Metal-based catalysts for producing polydienes

Abstract

Disclosed is a method for producing a polymer, the method comprising polymerizing a conjugated diene monomer in the presence of a lanthanide-based catalyst system, the lanthanide-based catalyst system comprising: (i) a lanthanide-containing compound, (ii) triethylaluminum, (iii) aluminum hydride, and (iv) a halogen-containing compound; or a method for producing a polymer, the method comprising polymerizing a conjugated diene monomer in the presence of a lanthanide-based catalyst system, the lanthanide-based catalyst system comprising: (i) a nickel-containing compound, (ii) triethylaluminum, (iii) aluminum hydride, and (iv) a halogen-containing compound selected from a fluorine-containing compound and a chlorine-containing compound.

Description

[0001] This application claims the benefit of U.S. Provisional Application Serial No. 63 / 002,407, filed March 31, 2020, which is incorporated herein by reference. Technical Field

[0002] One or more embodiments of the present invention relate to a method for polymerizing conjugated dienes using a metal-based catalyst system. Background Technology

[0003] Synthetic elastomers with linear backbones are commonly used in the manufacture of tire components, such as sidewalls and treads. These polymers are believed to offer favorable tensile properties, abrasion resistance, low hysteresis, and fatigue resistance. For example, cis-1,4-polydiene has been used in tires.

[0004] Cis-1,4-polydienes can be produced using either lanthanide-based or nickel-based catalyst systems. Lanthanide-based catalyst systems typically consist of a lanthanide-based compound, an alkylating agent, and a halogen source for activation. Nickel-based catalyst systems typically consist of a nickel-containing compound, an alkylating agent, and a halogen source for activation. Alkylaluminum compounds, such as trialkylaluminum compounds and alkylaluminum hydrides, are frequently used as alkylating agents. The type of each component chosen, their relative concentrations, and many other factors influence the polymerization process and the resulting polydiene. For example, triisobutylaluminum is known to produce higher monomer conversion and higher cis-1,4-microstructure content than triethylaluminum when used as an alkylating agent in lanthanide-based systems. Summary of the Invention

[0005] One or more embodiments of the present invention provide a method for preparing a polymer, the method comprising polymerizing a conjugated diene monomer in the presence of a lanthanide-based catalyst system comprising a lanthanide-containing compound, triethylaluminum, aluminum hydride and a halogen-containing compound.

[0006] Other embodiments of the present invention provide a polymer prepared by polymerizing a conjugated diene monomer in the presence of a lanthanide-based catalyst system comprising a lanthanide-containing compound, triethylaluminum, aluminum hydride, and a halogen-containing compound.

[0007] Other embodiments of the present invention provide a method for preparing a polymer, comprising polymerizing a conjugated diene monomer in the presence of a metal-based catalyst system comprising a nickel-containing compound, triethylaluminum, aluminum hydride, and a halogenated compound selected from fluorine-containing and chlorine-containing compounds.

[0008] Other embodiments of the present invention provide a polymer prepared by polymerizing a conjugated diene monomer in the presence of a metal-based catalyst system comprising a nickel-containing compound, triethylaluminum, aluminum hydride, and a halogen-containing compound. Detailed Implementation

[0009] Embodiments of the present invention are based, at least in part, on the discovery of a polymerization method for conjugated dienes employing a metal-based catalyst system comprising triethylaluminum and aluminum hydride as alkylating agents. The use of this particular combination of alkylating agents unexpectedly yielded advantageous results, including improved polymerization activity and favorable polymer properties. While prior art indicates that the use of triethylaluminum as an alkylating agent results in lower polymerization activity than other commonly used trialkylaluminum compounds (e.g., triisobutylaluminum), findings relevant to this invention suggest that this combination of triethylaluminum and aluminum hydride produces particularly advantageous results relative to other alkylating agents such as triisobutylaluminum, especially in terms of polymerization activity and resulting polymer properties with lanthanide-based catalysts. Other embodiments are based, at least in part, on the discovery of a polymerization method for conjugated dienes employing a nickel-based catalyst system comprising triethylaluminum and aluminum hydride as alkylating agents. This particular combination of alkylating agents also offers advantages over alkylating agents used with these catalyst systems in conventional methods.

[0010] The first set of embodiments provides a polymerization method in which a conjugated diene monomer is polymerized in the presence of a lanthanide-based catalyst system comprising (i) a lanthanide-containing compound, (ii) triethylaluminum, (iii) aluminum hydride, and (iv) a halogen-containing compound. In one or more embodiments, in addition to the above-described components, other organometallic compounds, Lewis bases, and / or catalyst modifiers may be used.

[0011] The second set of embodiments provides a polymerization method in which a conjugated diene monomer is polymerized in the presence of a nickel-based catalyst system comprising (i) a nickel-containing compound, (ii) triethylaluminum, (iii) aluminum hydride, and (iv) a halogenated compound selected from chlorine-containing and fluorine-containing compounds. In one or more embodiments, in addition to the above-described components, other organometallic compounds, Lewis bases, and / or catalyst modifiers may be used.

[0012] Compounds containing lanthanides

[0013] Lanthanide-containing compounds that can be used in lanthanide-based catalyst systems include those containing at least one atom selected from lanthanum, neodymium, cerium, praseodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, and neodymium-praseodymium. In one embodiment, these compounds may contain neodymium, lanthanum, samarium, or neodymium-praseodymium. As used herein, the term "neodymium-praseodymium" should refer to a commercially available mixture of rare earth elements obtained from monazite sands. Furthermore, lanthanide-containing compounds that can be used in this invention may be in the form of elemental lanthanides.

[0014] In lanthanide-containing compounds, the lanthanide atoms can be in various oxidation states, including but not limited to 0, +2, +3, and +4 oxidation states. In one embodiment, a trivalent lanthanide-containing compound in which the lanthanide atoms are in the +3 oxidation state may be used. Suitable lanthanide-containing compounds include, but are not limited to, lanthanide carboxylates, lanthanide organophosphates, lanthanide organophosphonates, lanthanide organosphines, lanthanide carbamates, lanthanide dithiocarbamates, lanthanide xanthates, lanthanide β-diketonates, lanthanide oxides, lanthanide alkoxides or phenolates, lanthanide halides, lanthanide pseudohalides, lanthanide halide oxides, and organolanthanide compounds.

[0015] In one or more embodiments, the lanthanide-containing compounds are soluble in hydrocarbon solvents such as aromatic hydrocarbons, aliphatic hydrocarbons, or alicyclic hydrocarbons. However, lanthanide-containing compounds that are insoluble in hydrocarbons can also be used in this invention because they can be suspended in the polymerization medium to form catalytically active substances.

[0016] For ease of explanation, further discussion of available lanthanide-containing compounds will focus on neodymium compounds, but those skilled in the art will be able to choose similar compounds based on other lanthanide metals.

[0017] Suitable neodymium carboxylates include, but are not limited to, neodymium formate, neodymium acetate, neodymium acrylate, neodymium methacrylate, neodymium valerate, neodymium gluconate, neodymium citrate, neodymium fumarate, neodymium lactate, neodymium maleate, neodymium oxalate, neodymium 2-ethylhexanoate, neodymium neodecanoate (also known as neodymium tertiary carbonate), neodymium naphthenate, neodymium stearate, neodymium oleate, neodymium benzoate, and neodymium pyridinecarboxylate.

[0018] Suitable organophosphorus phosphates include, but are not limited to, dibutylphosphorus phosphate, dipentylphosphorus phosphate, dihexylphosphorus phosphate, diheptylphosphorus phosphate, dioctylphosphorus phosphate, bis(1-methylheptyl)phosphorus phosphate, bis(2-ethylhexyl)phosphorus phosphate, didecylphosphorus phosphate, bisdodecylphosphorus phosphate, bisoctadecylphosphorus phosphate, dioleylphosphorus phosphate, diphenylphosphorus phosphate, bis(p-nonylphenyl)phosphorus phosphate, butyl(2-ethylhexyl)phosphorus phosphate, (1-methylheptyl)(2-ethylhexyl)phosphorus phosphate, and (2-ethylhexyl)(p-nonylphenyl)phosphorus phosphate.

[0019] Suitable organophosphonates of neodymium include, but are not limited to, neodymium butylphosphonate, neodymium pentylphosphonate, neodymium hexylphosphonate, neodymium heptaylphosphonate, neodymium octylphosphonate, neodymium (1-methylheptyl)phosphonate, neodymium (2-ethylhexyl)phosphonate, neodymium decylphosphonate, neodymium dodecylphosphonate, neodymium octadecylphosphonate, neodymium oleylphosphonate, neodymium phenylphosphonate, neodymium (p-nonylphenyl)phosphonate, neodymium butylbutylphosphonate, neodymium pentylpentylphosphonate, neodymium hexylhexylphosphonate, neodymium heptaylheptylphosphonate, neodymium octyloctylphosphonate, neodymium (1-methylheptyl)(1-methylheptyl)phosphonate, and neodymium (2-ethylhexyl)(2- Neodymium ethylhexyl)phosphonate, neodymium decyldecylphosphonate, neodymium dodecyldodecylphosphonate, neodymium octadecyloctadecylphosphonate, neodymium oleyl-oleylphosphonate, neodymium phenylphenylphosphonate, neodymium (p-nonylphenyl)(p-nonylphenyl)phosphonate, neodymium butyl(2-ethylhexyl)phosphonate, neodymium (2-ethylhexyl)butylphosphonate, neodymium (1-methylheptyl)(2-ethylhexyl)phosphonate, neodymium (2-ethylhexyl)(1-methylheptyl)phosphonate, neodymium (2-ethylhexyl)(p-nonylphenyl)phosphonate, and neodymium (p-nonylphenyl)(2-ethylhexyl)phosphonate.

