Modified high cis polybutadiene polymers, related methods and rubber compositions

Abstract

Disclosed herein are processes for preparing modified high cis polybutadiene polymers, modified high cis polybutadiene polymers, and tire components made using the modified high cis polybutadiene polymers. The processes use a functionalized compound of formula (I) to prepare the modified high cis polybutadiene from an amount of 1,3-butadiene monomer using a specific catalyst system.

Description

[Technical Field]

[0001] This application relates to modified high cis polybutadiene polymers, related processes and tire rubber compositions. [Background technology]

[0002] High cis polybutadiene polymers have many applications in industry, including use in tire rubber compositions for use in tire components such as tire treads. Modification of such high cis polybutadiene polymers with certain functionalizing compounds can result in polymers with desirable initial Mooney viscosities due to increased filler-polymer interaction, but such polymers can be prone to Mooney viscosity growth upon aging, creating challenges with storage of the modified polymers. Summary of the Invention

[0003] Disclosed herein are modified high cis polybutadiene polymers, processes for preparing the modified high cis polybutadiene polymers, and tire rubber compositions containing the modified high cis polybutadiene polymers.

[0004] In a first embodiment, a process for preparing a modified high cis polybutadiene polymer is provided. According to a first embodiment, the process comprises: (A) providing a catalyst system comprising: (a) a lanthanide-based catalyst system comprising: (i) a lanthanide compound; (ii) an alkylating agent; and (iii) a halogen source, which may optionally be provided by (i), (ii), or both (i) and (ii); (b) a nickel-based catalyst system comprising: (i) a nickel compound, optionally in combination with an alcohol; (ii) an organoaluminum, organomagnesium, organozinc compound, or a combination thereof; and (iii) a fluorine-containing compound or a complex thereof; or (c) a cobalt-based catalyst system comprising: (i) a cobalt compound; (ii) an organoaluminum halide; and (iii) optionally water; (B) polymerizing 1,3-butadiene using the catalyst system of (A) to produce polymer chains having living ends; and (C) reacting the living-ended polymer chains from (B) with a functionalizing compound having formula (I): [ka] wherein X is a group that reacts with a living terminal polymer chain and is selected from the group consisting of cyano, epoxy, ketone, aldehyde, ester, and acid anhydride; R 1 is C1~C 20 and R' is selected from the group consisting of hydrocarbylenes, each of which optionally contains one unsaturated carbon-carbon bond, and each R' is selected from the group consisting of C1 to C 20 and R'' is selected from C1 to C 20 Alkyl or C6-C 20 (D) isolating the modified high cis polybutadiene of (C) and having an initial Mooney viscosity at 100°C ML of 20 to 100. 1+4 and a matured Mooney viscosity ML of 120 or less at 100°C. 1+4 and producing a final modified high cis polybutadiene having

[0005] In a second embodiment, a modified high cis polybutadiene polymer is provided. According to the second embodiment, the modified high cis polybutadiene polymer has a polymer chain attached to a residue of a functionalizing compound having the following formula (I): [ka] wherein X is a group reactive with a living terminal polymer chain and is selected from the group consisting of cyano, epoxy, ketone, aldehyde, ester, and acid anhydride; R 1 is C1~C 20 and R' is selected from the group consisting of hydrocarbylenes of the formula: 20 and R″ is selected from C1-C 20 Alkyl or C6-C 20 and each polymer chain is attached to the residue of a functionalizing compound through an X group, and the polymer has an initial Mooney viscosity ML of 20 to 100 at 100°C. 1+4 and a matured Mooney viscosity ML of 120 or less at 100°C. 1+4 It has.

[0006] In a third embodiment, there is provided a tire component comprising a rubber composition comprising the high cis-modified polybutadiene of the second embodiment or the high cis-modified polybutadiene produced by the process of the first embodiment. According to the third embodiment, the rubber composition of the tire component comprises: (a) an elastomer component comprising: (i) 10 to 100 phr of the high cis-modified polybutadiene polymer of the second embodiment or the high cis-modified polybutadiene polymer obtained by the process of the first embodiment, and (ii) 0 to 90 phr of at least one additional polymer selected from the group consisting of unmodified polybutadiene, styrene-butadiene, natural rubber, and polyisoprene; and (b) a reinforcing filler. (i) a reinforcing filler component comprising 10-200 phr of a reinforcing silica filler and (ii) 0-50 phr of a reinforcing carbon black filler, wherein the reinforcing carbon black filler is present in an amount of 20% or less by weight of the reinforcing silica filler; (c) a plasticizing component comprising (i) 0-50 phr, preferably 0-30 phr of fluorine, and (ii) 0-60 phr of at least one hydrocarbon resin having a Tg of at least 30°C; and (d) a curing package. DETAILED DESCRIPTION OF THE INVENTION

[0007] Disclosed herein are modified high cis polybutadiene polymers, processes for preparing the modified high cis polybutadiene polymers, and tire rubber compositions containing the modified high cis polybutadiene polymers.

[0008] In a first embodiment, a process for preparing a modified high cis polybutadiene polymer is provided. According to a first embodiment, the process comprises: (A) providing a catalyst system comprising: (a) a lanthanide-based catalyst system comprising: (i) a lanthanide compound; (ii) an alkylating agent; and (iii) a halogen source, which may optionally be provided by (i), (ii), or both (i) and (ii); (b) a nickel-based catalyst system comprising: (i) a nickel compound, optionally in combination with an alcohol; (ii) an organoaluminum, organomagnesium, organozinc compound, or a combination thereof; and (iii) a fluorine-containing compound or a complex thereof; or (c) a cobalt-based catalyst system comprising: (ii) an organoaluminum halide; and (iii) optionally water; (B) polymerizing 1,3-butadiene using the catalyst system of (A) to produce polymer chains having living ends; and (C) reacting the living-ended polymer chains from (B) with a functionalizing compound having formula (I): [ka] wherein X is a group reactive with a living terminal polymer chain and is selected from the group consisting of cyano, epoxy, ketone, aldehyde, ester, and acid anhydride; R 1 is C1~C 20 , preferably C1 to C 10 and more preferably C1 to C3 hydrocarbylene, each of the foregoing containing one unsaturated carbon-carbon bond, and each R' is selected from C1 to C 20 and preferably C1 to C 10 alkoxy, more preferably C1 to C6 alkoxy, most preferably C1 or C2 alkoxy, and R″ is C1 to C 20 Alkyl or C6-C 20 aryl, preferably C1-C 10 Alkyl or C6-C 14and (D) isolating the modified high cis polybutadiene of (C), wherein the isolation is carried out by steam distillation and the initial Mooney viscosity ML at 100°C is 20 to 100, preferably 30 to 80. 1+4 and a matured Mooney viscosity ML at 100°C of 120 or less, preferably 105 or less. 1+4 and producing a final modified high cis polybutadiene having

[0009] In a second embodiment, a modified high cis polybutadiene polymer is provided. According to the second embodiment, the modified high cis polybutadiene polymer has a polymer chain attached to a residue of a functionalizing compound having the following formula (I): [ka] wherein X is a group that reacts with a living terminal polymer chain and is selected from the group consisting of cyano, epoxy, ketone, aldehyde, ester, and acid anhydride; R 1 is C1~C 20 , preferably C1 to C 10 and R' is selected from the group consisting of hydrocarbylenes, more preferably C1-C3, each of the above optionally containing one unsaturated carbon-carbon bond, and R' is selected from the group consisting of C1-C 20 Alkoxy, preferably C1-C 10 alkoxy, more preferably C1-C6 alkoxy, most preferably C1 or C2 alkoxy, and R'' is selected from C1-C 20 Alkyl or C6-C 20 aryl, preferably C1-C 10 Alkyl or C6-C 14 and each polymer chain is linked to the residue of a functionalizing compound via an X group, and the polymer has an initial Mooney viscosity ML of 20 to 100, preferably 30 to 80 at 100°C. 1+4and a matured Mooney viscosity ML at 100°C of 120 or less, preferably 105 or less. 1+4 is.

[0010] In a third embodiment, there is provided a tire component comprising a rubber composition comprising the high cis-modified polybutadiene of the second embodiment or the high cis-modified polybutadiene produced by the process of the first embodiment. According to the third embodiment, the rubber composition of the tire component comprises: (a) an elastomer component comprising: (i) 10 to 100 phr, preferably 20 to 80 phr, of the high cis-modified polybutadiene polymer of the second embodiment or the high cis-modified polybutadiene polymer obtained by the process of the first embodiment, and (ii) 0 to 90 phr of at least one additional polymer selected from the group consisting of unmodified polybutadiene, styrene-butadiene, natural rubber, and polyisoprene; and (b) a reinforcing filler component comprising: (i) 10 to 200 phr, preferably 30 to 200 phr, more preferably 50 to 150 phr of a reinforcing silica filler, and (ii) 0 to 50 phr of a reinforcing carbon black filler, The carbon black filler comprises: (a) a reinforcing filler component present in an amount of no more than 20% by weight of the reinforcing silica filler, preferably no more than 10% by weight of the reinforcing silica filler; (b) a plasticizing component comprising: (i) 0-50 phr, preferably 0-30 phr, more preferably 0-15 phr of at least one plasticizing oil; and (ii) 0-60 phr, preferably 5-60 phr, more preferably 10-50 phr of at least one hydrocarbon resin having a Tg of at least 30°C; and (c) a cure package (preferably comprising at least one vulcanizing agent, at least one vulcanization accelerator, and optionally vulcanization activators, vulcanization inhibitors, and / or scorch inhibitors, more preferably at least one of each of the foregoing). definition

[0011] The terminology used herein is for the purpose of describing the embodiments only and should not be construed as limiting the invention as a whole.

[0012] As used herein, the term "living end" (e.g., the living end of a polymer chain) is used to refer to a polymer species having a living end that is not yet terminated, and which is capable of reacting with a functionalizing compound and thus can be said to be reactive.

[0013] As used herein, the abbreviation Mn is used for number average molecular weight.

[0014] As used herein, the abbreviation Mw is used for weight average molecular weight.

[0015] Unless otherwise indicated herein, the term "Mooney viscosity" refers to Mooney viscosity, ML 1+4 As will be appreciated by those skilled in the art, the Mooney viscosity of a polymer or rubber composition is measured prior to vulcanization or curing.

[0016] As used herein, the term "natural rubber" means rubber of natural origin, such as that which can be harvested from rubber trees of the Hevea genus and from sources outside the Hevea genus, such as, for example, guayule shrubs and dandelions (e.g., TKS). In other words, the term "natural rubber" should be interpreted to exclude synthetic polyisoprene.

[0017] As used herein, the term "phr" means parts per hundred of rubber. 100 parts of rubber may also be referred to herein as 100 parts of the elastomer component.

[0018] As used herein, the term "polyisoprene" refers to synthetic polyisoprene. In other words, this term is used to refer to a polymer made from isoprene monomers and should not be interpreted as including naturally occurring rubber (e.g., Hevea rubber, guayule rubber, or dandelion rubber). However, the term "polyisoprene" should be interpreted as including polyisoprene made from natural sources of isoprene monomers.

[0019] As used herein, the term "tread" refers to both that portion of the tire that comes into contact with the road surface under normal inflation and load, and any subtreads. Method for preparing modified high cis polybutadiene polymers

[0020] Generally, the first embodiment process described herein can be considered a solution polymerization process. In this type of polymerization process, the polymerization reaction occurs in an organic solvent-based solution, which initially contains a certain amount of conjugated diene monomer and one of the specific catalyst systems. Generally, according to the first embodiment process, the organic solvent-based solution contains 20 to 90% by weight (wt%) of organic solvent, based on the total weight of the monomer, organic solvent, and polybutadiene in the solution. Preferably, the organic solvent is the major component of the solution, i.e., 50 to 90 wt% organic solvent, more preferably 70 to 90 wt% organic solvent, based on the total weight of the monomer, organic solvent, and polybutadiene. The solution polymerization process disclosed herein can be contrasted with gas-type or bulk-type polymerization, where the polymerization is carried out in the absence of any organic solvent, or where less than 20 wt% organic solvent is present, based on the total weight of the monomer, organic solvent, and polybutadiene.

[0021] Suitable organic solvents for use in the solution polymerization process according to the first embodiment described herein are solvents that are inert to the polymerization reaction so that the solvent is not a reactant in the polymerization reaction. Suitable organic solvents include aromatic hydrocarbons, aliphatic hydrocarbons, and cycloaliphatic hydrocarbons. Examples of suitable aromatic hydrocarbon solvents include, but are not limited to, benzene, toluene, ethylbenzene, diethylbenzene, naphthalene, mesitylene, xylene, and the like. Examples of suitable aliphatic hydrocarbon solvents include, but are not limited to, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, isopentane, hexane, isohexane, isopentane, isooctane, 2,2-dimethylbutane, petroleum ether, kerosene, mineral spirits, and the like. Non-limiting examples of suitable cycloaliphatic hydrocarbon solvents include cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, and the like. Mixtures of the aforementioned aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, and cycloaliphatic hydrocarbon solvents can also be used. In certain embodiments of the first embodiment, preferred organic solvents include aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, or mixtures thereof. Additional useful organic solvents suitable for use in the process of the first embodiment will be known to those skilled in the art.

[0022] The solution polymerization process according to the first embodiment disclosed herein is preferably carried out under anaerobic conditions under an inert gas blanket such as nitrogen, argon, or helium. The polymerization temperature may vary widely, ranging from -50°C to 150°C, with a preferred temperature range being 50°C to 120°C. The polymerization pressure may also vary widely, ranging from 1 atmosphere (atm) to 30 atm, preferably from 1 atm to 10 atm (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 atm).

[0023] The solution polymerization process according to the first embodiment disclosed herein can be carried out as a continuous, semi-continuous, or batch process. In a semi-continuous process, monomer is intermittently charged to replace already polymerized monomer. Polymerization of 1,3-butadiene monomer into high-cis polybutadiene according to the process described herein occurs when the monomer and lanthanide-based catalyst system are all present in an organic solvent-based solution. The order in which the monomer and catalyst are added to the organic solvent does not matter.

[0024] Generally, the polymerization process of the first embodiment disclosed herein can be terminated by adding any suitable terminator. Non-limiting examples of suitable terminators include protic compounds such as alcohols, carboxylic acids, inorganic acids, water, and mixtures thereof. Other suitable terminators are known to those skilled in the art. Furthermore, once the polymerization is terminated, the resulting high cis polydiene can be recovered (or isolated) from the solution using conventional methods, such as steam desolventization or steam distillation, coagulation with alcohol, filtration, purification, drying, and the like, known to those skilled in the art. In a preferred embodiment of the first embodiment, the high cis polybutadiene polymer is isolated by using steam distillation. catalyst system

[0025] As described above, according to the process of the first embodiment, the catalyst system is selected from one of (a) a lanthanide-based catalyst system, (b) a nickel-based catalyst system, or (c) a cobalt-based catalyst system. Preferably, a lanthanide-based catalyst system is used. The use of one of the specific catalyst systems in the process of the first embodiment provides advantages in modifying the living ends of polymer chains with functionalizing compounds, as further explained below. According to the process of the first embodiment, the catalyst system used avoids the use of anionic initiators (e.g., organolithium compounds such as n-butyllithium). Lanthanide-based catalysts

[0026] As described above, the process of the first embodiment may utilize a lanthanide-based catalyst system comprising (i) a lanthanide compound, (ii) an alkylating agent, and (iii) a halogen source, which may optionally be provided by (i), (ii), or both (i) and (ii). The lanthanide-based catalyst system is used to polymerize a quantity of conjugated diene monomer (described in more detail below) to produce polymer chains with living ends. Preferably, according to the process of the first embodiment, the lanthanide-based catalyst system is preformed before being added to any solution of conjugated diene monomer.

