USOO669981.3B2 (12) United States Patent (10) Patent No.: US 6,699,813 B2 Luo et al. (45) Date of Patent: Mar. 2, 2004

(54) LANTHANIDE-BASED CATALYST 3,541,063 A 11/1970 Throckmorton et al. COMPOSITION FOR THE MANUFACTURE 3,794,604. A 2/1974 Throckmorton et al. OF POLYDENES 4,242.232 A 12/1980 Sylvester et al. 4,260,707 A 4/1981 Sylvester et al...... 526/114 (75) Inventors: Steven Luo, Akron, OH (US); Yoichi 4,429,089 A 1/1984 Pedretti et al...... 526/153 Ozawa, Kodaira (JP); Koji Masaki, 4.575,538 A 3/1986 Hsieh et al...... 525/244 Fairlawn, OH (US); David Lawson 5,585,440 A 12/1996 Yamada et al...... 525/193 Uniontown, of (US) s 6,001,478 A 12/1999 Apecetche et al...... 428/407 s 6,114,483 A 9/2000 Coughlin et al...... 526/172 (73) Assignee: Bridgestone Corporation, Tokyo (JP) 6,136,919 A 10/2000 Zimmer et al...... 524/856 6,180,738 B1 1/2001 Wang et al...... 526/200 c: - - - 6,191,226 B1 2/2001 Matsuda et al...... 525/236 (*) Notice: Subiyility 6,239,063 B1 5/2001 Bogdan ...... 502/325 p 54(b) by Od 6.255.420 B1, 7/2001 Dietz, III et al...... 526/185 U.S.C. 154(b) by 0 days. 6,262,196 B1 7/2001 Mecking ...... 526/114 6,437.205 B1 * 8/2002 Miller et al...... 585/12 (21) Appl. No.: 10/287,205 6,451.934 B1 * 9/2002 Jang et al...... 526/117 (22) Filed: Nov. 4, 2002 OTHER PUBLICATIONS (65) Prior Publication Data US 2003/O176276 A1 Sep. 18, 2003 Z. Shen et al., J. of Polymer Science: Polymer Chem. f ep. 18, Edition, vol. 18; pp. 3345-3357 (1980). Related U.S. Application Data Hsieh et al., Rubber Chemistry and Technology, vol. 58. pp. (60) Provisional application No. 60/337,728, filed on Nov. 7, 117–145 (1985). 2001. (51) Int. Cl...... B01D 31/00; CO7C 2/08; * cited by examiner CO8F 4/44 (52) U.S. Cl...... 502/119; 502/103; 502/114; 502/115; 502/118; 502/129; 502/132; 502/133; Primary Examiner Elizabeth Wood 502/134: 502/150, 502/152; 502/153: 502/154; (74) Attorney, Agent, or Firm Arthur M. Reginelli 502/155;5s5507,526,66526,07,5260s: 502/162; 585/10; 585/12; 585/506; 52600: (57) ABSTRACT 526/103; 526/117; 526/135; 526/154; 526/172; A catalyst composition that is the combination of or the 58) Field of S h soil reaction product of ingredients comprising (a) an lanthanide (58) Field o ears,/114,115,119,129,132 133. 13 4. compound, (b) an alkylating agent, (c) a nickel-containing 150, 152, 153, 154, 155. 162. 585/10, 12. compound, and optionally (d) a halogen-containing 506, 507; 526/96, 97,98, 99, 103, 117, compound, with the proviso that the halogen-containing 135, 154, 172,943 compound must be present where none of the lanthanide (56) References Cited compound, the alkylating agent, and the nickel-containing compound contain a labile halogen atom. U.S. PATENT DOCUMENTS 3,297,667 A 1/1967 von Dohlen et al. 30 Claims, No Drawings US 6,699,813 B2 1 2 LANTHANDE-BASED CATALYST polymerizations that are catalyzed by lanthanide-based cata COMPOSITION FOR THE MANUFACTURE lyst Systems. In addition, the use of molecular weight OF POLYDENES regulators in Ziegler-Natta catalyst Systems generally results in decrease in catalyst activity. Furthermore, the use of This application gains priority from U.S. patent applica molecular weight regulators often adversely affects the tion Ser. No. 60/337,728, filed on Nov. 7, 2001. polymer microStructure Such as cis-1,4-linkage content. Therefore, there is a need to develop a new method of FIELD OF THE INVENTION regulating the molecular weight of polydienes produced The present invention relates to a catalyst composition with lanthanide-based catalyst Systems. There is also a need that is formed by combining a nickel-containing compound to develop an improved lower-cost lanthanide-based catalyst with a lanthanide-based catalyst composition. composition for producing low molecular weight polydienes, in particular low molecular weight cis-1,4- BACKGROUND OF THE INVENTION polydienes. Catalyst Systems based on lanthanide metals, in particular neodymium, are known to be useful for polymerizing con 15 SUMMARY OF THE INVENTION jugated diene monomers. These catalyst Systems are advan It has been unexpectedly discovered that nickel com tageously more active in aliphatic Solvents, which are envi pounds can be used as very efficient molecular weight ronmentally preferred, than in aromatic Solvents. They are regulators in conjugated diene polymerizations that are also often highly Stereospecific and can produce cis-1,4- catalyzed by lanthanide-based catalyst Systems. polydienes or trans-1,4-polydienes depending on the catalyst compositions. For example, lanthanide-based catalyst Sys The present invention provides a catalyst composition that tems including a neodymium compound, an alkylating is the combination of or the reaction product of ingredients agent, and a Source of halogen are particularly useful for comprising (a) an lanthanide compound, (b) an alkylating producing cis-1,4-polydienes from various conjugated diene agent, (c) a nickel-containing compound, and optionally (d) 25 a halogen-containing compound, with the proviso that the monomerS Such as 1,3-butadiene, isoprene, and 1,3- pentadiene. These catalyst Systems are also capable of halogen-containing compound must be present where none copolymerizing different types of conjugated diene mono of the lanthanide compound, the alkylating agent, and the mers to give Stereoregular cis-1,4-copolymer. nickel-containing compound contain a labile halogen atom. The present invention also includes a proceSS for lowering The cis-1,4-polydienes produced with a lanthanide-based the molecular weight of polydienes prepared with a catalyst have a linear backbone Structure and exhibit good lanthanide-based catalyst System, the process comprising green Strength and excellent Viscoelastic properties. The polymerizing conjugated dienes with a lanthanide-based linear backbone structure is believed to improve the tensile catalyst system that is formed by combining (a) a lanthanide properties and abrasion and fatigue resistance, and to reduce compound, (b) an alkylating agent, (c) a nickel-containing hysteresis loSS of rubber compounds. Therefore, these cis 35 compound, and optionally (d) a halogen-containing 1,4-polydienes are particularly Suitable for use in tire com compound, with the proviso that the halogen-containing ponents Such as Sidewall and tread. compound must be present where none of the lanthanide Low molecular weight polydienes, Such as low molecular compound, the alkylating agent, and the nickel-containing weight cis-1,4-polydienes, made with lanthanide-based cata compound contain a labile halogen atom. lysts are also useful in rubber compounds. They can be 40 The present invention further includes a process for blended with high molecular weight cis-1,4-polybutadiene forming conjugated diene polymers comprising the Step of to improve a variety of properties Such as fracture resistance, polymerizing conjugated diene monomers in the presence of Snow traction, wet traction, and rolling resistance. a catalytically effective amount of a catalyst composition Therefore, there is a demand for low or moderately high formed by combining (a) an lanthanide compound, (b) an molecular weigh polydienes. 45 alkylating agent, (c) a nickel-containing compound, and The molecular weight of polydienes produced with optionally (d) a halogen-containing compound, with the lanthanide-based catalysts can be controlled by varying the proviso that the halogen-containing compound must be amount of catalyst used or adjusting the amounts of present where none of the lanthanide compound, the alky co-catalyst concentrations within the catalyst System. As a lating agent, and the nickel-containing compound contain a result, polydienes having a wide range of molecular weights 50 can be produced with lanthanide-based catalyst Systems. In labile halogen atom. general, the molecular weight of the polydienes can be The addition of one or more nickel-containing compounds reduced by increasing the catalyst and co-catalyst concen to lanthanide-based catalyst compositions for polymerizing trations. Very high catalyst and co-catalyst concentrations, cis-1,4-polydienes advantageously provides a method by however, are required to produce low molecular weight 55 which the molecular weights of the resulting polydienes can polydienes Such as liquid polydienes, which results in very be easily regulated without Significantly deteriorating cata lyst activity and polymer microStructure. As a result, low high catalyst costs. In addition, the use of high catalyst levels molecular weight polydienes can be produced in high yields necessitates the removal of catalyst residues from the poly with low catalyst levels after relatively short polymerization mer because these residues can cause Subsequent adverse times. effects, Such as retardation of the Sulfur cure rate. The 60 removal of catalyst residues from polymer (also referred to DETAILED DESCRIPTION OF ILLUSTRATIVE as de-ashing) is time-consuming and adds to manufacturing EMBODIMENTS COStS. One approach to these problems is to use a molecular This invention is directed toward a method of regulating weight regulator without raising catalyst levels. 