[0020] Suitable organic neodymium phosphinates include, but are not limited to, butyl neodymium phosphinate, pentyl neodymium phosphinate, hexyl neodymium phosphinate, heptyl neodymium phosphinate, octyl neodymium phosphinate, (1-methylheptyl)nephrine, (2-ethylhexyl)nephrine, decyl neodymium phosphinate, dodecyl neodymium phosphinate, octadecyl neodymium phosphinate, oleyl neodymium phosphinate, phenyl neodymium phosphinate, (p-nonylphenyl)nephrine, dibutyl neodymium phosphinate, dipentyl neodymium phosphinate, dihexyl neodymium phosphinate, and diheptyl Neodymium phosphinate, neodymium dioctylphosphinate, neodymium bis(1-methylheptyl)phosphinate, neodymium bis(2-ethylhexyl)phosphinate, neodymium didecylphosphinate, neodymium bisdodecylphosphinate, neodymium bisoctadecylphosphinate, neodymium dioleylphosphinate, neodymium diphenylphosphinate, neodymium bis(p-nonylphenyl)phosphinate, neodymium butyl(2-ethylhexyl)phosphinate, neodymium (1-methylheptyl)(2-ethylhexyl)phosphinate, and neodymium (2-ethylhexyl)(p-nonylphenyl)phosphinate.

[0021] Suitable neodymium carbamates include, but are not limited to, neodymium dimethylcarbamate, neodymium diethylcarbamate, neodymium diisopropylcarbamate, neodymium dibutylcarbamate, and neodymium dibenzylcarbamate.

[0022] Suitable neodymium dithiocarbamates include, but are not limited to, neodymium dimethyl dithiocarbamate, neodymium diethyl dithiocarbamate, neodymium diisopropyl dithiocarbamate, neodymium dibutyl dithiocarbamate, and neodymium dibenzyl dithiocarbamate.

[0023] Suitable neodymium xanthate includes, but is not limited to, methyl neodymium xanthate, ethyl neodymium xanthate, isopropyl neodymium xanthate, butyl neodymium xanthate, and benzyl neodymium xanthate.

[0024] Suitable β-diketonate neodymium includes, but is not limited to, acetylated neodymium pyruvate, trifluoroacetylated neodymium pyruvate, hexafluoroacetylated neodymium pyruvate, benzoylpyruvate neodymium and 2,2,6,6-tetramethyl-3,5-heptanedione neodymium.

[0025] Suitable neodymium alcohols or neodymium phenols include, but are not limited to, neodymium methanol, neodymium ethanol, neodymium isopropanol, neodymium 2-ethylhexanol, neodymium phenyloxide, neodymium nonylphenyloxide, and neodymium naphthyloxide.

[0026] Suitable neodymium halides include, but are not limited to, neodymium fluoride, neodymium chloride, neodymium bromide, and neodymium iodide. Suitable pseudo-neodymium halides include, but are not limited to, neodymium cyanide, neodymium thiocyanate, neodymium azide, and neodymium ferrocyanide. Suitable neodymium halide oxyhalides include, but are not limited to, neodymium fluoride oxyhalide, neodymium chloride oxyhalide, and neodymium bromide oxyhalide. Neodymium oxide may also be used. Lewis bases, such as tetrahydrofuran (“THF”), can be used as auxiliaries to help dissolve these neodymium compounds in inert organic solvents. In the case of using lanthanide halides, lanthanide halide oxides, or other lanthanide-containing compounds containing halogen atoms, the lanthanide-containing compound may optionally provide all or part of the halogen source in the lanthanide-based catalyst system.

[0027] As used herein, the term organolane compound refers to any lanthanide-containing compound containing at least one lanthanide-carbon bond. These compounds are primarily, but not exclusively, those containing cyclopentadienyl (“Cp”), substituted cyclopentadienyl, allyl, and substituted allyl ligands. Suitable organolane compounds include, but are not limited to, Cp3Ln, Cp2LnR, Cp2LnCl, CpLnCl2, CpLn(cyclooctatetraene), (C5Me5)2LnR, LnR3, Ln(allyl)3, and Ln(allyl)2Cl, wherein Ln represents a lanthanide atom and R represents a hydrocarbon group. In one or more embodiments, the hydrocarbon group used in this invention may contain heteroatoms, such as, for example, nitrogen, oxygen, boron, silicon, sulfur, and phosphorus atoms.

[0028] Nickel compounds

[0029] Various nickel-containing compounds or mixtures thereof can be used in nickel-based catalyst systems. In one or more embodiments, these nickel-containing compounds are soluble in hydrocarbon solvents such as aromatic hydrocarbons, aliphatic hydrocarbons, or alicyclic hydrocarbons. In other embodiments, nickel-containing compounds insoluble in hydrocarbons that can be suspended in a polymerization medium to form a catalytically active substance can also be used.

[0030] Nickel atoms in nickel-containing compounds can be in various oxidation states, including but not limited to 0, +2, +3, and +4 oxidation states. Nickel-containing compounds include, but are not limited to, nickel carboxylate, nickel borate carboxylate, nickel organophosphate, nickel organophosphonate, nickel organosphines, nickel carbamate, nickel dithiocarbamate, nickel xanthate, nickel β-diketonate, nickel alkoxides or nickel phenolates, nickel halides, pseudohalides, nickel halide, and organonickel compounds.

[0031] Nickel carboxylate may include nickel formate, nickel acetate, nickel acetic acid, nickel acrylate, nickel methacrylate, nickel valerate, nickel gluconate, nickel citrate, nickel fumarate, nickel lactate, nickel maleate, nickel oxalate, nickel 2-ethylhexanoate, nickel neodecanoate, nickel naphthenate, nickel stearate, nickel oleate, nickel benzoate, and nickel pyridinecarboxylate.

[0032] Nickel carboxyborate may include compounds defined by the formula (RCOONiO)3B or (RCOONiO)2B(OR), wherein each R, which may be the same or different, is a hydrogen atom or a monovalent organic group. In one embodiment, each R may be a hydrocarbon group, such as, but not limited to, alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, aralkyl, alkylaryl, allyl, and alkynyl groups, wherein each group preferably contains one carbon atom (or the appropriate minimum number of carbon atoms forming the group) to a maximum of about 20 carbon atoms. These hydrocarbon groups may contain heteroatoms, such as, but not limited to, nitrogen, oxygen, silicon, sulfur, and phosphorus atoms. Nickel carboxyborate may include those disclosed in U.S. Patent No. 4,522,988, which is incorporated herein by reference. Specific examples of nickel borate carboxylate include nickel borate (II) neodecanoate, nickel borate (II) hexanoate, nickel borate (II) naphthenic acid, nickel borate (II) stearate, nickel borate (II) octanoate, nickel borate (II) 2-ethylhexanoate, and mixtures thereof.

[0033] Organophosphate nickel may include dibutyl phosphate, dipentyl phosphate, dihexyl phosphate, diheptyl phosphate, dioctyl phosphate, dioctyl phosphate, bis(1-methylheptyl) phosphate, bis(2-ethylhexyl) phosphate, didecyl phosphate, bisdodecyl phosphate, bisoctadecyl phosphate, dioleyl phosphate, diphenyl phosphate, bis(p-nonylphenyl) phosphate, butyl(2-ethylhexyl) phosphate, (1-methylheptyl)(2-ethylhexyl) phosphate, and (2-ethylhexyl)(p-nonylphenyl) phosphate.

[0034] Organophosphonates may include nickel butylphosphonate, nickel pentylphosphonate, nickel hexylphosphonate, nickel heptylphosphonate, nickel octylphosphonate, nickel (1-methylheptyl)phosphonate, nickel (2-ethylhexyl)phosphonate, nickel decylphosphonate, nickel dodecylphosphonate, nickel octadecylphosphonate, nickel oleylphosphonate, nickel phenylphosphonate, nickel (p-nonylphenyl)phosphonate, nickel butylbutylphosphonate, nickel pentylpentylphosphonate, nickel hexylhexylphosphonate, nickel heptylheptylphosphonate, nickel octyloctylphosphonate, nickel (1-methylheptyl)(1-methylheptyl)phosphonate, and nickel (2-ethylhexyl)(2-ethylhexyl)phosphonate. Nickel (2-ethylhexyl) phosphonate, nickel (decyldecyl) phosphonate, nickel (dodecyl dodecyl) phosphonate, nickel (octadecyl octadecyl) phosphonate, nickel (oil-based) phosphonate, nickel (phenylphenyl) phosphonate, nickel (p-nonylphenyl)(p-nonylphenyl) phosphonate, nickel (butyl(2-ethylhexyl) phosphonate, nickel (2-ethylhexyl) butyl phosphonate, nickel (1-methylheptyl)(2-ethylhexyl) phosphonate, nickel (2-ethylhexyl)(1-methylheptyl) phosphonate, nickel (2-ethylhexyl)(p-nonylphenyl) phosphonate, and nickel (p-nonylphenyl)(2-ethylhexyl) phosphonate.

[0035] Organic nickel phosphinates may include butyl nickel phosphinate, pentyl nickel phosphinate, hexyl nickel phosphinate, heptyl nickel phosphinate, octyl nickel phosphinate, (1-methylheptyl) nickel phosphinate, (2-ethylhexyl) nickel phosphinate, decyl nickel phosphinate, dodecyl nickel phosphinate, octadecyl nickel phosphinate, oleyl nickel phosphinate, phenyl nickel phosphinate, (p-nonylphenyl) nickel phosphinate, dibutyl nickel phosphinate, dipentyl nickel phosphinate, dihexyl nickel phosphinate, and diheptyl phosphinate. Nickel, nickel dioctylphosphinate, nickel bis(1-methylheptyl)phosphinate, nickel bis(2-ethylhexyl)phosphinate, nickel didecylphosphinate, nickel bisdodecylphosphinate, nickel bisoctadecylphosphinate, nickel dioleylphosphinate, nickel diphenylphosphinate, nickel bis(p-nonylphenyl)phosphinate, nickel butyl(2-ethylhexyl)phosphinate, nickel (1-methylheptyl)(2-ethylhexyl)phosphinate and nickel (2-ethylhexyl)(p-nonylphenyl)phosphinate.

[0036] Nickel carbamate may include nickel dimethylcarbamate, nickel diethylcarbamate, nickel diisopropylcarbamate, nickel dibutylcarbamate, and nickel dibenzylcarbamate.

[0037] Nickel dithiocarbamate may include nickel dimethyl dithiocarbamate, nickel diethyl dithiocarbamate, nickel diisopropyl dithiocarbamate, nickel dibutyl dithiocarbamate, and nickel dibenzyl dithiocarbamate.

[0038] Nickel xanthate includes nickel methyl xanthate, nickel ethyl xanthate, nickel isopropyl xanthate, nickel butyl xanthate, and nickel benzyl xanthate.