[0027] As previously mentioned, the lanthanide-based catalyst system used in the process of the first embodiment includes a lanthanide compound. Lanthanide compounds useful in the process of the first embodiment are compounds containing at least one lanthanide element atom. As used herein, "lanthanide element" refers to elements found in the lanthanide series of the periodic table (i.e., element numbers 57-71), as well as didymium, which is a mixture of rare earth elements obtained from monzarite sand. In particular, lanthanide elements disclosed herein include lanthanum, neodymium, cerium, praseodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, and didymium. Preferably, the lanthanide compound contains at least one atom of neodymium, gadolinium, samarium, or a combination thereof. Most preferably, the lanthanide compound contains at least one neodymium atom.

[0028] The lanthanide atom in the lanthanide compound may be in various oxidation states, including, but not limited to, 0, +2, +3, and +4. According to certain preferred embodiments of the process of the first embodiment, a trivalent lanthanide compound is used in which the lanthanide atom is in the +3 oxidation state. In general, lanthanide compounds suitable for use in the process of the first embodiment include, but are not limited to, lanthanide carboxylates, lanthanide organophosphates, lanthanide organophosphonates, lanthanide organophosphinates, lanthanide carbamates, lanthanide dithiocarbamates, lanthanide xanthates, lanthanide β-diketonates, lanthanide alkoxides or aryloxides, lanthanide halides, lanthanide pseudohalides, lanthanide oxyhalides, and organolanthanide compounds. Preferably, the lanthanide compound is a lanthanide carboxylate, more preferably a neodymium carboxylate, and most preferably neodymium versatate.

[0029] According to certain embodiments of the process of the first embodiment, the lanthanide compound may be soluble in a hydrocarbon solvent, such as an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, or a cycloaliphatic hydrocarbon solvent disclosed herein. However, hydrocarbon-insoluble lanthanide compounds may also be useful in the process of the first embodiment because they can be suspended in the polymerization medium to form the catalytically active species.

[0030] For ease of explanation, the further description of lanthanide compounds useful in the process of the first embodiment will focus on neodymium compounds, although one of ordinary skill in the art would be able to select similar compounds based on other lanthanide metals disclosed herein.

[0031] Examples of neodymium carboxylates suitable for use as the lanthanide compound in the process of the first embodiment 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 (i.e., neodymium versatate or NdV3), neodymium naphthenate, neodymium stearate, neodymium oleate, neodymium benzoate, and neodymium picolinate.

[0032] Examples of neodymium organophosphates suitable for use as the lanthanide compound in the process of the first embodiment 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 dioleyl 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.

[0033] Examples of neodymium organophosphonates suitable for use as the lanthanide compound in the process of the first embodiment include 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 butyl butyl phosphonate, neodymium pentyl pentyl phosphonate, neodymium hexyl hexyl phosphonate, neodymium heptyl heptyl phosphonate, neodymium octyloctyl phosphonate, neodymium (1-methylheptyl) (1- neodymium (2-ethylhexyl)phosphonate, neodymium (2-methylheptyl)phosphonate, neodymium (2-ethylhexyl)phosphonate, neodymium decyldecylphosphonate, neodymium dodecyldodecylphosphonate, neodymium octadecyloctadecylphosphonate, neodymium oleyloleylphosphonate, 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.

[0034] Examples of neodymium organophosphinates suitable for use as the lanthanide compound in the process of the first embodiment include neodymium butylphosphinate, neodymium pentylphosphinate, neodymium hexylphosphinate, neodymium heptylphosphinate, neodymium octylphosphinate, neodymium (1-methylheptyl)phosphinate, neodymium (2-ethylhexyl)phosphinate, neodymium decylphosphinate, neodymium dodecylphosphinate, neodymium octadecylphosphinate, neodymium oleylphosphinate, neodymium phenylphosphinate, neodymium (p-nonylphenyl)phosphinate, neodymium dibutylphosphinate, neodymium dipentylphosphinate, neodymium di neodymium hexyl phosphinate, neodymium diheptyl phosphinate, neodymium dioctyl phosphinate, neodymium bis(1-methylheptyl)phosphinate, neodymium bis(2-ethylhexyl)phosphinate, neodymium didecyl 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.

[0035] Examples of neodymium carbamates suitable for use as the lanthanide compound in the process of the first embodiment include, but are not limited to, neodymium dimethylcarbamate, neodymium diethylcarbamate, neodymium diisopropylcarbamate, neodymium dibutylcarbamate, and neodymium dibenzylcarbamate.

[0036] Examples of neodymium dithiocarbamates suitable for use as the lanthanide compound in the process of the first embodiment include, but are not limited to, neodymium dimethyldithiocarbamate, neodymium diethyldithiocarbamate, neodymium diisopropyldithiocarbamate, neodymium dibutyldithiocarbamate, and neodymium dibenzyldithiocarbamate.

[0037] Examples of neodymium xanthates suitable for use as the lanthanide compound in the process of the first embodiment include, but are not limited to, neodymium methyl xanthate, neodymium ethyl xanthate, neodymium isopropyl xanthate, neodymium butyl xanthate, and neodymium benzyl xanthate.

[0038] Examples of neodymium β-diketonates suitable for use as the lanthanide compound in the process of the first embodiment include, but are not limited to, neodymium acetylacetonate, neodymium trifluoroacetylacetonate, neodymium hexafluoroacetylacetonate, neodymium benzoylacetonate, and neodymium 2,2,6,6-tetramethyl-3,5-heptanedionate.

[0039] Examples of neodymium alkoxides or aryloxides suitable for use as the lanthanide compound in the process of the first embodiment include, but are not limited to, neodymium methoxide, neodymium ethoxide, neodymium isopropoxide, neodymium 2-ethylhexoxide, neodymium phenoxide, neodymium nonylphenoxide, and neodymium naphthoxide.

[0040] Examples of neodymium halides suitable for use as the lanthanide compound in the process of the first embodiment 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. A Lewis base (e.g., tetrahydrofuran ("THF")) may be used to aid in the solubilization of this class of neodymium compounds in an inert organic solvent. When a lanthanide halide, lanthanide oxyhalide, or other lanthanide compound containing a halogen atom is used, the lanthanide compound may optionally provide all or part of the halogen source in the lanthanide-based catalyst system.

[0041] As used herein, the term "organolanthanide compound" refers to any lanthanide compound containing at least one lanthanide-carbon bond. These compounds are primarily, but not exclusively, compounds containing cyclopentadienyl ("Cp"), substituted cyclopentadienyl, allyl, and substituted allyl ligands. Organolanthanide compounds suitable for use as the lanthanide compound in the process of the first embodiment include, but are not limited to, CpLn, CpLnR, CpLnCl, CpLnCl, CpLn(cyclooctatetraene), (C5Me5)2LnR, LnR3, Ln(allyl)3, and Ln(allyl)2Cl, where Ln represents a lanthanide atom and R represents a hydrocarbyl or substituted hydrocarbyl group. In one or more embodiments, the hydrocarbyl or substituted hydrocarbyl groups useful in the process of the first embodiment may contain heteroatoms such as nitrogen, oxygen, boron, silicon, sulfur, and phosphorus atoms.

[0042] As previously mentioned, the lanthanide-based catalyst system used in the process of the first embodiment includes an alkylating agent. According to one or more embodiments of the process of the first embodiment, the alkylating agent (sometimes referred to as a hydrocarbylating agent) includes an organometallic compound capable of transferring one or more hydrocarbyl groups to another metal. Generally, these agents include organometallic compounds of electropositive metals, such as Group 1, Group 2, and Group 3 metals (Groups IA, IIA, and IIIA metals). Alkylating agents useful in the process of the first embodiment include, but are not limited to, organoaluminum compounds and organomagnesium compounds. As used herein, the term "organoaluminum compound" refers to any aluminum-containing compound having at least one aluminum-carbon bond. In one or more embodiments, organoaluminum compounds that are soluble in hydrocarbon solvents can be used. As used herein, the term "organomagnesium compound" refers to any magnesium-containing compound having at least one magnesium-carbon bond. In one or more embodiments, organomagnesium compounds that are soluble in hydrocarbon solvents can be used. As described in more detail below, certain suitable alkylating agents can be in the form of halide compounds. Here, the alkylating agent contains a halogen atom, and the alkylating agent can optionally also provide all or part of the halogen source in the lanthanide-based catalyst system.

[0043] In one or more embodiments of the process of the first embodiment, the organoaluminum compound utilized may have the general formula AlR a n X 3-n In the formula, each R a are independently a monovalent organic group bonded to the aluminum atom through a carbon atom, each X is independently a hydrogen atom, a halogen atom, a carboxylate group, an alkoxide group, or an aryloxide group, and n is an integer ranging from 1 to 3. In one or more embodiments, each R aare independently hydrocarbyl or substituted hydrocarbyl groups, including alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, aralkyl, alkaryl, aryl, and alkynyl groups, each containing 1 carbon atom, or the appropriate minimum number of atoms, up to 20 carbon atoms (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms). These hydrocarbyl or substituted hydrocarbyl groups may optionally contain heteroatoms, including, but not limited to, nitrogen, oxygen, boron, silicon, sulfur, and phosphorus atoms.

[0044] General formula AlR a n X 3-n Examples of the types of organoaluminum compounds represented by the formula (I) for use as alkylating agents in the process of the first embodiment include, but are not limited to, trihydrocarbylaluminum, dihydrocarbylaluminum hydrides, hydrocarbylaluminum dihydrides, dihydrocarbylaluminum carboxylates, hydrocarbylaluminum bis(carboxylates), dihydrocarbylaluminum alkoxides, hydrocarbylaluminum dialkoxides, dihydrocarbylaluminum halides, hydrocarbylaluminum dihalides, dihydrocarbylaluminum aryloxides, and hydrocarbylaluminum diaryloxide compounds.

[0045] Examples of trihydrocarbylaluminum compounds suitable for use as alkylating agents in the process of the first embodiment include, but are not limited to, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, tri-t-butylaluminum, tri-n-pentylaluminum, trineopentylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tris(2-ethylhexyl)aluminum, tricyclohexylaluminum, tris(1-methylcyclopentyl)aluminum, triphenylaluminum, tri-p-tolylaluminum, tris(2,6-dimethylphenyl)aluminum, tribenzylaluminum, diethylphenylaluminum, diethyl-p-tolylaluminum, diethylbenzylaluminum, ethyldiphenylaluminum, ethyldi-p-tolylaluminum, and ethyldibenzylaluminum.

[0046] Examples of dihydrocarbylaluminum hydride compounds suitable for use as alkylating agents in the process of the first embodiment 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, and phenylisobutylaluminum hydride. Aluminum hydride, phenyl-n-octylaluminum 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.

[0047] Examples of hydrocarbylaluminum dihydrides suitable for use as alkylating agents in the process include, but are not limited to, ethylaluminum dihydride, n-propylaluminum dihydride, isopropylaluminum dihydride, n-butylaluminum dihydride, isobutylaluminum dihydride, and n-octylaluminum dihydride.

[0048] Examples of dihydrocarbylaluminum halide compounds suitable for use as alkylating agents in the process of the first embodiment include diethylaluminum chloride, di-n-propylaluminum chloride, diisopropylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, di-n-octylaluminum chloride, diphenylaluminum chloride, di-p-tolylaluminum chloride, dibenzylaluminum chloride, phenylethylaluminum chloride, phenyl-n-propylaluminum chloride, phenylisopropylaluminum chloride, phenyl-n-butylaluminum chloride, phenylisobutylaluminum chloride, and phenylisobutylaluminum chloride. Aluminum chloride, phenyl-n-octylaluminum chloride, p-tolylethylaluminum chloride, p-tolyl-n-propylaluminum chloride, p-tolylisopropylaluminum chloride, p-tolyl-n-butylaluminum chloride, p-tolylisobutylaluminum chloride, p-tolyl-n-octylaluminum chloride, benzylethylaluminum chloride, benzyl-n-propylaluminum chloride, benzylisopropylaluminum chloride, benzyl-n-butylaluminum chloride, benzylisobutylaluminum chloride, and benzyl-n-octylaluminum chloride.

[0049] Examples of hydrocarbylaluminum dihalide compounds suitable for use as alkylating agents in the process of the first embodiment include, but are not limited to, ethylaluminum dichloride, n-propylaluminum dichloride, isopropylaluminum dichloride, n-butylaluminum dichloride, isobutylaluminum dichloride, and n-octylaluminum dichloride.

[0050] General formula AlR a n X 3-nExamples of other organoaluminum compounds suitable for use as alkylating agents in the process of the first embodiment, represented by the formula: methoxide, diethylaluminum methoxide, diisobutylaluminum methoxide, dimethylaluminum ethoxide, diethylaluminum ethoxide, diisobutylaluminum ethoxide, dimethylaluminum phenoxide, diethylaluminum phenoxide, diisobutylaluminum phenoxide, methylaluminum dimethoxide, ethylaluminum dimethoxide, isobutylaluminum dimethoxide, methylaluminum diethoxide, ethylaluminum diethoxide, isobutylaluminum diethoxide, methylaluminum diphenoxide, ethylaluminum diphenoxide, and isobutylaluminum diphenoxide.

[0051] Another class of organoaluminum compounds suitable for use as alkylating agents in the process of the first embodiment are the aluminoxanes. Suitable aluminoxanes include oligomeric linear aluminoxanes, which can be represented by the general formula: [ka] and oligomeric cyclic aluminoxanes that can be represented by the following general formula: [ka] In the formula, x is an integer ranging from 1 to 100 (e.g., 1, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100), or from 10 to 50 (e.g., 10, 15, 20, 25, 30, 35, 40, 45, or 50), y is an integer ranging from 2 to 100 (e.g., 2, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100), or from 3 to 20 (e.g., 3, 5, 10, 15, or 20), and each R is independently a monovalent organic group bonded to an aluminum atom via a carbon atom. In one embodiment of the process of the first embodiment, each R is independently a hydrocarbyl group or a substituted hydrocarbyl group, including alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, aralkyl, alkaryl, aryl, and alkynyl groups, each group preferably containing 1 carbon atom or the appropriate minimum number of atoms, forming a maximum of 20 carbon atoms (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms). These hydrocarbyl or substituted hydrocarbyl groups may also contain heteroatoms, including, but not limited to, nitrogen, oxygen, boron, silicon, sulfur, and phosphorus atoms. As used herein, the number of moles of aluminoxane refers to the number of moles of aluminum atoms, not the number of moles of oligomeric aluminoxane molecules. This practice is widely used in the art of catalyst systems using aluminoxanes.

[0052] Aluminoxanes can be prepared by reacting a trihydrocarbylaluminum compound with water by known methods such as (1) dissolving the trihydrocarbylaluminum compound in an organic solvent and then contacting it with water, (2) reacting the trihydrocarbylaluminum compound with crystalline water contained in, for example, a metal salt or water adsorbed on an inorganic or organic compound, or (3) reacting the trihydrocarbylaluminum compound with water in the presence of the monomer or monomer solution to be polymerized.

[0053] Examples of aluminoxane compounds suitable for use as alkylating agents in the process of the first embodiment include, but are not limited to, methylaluminoxane ("MAO"), modified methylaluminoxane ("MMAO"), ethylaluminoxane, n-propylaluminoxane, isopropylaluminoxane, butylaluminoxane, isobutylaluminoxane, n-pentylaluminoxane, neopentylaluminoxane, n-hexylaluminoxane, n-octylaluminoxane, 2-ethylhexylaluminoxane, cyclohexylaluminoxane, 1-methylcyclopentylaluminoxane, phenylaluminoxane, and 2,6-dimethylphenylaluminoxane. In certain preferred embodiments of the process of the first embodiment, the alkylating agent comprises MAO. The modified methylaluminoxane can be prepared by converting 20 to 80 percent of the methyl groups of the methylaluminoxane to C using techniques known to those skilled in the art. 2~ C 12 Hydrocarbyl groups (e.g., C2, C3, C 4、 C5, C6, C7, C8, C9, C 10 , C 11 or C 12 ) preferably with an isobutyl group.

