has been quenched, the ing agents) may be employed, including Sulfur or peroxide polymer product can be recovered from the polymerization based curing systems. Curing agents are described in Kirk mixture by using any conventional procedures of desolventi 10 Othmer, ENCYCLOPEDIA OF CHEMICALTECHNOLOGY, Vol. 20, pgs. Zation and drying that are known in the art. For instance, the 365-468, (3" Ed. 1982), particularly Vulcanization Agents polymer can be recovered by Subjecting the polymer cement and Auxiliary Materials, pgs. 390-402, and A. Y. Coran, Vul to steam desolventization, followed by drying the resulting canization, ENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING, polymer crumbs in a hot air tunnel. Alternatively, the polymer (2" Ed. 1989), which are incorporated herein by reference. may be recovered by directly drying the polymer cement on a 15 Vulcanizing agents may be used alone or in combination. drum dryer. The content of the volatile substances in the dried Other ingredients that may be employed include accelera polymer can be below 1%, and in other embodiments below tors, oils, waxes, scorch inhibiting agents, processing aids, 0.5% by weight of the polymer. Zinc oxide, tackifying resins, reinforcing resins, fatty acids Where 1,3-butadiene is polymerized, the number average Such as Stearic acid, peptizers, and one or more additional molecular weight (M) of the polybutadiene may be from rubbers. about 5,000 to about 200,000, in other embodiments from These rubber compositions are useful for forming tire com about 25,000 to about 150,000, and in other embodiments ponents such as treads, Subtreads, black sidewalls, body ply from about 50,000 to about 120,000, as determined by using skins, bead filler, and the like. Preferably, the functional poly gel permeation chromatography (GPC) calibrated with poly 25 mers are employed in tread formulations. In one or more styrene standards and Mark-Houwink constants for polybuta embodiments, these tread formulations may include from diene. The polydispersity of the polymer may be from about about 10% to about 100% by weight, in other embodiments 1.5 to about 5.0, and in other embodiments from about 2.0 to from about 35% to about 90% by weight, and in other about 4.0. 30 embodiments from about 50% to 80% by weight of the func tional polymer based on the total weight of the rubber within Where cis-1,4-polydienes are prepared, they can have a the formulation. cis-1.4-linkage content that is greater than about 60%, in In one or more embodiments, the Vulcanizable rubber.com other embodiments greater than about 75%, in other embodi position may be prepared by forming an initial masterbatch ments greater than about 90%, and in other embodiments 35 that includes the rubber component and filler (the rubber greater than about 95%. Also, these polymers may have a component optionally including the functionalized polymer 1.2-linkage content that is less than about 7%, in other of this invention). This initial masterbatch may be mixed at a embodiments less than 5%, in other embodiments less than starting temperature of from about 25°C. to about 125° C. 2%, and in other embodiments less than 1%. The cis-1,4- and with a discharge temperature of about 135° C. to about 180° 1.2-linkage content can be determined by infrared spectros 40 C. To prevent premature Vulcanization (also known as copy. Scorch), this initial masterbatch may exclude Vulcanizing The functionalized polymers of this invention are particu agents. Once the initial masterbatch is processed, the Vulca larly useful in preparing tire components. These tire compo nizing agents may be introduced and blended into the initial nents can be prepared by using the functionalized polymers of 45 masterbatch at low temperatures in a final mixing stage, this invention alone or together with other rubbery polymers. which preferably does not initiate the Vulcanization process. Other rubbery polymers that may be used include natural and Optionally, additional mixing stages, sometimes called synthetic elastomers. The synthetic elastomers typically remills, can be employed between the masterbatch mixing derive from the polymerization of conjugated diene mono stage and the final mixing stage. Various ingredients includ mers. These conjugated diene monomers may be copolymer 50 ing the functionalized polymer of this invention can be added ized with other monomers such as vinyl aromatic monomers. during these remills. Rubber compounding techniques and Other rubbery polymers may derive from the polymerization the additives employed therein are generally known as dis of ethylene together with one or more C-olefins and option closed in The Compounding and Vulcanization of Rubber, in ally one or more diene monomers. 