65 the molecular weights of polydienes by using a lanthanide Unfortunately, traditional molecular weight regulatorS Such based composition that is modified with a nickel-containing as C-olefins and nonconjugated dienes are ineffective in compound. Various types of lanthanide-based compositions US 6,699,813 B2 3 4 can be employed to catalyze the polymerization of dienes to Stearate, neodymium oleate, neodymium benzoate, and produce polydienes. One type of lanthanide-based compo neodymium picolinate. Sition comprises a lanthanide compound, an alkylating Suitable neodymium organophosphates include neody agent, and a halogen-containing compound. When the lan mium dibutyl phosphate, neodymium dipentyl phosphate, thanide compound or the alkylating agent contain a halogen neodymium dihexyl phosphate, neodymium diheptyl atom, the halogen-containing compound is optional. phosphate, neodymium dioctyl phosphate, neodymium bis Another type of lanthanide-based composition comprises a (1-methylheptyl) phosphate, neodymium bis(2-ethylhexyl) phosphate, neodymium didecyl phosphate, neodymium lanthanide compound and an aluminoxane. Still another type didodecyl phosphate, neodymium dioctadecyl phosphate, of lanthanide-based composition comprises a lanthanide neodymium dioleyl phosphate, neodymium diphenyl compound, an alkylating agent, and a non-coordinating phosphate, neodymium bis(p-nonylphenyl) phosphate, anion or non-coordinating anion precursor. neodymium butyl (2-ethylhexyl) phosphate, neodymium In one embodiment, the catalyst composition is formed by (1-methylheptyl) (2-ethylhexyl) phosphate, and neodymium combining (a) a lanthanide compound, (b) an alkylating (2-ethylhexyl) (p-nonylphenyl) phosphate. agent, (c) a nickel-containing compound, and (d) a halogen Suitable neodymium organophosphonates include neody containing compound. Where the lanthanide compound, 15 mium butyl phosphonate, neodymium pentyl phosphonate, alkylating agent, or nickel-containing compound contains a neodymium hexyl phosphonate, neodymium heptyl labile halogen atom, the need for an additional compound phosphonate, neodymium octyl phosphonate, neodymium containing a labile halogen atom is optional. Therefore, the (1-methylheptyl) phosphonate, neodymium (2-ethylhexyl) catalyst System may be formed by combining (a) a lan phosphonate, neodymium decyl phosphonate, neodymium thanide compound, (b) an alkylating agent, and (c) a nickel dodecyl phosphonate, neodymium octadecyl phosphonate, containing compound, with the proviso that at least one of neodymium oleyl phosphonate, neodymium phenyl the lanthanide compound, the alkylating agent, or the nickel phosphonate, neodymium (p-nonylphenyl) phosphonate, containing compound includes a labile halogen atom. In neodymium butyl butylphosphonate, neodymium pentyl addition to the catalyst ingredients (a), (b), (c), and (d), other pentylphosphonate, neodymium hexyl hexylphosphonate, 25 neodymium heptyl heptylphosphonate, neodymium octyl organometallic compounds or Lewis bases can also be octylphosphonate, neodymium (1-methylheptyl) added, if desired. (1-methylheptyl)phosphonate, neodymium (2-ethylhexyl) Various lanthanide compounds or mixtures thereof can be (2-ethylhexyl) phosphonate, neodymium de cyl employed as ingredient (a) of the catalyst composition. de cylphospho nate, neo dymium do de cyl Preferably, these compounds are soluble in hydrocarbon do de cylphosphonate, neodymium octade cyl Solvents Such as aromatic hydrocarbons, aliphatic octadecylphosphonate, neodymium oleyl oleylphosphonate, hydrocarbons, or cycloaliphatic hydrocarbons. neodymium phenyl phenylphosphonate, neodymium Hydrocarbon-insoluble lanthanide compounds, however, (p-nonylphenyl) (p-nonylphenyl)phosphonate, neodymium can be Suspended in the polymerization medium to form the butyl (2-ethylhexyl) phosphonate, neodymium catalytically active species and are also useful. (2-ethylhexyl) butylphosphonate, neodymium Lanthanide compounds include at least one atom of 35 (1-methylheptyl) (2-ethylhexyl)phosphonate, neodymium lanthanum, neodymium, cerium, praseodymium, (2-ethylhexyl) (1-methylheptyl)phosphonate, neodymium promethium, Samarium, europium, gadolinium, terbium, (2-ethylhexyl) (p-nonylphenyl)phosphonate, and neody dySprosium, holmium, erbium, thulium, ytterbium, lutetium, mium (p-nonylphenyl) (2-ethylhexyl)phosphonate. and didymium. Preferably, these compounds include 40 Suitable neodymium organophosphinates include neody neodymium, lanthanum, Samarium, or didymium. Didy mium butylphosphinate, neodymium pentylphosphinate, mium is a commercial mixture of rare-earth elements neo dymium he Xylphosphinate, n e o dymium obtained from monazite Sand. heptylphosphinate, neodymium octylphosphinate, neody The lanthanide atom in the lanthanide compounds can be mium (1-methylheptyl) phosphinate, neodymium in various oxidation States including but not limited to the 0, 45 (2-ethylhexyl)phosphinate, neodymium decylphosphinate, +2, +3, and +4 oxidation States. Trivalent lanthanide neodymium do de cylphosphinate, neodymium compounds, where the lanthanide atom is in the +3 oxidation octadecylphosphinate, neodymium oleylphosphinate, State, are preferred. Suitable lanthanide compounds include, neodymium phenylphosphinate, ne Ody mium but are not limited to, lanthanide carboxylates, lanthanide (p - no nyl phenyl) phosphinate, neo dymium organophosphates, lanthanide organophosphonates, lan 50 dibutylphosphinate, neodymium dipentylphosphinate, thanide organophosphinates, lanthanide carbamates, lan neodymium dihe Xylphosphinate, neodymium thanide dithiocarbamates, lanthanide Xanthates, lanthanide diheptylphosphinate, neodymium dioctylphosphinate, 3-diketonates, lanthanide alkoxides or aryloxides, lan neodymium bis(1-methylheptyl)phosphinate, neodymium thanide halides, lanthanide pseudo-halides, lanthanide bis(2-ethylhexyl) phosphinate, n e o dymium Oxyhalides, and organolanthanide compounds. 55 didecylphosphinate, neodymium didodecylphosphinate, Because neodymium compounds are most advanta neodymium dioctadecylphosphinate, neodymium geously employed, further discussion will focus on neody dioleylphosphinate, neodymium diphenylphosphinate, mium compounds, although those skilled in the art will be neodymium bis(p-nonylphenyl) phosphinate, neodymium able to Select Similar compounds that are based upon other butyl (2-ethylhexyl) phosphinate, neodymium lanthanide metals. 60 (1-methylheptyl)(2-ethylhexyl)phosphinate, and neody Suitable neodymium carboxylates include neodymium mium (2-ethylhexyl)(p-nonylphenyl)phosphinate. formate, neodymium acetate, neodymium acetate, neody Suitable neodymium carbamates include neodymium mium acrylate, neodymium methacrylate, neodymium dimethylcarbamate, neodymium diethylcarbamate, neody Valerate, neodymium gluconate, neodymium citrate, neody mium diisopropylcarbamate, neodymium dibutylcarbamate, mium fumarate, neodymium lactate, neodymium maleate, 65 and neodymium dibenzylcarbamate. neodymium oxalate, neodymium 2-ethylhexanoate, neody Suitable neodymium dithiocarbamates include neody mium neodecanoate, neodymium naphthenate, neodymium mium dimethyld it hio carb amate, neo dymium US 6,699,813 B2 S 6 diethyld it hio carb amate, neo dymium mono-Valent organic group that is attached to the aluminum diisop ropyl dith io carb a mate, neo dymium atom via a carbon atom, where each X, which may be the dibutyldithiocarbamate, and neodymium dibenzyldithiocar Same or different, is a hydrogen atom, a halogen atom, a bamate. carboxylate group, an alkoxide group, or an aryloxide group, Suitable neodymium Xanthates include neodymium and where n is an integer of 1 to 3. Preferably, each R is a methylxanthate, neodymium ethylxanthate, neodymium hydrocarbyl group Such as, but not limited to, alkyl, isopropylxanthate, neodymium butylxanthate, and neody cycloalkyl, Substituted cycloalkyl, alkenyl, cycloalkenyl, mium benzylxanthate. Substituted cycloalkenyl, aryl, Substituted aryl, aralkyl, Suitable neodymium B-diketonates include neodymium alkaryl, allyl, and alkynyl groups, with each group prefer acetylacetonate, neodymium trifluoroacetylacetonate, ably containing from 1 carbon atom, or the appropriate neodymium hexafluoroacetylacetonate, neodymium minimum number of carbon atoms to form the group, up to benzoylacetonate, and neodymium 2,2,6,6-tetramethyl-3,5- about 20 carbon atoms. These hydrocarbyl groups may heptanedionate. contain heteroatoms Such as, but not limited to, nitrogen, Suitable neodymium alkoxides or aryloxides include oxygen, boron, Silicon, Sulfur, and phosphorus atoms. neodymium methoxide, neodymium ethoxide, neodymium 15 Suitable organoaluminum compounds include, but are not isopropoxide, neodymium 2-ethylhexoxide, neodymium limited to, trihydrocarbylaluminum, dihydrocarbylalumi phenoxide, neodymium nonylphenoxide, and neodymium num hydride, hydrocarbylaluminum dihydride, dihydrocar naphthoxide. bylaluminum carboxylate, hydrocarbylaluminum bis Suitable neodymium halides include neodymium fluoride, (carboxylate), dihydrocarbylaluminum alkoxide, neodymium chloride, neodymium bromide, and neodymium hydrocarbylaluminum dialkoxide, dihydrocarbylaluminum iodide. Suitable neodymium pseudo-halides include neody halide, hydrocarbylaluminum dihalide, dihydrocarbylalumi mium cyanide, neodymium cyanate, neodymium num aryloxide, and hydrocarbylaluminum diaryloxide com thiocyanate, neodymium azide, and neodymium ferrocya pounds. Trihydrocarbylaluminum, dihydrocarbylaluminum nide. Suitable neodymium oxyhalides include neodymium hydride, and hydrocarbylaluminum dihydride compounds oxyfluoride, neodymium oxychloride, and neodymium oxy 25 are preferred. bromide. Where neodymium halides, neodymium Suitable trihydrocarbylaluminum compounds include Oxyhalides, or other neodymium compounds containing trimethylaluminum, triethylaluminum, triisobutylaluminum, labile halogen atoms are employed, the neodymium tri-n-propylaluminum, triisopropylaluminum, tri-n- containing compound can Serve as both the lanthanide butylaluminum, tri-t-butylaluminum, tri-n-pentylaluminum, compound as well as the halogen-containing compound. A trine opentylaluminum, tri-n-hexylaluminum, tri-n- Lewis base such as tetrahydrofuran (THF) may be employed octyl aluminum, tris(2-ethylhexyl)aluminum, as an aid for Solubilizing this class of neodymium com tricyclohexylaluminum, tris(1-methylcyclope ntyl) pounds in inert organic Solvents. aluminum, triphenylaluminum, tri-p-tolylaluminum, tris(2, 6-dimethylphenyl)aluminum, tribe nZylaluminum, The