Metal-based catalysts for generating polydienes

Abstract

To provide a useful method for polymerizing conjugated dienes using a metal catalyst system. [Solution] A method for preparing a polymer, comprising the step of polymerizing a conjugated diene monomer in the presence of a catalyst system comprising (i) a nickel-containing compound, (ii) triethylaluminum, (iii) hydrocarbylaluminum hydride, and (iv) a halogen-containing compound.

Description

[Technical Field]

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

[0002] (Field of invention) One or more embodiments of the present invention relate to a method for polymerizing conjugated dienes using a metal catalyst system. [Background technology]

[0003] Synthetic elastomers having a linear backbone are used in tire components, for example, These polymers are often used in the manufacture of treads and treads. They are believed to offer advantageous tensile properties, wear resistance, low hysteresis, and fatigue resistance. For example, cis-1,4-polydiene is used in tires.

[0004] Cis-1,4-polydienes can be produced by using lanthanide-based or nickel-based catalyst systems. Lanthanide-based catalyst systems typically include a lanthanide compound, an alkylating agent, and a halogen source for activating the system. Nickel-based catalyst systems typically include a nickel-containing compound, an alkylating agent, and a halogen source for activating the system. Alkylaluminum compounds, such as trialkylaluminum compounds and alkylaluminum hydrides, are often used as alkylating agents. The species selected for each component, their relative concentrations, and many other factors can affect the polymerization process and the resulting polydiene that is ultimately synthesized. For example, triisobutylaluminum is known to result in higher monomer conversion rates and higher cis-1,4-microstructure content than when triethylaluminum is used as an alkylating agent in lanthanide systems. [Overview of the project]

[0005] One or more embodiments of the present invention provide a method for preparing a polymer, 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] A further embodiment of the present invention provides a polymer, which is 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] Another embodiment of the present invention provides a method for preparing a polymer, comprising polymerizing a conjugated diene monomer in the presence of a metal catalyst system comprising a nickel-containing compound, triethylaluminum, aluminum hydride, and a halogen-containing compound selected from a fluorine-containing compound and a chlorine-containing compound.

[0008] A further embodiment of the present invention provides a polymer, which is prepared by polymerizing a conjugated diene monomer in the presence of a metal catalyst system comprising a nickel-containing compound, triethylaluminum, aluminum hydride, and a halogen-containing compound. [Modes for carrying out the invention]

[0009] Embodiments of the present invention are based, at least in part, on the discovery of a process for the polymerization of conjugated dienes using a metal-based catalyst system comprising triethylaluminum and aluminum hydride as alkylating agents. The use of this particular combination of alkylating agents has unexpectedly yielded beneficial results, including improved polymerization activity and desirable polymer properties. While prior art teaches that the use of triethylaluminum as an alkylating agent results in lower polymerization activity than other commonly used trialkylaluminum compounds (e.g., triisobutylaluminum), the discovery relating to the present invention shows that the combination of triethylaluminum and aluminum hydride yields particularly beneficial results compared to other alkylating agents such as triisobutylaluminum, particularly with respect to the polymerization activity of lanthanide catalysts and the resulting polymer properties. Other embodiments are based, at least in part, on the discovery of a process for the polymerization of conjugated dienes using 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 conventionally used in these catalyst systems.

[0010] A first set of embodiments provides a polymerization process for polymerizing a conjugated diene monomer 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, other organometallic compounds, Lewis bases, and / or catalyst modifiers may be used in addition to the above components or components.

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

[0012] Lanthanide-containing compounds Lanthanide-containing compounds useful in lanthanide-based catalyst systems include compounds containing at least one atom from among lanthanum, neodymium, cerium, praseodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, and didymium. In one embodiment, these compounds may include neodymium, lanthanum, samarium, or didymium. As used herein, the term "didymium" refers to a commercially available mixture of rare earth elements obtained from monaz sand. In addition, lanthanide-containing compounds useful in the present invention may be in the form of elemental lanthanides.

[0013] The lanthanide atom in the lanthanide-containing compound may be in various oxidation states, for example, but not limited to, oxidation states of 0, +2, +3, and +4. In one embodiment, a trivalent lanthanide-containing compound (where the lanthanide atom is in the +3 oxidation state) can be used. Suitable lanthanide-containing compounds include, but are not limited to, lanthanide carboxylates, lanthanide organic phosphates, lanthanide organic phosphonates, lanthanide organic phosphinates, lanthanide carbamates, lanthanide dithiocarbamates, lanthanide xanthetes, lanthanide β-diketonates, lanthanide oxides, lanthanide alkoxides or aryl oxides, lanthanide halides, lanthanide pseudohalides, lanthanide oxyhalides, and organic lanthanide compounds.

[0014] In one or more embodiments, the lanthanide-containing compound may be soluble in hydrocarbon solvents (e.g., aromatic hydrocarbons, aliphatic hydrocarbons, or alicyclic hydrocarbons). However, hydrocarbon-insoluble lanthanide-containing compounds may also be useful in the present invention because they can be suspended in a polymerization medium to form catalytically active species.

[0015] For the sake of simplicity, further explanation of useful lanthanide-containing compounds will focus on neodymium compounds, although those skilled in the art will be able to select similar compounds based on other lanthanide metals.

[0016] 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 versate), neodymium naphthenate, neodymium stearate, neodymium oleate, neodymium benzoate, and neodymium picolinate.

[0017] Suitable neodymium organic phosphates include, but are not limited to, neodymium dibutyl phosphate, neodymium dipentyl phosphate, neodymium dihexyl phosphate, neodymium diheptyl phosphate, neodymium dioctyl phosphate, neodymium bis(1-methylheptyl) phosphate, neodymium bis(2-ethylhexyl) phosphate, neodymium didecyl phosphate, neodymium didodecyl phosphate, neodymium dioctadecyl phosphate, neodymium dioleil phosphate, neodymium diphenyl phosphate, neodymium bis(p-nonylphenyl) phosphate, neodymium butyl(2-ethylhexyl) phosphate, neodymium(1-methylheptyl)(2-ethylhexyl) phosphate, and neodymium(2-ethylhexyl)(p-nonylphenyl) phosphate.

[0018] Suitable neodymium organic phosphonates include, but are not limited to, neodymium butyl phosphonate, neodymium pentyl phosphonate, neodymium hexyl phosphonate, neodymium heptyl phosphonate, neodymium octyl phosphonate, neodymium (1-methylheptyl) phosphonate, neodymium (2-ethylhexyl) phosphonate, neodymium decyl phosphonate, neodymium dodecyl phosphonate, neodymium octadecyl phosphonate, neodymium oleyl phosphonate, neodymium phenyl phosphonate, neodymium (p-nonylphenyl) phosphonate, neodymium butylbutyl phosphonate, neodymium pentylpentyl phosphonate, neodymium hexylhexyl phosphonate, neodymium heptylheptyl phosphonate, neodymium octyloctyl phosphonate, neodymium (1-methylheptyl)(1-methylheptyl) phosphonate, neodymium (2-ethylhexyl)(2-ethylhexyl) phosphonate, neodymium decyldecyl phosphonate, neodymium dodecyldodecyl phosphonate, neodymium octadecyloctadecyl phosphonate, neodymium oleyl oleyl phosphonate, neodymium phenylphenyl phosphonate, neodymium (p-nonylphenyl)(p-nonylphenyl) phosphonate, neodymium butyl(2-ethylhexyl) phosphonate, neodymium (2-ethylhexyl)butyl phosphonate, 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.

[0019] Suitable neodymium organic phosphinates include neodymium butyl phosphinate, neodymium pentyl phosphinate, neodymium hexyl phosphinate, neodymium heptyl phosphi - octyl, neodymium octyl phosphinate, neodymium (1-methylheptyl) phosphinate, neodymium (2-ethylhexyl) phosphinate, neodymium decyl phosphinate, neodymium dodecyl phosphinate, neodymium octadecyl phosphinate, neodymium oleyl phosphinate, neodymium phenyl phosphinate, neodymium (p-nonylphenyl) phosphinate, neodymium dibutyl phosphinate, neodymium dipentyl phosphinate, neodymium dihexyl phosphinate, neodymium diheptyl phosphinate, neodymium dioctyl phosphinate, neodymium bis(1-methylheptyl) phosphinate, neodymium bis(2-ethylhexyl) phosphinate, neodymium didodecyl phosphinate, neodymium dioctadecyl phosphinate, neodymium dioleyl phosphinate, neodymium diphenyl phosphinate, neodymium bis(p-nonylphenyl) phosphinate, neodymium butyl(2-ethylhexyl) phosphinate, neodymium (1-methylheptyl)(2-ethylhexyl) phosphinate, and neodymium (2-ethylhexyl)(p-nonylphenyl) phosphinate are included, but not limited thereto.

[0020] Suitable neodymium carbamates include, but are not limited to, neodymium dimethylcarbamate, neodymium diethylcarbamate, neodymium diisopropylcarbamate, neodymium dibutylcarbamate, and neodymium dibenzylcarbamate.