[0039] Nickel β-diketoate may include nickel acetylacetonate, nickel trifluoroacetylacetonate, nickel hexafluoroacetylacetonate, nickel benzoylpyruvate, and nickel 2,2,6,6-tetramethyl-3,5-heptadecyl diketoate.

[0040] Nickel alkoxides or nickel phenolates may include nickel methoxide, nickel ethanol, nickel isopropoxide, nickel 2-ethylhexanol, nickel phenol, nickel nonylphenol, and nickel naphthol.

[0041] Nickel halides can include nickel fluoride, nickel chloride, nickel bromide, and nickel iodide. Pseudo-halides include nickel cyanide, nickel cyanate, nickel thiocyanate, nickel azide, and nickel ferrocyanide. Nickel halides include nickel fluoride oxychloride, nickel chloride oxychloride, and nickel bromide oxychloride. Where nickel halides, nickel halides, or other nickel-containing compounds contain unstable fluorine or chlorine atoms, the nickel-containing compounds can also be used as fluorine-containing or chlorine-containing compounds. Lewis bases, such as alcohols, can be used as solvent aids for these compounds.

[0042] The term organonitrile can refer to any nickel compound containing at least one nickel-carbon bond. Organonitrile compounds include bis(cyclopentadienyl)nickel (also known as nickel dicenocene), bis(pentamethylcyclopentadienyl)nickel (also known as decamethyl nickel dicenocene), bis(tetramethylcyclopentadienyl)nickel, bis(ethylcyclopentadienyl)nickel, bis(isopropylcyclopentadienyl)nickel, bis(pentadienyl)nickel, bis(2,4-dimethylpentadienyl)nickel, (cyclopentadienyl)(pentadienyl)nickel, bis(1,5-cyclooctadienyl)nickel, bis(allyl)nickel, bis(methylallyl)nickel, and bis(crotonyl)nickel.

[0043] Alkylation reagent blends

[0044] As mentioned above, in addition to triethylaluminum, lanthanide-based catalyst systems and nickel-based catalyst systems also include aluminum hydride compounds. The combination of aluminum hydride and triethylaluminum can be referred to as an alkylating agent blend or an alkylating agent system.

[0045] As understood by those skilled in the art, triethylaluminum can be defined by the formula Al(CH2CH3)3.

[0046] Aluminum hydride compounds, also known as hydrocarbon-based aluminum hydrides, can be derived from the general formula AlR. n H 3-nThis indicates that each R can independently be a monovalent organic group linked to an aluminum atom via a carbon atom, and n can be an integer ranging from 1 to 3. In one or more embodiments, each R can independently be a hydrocarbon group, such as, for example, alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, aralkyl, alkylaryl, allyl, and ynyl groups, wherein each group contains carbon atoms ranging from 1 carbon atom (or the appropriate minimum number of carbon atoms forming the group) to a maximum of about 20 carbon atoms. These hydrocarbon groups may contain heteroatoms, including but not limited to nitrogen, oxygen, boron, silicon, sulfur, and phosphorus atoms. In one or more embodiments, aluminum hydride can be dialkyl aluminum hydride, and in other embodiments, it can be alkyl dialkyl aluminum hydride.

[0047] Suitable dialkyl aluminum hydride compounds include, but are not limited to, diethyl aluminum hydride, di-n-propyl aluminum hydride, diisopropyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, di-n-octyl aluminum hydride, diphenyl aluminum hydride, di-p-tolyl aluminum hydride, dibenzyl aluminum hydride, phenylethyl aluminum hydride, phenyl-n-propyl aluminum hydride, phenyl isopropyl aluminum hydride, phenyl-n-butyl aluminum hydride, phenyl isobutyl aluminum hydride, phenyl-n-octyl aluminum hydride, p-tolylethyl aluminum hydride, p-tolyl-n-propyl aluminum hydride, p-tolyl-isopropyl aluminum hydride, p-tolyl-n-butyl aluminum hydride, p-tolyl-n-octyl aluminum hydride, benzylethyl aluminum hydride, benzyl-n-propyl aluminum hydride, benzyl isopropyl aluminum hydride, benzyl-n-butyl aluminum hydride, benzyl isobutyl aluminum hydride, and benzyl-n-octyl aluminum hydride.

[0048] Suitable alkyl aluminum dihydrogenates include, but are not limited to, ethyl aluminum dihydrogenate, n-propyl aluminum dihydrogenate, isopropyl aluminum dihydrogenate, n-butyl aluminum dihydrogenate, isobutyl aluminum dihydrogenate, and n-octyl aluminum dihydrogenate.

[0049] Halogenated compounds

[0050] As mentioned above, lanthanide-based catalyst systems and nickel-based catalyst systems contain halogen-containing compounds.

[0051] Various compounds, or mixtures thereof, containing one or more halogen atoms, can be used as halogen-containing compounds. Examples of halogen atoms include, but are not limited to, fluorine, chlorine, bromine, and iodine. Combinations of two or more halogen atoms can also be used. Halogen-containing compounds soluble in hydrocarbon solvents are suitable for use in this invention. However, halogen-containing compounds insoluble in hydrocarbons can be suspended in polymerization systems to form catalytically active substances, and are therefore also usable.

[0052] The types of halogen-containing compounds that can be used include, but are not limited to, elemental halogens, mixed halogens, hydrogen halides, organohalides, inorganic halides, metal halides, and organometallic halides.

[0053] Suitable elemental halogens include, but are not limited to, fluorine, chlorine, bromine, and iodine. Some specific examples of suitable mixed halogens include iodine monochloride, iodine monobromide, iodine trichloride, and iodine pentafluoride.

[0054] Suitable hydrogen halides include, but are not limited to, hydrogen fluoride, hydrogen chloride, hydrogen bromide, and hydrogen iodide.

[0055] Suitable organohalides include, but are not limited to, tert-butyl chloride, tert-butyl bromide, allyl chloride, allyl bromide, benzyl chloride, benzyl bromide, chloro-diphenylmethane, bromo-diphenylmethane, triphenylmethyl chloride, triphenylmethyl bromide, benzyl chloride, benzyl bromide, methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, trimethylchlorosilane, benzoyl chloride, benzoyl bromide, propionyl chloride, propionyl bromide, methyl chloroformate, and methyl bromoformate.

[0056] Suitable inorganic halides include, but are not limited to, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride, phosphorus oxybromide, boron trifluoride, boron trichloride, boron tribromide, silicon tetrafluoride, silicon tetrachloride, silicon tetrabromide, silicon tetraiodide, arsenic trichloride, arsenic tribromide, arsenic triiodide, selenium tetrachloride, selenium tetrabromide, tellurium tetrachloride, tellurium tetrabromide, and tellurium tetraiodide.

[0057] Suitable metal halides include, but are not limited to, tin tetrachloride, tin tetrabromide, aluminum trichloride, aluminum tribromide, antimony trichloride, antimony pentachloride, antimony tribromide, aluminum triiodide, aluminum trifluoride, gallium trichloride, gallium tribromide, gallium triiodide, gallium trifluoride, indium trichloride, indium tribromide, indium triiodide, indium trifluoride, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, zinc dichloride, zinc dibromide, zinc diiodide, and zinc difluoride.

[0058] Suitable organometallic halides include, but are not limited to, dimethylaluminum chloride, diethylaluminum chloride, dimethylaluminum bromide, diethylaluminum bromide, dimethylaluminum fluoride, diethylaluminum fluoride, methylaluminum dichloride, ethylaluminum dichloride, methylaluminum dibromide, ethylaluminum dibromide, methylaluminum difluoride, ethylaluminum difluoride, sesquimethylaluminum chloride, sesquiethylaluminum chloride, sesquiisobutylaluminum chloride, methylmagnesium chloride, methylmagnesium bromide, methylmagnesium iodide, ethylmagnesium chloride, ethylmagnesium bromide, butylmagnesium chloride, butylmagnesium bromide, phenylmagnesium chloride, phenylmagnesium bromide, benzylmagnesium chloride, trimethyltin chloride, trimethyltin bromide, triethyltin chloride, triethyltin bromide, di-tert-butyltin dichloride, di-tert-butyltin dibromide, dibutyltin dichloride, dibutyltin dibromide, tributyltin chloride, and tributyltin bromide.

[0059] In one or more embodiments, the lanthanide-based catalyst system may comprise a compound containing a noncoordinate anion or a noncoordinate anion precursor. In one or more embodiments, a compound containing a noncoordinate anion or a noncoordinate anion precursor may be used instead of the aforementioned halogen source. A noncoordinate anion is a spatially large anion that, due to steric hindrance, does not form a coordinate bond with, for example, the active site of the catalyst system. Noncoordinate anions that can be used in this invention include, but are not limited to, tetraarylborate anions and fluorinated tetraarylborate anions. The compound containing a noncoordinate anion may also contain a counter cation, such as a carbium, ammonium, or phosphonium cation. Exemplary counter cations include, but are not limited to, triarylcarbium cations and N,N-dialkylphenylammonium cations. Examples of compounds containing noncoordinate anions and countercations include, but are not limited to, triphenylcarbazium tetra(pentafluorophenyl)borate, N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate, triphenylcarbazium tetra[3,5-bis(trifluoromethyl)phenyl]borate, and N,N-dimethylphenylammonium tetra[3,5-bis(trifluoromethyl)phenyl]borate.

[0060] Those skilled in the art will understand that halogen-containing compounds may include compounds containing lanthanides or nickel, wherein those compounds contain unstable halogen atoms.

[0061] Noncoordinate anion precursors may also be used in this embodiment. A noncoordinate anion precursor is a compound capable of forming a noncoordinate anion under reaction conditions. Available noncoordinate anion precursors include, but are not limited to, the triarylboron compound BR3, where R is a strongly electron-withdrawing aryl group, such as pentafluorophenyl or 3,5-bis(trifluoromethyl)phenyl.

[0062] Fluorine compounds

[0063] In certain embodiments, the nickel-based catalyst system may comprise a fluorinated compound. The fluorinated compound may include various compounds or mixtures thereof containing one or more unstable fluorine atoms. In one or more embodiments, the fluorinated compound is soluble in a hydrocarbon solvent. In other embodiments, a hydrocarbon-insoluble fluorinated compound that can be suspended in a polymerization medium to form the catalytically active material may be useful.