55 Rubber Technology (2" Ed. 1973). Useful rubbery polymers include natural rubber, synthetic The mixing conditions and procedures applicable to silica polyisoprene, polybutadiene, polyisobutylene-co-isoprene, filled tire formulations are also well known as described in neoprene, poly(ethylene-co-propylene), poly(styrene-co U.S. Pat. Nos. 5,227,425, 5,719,207, 5,717,022, and Euro butadiene), poly(styrene-co-isoprene), and poly(styrene-co pean Patent No. 890,606, all of which are incorporated herein isoprene-co-butadiene), poly(isoprene-co-butadiene), poly 60 by reference. In one or more embodiments, where silica is (ethylene-co-propylene-co-diene), polysulfide rubber, employed as a filler (alone or in combination with other acrylic rubber, urethane rubber, silicone rubber, epichlorohy fillers), a coupling and/or shielding agent may be added to the drin rubber, and mixtures thereof. These elastomers can have rubber formulation during mixing. Useful coupling and a myriad of macromolecular structures including linear, 65 shielding agents are disclosed in U.S. Pat. Nos. 3,842,111, branched and starshaped. Other ingredients that are typically 3,873,489, 3,978,103, 3,997,581, 4,002,594, 5,580,919, employed in rubber compounding may also be added. 5,583,245, 5,663,396, 5,674,932, 5,684, 171, 5,684, 172 US 7,732,534 B2 17 18 5,696, 197, 6,608,145, 6,667,362, 6,579,949, 6,590,017, diene in hexane. A preformed catalyst was prepared by mix 6,525,118, 6.342,552, and 6,683,135, which are incorporated ing 7.35 ml of 4.32 M methylaluminoxane in toluene, 1.66 g herein by reference. In one embodiment, the initial master of 20.6 wt % 1,3-butadiene in hexane, 0.59 ml of 0.537 M batch is prepared by including the functionalized polymer of neodymium versatate in cyclohexane, 6.67 ml of 1.0 M this invention and silica in the Substantial absence of coupling disobutylaluminum hydride in hexane, and 1.27 ml of 1.0 M and shielding agents. diethylaluminum chloride in hexane. The catalyst was aged Where the Vulcanizable rubber compositions are employed for 15 minutes and charged into the reactor. The reactorjacket in the manufacture of tires, these compositions can be pro temperature was then set to 65° C. Fifty three minutes after cessed into tire components according to ordinary tire manu 10 addition of the catalyst, the polymerization mixture was facturing techniques including standard rubber shaping, cooled to room temperature. The resulting polymer cement molding and curing techniques. Typically, Vulcanization is was coagulated with 12 liters ofisopropanol containing 5 g of effected by heating the Vulcanizable composition in a mold; 2,6-di-tert-butyl-4-methylphenol and then drum-dried. The e.g., it may be heated to about 140 to about 180° C. Cured or Mooney viscosity (ML) of the resulting polymer was crosslinked rubber compositions may be referred to as Vulca 15 determined to be 29.4 at 100° C. by using a Monsanto nizates, which generally contain three-dimensional poly Mooney viscometer with a large rotor, a one-minute warm-up meric networks that are thermoset. The other ingredients, time, and a four-minute running time. As determined by gel Such as processing aides and fillers, may be evenly dispersed permeation chromatography (GPC), the polymer had a num throughout the Vulcanized network. Pneumatic tires can be ber average molecular weight (M) of 116,900, a weight made as discussed in U.S. Pat. Nos. 5,866,171, 5,876,527, average molecular weight (M) of 217.200, and a molecular 5.931,211, and 5,971,046, which are incorporated herein by weight distribution (M/M) of 1.86. The infrared spectro reference. scopic analysis of the polymer indicated a cis-1,4-linkage In order to demonstrate the practice of the present inven content of 94.5%, a trans-1.4-linkage content of 5.0%, and a tion, the following examples have been prepared and tested. 25 1.2-linkage content of 0.5%. The cold-flow characteristics of The examples should not, however, be viewed as limiting the the polymer was measured by using a Scott plasticity tester. scope of the invention. The claims will serve to define the Approximately 2.6 g of the polymer was molded, at 100° C. invention. for 20 minutes, into a cylindrical button with a diameter of 15 30 mm and a height of 12 mm. After cooling down to room EXAMPLES temperature, the button was removed from the mold and Example 1 placed in a Scott plasticity tester at room temperature. A 5-kg load was applied to the specimen. After 8 minutes, the Synthesis of Unmodified cis-1,4-Polybutadiene residual gauge (i.e., sample thickness) was measured and (Control Polymer) 35 taken as an indication of the cold-flow resistance of the poly mer. Generally, a higher residual gauge value indicates better To a 2-gallon reactor equipped with turbine agitator blades cold-flow resistance. The properties of the unmodified cis-1, was added 1403 g of hexane and 3083 g of 20.6 wt % buta 4-polybutadiene are summarized in Table 1.