[0021] Suitable neodymium dithiocarbamates include, but are not limited to, neodymium dimethyldithiocarbamate, neodymium diethyldithiocarbamate, neodymium diisopropyldithiocarbamate, neodymium dibutyldithiocarbamate, and neodymium dibenzyldithiocarbamate.

[0022] Suitable neodymium xanthates include, but are not limited to, neodymium methylxanthate, neodymium ethylxanthate, neodymium isopropylxanthate, neodymium butylxanthate, and neodymium benzylxanthate.

[0023] Suitable neodymium β-diketonates include, but are not limited to, neodymium acetylacetonate, neodymium trifluoroacetylacetonate, neodymium hexafluoroacetylacetonate, neodymium benzoylacetonate, and neodymium 2,2,6,6-tetramethyl-3,5-heptanedione.

[0024] Suitable neodymium alkoxides or aryl oxides include, but are not limited to, neodymium methoxide, neodymium ethoxide, neodymium isopropoxide, neodymium 2-ethylhexoxide, neodymium phenoxide, neodymium nonylphenoxide, and neodymium naphthoxide.

[0025] Suitable neodymium halides include, but are not limited to, neodymium fluoride, neodymium chloride, neodymium bromide, and neodymium iodide. Suitable neodymium pseudohalides include, but are not limited to, neodymium cyanide, neodymium cyanate, neodymium thiocyanate, neodymium azide, and neodymium ferrocyanide. Suitable neodymium oxyhalides include, but are not limited to, neodymium oxyfluoride, neodymium oxychloride, and neodymium oxybromide. Neodymium oxides may also be used. Lewis bases (e.g., tetrahydrofuran ("THF")) ) may be used to facilitate the solubilization of neodymium compounds of this class in inert organic solvents. When using lanthanide halides, lanthanide oxyhalides, or other lanthanide-containing compounds containing halogen atoms, the lanthanide-containing compounds may optionally provide all or part of the halogen source in the lanthanide-based catalyst system.

[0026] As used herein, the term organolanthanide compound refers to any lanthanide-containing compound that contains at least one lanthanide-carbon bond. These compounds are primarily, but not exclusively, compounds containing cyclopentadienyl ("Cp"), substituted cyclopentadienyl, allyl, and substituted allyl ligands. Suitable organolanthanide compounds include, but are not limited to, Cp3Ln, Cp2LnR, Cp2LnCl, CpLnCl2, CpLn(cyclooctatetraene), (C5Me5)2LnR, LnR3, Ln(allyl)3, and Ln(allyl)2Cl, where Ln represents a lanthanide atom and R represents a hydrocarbyl group. In one or more embodiments, the hydrocarbyl group useful in the present invention may contain heteroatoms, such as nitrogen, oxygen, boron, silicon, sulfur, and phosphorus.

[0027] Nickel-containing compounds In nickel-based catalyst systems, various nickel-containing compounds or mixtures thereof can be used. In one or more embodiments, such nickel-containing compounds may be soluble in hydrocarbon solvents, such as aromatic hydrocarbons, aliphatic hydrocarbons, or alicyclic hydrocarbons. In other embodiments, hydrocarbon-insoluble nickel-containing compounds that can be suspended in a polymerization medium to form catalytically active species may also be useful.

[0028] Nickel atoms in nickel-containing compounds can be in various oxidation states, including but not limited to oxidation states 0, +2, +3, and +4. Examples of nickel-containing compounds include, but are not limited to, nickel carboxylates, nickel carboxylate borates, nickel organic phosphates, nickel organic phosphonates, nickel organic phosphinates, nickel carbamates, nickel dithiocarbamates, nickel xanthetes, nickel β-diketonates, nickel alkoxides or aryl oxides, nickel halides, nickel pseudohalides, nickel oxyhalides, or organonickel compounds.

[0029] Examples of nickel carboxylates include nickel formate, nickel acetate, nickel acetate, 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 picolinate.

[0030] Examples of nickel carboxylate borates include compounds defined by the formula (RCOONiO)3B or (RCOONiO)2B(OR), where each R, which may or may not be the same, is a hydrogen atom or a monovalent organic group. In one embodiment, each R may be a hydrocarbyl group, for example, but not limited to alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, aralkyl, alkaryl, allyl, and alkynyl groups, each preferably containing one carbon atom (or the minimum number of carbon atoms suitable for forming the group) up to about 20 carbon atoms. These hydrocarbyl groups may contain heteroatoms such as, but not limited to, nitrogen, oxygen, silicon, sulfur, and phosphorus atoms. Examples of nickel carboxylate borates include those disclosed in U.S. Patent No. 4,522,988, incorporated herein by reference. Specific examples of nickel(II) carboxylates include nickel(II) boric acid neodecanoate, nickel(II) boric acid hexanoate, nickel(II) boric acid naphthenate, nickel(II) boric acid stearate, nickel(II) boric acid octoate, nickel(II) boric acid 2-ethylhexanoate, and mixtures thereof.

[0031] Examples of nickel organic phosphates include nickel dibutyl phosphate, nickel dipentyl phosphate, nickel dihexyl phosphate, nickel diheptyl phosphate, nickel dioctyl phosphate, nickel bis(1-methylheptyl) phosphate, nickel bis(2-ethylhexyl) phosphate, nickel didecyl phosphate, nickel didodecyl phosphate, nickel dioctadecyl phosphate, nickel dioleil phosphate, nickel diphenyl phosphate, nickel bis(p-nonylphenyl) phosphate, nickel butyl(2-ethylhexyl) phosphate, nickel(1-methylheptyl)(2-ethylhexyl) phosphate, and nickel(2-ethylhexyl)(p-nonylphenyl) phosphate.

[0032] Nickel organic phosphonates include nickel butyl phosphonate, nickel pentyl phosphonate, nickel hexyl phosphonate, nickel heptyl phosphonate, nickel octyl phosphonate, nickel (1-methylheptyl) phosphonate, nickel (2-ethylhexyl) phosphonate, nickel decyl phosphonate, nickel dodecyl phosphonate, nickel octadecyl phosphonate, nickel oleyl phosphonate, nickel phenyl phosphonate, nickel (p-nonylphenyl) phosphonate, nickel butyl butyl phosphonate, nickel pentyl pentyl phosphonate, nickel hexyl hexyl phosphonate, nickel heptyl heptyl phosphonate, nickel octyl octyl phosphonate, and nickel (1-methylheptyl)(1-methylheptyl) phosphonate. Examples include nickel(2-ethylhexyl)(2-ethylhexyl)phosphonate, nickeldecyldecylphosphonate, nickeldodecyldodecylphosphonate, nickeloctadecyloctadecylphosphonate, nickeloleyloleylphosphonate, nickelphenylphenylphosphonate, nickel(p-nonylphenyl)(p-nonylphenyl)phosphonate, nickelbutyl(2-ethylhexyl)phosphonate, nickel(2-ethylhexyl)butylphosphonate, 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.

[0033] Nickel organic phosphinates include nickel butyl phosphinate, nickel pentyl phosphinate, nickel hexyl phosphinate, nickel heptyl phosphinate, nickel octyl phosphinate, nickel (1-methylheptyl) phosphinate, nickel (2-ethylhexyl) phosphinate, nickel decyl phosphinate, nickel dodecyl phosphinate, nickel octadecyl phosphinate, nickel oleyl phosphinate, nickel phenyl phosphinate, nickel (p-nonylphenyl) phosphinate, nickel dibutyl phosphinate, nickel dipentyl phosphinate, nickel dihexyl phosphinate, nickel Examples include keldheptyl phosphinate, nickel dioctyl phosphinate, nickel bis(1-methylheptyl) phosphinate, nickel bis(2-ethylhexyl) phosphinate, nickel didecyl phosphinate, nickel didodecyl phosphinate, nickel dioctadecyl phosphinate, nickel dioleil phosphinate, nickel diphenyl phosphinate, nickel bis(p-nonylphenyl) phosphinate, nickel butyl(2-ethylhexyl) phosphinate, nickel(1-methylheptyl)(2-ethylhexyl) phosphinate, and nickel(2-ethylhexyl)(p-nonylphenyl) phosphinate.

[0034] Examples of nickel carbamates include nickel dimethyl carbamate, nickel diethyl carbamate, nickel diisopropyl carbamate, nickel dibutyl carbamate, and nickel dibenzyl carbamate.

[0035] Nickel dithiocarbamates include nickel dimethyl dithiocarbamate and nickel Examples include diethyldithiocarbamate, nickel diisopropyldithiocarbamate, nickel dibutyldithiocarbamate, and nickel dibenzyldithiocarbamate.

[0036] Examples of nickel xanthetes include nickel methyl xanthete, nickel ethyl xanthete, nickel isopropyl xanthete, nickel butyl xanthete, and nickel benzyl xanthete.

[0037] Examples of nickel β-diketonates include nickel acetylacetonate, nickel trifluoroacetylacetonate, nickel hexafluoroacetylacetonate, nickel benzoylacetonate, and nickel 2,2,6,6-tetramethyl-3,5-heptanedione.