[0064] The types of fluorinated compounds include, but are not limited to, elemental fluorine, halogenated fluorides, hydrogen fluoride, organofluorine compounds, inorganic fluorides, metal fluorides, organometallic fluorides, and mixtures thereof. In one or more embodiments, complexes of fluorinated compounds with Lewis bases such as ethers, alcohols, water, aldehydes, ketones, esters, nitriles, or mixtures thereof may be employed. Specific examples of such complexes include complexes of boron trifluoride and hydrogen fluoride with Lewis bases.

[0065] Halogenated fluorides may include iodine monofluoride, iodine trifluoride and iodine pentafluoride.

[0066] Organofluorine compounds may include tert-butyl fluoride, allyl fluoride, benzyl fluoride, fluorodiphenylmethane, triphenylmethyl fluoride, benzylene fluoride, methyltrifluorosilane, phenyltrifluorosilane, dimethyldifluorosilane, diphenyldifluorosilane, trimethylfluorosilane, benzoyl fluoride, propionyl fluoride, and methyl fluorocarbamate.

[0067] Inorganic fluorides may include phosphorus trifluoride, phosphorus pentafluoride, phosphorus oxyfluoride, boron trifluoride, silicon tetrafluoride, arsenic trifluoride, selenium tetrafluoride, and tellurium tetrafluoride.

[0068] Metal fluorides may include tin tetrafluoride, aluminum trifluoride, antimony trifluoride, antimony pentafluoride, gallium trifluoride, indium trifluoride, titanium tetrafluoride, and zinc difluoride.

[0069] Organometallic fluorides may include dimethyl aluminum fluoride, diethyl aluminum fluoride, methyl aluminum difluoride, ethyl aluminum difluoride, methyl sesquifluoride, ethyl sesquifluoride, isobutyl sesquifluoride, methyl magnesium fluoride, ethyl magnesium fluoride, butyl magnesium fluoride, phenyl magnesium fluoride, benzyl magnesium fluoride, trimethyl tin fluoride, triethyl tin fluoride, di-tert-butyl tin difluoride, dibutyl tin difluoride, and tributyl tin fluoride.

[0070] Various compounds or mixtures thereof containing one or more unstable chlorine atoms can be used as chlorine-containing compounds. In one or more embodiments, the chlorine-containing compound is soluble in a hydrocarbon solvent. In other embodiments, a hydrocarbon-insoluble chlorine-containing compound that can be suspended in a polymerization medium to form a catalytically active substance may be useful.

[0071] Catalyst component ratio

[0072] In the first set of embodiments, the lanthanide-based catalyst composition used in this invention can be formed by combining or mixing the aforementioned catalyst components. Although it is believed that one or more active catalyst substances are obtained by combining lanthanide-based catalyst components, the extent of interaction or reaction between the various catalyst components or components is not yet fully known. Therefore, the term "catalyst composition" has been used to encompass simple mixtures of the components, complexes of the components formed by physical or chemical attraction, chemical reaction products of the components, or combinations thereof.

[0073] In one or more embodiments, the molar ratio of triethylaluminum hydride to the lanthanide-containing compound (alkylating agent / Ln) may vary from about 2:1 to about 15:1, in other embodiments from about 3.5:1 to about 10:1, and in other embodiments from about 4.5:1 to about 7.5:1.

[0074] In one or more embodiments, the molar ratio of alkyl aluminum hydride to a lanthanide-containing compound (alkylating agent / Ln) may vary from about 1:1 to about 10:1, in other embodiments from about 2.5:1 to about 8:1, and in other embodiments from about 4:1 to about 6:1.

[0075] In one or more embodiments, the molar ratio of the halogen-containing compound to the lanthanide-containing compound is preferably described as the ratio of the number of moles of halogen atoms in the halogen source to the number of moles of lanthanide atoms in the lanthanide-containing compound (halogen / Ln). In one or more embodiments, the halogen / Ln molar ratio may vary from about 0.5:1 to about 20:1, in other embodiments from about 1:1 to about 10:1, and in still other embodiments from about 2:1 to about 6:1.

[0076] In yet another embodiment, the molar ratio of the uncoordinated anion or the uncoordinated anion precursor to the lanthanide-containing compound (An / Ln) may be from about 0.5:1 to about 20:1, in other embodiments from about 0.75:1 to about 10:1, and in other embodiments from about 1:1 to about 6:1.

[0077] In a second set of embodiments, the nickel-based catalyst composition used in this invention can be formed by combining or mixing the aforementioned catalyst components. Although it is believed that one or more active catalyst substances are obtained by combining nickel-based catalyst components, the extent of interaction or reaction between the various catalyst components or components is not yet fully known. Therefore, the term "catalyst composition" has been used to encompass simple mixtures of the components, complexes of the components formed by physical or chemical attraction, chemical reaction products of the components, or combinations thereof.

[0078] In one or more embodiments, the molar ratio of triethylaluminum to the nickel-containing compound (alkylating agent / nickel) may vary from about 1:1 to about 200:1, in other embodiments from about 2:1 to about 100:1, and in other embodiments from about 5:1 to about 50:1.

[0079] In one or more embodiments, the molar ratio of alkyl aluminum hydride to nickel-containing compound (alkylating agent / nickel) may vary from about 1:1 to about 500:1, in other embodiments from about 2:1 to about 100:1, and in other embodiments from about 3:1 to about 50:1.

[0080] In embodiments where the nickel-containing catalyst system includes a fluorine-containing compound, the molar ratio of the fluorine-containing compound to the nickel-containing compound is preferably described as the ratio of the number of moles of fluorine atoms in the fluorine-containing compound to the number of moles of nickel atoms in the nickel-containing compound (F / Ni). In one or more embodiments, the F / Ni molar ratio may vary from about 2:1 to about 500:1, in other embodiments from about 5:1 to about 300:1, and in still other embodiments from about 8:1 to about 200:1.

[0081] Catalyst formation

[0082] Various procedures can be used to prepare the lanthanide-based and nickel-based catalyst systems of the present invention. In one or more embodiments, the catalyst system can be formed in situ by adding the catalyst components individually to the monomers to be polymerized, either stepwise or simultaneously. In other embodiments, the catalyst system can be pre-formed. That is, the catalyst components are pre-mixed outside the polymerization system in the absence of any monomer or in the presence of a small amount of monomer. If desired, the resulting pre-formed catalyst composition can be aged before being added to the monomers to be polymerized.

[0083] Catalyst systems can be formed by various methods.

[0084] In one embodiment, the catalyst composition can be formed in situ by adding the catalyst components stepwise or simultaneously to a solution containing monomers and solvents, or to the bulk monomer. In one embodiment, an alkylating agent may be added first, followed by a lanthanide-containing compound or a nickel-containing compound, and then a halogen-containing compound or a compound containing a noncoordinate anion or a noncoordinate anion precursor.

[0085] In another embodiment, the catalyst composition can be pre-formed. That is, the catalyst components are pre-mixed outside the polymerization system in the absence of any monomers or in the presence of a small amount of at least one conjugated diene monomer at a suitable temperature, which may be from about -20°C to about 80°C. The amount of conjugated diene monomer that can be used to pre-form the catalyst can vary from about 1 mole to about 500 moles, in other embodiments from about 5 moles to about 250 moles, and in other embodiments from about 10 moles to about 100 moles, relative to each mole of a lanthanide compound or a nickel-containing compound. If desired, the resulting catalyst composition can be aged before being added to the monomers to be polymerized.

[0086] In another embodiment, the catalyst composition can be formed using a two-stage process. The first stage may include combining an alkylating agent with a lanthanide-containing compound or a nickel-containing compound in the absence of any monomer or in the presence of a small amount of at least one conjugated diene monomer at a suitable temperature, which may be from about -20°C to about 80°C. The amount of monomer used in the first stage may be similar to the amount of monomer used to pre-form the catalyst as described above. In the second stage, the mixture formed in the first stage, along with the halogen-containing compound, noncoordinate anion, or noncoordinate anion precursor, may be added to the monomer to be polymerized in a stepwise or simultaneous manner.

[0087] In one or more embodiments, the solvent may be used as a support to dissolve or suspend the catalyst or initiator, thereby facilitating the delivery of the catalyst to the polymerization system. In other embodiments, the monomer may be used as a support. In other embodiments, the catalyst may be used in its pure state without any solvent.

[0088] In one or more embodiments, suitable solvents include those organic compounds that do not polymerize or are incorporated into the growing polymer chains during monomer polymerization in the presence of a catalyst or initiator. In one or more embodiments, these organic substances are liquid at ambient temperature and pressure. In one or more embodiments, these organic solvents are inert to the catalyst or initiator. Exemplary organic solvents include hydrocarbons having low or relatively low boiling points, such as aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons. Non-limiting examples of aromatic hydrocarbons include benzene, toluene, xylene, ethylbenzene, diethylbenzene, and trimethylbenzene. Non-limiting examples of aliphatic hydrocarbons include n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, isopentane, isohexane, isopentane, isooctane, 2,2-dimethylbutane, petroleum ether, kerosene, and petroleum distillate. Moreover, non-limiting examples of alicyclic hydrocarbons include cyclopentane, cyclohexane, methylcyclopentane, and methylcyclohexane. Mixtures of the above hydrocarbons may also be used. As is known in the art, aliphatic and alicyclic hydrocarbons are desirable for environmental reasons. Low-boiling-point hydrocarbon solvents are typically separated from the polymer upon completion of polymerization.

[0089] Other examples of organic solvents include high-boiling-point hydrocarbons with high molecular weights, including hydrocarbon oils commonly used in oil-extended polymers. Examples of these oils include paraffin oils, aromatic oils, naphthenic oils, vegetable oils other than castor oil, and low-PCA oils (including MES, TDAE, SRAE), and heavy naphthenic oils. Because these hydrocarbons are non-volatile, they typically do not need to be separated and retained in the polymer.

[0090] Aggregation methods

[0091] The aforementioned lanthanide-based or nickel-based catalyst compositions exhibit relatively high catalytic activity for polymerizing conjugated dienes into polymers over a wide range of catalyst concentrations and component ratios. The polymer may be referred to as a polydiene, and in one or more embodiments may include cis-1,4-polydiene. Several factors may affect the optimal concentration of any of the catalyst components. For example, because the catalyst components can interact to form active substances, the optimal concentration of any one catalyst component may depend on the concentrations of the other catalyst components.

[0092] Examples of conjugated diene monomers include 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, and 2,4-hexadiene.