[0054] According to certain embodiments of the process of the first embodiment, the aluminoxane can be used alone or in combination with other organoaluminum compounds. In one embodiment of the first embodiment, methylaluminoxane and at least one organoaluminum compound other than an aluminoxane, such as AlR a n X 3-n

[0023] Organoaluminum compounds represented by the formula (I) are used in combination as alkylating agents. According to this and other embodiments, the alkylating agent comprises a dihydrocarbylaluminum hydride, a dihydrocarbylaluminum halide, an aluminoxane, or a combination thereof. For example, according to one embodiment, the alkylating agent comprises diisobutylaluminum hydride, diethylaluminum chloride, methylaluminoxane, or a combination thereof. U.S. Patent No. 8,017,695 provides other examples of aluminoxanes and organoaluminum compounds that can be used in combination, and this document is incorporated herein by reference in its entirety.

[0055] As noted above, suitable alkylating agents for use in the process of the first embodiment include organomagnesium compounds. According to one or more embodiments of the process of the first embodiment, suitable organomagnesium compounds include those having the general formula MgR b 2, wherein each R b are independently monovalent organic groups attached to the magnesium atom through a carbon atom. b are independently hydrocarbyl or substituted hydrocarbyl groups, including alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl, aryl, aryl, substituted aryl, aralkyl, alkaryl, and alkynyl groups, each group preferably containing 1 carbon atom or the appropriate minimum number of atoms, up to 20 carbon atoms (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms). These hydrocarbyl or substituted hydrocarbyl groups may also optionally contain heteroatoms, including, but not limited to, nitrogen, oxygen, silicon, sulfur, and phosphorus atoms.

[0056] General formula MgR bExamples of organomagnesium compounds suitable for use as alkylating agents in the process of the first embodiment, represented by 2, include, but are not limited to, diethylmagnesium, di-n-propylmagnesium, diisopropylmagnesium, dibutylmagnesium, dihexylmagnesium, diphenylmagnesium, and dibenzylmagnesium.

[0057] Another class of organomagnesium compounds suitable for use as alkylating agents according to embodiments of the process of the first embodiment has the general formula R c MgX c where R c is a monovalent organic group bonded to the magnesium atom through a carbon atom, and X is a hydrogen atom, a halogen atom, a carboxylate group, an alkoxide group, or an aryloxide group. c is a hydrocarbyl or substituted hydrocarbyl group, including alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl, aryl, aryl, substituted aryl, aralkyl, alkaryl, and alkynyl groups, each containing 1 carbon atom, or the appropriate minimum number of atoms, up to 20 carbon atoms (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms). These hydrocarbyl or substituted hydrocarbyl groups may also contain heteroatoms, including, but not limited to, nitrogen, oxygen, boron, silicon, sulfur, and phosphorus atoms. In one embodiment, X c is a carboxylate group, an alkoxide group, or an aryloxide group, each group containing from 1 carbon atom up to 20 carbon atoms (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms).

[0058] General formula R c MgX cExamples of the type of organomagnesium compound represented by the formula (I) suitable for use as the alkylating agent in the process of the first embodiment include, but are not limited to, hydrocarbyl magnesium hydrides, hydrocarbyl magnesium halides, hydrocarbyl magnesium carboxylates, hydrocarbyl magnesium alkoxides, and hydrocarbyl magnesium aryloxides.

[0059] General formula R c MgX c Examples of organomagnesium compounds suitable for use as alkylating agents in the process of the first embodiment, represented by the formula: , methyl magnesium hexanoate, ethyl magnesium hexanoate, butyl magnesium hexanoate, hexyl magnesium hexanoate, phenyl magnesium hexanoate, benzyl magnesium hexanoate, methyl magnesium ethoxide, ethyl magnesium ethoxide, butyl magnesium ethoxide, hexyl magnesium ethoxide, phenyl magnesium ethoxide, benzyl magnesium ethoxide, methyl magnesium phenoxide, ethyl magnesium phenoxide, butyl magnesium phenoxide, hexyl magnesium phenoxide, phenyl magnesium phenoxide, and benzyl magnesium phenoxide.

[0060] As previously mentioned, the lanthanide-based catalyst system used in the process of the first embodiment includes a halogen source. As used herein, the term "halogen source" refers to any substance containing at least one halogen atom. According to one or more embodiments of the process of the first embodiment, all or a portion of the halogen source may optionally be provided by the lanthanide compound, the alkylating agent, or both the lanthanide compound and the alkylating agent. In other words, the lanthanide compound can function as both the lanthanide compound and all or at least a portion of the halogen source. Similarly, the alkylating agent can function as both the alkylating agent and all or at least a portion of the halogen source.

[0061] According to certain embodiments of the process of the first embodiment, at least a portion of the halogen source can be present in the catalyst system in the form of separate and distinct halogen-containing compounds. Various compounds (or mixtures thereof) containing one or more halogen atoms can be used as the halogen source. 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 organic solvents, such as aromatic hydrocarbons, aliphatic hydrocarbons, and cycloaliphatic hydrocarbon solvents disclosed herein, are suitable for use as the halogen source in the process of the first embodiment. Furthermore, hydrocarbon-insoluble halogen-containing compounds that can be suspended in the polymerization system to form catalytically active species are also useful in certain embodiments of the process of the first embodiment.

[0062] Examples of types of halogen-containing compounds suitable for use in the process of the first embodiment include, but are not limited to, elemental halogens, mixed halogens, hydrogen halides, organic halides, inorganic halides, metal halides, and organometallic halides. In certain preferred embodiments of the process of the first embodiment, the halogen-containing compound comprises an organometallic halide.

[0063] Examples of elemental halogens suitable for use as the halogen source in the process of the first embodiment include, but are not limited to, fluorine, chlorine, bromine, and iodine. Some specific examples of suitable mixed halogens include, but are not limited to, iodine monochloride, iodine monobromide, iodine trichloride, and iodine pentafluoride.

[0064] Examples of hydrogen halides suitable for use as the halogen source in the disclosed process include, but are not limited to, hydrogen fluoride, hydrogen chloride, hydrogen bromide, and hydrogen iodide.

[0065] Examples of organic halides suitable for use as the halogen source in the process of the first embodiment include, but are not limited to, t-butyl chloride, t-butyl bromide, allyl chloride, allyl bromide, benzyl chloride, benzyl bromide, chloro-di-phenylmethane, bromo-di-phenylmethane, 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.

[0066] Examples of inorganic halides suitable for use as the halogen source in the process of the first embodiment 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.

[0067] Examples of metal halides suitable for use as the halogen source in the process of the first embodiment 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.

[0068] Examples of organometallic halides suitable for use as the halogen source in the process of the first embodiment include dimethylaluminum chloride, diethylaluminum chloride, dimethylaluminum bromide, diethylaluminum bromide, dimethylaluminum fluoride, diethylaluminum fluoride, methylaluminum dichloride, ethylaluminum dichloride, methylaluminum dibromide, ethylaluminum dibromide, methylaluminum difluoride, ethylaluminum difluoride, methylaluminum sesquichloride, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, methyl ... Examples of suitable halogen sources include, but are not limited to, magnesium chloride, methyl magnesium bromide, methyl magnesium iodide, ethyl magnesium chloride, ethyl magnesium bromide, butyl magnesium chloride, butyl magnesium bromide, phenyl magnesium chloride, phenyl magnesium bromide, benzyl magnesium chloride, trimethyl tin chloride, trimethyl tin bromide, triethyl tin chloride, triethyl tin bromide, di-t-butyl tin dichloride, di-t-butyl tin dibromide, dibutyl tin dichloride, dibutyl tin dibromide, tributyl tin chloride, and tributyl tin bromide. According to one embodiment, the halogen source comprises an organometallic halide. For example, according to certain embodiments, the halogen source comprises diethyl aluminum chloride, which, as described above, can also function as an alkylating agent in a lanthanide-based catalyst system. Thus, according to certain embodiments of the process of the first embodiment, the halogen source may be provided in whole or in part by the alkylating agent in the catalyst system disclosed herein.

[0069] The lanthanide-based catalyst system used in the process of the first embodiment can be formed by combining or mixing the aforementioned catalyst components. The terms "catalyst composition" and "catalyst system," as referred to herein, encompass a simple mixture of components, a composite of various components resulting from physical or chemical attraction, a chemical reaction product of the components, or a combination of the foregoing. The terms "catalyst composition" and "catalyst system" can be used interchangeably herein. Nickel-based catalyst

[0070] As noted above, the process of the first embodiment may utilize a nickel-based catalyst system comprising (i) a nickel compound, optionally in combination with an alcohol, (ii) an organoaluminum, organomagnesium, organozinc compound, or combinations thereof, and (iii) a fluorine-containing compound or complex thereof. The specific compounds used in each of (i), (ii), and (iii) may vary.

[0071] According to the process of the first embodiment, the nickel compound used in the nickel-based catalyst system may vary. The nickel atom in the nickel-containing compound may be in various oxidation states, including, but not limited to, the 0, +2, +3, and +4 oxidation states. Nickel-containing compounds suitable for use in the nickel-based catalyst system according to the process of the first embodiment include, but are not limited to, nickel carboxylates, nickel carboxylate borates, nickel organophosphates, nickel organophosphonates, nickel organophosphinates, nickel carbamates, nickel dithiocarbamates, nickel xanthates, nickel β-diketonates, nickel alkoxides or aryloxides, nickel halides, nickel pseudohalides, nickel oxyhalides, and organonickel compounds. In a preferred embodiment of the process of the first embodiment, when a nickel-based catalyst system is used, the nickel compound is nickel carboxylate.

[0072] Suitable nickel carboxylates may include nickel formate, 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.

[0073] Suitable nickel carboxylate borates can include compounds defined by the formula (RCOONiO)B or (RCOONiO)B(OR), where each R, which can be the same or different, is a hydrogen atom or a monovalent organic group. In one embodiment, each R can be a hydrocarbyl group, such as, but not limited to, alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, aralkyl, alkaryl, aryl, and alkynyl, each group preferably containing one carbon atom or the appropriate minimum number of carbon atoms to form the group, up to about 20 carbon atoms. These hydrocarbyl groups can contain heteroatoms, such as, but not limited to, nitrogen, oxygen, silicon, sulfur, and phosphorus atoms. Nickel carboxylate borates can include those disclosed in U.S. Pat. No. 4,522,988, incorporated herein by reference. Specific examples of nickel carboxylate borates include nickel(II) neodecanoate borate, nickel(II) hexanoate borate, nickel(II) naphthenate borate, nickel(II) stearate borate, nickel(II) octoate borate, nickel(II) 2-ethylhexanoate borate, and mixtures thereof.

[0074] Suitable nickel organophosphates 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 dioleyl 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.

[0075] Suitable 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 octyloctyl phosphonate, nickel (1-methylheptyl) (1-methylheptyl) phosphonate, phosphonate, nickel (2-ethylhexyl) (2-ethylhexyl) phosphonate, nickel decyldecyl phosphonate, nickel dodecyl dodecyl phosphonate, nickel octadecyl octadecyl phosphonate, nickel oleyl oleyl phosphonate, nickel phenyl phenyl 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, nickel (p-nonylphenyl) (2-ethylhexyl) phosphonate.

[0076] Suitable nickel organophosphinates include nickel butylphosphinate, nickel pentylphosphinate, nickel hexylphosphinate, nickel heptylphosphinate, nickel octylphosphinate, nickel (1-methylheptyl)phosphinate, nickel (2-ethylhexyl)phosphinate, nickel decylphosphinate, nickel dodecylphosphinate, nickel octadecylphosphinate, nickel oleylphosphinate, nickel phenylphosphinate, nickel (p-nonylphenyl)phosphinate, nickel dibutylphosphinate, nickel dipentylphosphinate, nickel dihexylphosphinate, phosphinate, nickel diheptylphosphinate, nickel dioctylphosphinate, nickel bis(1-methylheptyl)phosphinate, nickel bis(2-ethylhexyl)phosphinate, nickel didecylphosphinate, nickel didodecylphosphinate, nickel dioctadecylphosphinate, 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.

[0077] Suitable nickel carbamates include nickel dimethyl carbamate, nickel diethyl carbamate, nickel diisopropyl carbamate, nickel dibutyl carbamate, and nickel dibenzyl carbamate.

[0078] Suitable nickel dithiocarbamates include nickel dimethyldithiocarbamate, nickel diethyldithiocarbamate, nickel diisopropyldithiocarbamate, nickel dibutyldithiocarbamate, and nickel dibenzyldithiocarbamate.

[0079] Suitable nickel xanthates include nickel methyl xanthate, nickel ethyl xanthate, nickel isopropyl xanthate, nickel butyl xanthate, and nickel benzyl xanthate.

[0080] Suitable nickel β-diketonates include nickel acetylacetonate, nickel trifluoroacetylacetonate, nickel hexafluoroacetylacetonate, nickel benzoylacetonate, and nickel 2,2,6,6-tetramethyl-3,5-heptanedionate.

[0081] Suitable nickel alkoxides or aryloxides include nickel methoxide, nickel ethoxide, nickel isopropoxide, nickel 2-ethylhexoxide, nickel phenoxide, nickel nonylphenoxide, and nickel naphthoxide.

[0082] Suitable nickel halides include nickel fluoride, nickel chloride, nickel bromide, and nickel iodide. Nickel pseudohalides include nickel cyanide, nickel cyanate, nickel thiocyanate, nickel azide, and nickel ferrocyanide. Nickel oxyhalides include nickel oxyfluoride, nickel oxychloride, and nickel oxybromide. If the nickel halide, nickel oxyhalide, or other nickel-containing compound contains labile fluorine or chlorine atoms, the nickel-containing compound can also function as a fluorine-containing or chlorine-containing compound. Lewis bases, such as alcohols, can be used as solubilizers for this class of compounds.

[0083] The term organonickel compound can refer to any nickel compound containing at least one nickel-carbon bond. Organonickel compounds include bis(cyclopentadienyl)nickel (also called nickellocene), bis(pentamethylcyclopentadienyl)nickel (also called decamethylnickellocene), 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(crotyl)nickel.

[0084] According to the process of the first embodiment, the organoaluminum, organomagnesium compound, organozinc compound, or combination thereof used in component (ii) of the nickel-based catalyst system can be varied. In a preferred embodiment, when the process of the first embodiment utilizes a nickel-based catalyst system, component (ii) is an organoaluminum or organomagnesium compound, more preferably an organoaluminum compound. If the organoaluminum, organomagnesium, or organozinc compound contains labile fluorine, it can also function as a fluorine-containing compound (a separate fluorine-containing compound is not required). In certain embodiments, the organoaluminum, organomagnesium, or organozinc compound does not contain chlorine or bromine atoms.

[0085] Suitable compounds for use as the organoaluminum or organomagnesium compounds in nickel-based catalyst systems are described above in the section on lanthanide-based catalyst systems.

[0086] According to the process of the first embodiment, the fluorine-containing compound used in the nickel-based catalyst system may vary. Suitable fluorine-containing compounds may include various compounds or mixtures thereof containing one or more labile fluorine atoms. In one or more embodiments, the fluorine-containing compound may be soluble in a hydrocarbon solvent. In other embodiments, hydrocarbon-insoluble fluorine-containing compounds that can be suspended in the polymerization medium to form catalytically active species may be useful.

[0087] Suitable types of fluorine-containing compounds include, but are not limited to, elemental fluorine, halogen fluorides, hydrogen fluoride, organic fluorides, inorganic fluorides, metal fluorides, organometallic fluorides, and mixtures thereof. In one or more embodiments, complexes of fluorine-containing compounds with Lewis bases such as ethers, alcohols, water, aldehydes, ketones, esters, nitriles, or mixtures thereof may be used. Specific examples of these complexes include complexes of boron trifluoride with Lewis bases of hydrogen fluoride.

[0088] Halogen fluorides can include iodine monofluoride, iodine trifluoride, and iodine pentafluoride.

[0089] Organic fluorides can include t-butyl fluoride, allyl fluoride, benzyl fluoride, fluoro-di-phenylmethane, triphenylmethyl fluoride, benzylidene fluoride, methyltrifluorosilane, phenyltrifluorosilane, dimethyldifluorosilane, diphenyldifluorosilane, trimethylfluorosilane, benzoyl fluoride, propionyl fluoride, and methylfluoroformate.