TABLE 1

Example No.

Polymer type unmodified unmodified nitromethane nitrobenzene nitrotoluene modified modified modified Mooney viscosity 29.4 44.2 42.9 43.0 43.9 M 116,900 129,900 101,900 100,500 97,800 Mw 217,200 261,200 197,900 198,800 191,700 M/M 186 2.01 1.94 1.98 1.96 Cold-flow gauge 1.75 2.13 3.21 3.27 3.36 (mm) Microstructure:

% cis 94.5 95.0 94.2 94.2 94.2 % trans S.O 4.5 5.3 5.3 5.3 % vinyl O.S O.S O.S O.S O.S US 7,732,534 B2 19 20 Example 2 Example 4 Synthesis of Unmodified cis-1,4-Polybutadiene Synthesis of Nitrobenzene-Modified (Control Polymer) cis-1,4-Polybutadiene To a 2-gallon reactor equipped with turbine agitator blades 425 g of the unmodified polymer cement synthesized in was added 1651 g of hexane and 2835 g of 22.4 wt % buta Example 3 was transferred from the reactor to a nitrogen diene in hexane. A preformed catalyst was prepared by mix purged bottle, followed by addition of 6.02 ml of 0.385 M ing 5.88 ml of 4.32 M methylaluminoxane in toluene, 1.22g nitrobenzene (PhNO) in toluene. The bottle was tumbled for of 22.4 wt % 1,3-butadiene in hexane, 0.47 ml of 0.537 M 10 20 minutes in a water bath maintained at 65°C. The resulting neodymium versatate in cyclohexane, 5.33 ml of 1.0 M mixture was coagulated with 3 liters ofisopropanol contain disobutylaluminum hydride in hexane, and 1.02 ml of 1.0 M ing 0.5g of 2,6-di-tert-butyl-4-methylphenol and then drum diethylaluminum chloride in hexane. The catalyst was aged dried. The properties of the resulting nitrobenzene-modified for 15 minutes and charged into the reactor. The reactorjacket polymer are summarized in Table 1. temperature was then set to 65° C. Seventy minutes after 15 addition of the catalyst, the polymerization mixture was Example 5 cooled to room temperature. The resulting polymer cement was coagulated with 12 liters ofisopropanol containing 5 g of Synthesis of 4-Nitrotoluene-Modified 2,6-di-tert-butyl-4-methylphenol and then drum-dried. The cis-1,4-Polybutadiene properties of the resulting polymer are Summarized in Table 1. 429 g of the unmodified polymer cement made in Example Example 3 3 was transferred from the reactor to a nitrogen-purged bottle, followed by addition of 6.06 ml of 0.386 M 4-nitrotoluene (4-CHCHNO) in toluene. The bottle was tumbled for 20 Synthesis of Nitromethane-Modified 25 cis-1,4-Polybutadiene minutes in a water bath maintained at 65° C. The resulting mixture was coagulated with 3 liters ofisopropanol contain ing 0.5g of 2,6-di-tert-butyl-4-methylphenol and then drum To a 2-gallon reactor equipped with turbine agitator blades dried. The properties of the resulting 4-nitrotoluene-modified was added 1656 g of hexane and 2810 g of 22.6 wt % buta polymer are summarized in Table 1. diene in hexane. A preformed catalyst was prepared by mix 30 ing 9.55 ml of 4.32 M methylaluminoxane in toluene, 1.97g In FIG. 1, the cold-flow resistance of the unmodified and of 22.6 wt % 1,3-butadiene in hexane, 0.77 ml of 0.537 M modified polymers is plotted against the polymer Mooney neodymium versatate in cyclohexane, 8.67 ml of 1.0 M Viscosity. The data indicate that, at the same polymer Mooney disobutylaluminum hydride in hexane, and 1.65 ml of 1.0 M Viscosity, the modified polymers show much higher residual diethylaluminum chloride in hexane. The catalyst was aged 35 cold-flow gauge values and accordingly much better cold for 15 minutes and charged into the reactor. The reactorjacket flow resistance than the unmodified polymer. temperature was then set to 65° C. Fifty six minutes after addition of the catalyst, the polymerization mixture was Examples 6-10 cooled to room temperature. 435 g of the resulting unmodi fied polymer cement was transferred from the reactor to a 40 Compounding Evaluation of Unmodified Polymer nitrogen-purged bottle, followed by addition of 5.86 ml of vs. Modified Polymer 0.405 M. nitromethane (CHNO) in toluene. The bottle was tumbled for 20 minutes in a water bath maintained at 65° C. The polymer samples produced in Examples 1-5 were The resulting mixture was coagulated with 3 liters of isopro evaluated in a carbon black filled rubber compound. The panol containing 0.5g of 2,6-di-tert-butyl-4-methylphenol 45 compositions of the Vulcanizates are presented in Table 2. The and then drum-dried. The properties of the resulting numbers in the table are expressed as parts by weight per nitromethane-modified polymer are summarized in Table 1. hundred parts by weight of rubber (phr).