term organolanthanide compound refers to any lan 35 thanide compound containing at least one lanthanide-carbon diethylphenylaluminum, diethyl-p-tolylaluminum, bond. These compounds are predominantly, though not diethylbenzylaluminum, ethyldiphenylaluminum, ethyldi-p- exclusively, those containing cyclopentadienyl (Cp), Substi tolylaluminum, and ethyldibenzylaluminum. tuted cyclopentadienyl, allyl, and Substituted allyl ligands. Suitable dihydrocarbylaluminum hydride compounds Suitable organolanthanide compounds include Cp Ln, include diethylaluminum hydride, di-n-propylaluminum Cp LinR, Cp LnCl, Cpl nCl, Cpl n(cyclooctatetraene), 40 hydride, diisopropylaluminum hydride, di-n-butylaluminum (C5Me5)-LnR, LinRs, Ln(allyl)3, and Ln(allyl)-Cl, where Ln hydride, diisobutylaluminum hydride, di-n-octylaluminum represents a lanthanide atom, and R represents a hydrocarbyl hydride, diphenylaluminum hydride, di-p-tolylaluminum grOup. hydride, dibenzylaluminum hydride, phenylethylaluminum Various alkylating agents, or mixtures thereof, can be 45 hydride, phenyl-n-propylaluminum hydride, phenylisopro used as component (b) of the catalyst composition. Alky pylaluminum hydride, phenyl-n-butylaluminum hydride, lating agents, which may also be referred to as hydrocarby phenylisobutylaluminum hydride, phenyl-n-octylaluminum lating agents, are organometallic compounds that can trans hydride, p-tolylethylaluminum hydride, p-tolyl-n- fer hydrocarbyl groups to another metal. Typically, these propylaluminum hydride, p-tolylisopropylaluminum agents are organometallic compounds of electropositive 50 hydride, p-tolyl-n-butyl aluminum hydride, metals Such as Groups 1, 2, and 3 metals (Groups IA, IIA, p-tolylisobutylaluminum hydride, p-tolyl-n-octylaluminum and IIIA metals). Preferred alkylating agents include orga hydride, benzylethylaluminum hydride, benzyl-n- noaluminum and organomagnesium compounds. Where the propylaluminum hydride, ben Zylisopropylaluminum alkylating agent includes a labile halogen atom, the alky hydride, benzyl-n-butylaluminum hydride, benzylisobutyla lating agent may also serve as the halogen-containing com 55 luminum hydride, and benzyl-n-octylaluminum hydride. pound. Suitable hydrocarbylaluminum dihydrides include ethy The term “organoaluminum compound” refers to any laluminum dihydride, n-propylaluminum dihydride, isopro aluminum compound containing at least one aluminum pylaluminum dihydride, n-butylaluminum dihydride, isobu carbon bond. Organoaluminum compounds that are Soluble tylaluminum dihydride, and n-octylaluminum dihydride. in a hydrocarbon solvent are preferred. Where the alkylating 60 Suitable dihydrocarbylaluminum chloride compounds agent is an organoaluminum compound that includes a labile include diethylaluminum chloride, di-n-propylaluminum halogen atom, the organoaluminum compound can Serve as chloride, diisopropylaluminum chloride, di-n- both the alkylating agent and the halogen-containing com butylaluminum chloride, diisobutylaluminum chloride, di-n- pound. octylaluminum chloride, diphenylaluminum chloride, di-p- A preferred class of organoaluminum compounds that can 65 tolylaluminum chloride, dibenzylaluminum chloride, be utilized is represented by the general formula AllRX, phenylethylaluminum chloride, phenyl-n-propylaluminum where each R, which may be the same or different, is a chloride, phenylisopropylaluminum chloride, phenyl-n- US 6,699,813 B2 7 8 butylaluminum chloride, phenylisobutylaluminum chloride, should be noted that the number of moles of the aluminox phenyl-n-octylaluminum chloride, p-tolylethylaluminum ane as used in this application refers to the number of moles chloride, p-tolyl-n-propylaluminum chloride, of the aluminum atoms rather than the number of moles of p-toly liSopropylaluminum chloride, p-tolyl-n- the oligomeric aluminoxane molecules. This convention is butylaluminum chloride, p-tolylisobutylaluminum chloride, commonly employed in the art of catalysis utilizing alumi p-tolyl-n-octylaluminum chloride, benzylethylaluminum OXCS. chloride, benzyl-n-propylaluminum chloride, benzylisopro Aluminoxanes can be prepared by reacting trihydrocar bylaluminum compounds with water. This reaction can be pylaluminum chloride, benzyl-n-butylaluminum chloride, performed according to known methods, Such as (1) a ben Zylisobutylaluminum chloride, and benzyl-n- method in which the trihydrocarbylaluminum compound is octylaluminum chloride. dissolved in an organic Solvent and then contacted with Suitable hydrocarbylaluminum dichloride include ethyla water, (2) a method in which the trihydrocarbylaluminum luminum dichloride, n-propylaluminum dichloride, isopro compound is reacted with water of crystallization contained pylaluminum dichloride, n-butylaluminum dichloride, in, for example, metal Salts, or water adsorbed in inorganic isobutylaluminum dichloride, and n-octylaluminum dichlo or organic compounds, and (3) a method in which the ride. 15 trihydrocarbylaluminum compound is reacted with water in Other organoaluminum compounds include dimethylalu the presence of the monomer or monomer Solution that is to minum hexanoate, diethylaluminum Octoate, diisobutylalu be polymerized. minum 2-ethylhexanoate, dimethylaluminum neodecanoate, Suitable aluminoxane compounds include methylalumi diethylaluminum Stearate, diisobutylaluminum oleate, noxane (MAO), modified methylaluminoxane (MMAO), methylaluminum bis(hexanoate), ethylaluminum bis ethyl alumino Xane, n-propyl alumino X a ne, (Octoate), isobutylaluminum bis (2-ethylhexanoate), methy is op ropyl alumino Xane, butyl alumino Xane, laluminum bis (neodecanoate), ethylaluminum bis(Stearate), is obutyl alumino Xane, n-penty la lumino Xane, isobutylaluminum bis(oleate), dimethylaluminum ne op enty la lumino Xane, n-he Xylalumino Xane, methoxide, diethylaluminum methoxide, diisobutylalumi n-octylalumino Xane, 2-ethylhexylalumino Xane, num methoxide, dimethylaluminum ethoxide, diethylalumi 25 cylcohexylaluminoxane, 1-methylcyclopentylaluminoxane, num ethoxide, disobutylaluminum ethoxide, dimethylalu phenylaluminoxane, 2,6-dimethylphenylaluminoxane, and minum phenoxide, diethylaluminum phenoxide, the like, and mixtures thereof. Isobutylaluminoxane is par diisobutylaluminum phenoxide, methylaluminum ticularly useful on the grounds of its availability and its dimethoxide, ethylaluminum dimethoxide, isobutylalumi Solubility in aliphatic and cycloaliphatic hydrocarbon Sol num dimethoxide, methylaluminum diethoxide, ethylalumi vents. Modified methylaluminoxane can be formed by Sub num diethoxide, isobutylaluminum diethoxide, methylalu stituting about 20-80% of the methyl groups of methylalu minum diphenoxide, ethylaluminum diphenoxide, minoxane with C to C2 hydrocarbyl groups, preferably isobutylaluminum diphenoxide, and the like, and mixtures with isobutyl groups, by using techniques known to those thereof. skilled in the art. Another class of Suitable organoaluminum compounds is 35 Aluminoxanes can be used alone or in combination with aluminoxanes. Aluminoxanes comprise oligomeric linear other organoaluminum compounds. In one preferred aluminoxanes that can be represented by the general for embodiment, methyl aluminoxane and disobutyl aluminum mula: hydride are employed in combination. The term organomagnesium compound refers to any 40 magnesium compound that contains at least one magnesium V W carbon bond. Organomagnesium compounds that are Soluble in a hydrocarbon Solvent are preferred. A preferred class of R1Al-o-c-o-A R1 R1 organomagnesium compounds that can be utilized is repre sented by the general formula MgRf, where each R, which 45 may be the same or different, is a mono-Valent organic and oligomeric cyclic aluminoxanes that can be represented group, with the proviso that the group is attached to the by the general formula: magnesium atom via a carbon atom. Preferably, each R is a hydrocarbyl group Such as, but not limited to, alkyl, cycloalkyl, Substituted cycloalkyl, alkenyl, cycloalkenyl, 50 Substituted cycloalkenyl, aryl, allyl, Substituted aryl, aralkyl, ...y alkaryl, and alkynyl groups, with each group preferably R1 containing from 1 carbon atom, or the appropriate minimum number of carbon atoms to form the group, up to about 20 where X is an integer of 1 to about 100, preferably about 10 carbon atoms. These hydrocarbyl groups may contain het to about 50; y is an integer of 2 to about 100, preferably 55 eroatoms Such as, but not limited to, nitrogen, oxygen, about 3 to about 20; and where each R', which may be the Silicon, Sulfur, and phosphorus atom. Same or different, is a mono-Valent organic group that is Some specific examples of Suitable dihydrocarbylmagne attached to the aluminum atom via a carbon atom. Sium compounds that can be utilized include Preferably, each R" is a hydrocarbyl group such as, but not diethylmagne Sium, di-n-propyl magne Sium, limited to, alkyl, cycloalkyl, Substituted cycloalkyl, alkenyl, 60 diisop ropyl magne Sium, dibutyl magne Sium, cycloalkenyl, Substituted cycloalkenyl, aryl, Substituted aryl, dihe Xyl magne Sium, dip he nyl magne Sium, aralkyl, alkaryl, allyl, and alkynyl groups, with each group dibenzylmagnesium, and mixtures thereof. Dibutylmagne preferably containing from 1 carbon atom, or the appropriate sium is particularly useful due to its availability and its minimum number of carbon atoms to form the group, up to Solubility in aliphatic and cycloaliphatic hydrocarbon Sol about 20 carbon atoms. These hydrocarbyl groups may 65 VentS. contain heteroatoms Such as, but not limited to, nitrogen, Another class of organomagnesium compounds that can oxygen, boron, Silicon, Sulfur, and phosphorus atoms. It be utilized as ingredient (b) is represented by the general US 6,699,813 B2 9 10 formula RMgX, where R is a mono-valent organic group, Suitable nickel carboxylates include