[0038] Examples of nickel alkoxides or aryl oxides include nickel methoxide, nickel ethoxide, nickel isopropoxide, nickel 2-ethylhexoxide, nickel phenoxide, nickel nonylphenoxide, and nickel naphthoxide.

[0039] Examples of nickel halides include nickel fluoride, nickel chloride, nickel bromide, and nickel iodide. Examples of nickel pseudohalides include nickel cyanide, nickel cyanate, nickel thiocyanate, nickel azide, and nickel ferrocyanide. Examples of nickel oxyhalides include nickel oxyfluoride, nickel oxychloride, and nickel oxybromide. If a nickel halide, nickel oxyhalide, or other nickel-containing compound contains an unstable fluorine or chlorine atom, the nickel-containing compound may also function as a fluorine-containing compound or a chlorine-containing compound. Lewis bases such as alcohols can be used as solubilizers for this type of compound.

[0040] The term "organic nickel compound" can refer to any nickel compound containing at least one nickel-carbon bond. Examples of organic nickel compounds include bis(cyclopentadienyl)nickel (also known as nickerosene), bis(pentamethylcyclopentadienyl)nickel (also known as decamethylnickerosene), bis(tetramethylcyclopentadienyl)nickel, bis(ethylcyclopentadienyl)nickel, bis(isopropylcyclopentadienyl)nickel, bis(pentadienyl)nickel, bis(2,4-dimethylpentadienyl)nickel, (cyclopentadienyl)(pentadienyl)nickel, bis(1,5-cyclooctadiene)nickel, bis(allyl)nickel, bis(methallyl)nickel, and bis(clotyl)nickel.

[0041] Alkylating agent blend As described above, lanthanide-based catalyst systems and nickel-based catalyst systems contain aluminum hydride compounds in addition to triethylaluminum. Aluminum hydride and triethylaluminum can be combined and referred to as an alkylating agent blend or alkylating agent system.

[0042] As those skilled in the art will understand, triethylaluminum can be defined by the formula Al(CH2CH3)3.

[0043] Aluminum hydride compounds, also known as hydrocarbyl aluminum hydride, have the general formula AlR n H 3-n It can be expressed as, where each R is independently a monovalent organic group bonded to an aluminum atom via a carbon atom, and n can be an integer in the range of 1 to 3. In one or more embodiments, each R is independently a hydrocarbyl group, for example, alkyl, cy These groups may be chloroalkyl, substituted cycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, aralkyl, alkaryl, allyl, and alkynyl groups, each containing one carbon atom (or the minimum number of carbon atoms suitable for forming the group) up to about 20 carbon atoms. These hydrocarbyl groups may contain heteroatoms, such as, but are not limited to, nitrogen, oxygen, boron, silicon, sulfur, and phosphorus atoms. In one or more embodiments, the aluminum hydride may be dihydrocarbyl aluminum hydride, and in other embodiments, it may be hydrocarbyl aluminum dihydride.

[0044] Suitable dihydrocarbyl aluminum hydride compounds include 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, phenylisobutylaluminum hydride, and phenyl- This includes, but is not limited to, n-octyl aluminum hydride, p-tolylethyl aluminum hydride, p-tolyl-n-propyl aluminum hydride, p-tolylisopropyl aluminum hydride, p-tolyl-n-butyl aluminum hydride, p-tolylisobutyl aluminum hydride, p-tolyl-n-octyl aluminum hydride, benzylethyl aluminum hydride, benzyl-n-propyl aluminum hydride, benzylisopropyl aluminum hydride, benzyl-n-butyl aluminum hydride, benzylisobutyl aluminum hydride, and benzyl-n-octyl aluminum hydride.

[0045] Suitable hydrocarbyl aluminum dihydrides include, but are not limited to, ethyl aluminum dihydride, n-propyl aluminum dihydride, isopropyl aluminum dihydride, n-butyl aluminum dihydride, isobutyl aluminum dihydride, and n-octyl aluminum dihydride.

[0046] Halogen-containing compounds As described above, lanthanide-based catalyst systems and nickel-based catalyst systems contain halogen-containing compounds.

[0047] Various compounds containing one or more halogen atoms, or mixtures thereof, 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 that are soluble in hydrocarbon solvents are suitable for use in this invention. However, halogen-containing compounds that are insoluble in hydrocarbon solvents are also useful because they can be suspended in a polymerization system to form catalytically active species.

[0048] Useful types of halogen-containing compounds that can be used include, but are not limited to, elemental halogens, mixed halogens, hydrogen halides, organic halides, inorganic halides, metal halides, and organometallic halides.

[0049] Suitable elemental halogens include, but are not limited to, fluorine, chlorine, bromine, and iodine. Some specific examples of suitable halogen mixtures include iodine monochloride, iodine monobromide, iodine trichloride, and iodine pentafluoride.

[0050] Suitable hydrogen halides include hydrogen fluoride, hydrogen chloride, hydrogen bromide, and hydrogen iodide. However, it is not limited to these.

[0051] Suitable organic halides include, but are not limited to, t-butyl chloride, t-butyl bromide, allyl chloride, allyl bromide, benzyl chloride, benzyl bromide, chloro-diphenylmethane, bromo-diphenylmethane, triphenylmethyl chloride, triphenylmethyl bromide, benzylidene chloride, benzylidene bromide, methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, trimethylchlorosilane, benzoyl chloride, benzoyl bromide, propionyl chloride, propionyl bromide, methyl chloroformate, and methyl bromoformate.

[0052] Suitable inorganic halides include, but are not limited to, phosphate trichloride, phosphate tribromide, phosphate pentachloride, phosphate oxychloride, phosphate 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.

[0053] 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.

[0054] Suitable organometallic halides include dimethylaluminum chloride, diethylaluminum chloride, dimethylaluminum bromide, diethylaluminum bromide, dimethylaluminum fluoride, diethylaluminum fluoride, methylaluminum dichloride, ethylaluminum dibromide, methylaluminum difluoride, ethylaluminum difluoride, methylaluminum sesquichloride, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, methylmagnesium chloride, and methylmagnesium This includes, but is not limited to, magnesium 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-t-butyltin dichloride, di-t-butyltin dibromide, dibutyltin dichloride, dibutyltin dibromide, tributyltin chloride, and tributyltin bromide.

[0055] In one or more embodiments, the lanthanide catalyst system may include a compound containing a non-coordinating anion or a non-coordinating anion precursor. In one or more embodiments, a compound containing a non-coordinating anion or a non-coordinating anion precursor can be used in place of the halogen source described above. A non-coordinating anion is a sterically bulky anion that, due to steric hindrance, does not form a coordination bond with the active center of the catalyst system, for example. Non-coordinating anions useful in the present invention include, but are not limited to, tetraarylborate anions and fluorinated tetraarylborate anions. Furthermore, compounds containing non-coordinating anions are used against catio For example, the compound may contain carbonium, ammonium, or phosphonium cations. Exemplary countercations include, but are not limited to, triarylcarbonium cations and N,N-dialkylanilinium cations. Examples of compounds containing non-coordinating anions and countercations include, but are not limited to, triphenylcarboniumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarboniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, and N,N-dimethylaniliniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate.

[0056] Those skilled in the art will understand that halogen-containing compounds may include lanthanide-containing compounds or nickel-containing compounds, and that these compounds may contain unstable halogen atoms.

[0057] In this embodiment, a non-coordinating anion precursor may also be used. A non-coordinating anion precursor is a compound that can form a non-coordinating anion under reaction conditions. Useful non-coordinating anion precursors include, but are not limited to, triarylboron compounds and BR3, where R is an electron-withdrawing aryl group, such as pentafluorophenyl or 3,5-bis(trifluoromethyl)phenyl group.

[0058] Fluorine-containing compounds In certain embodiments, the nickel-based catalyst system may include a fluorine-containing compound. Examples of fluorine-containing compounds include various compounds containing one or more unstable fluorine atoms, or mixtures thereof. In one or more embodiments, the fluorine-containing compound may be soluble in hydrocarbon solvents. In other embodiments, hydrocarbon-insoluble fluorine-containing compounds that can be suspended in a polymerization medium to form catalytically active species may be useful.

[0059] Examples of fluorine-containing compounds include, but are not limited to, elemental fluorine, halogen fluorides, hydrogen fluoride, organofluorides, inorganic fluorides, metallic fluorides, organometallic fluorides, and mixtures thereof. In one or more embodiments, a complex of a fluorine-containing compound with a Lewis base such as an ether, alcohol, water, aldehyde, ketone, ester, nitrile, or mixture thereof may be used. Specific examples of these complexes include a complex of boron trifluoride with a Lewis base of hydrogen fluoride.

[0060] Examples of halogen fluorides include iodine monofluoride, iodine trifluoride, and iodine pentafluoride.

[0061] Examples of organic fluorides include t-butyl fluoride, allyl fluoride, benzyl fluoride, fluorodiphenylmethane, triphenylmethyl fluoride, benzylidene fluoride, methyltrifluorosilane, phenyltrifluorosilane, dimethyldifluorosilane, diphenyldifluorosilane, trimethylfluorosilane, benzoyl fluoride, propionyl fluoride, and methylfluoroformate.