[0090] Inorganic fluorides can include phosphorus trifluoride, phosphorus pentafluoride, phosphorus oxyfluoride, boron trifluoride, silicon tetrafluoride, arsenic trifluoride, selenium tetrafluoride, and tellurium tetrafluoride.

[0091] Metal fluorides can include tin tetrafluoride, aluminum trifluoride, antimony trifluoride, antimony pentafluoride, gallium trifluoride, indium trifluoride, titanium tetrafluoride, and zinc difluoride.

[0092] 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.

[0093] As noted above, when the process of the first embodiment utilizes a nickel-based catalyst system, a nickel compound may be used in combination with an alcohol. Various alcohols and mixtures may be used. In one or more embodiments, the alcohol comprises a monohydric alcohol (i.e., one containing one hydroxyl group), while in other embodiments, the alcohol comprises a polyhydric alcohol (i.e., an alcohol containing two or more hydroxyl groups), including glycols or diols, trihydric alcohols, which may be referred to as glycerol, and polyhydric alcohols. In one or more embodiments, the alcohol comprises a primary and / or secondary alcohol. Primary and secondary alcohols include alcohols in which the α-carbon (i.e., the carbon adjacent to the carbon containing the hydroxyl group) is primary or secondary. In certain preferred embodiments, when a nickel-based catalyst system is used, a monohydric alcohol, preferably hexanol, is utilized.

[0094] The alcohol may include an aliphatic alcohol, including a straight-chain or branched-chain alcohol. In other embodiments, the alcohol may include a cyclic alcohol, in other embodiments an aromatic alcohol, in other embodiments a heterocyclic alcohol, and in other embodiments a polycyclic alcohol.

[0095] In these or other embodiments, the alcohols may be saturated, and in other embodiments, they may be unsaturated. In certain embodiments, useful alcohols include those that are soluble or at least partially soluble in the reaction medium in which the polymerization is carried out.

[0096] In one or more embodiments, useful alcohols can be defined by the formula R—OH, where R is a monovalent organic group and —OH is a hydroxyl group. Monovalent organic groups include hydrocarbyl groups or substituted hydrocarbyl groups, such as, but not limited to, alkyl groups, cycloalkyl groups, substituted cycloalkyl groups, alkenyl groups, cycloalkenyl groups, substituted cycloalkenyl groups, aryl groups, aryl groups, substituted aryl groups, aralkyl groups, alkaryl groups, and alkynyl groups. Substituents include groups in which a hydrogen atom of the group is replaced with a monovalent organic group. These hydrocarbyl groups can contain heteroatoms, such as, but not limited to, nitrogen, oxygen, silicon, tin, sulfur, boron, and phosphorus atoms. In certain embodiments, the hydrocarbyl group can be free of halogen atoms, such as chlorine or bromine atoms. In certain embodiments, the monovalent organic group can contain one or more hydroxyl groups attached thereto. As a result, the alcohol can contain two or more hydroxyl groups. In other embodiments, the hydrocarbyl group does not contain any heteroatoms.

[0097] In one or more embodiments, useful alcohols contain from 1 to about 40 carbon atoms, in other embodiments from about 2 to about 26 carbon atoms, in other embodiments from about 4 to about 18 carbon atoms, and in other embodiments from about 6 to about 12 carbon atoms.

[0098] Exemplary aliphatic alcohols include methanol, ethanol, propanol, isopropanol, n-butanol, t-butanol, isobutanol, n-pentanol, n-hexanol, 2-ethylhexanol, n-heptanol, octanol, decanol, and mixtures thereof.

[0099] Exemplary cyclic alcohols include cyclohexanol, methanol, t-butylcyclohexanol, cyclopentanol, cycloheptanol, cyclooctanol, and mixtures thereof.

[0100] Exemplary unsaturated alcohols include allyl alcohol, and mixtures thereof.

[0101] Exemplary aromatic alcohols include substituted phenols, phenol, benzyl alcohol, and mixtures thereof.

[0102] Exemplary heterocyclic alcohols include furfuryl alcohol, and mixtures thereof.

[0103] Exemplary polycyclic alcohols include sterols, and mixtures thereof.

[0104] The aforementioned catalyst compositions may have high catalytic activity for polymerizing conjugated dienes into stereospecific polydienes over a wide range of catalyst concentrations and catalyst component ratios. It is believed that the catalyst components may interact to form active catalyst species. It is also believed that the optimum concentration of any one catalyst component may depend on the concentrations of the other catalyst components.

[0105] In one or more embodiments, the molar ratio of component (ii) to the nickel-containing compound can vary from about 1:1 to about 200:1, from about 3:1 to about 30:1 in other embodiments, and from about 5:1 to about 15:1 in other embodiments. As used herein, the term molar ratio refers to the ratio of equivalents of the relative components of the components, e.g., the ratio of equivalents of aluminum atoms on the aluminum-containing compound to equivalents of nickel atoms on the nickel-containing compound. In other words, when a bifunctional or polyfunctional compound (e.g., a compound containing two or more carboxylic acid groups) is used, fewer moles of the compound are required to achieve the desired equivalent ratio.

[0106] In one or more embodiments, the molar ratio of the fluorine-containing compound to the nickel-containing compound (F / Ni) can vary from about 7:1 to about 500:1, in other embodiments from about 7.5:1 to about 450:1, and in other embodiments from about 8:1 to about 400:1.

[0107] In one or more embodiments, the molar ratio of alcohol to nickel-containing compound (—OH / Ni) can vary from about 0.4:1 to about 80:1, in other embodiments from about 0.5:1 to about 75:1, and in other embodiments from about 0.7:1 to about 65:1. As used herein, the term molar ratio refers to the ratio of equivalents of the relative components, e.g., the ratio of equivalents of chlorine atoms on the chlorine-containing compound to equivalents of nickel atoms on the nickel-containing compound.

[0108] In general, nickel-based catalyst systems may be formed by combining or mixing catalyst components. It is believed that an active catalytic species results from this combination, but the extent of interaction or reaction between the various components or constituents is not known with any degree of certainty. Thus, the term "catalytic system" is used to encompass a simple mixture of components, a complex of the various components caused by physical or chemical attractions, a chemical reaction product of the components, or a combination of the foregoing.

[0109] The nickel-based catalyst system can be formed by using one of the following methods. In one or more embodiments, the nickel-based catalyst system may be formed in situ by adding the catalyst components to a solution containing the monomer and solvent or simply the bulk monomer, either stepwise or simultaneously. In one embodiment, (ii) a mixture of the components, the nickel-containing compound, and the alcohol (if present) is formed. This mixture may be formed in a solvent. This mixture and the fluorine-containing compound may then be added to the monomer to be polymerized.

[0110] In one or more embodiments, the selected catalyst components of the nickel-based catalyst system may be premixed outside the polymerization system at a suitable temperature, which may be from about −20° C. to about 80° C., and the resulting catalyst system may be aged for a period ranging from a few seconds to several days, and then added to the monomer.

[0111] In one or more embodiments, the mixture of component (ii), the nickel-containing compound, and the alcohol (if present) is formed in the presence of a small amount of monomer and, optionally, a solvent. That is, the selected catalyst components may be formed in the presence of a small amount of 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 may be used to form this mixture may range from about 1 to about 500 moles, in other embodiments from about 5 to about 250 moles, and in other embodiments from about 10 to about 100 moles per mole of nickel-containing compound. The resulting composition may be aged for a period ranging from a few seconds to a few days and then added to the remainder of the conjugated diene monomer to be polymerized together with the fluorine-containing compound.

[0112] When a solution of the nickel-based catalyst system or one or more of its catalyst components is prepared outside the polymerization system described in the foregoing method, an organic solvent or carrier may be used. The organic solvent may function to dissolve the catalyst composition or components, or the solvent may function as a carrier in which the catalyst composition or components may be suspended. The organic solvent may be inert to the catalyst composition. Useful solvents include aromatic hydrocarbons, aliphatic hydrocarbons, cycloaliphatic hydrocarbons, and / or mixtures of two or more thereof. Non-limiting examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, ethylbenzene, diethylbenzene, mesitylene, etc. Non-limiting examples of aliphatic hydrocarbon solvents include n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, isopentane, isohexane, isopentane, isooctane, 2,2-dimethylbutane, petroleum ether, kerosene, mineral spirits, etc. Non-limiting examples of cycloaliphatic hydrocarbon solvents include cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, etc. Commercial mixtures of the above hydrocarbons may also be used. Cobalt-based catalyst system

[0113] As noted above, the process of the first embodiment may utilize a cobalt-based catalyst system that includes (i) a cobalt compound, (ii) an organoaluminum halide, and (iii) optionally water. The specific compounds used in each of (i) and (ii) may vary.

[0114] Suitable cobalt compounds for use in the cobalt-based catalyst system include, but are not limited to, cobalt benzoate, cobalt acetate, cobalt boroacylate, cobalt naphthenate, bis(α-furildioxime)cobalt, cobalt hexanoate, cobalt octanoate, cobalt oxalate, cobalt tartrate, cobalt sorbate, cobalt adipate, cobalt palmitate, cobalt stearate, cobalt acetylacetonate, bis(salicylaldehyde ethylenediimine)cobalt, cobalt salicylaldehyde, dicobalt octacarbonyl, and mixtures thereof. According to a preferred embodiment, when the process of the first embodiment uses a cobalt-based catalyst system, the cobalt compound is a cobalt salt (the cobalt salt contains either two monovalent anions or one divalent anion). The anion in the cobalt salt is preferably C6-C8. 20 It is derived from organic acids.

[0115] Suitable organoaluminum halide compounds for use in cobalt-based catalyst systems include, but are not limited to, those described above for lanthanide-based catalyst systems. Suitable examples of such organoaluminum halide compounds include dihydrocarbylaluminum halides and hydrocarbylaluminum dihalides.

[0116] Preferably, the organic aluminum halide compound comprises a compound having the formula: R 5 p AlX q In the formula, R 5 is C2~C 12 is an alkyl group, X is a halogen, and p+q is 3.

[0117] More preferably, the organoaluminum halide compound is selected from the group comprising diorgano (preferably dialkyl)aluminum chloride compounds, alkylaluminum sesquichloride compounds, and mixtures thereof.

[0118] Even more preferably, the organoaluminum halide compound is a mixture of (I) (a) an alkylaluminum chloride selected from diethylaluminum chloride and ethylaluminum sesquichloride (which can be achieved by a mixture containing about equimolar amounts of diethylaluminum chloride and ethylaluminum chloride), and (b) an organoaluminum compound of formula RAl, where R is a C-C 12 and (II) alkyl aluminum chlorides in which the alkyl group has 8 to 12 carbon atoms (e.g., dioctyl chloride, didecyl aluminum chloride, etc.).

[0119] Embodiment (I) is more preferred. In this preferred embodiment, an organoaluminum compound of formula R3Al is used, which is particularly preferred to be present in an amount of 0 to 1% by weight of the mixture of (I) and (II). A particularly preferred organoaluminum compound of formula R3Al includes trioctylaluminum.

[0120] A preferred catalyst system for use in the present process comprises a cobalt salt selected from cobalt octoate and cobalt naphthenate, and an organoaluminum halide compound selected from (i) mixtures of diethylaluminum chloride with one or more of trioctylaluminum, tridecylaluminum, and tridodecylaluminum, and (ii) mixtures of dioctylaluminum chloride, didecylaluminum chloride, and didodecylaluminum chloride.

[0121] When a cobalt-based catalyst system is used in the process of the first embodiment, the ratio of components (i), (ii), and (iii) can vary. In certain embodiments, the molar ratio of cobalt compound to total organoaluminum halide (e.g., diethylaluminum chloride with trioctylaluminum) is about 1:15 to about 1:30 (e.g., 1:15, 1:20, 1:25, or 1:30), preferably about 1:15 to about 1:20 (e.g., 1:15, 1:16, 1:17, 1:18, 1:19, or 1:20), and the molar ratio of halide (e.g., diethylaluminum chloride with trioctylaluminum) is about 1:15 to about 1:30 (e.g., 1:15, 1:16, 1:17, 1:18, 1:19, or 1:20). The molar ratio of water to the total metal content in the organoaluminum halide (e.g., diethylaluminum chloride + aluminum in trioctylaluminum) is about 0.7:1 to about 0.95:1 (e.g., 0.7:1, 0.75:1, 0.8:1, 0.85:1, 0.9:1, or 0.95:1), preferably about 0.8:1 to about 0.9:1 (e.g., 0.82:1, 0.84:1, 0.86:1, 0.88:1, or 0.9:1). In certain embodiments, the amount of water is about 0.3 to about 0.8 (e.g., 0.4:1, 0.5:1, 0.6, 0.7, or 0.8), preferably about 0.5 to about 0.65 (e.g., 0.5, 0.55, 0.6, or 0.65) millimoles per millimole of organoaluminum halide (e.g., alkylaluminum chloride) used. functional compound

[0122] As noted above, the process of the first embodiment comprises reacting living terminal polymer chains with a functionalizing compound having formula (I). As noted above, according to the second and third embodiments, the modified high cis polybutadiene polymer comprises polymer chains resulting from the polymerization of 1,3-butadiene that are attached to residues of a functionalizing compound having formula (I), each polymer chain being attached to the residue of the functionalizing compound via an X group.

[0123] According to the first to third embodiments, formula (I) is as follows: [ka] wherein X is a group reactive with a living terminal polymer chain and is selected from the group consisting of cyano, epoxy, ketone, aldehyde, ester, and acid anhydride; and each R 1 is C1~C 20 Hydrocarbylene (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C 10 , C 11 , C 12 , C 13 , C 14 , C 15 , C 16 , C 17 , C 18 , C 19 or C 20 ), preferably C1 to C 10 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9 or C 10 ), more preferably C1 to C3 (e.g., C1, C2, or C3), each of the above containing one unsaturated carbon-carbon bond; R ’ is C1~C 20 Alkoxy (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C 10 , C 11 , C 12 , C 13 , C 14 , C 15 , C 16 , C 17 , C 18 , C 19 or C 20 ), preferably C1 to C 10 Alkoxy (e.g. 、 C1, C2, C3, C4, C5, C6, C7, C8, C9 or C 10 ), more preferably C1 to C6 alkoxy (e.g., C1, C2, C3, C4, C5 or C6) alkoxy, most preferably C1 or C2 alkoxy, and R'' is selected from C1 to C 20 Alkyl or C6-C 20 aryl (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C 10 , C 11 , C 12 , C 13 , C14 , C 15 , C 16 , C 17 , C 18 , C 19 or C 20 ), preferably C1 to C 10 alkyl (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9 or C 10 ), or C6~C 14 Aryl (e.g., C6, C7, C8, C9, C 10 , C 11 , C 12 , C 13 or C 14 ), more preferably selected from C1 to C6 alkyl or C6 aryl. 1 In certain embodiments of the first to third embodiments, the functionalized compound of formula (I) may be represented as -Si(R')2(R''). 1 In another embodiment of the first to third embodiments, the functionalized compound of formula (I) has a structure in which R 1 R' and R'' all have a structure selected from the groups described as preferred. Because the functionalized compounds of formula (I) have two alkoxy groups on Si, the compounds can be called dialkoxysilanes (more specifically, alkyldialkoxysilanes or aryldialkoxysilanes, depending on the presence of the R'' groups). R 1 is a hydrocarbylene group means that it is bonded to two other components (i.e., an X group and Si). In certain preferred embodiments of the first to third embodiments, R 1 is aliphatic and unsaturated. In another embodiment of the first to third embodiments, R 1 is aliphatic and may contain one unsaturated carbon-carbon bond. Generally, according to the first to third embodiments, R 1 The carbons in the group may be arranged in a linear chain or may be branched.