nickel formate, with the proviso that the group is attached to the magnesium nickel acetate, nickel acetate, nickel acrylate, nickel atom via a carbon atom, and X is a hydrogen atom, a halogen methacrylate, nickel Valerate, nickel gluconate, nickel atom, a carboxylate group, an alkoxide group, or an arylox citrate, nickel fumarate, nickel lactate, nickel maleate, nickel ide group. Where the alkylating agent is an organomagne oxalate, nickel 2-ethylhexanoate, nickel neodecanoate, sium compound that includes a labile halogen atom, the organomagnesium compound can Serve as both the alkylat nickel naphthenate, nickel Stearate, nickel oleate, nickel ing agent and the halogen-containing compound. Preferably, benzoate, and nickel picolinate. R is a hydrocarbyl group Such as, but not limited to, alkyl, Suitable nickel organophosphates include nickel dibutyl cycloalkyl, Substituted cycloalkyl, alkenyl, cycloalkenyl, phosphate, nickel dipentyl phosphate, nickel dihexyl Substituted cycloalkenyl, aryl, allyl, Substituted aryl, aralkyl, phosphate, nickel diheptyl phosphate, nickel dioctyl alkaryl, and alkynyl groups, with each group preferably phosphate, nickel bis(1-methylheptyl) phosphate, nickel bis containing from 1 carbon atom, or the appropriate minimum (2-ethylhexyl) phosphate, nickel didecyl phosphate, nickel number of carbon atoms to form the group, up to about 20 didodecyl phosphate, nickel dioctadecyl phosphate, nickel carbon atoms. These hydrocarbyl groups may contain het dioleyl phosphate, nickel diphenyl phosphate, nickel bis(p- eroatoms Such as, but not limited to, nitrogen, oxygen, 15 nonylphenyl) phosphate, nickel butyl (2-ethylhexyl) boron, Silicon, Sulfur, and phosphorus atoms. Preferably, X phosphate, nickel (1-methylheptyl) (2-ethylhexyl) is a carboxylate group, an alkoxide group, or an aryloxide phosphate, and nickel (2-ethylhexyl) (p-nonylphenyl) phos group, with each group preferably containing 1 to 20 carbon phate. atOmS. Suitable nickel organophosphonates include nickel butyl Some Suitable types of organomagnesium compounds phosphonate, nickel pentyl phosphonate, nickel hexyl that are represented by the general formula RMgX include, phosphonate, nickel heptyl phosphonate, nickel octyl but are not limited, hydrocarbylmagnesium hydride, hydro phosphonate, nickel (1-methylheptyl) phosphonate, nickel carbylmagnesium halide, hydrocarbylmagnesium (2-ethylhexyl) phosphonate, nickel decyl phosphonate, carboxylate, hydrocarbylmagnesium alkoxide, hydrocarby nickel dodecyl phosphonate, nickel octadecyl phosphonate, lmagnesium aryloxide, and mixtures thereof. 25 nickel oleyl phosphonate, nickel phenyl phosphonate, nickel Some Specific examples of Suitable organomagnesium (p - no nyl phenyl) phospho nate, nickel butyl compounds that are represented by the general formula butylphosphonate, nickel pentyl pentylphosphonate, nickel RMgX include methylmagnesium hydride, ethylmagne hexyl hexylphosphonate, nickel heptyl heptylphosphonate, sium hydride, butylmagnesium hydride, hexylmagnesium nickel octyl octylphosphonate, nickel (1-methylheptyl) hydride, phenylmagnesium hydride, benzylmagnesium (1-methylheptyl) phosphonate, nickel (2-ethylhexyl) hydride, methylmagnesium chloride, ethylmagnesium (2-ethylhexyl)phosphonate, nickel decyl decylphosphonate, chloride, butylmagnesium chloride, hexylmagnesium nickel dodecyl dodecylphosphonate, nickel octadecyl chloride, phenylmagnesium chloride, benzylmagnesium octadecylphosphonate, nickel oleyl oleylphosphonate, chloride, methylmagnesium bromide, ethylmagnesium nickel phenyl phenylphosphonate, nickel (p-nonylphenyl) bromide, butylmagnesium bromide, hexylmagnesium 35 (p-nonylphenyl)phosphonate, nickel butyl (2-ethylhexyl) bromide, phenylmagnesium bromide, benzylmagnesium phosphonate, nickel (2-ethylhexyl) butylphosphonate, bromide, methylmagnesium hexanoate, ethylmagnesium nickel (1-methylheptyl) (2-ethylhexyl)phosphonate, nickel hexanoate, butylmagnesium hexanoate, hexylmagnesium (2-ethylhexyl) (1-methylheptyl)phosphonate, nickel hexanoate, phenylmagnesium hexanoate, benzylmagnesium (2-ethylhexyl) (p-nonylphenyl)phosphonate, and nickel hexanoate, methylmagnesium ethoxide, ethylmagnesium 40 (p-nonylphenyl) (2-ethylhexyl)phosphonate. ethoxide, butylmagnesium ethoxide, hexylmagnesium Suitable nickel organophosphinates include nickel ethoxide, phenylmagnesium ethoxide, benzylmagnesium butylphosphinate, nickel pentylphosphinate, nickel ethoxide, methylmagnesium phenoxide, ethylmagnesium heXylphosphinate, nickel heptylphosphinate, nickel phenoxide, butylmagnesium phenoxide, hexylmagnesium octylphosphinate, nickel (1-methylheptyl)phosphinate, phenoxide, phenylmagnesium phenoxide, benzylmagne 45 nickel (2-ethylhexyl)phosphinate, nickel decylphosphinate, sium phenoxide, and the like, and mixtures thereof. nickel dodecylphosphinate, nickel octadecylphosphinate, Various nickel-containing compounds or mixtures thereof nickel oleylphosphinate, nickel phenylphosphinate, nickel can be employed as ingredient (c) of the catalyst composi (p-nonylphenyl)phosphinate, nickel dibutylphosphinate, tion. Preferably, these nickel-containing compounds are nickel dipentylphosphinate, nickel dihexylphosphinate, Soluble in hydrocarbon Solvents Such as aromatic 50 nickel diheptylphosphinate, nickel dioctylphosphinate, hydrocarbons, aliphatic hydrocarbons, or cycloaliphatic nickel bis(1-methylheptyl)phosphinate, nickel bis(2- hydrocarbons. Hydrocarbon-insoluble nickel-containing ethylhexyl)phosphinate, nickel didecylphosphinate, nickel compounds, however, can be Suspended in the polymeriza didodecylphosphinate, nickel dioctadecylphosphinate, tion medium to form the catalytically active Species and are nickel dioleylphosphinate, nickel diphenylphosphinate, also useful. 55 nickel bis(p-nonylphenyl)phosphinate, nickel butyl(2- The nickel atom in the nickel-containing compounds can ethylhexyl) phosphinate, nickel (1-methylheptyl) be in various oxidation States including but not limited to the (2-ethylhexyl)phosphinate, and nickel (2-ethylhexyl)(p- 0, +2, +3, and +4 oxidation States. Divalent nickel nonylphenyl)phosphinate. compounds, where the nickel atom is in the +2 oxidation Suitable nickel carba mate S include nickel State, are preferred. Suitable nickel-containing compounds 60 dimethylcarbamate, nickel diethylcarbamate, nickel include, but are not limited to, nickel carboxylates, nickel diisopropylcarbamate, nickel dibutylcarbamate, and nickel organophosphates, nickel organophosphonates, nickel dibenzylcarbamate. organophosphinate S, nickel carb amate S, nickel Suitable nickel dithiocarbamates include nickel dithiocarbamates, nickel Xanthates, nickel 3-diketonates, dimethyldithiocarbamate, nickel diethyldithiocarbamate, nickel alkoxides or aryloxides, nickel halides, nickel 65 nickel diisopropyl dithiocarb a mate, nickel pseudo-halides, nickel oxyhalides, and organonickel com dibutyldithiocarbamate, and nickel dibenzyldithiocarbam pounds. ate. US 6,699,813 B2 11 12 Suitable nickel Xanthates include nickel methylxanthate, rus Oxychloride, phosphorus oxybromide, boron trifluoride, nickel ethylxanthate, nickel isopropylxanthate, nickel boron trichloride, boron tribromide, silicon tetrafluoride, butylxanthate, and nickel benzylxanthate. Silicon tetrachloride, Silicon tetrabromide, Silicon Suitable nickel f-dike to nates include nickel tetraiodide, arsenic trichloride, arsenic tribromide, arsenic acetylacetonate, nickel trifluoroacetylacetonate, nickel triiodide, Selenium tetrachloride, Selenium tetrabromide, tel hexafluoroacetylacetonate, nickel benzoylacetonate, and lurium tetrachloride, tellurium tetrabromide, and tellurium nickel 2.2,6,6-tetramethyl-3,5-heptanedionate. tetraiodide. Suitable nickel alkoxides or aryloxides include nickel methoxide, nickel ethoxide, nickel isopropoxide, nickel Suitable metallic halides include tin tetrachloride, tin 2-ethylhexoxide, nickel phenoxide, nickel nonylphenoxide, tetrabromide, aluminum trichloride, aluminum tribromide, and nickel naphthoxide. antimony trichloride, antimony pentachloride, antimony Suitable nickel halides include nickel fluoride, nickel tribromide, aluminum triiodide, aluminum trifluoride, gal chloride, nickel bromide, and nickel iodide. Suitable nickel lium trichloride, gallium tribromide, gallium triiodide, gal pseudo-halides include nickel cyanide, nickel cyanate, lium trifluoride, indium trichloride, indium tribromide, nickel thiocyanate, nickel azide, and nickel ferrocyanide. indium triiodide, indium trifluoride, titanium tetrachloride, Suitable nickel oxyhalides include nickel oxyfluoride, nickel 15 titanium tetrabromide, titanium tetraiodide, Zinc dichloride, oxychloride and nickel oxybromide. Where nickel halides, Zinc dibromide, Zinc diiodide, and Zinc difluoride. nickel oxyhalides, or other nickel compounds containing Suitable organometallic halides include dimethylalumi labile halogen atoms are employed, the nickel-containing num chloride, diethylaluminum chloride, dimethylalumi compound can Serve as both a molecular weight regulator as num bromide, diethylaluminum bromide, dimethylalumi well as the halogen-containing compound. A Lewis base num fluoride, diethylaluminum fluoride, methylaluminum Such as an alcohol can be used as a Solubility aid for this dichloride, ethylaluminum dichloride, methylaluminum class of compounds. dibromide, ethylaluminum dibromide, methylaluminum The term organonickel compound refers to any nickel difluoride, ethylaluminum difluoride, methylaluminum compound containing at least one nickel-carbon bond. Suit SeSquichloride, ethylaluminum Sesquichloride, isobutylalu able organonickel compounds include bis(cyclopentadienyl) 25 minum Sesquichloride, methylmagnesium chloride, methyl nickel (also called nicke locene), b is magnesium bromide, methylmagnesium iodide, ethylmag (pentamethylcyclopentadienyl) nickel (also called nesium chloride, ethyl magnesium bromide, decamethylnickelocene), bis(tetramethylcyclopentadienyl) butylmagnesium chloride, butylmagnesium bromide, phe nickel, bis(ethylcyclope inta die nyl) nickel, bis nylmagnesium chloride, phenylmagnesium bromide, ben (isopropylcyclopentadienyl)nickel, bis(pentadienyl)nickel, Zylmagnesium chloride, trimethyltin chloride, trimethyltin bis(2,4-dimethylpentadienyl) nickel, (cyclopentadienyl) bromide, triethyltin chloride, triethyltin bromide, di-t- (pentadienyl) nickel, bis(1,5-cyclooctadiene) nickel, bis butyltin dichloride, di-t-butyltin dibromide, dibutyltin (allyl)nickel, bis(methallyl)nickel, and bis(crotyl)nickel. dichloride, dibutyltin dibromide, tributyltin chloride, and Various compounds, or mixtures thereof, that contain one tributyltin bromide. or more labile halogen atoms can be employed as ingredient 35 The catalyst composition of this invention has very high (d) of the catalyst composition. These compounds may catalytic activity for polymerizing conjugated dienes into Simply be referred to as halogen-containing compounds. Stereospecific polydienes over a wide range of catalyst Examples of halogen atoms include, but are not limited to, concentrations and catalyst ingredient ratioS. The polymers fluorine, chlorine, bromine, and iodine. A combination of having the most desirable properties, however, are obtained two or more halogen atoms can also be utilized. Halogen 40 within a narrower range of catalyst concentrations and containing compounds that are Soluble in a hydrocarbon catalyst ingredient ratioS. Further, it is believed that the Solvent are preferred. Hydrocarbon-insoluble halogen catalyst ingredients (a), (b), (c), and (d) may interact to form containing compounds, however, can be Suspended in the an active catalyst Species. Accordingly, the optimum con oligomerization medium to form the catalytically active centration for any one catalyst ingredient is dependent upon Species, and are therefore useful. 45 the concentrations of the other catalyst ingredients. The Useful types of halogen-containing compounds include, molar ratio of the nickel-containing compound to the lan but are not limited to, elemental halogens, mixed halogens, thanide compound (Ni/Ln) can be varied from about 0.001:1 hydrogen halides, organic halides, inorganic halides, metal to about 1:1, more preferably from about 0.005:1 to about lic halides, organometallic halides, and mixtures thereof. 0.5:1, and even more preferably from about 0.01:1 to about Suitable elemental halogens include fluorine, chlorine, 50 0.2:1. The molar ratio of the alkylating agent to the lan bromine, and iodine. Some specific examples of Suitable thanide compound (alkylating agent/Ln) can be varied from mixed halogens include iodine monochloride, iodine about 1:1 to about 200:1, more preferably from about 2:1 to monobromide, iodine trichloride, and iodine pentafluoride. about 100:1, and even more preferably from about 5:1 to Suitable hydrogen halides include hydrogen fluoride, about 50:1. The molar ratio of the halogen-containing com hydrogen chloride, hydrogen bromide, and hydrogen iodide. 55 pound to the lanthanide compound (halogen atom/Ln) can Suitable organic halides include t-butyl chloride, t-butyl be varied from about 0.5:1 to about 20:1, more preferably bromides, allyl chloride, allyl bromide, benzyl chloride, from about 1:1 to about 10:1, and even more preferably from benzyl bromide, chloro-di-phenylmethane, bromo-di about 2:1 to about 6:1. The term molar ratio, as used herein, phenylmethane, triphenylmethyl chloride, triphenylmethyl refers to the equivalent ratio of relevant components of the bromide, benzylidene chloride, benzylidene bromide, 60 ingredients, e.g., equivalents of halogen atoms on the methyltrichlorosilane, phenyltrichloro Silane, halogen-containing compound to lanthanide atoms on the dimethyldichlorosilane, diphenyldichlorosilane, lanthanide compound. trimethylchlorosilane, benzoyl chloride, benzoyl bromide, In another embodiment, the catalyst composition com propionyl chloride, propionyl bromide, methyl prises (a) a lanthanide compound, (b) an aluminoxane, and chloroformate, and methyl bromoformate. 65 (c) a nickel-containing compound, with the proviso that the Suitable inorganic halides include phosphorus trichloride, molar ratio of the aluminoxane to the lanthanide compound phosphorus tribromide, phosphorus pentachloride, phospho (Al/Ln) is from about 50:1 to about 50,000:1, preferably US 6,699,813 B2 13 14 from about 75:1 to about 30,000:1, and more preferably Third, the catalyst composition may be pre-formed in the from about 100:1 to about 1,000:1, where the molar ratio presence of at least one conjugated diene monomer. That is, refers to equivalents of aluminum atoms on the aluminoxane the catalyst ingredients are pre-mixed in the presence of a to equivalents of lanthanide atoms in the lanthanide com Small amount of conjugated diene monomer at an appropri pound. Useful lanthanide compounds, aluminoxanes, and ate temperature, which is generally from about -20° C. to nickel-containing compounds are described above. about 80°C. The amount of conjugated diene monomer that In yet another embodiment, the catalyst composition of is used for pre-forming the catalyst can range from about 1 the present invention comprises (a) a lanthanide compound, to about 500 moles per mole, more preferably from about 5 (b) an alkylating agent, (c) a nickel-containing compound, to about 250 moles per mole, and even more preferably from and (d) a non-coordinating anion or non-coordinating anion 1O about 10 to about 100 moles per mole of the lanthanide precursor. Useful lanthanide compounds, alkylating agents, compound. The resulting catalyst composition is then added and nickel-containing compounds are described above. Use to the remainder of the conjugated diene monomer that is to ful molar ratios of non-coordinating anion or non be polymerized. coordinating anion precursor to lanthanide compound (An/ Fourth, the catalyst composition may be formed by using Ln) include from about 0.5:1 to about 20:1, preferably from 15 a two-stage procedure. The first Stage involves combining about 0.75:1 to about 10:1, and more preferably from about the alkylating agent with the lanthanide compound in the 1:1 to about 6:1. absence of conjugated diene monomer or in the presence of A non-coordinating anion is a Sterically bulky anion that a Small amount of conjugated diene monomer at an appro does not form coordinate bonds with, for example, the active priate temperature, which is generally from about -20°C. to center of a catalyst System, due to Steric hindrance. Preferred about 80 C. In the Second stage, the foregoing reaction non-coordinating anions include tetraarylborate anions. mixture and the remaining catalyst components are charged More Specifically, preferred non-coordinating anions in either a Stepwise or Simultaneous manner to the remainder include fluorinated tetraarylborate anions. Ionic compounds of the conjugated diene monomer that is to be polymerized. containing non-coordinating anions are known in the art, Fifth, the catalyst composition may be formed by using a and also include a counter cation Such as a carbonium, 25 different two-stage procedure. The first stage involves com ammonium, or phosphonium cation. Triarylcarbonium cat bining the alkylating agent with the lanthanide compound ions are preferred. A Specific example of a preferred com and the nickel-containing compound in the absence of pound containing a non-coordinating anion that may be conjugated diene monomer or in the presence of a Small utilized as ingredient (d) of the catalyst composition of this amount of conjugated diene monomer at an appropriate embodiment is trip he nyl carbonium tetrakis temperature, which is generally from about -20° C. to about (pentafluoropheynyl)borate. 80 C. In the Second Stage, the foregoing reaction mixture A non-coordinating anion precursor may also be used as and the halogen-containing compound, non-coordinating ingredient (d) of this embodiment. A non-coordinating anion anion, or non-coordinating anion precursor are charged in precursor is a Substance that is able to form a non either a Stepwise or Simultaneous manner to the remainder of coordinating anion under reaction conditions. Useful non 35 the conjugated diene monomer that is to be polymerized. coordinating anion precursors include trialkyl boron When a Solution of the catalyst composition or one or compounds, BR, where R is a strong electron-withdrawing more of the catalyst ingredients is prepared outside the group, Such as pentafluorophenyl group. polymerization System as Set forth in the foregoing methods, The catalyst composition is formed by combining or an organic Solvent or carrier is preferably employed. The mixing the catalyst ingredients (a), (b), (c), and (d). 