[0062] Examples of inorganic fluorides include phosphorus trifluoride, phosphorus pentafluoride, phosphorus oxyfluoride, boron trifluoride, silicon tetrafluoride, arsenic trifluoride, selenium tetrafluoride, and tellurium tetrafluoride.

[0063] Examples of metallic fluorides include tin tetrafluoride, aluminum trifluoride, antimony trifluoride, antimony pentafluoride, gallium trifluoride, indium trifluoride, titanium tetrafluoride, and zinc difluoride.

[0064] Examples of organometallic fluorides include dimethylaluminum fluoride, diethylaluminum fluoride, methylaluminum difluoride, ethylaluminum difluoride, methylaluminum sesquifluoride, ethylaluminum sesquifluoride, isobutylaluminum sesquifluoride, methylmagnesium fluoride, ethylmagnesium fluoride, butylmagnesium fluoride, phenylmagnesium fluoride, benzylmagnesium fluoride, trimethyltin fluoride, triethyltin fluoride, di-t-butyltin difluoride, dibutyltin difluoride, and tributyltin fluoride.

[0065] Various compounds containing one or more unstable chlorine atoms, or mixtures thereof, can be used as chlorine-containing compounds. In one or more embodiments, the chlorine-containing compound may be soluble in hydrocarbon solvents. In other embodiments, hydrocarbon-insoluble chlorine-containing compounds that can be suspended in a polymerization medium to form catalytically active species may be useful.

[0066] Catalyst component ratio In the first set of embodiments, the lanthanide catalyst compositions used in the present invention may be formed by combining or mixing the above-mentioned catalyst components. One or more active catalyst species are thought to be obtained from combinations of lanthanide catalyst components, but the various catalyst components or the degree of interaction or reaction between components are not so precisely known. Therefore, the term “catalyst composition” is used to encompass simple mixtures of components, complexes of various components resulting from physical or chemical attraction, chemical reaction products of components, or combinations thereof.

[0067] 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.

[0068] In one or more embodiments, the molar ratio (alkylating agent / Ln) of hydrocarbyl aluminum hydride to lanthanide-containing compound 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.

[0069] In one or more embodiments, the molar ratio of the halogen-containing compound to the lanthanide-containing compound is best described in terms of the ratio of moles of halogen atoms in the halogen source to 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 other embodiments from about 2:1 to about 6:1.

[0070] In yet another embodiment, the molar ratio (An / Ln) of the non-coordinating anion or non-coordinating anion precursor to the lanthanide-containing compound may be about 0.5:1 to about 20:1, in another embodiment about 0.75:1 to about 10:1, and in yet another embodiment about 1:1 to about 6:1.

[0071] In a second set of embodiments, the nickel-based catalyst compositions used in the present invention may be formed by combining or mixing the above-described catalyst components. While one or more active catalyst species are thought to be obtained from combinations of nickel-based catalyst components, the extent of interaction or reaction between various catalyst components or components is not so precisely known. Therefore, the term “catalyst composition” is used to encompass simple mixtures of components, complexes of various components resulting from physical or chemical attraction, chemical reaction products of components, or combinations thereof.

[0072] In one or more embodiments, the molar ratio of triethylaluminum to the nickel-containing compound (alkylating agent / Ni) 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.

[0073] In one or more embodiments, the molar ratio of hydrocarbyl aluminum hydride to nickel-containing compound (alkylating agent / Ni) 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.

[0074] In embodiments in which the nickel-containing catalyst system includes a fluorine-containing compound, the molar ratio of the fluorine-containing compound to the nickel-containing compound is best described in terms of the ratio of moles of fluorine atoms in the fluorine-containing compound to 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 other embodiments from about 8:1 to about 200:1.

[0075] catalyst formation Lanthanide-based and nickel-based catalyst systems of the present invention can be prepared using various procedures. In one or more embodiments, the catalyst system can be formed in situ by separately adding the catalyst components to the monomers to be polymerized, either stepwise or simultaneously. In other embodiments, the catalyst system can be formed in advance. That is, the catalyst components are pre-mixed outside the polymerization system in the absence of monomers or in the presence of small amounts of monomers. The resulting pre-formed catalyst composition can be aged as needed and then added to the monomers to be polymerized.

[0076] Catalyst systems can be formed by various methods.

[0077] In one embodiment, the catalyst composition may be formed in situ by adding catalyst components to a solution containing monomers and a solvent, or to a bulk monomer, either stepwise or simultaneously. In one embodiment, an alkylating agent may be added first, followed by a lanthanide-containing or nickel-containing compound, and then a halogen-containing compound or a compound containing a non-coordinating anion or a non-coordinating anion precursor.

[0078] In another embodiment, the catalyst composition may be pre-formed. That is, the catalyst components are pre-mixed outside the polymerization system at a suitable temperature, which may be about -20°C to about 80°C, in the absence of monomers or in the presence of small amounts of at least one conjugated diene monomer. The amount of conjugated diene monomer that can be used to pre-form the catalyst may range from about 1 to about 500 moles per mole of the lanthanide-containing or nickel-containing compound, in other embodiments from about 5 to about 250 moles, and in other embodiments from about 10 to about 100 moles. The resulting catalyst composition may be aged as needed before being added to the monomers to be polymerized.

[0079] In yet another embodiment, the catalyst composition may be formed by using a two-step procedure. The first step may involve combining an alkylating agent with a lanthanide-containing or nickel-containing compound at a suitable temperature, which may be about -20°C to about 80°C, in the absence of monomers or in the presence of small amounts of at least one conjugated diene monomer. The amount of monomer used in the first step may be the same as that described above for pre-forming the catalyst. In the second step, the mixture formed in the first step and a halogen-containing compound, a non-coordinating anion, or a non-coordinating anion precursor may be loaded into the monomer to be polymerized in a stepwise or simultaneous manner.

[0080] In one or more embodiments, a solvent is used as a support to dissolve or suspend a catalyst or initiator. This facilitates the supply of the catalyst to the polymerization system. In other embodiments, a monomer can be used as a support. In yet another embodiment, the catalyst can be used undiluted without the use of any solvent.

[0081] In one or more embodiments, preferred solvents include organic compounds that are neither polymerized nor incorporated into the propagating polymer chain during polymerization of monomers in the presence of a catalyst or initiator. In one or more embodiments, these organic species 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 with 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 mesitylene. 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 spirits. Non-limiting examples of alicyclic hydrocarbons include cyclopentane, cyclohexane, methylcyclopentane, and methylcyclohexane. A mixture of the above hydrocarbons can also be used. As is known in the art, for environmental reasons, it may be preferable to use aliphatic and alicyclic hydrocarbons. Low-boiling hydrocarbon solvents are typically separated from the polymer when polymerization is complete.

[0082] Other examples of organic solvents include high molecular weight, high boiling hydrocarbons, including hydrocarbon oils commonly used in oil-expanding polymers. Examples of these oils include paraffinic oils, aromatic oils, naphthenic oils, vegetable oils other than castor oil, and low PCA oils, such as MES, TDAE, SRAE, and heavy naphthenic oils. Because these hydrocarbons are non-volatile, they typically do not need to be separated and remain incorporated into the polymer.

[0083] Polymerization process The above-described lanthanide-based or nickel-based catalyst compositions have relatively high catalytic activity for polymerizing conjugated dienes over a wide range of catalyst concentrations and catalyst 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 one of the catalyst components. For example, since the catalyst components can interact to form active species, the optimal concentration for any one catalyst component may depend on the concentrations of the other catalyst components.

[0084] 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.

[0085] The production of reactive polymers according to the present invention can be achieved by polymerizing a conjugated diene monomer with a monomer copolymerizable with the conjugated diene monomer in the presence of a catalytically effective amount of catalyst. The introduction of the catalyst, the conjugated diene monomer, optionally the comonomer, and, if used, any solvent, forms a polymerization mixture in which the reactive polymer is formed. The amount of catalyst or initiator used may 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 rate, the desired molecular weight, and many other factors. Therefore, regarding the specific amount of catalyst or initiator, it is not clear to say anything other than that a catalytically effective amount of catalyst or initiator can be used. I cannot say that.

[0086] In one or more embodiments, the amount of coordination metal compound used (e.g., lanthanide-containing compound or nickel-containing compound) may vary from about 0.001 to about 2 mmol per 100 grams of monomer, in other embodiments from about 0.005 to about 1 mmol, and in yet another embodiment from about 0.01 to about 0.2 mmol.

[0087] In one or more embodiments, polymerization may be carried out in a polymerization system containing a substantial amount of solvent. In one embodiment, a solution polymerization system may be used in which both the monomer to be polymerized and the formed polymer are soluble in the solvent. In another embodiment, a precipitation polymerization system may be used by selecting a solvent in which the formed polymer is insoluble. In both cases, a certain amount of solvent is usually added to the polymerization system in addition to the amount of solvent that may be used when preparing the catalyst. The further solvent may be the same as or different from the solvent used when preparing the catalyst. Exemplary solvents have been described above. In one or more embodiments, the solvent content of the polymerization mixture may be more than 20% by weight, more than 50% by weight in other embodiments, and more than 80% by weight in yet another embodiment, based on the total weight of the polymerization mixture.