TABLE 2 Example No. Example 6 Example 7 Example 8 Example 9 Example 10 Polymer used Example 1 Example 2 Example 3 Example 4 Example 5 Polymer type Unmodified Unmodified Nitromethane- Nitrobenzene- 4 modified modified Nitrotoluene modified Polymer (phr) 8O 8O 8O 8O 8O Polyisoprene 2O 2O 2O 2O 2O (phr) Carbon black 50 50 50 50 50 (phr) Oil (phr) 10 10 10 10 10 Wax (phr) 2 2 2 2 2 Antioxidant (phr) 1 1 1 1 1 Stearic acid (phr) 2 2 2 2 2 Zinc oxide (phr) 2.5 2.5 2.5 2.5 2.5 US 7,732,534 B2 21 22

TABLE 2-continued Example No. Example 6 Example 7 Example 8 Example 9 Example 10 Accelerators 1.3 1.3 1.3 1.3 1.3 (phr) Sulfur (phr) 1.5 1.5 1.5 1.5 1.5

Total 170.3 170.3 170.3 170.3 170.3

The Mooney viscosity (ML) of the uncured compound 3. The method of claim 1, where said step of reacting the was determined at 130° C. by using a Alpha Technologies reactive polymer with a nitro compound takes place within a Mooney viscometer with a large rotor, a one-minute warm-up solvent. time, and a four-minute running time. The Payne effect data 4. The method of claim 1, where the molar ratio of the nitro (AG) and hysteresis data (tan 8) of the Vulcanizates were compound to the lanthanide metal of the lanthanide-based obtained from a dynamic strain Sweep experiment, which was catalyst is from about 1:1 to about 200:1. conducted at 50° C. and 15 Hz with strain sweeping from 5. The method of claim 1, where the molar ratio of the nitro 0.1% to 20%. AG' is the difference between G' at 0.1% strain 20 compound to the lanthanide metal of the lanthanide-based and G' at 20% strain. The physical properties of the Vulcani catalyst is from about 5:1 to about 150:1. Zates are Summarized in Table 3, and graphically represented 6. The method of claim 1, where the lanthanide-based in FIG. 2 and FIG. 3. catalyst is formed by combining a lanthanide compound, an

TABLE 3 Property Example 6 Example 7 Example 8 Example 9 Example 10 Polymer type unmodified unmodified nitromethane- Nitrobenzene modified modified Nitrotoluene modified Polymer ML 29.4 44.2 42.9 43.O 43.9 at 100° C. Compound SO.8 63.1 53.4 52.3 51.6 ML at 130° C. AG' (MPa) 2.76 2.63 2.05 1.65 140 tané at 50° C., O.133 O.124 O.113 O-111 O112 3% strain

As can be seen in FIG. 2, at the same polymer Mooney alkylating agent, and optionally a halogen-containing com Viscosity, the polymers modified with nitro compounds give pound, with the proviso that the lanthanide compound or the lower compound Mooney viscosity and accordingly better alkylating agent include a labile halogenatom in the absence processability than the unmodified polymer. FIG. 3 indicates of the optional halogen-containing compound. that the polymers modified with nitro compounds give Vul canizates characterized by lower tan 8 at 50° C. than those 7. The method of claim 1, where said step of reacting the prepared from the unmodified polymer, indicating that modi 45 reactive polymer with a nitro compound occurs before the fication of the polymer with nitro compounds reduces hyster reactive polymer is quenched. esis of the Vulcanizates. In addition, as shown in Table 3, the 8. The method of claim 6, where the alkylating agent modified polymers also provide Vulcanizates within lower includes an aluminoxane and an organoaluminum compound AG' than the unmodified