40 organic Solvent may serve to dissolve the catalyst compo Although an active catalyst Species is believed to result from Sition or ingredients, or the Solvent may simply Serve as a this combination, the degree of interaction or reaction carrier in which the catalyst composition or ingredients may between the various ingredients or components is not known be Suspended. The organic Solvent is preferably inert to the with any great degree of certainty. Therefore, the term catalyst composition. Useful Solvents include hydrocarbon “catalyst composition' has been employed to encompass a 45 Solvents Such as aromatic hydrocarbons, aliphatic Simple mixture of the ingredients, a complex of the various hydrocarbons, and cycloaliphatic hydrocarbons. Non ingredients that is caused by physical or chemical forces of limiting examples of aromatic hydrocarbon Solvents include attraction, a chemical reaction product of the ingredients, or benzene, toluene, Xylenes, ethylbenzene, diethylbenzene, a combination of the foregoing. mesitylene, and the like. Non-limiting examples of aliphatic The catalyst composition of this invention can be formed 50 hydrocarbon Solvents include n-pentane, n-hexane, by using one of the following methods. n-heptane, n-octane, n-nonane, n-decane, isopentane, First, the catalyst composition may be formed in Situ by isohexanes, isopentanes, isooctanes, 2,2-dimethylbutane, adding the catalyst ingredients to a Solution containing petroleum ether, kerosene, petroleum Spirits, and the like. monomer and Solvent, or simply bulk monomer, in either a And, non-limiting examples of cycloaliphatic hydrocarbon Stepwise or simultaneous manner. When adding the catalyst 55 Solvents include cyclope ntane, cyclohexane, ingredients in a stepwise manner, the Sequence in which the methylcyclopentane, methylcyclohexane, and the like. catalyst ingredients are added is not critical. Preferably, Commercial mixtures of the above hydrocarbons may also however, the alkylating agent is added first, followed by the be used. For environmental reasons, aliphatic and lanthanide compound, followed by the nickel-containing cycloaliphatic Solvents are highly preferred. compound, and then followed by the halogen-containing 60 The catalyst composition of this invention exhibits very compound, if used, or by the non-coordinating anion or high catalytic activity for polymerizing conjugated dienes non-coordinating anion precursor. into cis-1,4-polydienes. Although one preferred embodiment Second, the catalyst ingredients may be pre-mixed outside is directed toward the polymerization of 1,3-butadiene into the polymerization System at an appropriate temperature, cis-1,4-polybutadiene, other conjugated dienes can also be which is generally from about -20° C. to about 80 C., and 65 polymerized. Some specific examples of other conjugated the resulting catalyst composition is then added to the dienes that can be polymerized include isoprene, 1,3- monomer Solution. pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, US 6,699,813 B2 15 16 2-ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl ing by evaporation of the monomer or the Solvent, or a 1,3-pentadiene, 4-methyl-1,3-pentadiene, and 2,4- combination of the two methods. Although the polymeriza hexadiene. Mixtures of two or more conjugated dienes may tion pressure employed may vary widely, a preferred pres also be utilized in copolymerization. Sure range is from about 1 atmosphere to about 10 atmo The production of cis-1,4-polydiene is accomplished by Spheres. polymerizing conjugated diene monomer in the presence of Once a desired conversion is achieved, the polymerization a catalytically effective amount of the foregoing catalyst can be stopped by adding a polymerization terminator that composition. The total catalyst concentration to be inactivates the catalyst. Typically, the terminator employed employed in the polymerization mass depends on the inter is a protic compound, which includes, but is not limited to, play of various factorS Such as the purity of the ingredients, an alcohol, a carboxylic acid, an inorganic acid, water, or a the polymerization temperature, the polymerization rate and mixture thereof. conversion desired, the molecular weight desired, and many The polymers prepared by using the catalyst composition other factors. Accordingly, a specific total catalyst concen of this invention advantageously have Some degree of tration cannot be definitively Set forth except to Say that pseudo-living characteristics. As a result, these polymers can catalytically effective amounts of the respective catalyst 15 be coupled or functionalized by reacting them with Suitable ingredients should be used. Generally, the amount of the coupling agents or functonalizing agents prior to or in lieu lanthanide compound used can be varied from about 0.01 to of terminating the polymer. Exemplary coupling and func about 2 mmol, more preferably from about 0.02 to about 1 tionalizing agents include, but are not limited to, metal mmol, and even more preferably from about 0.05 to about halides, metalloid halides, alkoxysilanes, imine-containing 0.5 mmol per 100 g of conjugated diene monomer. compounds, esters, ester-carboxylate metal complexes, alkyl The polymerization is preferably carried out in an organic ester carboxylate metal complexes, aldehydes or ketones, Solvent as the diluent. In one embodiment, a Solution poly amides, isocyanates, isothiocyanates, imines, and epoxides. merization System is employed, which is a System where the These types of coupling and functionalizing agents are monomer to be polymerized and the polymer formed are described in, among other places, International Application Soluble in the polymerization medium. Alternatively, a pre 25 Nos. PCT/US00/30743, PCT/US00/30875, and PCT/US00/ cipitation polymerization System may be employed by 30743; U.S. Pat. Nos. 4,906,706, 4,990,573, 5,064,910, choosing a Solvent in which the polymer formed is insoluble. 5,567,784, 4,736,001, 4,699,960, and 5,844,050; Japanese In both cases, the monomer to be polymerized is in a Patent Application Nos. 05-051406A, 05-059103A, condensed phase. Also, the catalyst ingredients are prefer 10-306113A, and 11-035633A, which are incorporated ably Solubilized or Suspended within the organic Solvent. In herein by reference. These coupling and functionalizing other words, the catalyst ingredients are preferably not agents can be reacted with the pseudo-living polymers by impregnated onto a catalyst Support. admixing them together. The amount of functionalizing In performing these polymerizations, an amount of agent that is used can vary. Preferably, from about 0.01 to organic Solvent in addition to the amount of organic Solvent about 200 moles, and more preferably from about 0.1 to that may be used in preparing the catalyst composition is 35 about 150 moles, of functionalizing agent per mole of preferably added to the polymerization System. The addi lanthanide compound should be employed. tional organic Solvent may be the same as or different from An antioxidant Such as 2,6-di-tert-butyl-4-methylphenol the organic Solvent used in preparing the catalyst composi may be added along with, before, or after the addition of the tion. An organic Solvent that is inert with respect to the terminator. The amount of the antioxidant employed is catalyst composition employed to catalyze the polymeriza 40 usually in the range of 0.2% to 1% by weight of the polymer tion is preferably Selected. Exemplary hydrocarbon Solvents product. have been set forth above. When a solvent is employed, the When the polymerization has been Stopped, the cis-1,4- concentration of the monomer to be polymerized is not polydiene product can be recovered from the polymerization limited to a Special range. Preferably, however, the concen mixture by utilizing conventional procedures of desolventi tration of the monomer present in the polymerization 45 Zation and drying. For instance, the polymer may be isolated medium at the beginning of the polymerization should be in from the polymerization mixture by coagulating the poly a range of from about 3% to about 80% by weight, more merization mixture with an alcohol Such as methanol, preferably from about 5% to about 50% by weight, and even ethanol, or isopropanol, followed by filtration, or by Steam more preferably from about 10% to about 30% by weight. distilling the Solvent and the unreacted monomer, followed The polymerization of conjugated dienes may also be 50 by filtration. The isolated polymer product is then dried to carried out by means of bulk polymerization, which refers to remove residual amounts of Solvent and water. Alternatively, a polymerization environment where no Solvents are the polymer may be isolated from the polymerization mix employed. The bulk polymerization can be conducted either ture by directly drum drying the polymer cement. in a condensed liquid phase or in a gas phase. The isolation, drying, and handling of low molecular The polymerization of conjugated dienes may be carried 55 weight polydiene (especially, liquid polydiene) by itself is out as a batch process, a continuous process, or a Semi generally difficult. Therefore, when a low molecular weigh continuous process. In the Semi-continuous process, mono polydiene is produced by polymerization, the resulting poly mer is intermittently charged as needed to replace that mercement is preferably blended with the cement of a high monomer already polymerized. In any case, the polymer molecular weight polydiene, and the resultant cement blend ization is preferably conducted under anaerobic conditions 60 is then worked up by using the conventional procedures of by using an inert protective gas Such as nitrogen, argon or deSolventization and drying, as described above. helium, with moderate to Vigorous agitation. The polymer Where 1,3-butadiene is polymerized, the number average ization temperature may vary widely from a low molecular weight (M) of the cis-1,4-polybutadiene is temperature, Such as -10°C. or below, to a high temperature advantageously from about 5,000 to about 150,000, more such as 100° C. or above, with a preferred temperature range 65 advantageously from about 10,000 to about 80,000, and being from about 20° C. to about 90° C. The heat of even more advantageously from about 20,000 to about polymerization may be removed by external cooling, cool 50,000, as determined by using gel permeation chromatog US 6,699,813 B2 17 18 raphy (GPC) with polystyrene standards. The polydispersity The polymer had a Mooney viscosity of 48.6. The Mooney of these polymers is preferably from about 1.5 to about 5.0, viscosity (ML) was determined at 100° C. with a Mon and more preferably from about 2.0 to about 4.0. A broad Santo