Modified high cis polybutadiene polymers, related methods and tire components

Abstract

Disclosed herein is a method for preparing a modified high-cis polybutadiene polymer, a modified high-cis polybutadiene polymer, and a tire having a component prepared using the modified high-cis polybutadiene polymer. The method uses a specified catalyst system to prepare the modified high-cis polybutadiene from a certain amount of 1,3-butadiene monomer using a functionalized compound of formula (I).

Description

Technical Field

[0001] The present application relates to modified high-cis polybutadiene polymers, related methods, and tires having components comprising the modified high-cis polybutadiene polymers. Background Art

[0002] High cis polybutadiene polymers have many uses in industry, including use in tire rubber compositions for tire components such as tire treads. Modification of such high cis polybutadiene polymers by certain functionalizing compounds to increase filler-polymer interactions can result in polymers having a desirable initial Mooney viscosity, but such polymers may be prone to an increase in Mooney viscosity upon aging, creating challenges in storing the modified polymers. Summary of the invention

[0003] Disclosed herein are a modified high-cis polybutadiene polymer, a method for preparing the modified high-cis polybutadiene polymer, and a tire having a component made of a rubber composition containing the modified high-cis polybutadiene polymer.

[0004] In a first embodiment, a method for preparing a modified high-cis polybutadiene polymer is provided. According to a first embodiment, the method 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, wherein (iii) may be optionally provided by (i), (ii), or both (i) and (ii); (b) a nickel-based catalyst system comprising (i) a nickel compound, the nickel compound optionally being combined 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 a polymer chain having an active terminal, and (C) reacting the active terminal polymer chain from (B) with a functionalized compound having the following formula (I):

[0005]

[0006] Where X is a cyano group, R 1 Independently selected from C1-C 20 The alkylene group, each R' is independently selected from C1-C 20(D) reacting the modified high cis polybutadiene from (C) with: (1) a stabilizer of formula (II) as follows:

[0007] R 2 n Si(OR 3 ) 4-n

[0008] Where R 2 Choose from C1 to C 20 Alkyl, C4 to C 10 Cycloalkyl or C5 to C 20 Aromatic groups; wherein R 3 Can be used with R 2 The same or different and selected from C1 to C 20 Alkyl, C4 to C 10 Cycloalkyl or C5 to C 20 an aromatic group; and n is an integer from 1 to 3, and (2) a quencher of formula (III) as follows

[0009] R 4 COOH

[0010] Where R 4 Selected from H and C1 to C 18 and (E) separating the modified high cis polybutadiene of (D) to produce a final modified high cis polybutadiene having an initial Mooney viscosity ML of 20-100 at 100°C 1+4 , and an aged Mooney viscosity ML not exceeding 120 at 100C 1+4 .

[0011] In a second embodiment, a modified high cis polybutadiene polymer is provided. According to a second embodiment, a modified high cis polybutadiene polymer is provided, the modified high cis polybutadiene polymer having a polymer chain bonded to a residue of a functionalized compound having the following formula (I):

[0012]

[0013] Where X is a cyano group, R 1 Independently selected from C1-C 20 The alkylene group, each R' is independently selected from C1-C 20 wherein each polymer chain is bonded to the residue of the functionalized compound via an X group, and the polymer has an initial Mooney viscosity ML of 20-100 at 100°C 1+4and an aged Mooney viscosity ML not exceeding 120 at 100°C 1+4 .

[0014] In a third embodiment, a tire having a component comprising a rubber composition is provided, the rubber composition comprising the high cis-modified polybutadiene of the second embodiment or the high cis-modified polybutadiene prepared by the method of the first embodiment. According to the third embodiment, the component of the tire comprises a rubber composition, the rubber composition comprising (a) an elastomeric component, the elastomeric component comprising: (i) 10 phr to 100 phr of a high cis-modified polybutadiene polymer according to the second embodiment or a high cis-modified polybutadiene polymer produced by the method of the first embodiment, and (ii) 0 phr to 90 phr of at least one additional polymer selected from the group consisting of unmodified polybutadiene, styrene-butadiene, natural rubber, and polyisoprene; (b) a reinforcing A filler component, the reinforcing filler component comprising: (i) 10 phr-200 phr of a reinforcing silica filler, and (ii) 0 phr-50 phr of a reinforcing carbon black filler, wherein the reinforcing carbon black filler is present in an amount not exceeding 20% ​​by weight of the reinforcing silica filler; (c) a plasticizing component, the plasticizing component comprising: (i) 0 phr-50 phr of at least one plasticizing oil, and (ii) 0 phr-60 phr of at least one hydrocarbon resin having a Tg of at least 30°C; and (d) a curing package. DETAILED DESCRIPTION

[0015] Disclosed herein are a modified high-cis polybutadiene polymer, a method for preparing the modified high-cis polybutadiene polymer, and a tire having a component made of a rubber composition containing the modified high-cis polybutadiene polymer.