polymer, indicating that the Payne represented by the formula AlRX, where each R, which Effect has been reduced due to the interaction between the 50 may be the same or different, is a mono-valent organic group modified polymers and carbon black. that is attached to the aluminum atom via a carbon atom, Various modifications and alterations that do not depart where each X, which may be the same or different, is a from the scope and spirit of this invention will become appar hydrogen atom, a halogen atom, a carboxylate group, an ent to those skilled in the art. This invention is not to be duly 55 alkoxide group, or an aryloxide group, and where n is an limited to the illustrative embodiments set forth herein. integer of 1 to 3. What is claimed is: 9. The method of claim 2, where the monovalent organic 1. A method for preparing a functionalized polymer, the group is an aliphatic group. method comprising the steps of 60 10. The method of claim 9, where the nitro compound (i) polymerizing conjugated diene monomer by employing includes nitromethane, nitroethane, 1-nitropropane, 2-nitro a lanthanide-based catalyst to form a reactive polymer, propane, 1-nitrobutane, 1-nitropentane, 1-nitrohexane, 5-ni and tro-1-pentene, 1-(dimethylamino)-2-nitroethylene, 2-(2-ni (ii) reacting the reactive polymer with a nitro compound. trovinyl)furan, 2-(2-nitrovinyl)thiophene, trans-B- 2. The method of claim 1, where the nitro compound is an 65 nitrostyrene, and mixtures thereof. organic nitro compound defined by the formula R NO, 11. The method of claim 2, where the monovalent organic where R is a monovalent organic group. group includes a cycloaliphatic group. US 7,732,534 B2 23 24 12. The method of claim 11, where the nitro compound 16. The method of claim 15, where the nitro compound includes 1-nitro-1-cyclohexene, 2-nitrocyclohexanone, 2-ni includes include 5-nitro-2-thiophenecarboxaldehyde, 5-nit trocyclododecanone, nitrocyclopentane, nitrocyclohexane, roquinoline, 6-nitroquinoline, 7-nitroquinoline, 8-nitro or mixtures thereof. quinoline, 5-nitroisoquinoline, 6-nitroisoquinoline, 7-ni 13. The method of claim 2, where the monovalent organic troisoquinoline, 8-nitroisoquinoline, 3-nitro-2,6-lutidine, group includes an aromatic Substituent. 4-nitro-2.3-lutidine-N-oxide, 8-nitroquinaldine, 5-nitro-2- 14. The method of claim 13, where the nitro compound furaldehyde, 1-nitropyrazole, 2-nitropyridine, 3-nitropyri includes nitrobenzene, 2-nitrotoluene, 3-nitrotoluene, 4-ni dine, 4-nitropyridine, 2-nitrofuran, 2-nitrothiophene, 4-nitro trotoluene, 4-nitrodiphenylmethane, 2-nitrobiphenyl, 3-ni pyridine N-oxide, 4-nitro-2-picoline N-oxide, trobiphenyl, 2-nitromesitylene, 3-nitrostyrene, 1-nitronaph 10 4-nitroquinoline 1-oxide, and mixtures thereof. thalene, 9-nitroanthracene, 4-nitroaZobenzene, 17. The method of claim 1, where the nitro compound is 2-nitrobenzonitrile, 3-nitrobenzonitrile, 4-nitrobenzonitrile, selected from the group consisting of nitromethane, nitroben 2-nitrobenzaldehyde, 3-nitrobenzaldehyde, 4-nitrobenzalde Zene, and 4-nitrotoluene. hyde, 4-nitroindan, 5-nitropseudocumene, 4-nitrochalcone, 18. The method of claim 1, where the nitro compound 6-nitrochromone, 6-nitrochrysene, 2-nitrofluorene, 3-nitrof 15 contains two or more nitro groups. luoranthene, 1-nitropyrene, 