Mooney Viscometer using a large rotor, a one-minute range of polymer molecular weights can be achieved by warm-up time, and a four-minute running time. AS deter using the catalyst System of this invention with Significantly mined by gel permeation chromatography (GPC) that was leSS catalyst and co-catalyst levels than conventional catalyst calibrated by using polystyrene Standards and Mark that do not employ nickel-containing compounds. Houwink constants for cis-polybutadiene, the polymer had a The preferred cis-1,4-polydienes are low molecular number average molecular weight (M) of 131,000, a weight weight polydienes. These low molecular weight polydienes average molecular weight (M) of 330,000, and a polydis are prepared with Surprisingly low catalyst levels. For persity index (M/M) of 2.5. The infrared spectroscopic example, cis-1,4-polybutadiene having an M., of less than analysis of the polymer indicated a cis-1,4-linkage content 50,000, advantageously less than 40,000, more advanta of 97.1%, a trans-1,4-linkage content of 2.3%, and a 1,2- geously less than 30,000, and even more advantageously linkage content of 0.7%. The monomer charge, the amounts less than 20,000 can be prepared by using less than 0.5 of the catalyst ingredients, and the properties of the resulting mmol, advantageously less than 0.4 mmol, more advanta 15 cis-1,4-polybutadiene are Summarized in Table I. geously less than 0.3 mmol, and even more advantageously less than 0.2 mmol of lanthanide compound per 100 g of TABLE I 1,3-butadiene monomer. In the absence of the nickel containing compounds, preferably high levels of lanthanide Example No. 1. 2 3 4 5 compound would be required to produce these low molecu Hexanes (g) 125.6 125.6 125.6 125.6 125.6 lar weight polymers. 22.4%. 1,3-butadienef 231.5 231.5 231.5 231.5 231.5 The cis-1,4-polydienes prepared with the catalyst com hexanes (g) i-BusAl (mmol) 2.55 2.55 2.55 2.55 2.55 position of this invention advantageously can have a cis-1, Nd(versatate) (mmol) O.O85 O.085 O.O85 O.O85 O.O85 4-linkage content that is greater than about 60%, more Ni(EHA), (mmol) O O.OOO85 O.OO255 O.OO51 O.OO85 advantageously greater than about 75%, Still more advanta 25 EtAICl (mmol) O.128 O.128 O.128 O.128 O.128 geously greater than about 90%, and even more advanta NdiAlfC molar ratio 1:30:3 1:30:3 1:30:3 1:30:3 1:30:3 Ni/Nd molar ratio O O.O10 O.O3O O.O60 O.10 geously greater than about 95%. Also, these polymers may Polymer yield (%) after 96 96 96 95 95 advantageously have a 1.2-linkage content that is less than 1 hr at 65° C. about 7%, more advantageously less than 5%, still more Mooney viscosity 48.6 38.1 28.1 19.O 16.9 advantageously less than 2%, and even more advanta (ML) M 131,000 120,000 97,000 76,000 68,000 geously less than 1%. The cis-1,4- and 1.2-linkage content Mw 330,000 282,000 246,000 210,000 206,000 can be determined by infrared spectroScopy. MwFM 2.5 2.4 2.5 2.8 3.1 The high cis-1,4-polydienes produced with the catalyst Polymer microstructure: composition of this invention has many uses. It can be 35 cis-1,4-linkage content 97.1 96.4 96.O 95.7 96.O blended into and concurred with various natural or Synthetic (%) rubbers in order to improve the properties thereof. For trans-1,4-linkage content 2.3 3.0 3.3 3.6 3.3 example, it can be incorporated into elastomers in order to (%) improve tensile properties, abrasion and fatigue resistance, 1.2-linkage content (%) O.7 O6 O.7 O.7 O.6 and to reduce hysteresis loss. Accordingly, the cis-1,4- polydienes, especially high cis-1,4-polybutadiene, is useful 40 in rubber compositions that are useful for tire treads and tire sidewalls. Examples 2-5 In order to demonstrate the practice of the present In Examples 2–5, the procedure in Example 1 was invention, the following examples have been prepared and repeated except that various amounts of Ni(II) tested. The examples should not, however, be viewed as 45 2-ethylhexanoate were included as an additional ingredient limiting the scope of the invention. The claims will serve to of the catalyst composition. The catalyst ingredients were define the invention. charged into the bottle in the following order: (1) triisobutylaluminum, (2) neodymium(III) versatate, (3) EXAMPLES Ni(II) 2-ethylhexanoate, and (4) ethylaluminum dichloride. Example 1 (Control) 50 The molar ratio of the nickel compound to the neodymium compound was varied. The monomer charge, the amounts of An oven-dried 1-liter glass bottle was capped with a the catalyst ingredients, and the properties of the resulting Self-sealing rubber liner and a perforated metal cap. After the bottle was thoroughly purged with a stream of dry nitrogen, cis-1,4-polybutadiene are Summarized in Table I. the bottle was charged with 125.6 g of hexanes and 231.5 g. 55 The results described in Examples 1-5 show that small of a 1,3-butadiene/hexanes blend containing 21.6% by amounts of a nickel compound can effectively reduce the weight of 1,3-butadiene. The following catalyst ingredients molecular weight of cis-1,4-polybutadiene without affecting were then charged into the bottle in the following order: (1) the catalyst activity and polymer microStructure Such as 2.55 mmol of triisobutylaluminum, (2) 0.085 mmol of cis-1,4-linkage content. neodymium(III) versatate, and (3) 0.128 mmol of ethylalu 60 minum dichloride. The bottle was placed in a water bath Examples 6-9 maintained at 65° C. After 1 hour, the polymerization was terminated by addition of 3 mL of isopropanol containing In Examples 6-9, the procedures in Example 1-5 were 0.30 g of 2,6-di-tert-butyl-4-methylphenol. The resulting repeated except that diisobutylaluminum hydride was Sub polymer cement was coagulated with 3 liters of isopropanol 65 Stituted for triisobutylaluminum. The monomer charge, the containing 0.5 g of 2,6-di-tert-butyl-4-methylphenol, and amounts of the catalyst ingredients, and the properties of the then drum-dried. The yield of the polymer was 48.0 g (96%). resulting cis-1,4-polybutadiene are Summarized in Table II. US 6,699,813 B2 19 20 6. The composition of claim 1, where Said alkylating TABLE II agent is an organoaluminum compound represented by the formula AllR.X., where each R, which may be the same or Example No. different, is a mono-Valent organic group that is attached to the aluminum atom via a carbon atom, where each X, which 6 7 8 9 may be the same or different, is a hydrogen atom, a halogen Hexanes (g) 125.6 125.6 125.6 125.6 atom, a carboxylate group, an alkoxide group, or an arylox 22.4%. 1,3-butadiene/hexanes (g) 231.5 231.5 231.5 231.5 ide group, and where n is an integer of 1 to 3. i-BuAIH (mmol) 1.7O 1.70 1.70 1.70 7. The composition of claim 1, where said halogen Nd(versatate) (mmol) O.O85 0.085 O.O85 O.O85 Ni(EHA), (mmol) O O.OO17 O.OO34 O.OO51 containing compound includes elemental halogen, mixed EtAICl (mmol) O.128 0.128 O.128 O.128 halogen, hydrogen halide, organic halide, inorganic halide, NdiAlfC molar ratio 1:30:3 1:30:3 1:30:3 1:30:3 metallic halide, organometallic halide, or mixtures thereof. Ni/Nd molar ratio O O.O2O O.O40 O.O60 8. The composition of claim 1, where the molar ratio of Polymer yield (%) after 1 hr at 97 96 97 96 65° C. Said alkylating agent to Said lanthanide compound is from Mooney viscosity (ML) 18.6 4.7 15 about 1:1 to about 200:1, and the molar ratio of said M 62,657 38,842 33,036 31,500 halogen-containing compound to Said lanthanide compound Mw 356,022 165,811 134,695 127,998 is from about 0.5:1 to about 20:1. M/M 5.7 4.3 4.1 4.1 9. The composition of claim 1, where the molar ratio of Polymer microstructure: Said alkylating agent to Said lanthanide compound is from cis-1,4-linkage content (%) 96.4 93.6 92.2 92.5 about 2:1 to about 100:1, and the molar ratio of said trans-1,4-linkage content (%) 2.6 5.6 6.9 6.6 halogen-containing compound to Said lanthanide compound 1.2-linkage content (%) 1.O O.9 O.9 O.9 is from about 1:1 to about 10:1. 10. The composition of claim 1, where the lanthanide The Mooney Viscosities of the polymer Samples made in compound, the alkylating agent, the nickel-containing compound, and the optional halogen-containing compound Examples 8 and 9 were too low to be measured. 25 Various modifications and alterations that do not depart are dissolved or Suspended in an organic Solvent. from the scope and spirit of this invention will become 11. A catalyst composition formed by a proceSS compris apparent to those skilled in the art. This invention is not to ing the Step of combining ingredients consisting essentially be duly limited to the illustrative embodiments set forth of: herein. (a) an lanthanide compound; What is claimed is: (b) an alkylating agent; 1. A catalyst composition that is the combination of or the (c) a nickel-containing compound; and optionally reaction product of ingredients consisting essentially of (d) a halogen-containing compound that includes one or (a) an lanthanide compound; more labile halogen atoms, where each labile halogen (b) an alkylating agent; 35 atom, which may be the same or different, is a chlorine, (c) a nickel-containing compound; and optionally bromine, or iodine atom, with the proviso that the (d) a halogen-containing compound that includes one or halogen-containing compound must be present where more labile halogen atoms, where each labile halogen none of the lanthanide compound, the alkylating agent, atom, which may be the same or different, is a chlorine, and the nickel-containing compound contain a labile bromine, or iodine atom, with the proviso that the 40 halogen atom. halogen-containing compound must be present where 12. A proceSS for lowering the molecular weight of none of the lanthanide compound, the alkylating agent, polydienes prepared with a lanthanide-based catalyst and the nickel-containing compound contain a labile System, Said process comprising: halogen atom. polymerizing conjugated dienes with a lanthanide-based 2. The composition of claim 1, where Said nickel 45 catalyst System that is formed by the ingredients con containing compound is a nickel carboxylate, nickel Sisting essentially of (a) a lanthanide compound, (b) an organophosphate, nickel organophosphonate, nickel alkylating agent, (c) a nickel-containing compound, organophosphinate, nickel carb amate, nickel and optionally (d) a halogen-containing compound that dithiocarbamate, nickel Xanthate, nickel B-diketonate, nickel includes one or more labile halogen atoms, where each alkoxide or aryloxide, nickel halide, nickel pseudo-halide, 50 labile halogen atom, which may be the same or nickel oxyhalide, organonickel compound, or mixture different, is a chlorine, bromine, or iodine atom, with thereof. the proviso that the halogen-containing compound 3. The composition of claim 1, where the molar ratio of must be present where none of the lanthanide Said nickel-containing compound to Said lanthanide com compound, the alkylating agent, and the nickel pound is 0.001:1 to about 1:1. 