[0016] In a first embodiment, a method for preparing a modified high-cis polybutadiene polymer is provided. According to a first embodiment, the method 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, wherein (iii) may be optionally provided by (i), (ii), or both (i) and (ii); (b) a nickel-based catalyst system comprising (i) a nickel compound, the nickel compound optionally being combined 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 a polymer chain having an active terminal, and (C) reacting the active terminal polymer chain from (B) with a functionalized compound having the following formula (I):

[0017]

[0018] Where X is a cyano group, R 1 Independently selected from C1-C 20 The alkylene group, each R' is independently selected from C1-C 20 (D) reacting the modified high cis polybutadiene from (C) with: (1) a stabilizer of formula (II) as follows:

[0019] R 2 n Si(OR 3 ) 4-n

[0020] Where R 2 Choose from C1 to C 20 Alkyl, C4 to C 10 Cycloalkyl or C5 to C 20 Aromatic groups; wherein R 3 Can be used with R 2 The same or different and selected from C1 to C 20 Alkyl, C4 to C 10 Cycloalkyl or C5 to C 20 an aromatic group; and n is an integer from 1 to 3, and (2) a quencher of formula (III) as follows

[0021] R 4 COOH

[0022] Where R4 Selected from H and C1 to C 18 and (E) separating the modified high cis polybutadiene of (D) to produce a final modified high cis polybutadiene having an initial Mooney viscosity ML of 20-100 at 100°C 1+4 , and an aged Mooney viscosity ML not exceeding 120 at 100C 1+4 .

[0023] In a second embodiment, a modified high cis polybutadiene polymer is provided. According to a second embodiment, a modified high cis polybutadiene polymer is provided, the modified high cis polybutadiene polymer having a polymer chain bonded to a residue of a functionalized compound having the following formula (I):

[0024]

[0025] Where X is a cyano group, R 1 Independently selected from C1-C 20 The alkylene group, each R' is independently selected from C1-C 20 wherein each polymer chain is bonded to the residue of the functionalized compound via an X group, and the polymer has an initial Mooney viscosity ML of 20-100 at 100°C 1+4 and an aged Mooney viscosity ML not exceeding 120 at 100°C 1+4 .

[0026] In a third embodiment, a tire having a component comprising a rubber composition is provided, the rubber composition comprising the high cis-modified polybutadiene of the second embodiment or the high cis-modified polybutadiene prepared by the method of the first embodiment. According to the third embodiment, the component of the tire comprises a rubber composition, the rubber composition comprising (a) an elastomeric component, the elastomeric component comprising: (i) 10 phr to 100 phr of a high cis-modified polybutadiene polymer according to the second embodiment or a high cis-modified polybutadiene polymer produced by the method of the first embodiment, and (ii) 0 phr to 90 phr of at least one additional polymer selected from the group consisting of unmodified polybutadiene, styrene-butadiene, natural rubber, and polyisoprene; (b) a reinforcing A filler component, the reinforcing filler component comprising: (i) 10 phr-200 phr of a reinforcing silica filler, and (ii) 0 phr-50 phr of a reinforcing carbon black filler, wherein the reinforcing carbon black filler is present in an amount not exceeding 20% ​​by weight of the reinforcing silica filler; (c) a plasticizing component, the plasticizing component comprising: (i) 0 phr-50 phr of at least one plasticizing oil, and (ii) 0 phr-60 phr of at least one hydrocarbon resin having a Tg of at least 30°C; and (d) a curing package.

[0027] definition

[0028] The terms described herein are used only to describe the embodiments and should not be construed to limit the invention as a whole.

[0029] As used herein, the term "living end" (eg, the living end of a polymer chain) is used to refer to a polymeric species having a living end that has not been capped. The living end is capable of reacting with a functionalizing compound and, therefore, can be described as reactive.

[0030] As used herein, the abbreviation Mn is used for number average molecular weight.

[0031] As used herein, the abbreviation Mw is used for weight average molecular weight.

[0032] Unless otherwise specified herein, the term "Mooney viscosity" refers to the Mooney viscosity ML 1+4 As will be appreciated by those skilled in the art, the Mooney viscosity of a rubber is measured prior to vulcanization or curing.

[0033] As used herein, the term "natural rubber" refers to naturally occurring rubber, such as rubber that can be harvested from sources such as the Hevea rubber tree and non-Hevea sources (e.g., guayule shrubs and dandelions such as TKS). In other words, the term "natural rubber" should be interpreted as not including synthetic polyisoprene.

[0034] As used herein, the term "phr" means parts per hundred parts of rubber. One hundred parts of rubber may also be referred to herein as 100 parts of the elastomeric component.

[0035] As used herein, the term "polyisoprene" refers to synthetic polyisoprene. In other words, the term is used to refer to polymers made from isoprene monomers and should not be interpreted to include naturally occurring rubbers (e.g., Hevea natural rubber, guayule-derived natural rubber, or dandelion-derived natural rubber). However, the term "polyisoprene" should be interpreted to include polyisoprene made from natural sources of isoprene monomers.

[0036] As used herein, the term "tread" refers to both that portion of the tire that comes in contact with the road when normally inflated and loaded, and any subtread.