[0093] The preparation of the reactive polymer according to the invention can be accomplished by polymerizing a conjugated diene monomer, optionally with a monomer capable of copolymerizing with the conjugated diene monomer, in the presence of a catalytically effective amount of catalyst. A catalyst, conjugated diene monomer, optional comonomer, and any solvent (if used) are introduced to form a polymerization mixture in which the reactive polymer is formed. The amount of catalyst or initiator to be used can depend on the interaction of various factors, such as the type of catalyst or initiator used, the purity of the components, the polymerization temperature, the desired polymerization rate and conversion, the desired molecular weight, and many other factors. Therefore, the specific amount of catalyst or initiator can not be explicitly stated except that a catalytically effective amount of catalyst or initiator can be used.

[0094] In one or more embodiments, the amount of coordination metal compound (e.g., a lanthanide-containing compound or a nickel-containing compound) used per 100 grams of monomer can vary from about 0.001 mmol to about 2 mmol in other embodiments, from about 0.005 mmol to about 1 mmol in other embodiments, and from about 0.01 mmol to about 0.2 mmol in other embodiments.

[0095] In one or more embodiments, polymerization can be carried out in a polymerization system containing a large amount of solvent. In one embodiment, a solution polymerization system may be used, wherein both the monomer to be polymerized and the resulting polymer are soluble in the solvent. In another embodiment, a precipitation polymerization system may be used, wherein the resulting polymer is insoluble in the solvent. In both cases, a certain amount of solvent, in addition to the amount of solvent that can be used in preparing the catalyst, is typically added to the polymerization system. The additional solvent may be the same as or different from the solvent used in preparing the catalyst. Exemplary solvents have been described above. In one or more embodiments, the solvent content of the polymerization mixture may exceed 20% by weight, exceed 50% by weight in other embodiments, and exceed 80% by weight in still other embodiments, based on the total weight of the polymerization mixture.

[0096] In other embodiments, the polymerization system employed can generally be considered a bulk polymerization system, which is substantially solvent-free or contains very small amounts of solvent. Those skilled in the art will understand the beneficial effects of bulk polymerization processes (i.e., processes in which monomers act as solvents), and therefore, the polymerization system contains less solvent than would adversely affect the benefits sought in carrying out the bulk polymerization. In one or more embodiments, the solvent content of the polymerization mixture may be less than about 20% by weight of the total weight of the polymerization mixture, less than about 10% by weight in other embodiments, and less than about 5% by weight in still other embodiments. In another embodiment, the polymerization mixture contains no other solvents besides those inherent to the raw materials used. In yet another embodiment, the polymerization mixture is substantially solvent-free, meaning that there is no amount of solvent that would otherwise have a considerable impact on the polymerization process. A substantially solvent-free polymerization system may be referred to as substantially solvent-free. In a particular embodiment, the polymerization mixture is solvent-free.

[0097] The polymerization can be carried out in any conventional polymerization vessel known in the art. In one or more embodiments, solution polymerization can be carried out in a conventional stirred tank reactor. In other embodiments, bulk polymerization can be carried out in a conventional stirred tank reactor, particularly when the monomer conversion is less than about 60%. In other embodiments, particularly where the monomer conversion during bulk polymerization is greater than about 60% (which typically results in highly viscous solids), bulk polymerization can be carried out in an elongated reactor, wherein the viscous solids under polymerization are moved by a piston or substantially by a piston drive. For example, an extruder in which the solids are driven by a self-cleaning single-screw or twin-screw mixer is suitable for this purpose. Examples of available bulk polymerization processes are disclosed in U.S. Patent No. 7,351,776, which is incorporated herein by reference.

[0098] In one or more embodiments, all components used for polymerization can be combined within a single container (e.g., a conventional stirred tank reactor), and all steps of the polymerization process can be carried out within that container. In other embodiments, two or more components can be pre-combined in one container and then transferred to another container, in which the polymerization of monomers (or at least most of them) can be carried out.

[0099] Polymerization can be carried out using batch, continuous, or semi-continuous methods. In a semi-continuous method, monomers are intermittently added as needed to replace polymerized monomers. In one or more embodiments, the conditions under which polymerization takes place can be controlled to maintain the temperature of the polymerization mixture from about -10°C to about 200°C, from about 0°C to about 150°C in other embodiments, and from about 20°C to about 100°C in other embodiments. In one or more embodiments, the heat of polymerization can be removed by external cooling via a thermally controlled reactor jacket, by internal cooling (using a reflux condenser connected to the reactor to evaporate and condense the monomers), or a combination of both. Additionally, polymerization conditions can be controlled to carry out polymerization at pressures from about 0.1 atm to about 50 atm, from about 0.5 atm to about 20 atm in other embodiments, and from about 1 atm to about 10 atm in other embodiments. In one or more embodiments, the pressures under which polymerization can take place include those that ensure that the monomers are predominantly in the liquid phase. In these or other embodiments, the polymerization mixture can be maintained under anaerobic conditions.

[0100] As described above, the catalyst system and polymerization method of the present invention exhibit advantageous polymerization activity. In one or more embodiments, the polymerization activity can be expressed as the monomer conversion rate of the polymerization method. In one or more embodiments, the monomer conversion rate achieved by the catalyst system and polymerization method is greater than 80%, greater than 85% in other embodiments, and greater than 90% in still other embodiments.

[0101] reactive polymers

[0102] In one or more embodiments, the polymerization method of the present invention produces reactive polymers. These reactive polymers are believed to be prepared via a coordination polymerization mechanism. Key mechanistic features of coordination polymerization have been discussed in books (e.g., Kuran, W., Principles of Coordination Polymerization; John Wiley & Sons: New York, 2001) and review articles (e.g., Mulhaupt, R., *Macromolecular Chemistry and Physics*, 2003, Vol. 204, pp. 289-327). Coordination catalysts are believed to initiate monomer polymerization through a mechanism involving coordination or complexation of the monomer with the active metal center prior to insertion into the grown polymer chain. An advantageous feature of coordination catalysts is their ability to provide stereochemical control over polymerization, resulting in stereoregular polymers. As is known in the art, many methods exist for producing coordination catalysts, but all methods ultimately produce active intermediates capable of coordinating with the monomer and inserting the monomer into the covalent bond between the active metal center and the grown polymer chain. It is believed that the coordination polymerization of conjugated dienes is carried out via π-allyl complexes as intermediates. The coordination catalyst can be a mono-, di-, tri-, or multi-component system. In one or more embodiments, the coordination catalyst can be formed by combining a heavy metal compound (e.g., a lanthanide-containing compound), an alkylating agent (e.g., an organoaluminum compound), and optionally other co-catalyst components (e.g., Lewis acids or Lewis bases). In one or more embodiments, the heavy metal compound may be referred to as a coordination metal compound.

[0103] In one or more embodiments, particularly when employing a lanthanide-based catalyst system, the resulting polymer chains have reactive chain ends before the polymerization mixture is quenched. Therefore, reference to a reactive polymer refers to a polymer with reactive chain ends derived from a polymer synthesized using a coordination catalyst; this reactive polymer may be referred to as a pseudo-active polymer. In one or more embodiments, the polymerization mixture containing the reactive polymer may be referred to as an active polymerization mixture. The percentage of polymer chains with reactive ends depends on various factors, such as the type of catalyst or initiator, the type of monomer, the purity of the components, the polymerization temperature, monomer conversion, and many other factors. In one or more embodiments, at least about 5% of the polymer chains have reactive ends; in other embodiments, at least about 10% of the polymer chains have reactive ends; and in still other embodiments, at least about 15% of the polymer chains have reactive ends. In any case, the reactive polymer may react with a functionalizing agent to form the coupling polymer of the present invention.

[0104] Functionalization

[0105] In one or more embodiments, a functionalizing agent may optionally be added to the polymerization mixture to functionalize at least a portion of the polymer chains, particularly those with reactive chain ends. A mixture of two or more functionalizing agents may also be used.

[0106] In one or more embodiments, the functionalizing agent comprises a compound or reagent that reacts with the reactive polymer prepared by the present invention to provide the polymer with a functional group that is distinct from the growing chain that does not react with the functionalizing agent. The functional group may react or interact with other polymer chains (growing and / or non-growing) or with other components that can be mixed with the polymer, such as reinforcing fillers (e.g., carbon black). In one or more embodiments, the reaction between the functionalizing agent and the reactive polymer is carried out via an addition or substitution reaction.

[0107] Available functionalizing agents may include compounds that provide functional groups only at the ends of polymer chains. In one or more embodiments, the functionalizing agent includes compounds that add or impart heteroatoms to the polymer chain. In a particular embodiment, the functionalizing agent includes those compounds that impart functional groups to the polymer chain to form a functionalized polymer, which reduces the hysteresis loss by 50°C compared to similar carbon black-filled vulcanizates prepared from non-functionalized polymers.

[0108] In other embodiments, additional coupling agents may be used in combination with functionalizing agents. These compounds (which may be referred to as co-coupling agents) can link two or more polymer chains together to form a single macromolecule. Since some functionalizing agents can also be used to couple polymer chains in addition to providing usable functional groups, co-coupling agents may be referred to herein as functionalizing agents.

[0109] In one or more embodiments, suitable functionalizing agents include compounds containing groups that can react with reactive polymers prepared according to the present invention. Exemplary functionalizing agents include ketones, quinones, aldehydes, amides, esters, isocyanates, isothiocyanates, epoxides, imines, aminoketones, aminothiophenes, and acid anhydrides. Examples of these compounds are disclosed in the following patent documents: U.S. Patent Nos. 4,906,706, 4,990,573, 5,064,910, 5,567,784, 5,844,050, 6,838,526, 6,977,281, and 6,992,147; U.S. Publication Nos. 2006 / 0004131 A1, 2006 / 0025539 A1, 2006 / 0030677 A1, and 2004 / 0147694 A1; and Japanese Patent Application Nos. 05-051406A, 05-059103A, 10-306113A, and 11-035633A; these patent documents are incorporated herein by reference. Other examples of functionalizing agents include azazine compounds described in U.S. Patent Application No. 11 / 640,711, hydrogenated benzamide compounds disclosed in U.S. Patent Application No. 11 / 710,713, nitro compounds disclosed in U.S. Patent Application No. 11 / 710,845, and protected oxime compounds disclosed in U.S. Patent Application No. 60 / 875,484, all of which are incorporated herein by reference.