[0088] In other embodiments, the polymerization system used may generally be considered a bulk polymerization system that is substantially solvent-free or contains minimal amounts of solvent. Those skilled in the art will understand the advantages of the bulk polymerization process (i.e., the process in which monomers act as solvents), and therefore the polymerization system contains less solvent that would have a detrimental effect on the advantages sought by performing bulk polymerization. In one or more embodiments, the solvent content of the polymerization mixture may be less than about 20% by weight, less than about 10% by weight in other embodiments, and less than about 5% by weight in yet another embodiment, based on the total weight of the polymerization mixture. In yet another embodiment, the polymerization mixture contains no solvents other than those inherent to the raw materials used. In yet another embodiment, the polymerization mixture is substantially solvent-free. This means that an amount of solvent that would have a significant effect on the polymerization process if present is absent. A polymerization system that is substantially solvent-free can also be said to be substantially solvent-free. In certain embodiments, the polymerization mixture is solvent-free.

[0089] Polymerization may 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 rate is less than about 60%. In yet another embodiment, bulk polymerization may be carried out in an elongated reactor (where the viscous cement during polymerization is moved by a piston or substantially by a piston), particularly when the monomer conversion rate in the bulk polymerization process exceeds about 60% (in which case, typically, a highly viscous cement is obtained). For example, an extruder in which the cement is pushed out by a self-cleaning uni-screw or twin-screw agitator is suitable for this purpose. Examples of useful bulk polymerization processes are disclosed in U.S. Patent No. 7,351,776, which is incorporated herein by reference.

[0090] In one or more embodiments, all components used for polymerization may be mixed in a single container (e.g., a conventional stirred tank reactor), and all steps of the polymerization process may be carried out in this container. In other embodiments, two or more components may be pre-combined in one container and then transferred to another container where the polymerization of monomers (or at least a large portion thereof) can be carried out.

[0091] Polymerization can be carried out as a batch process, a continuous process, or a semi-continuous process. In a semi-continuous process, monomers are intermittently filled as needed to replace already polymerized monomers. In one or more embodiments, the conditions under which polymerization proceeds are controlled to set the temperature of the polymerization mixture from about -10°C to about 200°C, in other embodiments from about 0°C to about 150°C, and other embodiments. In the application, the temperature can be maintained in the range of approximately 20°C to approximately 100°C. In one or more embodiments, the heat of polymerization may be removed by external cooling with a thermally controlled reactor jacket, internal cooling by vaporization and condensation of monomers using a reflux condenser connected to the reactor, or a combination of the two methods. The polymerization conditions can also be controlled to carry out polymerization under pressures of approximately 0.1 atmospheres to approximately 50 atmospheres, approximately 0.5 atmospheres to approximately 20 atmospheres in other embodiments, and approximately 1 atmosphere to approximately 10 atmospheres in other embodiments. In one or more embodiments, the pressures under which polymerization can occur include pressures at which the majority of monomers are reliably in the liquid phase. In these or other embodiments, the polymerization mixture may be maintained under anaerobic conditions.

[0092] As described above, the catalyst system and polymerization process of the present invention yield beneficial polymerization activity. In one or more embodiments, polymerization activity can be expressed in terms of the monomer conversion rate of the polymerization process. In one or more embodiments, the catalyst system and polymerization process achieve monomer conversion rates of over 80%, in other embodiments over 85%, and in other embodiments over 90%.

[0093] Reactive polymers In one or more embodiments, the polymerization process of the present invention produces a reactive polymer. This reactive polymer is thought to be prepared by a coordination polymerization mechanism. Key mechanistic features of coordination polymerization are discussed in books (e.g., Kuran, W., Principles of Coordination Polymerization; John Wiley & Sons: New York, 2001) and reviews (e.g., Mulhaupt, R., Macromolecular Chemistry and Physics 2003, volume 204, pages 289-327). Coordination catalysts are thought to initiate monomer polymerization by a mechanism involving the coordination or complexation of the monomer to an active metal center before insertion of the monomer into the growing polymer chain. A beneficial feature of coordination catalysts is their ability to produce stereoregular polymers by stereochemically controlling the polymerization. As is known in the art, there are many methods for forming coordination catalysts. However, all methods ultimately produce an active intermediate that can coordinate with the monomer and insert the monomer into the covalent bond between the active metal center and the growing polymer chain. The coordination polymerization of conjugated dienes is thought to proceed via a π-allyl complex as an intermediate. The coordination catalyst can be a one-component, two-component, three-component, or multi-component system. In one or more embodiments, the coordination catalyst may 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., a Lewis acid or Lewis base). In one or more embodiments, the heavy metal compound may be referred to as a coordination metal compound.

[0094] In one or more embodiments, particularly when a lanthanide catalyst system is used, the resulting polymer chains have reactive chain ends before the polymerization mixture is quenched. Therefore, when referring to a reactive polymer, it means a polymer having reactive chain ends derived from the synthesis of the polymer using a coordination catalyst; the reactive polymer may be called a pseudo-living polymer. In one or more embodiments, the polymerization mixture containing the reactive polymer may also be called an active polymerization mixture. The percentage of polymer chains possessing reactive ends depends on various factors (e.g., the type of catalyst or initiator, the type of monomer, the purity of the components, the polymerization temperature, the monomer conversion rate, 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 yet another embodiment, at least about 15% of the polymer chains have reactive ends. In any case, the reactive polymer can be reacted with a functionalizing agent to form the bound polymer of the present invention.

[0095] sensualization In one or more embodiments, a functionalizing agent may be optionally added to the polymerization mixture to functionalize at least a portion of the polymer chains, particularly those having reactive chain ends. A mixture of two or more functionalizing agents may also be used.

[0096] In one or more embodiments, the functionalizing agent includes a compound or reagent that reacts with the reactive polymer produced by the present invention, resulting in the polymer being conferred with functional groups different from those on the propagating chain that has not reacted with the functionalizing agent. The functional groups may be reactive or interacting with other polymer chains (propagating and / or non-propagating), or with other components that may be combined 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 proceeds via an addition or substitution reaction.

[0097] Useful functionalizing agents may include compounds that simply provide functional groups at the ends of polymer chains. In one or more embodiments, the functionalizing agent includes compounds that will add or impart heteroatoms to the polymer chains. In certain embodiments, the functionalizing agent includes compounds that impart functional groups to polymer chains to form a functionalized polymer, the functionalized polymer reducing the 50°C hysteresis loss of carbon black-filled vulcanized products prepared from the functionalized polymer compared to similar carbon black-filled vulcanized products prepared from unfunctionalized polymers.

[0098] In other embodiments, additional binders may be used in combination with functionalizing agents. These compounds, which may be called co-binders, may bond two or more polymer chains together to form a single polymer. Some functionalizing agents may function to bond polymer chains in addition to providing polymer chains with useful functionality, and co-binders may be simply referred to herein as functionalizing agents.

[0099] In one or more embodiments, preferred functionalizing agents include compounds containing groups that can react with the reactive polymer produced according to the present invention. Exemplary functionalizing agents include ketones, quinones, aldehydes, amides, esters, isocyanates, isothiocyanates, epoxides, imines, aminoketones, aminothioketones, and acid anhydrides. Examples of these compounds are cited in U.S. Patents 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, and U.S. Patent Application Publication 2006 / 0004131(A1). This is disclosed in Patent Nos. 2006 / 0025539(A1), 2006 / 0030677(A1), and 2004 / 0147694(A1), as well as in Japanese Patent Applications Nos. 05-051406(A), 05-059103(A), 10-306113(A), and 11-035633(A). These documents are incorporated herein by reference. Other examples of functionalizing agents include azine compounds described in U.S. Patent Serial No. 11 / 640,711, hydrobenzamide compounds disclosed in U.S. Patent Serial No. 11 / 710,713, nitro compounds disclosed in U.S. Patent Serial No. 11 / 710,845, and protected oxime compounds disclosed in U.S. Patent Serial No. 60 / 875,484. All of these documents are incorporated herein by reference.

[0100] In certain embodiments, the functionalizing agents used may be epoxides, isocyanates, metal carboxylates, hydrocarbyl metal carboxylates, and hydrocarbyl metal ester carboxylates.

[0101] In one or more embodiments, the exemplary epoxy compounds are (3-glycidyloxypropyl)trimethoxysilane, (3-glycidyloxypropyl)triethoxysilane, (3 (3-glycidyloxypropyl)triphenoxysilane, (3-glycidyloxypropyl)methyldimethoxysilane, (3-glycidyloxypropyl)methyldiethoxysilane, (3-glycidyloxypropyl)methyldiphenoxysilane, [2-(3,4-epoxycyclohexyl)ethyl]trimethoxysilane, and [2-(3,4-epoxycyclohexyl)ethyl]triethoxysilane can be selected from these.