[0037] Method for preparing modified high-cis polybutadiene polymer

[0038] Generally speaking, the method of the first embodiment described herein can be regarded as a solution polymerization method. In this type of polymerization method, the polymerization reaction occurs in an organic solvent-based solution. Here, the organic solvent-based solution initially contains a certain amount of conjugated diene monomers and one of the specified catalyst systems. Generally speaking, according to the method of the first embodiment, the organic solvent-based solution contains 20% by weight (wt%)-90% by weight of organic solvent based on the total weight of monomers, organic solvents and polybutadiene in the solution. Preferably, the organic solvent contains the main component of the solution, i.e., 50% by weight-90% by weight of organic solvent based on the total weight of monomers, organic solvents and polybutadiene, and more preferably 70% by weight to 90% by weight of organic solvent. The solution polymerization method disclosed herein can be contrasted with gas-type or bulk-type polymerization, wherein the polymerization is carried out in the absence of any organic solvent or in the presence of less than 20% by weight of organic solvent based on the total weight of monomers, organic solvents and polybutadiene.

[0039] Organic solvents suitable for the solution polymerization method according to the first embodiment described herein are those 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 alicyclic hydrocarbons. Examples of suitable aromatic hydrocarbon solvents include, but are not limited to, benzene, toluene, ethylbenzene, diethylbenzene, naphthalene, mesitylene, xylene, etc. 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, petroleum spirit, etc. Non-limiting examples of suitable alicyclic hydrocarbon solvents include cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, etc. Mixtures of the above-mentioned aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents and alicyclic hydrocarbon solvents may also be used. In certain embodiments of the first embodiment, preferred organic solvents include aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, or mixtures thereof. Additional available organic solvents suitable for the method of the first embodiment are known to those skilled in the art.

[0040] The solution polymerization process according to the first embodiment disclosed herein is preferably carried out under anaerobic conditions under a blanket of inert gas such as nitrogen, argon or helium. The polymerization temperature can vary widely, ranging from -50°C to 150°C, with a preferred temperature range of 50°C to 120°C. The polymerization pressure can also vary widely, ranging from 1 atmosphere (atm) to 30 atm, preferably 1 atm to 10 atm (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 atm).

[0041] The solution polymerization process according to the first embodiment disclosed herein can be carried out in a continuous, semi-continuous or batch process. In a semi-continuous process, monomer is intermittently charged to replace the monomer that has been polymerized. When the monomer and the lanthanide-based catalyst system (or other catalyst system, as described herein) are all present in an organic solvent-based solution, the polymerization of 1,3-butadiene monomer to high cis-polybutadiene occurs according to the process described herein. The order in which the monomer and catalyst are added to the organic solvent is not important.

[0042] Generally speaking, the polymerization method of the first embodiment as disclosed herein can be stopped by adding any suitable terminator. The non-limiting example of suitable terminator includes protic compounds, such as alcohol, carboxylic acid, mineral acid, water and their mixture. Other suitable terminators are well known to those skilled in the art. In addition, once the polymerization stops, the high cis polydiene obtained can be recovered (or separated) from the solution using conventional methods known to those skilled in the art (for example, steam desolventization or steam distillation, condensation with alcohol, filtration, purification, drying, etc.). In a preferred embodiment of the first embodiment, the high cis polybutadiene polymer is separated by using steam distillation.

[0043] Catalyst system

[0044] As described above, according to the method 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. Using one of the specified catalyst systems in the method of the first embodiment provides the advantage of modifying the active ends of the polymer chains with functionalized compounds, as discussed further below. According to the method of the first embodiment, the catalyst system used avoids the use of anionic initiators (e.g., organic lithium compounds such as n-butyllithium).

[0045] Lanthanide-based catalyst systems

[0046] As described above, the method of the first embodiment can utilize a lanthanide-based catalyst system, which comprises: (i) a lanthanide compound, (ii) an alkylating agent, and (iii) a halogen source, wherein (iii) can be optionally provided by (i), (ii), or both (i) and (ii). The lanthanide-based catalyst system is used to polymerize an amount of conjugated diene monomer (discussed in more detail below) to produce a polymer chain having an active end. Preferably, according to the method of the first embodiment, the lanthanide-based catalyst system is preformed before being added to any solution of the conjugated diene monomer.

[0047] As described above, the lanthanide-based catalyst system used in the method of the first embodiment includes lanthanide compounds. The lanthanide compounds that can be used in the method of the first embodiment are those compounds that contain at least one atom of a lanthanide. As used herein, "lanthanide" refers to the elements present in the lanthanide series (i.e., element numbers 57-71) of the periodic table and didymium, which is a mixture of rare earth elements obtained from monazite sand. Specifically, the lanthanides as 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.

[0048] The lanthanide atom in the lanthanide compound can be in various oxidation states, including but not limited to 0, +2, +3 and +4 oxidation states. According to certain embodiments of the method of the first embodiment, a trivalent lanthanide compound is used, wherein the lanthanide atom is in the +3 oxidation state. Generally speaking, suitable lanthanide compounds for the method 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 phenolates, lanthanide halides, lanthanide pseudohalides, lanthanide oxyhalides and organolanthanide compounds. Preferably, the lanthanide compound is a lanthanide carboxylate, more preferably neodymium carboxylate, and most preferably neodymium versatate.

[0049] According to certain embodiments of the method of the first embodiment, the lanthanide compound can be soluble in a hydrocarbon solvent, such as an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, or an alicyclic hydrocarbon solvent disclosed herein. However, lanthanide compounds that are insoluble in hydrocarbons can also be used in the method of the first embodiment because they can be suspended in the polymerization medium to form a catalytically active species.