[0110] In a particular embodiment, the functionalizing agent used may be an epoxide, isocyanate, metal carboxylate, hydrocarbon-based metal carboxylate, or hydrocarbon-based metal ester carboxylate.

[0111] In one or more embodiments, the exemplary epoxide compound may be selected from (3-glycidoxypropyl)trimethoxysilane, (3-glycidoxypropyl)triethoxysilane, (3-glycidoxypropyl)triphenoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, (3-glycidoxypropyl)methyldiphenoxysilane, [2-(3,4-epoxycyclohexyl)ethyl]trimethoxysilane, and [2-(3,4-epoxycyclohexyl)ethyl]triethoxysilane.

[0112] Exemplary isocyanate compounds include (3-isocyanopropyl)trimethoxysilane, (3-isocyanopropyl)triethoxysilane, (3-isocyanopropyl)triphenoxysilane, (3-isocyanopropyl)methyldimethoxysilane, (3-isocyanopropyl)methyldiethoxysilane, (3-isocyanopropyl)methyldiphenoxysilane, and (isocyanopropyl)methyldimethoxysilane.

[0113] Exemplary metal carboxylate compounds include tin tetraacetate, tin bis(2-ethylhexanoate), and tin bis(neodecanoate).

[0114] Exemplary hydrocarbon-based metal carboxylate compounds include tin triphenyl-2-ethylhexanoate, tin tri-n-butyl-2-ethylhexanoate, tin tri-n-butylneodecanate, tin triisobutyl-2-ethylhexanoate, tin diphenylbis(2-ethylhexanoate), tin di-n-butylbis(2-ethylhexanoate), tin di-n-butylbis(neodecanate), tin phenyltri(2-ethylhexanoate), and tin n-butyltri(2-ethylhexanoate).

[0115] Exemplary hydrocarbon-based metal ester carboxylate compounds include di-n-butylbis(n-octylmaleic acid)tin, di-n-octylbis(n-octylmaleic acid)tin, diphenylbis(n-octylmaleic acid)tin, di-n-butylbis(2-ethylhexylmaleic acid)tin, di-n-octylbis(2-ethylhexylmaleic acid)tin, and diphenylbis(2-ethylhexylmaleic acid)tin.

[0116] Exemplary metal alkoxide compounds include dimethoxytin, diethoxytin, tetraethoxytin, tetra-n-propoxytin, tetraisopropoxytin, tetra-n-butoxytin, tetraisobutoxytin, tetratert-butoxytin, and tetraphenoxytin.

[0117] The amount of functionalizing agent that can be added to the polymerization mixture can depend on various factors, including the type and amount of catalyst or initiator used to synthesize the reactive polymer and the desired degree of functionalization. In one or more embodiments, the amount of functionalizing agent used can be described in conjunction with the lanthanide metal in the lanthanide-containing compound. For example, the molar ratio of the functionalizing agent to the lanthanide metal can be from about 1:1 to about 200:1, from about 5:1 to about 150:1 in other embodiments, and from about 10:1 to about 100:1 in other embodiments.

[0118] Post-polymerization processing

[0119] In one or more embodiments, after polymerization and optionally after functionalization of the reactive polymer, a quencher may be added to the polymerization mixture to protonate the reaction products between the reactive polymer and the functionalizing agent, deactivate any residual reactive polymer chains, and / or deactivate the catalyst or catalyst component. The quencher may include protonated compounds, including but not limited to alcohols, carboxylic acids, inorganic acids, water, or mixtures thereof. An antioxidant, such as 2,6-di-tert-butyl-4-methylphenol, may be added simultaneously with, before, or after the addition of the quencher. The amount of antioxidant used may range from 0.01% by weight to 1% by weight of the polymer product. Alternatively, the polymer product may be oiled by adding oil, which may be in the form of a polymer paste or a polymer dissolved or suspended in monomers. The amount of oil that can be added is not limited in practice, and conventional amounts (e.g., 5 phr to 50 phr) can be added. Available oils or extenders include, but are not limited to, aromatic oils, paraffin oils, naphthenic oils, vegetable oils other than castor oil, low PCA oils (including MES, TDAE, and SRAE), and heavy naphthenic oils.

[0120] Once the polymerization mixture has been quenched, its various components can be recovered. In one or more embodiments, unreacted monomers can be recovered from the polymerization mixture. For example, monomers can be distilled from the polymerization mixture using techniques known in the art. Once the monomers have been removed from the polymerization mixture, they can be purified, stored, and / or recycled back into the polymerization process.

[0121] Polymer products can be recovered from the polymerization mixture using techniques known in the art. In one or more embodiments, desolventizing and drying techniques can be used. The polymer can be recovered by subjecting the polymerization mixture to steam desolventizing, followed by drying the resulting polymer debris in a hot air tunnel. Alternatively, the polymer can be recovered by passing it through an expander-expander. The polymer can also be recovered by drying the polymerization mixture directly on a drum dryer.

[0122] Polymer properties

[0123] In one or more embodiments, the polymer prepared according to the present invention may contain unsaturated groups. In these or other embodiments, the coupling polymer is vulcanizable. In one or more embodiments, the coupling polymer may have a glass transition temperature (Tg) less than 0°C, less than -40°C in other embodiments, and less than -60°C in other embodiments. g ).

[0124] In one or more embodiments, the coupling polymer of the present invention may be a cis-1,4-polydiene having a cis-1,4-bond content greater than 85%, greater than about 90% in other embodiments, greater than about 92% in other embodiments, and greater than about 94% in other embodiments, wherein the percentage is based on the number of diene unit cells employing cis-1,4-bonds relative to the total number of diene unit cells. The cis-1,4-, 1,2-, and trans-1,4-bond contents can be determined by infrared spectroscopy.

[0125] In one or more embodiments, the number-average molecular weight (M) of these polymers produced according to the present invention n The molecular weight distribution or polydispersity (M) of these polymers can be from about 10 to about 1,000, from about 50 to about 500 in other embodiments, from about 100 to about 400 in other embodiments, and from about 200 kg / mol to about 300 kg / mol in other embodiments, as determined by gel permeation chromatography (GPC) calibrated with polystyrene standards. In one or more embodiments, the molecular weight distribution or polydispersity (M) of these polymers... w / M n The molecular weight distribution (M) can be from about 1.0 to about 7.0, in other embodiments from about 1.5 to about 5.0, and in other embodiments from about 2.0 to about 4.0. In these or other embodiments, the molecular weight distribution or polydispersity (M...) of these polymers... w / M n It may be less than 7.0, less than 5.0 in other embodiments, less than 4.0 in other embodiments, and less than 3.0 in other embodiments.

[0126] In cases where the polymer is functionalized, it is believed that the reactive polymer and a functionalizing agent (and optionally a functionalizing agent) react to produce a functionalized or coupled polymer, wherein residues of the functionalizing agent are endowed at the end of at least one polymer chain. It is believed that the reactive ends of the polymer chain can react with the functionalizing agent, and in some embodiments, up to three chain ends react with the functionalizing agent to form a coupled polymer. However, the exact chemical structure of the coupled polymer prepared in each embodiment is not known precisely, specifically because the structure involves residues endowed at the ends of the polymer chain by the functionalizing agent and optionally a functionalizing agent. In fact, it is presumed that the structure of the coupled polymer can depend on various factors, such as the conditions used to prepare the reactive polymer (e.g., the type and amount of catalyst or initiator) and the conditions used to react the functionalizing agent (and optionally a functionalizing agent) with the reactive polymer (e.g., the type and amount of the functionalizing agent and the functionalizing agent itself). The coupled polymer obtained from the reaction between the reactive polymer and the functionalizing agent can be protonated or further modified.

[0127] Use of polymers

[0128] Rubber compositions can be prepared by using the polymers of the present invention alone or in combination with other elastomers (i.e., polymers that can be vulcanized to form compositions having rubber or elastomer properties). Other elastomers that can be used include natural rubber and synthetic rubber. Synthetic rubber is typically derived from the polymerization of conjugated diene monomers, copolymerization of conjugated diene monomers with other monomers (such as vinyl-substituted aromatic monomers), or copolymerization of ethylene with one or more α-olefins and optionally one or more diene monomers.

[0129] Exemplary elastomers include natural rubber, synthetic polyisoprene, polybutadiene, polyisobutylene-coisoprene, chloroprene rubber, poly(ethylene-copropylene), poly(styrene-cobutadiene), poly(styrene-coisoprene), poly(styrene-coisoprene-cobutadiene), poly(isoprene-cobutadiene), poly(ethylene-copropylene-cobutadiene), polysulfide rubber, acrylic rubber, polyurethane rubber, silicone rubber, epichlorohydrin rubber, and mixtures thereof. These elastomers can have a wide variety of macromolecular structures, including linear, branched, and star-shaped structures.

[0130] Rubber compositions may contain fillers, such as inorganic and organic fillers. Examples of organic fillers include carbon black and starch. Examples of inorganic fillers include silica, aluminum hydroxide, magnesium hydroxide, mica, talc (hydrated magnesium silicate), and clay (hydrated aluminum silicate). Carbon black and silica are the most commonly used fillers in tire manufacturing. In some embodiments, mixtures of different fillers may be advantageously used.

[0131] In one or more embodiments, carbon black includes furnace black, channel black, and lamp black. More specific examples of carbon black include ultra-abrasion furnace black, medium-ultra-abrasion furnace black, high-abrasion furnace black, fast extrusion furnace black, fine furnace black, semi-reinforced furnace black, medium-process channel black, difficult-to-process channel black, conductive channel black, and acetylene black.

[0132] In a particular embodiment, the surface area (EMSA) of the carbon black may be at least 20 m². 2 / g, and in other embodiments at least 35m 2 / g; Surface area values ​​can be determined using the cetyltrimethylammonium bromide (CTAB) technique according to ASTM D-1765. Carbon black can be in granular or non-granular flocculent form. The preferred form of carbon black may depend on the type of mixing equipment used to blend the rubber compounds.

[0133] The amount of carbon black used in the rubber composition can be up to about 50 parts by weight per 100 parts by weight of rubber (phr), typically about 5 phr per 100 parts by weight of rubber (phr) to about 40 phr per 100 parts by weight of rubber (phr).