[0124] In certain preferred embodiments of the first to third embodiments, X is a cyano group or an epoxy group, more preferably an epoxy group. According to the first to third embodiments, when X is a cyano group, its specific structure can vary as described in more detail below. According to the first to third embodiments, when X is an epoxy group, it preferably has 2 to 4 carbon atoms (e.g., 2, 3, or 4 carbon atoms) in the epoxy ring.

[0125] As mentioned above, according to the first to third embodiments, X in the functionalized compound of formula (I) (or the residue obtained therefrom) is selected from an epoxy group, and more preferably, the epoxy group is a glycidoxy group. Suitable compounds for use as the functionalized compound of formula (I) where X is an epoxy group include, but are not limited to, (2-glycidoxyethyl)methyldimethoxysilane, (2-glycidoxyethyl)methyldiethoxysilane, (2-glycidoxyethyl)ethyldimethoxysilane, (2-glycidoxyethyl)ethyldiethoxysilane, (3-glycidoxypropyl)methyldimethoxysilane, (3-glycidoxypropyl)methyldiethoxysilane, Examples of suitable silanes include (3-glycidoxypropyl)ethyldimethoxysilane, (3-glycidoxypropyl)ethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl(methyldimethoxy)silane, 2-(3,4-epoxycyclohexyl)ethyl(methyldiethoxy)silane, 2-(3,4-epoxycyclohexyl)ethyl(ethyldimethoxy)silane, and 2-(3,4-epoxycyclohexyl)ethyl(ethyldiethoxy)silane. Among these, (3-glycidoxypropyl)methyldimethoxysilane and (3-glycidoxypropyl)methyldiethoxysilane are particularly preferred.

[0126] As noted above, according to the first to third embodiments, X of the functionalized compound of formula (I) (or a residue derived therefrom) is preferably selected from a cyano group. Non-limiting examples of suitable cyano groups that may be used as X in formula (I) according to certain embodiments of the first to third embodiments include compounds in which the cyano group and Si are separated by a hydrocarbylene group having 1 to 10 carbons, preferably 3 to 8 carbons. Non-limiting examples of suitable cyano groups that may be used as X in formula (I) according to certain embodiments of the first to third embodiments include 2-cyanoethylmethyldiethoxysilane and 3-cyanopropylmethyldiethoxysilane. In these embodiments of the first to third embodiments, X of the functionalized compound of formula (I) (or a residue derived therefrom) is selected from a ketone group, and a variety of compounds may be suitable as the functionalized compound.

[0127] In these embodiments of the first to third embodiments, X of the functionalized compound of formula (I) (or residue thereof) is selected from a ketone group, and a variety of compounds may be suitable as the functionalized compound. A non-limiting example of such a compound is p-(methyldiethoxysilyl)acetophenone.

[0128] In these embodiments of the first to third embodiments, X of the functionalized compound of formula (I) (or residue thereof) is selected from an aldehyde group, and various compounds may be suitable as the functionalized compound. A non-limiting example of such a compound is (methyldiethoxysilyl)undecanal.

[0129] In these first to third embodiments, X in the functionalized compound of formula (I) (or a residue derived therefrom) is selected from an ester group, and various compounds may be suitable as the functionalized compound. Non-limiting examples of suitable such compounds include hydrocarbyloxysilane compounds having a carboxylic acid hydrocarbyl ester residue. Specific examples of such compounds include, but are not limited to, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylethyldimethoxysilane, 3-methacryloyloxypropylethyldiethoxysilane, and 3-methacryloyloxypropylmethyldiisopropoxysilane. Of the above, 3-methacryloyloxypropylmethyldimethoxysilane and 3-methacryloyloxypropylmethyldiethoxysilane are preferred.

[0130] In these first to third embodiments, X in the functionalized compound of formula (I) (or a residue derived therefrom) is selected from an acid anhydride group, and various compounds may be suitable as the functionalized compound. Non-limiting examples of suitable such compounds include hydrocarbyloxysilane compounds having a carboxylic acid anhydride residue. Specific examples of such compounds include, but are not limited to, 3-(methyldiethoxysilyl)propylsuccinic anhydride and 3-(methyldimethoxysilyl)propylsuccinic anhydride. Among these, 3-(methyldiethoxysilyl)propylsuccinic anhydride is preferred.

[0131] According to the first to third embodiments, the polymer chain (obtained from the polymerization of 1,3-butadiene using one of the defined catalyst systems) is attached to the functionalized compound via the X group. Because the structure of the functionalized compound changes somewhat when a polymer chain is attached to the X group, the portion to which the polymer chain is attached is described as the residue of the functionalized compound. Generally, one polymer chain is attached to the residue of the functionalized compound via the X group of each molecule of the functionalized compound. However, depending on the structure of the X group, two or more polymer chains are possible for attachment to the residue of the functionalized compound. The polymer chain attachment by the process of the first embodiment (i.e., using one of the defined catalyst systems) can be contrasted with the position on the functionalized compound to which the polymer chain is attached when an anionic initiator (e.g., n-butyllithium) is used to polymerize 1,3-butadiene. More specifically, when an anionic initiator is used, the polymer chain may be attached to the functionalized compound via an alkoxy group on the Si (substituting the OR of the alkoxy group and attaching directly to the Si) as well as via an X group. When 1,3-butadiene is polymerized using one of the defined catalyst systems to produce living terminal polymer chains, the polymer chains are (only) bonded to the functionalizing compound via the X group. As a non-limiting example, if the X of the functionalizing compound is an epoxy group, the polymer chain bonds to one of the carbon atoms alpha to the oxygen of the epoxy ring. More specifically, according to such a bonding reaction, one polymer chain bonds to one of the carbon atoms alpha to the oxygen of the epoxy ring, and the bond causes ring opening with conversion of the oxygen atom to OH.

[0132] According to the first to third embodiments, the amount of functionalizing compound of formula (I) used to react with the living terminal polymer chains (i.e., according to the process of the first embodiment) or present as a residue in the modified high cis polybutadiene polymer (i.e., according to the second and third embodiments) can vary. In certain embodiments of the first to third embodiments, the functionalizing compound is used in a ratio of 100:1 to 0.5:1 (e.g., 100:1, 90:1, 80:1, 70:1, 60:1, 50:1, 40:1, 30:1, 20:1, 10:1, 8:1, 6:1, 4:1, 2:1, 1:1, 0.5:1), preferably 50:1 to 1:1 (e.g., 50:1, 40:1, 30:1, 20:1, 10:1, 8:1, 6:1, 4:1, More preferably, the functionalizing compound is used in a molar ratio of 2:1 or 1:1, more preferably 30:1 to 2:1 (e.g., 30:1, 25:1, 20:1, 15:1, 10:1, 8:1, 6:1, 4:1, or 2:1), the molar ratio being based on moles of functionalizing compound to moles of primary metal in the catalyst system (i.e., moles of lanthanide in a lanthanide-based catalyst system, moles of nickel in a nickel-based catalyst system, or moles of cobalt in a cobalt-based catalyst system). stabilizers

[0133] In certain embodiments of the process of the first embodiment, the process for preparing a modified high cis polybutadiene polymer further comprises (or further comprises) the step of reacting the modified high cis polybutadiene (from step C) with a stabilizer of formula (II) below: R 2 n Si(OR 3 ) 4-n In the formula, R 2 is C1~C 20 Alkyl, C4-C 10 Cycloalkyl or C5-C 20 Aromatic groups are selected from the group consisting of C1 to C 10 Alkyl, C4-C6 cycloalkyl, or C6-C 14 aromatic groups, more preferably C1-C6 alkyl, C4-C6 cycloalkyl, or C6 aromatic groups; R 3 is R 2may be the same as or different from C1 to C 20 Alkyl, C4-C 10 Cycloalkyl or C5-C 20 Aromatic groups are selected from C1 to C 10 Alkyl, C4-C6 cycloalkyl, or C6-C 14 In certain embodiments of the process of the first embodiment, the stabilizer of formula (II) has an R selected from the preferred groups or values ​​set forth above. 2 , R 3 In another embodiment of the process of the first embodiment, the stabilizer of formula (II) has R selected from the more preferred groups or values ​​set forth above. 2 , R 3 In a particularly preferred embodiment of the process of the first embodiment, the stabilizer is a trialkoxy(alkyl)silane (i.e., as described above, n is 3 and R 2 (wherein is alkyl), octyltriethoxysilane is particularly preferred. In embodiments of the first embodiment in which a stabilizer is utilized, it is added after (C) but before (D), i.e., before isolating the modified high cis polybutadiene. The use of a stabilizer can be beneficial in producing a modified high cis polybutadiene polymer, which results in improved snow or ice performance in tire treads incorporating the modified high cis polybutadiene polymer. As will be appreciated by those skilled in the art, the snow or ice performance of a rubber composition when incorporated into a tire tread can be predicted by measuring the G' value of the rubber composition at -20°C, with higher values ​​indicating favorable performance.

[0134] In certain embodiments of the first embodiment, no stabilizers are used in the process. Avoiding the use of stabilizers can result in an overall cost reduction in the production of the modified high cis polybutadiene polymer due to the use of one raw material and the elimination of a step in the overall process.

[0135] In embodiments of the first embodiment in which a stabilizer is utilized, the amount utilized in the process can vary. In certain embodiments of the first embodiment, the stabilizer is utilized in a molar ratio of 0.01:1 to 10:1 (e.g., 0.01:1, 0.05:1, 0.1:1, 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, or 10:1), preferably 0.1:1 to 5:1 (e.g., 0.1:1, 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1). , 4:1, 4.5:1 or 5:1), more preferably in a molar ratio of 0.5:1 to 2:1 (e.g., 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1 or 2:1), where the molar ratio is based on moles of stabilizer to moles of functionalized compound. quenching agent

[0136] As mentioned above, according to the first embodiment process, a quenching agent of formula (III) is used in combination with a stabilizer of formula (II). According to the first embodiment process, the quenching agent of formula (III) is as follows: R 4 COOH In the formula, R 4 is selected from H, C1 to C 18 alkyl, preferably H, and C1-C 10 In certain preferred embodiments of the first embodiment, the quenching agent comprises 2-ethylhexanoic acid or acetic acid, more preferably 2-ethylhexanoic acid, and in certain such embodiments, the quenching agent consists of 2-ethylhexanoic acid. In embodiments of the first embodiment in which a quenching agent is utilized, the amount utilized in the process can vary. In certain embodiments of the first embodiment, the quenching agent is used in a molar ratio of 0.1:1 to 10:1 (e.g., 0.1:1, 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, or 10:1), preferably 0.1:1 to 5:1 (e.g., 0.1:1, 0.5:1, 1:1, 2:1, 3:1, 4:1, or 5:1), more preferably 0.5:1 to 2:1 (e.g., 0.5:1, 1:1, 1.5:1, or 2:1), where the molar ratio is based on moles of quenching agent to moles of stabilizer of Formula (II). Properties of modified high cis polybutadiene polymers.

[0137] As mentioned above, the process of the first embodiment involves producing a modified high cis polybutadiene polymer having a cis 1,4-linkage content of at least 92%, preferably at least 94%, an initial Mooney viscosity ML of 20 to 100, preferably 30 to 80 at 100°C. 1+4 and a matured Mooney viscosity ML of 20 to 100, preferably 30 to 80 at 100°C. 1+4 As also noted above, the modified high cis polybutadiene polymer of the second embodiment has a cis 1,4-content of at least 92%, preferably at least 94%, and an initial Mooney viscosity ML of 20 to 100, preferably 30 to 80 at 100°C. 1+4 and a matured Mooney viscosity ML of 20 to 100, preferably 30 to 80 at 100°C. 1+4 Because the tire rubber composition of the third embodiment utilizes either the modified high cis polydiene polymer of the second embodiment or a modified high cis polydiene polymer made by the process of the first embodiment, the modified high cis polydiene polymer of the third embodiment can also be understood as having a cis 1,4-bond content of at least 92%, preferably at least 94%, and an initial Mooney viscosity ML at 100° C. of 20 to 100, preferably 30 to 80. 1+4 and a matured Mooney viscosity ML of 20 to 100, preferably 30 to 80 at 100°C. 1+4The term "cis 1,4-bond content of at least 92%" refers to 92% or more (e.g., 92%, 93%, 94%, 95%, 96%, 97%, 98%, 98.5%, 99% or more), which should be understood to include ranges such as 92-99%, 92-98%, 92-97%, 92-96%, and 92-95%. In preferred embodiments of the first to third embodiments, the cis 1,4-bond content of the modified high cis polybutadiene polymer is at least 94%. The term "cis 1,4-bond content of at least 94%" refers to 94% or more (e.g., 94%, 95%, 96%, 97%, 98%, 98.5%, 99% or more), which should be understood to include ranges such as 94-99%, 94-98%, 94-97%, 94-96%, and 94-95%. The cis 1,4-bond content referred to herein is determined by FTIR (Fourier Transform Infrared Spectroscopy). Specifically, a polymer sample is dissolved in CS2 and then subjected to FTIR.

[0138] Initial Mooney viscosity ML at 100°C 1+4 refers to a Mooney viscosity measurement taken on the final modified high-cis polybutadiene polymer (the polymer has been isolated, for example, by steam distillation and dried) before being heat-aged (as described below). Initial Mooney viscosity ML at 100°C 1+4 is 20 to 100 means that it can vary from 20 to 100 (e.g., 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100). Preferably, according to the first to third embodiments, the initial Mooney viscosity ML at 100°C is 1+4 is 30 to 80 (e.g., 30, 32, 34, 35, 36, 38, 40, 42, 44, 45, 46, 48, 50, 52, 54, 55, 56, 58, 60, 62, 64, 65, 68, 70, 72, 74, 75, 76, 78, or 80). 1+4refers to a Mooney viscosity measurement obtained on a sample of a heat-aged high-cis polybutadiene polymer. More specifically, the polymer sample is aged at 100°C for at least two days (more preferably two days). Generally, the aged Mooney viscosity of a modified high-cis polybutadiene polymer is somewhat higher than the initial viscosity of the polymer. In certain embodiments of the first through third embodiments, in addition to meeting the aged Mooney viscosity values ​​described above, the final modified high-cis polybutadiene polymer also has a aged Mooney viscosity ML at 100°C that is 30% or less, 120 or less (e.g., 120, 110, 100, 90, 80, 70, 60, 50 or less) of the initial Mooney viscosity (e.g., more than 30% or less, more than 25% or less, more than 20% or less, more than 15% or less, more than 10% or less, more than 5% or less, or less). 1+4 In a preferred embodiment of the first to third embodiments, the final modified high-cis polybutadiene polymer has a Mooney viscosity at 100° C. aged ML that is 20% or less and 105 or less (e.g., 105, 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50 or less) lower than the initial Mooney viscosity (e.g., 20% or less, 18% or less, 16% or less, 15% or less, 14% or less, 12% or less, 10% or less, 8% or less, 6% or less, 5% or less, 4% or less, or less). 1+4 As a non-limiting example, if a modified high cis polybutadiene polymer had an initial Mooney viscosity of 80 and a aged Mooney viscosity of 88, the increase in Mooney viscosity is 10%.