[0050] For ease of illustration, further discussion of lanthanide compounds useful in the process of the first embodiment will focus on neodymium compounds, but one skilled in the art will be able to select similar compounds based on other lanthanide metals disclosed herein.

[0051] Examples of suitable neodymium carboxylates for use as lanthanide compounds in the method 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 cyclohexaneate, neodymium stearate, neodymium oleate, neodymium benzoate, and neodymium picolinate.

[0052] Examples of suitable neodymium organophosphates for use as the lanthanide compound in the method of the first embodiment include, but are not limited to, dibutyl neodymium phosphate, diamyl neodymium phosphate, dihexyl neodymium phosphate, diheptyl neodymium phosphate, dioctyl neodymium phosphate, bis(1-methylheptyl) neodymium phosphate, bis(2-ethylhexyl) neodymium phosphate, didecyl neodymium phosphate, didodecyl neodymium phosphate, dioctadecyl neodymium phosphate, dioleyl neodymium phosphate, diphenyl neodymium phosphate, bis(p-nonylphenyl) neodymium phosphate, butyl(2-ethylhexyl) neodymium phosphate, (1-methylheptyl)(2-ethylhexyl) neodymium phosphate, and (2-ethylhexyl)(p-nonylphenyl) neodymium phosphate.

[0053] Examples of suitable neodymium organophosphonates for use as the lanthanide compound in the process of the first embodiment include, but are not limited to, neodymium butylphosphonate, neodymium pentylphosphonate, neodymium hexylphosphonate, neodymium heptylphosphonate, neodymium octylphosphonate, neodymium (1-methylheptyl)phosphonate, neodymium (2-ethylhexyl)phosphonate, neodymium decylphosphonate, neodymium dodecylphosphonate, neodymium octadecylphosphonate, neodymium oleylphosphonate, neodymium phenylphosphonate, neodymium (p-nonylphenyl)phosphonate, neodymium butylbutylphosphonate, neodymium pentylpentylphosphonate, neodymium hexylhexylphosphonate, neodymium heptylheptylphosphonate, neodymium octyloctylphosphonate, neodymium (1-methylheptyl)(1-methylheptyl)phosphonate , (2-ethylhexyl)(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 neodymium and (p-nonylphenyl)(2-ethylhexyl)phosphonate neodymium.

[0054] Examples of suitable neodymium organophosphites for use as the lanthanide compound in the method of the first embodiment include, but are not limited to, neodymium butylphosphite, neodymium amylphosphite, neodymium hexylphosphite, neodymium heptylphosphite, neodymium octylphosphite, neodymium (1-methylheptyl)phosphite, neodymium (2-ethylhexyl)phosphite, neodymium decylphosphite, neodymium dodecylphosphite, neodymium octadecylphosphite, neodymium oleylphosphite, neodymium phenylphosphite, neodymium (p-nonylphenyl)phosphite, neodymium dibutylphosphite, neodymium dipentylphosphite. , neodymium dihexylphosphite, neodymium diheptylphosphite, neodymium dioctylphosphite, neodymium bis(1-methylheptyl)phosphite, neodymium bis(2-ethylhexyl)phosphite, neodymium didecylphosphite, neodymium didodecylphosphite, neodymium dioctadecylphosphite, neodymium dioleylphosphite, neodymium diphenylphosphite, neodymium bis(p-nonylphenyl)phosphite, neodymium butyl(2-ethylhexyl)phosphite, (1-methylheptyl)(2-ethylhexyl)phosphite, and neodymium (2-ethylhexyl)(p-nonylphenyl)phosphite.

[0055] Examples of suitable neodymium carbamates for use as the lanthanide compound in the method of the first embodiment include, but are not limited to, neodymium dimethylcarbamate, neodymium diethylcarbamate, neodymium diisopropylcarbamate, neodymium dibutylcarbamate, and neodymium dibenzylcarbamate.

[0056] Examples of suitable neodymium dithiocarbamates for use as the lanthanide compound in the method of the first embodiment include, but are not limited to, neodymium dimethyldithiocarbamate, neodymium diethyldithiocarbamate, neodymium diisopropyldithiocarbamate, neodymium dibutyldithiocarbamate, and neodymium dibenzyldithiocarbamate.

[0057] Examples of suitable neodymium xanthates for use as the lanthanide compound in the method 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.

[0058] Examples of suitable neodymium beta-diketonates for use as the lanthanide compound in the method 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-heptanedione.

[0059] Examples of suitable neodymium alkoxides or phenoxides for use as the lanthanide compound in the method of the first embodiment include, but are not limited to, neodymium methoxide, neodymium ethoxide, neodymium isopropoxide, neodymium 2-ethylhexoxide, neodymium phenoxide, nonylbenzene neodymium oxide, and neodymium naphthalene oxide.

[0060] Examples of suitable neodymium halides for use as lanthanide compounds in the method 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. Lewis bases, such as tetrahydrofuran ("THF"), may be used as an auxiliary agent to dissolve such neodymium compounds in an inert organic solvent. In the case of using lanthanide halides, lanthanide oxyhalides, or other lanthanide compounds containing halogen atoms, the lanthanide compound may also optionally provide all or part of the halogen source in the lanthanide-based catalyst system.