[0134] Some commercially available silica that can be used includes Hi-Sil TM 215. Hi-Sil TM 233 and Hi-Sil TM 190 (PPG Industries, Inc., Pittsburgh, PA). Other commercially available suppliers of silica include Grace Davison (Baltimore, Md.) of Baltimore, Maryland; Degussa Corp. (Parsippany, NJ) of Parsippany, NJ; Rhodia Silica Systems (Cranbury, NJ) of Cranbury, NJ; and JM Huber Corp. (Edison, NJ) of Edison, NJ.

[0135] In one or more embodiments, silica can be characterized by its surface area, which provides a measure of its reinforcing properties. The Brunauer, Emmet, and Teller (“BET”) method (described in J. Am. Chem. Soc., vol. 60, p. 309 et eq., Journal of the American Chemical Society, Vol. 60, p. 309 onwards) is a recognized method for determining surface area. The BET surface area of ​​silica is typically less than 450 m². 2 / g. The useful range of surface area includes approximately 32m². 2 / g to approximately 400m 2 / g, approximately 100m 2 / g to approximately 250m 2 / g and approximately 150m 2 / g to approximately 220m 2 / g.

[0136] The pH of silica is typically from about 5 to about 7 or slightly above 7, or from about 5.5 to about 6.8 in other embodiments.

[0137] In one or more embodiments, when silica is used as a filler (alone or in combination with other fillers), silica coupling agents and / or silica masking agents may be added to the rubber composition during mixing to enhance the interaction between silica and the elastomer. Available silica coupling agents and silica masking agents are disclosed in U.S. Patent Nos. 3,842,111, 3,873,489, 3,978,103, 3,997,581, 4,002,594, 5,580,919, 5,583,245, 5,663,396, 5,674,932, 5,684,171, 5,684,172, 5,696,197, 6,608,145, 6,667,362, 6,579,949, 6,590,017, 6,525,118, 6,342,552, and 6,683,135, which are incorporated herein by reference.

[0138] The amount of silica used in the rubber composition can be from about 1 phr to about 100 phr, or in other embodiments from about 5 phr to about 80 phr. The upper limit is limited by the high viscosity imparted by silica. When silica is used with carbon black, the amount of silica can be reduced to as low as about 1 phr; as the amount of silica decreases, less coupling agent and masking agent can be used. Typically, the amount of coupling agent and masking agent ranges from about 4% to about 20% based on the weight of silica used.

[0139] Many types of rubber curing agents (also known as vulcanizing agents) can be used, including sulfur-based or peroxide-based curing systems. Curing agents are described in the following literature: Kirk-Othmer, Enzyclecupedia of Chemicaltschnologia, Vol. 20, pgs. 365-468, (3 rd Ed. 1982 (Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd ed. (1982), Vol. 20, pp. 365-468), especially in Vulcanization Agents and Auxiliary Materials, pp. 390-402, and AY Coran, Vulcanization, Encyclopedia of Polymer Science and Engineering, (2 nd Ed. 1989 (AY Coran, Encyclopedia of Vulcanization, Polymer Science and Engineering, 2nd ed. (1989)), these references are incorporated herein by reference. Vulcanizing agents can be used alone or in combination.

[0140] Other components commonly used in rubber compounding may also be added to the rubber composition. These components include accelerators, accelerator activators, oils, plasticizers, waxes, scorch inhibitors, processing aids, zinc oxide, tackifying resins, reinforcing resins, fatty acids (such as stearic acid), plasticizers, and anti-degradation agents (such as antioxidants and anti-ozone agents). In certain embodiments, the oils used include those commonly used as incrementing oils, as described above.

[0141] All components of the rubber composition can be mixed using standard mixing equipment such as Banbury or Brabender mixers, extruders, kneaders, and two-roll mills. In one or more embodiments, the components are mixed in two or more stages. In the first stage (often referred to as the masterbatch mixing stage), a so-called masterbatch is prepared, which typically contains rubber components and fillers. To prevent premature vulcanization (also known as scorching), the masterbatch may be vulcanizing agent-free. The masterbatch can be mixed at an initial temperature of about 25°C to about 125°C and an outlet temperature of about 135°C to about 180°C. Once the masterbatch is prepared, a vulcanizing agent can be introduced and mixed into the masterbatch in the final mixing stage, which is typically carried out at relatively low temperatures to reduce the chance of premature vulcanization. Optionally, an additional mixing stage, sometimes referred to as re-mixing, can be used between the masterbatch mixing stage and the final mixing stage. In cases where the rubber composition contains silica as a filler, one or more re-mixing stages are typically used. Various components, including the coupling polymers of the present invention, can be added during these re-mixing processes.

[0142] Mixing procedures and conditions particularly suitable for silica-filled tire formulations are described in U.S. Patent Nos. 5,227,425, 5,719,207, and 5,717,022 and European Patent No. 890,606, which are incorporated herein by reference. In one embodiment, the initial masterbatch is prepared by including the coupling polymer of the present invention and silica in the substantially absence of silica coupling agents and silica masking agents.

[0143] Rubber compositions prepared from the polymers of the present invention are particularly suitable for forming tire components, such as treads, sub-treads, sidewalls, carcass separators, sidewall cores, etc. For example, the polymers of the present invention are used in tread and sidewall formulations. In one or more embodiments, these tread or sidewall formulations may contain about 10% to about 100% by weight, about 35% to about 90% by weight in other embodiments, and about 50% to about 80% by weight of the polymers of the present invention, based on the total weight of the rubber in the formulation.

[0144] When the rubber composition is used to manufacture tires, it can be processed into tire parts using common tire manufacturing techniques, including standard rubber molding, forming, and curing techniques. Typically, vulcanization is achieved by heating the vulcanizable composition in a mold; for example, it can be heated to about 140°C to about 180°C. The cured or crosslinked rubber composition, referred to as vulcanized rubber, typically contains a thermosetting three-dimensional polymer network. Other components, such as fillers and processing aids, can be uniformly dispersed throughout the crosslinked network. Pneumatic tires can be prepared as discussed in U.S. Patent Nos. 5,866,171, 5,876,527, 5,931,211, and 5,971,046, which are incorporated herein by reference.

[0145] To demonstrate the practice of the invention, the following embodiments have been prepared and tested. However, these embodiments should not be considered as limiting the scope of the invention. The claims will be used to define the invention.

[0146] Example

[0147] Examples 1-5

[0148] The following examples illustrate an implementation scheme for a lanthanide-based catalyst system. Polymerization was carried out in 750 mL glass vials purified with N2. Approximately 20 wt% of a butadiene / n-hexane mixture and pure n-hexane were added to each vial, sufficient to prepare 333 g of a butadiene solution containing approximately 14 wt%. An appropriate amount of 1.0 M alkylaluminum reagent solution (see Table 1) was added to each vial, followed by 1.64 mL of a neodymium tert-carbonate solution (0.054 M hexane solution). The vials were allowed to stand for 3 minutes, and then 0.13 mL of an ethylaluminum dichloride solution (1.09 M hexane solution) was added. The vials were placed in a stirred bath at 80 °C. After stirring for 30 minutes, the vials were removed from the bath. The polymerization was terminated by adding 4.0 mL of a 10 wt% isopropanol solution of 2,6-di-tert-butyl-4-methylphenol to the polymerization mixture. The polymer was condensed in 8 L of isopropanol containing 15 g of 2,6-di-tert-butyl-4-methylphenol and then drum-dried. The polymer was analyzed by Mooney, GPC, and IR, and these values ​​are reported in Table 1.

[0149] Table 1

[0150] Example # 1 2 3 4 5 type Comparison Comparative example Comparative example This invention Comparative example DIBA / Nd (mol / mol) 4.22 0 0 4.22 4.22 TIBA / Nd (mol / mol) 6.33 0 0 0 0 TEAL / Nd(mol / mol) 0 10.00 20.00 6.33 0 % conversion 87.47 70.31 89.17 91.54 87.43 <![CDATA[ML 1+4 ]]> 85.35 82.90 38.71 90.26 35.06 T80(s) 4.46 4.35 3.85 4.32 11.07 <![CDATA[Mn(X10 3 )(g / mol)]]> 320 247 135 295 325 <![CDATA[Mw(X10 3 )(g / mol)]]> 1,161 1,162 816 1,020 735 Mw / Mn 3.63 4.71 6.03 3.45 2.26 %cis 98.41 96.66 92.58 96.75 95.67 % trans 0.73 2.47 6.37 2.37 3.95 % vinyl 0.86 0.86 1.05 0.88 0.38

[0151] The Mooney viscosity (MLV) of the polymer samples was determined at 100°C using a Monsanto Mooney viscometer with a large rotor, a heating time of one minute, and a running time of four minutes. 1+4The number-average molecular weight (Mn) of polymer samples was determined by gel permeation chromatography (GPC) using a Tosoh Ecosec HLC-8320 GPC system and a Tosoh TSKgel GMHxl-BS column, with THF as the solvent. n ) and weight-average molecular weight (M w The system was calibrated using a series of polystyrene standards, with polystyrene as the reference. The contents of cis-1,4-, trans-1,4-, and 1,2-bonds in the polymer samples were determined by infrared spectroscopy.

[0152] As can be seen from the data in Table 1, the conversion rates obtained by using triethylaluminum (TEAL) alone (Examples 2 and 3) were lower than those obtained by the control mixture of triisobutylaluminum (TIBA) and diisobutylaluminum hydride (DIBA) (Example 1). Similarly, the conversion rate obtained by using DIBA alone (Example 5) was lower than that obtained by the control mixture of TIBA and DIBA (Example 1). In contrast, the conversion rate obtained by the mixture of DIBA and TEAL (Example 4) was higher than that obtained by the TIBA / DIBA mixture or TEAL alone.

[0153] Examples 6-12

[0154] The following examples illustrate an implementation scheme for a nickel-based catalyst system. Polymerization was carried out in 750 mL glass vials purified with N2. Approximately 20 wt% of a butadiene / n-hexane mixture and pure n-hexane were added to each vial, sufficient to prepare 300 mL of approximately 15 wt% butadiene solution. An appropriate amount of 1.0 M alkylaluminum reagent solution (see Table 2) was added to each vial, followed by 1.36 mL of nickel 2-ethylhexanoate solution (0.012 M hexane solution). Then, an appropriate amount of 4.56 M BF3 and n-hexanol solution was added to obtain 1.68 equivalents of B / Al (0.10 mL–0.13 mL). The vials were placed in a stirred bath at 80 °C. After stirring for 40 minutes, the vials were removed from the bath. The polymerization was terminated by adding 4.0 mL of 10 wt% 2,6-di-tert-butyl-4-methylphenol isopropanol solution to the polymerization mixture. The polymer was condensed in 8 L of isopropanol containing 15 g of 2,6-di-tert-butyl-4-methylphenol and then drum-dried. The polymer was analyzed by Mooney, GPC, and IR, and these values ​​are reported in Table 2.