[0102] Examples of isocyanate compounds include (3-isocyanatetopropyl)trimethoxysilane, (3-isocyanatetopropyl)triethoxysilane, (3-isocyanatetopropyl)triphenoxysilane, (3-isocyanatetopropyl)methyldimethoxysilane, (3-isocyanatetopropyl)methyldiethoxysilane, (3-isocyanatetopropyl)methyldiphenoxysilane, and (isocyanatemethyl)methyldimethoxysilane.

[0103] Exemplary metal carboxylate compounds include tin tetraacetate, tinbis(2-ethylhexanoate), and tinbis(neodecanoate).

[0104] Exemplary hydrocarbyl metal carboxylate compounds include triphenyltin 2-ethylhexanoate, tri-n-butyltin 2-ethylhexanoate, tri-n-butyltin neodecanoate, triisobutyltin 2-ethylhexanoate, diphenyltinbis(2-ethylhexanoate), di-n-butyltinbis(2-ethylhexanoate), di-n-butyltinbis(neodecanoate), phenyltin tris(2-ethylhexanoate), and n-butyltin tris(2-ethylhexanoate).

[0105] Exemplary hydrocarbyl metal ester-carboxylate compounds include di-n-butylsutusubis(n-octyl maleate), di-n-octylsutusubis(n-octyl maleate), diphenylsutusubis(n-octyl maleate), di-n-butylsutusubis(2-ethylhexyl maleate), di-n-octylsutusubis(2-ethylhexyl maleate), and diphenylsutusubis(2-ethylhexyl maleate).

[0106] Exemplary metal alkoxide compounds include dimethoxytin, diethoxytin, tetraethoxytin, tetra-n-propoxytin, tetraisopropoxytin, tetra-n-butoxytin, tetraisobutoxytin, tetra-t-butoxytin, and tetraphenoxytin.

[0107] The amount of functionalizing agent that can be added to the polymerization mixture may depend on various factors (e.g., 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 may be described in terms of the lanthanide metal of the lanthanide-containing compound. For example, the molar ratio of the functionalizing agent to the lanthanide metal may be about 1:1 to about 200:1, in other embodiments about 5:1 to about 150:1, and in other embodiments about 10:1 to about 100:1.

[0108] Workup after polymerization In one or more embodiments, a quenching agent may be added to the polymerization mixture after polymerization and optionally after functionalization of the reactive polymer to protonate the reaction product between the reactive polymer and the functionalizing agent, inactivate any remaining reactive polymer chains, and / or deactivate the catalyst or catalytic component. Examples of quenching agents include, but are not limited to, protic compounds, including alcohols, carboxylic acids, inorganic acids, water, or mixtures thereof. Antioxidants, such as 2,6-di-tert-butyl-4-methylphenol, may be added together with, or before, the addition of the quenching agent. This may be done after the addition. The amount of antioxidant used may be in the range of 0.01% to 1% by weight of the polymer product. In addition, the polymer product can be oil-expanded by adding oil to the polymer, which may be in the form of polymer cement or polymer dissolved or suspended in the monomer. The amount of oil that can be added in the embodiment of the present invention is not limited, and therefore ordinary amounts may be added (e.g., 5 to 50 phr). Useful oils or spreaders that can be used include, but are not limited to, aromatic oils, paraffinic oils, naphthenic oils, vegetable oils (other than castor oil), low PCA oils (e.g., MES, TDAE, and SRAE, etc.), and heavy naphthenic oils.

[0109] After quenching the polymerization mixture, various components of the polymerization mixture may 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. After the monomers are removed from the polymerization mixture, they may be purified, stored, and / or recycled back into the polymerization process.

[0110] The polymer product may be recovered from the polymerization mixture using techniques known in the art. In one or more embodiments, desolvation and drying techniques may be used. The polymer may be recovered by vapor desolvation of the polymerization mixture, followed by drying the resulting polymer crumb in a hot air tunnel. Alternatively, the polymer may be recovered by passing it through an expander expeller. The polymer may also be recovered by drying the polymerization mixture directly on a drum dryer.

[0111] Polymer properties In one or more embodiments, the polymer prepared according to the present invention may contain unsaturated polymers. In these or other embodiments, the binding polymer is vulcanizable. In one or more embodiments, the binding polymer has a glass transition temperature (T) of less than 0°C, less than -40°C in other embodiments, and less than -60°C in other embodiments. g ) may have.

[0112] In one or more embodiments, the binding polymer of the present invention may be a cis-1,4-polydiene having a cis-1,4-bond content of more than 85%, more than about 90% in other embodiments, more than about 92% in other embodiments, and more than about 94% in other embodiments, the percentages being based on the number of diemer units, with cis-1,4-bonds versus the total number of diemer units being used. The cis-1,4-, 1,2-, and trans-1,4-bond content may be measured by infrared spectroscopy.

[0113] In one or more embodiments, the number average molecular weight (M) of these polymers produced according to the present invention n ) is determined by using gel permeation chromatography (GPC) calibrated with polystyrene standards, and is approximately 10 to approximately In other embodiments, the molecular weight distribution or polydispersity (M) of these polymers may be 1,000, about 50 to about 500, about 100 to about 400, and about 200 to about 300 kg / mol. w / M n The molecular weight distribution or polydispersity (M) of these polymers may be about 1.0 to about 7.0, in other embodiments about 1.5 to about 5.0, and in other embodiments about 2.0 to about 4.0. In these or other embodiments, the molecular weight distribution or polydispersity (M) of these polymers may be about 1.0 to about 7.0, in other embodiments about 1.5 to about 5.0, and in other embodiments about 2.0 to about 4.0. w / M n ) 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.

[0114] When a polymer is functionalized, the reactive polymer and the functionalizing agent (and optionally the functionalizing agent) react to form a functionalized or bound polymer, and it is thought that residues of the functionalizing agent are attached to at least one end of the polymer chain. The reactive end of the polymer chain reacts with the functionalizing agent, and in some embodiments, up to three chain ends react with the functionalizing agent to form a bound polymer. It is thought that such polymers are formed. Nevertheless, the exact chemical structure of the conjugated polymers produced in all embodiments is not so precisely known, in particular, because the structure relates to the functionalizing agent and the residues optionally conferred to the polymer chain ends by the functionalizing agent. In practice, it is presumed that the structure of the conjugated polymer may 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 the functionalizing agent) with the reactive polymer (e.g., the type and amount of the functionalizing agent). The conjugated polymer resulting from the reaction between the reactive polymer and the functionalizing agent may be protonated or further modified.

[0115] Use of polymers Rubber compositions can be prepared by using the polymer of the present invention alone or in combination with other elastomers (i.e., polymers that can be vulcanized to form a composition having rubber or elastomer properties). Other elastomers that may be used include natural and synthetic rubbers. Synthetic rubbers are typically obtained from 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.

[0116] Exemplary elastomers include natural rubber, synthetic polyisoprene, polybutadiene, polyisobutylene-co-isoprene, neoprene, poly(ethylene-co-propylene), poly(styrene-co-butadiene), poly(styrene-co-isoprene), poly(styrene-co-isoprene-co-butadiene), poly(isoprene-co-butadiene), poly(ethylene-co-propylene-co-diene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, and mixtures thereof. These elastomers can have innumerable macromolecular structures, for example, linear, branched, and star-shaped structures.

[0117] The rubber composition may contain fillers, for example, 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 common fillers used in the manufacture of tires. In certain embodiments, mixtures of different fillers may be advantageously used.

[0118] In one or more embodiments, examples of carbon black include furnace black, channel black, and lamp black. More specific examples of carbon black include super abrasion furnace black, intermediate super abrasion furnace black, high abrasion furnace black, high speed extrusion furnace black, fine furnace black, semi-reinforcing furnace black, medium processing channel black, hard processing channel black, conductive channel black, and acetylene black.

[0119] In certain embodiments, the carbon black is at least 20 m 2 / g, and in other embodiments, at least 35 m 2It may have a surface area (EMSA), and the surface area value can be determined using cetyltrimethylammonium bromide (CTAB) technology according to ASTM standard D-1765. Carbon black is pe It may be in a pelletized form or in an unpelletized, cotton-like form. The preferred form of carbon black may depend on the type of mixing equipment used to mix the rubber compound.

[0120] The amount of carbon black used in the rubber composition may be up to about 50 parts by weight per 100 parts by weight (phr) of rubber, and is typically about 5 to about 40 parts by weight.

[0121] Some commercially available silica products that can be used include Hi-Sil® 215, Hi-Sil® 233, and Hi-Sil® 190 (PPG Industries, Inc.; Pittsburgh, Pa.). Other suppliers of commercially available silica include Grace Davison (Baltimore, Md.), Degussa Corp. (Parsippany, NJ), and Rhodia Silica. Examples include Systems (Cranbury, NJ) and JMHuber Corp. (Edison, NJ).

[0122] In one or more embodiments, silica can be characterized by its surface area, which serves as a measure of its reinforcing properties. The Brunauer, Emmet, and Teller ("BET") method (described in J.Am.Chem.Soc., vol.60, p.309 et seq.) is a recognized method for determining surface area. The BET surface area of ​​silica is generally 450 m². 2 It is less than / g. The useful range for surface area is approximately 32 to 400 m². 2 / g, about 100~250m 2 / g, and approximately 150-220m 2 / g is one example.