[0061] As used herein, the term "organolanthate compound" refers to any lanthanide compound containing at least one lanthanide-carbon bond. These compounds are primarily, but not exclusively, those containing cyclopentadienyl ("Cp"), substituted cyclopentadienyl, allyl, and substituted allyl ligands. Suitable organolanthate compounds for use as lanthanide compounds in the method of the first embodiment include, but are not limited to, Cp3Ln, Cp2LnR, Cp2LnCl, CpLnCl2, CpLn(cyclooctatetraene), (C5Me5)2LnR, LnR3, Ln(allyl)3, and Ln(allyl)2Cl, where Ln represents a lanthanide atom and R represents a hydrocarbyl group or a substituted hydrocarbyl group. In one or more embodiments, the hydrocarbyl group or substituted hydrocarbyl group useful in the method of the first embodiment may contain heteroatoms, such as, for example, nitrogen, oxygen, boron, silicon, sulfur, and phosphorus atoms.

[0062] As mentioned above, the lanthanide-based catalyst system employed in the method of the first embodiment comprises an alkylating agent. According to one or more embodiments of the method of the first embodiment, the alkylating agent (also referred to as a hydrocarbylating agent) comprises an organometallic compound that can transfer one or more hydrocarbyl groups to another metal. Generally speaking, these agents include electropositive metals, such as organometallic compounds of Group 1, Group 2, and Group 3 metals (Group IA, IIA, and IIIA metals). Alkylating agents useful in the method of the first embodiment include, but are not limited to, organoaluminum 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, an organoaluminum compound soluble in a hydrocarbon solvent may 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, an organomagnesium compound soluble in hydrocarbons may be used. As will be described in more detail below, certain suitable alkylating agents may be in the form of halogenated compounds. In the case where the alkylating agent comprises a halogen atom, the alkylating agent may also optionally provide all or part of the halogen source in the lanthanide-based catalyst system.

[0063] In one or more embodiments of the method of the first embodiment, the organoaluminum compound utilized comprises a compound of the general formula AlR a n X 3-n Those represented by each R a is independently a monovalent organic group connected to the aluminum atom via a carbon atom; wherein each X is independently a hydrogen atom, a halogen atom, a carboxylate group, an alkoxide group, or an aryloxide group; and wherein n is an integer in the range of 1 to 3. In one or more embodiments, each R a Independently, a hydrocarbyl group or a substituted hydrocarbyl group includes, but is not limited to, alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, aralkyl, alkaryl, allyl, and alkynyl groups, each of which contains 1 carbon atom or the appropriate minimum number of atoms to form the group, 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 groups or substituted hydrocarbyl groups may optionally contain heteroatoms, including, but not limited to, nitrogen, oxygen, boron, silicon, sulfur, and phosphorus atoms.

[0064] In the process of the first embodiment, the alkylating agent used is a compound of the general formula AlR a n X 3-nExamples of the types of organoaluminum compounds represented include, but are not limited to, trialkylaluminum, dialkylaluminum hydride, alkylaluminum dihydride, dialkylaluminum carboxylate, alkylaluminum bis(carboxylate), dialkylaluminum alkoxide, alkylaluminum dialkoxide, dialkylaluminum halide, alkylaluminum dihalide, dialkylaluminum phenolate, and alkylaluminum diphenolate compounds.

[0065] Examples of suitable trihydrocarbyl aluminum compounds for use as the alkylating agent in the process of the first embodiment include, but are not limited to, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tri-n-propyl aluminum, triisopropyl aluminum, tri-n-butyl aluminum, tri-tert-butyl aluminum, tri-n-pentyl aluminum, triphenopenty aluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri(2-ethylhexyl)aluminum, tricyclohexyl aluminum, tri(1-methylcyclopentyl)aluminum, triphenyl aluminum, tri-p-tolylaluminum, tris(2,6-dimethylphenyl)aluminum, tribenzyl aluminum, diethylphenyl aluminum, diethyl-p-tolylaluminum, diethylbenzyl aluminum, ethyldiphenyl aluminum, ethyldi-p-tolylaluminum, and ethyldibenzyl aluminum.

[0066] Examples of suitable dihydrocarbyl aluminum hydride compounds for use as the alkylating agent in the process of the first embodiment include, but are not limited to, 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, Aluminum hydride, phenyl isobutyl aluminum hydride, phenyl-n-octyl aluminum hydride, p-tolyl ethyl aluminum hydride, p-tolyl-n-propyl aluminum hydride, p-tolyl isopropyl aluminum hydride, p-tolyl-n-butyl aluminum hydride, p-tolyl isobutyl aluminum hydride, p-tolyl-n-octyl aluminum hydride, benzyl ethyl aluminum hydride, benzyl-n-propyl aluminum hydride, benzyl isopropyl aluminum hydride, benzyl-n-butyl aluminum hydride, benzyl isobutyl aluminum hydride and benzyl-n-octyl aluminum hydride.

[0067] Examples of suitable hydrocarbyl aluminum hydrides for use as the alkylating agent in this process include, but are not limited to, ethylaluminum dihydride, n-propylaluminum dihydride, isopropylaluminum dihydride, n-butylaluminum dihydride, isobutylaluminum dihydride, and n-octylaluminum dihydride.