[0139] Other properties of the modified high cis polybutadiene polymer may vary according to the first through third embodiments. For example, the polymer may have various Mw, Mn, and Mw / Mn values. In certain embodiments of the first through third embodiments, the modified high cis polybutadiene polymer meets at least one of the following: (a) a molecular weight of 150,000 to 2,000,000 grams / mole (e.g., 150,000, 200,000, 250,000, 300,000, 350,000, 400,000, 450,000, 500,000, 600,000, 700,000, 800,000, 900,000, 1,000,000, 1,100,000, 1,200,000, 1,300,000, 1,400,000, 1,500,000, 1,600,000, 1,700,000, 1,800,000, 1,900,000, or 2,000,000 grams / mole), preferably 90,000 to 1,000,000 grams / mole (e.g., 90,000, 150,000, 200,000, 250,000, 300,000, 350,000, 400,000, 450,000, 500,000, 600,000, 700,000, 800,000, 900,000, or 1,000,000 grams / mole), more preferably (b) having a Mw of 300,000 to 800,000 grams / mol (e.g., 300,000, 325,000, 350,000, 375,000, 400,000, 425,000, 450,000, 475,000, 500,000, 550,000, 600,000, 650,000, 700,000, 750,000, or 800,000 grams / mol); ,000, 200,000, 250,000, 300,000, 350,000, 400,000, 450,000, 500,000, 550,000, 600,000, 650,000, 700,000, 750,000, or 800,000 grams / mole), preferably 90,000 to 500,000 grams / mole (e.g., 90,000, 110,000, 130,000, 150,000, 170,000, 190,000, 210,000, 230,000, 250,000, 270,000, 290,(c) a Mn of 1.5 to 3.5 (e.g., 150,000, 160,000, 180,000, 200,000, 250,000, 300,000, 350,000, or 400,000 grams / mol), more preferably 150,000 to 400,000 grams / mol (e.g., 150,000, 160,000, 180,000, 200,000, 250,000, 300,000, 350,000, or 400,000 grams / mol); , 1.5, 1.7, 1.9, 2.1, 2.3, 2.5, 2.7, 2.9, 3.1, 3.3, or 3.5), preferably 1.8 to 3 (e.g., 1.8, 2, 2.2, 2.4, 2.6, 2.8, or 3), more preferably 2 to 2.5 (e.g., 2, 2.1, 2.2, 2.3, 2.4, or 2.5); or (d) an initial Mooney viscosity ML at 100°C of 40 to 70 (e.g., 40, 42, 44, 45, 46, 48, 50, 52, 54, 55, 56, 58, 60, 62, 64, 65, 66, 68, or 70), 1+4 In certain embodiments of the first to third embodiments, the modified high cis polybutadiene polymer satisfies each of (a) to (d). In certain embodiments of the first to third embodiments, the modified high cis polybutadiene polymer satisfies each of the preferred ranges of (a) to (d). In certain embodiments of the first to third embodiments, the modified high cis polybutadiene polymer satisfies each of the more preferred ranges of (a) to (d). Mn denotes the number average molecular weight in grams / mole (by GPC), Mw denotes the weight average molecular weight in grams / mole (by GPC), and Mw / Mn denotes the molecular weight distribution or polydispersity of the polymer. Generally, the Mn and Mw of these polymers can be determined by using gel permeation chromatography (GPC) calibrated with polystyrene standards.

[0140] The process of the first embodiment (and the polymer of the second embodiment may be present), and the rubber composition of the third embodiment may utilize a polymer that is a modified high cis-polybutadiene polymer product containing a minor portion of high molecular weight polymeric material. Generally, such high molecular weight material may be filtered out prior to use of the polymer (e.g., in a rubber composition) or sale of the polymer. The amount of high molecular weight material is generally less than about 10%, and sometimes less than about 5% by weight. The Mw, Mn, and Mw / Mn values ​​provided in the preceding paragraphs refer to values ​​that encompass Mw and Mn values ​​of high molecular weight material that may be determined via GPC on a sample of material made by the process of the first embodiment and / or on a sample of material according to the second or third embodiments, and that may be filtered. The Mw and Mn values ​​provided in the examples are to be considered as an indication of potential damage to GPC. The Mw is measured by GPC on a sample that has been filtered to remove high molecular weight materials and gels to avoid cleavage. Also disclosed herein is a polymer product produced by the process of the first embodiment (and the polymer of the second embodiment and the polymer that can be used in the third embodiment), wherein at least 90% by weight, preferably at least 95% by weight, or even at least 98% by weight of the polymer in the polymer product has a Mw of 150,000 to 800,000 grams / mol, preferably 250,000 to 600,000 grams / mol, more preferably 300,000 to 500,000 grams / mol, and a Mn of 80,000 to 400,000 grams / mol, preferably 90,000 to 300,000 grams / mol, more preferably 150,000 to 300,000 grams / mol. Tire components containing modified high cis polybutadiene polymers

[0141] As described above, the modified high cis polybutadiene produced according to the process of the first embodiment and the modified high cis polybutadiene of the second embodiment are particularly useful in rubber compositions used in tire components. According to a third embodiment disclosed herein, there is provided a tire component comprising a rubber composition containing the high cis polybutadiene of the second embodiment, or a high cis modified polybutadiene produced by the process of the first embodiment. More specifically, according to the third embodiment, the rubber composition of the tire component comprises: (a) an elastomer component, which comprises: (i) 10 to 100 phr, preferably 20 to 80 phr, of the high cis-modified polybutadiene polymer according to the second embodiment or the high cis-modified polybutadiene polymer obtained from the process of the first embodiment, and (ii) 0 to 90 phr of at least one additional polymer selected from the group consisting of unmodified polybutadiene, styrene-butadiene, natural rubber, and polyisoprene; and (b) a reinforcing filler component, which comprises: (i) 10 to 200 phr, preferably 30 to 200 phr, more preferably 50 to 150 phr of a reinforcing silica filler; and (ii) 0 to 50 phr of a reinforcing carbon black filler. The reinforcing carbon black filler comprises: (a) a reinforcing filler component, the reinforcing carbon black filler being present in an amount of no more than 20% by weight of the reinforcing silica filler, preferably no more than 10% by weight of the reinforcing silica filler; (c) a plasticizing component comprising: (i) 0 to 50 phr, preferably 0 to 30 phr, more preferably 0 to 15 phr of at least one plasticizing oil; and (ii) 0 to 60 phr, preferably 5 to 60 phr, more preferably 10 to 50 phr of at least one hydrocarbon resin having a Tg of at least 30°C; and (d) a cure package (preferably comprising at least one vulcanizing agent, at least one vulcanization accelerator, and optionally vulcanization activator, vulcanization inhibitor, and / or scorch inhibitor, more preferably at least one of each of the foregoing). In a preferred embodiment of the third embodiment, the tire component is a tire tread, and thus the rubber composition can alternatively be described as a tire tread rubber composition or as a rubber composition for use in a tire tread.

[0142] As noted above, according to the third embodiment, the amount of modified high cis polybutadiene polymer (a)(i) present in the rubber composition can vary from 10 to 100 phr (e.g., 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100 phr). In certain preferred embodiments of the third embodiment, the amount of modified high cis polybutadiene polymer (a)(i) present in the rubber composition is 20 to 80 phr (e.g., 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80 phr). Amounts of (a)(i) within the above ranges may also be used in the rubber compositions of the third embodiment, e.g., 40 to 80 phr, 50 to 80 phr, 40 to 70 phr, 40 to 60 phr, etc. Other rubber

[0143] As also described above, according to the third embodiment, the rubber composition can include 0 to 90 phr (e.g., 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90 phr) of at least one additional polymer selected from the group consisting of unmodified polybutadiene, styrene butadiene rubber, natural rubber, polyisoprene, and combinations thereof. In certain preferred embodiments of the third embodiment, the amount of additional polymer (b)(ii) is 20 to 80 phr (e.g., 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80 phr). Amounts of (b)(ii) within the above ranges may also be utilized in the rubber compositions of the third embodiment, e.g., 20 to 60, 20 to 50, 30 to 60, 40 to 60, etc. In certain embodiments of the third embodiment, the rubber composition comprises one or more additional rubbers, i.e., in addition to (a) and (b). In preferred embodiments of the third embodiment, the entire 100 phr of the elastomer component for the rubber composition consists of the combination of (a)(i) and (a)(ii). In other words, in such embodiments, no other rubbers are present other than the rubbers of (a)(i) and (a)(ii). In certain embodiments of the third embodiment, the rubber composition does not contain polyisoprene (i.e., 0 phr of polyisoprene). In certain embodiments of the third embodiment, the rubber composition does not contain any modified high-cis polybutadiene other than the polybutadiene according to (a)(i). In certain embodiments of the third embodiment, the rubber composition does not contain natural rubber and does not contain polyisoprene. Filler

[0144] As described above, according to the third embodiment, the rubber composition also includes 10 to 200 phr of a reinforcing silica filler (e.g., 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, or 200 phr), and 0 to 50 phr (e.g., 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50 phr) of a reinforcing carbon black filler as filler components. In other words, according to the above, the silica filler can be considered to always be present, while the carbon black filler is optionally present. In a preferred embodiment of the third embodiment, the rubber composition comprises a reinforcing silica filler in an amount of 50 to 150 phr (e.g., 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 105, 110, 115, 120, 125, 130, 135, 140, 145, or 150 phr). In a preferred embodiment of the third embodiment, the rubber composition comprises a reinforcing carbon black filler in an amount of 1 to 20 phr (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, or 20 phr), more preferably 1-10 phr (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 phr). In certain embodiments of the third embodiment, the amount of reinforcing silica filler and the amount of reinforcing carbon black filler are both within the aforementioned preferred amount ranges. In certain preferred embodiments of the third embodiment, the reinforcing carbon black filler is present in an amount of 20% or less by weight of the reinforcing silica filler (e.g., if 100 phr of silica filler is used, the amount of reinforcing carbon black filler is 20 phr or less), and preferably in an amount of 10% or less by weight of the reinforcing silica filler.

[0145] As used herein, the term "reinforcing" as used with respect to "reinforcing carbon black filler," "reinforcing silica filler," and "reinforcing filler" should generally be understood to encompass both fillers conventionally described as reinforcing, as well as fillers that may conventionally be described as semi-reinforcing. Conventionally, the term "reinforcing filler" refers to a filler having a nitrogen adsorption specific surface area (N2SA) of about 100 m 2 / g or more, in some cases, 100m 2 / g, about 125m 2 / g, 125m 2 / g or more, or even about 150m 2 / g or more than 150m 2 / g. Alternatively (or in addition), the term "reinforcing filler" can be used traditionally to refer to particulate materials having a particle size of about 10 nm to about 50 nm, inclusive. Traditionally, the term "semi-reinforcing filler" is used to refer to fillers that are intermediate between non-reinforcing fillers (as discussed below) and reinforcing fillers in either particle size, surface area (N2SA), or both. In certain embodiments of the third embodiment disclosed herein, the term "reinforcing filler" refers to a filler having a nitrogen adsorption specific surface area (N2SA) of about 20 m 2 / g or more (20m 2 / g or more), approximately 50m 2 / g over (50m 2 / g), approximately 100m 2 / g over (100m 2 / g), and approximately 125m 2 / g over (125m 2 / g). In certain embodiments of the third embodiment disclosed herein, the term "reinforcing filler" is used to refer to a particulate material having a particle size of from about 10 nm to about 1000 nm, inclusive, from about 10 nm to about 50 nm, inclusive.

[0146] According to the third embodiment, the particular type of carbon black used may vary. Generally, suitable carbon blacks for use as reinforcing fillers in the rubber compositions of the third embodiment include those having a carbon black content of at least about 20 mPa. 2 / g (at least 20m 2 / g) and, more preferably, at least about 35m 2 / g~about 200m 2 / g or higher (35m 2 / g~200m 2 The surface area values ​​used herein for carbon blacks are determined by ASTM D-1765 using the cetyltrimethylammonium bromide (CTAB) technique. Useful carbon blacks include furnace blacks, channel blacks, and lamp blacks. More specifically, useful carbon blacks include super abrasion furnace (SAF) blacks, high abrasion furnace (HAF) blacks, fine extrudability furnace (FEF) blacks, fine furnace (FF) blacks, semi-super abrasion furnace (ISAF) blacks, medium reinforcing furnace (SRF) blacks, medium processability channel blacks, difficult processability channel blacks, and conductive channel blacks. Other carbon blacks that may be utilized include acetylene black. In certain embodiments of the third embodiment, the rubber composition comprises a mixture of two or more of the aforementioned blacks. Preferably, according to the third embodiment, if a carbon black filler is present, it consists of only one type (or grade) of reinforcing carbon black. Typical carbon blacks suitable for use in certain embodiments of the third embodiment are designated by ASTM D-1765-82a as N-110, N-220, N-339, N-330, N-351, N-550, and N-660. The carbon black used can be in pelletized form or non-pelletized floc. Preferably, non-pelletized carbon black is preferred for more homogeneous mixing.

[0147] The specific type of reinforcing silica filler used in the rubber composition for tires of the third embodiment may vary. Non-limiting examples of reinforcing silica fillers suitable for use in certain embodiments of the third embodiment include, but are not limited to, precipitated amorphous silica, wet silica (hydrated silicic acid), dry silica (anhydrous silicic acid), fumed silica, calcium silicate, and the like. Other reinforcing silica fillers suitable for use in certain embodiments of the third embodiment include, but are not limited to, aluminum silicate, magnesium silicate (Mg2SiO4, MgSiO3, etc.), magnesium calcium silicate (CaMgSiO4), calcium silicate (Ca2SiO4, etc.), aluminum silicate (Al2SiO5, Al4.3SiO4.5H2O, etc.), aluminum calcium silicate (Al2O3.CaO2SiO2, etc.), and the like. Of the reinforcing silica fillers listed, precipitated amorphous wet-process, hydrous silica fillers are preferred. Such reinforcing silica fillers are produced by a chemical reaction in water, from which they are precipitated as very fine spherical particles, with the primary particles strongly bound into primary agglomerates, which in turn are less strongly bound into secondary agglomerates. Surface area, as measured by the BET method, is a preferred measurement for characterizing the reinforcing properties of various reinforcing silica fillers. In certain embodiments of the third embodiment disclosed herein, the rubber composition comprises a surface area of ​​100 m 2 / g~400m 2 / g (e.g., 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, or 400 m 2 / g), 150m 2 / g~350m 2 / g, 200m 2 / g~300m 2 / g, or 150m 2 / g~250m 2 / g surface area (measured by BET method).

[0148] In certain embodiments of the third embodiment disclosed herein, the rubber composition comprises a reinforcing silica filler having a pH of 5.5 to 8 (e.g., 5.5, 5.7, 5.9, 6.1, 6.3, 6.5, 6.7, 6.9, 7.1, 7.3, 7.5, 7.7, 7.9, or 8), 6 to 8 (e.g., 6, 6.2, 6.4, 6.6, 6.8, 7, 7.2, 7.4, 7.6, 7.8, or 8), 6 to 7.5, 6.5 to 8, 6.5 to 7.5, or 5.5 to 6.8. Some commercially available reinforcing silica fillers that can be used in certain embodiments of the third embodiment include Hi-Sil® EZ 120G, Hi-Sil® EZ 120G-D, Hi-Sil® 134G, Hi-Sil® EZ 160G, Hi-Sil® EZ 160G-D, Hi-Sil® 190, Hi-Sil® 190G-D, Hi-Sil® EZ 200G, Hi-Sil® EZ 200G, Hi-Sil® EZ 200G-D ... 200G-D, Hi-Sil® 210, Hi-Sil® 233, Hi-Sil® 243LD, Hi-Sil® 255CG-D, Hi-Sil® 315-D, Hi-Sil® 315G-D, Hi-Sil® HDP 320G, and the like.Similarly, several useful commercially available different reinforcing silica fillers are also available from Evonik Corporation (e.g., Ultrasil® 320 GR, Ultrasil® 5000 GR, Ultrasil® 5500 GR, Ultrasil® 7000 GR, Ultrasil® VN2 GR, Ultrasil® VN2, Ultrasil® VN3, Ultrasil® VN3 GR, Ultrasil® 7000 GR, Ultrasil® 7005, Ultrasil® 7500 GR, Ultrasil® 7800 GR, Ultrasil® 9500 GR, Ultrasil® 9000 GR, Ultrasil® 9100 GR, Ultrasil® 9200 GR, Ultrasil® 9300 GR, Ultrasil® 9400 GR, Ultrasil® 9500 GR, Ultrasil® 9600 GR, Ultrasil® 9700 GR, Ultrasil® 9800 GR, Ultrasil® 9900 GR, Ultrasil® 1000 GR, Ultrasil® 10100 GR, Ultrasil® 10200 GR, Ultrasil® 10300 GR, Ultrasil® 10400 GR, Ultrasil® 10500 GR, Ultrasil® 10600 GR, Ultrasil® 10700 GR, Ultrasil® 10800 GR, Ultrasil® 10900 GR, Ultrasil® 1100 GR, Ultrasil® 11600 GR, Ultrasil® 11700 GR, Ultrasil® 11800 GR, Ultrasil® 119 ... GR) and Solvay (e.g., Zeosil® 1115MP, Zeosil® 1085GR, Zeosil® 1165MP, Zeosil® 1200MP, Zeosil® Premium, Zeosil® 195HR, Zeosil® 195GR, Zeosil® 185GR, Zeosil® 175GR, and Zeosil® 165 GR).