[0123] The pH of silica is generally about 5 to about 7, or slightly higher than 7, or in other embodiments, about 5.5 to about 6.8.

[0124] In one or more embodiments, when silica is used as a filler (alone or in combination with other fillers), silica binders and / or silica shielding agents may be added to the rubber composition during mixing to enhance the interaction of silica with the elastomer. Useful silica binders and silica shielding agents are listed in U.S. Patents No. 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, and 5,684,171. Disclosed in Nos. 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.

[0125] The amount of silica used in the rubber composition may be about 1 to about 100 phr, or in other embodiments, about 5 to about 80 phr. The useful upper limit is limited by the high viscosity provided by the silica. When silica is used with carbon black, the amount of silica can be reduced to about 1 phr. Because the amount of silica is low, the amount of binder and shielding agent used can be reduced. Generally, the amount of binder and shielding agent is in the range of about 4% to about 20% by weight, based on the weight of silica used.

[0126] Numerous rubber curing agents (also called vulcanizing agents) containing sulfur or peroxide-based curing systems may be used. (See Kirk-Othmer, Encyclopedia of Chemical Technology, Vol.20, pgs.365-468, (3) rdEd.1982), especially Vulcanization Agents and Auxiliary Materials, pgs.390-402, and AYCoran, Vulcanization, Encyclopedia of Polymer Science and Engineering, (2 nd These are described in Ed. 1989, and are incorporated herein by reference. The vulcanizing agents may be used alone or in combination. They can be used together.

[0127] Other components typically used in rubber compounding may also be added to the rubber composition. These include accelerators, activators, oils, plasticizers, waxes, anticorrosion agents, processing aids, zinc oxide, tackifying resins, reinforcing resins, fatty acids, such as stearic acid, anti-corrosion agents, such as antioxidants and anti-ozone agents. In certain embodiments, oils used may include those conventionally used as spreadable oils, as described above.

[0128] All components of a rubber composition can be mixed using standard mixing equipment, such as a Banbury or Bravender mixer, extruder, kneader, and two-roll mill. In one or more embodiments, the components are mixed in two or more stages. In the first stage (often also called the masterbatch mixing stage), a so-called masterbatch (typically containing rubber components and fillers) is prepared. To prevent premature vulcanization (also known as scorching), the vulcanizing agent may be removed from the masterbatch. The masterbatch may be mixed at a starting temperature of about 25°C to about 125°C and an extrusion temperature of about 135°C to about 180°C. Once the masterbatch is prepared, in the final mixing stage, the vulcanizing agent may be introduced into the masterbatch and mixed. This final mixing stage is typically carried out at a relatively low temperature to reduce the possibility of premature vulcanization. Optionally, an additional mixing stage, often called a re-mill, can be used between the masterbatch mixing stage and the final mixing stage. If silica is included as a filler in the rubber composition, one or more re-mill stages are often used. Various components, including the binding polymer of the present invention, can be added during these milling processes.

[0129] Mixing procedures and conditions particularly applicable to silica-filled tire formulations are described in U.S. Patents No. 5,227,425, 5,719,207, and 5,717,022, and European Patent No. 890,606, all of which are incorporated herein by reference. In one embodiment, the preparation of the initial masterbatch is carried out by including the binding polymer of the present invention and silica substantially in the absence of silica binders and silica shielding agents.

[0130] Rubber compositions prepared from the polymer of the present invention are particularly useful in forming tire components, such as treads, sub-treads, sidewalls, body ply skims, and bead fillers. For example, the polymer of the present invention is 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 of the polymer of the present invention, based on the total weight of rubber in the formulation; in other embodiments, about 35% to about 90% by weight; and in other embodiments, about 50% to about 80% by weight.

[0131] When rubber compositions are used in the manufacture of tires, these compositions can be processed into tire components using conventional tire manufacturing techniques, such as standard rubber molding techniques, molding techniques, and curing techniques. Typically, vulcanization is carried out by heating the vulcanizable composition in a mold, for example, which may be heated to about 140°C to about 180°C. The cured or crosslinked rubber composition may be referred to as a vulcanized product, which generally contains a thermosetting three-dimensional polymer network structure. Other components (e.g., fillers and processing aids) may be uniformly dispersed throughout the crosslinked network structure. Pneumatic tires can be manufactured as described in U.S. Patents 5,866,171, 5,876,527, 5,931,211, and 5,971,046, which are incorporated herein by reference.

[0132] To demonstrate the implementation of the present invention, the following embodiments were prepared and tested. However, these embodiments should not be considered to limit the scope of the invention. The claims shall define the present invention. [Examples]

[0133] Examples 1-5 The following examples illustrate embodiments for lanthanide-based catalyst systems. Polymerization was carried out in glass vials purged with 750 mL of N2. Approximately 20% by weight of butadiene / hexane mixture and high-purity hexane were individually packed into the vials, sufficient to prepare 333 g of 14% by weight butadiene solution. Each vial was packed with an appropriate amount of 1.0 M alkylaluminum reagent solution from Table 1, followed by 1.64 mL of neodymium versatate solution (0.054 M in hexane). The vials were allowed to stand for 3 minutes, and then 0.13 mL of ethylaluminum dichloride solution (1.09 M in hexane) was added. The vials were placed in a stirring bath at 80°C. After stirring for 30 minutes, the vials were removed from the bath. Polymerization was stopped by packing the polymerization mixture with 4.0 mL of 2,6-di-tert-butyl-4-methylphenol solution in 10% by weight isopropanol. The polymer was coagulated in 8 liters 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 the values ​​are reported in Table 1.

[0134] [Table 1]

[0135] Mooney viscosity of polymer samples (ML) 1+4 The number average (M) of polymer samples was determined by using a Monsanto Mooney viscometer with a large rotor at 100°C, with a 1-minute pre-residue and a 4-minute run time. n ) and weight average (M w The molecular weight was determined by gel permeation chromatography (GPC) using a Tosoh Ecosec HLC-8320GPC system and a Tosoh TSKgel GMHxl-BS column with THF as the solvent. The system was calibrated using a series of polystyrene standards, with polystyrene as the reference. The cis-1,4-bond, trans-1,4-bond, and 1,2-bond content of the polymer samples was determined by infrared spectroscopy.

[0136] As can be seen from the data in Table 1, the use of triethylaluminum (TEAL) alone (Examples 2 and 3) is not as effective as that of triisobutylaluminum (TIBA) and diisobutylaluminum hydride (DIB). This results in a lower conversion rate than the control mixture (Example 1) in A). Similarly, DIBA alone (actual Example 5) yielded a lower conversion rate than the control mixture of TIBA and DIBA (Example 1). In contrast, the mixture of DIBA and TEAL (Example 4) yielded a higher conversion rate than either the TIBA / DIBA mixture or TEAL alone.

[0137] Examples 6-12 The following examples illustrate embodiments for nickel-based catalyst systems. Polymerization was carried out in glass bottles purged with 750 mL of N2. Approximately 20 wt% butadiene / hexane mixture and high-purity hexane were individually packed into the bottles, sufficient to prepare 300 mL of 15 wt% butadiene solution. Each bottle was packed with an appropriate amount of 1.0 M alkylaluminum reagent solution from Table 2, followed by 1.36 mL of nickel 2-ethylhexanoate solution (0.012 M in hexane). Then, appropriate amounts of 4.56 M BF3 solution and hexanol were added to obtain 1.68 equivalents of B (0.10-0.13 mL) per Al. The bottles were placed in a stirring bath at 80°C. After stirring for 40 minutes, the bottles were removed from the bath. Polymerization was stopped by packing the polymerization mixture with 4.0 mL of 2,6-di-tert-butyl-4-methylphenol solution in 10 wt% isopropanol. The polymer was coagulated in 8 liters 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 the values ​​are reported in Table 2.

[0138] [Table 2]

[0139] Mooney viscosity of polymer samples (ML) 1+4 ), number average (M n ) and weight average (M w The molecular weight and the cis-1,4-bond, trans-1,4-bond, and 1,2-bond content of the polymer samples were determined as provided above for Examples 1 to 5.

[0140] As can be seen from the data in Table 2, the use of a mixture of DIBA and TEAL results in a better overall balance of polymerization and polymer properties.