[0068] Examples of suitable dihydrocarbyl aluminum halide compounds for use as the alkylating agent in the process of the first embodiment include, but are not limited to, 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, 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.

[0069] Examples of suitable hydrocarbyl aluminum dihalide compounds for use as the alkylating agent 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.

[0070] In the process of the first embodiment, the alkylating agent used is a compound of the general formula AlR a n X 3-n Examples of other suitable organoaluminum compounds include, but are not limited to, dimethylaluminum hexanoate, diethylaluminum octoate, diisobutylaluminum 2-ethylhexanoate, dimethylaluminum neodecanoate, diethylaluminum stearate, diisobutylaluminum oleate, methylaluminum bis(hexanoate), ethylaluminum bis(octoate), isobutylaluminum bis(2-ethylhexanoate), methylaluminum bis(neodecanoate), ethylaluminum bis(stearate), isobutylaluminum bis(oleate), dimethylaluminum methoxide, diethylaluminum methoxide, diisobutylaluminum methoxide, dimethylaluminum ethoxide, diethylaluminum ethoxide, diisobutylaluminum ethoxide, dimethylbenzenealuminum oxide, diethylbenzenealuminum oxide, diisobutylbenzenealuminum oxide, methylaluminum dimethanol, ethylaluminum dimethanol, isobutylaluminum dimethanol, methylaluminum diethoxide, ethylaluminum diethoxide, isobutylaluminum diethoxide, methyldiphenylaluminum oxide, ethyldiphenylaluminum oxide, and isobutyldiphenylaluminum oxide.

[0071] Another class of organoaluminum compounds suitable for use as alkylating agents in the process of the first embodiment is aluminoxanes. Suitable aluminoxanes include oligomeric linear aluminoxanes, which can be represented by the following general formula:

[0072]

[0073] and oligomeric cyclic aluminoxanes, which can be represented by the following general formula:

[0074]

[0075] wherein x is an integer in the range of 1 to 100 (e.g., 1, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100) or 10 to 50 (e.g., 10, 15, 20, 25, 30, 35, 40, 45, or 50); y is an integer in the range of 2 to 100 (e.g., 2, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100) or 3 to 20 (e.g., 3, 5, 10, 15, or 20); and wherein each R is independently a monovalent organic group attached to the aluminum atom via a carbon atom. In one embodiment of the method of the first embodiment, each R is independently a hydrocarbyl group or a substituted hydrocarbyl group, including but not limited to alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, aralkyl, alkaryl, allyl, and alkynyl groups, wherein each group preferably contains 1 carbon atom or the appropriate minimum number of atoms to form the group, 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 groups 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 convention is commonly used in the field of catalyst systems utilizing aluminoxanes.

[0076] Aluminoxane can be prepared by reacting a trihydrocarbylaluminum compound with water. The reaction can be carried out according to a known method, such as, for example, (1) a method in which a trihydrocarbylaluminum compound is dissolved in an organic solvent and then contacted with water, (2) a method in which a trihydrocarbylaluminum compound is reacted with, for example, crystal water contained in a metal salt or water adsorbed in an inorganic or organic compound, or (3) a method in which a trihydrocarbylaluminum compound is reacted with water in the presence of a monomer to be polymerized or a monomer solution.

[0077] Examples of suitable aluminoxane compounds for use as the alkylating agent 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 may be prepared by using techniques known to those skilled in the art with C2 to C 12Hydrocarbyl groups (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C 10 , C 11 or C 12 ), preferably formed by substituting 20% ​​to 80% of the methyl groups of methylaluminoxane with isobutyl groups.

[0078] According to certain embodiments of the method of the first embodiment, 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 aluminoxane (e.g., AlR a n X 3-n ) is used as an alkylating agent in combination with an organoaluminum compound represented by . According to this embodiment and other embodiments, the alkylating agent includes a dihydrocarbyl aluminum hydride, a dihydrocarbyl aluminum halide, an aluminoxane, or a combination thereof. For example, according to one embodiment, the alkylating agent includes diisobutyl aluminum hydride, diethyl aluminum chloride, methylaluminoxane, or a combination thereof. U.S. Pat. No. 8,017,695 (the entire text of which is incorporated herein by reference) provides other examples in which aluminoxane and an organoaluminum compound can be used in combination.

[0079] As described above, suitable alkylating agents for use in the method of the first embodiment include organomagnesium compounds. According to one or more embodiments of the method of the first embodiment, suitable organomagnesium compounds include compounds of the general formula MgR b 2 represents those where each R b is independently a monovalent organic group connected to the magnesium atom via a carbon atom. In one or more embodiments, each R b Independently, a hydrocarbyl group or a substituted hydrocarbyl group includes, but is not limited to, an alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl, aryl, allyl, substituted aryl, aralkyl, alkaryl, and alkynyl group, each of which preferably contains 1 carbon atom or the appropriate minimum number of atoms to form the group, 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 groups or substituted hydrocarbyl groups may also optionally contain heteroatoms, including, but not limited to, nitrogen, oxygen, silicon, sulfur, and phosphorus atoms.