2-nitro-9-fluorenone, 2-nitro-p- 19. The method of claim 18, where the nitro compound is cymene, 2-nitroanisole, 3-nitroanisole, 4-nitroanisole, 4-ni an aliphatic di-nitro compound selected from the group con trothioanisole, 2-nitrocinnamaldehyde, sisting of 2,3-dimethyl-2,3-dinitrobutane, 1,3-dinitro-2- 4-nitrocinnamaldehyde, 4-dimethylamino-2-nitrobenzalde ethyl-2-methylpropane, 1,4-dinitro-1,1,4,4-tetrabromobu hyde, 2-nitroacetophenone, 3-nitroacetophenone, 4-nitroac tane, 1,4-dinitro-1,1,4,4-tetrachlorobutane, 2,3-dimethyl-2, etophenone, 3-nitrobenzophenone, 4-nitrobenzophenone, 3-dinitro-1,4-diphenylbutane and mixtures thereof. 2-nitrophenyl isocyanate, 2-nitrophenyl isocyanate, 3-nitro 20. The method of claim 18, where the nitro compound is phenyl isocyanate, 4-nitrophenyl isocyanate, 2-nitrophenyl an aromatic di-nitro compound selected from the group con isothiocyanate, 3-nitrophenyl isothiocyanate, 4-nitrophenyl sisting of 1,2-dinitrobenzene, 1,3-dinitrobenzene, 1,4-dini isothiocyanate, N,N-dimethyl-2-nitroaniline, N,N-dimethyl 25 trobenzene, 2,3-dinitrotoluene, 2,4-dinitrotoluene, 2,5-dini 3-nitroaniline, N,N-dimethyl-4-nitroaniline, 3-nitro-1.8- trotoluene, 2,6-dinitrotoluene, 3,4-dinitrotoluene, 3.5- naphthalic anhydride, 3-nitrophthalic anhydride, 4-nitro dinitrotoluene, 2,2'-dinitrobiphenyl, 4,4'-dinitrobibenzyl, phthalic anhydride, 6-nitrophthalide, 2-nitrophenyl phenyl 1,3-dinitronaphthalene, 1,5-dinitronaphthalene, 1,3-dinitro ether, 2-nitrophenyl phenyl Sulfide, 4-nitrophenyl phenyl Sul pyrene, 1,6-dinitropyrene, 1,8-dinitropyrene, 4,4'-dini fide, 2-nitrophenyl disulfide, 3-nitrophenyl disulfide, 4-nitro 30 trodiphenyl ether, 2.7-dinitrofluorene, 2,7-dinitro-9-fluo phenyl disulfide, 2-nitrophenyl phenyl sulfone, 3-nitrophtha renone, ethyl 3,5-dinitrobenzoate, 2,4-dinitrobenzaldehyde, lonitrile, 4-nitrophthalonitrile, 2-nitrophenylacetonitrile, 2,6-dinitrobenzaldehyde, 3,5-dinitroacetophenone, 3,5-dini 3-nitrophenylacetonitrile, 4-nitrophenylacetonitrile, 2-(4-ni trobenzoyl chloride, 1,5-dinitroanthraquinone, 1,8-dinitroan trophenyl)propionitrile, 5-(2-nitrophenyl)-2-furonitrile, thraquinone, 2,4-dinitrobenzenesulfonyl chloride, 2,4-dini diethyl (4-nitrobenzyl)phosphonate, 6-nitropiperonal, 1-(2- 35 trobenzonitrile, 3,5-dinitrobenzonitrile, 3,5-dinitrophenyl nitrophenyl)piperidine, 1-(4-nitrophenyl)piperidine, 1-(4-ni isocyanate, 3.8-dinitrophenanthridine, 1-(2,4-dinitrophenyl trophenyl)-2-pyrrolidinone, 4-(4-nitrobenzyl)pyridine, 5-(2- Sulfanyl)aziridine, 1-(2,4-dinitrophenylsulfanyl)dodecane, nitrophenyl)furfural, 5-(3-nitrophenyl)furfural, 5-(4- 3,6-dinitro-9-ethylcarbazole, and mixtures thereof. nitrophenyl)furfural, 1-(4-nitrophenyl)-1H-imidazole, 1-(4- 21. The method of claim 18, where the nitro compound is nitrophenyl)-1H-pyrrole, 4-(4-nitrophenyl)-1,2,3- 40 a heterocyclic di-nitro compound selected from the group thiadiazole, 4-nitro-2,1,3-benzothiadiazole, consisting of 1,4-dinitropiperazine, 2,3-dimethoxy-5,6-dini 6-nitrobenzothiazole, 2-(4-nitrophenyl)oxazole, and mix tropyridine, 2-ethoxy-1-methyl-6,8-dinitroquinoline, 3.5- tures thereof. dinitro-2(1H)-pyridinone, 3,5-dinitro-4(1H)-pyridinone, and 15. The method of claim 2, where the monovalent organic mixtures thereof. group includes a heterocyclic Substituent.