[0149] In certain embodiments of the third embodiment, one or more silica coupling agents may also be (optionally) utilized. Silica coupling agents are useful for preventing or reducing agglomeration of silica fillers in rubber compositions. Agglomeration of silica filler particles is believed to increase the viscosity of the rubber composition, and therefore, preventing this agglomeration reduces the viscosity, improving the processability and blending of the rubber composition.

[0150] Generally, any conventional silica coupling agent type can be used, such as silanes and components, or those having moieties capable of reacting with polymers, particularly vulcanizable polymers. The silica coupling agent acts as a connecting bridge between the silica and the polymer. Suitable silica coupling agents for use in certain embodiments of the third embodiment include those containing groups such as alkylalkoxy, mercapto, blocked mercapto, sulfide-containing (e.g., monosulfide-based alkoxy-containing, disulfide-based alkoxy-containing, tetrasulfide-based alkoxy-containing), amino, vinyl, epoxy, and combinations thereof. In certain embodiments, the silica coupling agent may be added to the rubber composition in the form of a pretreated silica. The pretreated silica is pretreated with a silane before being added to the rubber composition. The use of pretreated silica allows for the addition of two components (i.e., silica and silica coupling agent) into one component, which generally tends to facilitate rubber compounding.

[0151] When a silica coupling agent is utilized in a tire rubber composition according to the third embodiment, the amount used may vary. In certain embodiments of the third embodiment, the rubber composition does not include any silica coupling agent. In other embodiments of the third embodiment, the silica coupling agent is present in an amount sufficient to provide a ratio of the total amount of silica coupling agent to silica filler of 0.1:100 to 1:5 (i.e., 0.1 to 20 parts by weight per 100 parts of silica), 1:100 to 1:10, 1:100 to 1:20, and 1:100 to 1:25, and from about 1:100 to about 0:100 and 1:100 to 0:100. In certain embodiments according to the third embodiment, the tire rubber composition comprises the silica coupling agent in an amount of 0.1 to 15 phr (e.g., 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 phr), 0.1 to 12 phr, 0.1 to 10 phr, 0.1 to 5 phr, 1 to 15 phr (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 phr), 1 to 10 phr (e.g., 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, or 10 phr), 1 to 5 phr, or 1 to 3 phr. plasticizer

[0152] As described above, according to the third embodiment, the rubber composition includes a plasticizing component comprising 0 to 50 phr (e.g., 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50 phr) of at least one plasticizing oil and 0 to 60 phr (e.g., 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, or 60 phr) of at least one hydrocarbon resin having a Tg of at least 30°C. Preferably, at least one of the plasticizing oil or the hydrocarbon resin is present in the rubber composition. In a preferred embodiment of the third embodiment, the plasticizing component comprises 0 to 30 phr of the plasticizing oil and 5 to 60 phr of the hydrocarbon resin. In a more preferred embodiment of the third embodiment, the plasticizing component comprises 0 to 15 phr of the plasticizing oil and 5 to 50 phr of the hydrocarbon resin. In certain embodiments of the third embodiment, the plasticizing oil is present in an amount of at least 1 phr (eg, 1-50 phr, 1-30 phr, 1-15 phr, 1-10 phr, 1-5 phr, etc.).

[0153] Various types of plasticizing oils can be utilized, including, but not limited to, aromatic, naphthenic, and low PCA oils. Preferably, the plasticizing oil is liquid (pourable) at 25°C. Suitable low PCA oils include those having a polycyclic aromatic content of less than 3% by weight as measured by the IP346 method. The procedure for the IP346 method can be found in Standard Methods for Analysis & Testing of Petroleum and Related Products and British Standard 2000 Parts, 62nd Edition, 2003, published by the Institute of Petroleum (UK). Suitable low PCA oils include mild extractive solvates (MES), treated distillate aromatic extracts (TDAE), TRAE, and heavy naphthenic. Suitable MES oils are commercially available as CATENEX SNR (from SHELL), PROREX 15 and FLEXON 683 (from EXXONMOBIL), VIVATEC 200 (from BP), PLAXOLENE MS (from TOTAL FINA ELF), TUDALEN 4160 / 4225 (from DAHLEKE), MES-H (from REPSOL), MES (from Z8), and OLIO MES S201 (from AGIP). Suitable TDAE oils are available as TYREX 20 (from EXXONMOBIL), VIVATEC 500, VIVATEC 180, and ENERTHENE 1849 (from BP), and EXTENSOIL 1996 (from REPSOL). Suitable heavy naphthenic oils are available as SHELLFELX 794, ERGON BLACK OIL, ERGON H2000, CROSS C2000, CROSS C2400, and SAN JOAQUIN 2000 L. Suitable low PCA oils also include oils of various plant origin, such as those obtained from vegetables, nuts, and seeds.Non-limiting examples include, but are not limited to, soybean oil, sunflower oil (including high oleic sunflower oil having an oleic acid content of at least 60%, at least 70%, or at least 80%), safflower oil, corn oil, linseed oil, cottonseed oil, rapeseed oil, cashew oil, sesame oil, camellia oil, jojoba oil, macadamia nut oil, coconut oil, and palm oil. In certain embodiments of the third embodiment, the tire rubber composition includes limited amounts of oil, such as less than 10 phr (e.g., 9, 8, 7, 6, 5, 4, 3, 2, 1, or 0 phr), less than 5 phr, between 1 and 5 phr, or even 0 phr.

[0154] Various types of hydrocarbon resins, including plasticizers, may be used in the plasticizing component. As used herein, the term plasticizer refers to a compound that is solid at room temperature (23°C) and is miscible in the rubber composition in an amount typically at least 5 phr. Generally, plasticizers act as diluents, as opposed to tackifier resins, which are generally immiscible, and can migrate to provide viscosity to the surface of the rubber composition. In certain embodiments of the third embodiment in which a plasticizer is used, the plasticizer comprises a hydrocarbon resin, which, depending on the monomers contained therein, can be an aliphatic, aromatic, or aliphatic / aromatic type. Examples of suitable plasticizers for use in the rubber composition of the third embodiment include, but are not limited to, cyclopentadiene (abbreviated as CPD) or dicyclopentadiene (abbreviated as DCPD) homopolymer or copolymer resins, terpene homopolymer or copolymer resins, and C5 homopolymer or copolymer resins. Such resins can be used, for example, individually or in combination. In a specific embodiment of the third embodiment, a plastic resin is used that satisfies at least one of the following: a Tg of greater than 30°C (preferably greater than 40°C and / or 120°C or less or 100°C or less), a number average molecular weight (Mn) of 400 to 2000 g / mol (preferably 500 to 2000 g / mol), and a polydispersity index (PI) of less than 3 (preferably less than 2) (PI = Mvv / Mn, where Mvv is the weight average molecular weight of the resin). The Tg of the resin can be measured by DSC (differential scanning calorimetry) in accordance with ASTM D3418 (1999). The Mw, Mn, and PI of the resin can be determined by size exclusion chromatography (SEC) using THF, 35°C, a concentration of 1 g / l, a flow rate of 1 milliliter / min, the solution filtered through a filter with a porosity of 0.45 μm before injection, Moore calibration with polystyrene standards, a set of three "Waters" columns ("Styragel" HR4E, HR1, and HR0.5) in series, and detection with a differential refractometer ("Waters 2410") and its associated operating software ("Waters Empower"). Hardening Package

[0155] As described above, according to the third embodiment, the rubber composition includes a curing package. Generally, the curing package includes at least one of a vulcanizing agent, a vulcanization accelerator, a vulcanization activator (e.g., zinc oxide, stearic acid, etc.), a vulcanization inhibitor, and a scorch inhibitor. In certain embodiments, the curing package includes at least one vulcanizing agent, at least one vulcanization accelerator, at least one vulcanization activator, and optionally, a vulcanization inhibitor and / or a scorch inhibitor. The vulcanization accelerator and the vulcanization activator act as catalysts for the vulcanization agent. Various vulcanization inhibitors and scorch inhibitors are known in the art and can be selected by those skilled in the art based on the desired vulcanization properties.

[0156] Examples of types of vulcanizing agents suitable for use in certain embodiments of the third embodiment include, but are not limited to, sulfur- or peroxide-based curing components. Examples of particularly suitable sulfur-vulcanizing agents include "rubbermaker's" soluble sulfur, sulfur-donating curatives such as amine disulfide, polymeric polysulfides, or sulfur olefin adducts, and insoluble polymeric sulfur. Preferably, the sulfur-vulcanizing agent is soluble sulfur or a mixture of soluble and insoluble sulfur polymers. Generally, vulcanizing agents may be used in amounts ranging from 1 to 5 phr, including 1 to 7.5 phr, and preferably 0.1 to 10 phr, including 1 to 3.5 phr.

[0157] Vulcanization accelerators are used to control the time and / or temperature required for vulcanization and to improve the properties of the vulcanizate. Examples of suitable vulcanization accelerators include, but are not limited to, thiazole vulcanization accelerators such as 2-mercaptobenzothiazole, 2,2'-dithiobis(benzothiazole) (MBTS), N-cyclohexyl-2-benzothiazole-sulfenamide (CBS), N-tert-butyl-2-benzothiazole-sulfenamide (TBBS), and the like, guanidine vulcanization accelerators such as diphenylguanidine (DPG), thiuram vulcanization accelerators, carbamate vulcanization accelerators, etc. Generally, the amount of vulcanization accelerator used ranges from 0.1 to 10 phr, preferably from 0.5 to 5 phr.

[0158] Vulcanization activators are additives used to aid vulcanization. Generally, vulcanization activators include both inorganic and organic components. Zinc oxide is the most widely used inorganic vulcanization activator. A variety of organic vulcanization activators, including stearic acid, palmitic acid, lauric acid, and their respective zinc salts, are commonly used. Generally, the amount of vulcanization activator used ranges from 0.1 to 6 phr (e.g., 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, or 6 phr), preferably 0.5 to 4 phr (e.g., 0.5, 1, 1.5, 2, 2.5, 3, 3.5, or 4 phr).

[0159] Vulcanization inhibitors are used to control the vulcanization process, typically slowing or inhibiting vulcanization until a desired time and / or temperature is reached. Common vulcanization inhibitors include, but are not limited to, PVI (cyclohexylthiophthalamide) manufactured by Santogard. Typically, the amount of vulcanization inhibitor used is 0.1 to 3 phr, preferably 0.5 to 2 phr. Other ingredients

[0160] Various other ingredients that may optionally be added to the rubber composition of the third embodiment disclosed herein include waxes, processing aids, tackifying resins, reinforcing resins, deflocculants, and antioxidants. Method for preparing rubber composition

[0161] The rubber composition according to the third embodiment disclosed herein can generally be formed by mixing the components of the rubber composition (disclosed above) together by methods known in the art, such as compounding the components in a Banbury mixer or a mill. These methods generally include at least one non-productive masterbatch mix stage and a final productive mix stage. The term non-productive masterbatch mix stage is known to those skilled in the art and is generally understood to be a mix stage in which no vulcanizing agents or vulcanization accelerators are added. The term final productive mix stage is also known to those skilled in the art and is generally understood to be a mix stage in which vulcanizing agents and vulcanization accelerators are added to the rubber composition. In certain embodiments of the third embodiment, one non-productive masterbatch mix stage may be used in preparing the rubber composition. In certain embodiments of the third embodiment, two or more non-productive masterbatch mix stages are used. In certain embodiments of the third embodiment in which silica and a silica binder are used, multiple non-productive masterbatch mix stages are used, with at least a portion of the silica filler being added in the second non-productive masterbatch mix stage (also described as a re-mill stage), and in certain such embodiments, all of the silica coupling agent is added only in the second non-productive masterbatch mix stage (with at least a portion of the silica filler), and no silica coupling agent is added in the earlier non-productive masterbatch mix stage.

[0162] In certain embodiments of the third embodiment, the masterbatch mixing stage includes at least one of tandem mixing or intermeshing mixing. Tandem mixing can be understood to include the use of a mixer having two mixing chambers, each chamber having a set of mixing rotors; typically, the two mixing chambers are stacked together with an upper mixer, which is the primary mixer, and the lower mixer receives the batch from the upper or primary mixer. In certain embodiments, the primary mixer utilizes intermeshing rotors, while in other embodiments, the primary mixer utilizes tangential rotors. Preferably, the lower mixer utilizes intermeshing rotors. Intermeshing mixing can be understood to include the use of a mixer with intermeshing rotors. Intermeshing rotors refer to a set of rotors in which the larger diameter of one rotor in the set interacts with the smaller diameter of the opposing rotor in the set so that the rotors intermesh with each other. Intermeshing rotors must be driven at a uniform speed due to the interaction between the rotors. In contrast to intermeshing rotors, tangential rotors refer to a set of rotors in which each rotor rotates independently of the other within a cavity that may be referred to as a flank. Generally, mixers with tangential rotors include a ram, whereas a ram is not necessary in mixers with intermeshing rotors.

[0163] In certain embodiments of the third embodiment, the rubber composition is prepared by a process involving non-production masterbatch mix stage(s) conducted at a temperature of about 130° C. to about 200° C. In certain embodiments of the third embodiment, the rubber composition is prepared by a process involving a final productive mix stage conducted at a temperature below the vulcanization temperature to avoid undesirable pre-curing of the rubber composition. Thus, the temperature of the productive mix stage should not exceed about 120° C., and is typically about 40° C. to about 120° C., or about 60° C. to about 110° C., and particularly about 75° C. to about 100° C. [Example]

[0164] The following examples illustrate particular and exemplary embodiments and / or embodiment features of the present disclosure. The examples are provided for illustrative purposes only and should not be construed as limiting the present disclosure. Many variations on these specific examples are possible without departing from the spirit and scope of the embodiments of the present disclosure. Specifically, it should be understood that the modified high cis polybutadiene polymers can be modified using different functional compounds (i.e., according to formula (I) as described above), different stabilizers, or no stabilizers (as described above), or different combinations of functional compounds and stabilizers used in the rubber composition. It should also be understood that the high cis polybutadiene polymers can be utilized in rubber compositions with components (e.g., additional rubbers, fillers, curing package components) that differ in relative amounts, composition, or both from those used in the examples (i.e., as completely as disclosed in the preceding paragraph).

[0165] High cis polybutadiene polymers were prepared in Examples 1-5, as described in detail below. Examples 3-5 can be considered modified high cis polybutadiene polymers of the second embodiment and can be prepared according to a process that is exemplary of the first embodiment, while Examples 1-2 should be considered comparative or control examples (because they do not utilize a functionalized compound satisfying formula (I)). The polymers produced in Examples 1-5 were then used to prepare a rubber composition in Example 6. Rubber compositions 6-3, 6-4, and 6-5 can be considered exemplary of the third embodiment disclosed herein, while Examples 6-1 and 6-2 should be considered comparative or control examples. General Polymerization Procedure

[0166] Example 1: To a dry, nitrogen-purged 378 liter reactor was added 55,755 grams of hexane and 78,361 grams of a 23.4 wt % 1,3-butadiene solution in hexane. The solution was maintained at 32°C. 260 grams / 288 milliliters of COMCAT Nd-FC / SF catalyst (available from Comar Chemical Ltd.) was used as a preformed catalyst. Additional diisobutylaluminum hydride was added as needed to achieve a base ML ranging from 25 MU to 45 MU. 1+4 The temperature was maintained at 91°C. The reactor jacket was then set to 91°C. The mixture was allowed to polymerize until a peak temperature of 52°C was reached. The jacket temperature was then increased to 66°C. After 20 minutes, 69,622 grams of hexane and 93.9 grams of neat 2-cyanoethyltriethoxysilane (CETEOS) were charged to the reactor. The molar ratio of CETEOS to Nd in the neodymium versatic was 20:1. After 30 minutes, 120 grams of neat triethoxy(octyl)silane was added, followed by 39 grams of neat 2-cyanoethyltriethoxysilane. Ethylhexanoic acid was added. After about 30 minutes, the polymerization mixture was allowed to cool. The resulting polymer cement was quenched and coagulated using 46 grams of neat isopropanol, followed by 183 grams of neat dibutylhydroxytoluene, and then steam distilled to dryness. The properties of the resulting polymer are summarized in Table 1-A below. The polymer of Example 1 can be considered the control polymer.