[0080] In the process of the first embodiment, the alkylating agent used is a sulfhydryl group having the general formula MgR b Examples of suitable organomagnesium compounds represented by 2 include, but are not limited to, diethylmagnesium, di-n-propylmagnesium, diisopropylmagnesium, dibutylmagnesium, dihexylmagnesium, diphenylmagnesium, and dibenzylmagnesium.

[0081] Another class of organomagnesium compounds suitable for use as alkylating agents according to an embodiment of the method of the first embodiment is composed of the general formula R c MgX c Indicates that R c is a monovalent organic group connected to the magnesium atom via a carbon atom, and X is a hydrogen atom, a halogen atom, a carboxylate group, an alkoxide group, or an aryloxy group. c is a hydrocarbyl group or a substituted hydrocarbyl group, including, but not limited to, alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl, aryl, allyl, substituted aryl, aralkyl, alkaryl, and alkynyl groups, each of which contains 1 carbon atom or the appropriate minimum number of atoms to form the group, 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 groups 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 aryloxy group, wherein each group contains 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).

[0082] In the process of the first embodiment, the alkylating agent used is a c MgX c Examples of suitable types of organomagnesium compounds include, but are not limited to, hydrocarbylmagnesium hydrides, hydrocarbylmagnesium halides, hydrocarbylmagnesium carboxylates, hydrocarbylmagnesium alkoxides, and hydrocarbylmagnesium aryloxides.

[0083] In the process of the first embodiment, the alkylating agent used is a c MgX c Examples of suitable organomagnesium compounds include, but are not limited to, methylmagnesium hydride, ethylmagnesium hydride, butylmagnesium hydride, hexylmagnesium hydride, phenylmagnesium hydride, benzylmagnesium hydride, methylmagnesium chloride, ethylmagnesium chloride, butylmagnesium chloride, hexylmagnesium chloride, phenylmagnesium chloride, benzylmagnesium chloride, methylmagnesium bromide, ethylmagnesium bromide, butylmagnesium bromide, hexylmagnesium bromide, phenylmagnesium bromide, benzylmagnesium bromide, methylmagnesium hexanoate, ethylmagnesium hexanoate, butylmagnesium hexanoate, hexylmagnesium hexanoate, phenylmagnesium hexanoate, benzylmagnesium hexanoate, methylmagnesium ethoxide, ethylmagnesium ethoxide, butylmagnesium ethoxide, hexylmagnesium ethoxide, phenylmagnesium ethoxide, benzylmagnesium ethoxide, methylmagnesium oxide, ethylmagnesium oxide, butylmagnesium oxide, hexylmagnesium oxide, phenylmagnesium oxide, and benzylmagnesium oxide.

[0084] As described above, the lanthanide-based catalyst system employed in the method of the first embodiment comprises a halogen source. As used herein, the term "halogen source" refers to any substance comprising at least one halogen atom. According to one or more embodiments of the method of the first embodiment, all or part of the halogen source may optionally be provided by a lanthanide compound, an alkylating agent, or both a lanthanide compound and an alkylating agent. In other words, the lanthanide compound can be used as both the lanthanide compound and all or at least a portion of the halogen source. Similarly, the alkylating agent can be used as both the alkylating agent and all or at least a portion of the halogen source.

[0085] According to certain embodiments of the method 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 different halogen-containing compounds. Various compounds containing one or more halogen atoms or mixtures thereof can be used as halogen sources. Examples of halogen atoms include, but are not limited to, fluorine, chlorine, bromine and iodine. Combinations of two or more halogen atoms can also be used. Halogen-containing compounds soluble in organic solvents (such as aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbon solvents disclosed herein) are suitable for use as halogen sources in the method of the first embodiment. In addition, hydrocarbon-insoluble halogen-containing compounds that can be suspended in the polymerization system to form catalytically active substances can also be used in certain embodiments of the method of the first embodiment.

[0086] Examples of suitable types of halogen-containing compounds used in the method 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 method of the first embodiment, the halogen-containing compound comprises an organometallic halide.

[0087] Examples of elemental halogens suitable for use as halogen sources in the method 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.

[0088] Examples of suitable hydrogen halides for use as a halogen source in the disclosed methods include, but are not limited to, hydrogen fluoride, hydrogen chloride, hydrogen bromide, and hydrogen iodide.

[0089] Examples of suitable organic halides for use as a halogen source in the method of the first embodiment include, but are not limited to, tert-butyl chloride, tert-butyl bromide, allyl chloride, allyl bromide, benzyl chloride, benzyl bromide, chloro-diphenylmethane, bromo-diphenylmethane, triphenylmethyl chloride, triphenylmethyl bromide, benzal chloride, benzal bromide, methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, trimethylchlorosilane, benzoyl chloride, benzoyl bromide, propionyl chloride, propionyl bromide, methyl chloroformate, and methyl bromoformate.

[0090] Examples of suitable inorganic halides for use as a halogen source in the method 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.

[0091] Examples of suitable metal halides for use as a halogen source in the method 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.