55 containing compound contain a labile halogen atom. 4. The composition of claim 1, where the molar ratio of 13. The process of claim 12, where said conjugated dienes Said nickel-containing compound to Said lanthanide com are in their condensed phase. pound is 0.005:1 to about 0.5:1. 14. The process of claim 12, where the molar ratio of said 5. The composition of claim 1, where said lanthanide nickel-containing compound to Said lanthanide compound is compound is a neodymium carboxylate, neodymium 60 from about 0.001:1 to about 1:1. organophosphate, neodymium organophosphonate, neody 15. The process of claim 12, where said step of combining mium organophosphinate, neodymium carbamate, neody comprises combining Said alkylating agent with Said lan mium dithiocarbamate, neodymium Xanthate, neodymium thanide compound to form a mixture, and Subsequendy 3-diketonate, neodymium alkoxide or aryloxide, neody adding Said nickel-containing compound and Said halogen mium halide, neodymium pseudo-halide, neodymium 65 containing compound to Said mixture. oxyhalide, organoneodymium compound, or mixture 16. The process of claim 12, where said Step of combining thereof. comprises combining Said alkylating agent, Said lanthanide US 6,699,813 B2 21 22 compound, and Said nickel-containing compound to form a dimethylaluminum bromide, diethylaluminum bromide, mixture, and Subsequendy adding Said halogen-containing methylaluminum dichloride, ethylaluminum dichloride, compound to Said mixture. methylaluminum dibromide, ethylaluminum dibromide, 17. The process of claim 12, where said nickel-containing methylaluminum Sesquichloride, ethylaluminum compound is a nickel carboxylate, nickel organophosphate, SeSquichioride, isobutylaluminum Sesquichloride, methyl nickel organophosphonate, nickel organophosphinate, magnesium chloride, methylmagnesium bromide, methyl nickel carbamate, nickel dithiocarbamate, nickel Xanthate, magnesium iodide, ethylmagnesium chloride, ethylmagne nickel B-diketonate, nickel alkoxide or aryloxide, nickel sium bromide, butylmagnesium chloride, butylmagnesium halide, nickel pseudo-halide, nickel oxyhalide, organonickel bromide, phenylmagnesium chloride, phenylmagnesium compound, or mixture thereof. bromide, benzylmagnesium chloride, trimethyltin chloride, 18. The process of claim 12, where the molar ratio of said trimethyltin bromide, triethyltin chloride, triethyltin alkylating agent to Said lanthanide compound is from about bromide, di-t-butyltin dichloride, di-t-butyltin dibromide, 1:1 to about 200:1, and the molar ratio of said halogen dibutyltin dichloride, dibutyltin dibromide, tributyltin containing compound to Said lanthanide compound is from chloride, tributyltin bromide, or mixtures thereof. about 0.5:1 to about 20:1. 15 22. The catalyst composition of claim 21, where Said 19. A proceSS for forming conjugated diene polymers halogen-containing compound is dimethylaluminum comprising the Step of: chloride, diethylaluminum chloride, dimethylaluminum polymerizing conjugated diene monomers in the presence bromide, diethylaluminum bromide, methylaluminum of a catalytically effective amount of a catalyst com dichioride, ethylaluminum dichioride, methylaluminum position formed by combining the ingredients consist dibromide, ethylaluminum dibromide, methylaluminum ing essentially of: SeSquichioride, ethylaluminum Sesquichioride, isobutylalu (a) an lanthanide compound; minum Sesquichioride, methylmagnesium chloride, methyl (b) an alkylating agent; magnesium bromide, methylmagnesium iodide, ethylmag (c) a nickel-containing compound; and optionally nesium chloride, ethyl magnesium bromide, (d) a halogen-containing compound that includes one 25 butylmagnesium chloride, butylmagnesium bromide, phe or more labile halogen atoms, where each labile nylmagnesium chloride, phenylmagnesium bromide, halogen atom, which may be the Same or different, is beuZylmagnesium chloride, trimethyltin chloride, trimeth a chlorine, bromine, or iodine atom, with the proviso yltin bromide, triethyltin chloride, triethyltin bromide, di-t- that the halogen-containing compound must be butyltin dichioride, di-t-butyltin dibromide, dibutyltin present where none of the lanthanide compound, the dichioride, dibutyltin dibromide, tributyltin chloride, tribu alkylating agent, and the nickel-containing com tyltin bromide, or mixtures thereof. pound contain a labile halogen atom. 23. The catalyst composition of claim 21, where said 20. The process of claim 19, where Said conjugated diene lanthanide compound is a lanthanide carboxylate, lanthanide monomers consist essentially of 1,3-butadiene, thereby organophosphate, lanthanide organophosphonate, lan forming cis-1,4-polybutadiene, where Said catalytically 35 thanide organophosphinate, lanthanide carbamate, lan effective amount includes from about 0.01 to about 2 mmol thanide dithiocarbamate, lanthanide Xanthate, lanthanide of lanthanide-containing compound per 100 g of monomer; 3-diketonate, lanthanide alkoxide or aryloxide, lanthanide and where Said 1,3-butadiene is in its condensed phase. pseudo-halide, organolanthanide compound, or mixture 21. The catalyst composition of claim 1, where said thereof. halogen-containing compound is elemental chlorine, 40 24. The catalyst composition of claim 21, where Said elemental bromine, elemental iodine, hydrogen chloride, lanthanide compound is a neodymium oxychloride, neody hydrogen bromide, hydrogen iodide, iodine monochioride, mium oxybromide, or mixtures thereof. iodine monobromide, iodine trichioride, t-butyl chloride, 25. The catalyst composition of claim 23, where said t-butyl bromides, allyl chloride, allyl bromide, benzyl nickel-containing compound is a nickel carboxylate, nickel chloride, benzyl bromide, chioro-di-phenylmethane, bromo 45 organophosphate, nickel organophosphonate, nickel di-phenylmethane, triphenylmethyl chloride, triphenylm organophosphlnate, nickel carb amate, nickel ethyl bromide, benzylidene chloride, benzylidene bromide, dithiocarbamate, nickel Xanthate, nickel B-diketonate, nickel methyltrichlorosilane, phenyltrichloro Silane, alkoxide or aryloxide, nickel pseudo-halide, organonickel dimethyldichlorosilane, diphenyldichioro Silane, compound, or mixture thereof. trimethylchlorosilane, benzoyl chloride, benzoyl bromide, 50 26. The catalyst composition of claim 23, where said propionyl chloride, propionyl bromide, methyl nickel-containing compound is a nickel chloride, nickel chioroformate, methyl bromoformate, phosphorus bromide, and nickel iodide, oxychioride, nickel oxybromide, trichloride, phosphorus tribromide, phosphorus or mixtures thereof. pent achioride, phosphorus oxychloride, phosphorus 27. The catalyst composition of claim 25, where said oxybromide, boron trichloride, boron tribromide, silicon 55 alkylating agent is an organoaluminum compound repre tetrachloride, Silicon tetrabromide, Silicon tetraiodide, Sented by the formula AlRX, where each R, which may arsenic trichloride, arsenic tribromide, arsenic triiodide, be the same or different, is a mono-Valent organic group that Selenium tetrachloride, Selenium tetrabromide, tellurium is attached to the aluminum atom via a carbon atom, where tetrachloride, tellurium tetrabromide, tellurium tetraiodide, each X, which may be the Same or different, is a hydrogen tin tetrachloride, tin tetrabromide, aluminum trichloride, 60 atom, a chlorine atom, bromine atom, iodine atom, a car aluminum tribromide, antimony trichloride, antimony boxylate group, an alkoxide group, or an aryloxide group, pentachloride, antimony tribromide, aluminum triiodide, and where n is an integer of 1 to 3. gallium trichloride, gallium tribromide, gallium triiodide, 28. The catalyst composition of claim 25, where said indium trichloride, indium tribromide, indium triiodide, alkylating agent is an aluminoxane. titanium tetrachloride, titanium tetrabromide, titanium 65 29. The catalyst composition of claim 25, where said tetraiodide, Zinc dichioride, Zinc dibromide, Zinc diiodide, alkylating agent is an organomagnesium compound repre dimethylaluminum chloride, diethylaluminum chloride, sented by the formula MgRf, where each R, which may be US 6,699,813 B2 23 24 the same or different, is a mono-Valent organic group, with organic group, with the proviso that the group is attached to the proviso that the group is attached to the magnesium atom the magnesium atom via a carbon atom, and X is a hydrogen via a carbon atom. atom, a chlorine atom, a bromine atom, an iodine atom, a 30. The catalyst composition of claim 25, where said carboxylate group, an alkoxide group, or an aryloxide group. alkylating agent is an organomagnesium compound repre- 5 sented by the formula RMgX, where R is a mono-valent k . . . .