[0167] Example 2: The polymer of Example 2 was made according to the procedure described above for Example 1, except that 100.0 grams of neat 3-cyanopropyltriethoxysilane (CPTEOS) was used instead of CETEOS. The polymer of Example 2 can be considered a control polymer.

[0168] Example 3: The polymer of Example 3 was made according to the procedure described above for Example 1, except that 100.0 grams of neat 3-3-glycidoxypropylmethyldiethoxysilane (GPMDEOS) was used instead of CETEOS.

[0169] Example 4: The polymer of Example 4 was made according to the procedure described above for Example 3, except that less stabilizer (75.3 grams of OTES) was used.

[0170] Example 5: The polymer of Example 5 was made according to the procedure described above for Example 3, except that no stabilizer (ie, 0 grams of OTES) was used.

[0171] Examples 6-11: High-cis polybutadiene polymers were prepared using GPTEOS / 3-glycidoxypropyltriethoxysilane (Examples 6 and 9), GPMDEOS / 3-glycidoxypropylmethyldiethoxysilane (Examples 7 and 10), or GPDMEOS / 3-glycidoxydimethylethoxysilane (Examples 8 and 11). Examples 6, 7, and 8 used 5 equivalents of OTES (i.e., a molar ratio of OTES:Nd of 5:1). Examples 9, 10, and 11 did not use OTES. Examples 7 and 9 are inventive, while Examples 6, 8, 9, and 11 are control examples (comparing triethoxysilane and monoethoxysilane with diethoxysilane). Generally, the same procedures as described in Examples 1-5 were used to prepare the polymers, except for the use of the modifiers mentioned above (and in the amounts listed in Table 1-B). For a particular polymer, the use of stabilizers (as indicated and in the amounts listed in Table 1-B) was used. The properties of the resulting polymers are summarized in Table 1-B below. [Table 1] 1 Molar ratio of functionalized compound: neodymium 2 Molar ratio of stabilizer: neodymium 3 Measured by FTIR as described above for cis-1,4 bond measurements 4 The functionalized compound does not conform to formula (I) [Table 2] 1 Molar ratio of functionalized compound: neodymium 2 Molar ratio of stabilizer: neodymium 3 Measured by FTIR as described above for cis-1,4 bond measurements 4 The functionalized compound does not conform to formula (I)

[0172] The Mooney viscosities disclosed in Tables 1-A and 1-B are polymer values ​​(determined on the polymer) determined at 100°C using an Alpha Technologies Mooney viscometer with a large rotor, a 1 minute warm-up time, and a 4 minute run time; therefore, the ML 1+4 More specifically, Mooney viscosity was measured from each batch by preheating the sample to 100°C for 1 minute before the rotor started. The Mooney viscosity of each sample was recorded as torque 4 minutes after the rotor started. Initial and aged values ​​were measured on the samples as follows: Mn, Mw, cis-1,4 bond, and vinyl bond content were all determined on the samples as generally described below. Gel content (wt%) was determined by soaking the sample in toluene for 2 days, then capturing any gel on a mesh screen and calculating the gel content (after drying the screen under vacuum at 60°C for 2 hours).

[0173] As can be seen from the data in Table 1-B, the use of functionalized compounds according to formula (I), i.e., those having diethoxysilane groups, compared with the use of similar compounds having triethoxysilane groups, resulted in modified high-cis polybutadienes with significantly lower insoluble content (0.8% vs. 12.7% or 2.6% vs. 27.6%), regardless of whether a stabilizer (i.e., OTES) was used. The increase in Mooney viscosity from initial aging in the presence of a stabilizer was smaller (21% vs. 32%). As described in more detail below, the use of functionalized compounds according to formula (I), i.e., those having diethoxysilane groups, resulted in improved properties when the polymer was incorporated into a rubber composition, compared with the use of similar compounds having monoethoxysilane groups. Similar to the data in Table 1-A, the use of functionalized compounds according to formula (I), compared with epoxy-containing compounds containing triethoxysilane groups, resulted in modified high-cis polybutadienes with lower insoluble content, an effect that was more pronounced in the presence of increased amounts of stabilizer (i.e., OTES). Furthermore, the use of functionalized compounds according to formula (I) results in modified high-cis polybutadienes having both low initial Mooney viscosities (values ​​all within the range of 30 to 80) and lower aged Mooney viscosities (all less than 105) compared to epoxy-containing compounds containing triethoxysilane groups. Compared to epoxy-containing compounds containing monoethoxy groups, the use of functionalized compounds according to formula (I) results in modified high-cis polybutadienes having Mooney viscosities that are particularly advantageous for polymer processing. More specifically, a aged or final Mooney viscosity of at least 50 or at least 60 can be advantageous in that such polymers exhibit less tack.

[0174] Example 12: Rubber compositions (12-C1, 12-C2, and 12-1 to 12-11) were prepared utilizing the polymers produced in Examples 1 to 11 according to the formulas set forth in Table 2 below. Rubber composition 12-1 was prepared using the polymer of Example 1. Rubber composition 12-2 was prepared using the polymer of Example 2, and so on. In addition to using the polymers produced in Examples 1 to 11, a commercially available neodymium-catalyzed polymer from Firestone Polymers (cis 1,4 bond content 96%, vinyl bond content 0%, trans bond content 4%, Tg -109°C, and initial ML at 100°C of 45) was also prepared. 1+4 Additional control rubber compositions were prepared using 140ND Diene™ polybutadiene (having 12-C1). Samples of 140ND were used with OTES (12-C1) and without OTES (12-C2). The mixing procedure described in Table 3 was used to prepare the rubber composition of Example 12. The rubber compositions of Examples 12-C1, 12-C2, 12-1, 12-2, 12-6, 12-8, 12-9, and 12-11 can be considered control examples. The rubber compositions of Examples 12-3, 12-4, 12-5, 12-7, and 12-10 can be considered in accordance with the present invention. [Table 3] 1 Low PCA Oil, Black Oil from Ergon Manufacturing 2 Bis(triethoxysilylpropyl) disulfide 3 TBBS and DPG [Table 4]

[0175] After preparation of rubber compositions 12-C and 12-1 through 12-11, samples were taken and properties were measured according to the following procedures. The results are reported in Tables 4-A and 4-B below. The Mooney viscosities of the rubber compositions listed in Tables 4-A and 4-B were measured at 100°C using an Alpha Technologies Mooney viscometer with a large rotor, a 1-minute warm-up time, and a 4-minute run time.

[0176] The tan δ and G' values ​​were measured using a strain sweep test performed on an Advanced Rheometric Expansion System (ARES) from TA Instruments. The test specimens had a rectangular shape, measuring 47 mm in length, 2 mm in thickness, and 12.7 mm in width. The length of the specimen between the grips of the tester (i.e., the gap) was approximately 27 mm. The test was performed using a frequency of 3.14 rad / s. The temperature was swept from -80°C to 80°C with a strain of 0.25% used for temperatures from -80°C to -10°C, and the strain was increased by 2% from -10°C to 80°C. The tan δ of a rubber composition at 65°C indicates its rolling resistance when incorporated into a tire tread, its tan G'-20°C indicates its snow performance when incorporated into a tire tread, and its tan δ at 0°C indicates its wet performance when incorporated into a tire tread. Tan δ values ​​are reported as an index number (calculated by comparing the value of a given example with that of a control rubber composition), with numbers above 100 being considered an improvement. [Table 5] * Examples 12-4 and 12-5 were mixed at a different time than Examples 12-1 through 12-3 and indexed to a control having the same composition as listed in Table 4-A, but mixed at the same time as Examples 12-4 and 12-5. [Table 6]

[0177] Comparing the data in Table 4-A, it can be seen that the use of functionalized compounds according to Formula (I), compared to cyano-containing compounds containing triethoxysilane groups, results in rubber compositions with improved tan δ values ​​at 65°C (indicating improved rolling resistance when the rubber compositions are incorporated into tire treads). More specifically, the tan δ index values ​​at 65°C for Examples 12-3, 12-4, and 12-5 are higher than those for Examples 12-1 and 12-2. Comparing the data in Table 4-B, it can be seen that the use of functionalized compounds according to Formula (I) (when compared to their respective control compositions) results in improvements in all properties of Compositions 12-7 and 12-10, except for tan δ at 0°C. In particular, rubber composition 12-10 of the present invention showed the greatest improvement in tan δ at 65°C. Similarly, based on the data in Table 4-B, the use of a stabilizer (i.e., OTES) appears to provide a benefit to snow properties (i.e., G' at -20°C), as exemplified by the increased values ​​for Composition 12-7 versus its control Composition 12-C1 compared to Composition 12-10 versus its control Composition 12-C2.

[0178] The present application discloses several numerical range limits that support any range within the disclosed numerical ranges, even if an explicit range limit is not explicitly stated in the specification, because embodiments of the compositions and methods disclosed herein can be practiced throughout the disclosed numerical ranges. With respect to the use of virtually any plural or singular term herein, one of ordinary skill in the art can substitute plural for singular or singular for plural as appropriate to the situation or application. Various singular or plural substitutions may be explicitly stated herein for the sake of brevity.

[0179] In general, those skilled in the art will understand that the terms used in this specification, and particularly in the appended claims, are generally intended to be "open" terms. For example, the term "including" should be interpreted as "including but not limited to," the term "having" should be interpreted as "having at least," and the term "including" should be interpreted as "including but not limited to." Furthermore, those skilled in the art will understand that where a specific number is intended in a prefaced claim recitation, such intention shall be expressly recited in the claim; otherwise, no such intention exists. For example, as an aid to understanding, the following appended claims may include the use of the preface terms "at least one" and "one or more" to preface the claim recitation. However, the use of such phrases should not be construed as meaning that the preface of a claim recitation with the indefinite article "a" or "an" limits any particular claim containing the claim recitation so prefaced to inventions containing only one such recitation, even if the same claim also includes the preface phrase "one or more" or "at least one" and an indefinite article such as "a" or "an" (e.g., "a" or "an" should typically be interpreted to mean "at least one" or "one or more"). The same is true for the use of definite articles used to preface claim recitations. Additionally, even when a particular number is explicitly recited in a prefaced claim recitation, those skilled in the art will understand that such a recitation should typically be interpreted to mean at least the recited number (e.g., the explicit recitation "two recitations" without any other modifiers typically means at least two or more recitations). Furthermore, when a conventional expression similar to "at least one of A, B, and C, etc." is used, such a configuration is generally intended in the sense that one of ordinary skill in the art would understand the convention (e.g., "a system having at least one of A, B, and C" may include, but is not limited to, a system having only A, only B, only C, A and B together, A and C together, B and C together, and / or A, B, and C together, etc.).Furthermore, those skilled in the art will understand that virtually any disjunctive word or phrase presenting two or more alternative terms, whether in the specification, claims, or drawings, should be understood to contemplate the possibility of including one of those terms, either of those terms, or both of those terms. For example, the phrase "A or B" will be understood to include the possibilities of "A" or "B" or "A and B." All references, including but not limited to patents, patent applications, and non-patent literature, are incorporated herein by reference in their entirety. While various aspects and embodiments of the compositions and methods have been disclosed herein, other aspects and embodiments will be apparent to those skilled in the art. The various aspects and embodiments disclosed herein are for illustrative purposes only and are not intended to limit the true scope and spirit of the appended claims.

Claims

1. 1. A process for preparing a modified high cis polybutadiene polymer, comprising: The modified high cis polybutadiene polymer is having a polymer chain attached to a residue of a functionalized compound having the following formula (I): 【Chemistry 1】 wherein X is a group that reacts with a living terminal polymer chain and is selected from the group consisting of cyano, epoxy, ketone, aldehyde, ester, and acid anhydride; R １ is C １ ~C ２０ each of the foregoing optionally containing one unsaturated carbon-carbon bond; Each R' is C １ ~C ２０ and R'' is C １ ~C ２０ alkyl or C ６ ~C ２０ is selected from the group consisting of aryl Each polymer chain is attached to the residue of the functionalizing compound via the X group, and the polymer comprises: 92-98% cis 1,4-bond content Initial Mooney viscosity at 100°C ML １＋４ is between 20 and 100, and Matured Mooney viscosity ML at 100°C after aging at 100°C for 2 days １＋４ is 120 or less, The modified high-cis polybutadiene polymer satisfies all of the following: a. having a Mw of 150,000 to 2,000,000 grams / mole; b. having an Mn of 80,000 to 800,000 grams / mole; c. having a Mw / Mn of 1.5 to 4; and d. Initial Mooney viscosity ML of 40 to 70 at 100°C １＋４ having The process comprises: A. Providing a catalyst system, a. a lanthanide-based catalyst system comprising: (i) a lanthanide compound; (ii) an alkylating agent; and (iii) a halogen source, wherein (iii) may optionally be provided by (i), (ii), or both (i) and (ii); or b. A nickel-based catalyst system comprising: (i) a nickel compound, optionally in combination with an alcohol; (ii) an organoaluminum, organomagnesium, or organozinc compound, or a combination thereof; or (iii) a fluorine-containing compound or a complex thereof; or c. A cobalt-based catalyst system comprising: (i) a cobalt compound; (ii) an organoaluminum halide; and (iii) optionally, water; B. polymerizing 1,3-butadiene using the catalyst system of (A) to produce polymer chains having living ends; C. reacting said living terminal polymer chains of (B) with a functionalizing compound having formula (I): thereby producing a modified high cis polybutadiene having a cis 1,4-bond content of 92 to 98%; D. Isolating the modified high cis polybutadiene of (C), Initial Mooney viscosity at 100°C ML １＋４ is 20 to 100, Matured Mooney viscosity ML at 100°C after aging at 100°C for 2 days １＋４ producing a final modified high cis polybutadiene having a β-dispersity of 120 or less; Including, wherein the functionalizing compound is used in a molar ratio of moles of functionalizing compound to moles of lanthanide in a lanthanide-based catalyst system, moles of nickel in a nickel-based catalyst system, or moles of cobalt in a cobalt-based catalyst system of the catalyst system of 50:1 to 2:

1.

2. 2. The process of claim 1, wherein X in formula (I) is an epoxy group.

3. 3. The process of claim 2, wherein X in formula (I) is a glycidoxy group and the polymer chain is attached to a carbon atom from the epoxy group.

4. 2. The process of claim 1, wherein X in formula (I) is a cyano group.

5. (D) before reacting the modified high cis polybutadiene of (C) with a stabilizer of formula (II): R ２ ｎ Si(OR ３ ) ４－ｎ In the formula, R ２ is C １ ~C ２０ Alkyl, C ４ ~C １０ cycloalkyl, or C ５ ~C ２０ selected from the group consisting of aromatic groups; In the formula, R ３ is R ２ may be the same as or different from C １ ~C ２０ Alkyl, C ４ ~C １０ cycloalkyl, or C ５ ~C ２０ selected from aromatic groups, 5. The process of any one of claims 1 to 4, further comprising: n is an integer from 1 to 3.

6. The stabilizer is used together with a quenching agent of formula (III): R ４ COOH In the formula, R ４ is H and C １ ~C １８ 6. The process of claim 5, wherein the alkyl group is selected from the group consisting of alkyl.

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