[0141] Various modifications and changes that do not depart from the scope and spirit of the present invention will be apparent to those skilled in the art. The present invention is not formally limited to the exemplary embodiments described herein. This disclosure includes the following embodiments. <1> A method for preparing a polymer, (i) Lanthanide-containing compounds, (ii) Triethylaluminum and (iii) Aluminum hydride and (iv) A method comprising polymerizing a conjugated diene monomer in the presence of a lanthanide-based catalyst system containing a halogen-containing compound. <2> The lanthanide-containing compound is selected from the group consisting of lanthanide carboxylate, lanthanide organic phosphate, lanthanide organic phosphonate, lanthanide organic phosphinate, lanthanide carbamate, lanthanide dithiocarbamate, lanthanide xanthate, lanthanide β-diketonate, lanthanide alkoxide or aryl oxide, lanthanide halide, lanthanide pseudo-halide, lanthanide oxyhalide, and organic lanthanide compounds. <1> Methods used. <3> The aforementioned aluminum hydride has the general formula AlR n H (3-n) Represented by the formula, where each R can be an independent monovalent organic group bonded to the aluminum atom via a carbon atom, and n can be an integer in the range of 1 to 3. <1> Methods used. <4> The aluminum hydride is dihydrocarbyl aluminum hydride. <1> Methods used. <5> The aluminum hydride is hydrocarbyl aluminum dihydride. <1> Methods used. <6> The aluminum hydride is 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, phenylisobutylaluminum hydride, phenyl-n-octylaluminum hydride Selected from the group consisting of aluminum hydride, p-tolylethylaluminum hydride, p-tolyl-n-propylaluminum hydride, p-tolylisopropylaluminum hydride, p-tolyl-n-butylaluminum hydride, p-tolylisobutylaluminum hydride, p-tolyl-n-octylaluminum hydride, benzylethylaluminum hydride, benzyl-n-propylaluminum hydride, benzylisopropylaluminum hydride, benzyl-n-butylaluminum hydride, benzylisobutylaluminum hydride, and benzyl-n-octylaluminum hydride, <1> Methods used. <7> The aluminum hydride is selected from the group consisting of ethylaluminum dihydride, n-propylaluminum dihydride, isopropylaluminum dihydride, n-butylaluminum dihydride, isobutylaluminum dihydride, and n-octylaluminum dihydride. <1> Methods used. <8> The halogen source is a compound selected from the group consisting of elemental halogens, mixed halogens, hydrogen halides, organic halides, inorganic halides, metal halides, and organometallic halides. <1> Methods used. <9> The molar ratio (alkylating agent / Ln) of the triethylaluminum hydride to the lanthanide-containing compound is approximately 2:1 to approximately 15:1. <1> Methods used. <10> The molar ratio (alkylating agent / Ln) of the hydrocarbyl aluminum hydride to the lanthanide-containing compound is approximately 1:1 to approximately 10:1. <1> Methods used. <11> The halogen / Ln molar ratio is approximately 0.5:1 to approximately 20:1. <1> Methods used. <12> 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. <1> Methods used. <13> In the polymerization step, approximately 0.001 to 2 mmol of lanthanide compound is used per 100 g of monomer. <1> Methods used. <14> The polymerization step further includes a step of obtaining a polydiene and functionalizing the polydiene. <1> Methods used. <15> The polymerization step further includes a quenching step, <1> Methods used. <16> The polymerization step yields a polydiene having a cis-1,4-bond content of more than 95%, <1> Methods used. <17> The polymerization step results in a monomer conversion rate of more than 85%. <1> Methods used. <18> The polymerization step results in a monomer conversion rate of more than 90%. <1> Methods used. <19> It is a polymer, (i) Lanthanide-containing compounds, (ii) Triethylaluminum and (iii) Aluminum hydride and (iv) A polymer prepared by polymerizing a conjugated diene monomer in the presence of a lanthanide-based catalyst system containing a halogen-containing compound. <20> The aforementioned <19> A tire component prepared by using the polymer described above. <21> The aforementioned <19> A vulcanizable composition comprising the polymer described in [reference], a filler, and a curing agent. <22> A method for preparing a polymer, (i) Nickel-containing compounds and (ii) Triethylaluminum and (iii) Aluminum hydride and (iv) A method comprising polymerizing a conjugated diene monomer in the presence of a nickel-based catalyst system comprising a halogen-containing compound selected from a fluorine-containing compound and a chlorine-containing compound. <23> The nickel-containing compound is selected from the group consisting of nickel carboxylate, nickel carboxylate borate, nickel organic phosphate, nickel organic phosphonate, nickel organic phosphinate, nickel carbamate, nickel dithiocarbamate, nickel xanthate, nickel β-diketonate, nickel alkoxide or aryl oxide, nickel halide, nickel pseudo-halide, nickel oxyhalide, or organonicickel compounds. <22> Methods used. <24> The aforementioned aluminum hydride has the general formula AlR n H (3-n) Represented by the formula, where each R can be an independent monovalent organic group bonded to the aluminum atom via a carbon atom, and n can be an integer in the range of 1 to 3. <22> or <23> Methods used. <25> The aluminum hydride is dihydrocarbyl aluminum hydride. <22> ~ <24> The method described in any one of the items. <26> The aluminum hydride is hydrocarbyl aluminum dihydride. <22> ~ <25> The method described in any one of the items. <27> The aluminum hydride is 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, phenylisobutylaluminum hydride, phenyl-n-octylaluminum hydride, p-tolylethylaluminum hydride, p-tolyl-n-propylaluminum hydride, p-tolylisopropylaluminum hydride Selected from the group consisting of lydo, p-tolyl-n-butylaluminum hydride, p-tolyl-isobutylaluminum hydride, p-tolyl-n-octylaluminum hydride, benzylethylaluminum hydride, benzyl-n-propylaluminum hydride, benzylisopropylaluminum hydride, benzyl-n-butylaluminum hydride, benzylisobutylaluminum hydride, and benzyl-n-octylaluminum hydride, <22> ~ <26> The method described in any one of the items. <28> The aluminum hydride is selected from the group consisting of ethylaluminum dihydride, n-propylaluminum dihydride, isopropylaluminum dihydride, n-butylaluminum dihydride, isobutylaluminum dihydride, and n-octylaluminum dihydride. <22> ~ <27> The method described in any one of the items. <29> The halogen-containing compound is a fluorine-containing compound, <22> ~ <28> The method described in any one of the items. <30> The molar ratio of the triethylaluminum to the nickel-containing compound is approximately 2:1 to approximately 100:1. <22> ~ <29> The method described in any one of the items. <31> The molar ratio of the hydrocarbyl aluminum hydride to the nickel-containing compound is approximately 1:1 to approximately 500:1. <22> ~ <30> The method described in any one of the items. <32> The F / Ni molar ratio is approximately 2:1 to approximately 500:1. <22> ~ <31> The method described in any one of the items. <33> 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. <22> ~ <32> The method described in any one of the items. <34> In the polymerization step, approximately 0.001 to approximately 2 mmol of nickel compound is used per 100 g of monomer. <22> ~ <33> The method described in any one of the items. <35> The polymerization step further includes a step of obtaining a polydiene and functionalizing the polydiene. <22> ~ <34> The method described in any one of the items. <36> The polymerization step further includes a quenching step, <22> ~ <35> The method described in any one of the items. <37> The fluorine-containing compound is selected from the group consisting of elemental fluorine, halogen fluorides, hydrogen fluoride, organic fluorides, inorganic fluorides, metallic fluorides, organometallic fluorides, and mixtures thereof. <22> ~ <36> The method described in any one of the items. <38> The polymerization step results in a monomer conversion rate of more than 85%. <22> ~ <37> The method described in any one of the items. <39> The polymerization step results in a monomer conversion rate of more than 90%. <22> ~ <38> The method described in any one of the items. <40> It is a polymer, (i) Nickel-containing compounds and (ii) Triethylaluminum and (iii) Aluminum hydride and (iv) A polymer prepared by polymerizing a conjugated diene monomer in the presence of a nickel-based catalyst system containing a halogen-containing compound. <41> The aforementioned <40> A tire component prepared by using the polymer described above. <42> The aforementioned <41> A vulcanizable composition comprising the polymer described in [reference], a filler, and a curing agent.

Claims

1. A method for preparing polydienes, (i) A step of preparing a mixture of a conjugated diene monomer and a solvent selected from aliphatic hydrocarbons and alicyclic hydrocarbons, (ii) A step of introducing a catalyst component comprising a nickel-containing compound, triethylaluminum, hydrocarbylaluminum hydride, and a fluorine-containing compound into the mixture, (a) The molar ratio of the triethylaluminum to the nickel-containing compound is 5:1 to 100:1, (b) The molar ratio of the hydrocarbyl aluminum hydride to the nickel-containing compound is 3:1 to 500:

1. (c) The molar ratio of fluorine atoms in the fluorine-containing compound to nickel atoms in the nickel-containing compound is 8:1 to 500:

1. (d) The amount of the nickel-containing compound is 0.01 mmol to 0.2 mmol per 100 g of the conjugated diene monomer. A step of introducing a catalyst component into the mixture, (iii) A step of polymerizing the conjugated diene monomer to form a polydiene, The polydiene has a cis-1,4-bond content exceeding 95%, More than 80% by weight of the conjugated diene monomer is converted to polydiene. The process of forming a polydiene, Methods that include...

2. The method according to claim 1, wherein the hydrocarbyl aluminum hydride is dihydrocarbyl aluminum hydride or hydrocarbyl aluminum dihydride.

3. The method according to claim 1, further comprising the step of functionalizing the polydiene.

4. The method according to claim 1, wherein more than 84% by weight of the conjugated diene monomer is converted to a polydiene.

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