[0155] Table 2

[0156]

[0157] Mooney viscosity (ML) of polymer samples 1+4 The number average (M) of polymer samplesn ) and weight average (M w The molecular weight, as well as the cis-1,4-bond content, trans-1,4-bond content, and 1,2-bond content of the polymer sample, were determined according to the provisions above regarding Examples 1-5.

[0158] As can be seen from the data in Table 2, using a mixture of DIBA and TEAL can achieve a better balance between polymerization and the overall performance of the polymer.

[0159] Various modifications and alterations without departing from the scope and spirit of the invention will be apparent to those skilled in the art. The invention should not be unduly limited to the exemplary embodiments shown herein.

Claims

1. A method for preparing a polymer, the method comprising: Provide conjugated diene monomers; A lanthanide-containing compound, triethylaluminum, and aluminum hydride are introduced into the conjugated diene monomer; Following the step of introducing a lanthanide-containing compound, triethylaluminum, and aluminum hydride into the conjugated diene monomer, a halogen-containing compound is introduced into the conjugated diene monomer, wherein the molar ratio of triethylaluminum to the lanthanide-containing compound is 2:1 to 15:1, the molar ratio of aluminum hydride to the lanthanide-containing compound is 1:1 to 10:1, and the molar ratio of the halogen in the halogen-containing compound to the lanthanide-containing compound is 0.5:1 to 20:1; and The conjugated diene monomer is polymerized.

2. The method according to claim 1, wherein, Compounds containing lanthanides are organolanthanide compounds.

3. The method according to claim 1, wherein, Compounds containing lanthanides are selected from the group consisting of: lanthanide carboxylates, lanthanide organophosphates, lanthanide organophosphonates, lanthanide organosphines, lanthanide carbamates, lanthanide dithiocarbamates, lanthanide xanthates, lanthanide β-diketones, lanthanide alkoxides or phenolates, lanthanide halides, lanthanide pseudohalides, and lanthanide halide oxides.

4. The method according to claim 1, wherein, The aluminum hydride is made of the general formula AlR n H (3-n) The expression is represented as follows, where each R is an independent monovalent organic group connected to an aluminum atom via a carbon atom, and where n is an integer in the range of 1 to 3.

5. The method according to claim 1, wherein, The aluminum hydride is dihydrocarbon aluminum hydride.

6. The method according to claim 1, wherein, The aluminum hydride is hydrocarbon-based aluminum dihydride.

7. The method according to claim 1, wherein, The aluminum hydride is selected from the group consisting of: diethylaluminum hydride, di-n-propylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, di-n-octylaluminum hydride, diphenylaluminum hydride, di-p-tolylaluminum hydride, dibenzylaluminum hydride, phenylethylaluminum hydride, phenyl-n-propylaluminum hydride, phenylisopropylaluminum hydride, phenyl-n-butylaluminum hydride, and phenylisobutylaluminum hydride. Aluminum hydride of phenyl-n-octyl, aluminum hydride of p-tolylethyl, aluminum hydride of p-tolyl-n-propyl, aluminum hydride of p-tolyl-isopropyl, aluminum hydride of p-tolyl-n-butyl, aluminum hydride of p-tolyl-isobutyl, aluminum hydride of p-tolyl-n-octyl, aluminum hydride of benzylethyl, aluminum hydride of benzyl-n-propyl, aluminum hydride of benzyl-isopropyl, aluminum hydride of benzyl-n-butyl, aluminum hydride of benzyl-isobutyl, and aluminum hydride of benzyl-n-octyl.

8. The method according to claim 1, wherein, The aluminum hydride is selected from the group consisting of: ethyl aluminum hydride, n-propyl aluminum hydride, isopropyl aluminum hydride, n-butyl aluminum hydride, isobutyl aluminum hydride and n-octyl aluminum hydride.

9. The method according to claim 1, wherein, The halogen source is a compound selected from the group consisting of: elemental halogens, mixed halogens, organohalides, inorganic halides, and organometallic halides.

10. The method according to claim 1, wherein, The halogen source is a compound selected from the group consisting of hydrogen halides and metal halides.

11. The method according to claim 1, wherein, The conjugated diene monomer is selected from the group consisting of: 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, and 2,4-hexadiene.

12. The method according to claim 1, wherein, In the polymerization step, 0.001 mmol to 2 mmol of a lanthanide-containing compound is used per 100 grams of monomer.

13. The method according to claim 1, wherein, The polymerization step produces polydiene, and also includes a step of functionalizing the polydiene.

14. The method according to claim 1, wherein, It also includes a step to quench the polymerization process.

15. The method according to claim 1, wherein, The polymerization step produces a polydiene, wherein the polydiene has a cis-1,4-bond content of greater than 95%.

16. The method according to claim 1, wherein, The monomer conversion rate generated in the polymerization step is greater than 85%.

17. The method according to claim 1, wherein, The monomer conversion rate generated in the polymerization step is greater than 90%.

18. A polymer prepared by any one of claims 1 to 17.

19. A tire component, said tire component being prepared using the polymer according to claim 18.

20. A vulcanizable composition comprising the polymer, filler, and curing agent according to claim 18.

21. A method for preparing a polymer, the method comprising polymerizing a conjugated diene monomer in the presence of a nickel-based catalyst system, the nickel-based catalyst system comprising: (i) Nickel-containing compounds, (ii) Triethylaluminum, (iii) Aluminum hydride, and (iv) Halogenated compounds selected from fluorine-containing and chlorine-containing compounds, (v) The molar ratio of the triethylaluminum to the nickel-containing compound is from 2:1 to 100:1; (vi) The molar ratio of the aluminum hydride to the nickel-containing compound is from 1:1 to 500:1; and (vii) The molar ratio of the halogen in the halogen-containing compound to the nickel-containing compound is from 2:1 to 500:

1.

22. The method according to claim 21, wherein, Nickel-containing compounds are selected from the group consisting of: nickel carboxylate, nickel borate carboxylate, nickel organophosphate, nickel organophosphonate, nickel organophosphonate, nickel carbamate, nickel dithiocarbamate, nickel xanthate, nickel β-diketoate, nickel alkoxides or nickel phenolates, nickel halides, nickel pseudohalides or nickel halide.

23. The method according to claim 21, wherein, The aluminum hydride is made of the general formula AlR n H (3-n) The expression is represented as follows, where each R is an independent monovalent organic group connected to an aluminum atom via a carbon atom, and where n is an integer in the range of 1 to 3.

24. The method according to claim 21, wherein, The aluminum hydride is dihydrocarbon aluminum hydride.

25. The method of claim 21, wherein the aluminum hydride is hydrocarbon-based aluminum dihydride.

26. The method according to claim 21, wherein, The aluminum hydride is selected from the group consisting of: diethylaluminum hydride, di-n-propylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, di-n-octylaluminum hydride, diphenylaluminum hydride, di-p-tolylaluminum hydride, dibenzylaluminum hydride, phenylethylaluminum hydride, phenyl-n-propylaluminum hydride, phenylisopropylaluminum hydride, phenyl-n-butylaluminum hydride, and phenylisobutylaluminum hydride. Aluminum hydride of phenyl-n-octyl, aluminum hydride of p-tolylethyl, aluminum hydride of p-tolyl-n-propyl, aluminum hydride of p-tolyl-isopropyl, aluminum hydride of p-tolyl-n-butyl, aluminum hydride of p-tolyl-isobutyl, aluminum hydride of p-tolyl-n-octyl, aluminum hydride of benzylethyl, aluminum hydride of benzyl-n-propyl, aluminum hydride of benzyl-isopropyl, aluminum hydride of benzyl-n-butyl, aluminum hydride of benzyl-isobutyl, and aluminum hydride of benzyl-n-octyl.

27. The method according to claim 21, wherein, The aluminum hydride is selected from the group consisting of: ethylaluminum dihydrogenide, n-propyl aluminum dihydrogenide, isopropyl aluminum dihydrogenide, n-butyl aluminum dihydrogenide, isobutyl aluminum dihydrogenide, and n-octyl aluminum dihydrogenide.

28. The method according to claim 21, wherein, The halogen-containing compound is a fluorine-containing compound.

29. The method according to claim 21, wherein, The conjugated diene monomer is selected from the group consisting of: 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, and 2,4-hexadiene.

30. The method according to claim 21, wherein, In the polymerization step, 0.001 mmol to 2 mmol of nickel-containing compound is used per 100 g of monomer.

31. The method according to claim 21, wherein, The polymerization step produces polydiene, and also includes a step of functionalizing the polydiene.

32. The method according to claim 21, wherein, It also includes a step to quench the polymerization process.

33. The method according to claim 21, wherein, The fluorinated compounds are selected from the group consisting of: elemental fluorine, organic fluorides, inorganic fluorides, and mixtures thereof.

34. The method according to claim 21, wherein, The fluorinated compound is selected from the group consisting of hydrogen fluoride and metal fluorides.

35. The method according to claim 21, wherein, The fluorine-containing compound is an organometallic fluoride.

36. The method according to claim 21, wherein, The monomer conversion rate produced by the polymerization step is greater than 85%.

37. The method according to claim 21, wherein, The monomer conversion rate produced by the polymerization step is greater than 90%.

38. A polymer prepared by means of polymerizing a conjugated diene monomer in the presence of a nickel-based catalyst system, the nickel-based catalyst system comprising: (i) Nickel-containing compounds, (ii) Triethylaluminum, (iii) Aluminum hydride, and (iv) Halogen-containing compounds, (v) The molar ratio of the triethylaluminum to the nickel-containing compound is from 2:1 to 100:1; (vi) The molar ratio of the aluminum hydride to the nickel-containing compound is from 1:1 to 500:1; and (vii) The molar ratio of the halogen in the halogen-containing compound to the nickel-containing compound is from 2:1 to 500:

1.

39. A tire component, said tire component being prepared using the polymer according to claim 38.

40. A vulcanizable composition comprising the polymer, filler, and curing agent according to claim 38.

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