[0092] Examples of suitable organometallic halides for use as a halogen source in the process of the first embodiment include, but are not limited to, dimethylaluminum chloride, diethylaluminum chloride, dimethylaluminum bromide, diethylaluminum bromide, dimethylaluminum fluoride, diethylaluminum fluoride, methylaluminum dichloride, ethylaluminum dichloride, methylaluminum dibromide, ethylaluminum dibromide, methylaluminum difluoride, ethylaluminum difluoride, sesquimethylaluminum chloride, sesquiethylaluminum chloride, sesquiisobutylaluminum chloride, methylmagnesium chloride, methylmagnesium bromide, methylmagnesium iodide, ethylmagnesium chloride, ethylmagnesium bromide, butylmagnesium chloride, butylmagnesium bromide, phenylmagnesium chloride, phenylmagnesium bromide, benzylmagnesium chloride, trimethyltin chloride, trimethyltin bromide, triethyltin chloride, triethyltin bromide, di-tert-butyltin dichloride, di-tert-butyltin dibromide, dibutyltin dichloride, dibutyltin dibromide, tributyltin chloride, and tributyltin bromide. According to one embodiment, the halogen source comprises an organometallic halide. For example, according to certain embodiments, the halogen source includes diethylaluminum chloride, which, as described above, can also be used as an alkylating agent in a lanthanide-based catalyst system. Thus, according to certain embodiments of the method of the first embodiment, the halogen source can be provided in whole or in part by an alkylating agent in the catalyst system disclosed herein.

[0093] The lanthanide-based catalyst system used in the method of the first embodiment can be formed by combining or mixing the above-mentioned catalyst components. As referred to herein, the terms "catalyst composition" and "catalyst system" encompass simple mixtures of the components, composites of the various components caused by physical or chemical attraction, chemical reaction products of the components, or combinations of the above-mentioned components. The terms "catalyst composition" and "catalyst system" are used interchangeably herein.

[0094] Nickel-based catalyst system

[0095] As mentioned above, the process of the first embodiment can utilize 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. The specific compounds used for each of (i), (ii), and (iii) can vary.

[0096] According to the method of the first embodiment, the nickel compound used in the nickel-based catalyst system can be varied. The nickel atom in the nickel-containing compound can be various oxidation states, including but not limited to 0, +2, +3 and +4 oxidation states. The suitable nickel-containing compound used in the nickel-based catalyst system according to the method of the first embodiment includes but is not limited to nickel carboxylates, nickel carboxylates, nickel borate, nickel organophosphates, nickel organophosphonates, nickel organophosphinates, nickel carbamates, nickel dithiocarbamates, nickel xanthates, nickel beta-diketonates, nickel alkoxides or nickel aryls, nickel halides, nickel quasi-halides, nickel oxyhalides and organic nickel compounds. In a preferred embodiment of the method of the first embodiment, when using a nickel-based catalyst system, the nickel compound is a nickel carboxylate.

[0097] 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.

[0098] Suitable nickel carboxylborates may include compounds defined by the formula (RCOONiO)3B or (RCOONiO)2B(OR), wherein each R, which may be the same or different, is a hydrogen atom or a monovalent organic group. In one embodiment, each R may be a hydrocarbyl group such as, but not limited to, an alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, aralkyl, alkaryl, allyl, and alkynyl groups, wherein each group preferably contains carbon atoms from 1 carbon atom (or the appropriate minimum number of carbon atoms to form the group) up to about 20 carbon atoms. These hydrocarbyl groups may contain heteroatoms such as, but not limited to, nitrogen, oxygen, silicon, sulfur, and phosphorus atoms. Nickel carboxylborates may include those disclosed in U.S. Pat. No. 4,522,988, which is incorporated herein by reference. Specific examples of the nickel carboxylate borate include nickel (II) neodecanoate borate, nickel (II) hexanoate borate, nickel (II) naphthenate borate, nickel (II) stearate borate, nickel (II) octanoate borate, nickel (II) 2-ethylhexanoate borate, and mixtures thereof.

[0099] Suitable nickel organophosphates may include dibutyl nickel phosphate, diamyl nickel phosphate, dihexyl nickel phosphate, diheptyl nickel phosphate, dioctyl nickel phosphate, bis(1-methylheptyl) nickel phosphate, bis(2-ethylhexyl) nickel phosphate, didecyl nickel phosphate, didodecyl nickel phosphate, dioctadecyl nickel phosphate, dioleyl nickel phosphate, diphenyl nickel phosphate, bis(p-nonylphenyl) nickel phosphate, butyl(2-ethylhexyl) nickel phosphate, (1-methylheptyl)(2-ethylhexyl) nickel phosphate, and (2-ethylhexyl)(p-nonylphenyl) nickel phosphate.

[0100] Suitable nickel organic phosphonates may include nickel butylphosphonate, nickel pentylphosphonate, nickel hexylphosphonate, nickel heptylphosphonate, nickel octylphosphonate, nickel (1-methylheptyl)phosphonate, nickel (2-ethylhexyl)phosphonate, nickel decylphosphonate, nickel dodecylphosphonate, nickel octadecylphosphonate, nickel oleylphosphonate, nickel phenylphosphonate, nickel (p-nonylphenyl)phosphonate, nickel butylbutylphosphonate, nickel pentylpentylphosphonate, nickel hexylhexylphosphonate, nickel heptylheptylphosphonate, nickel octyloctylphosphonate, nickel (1-methylheptyl)(1-methylheptyl)phosphonate, nickel (2-ethylhexyl)(2-ethylhexyl)phosphonate, nickel ...octylphosphonate, nickel octylphosphonate, nickel octylphosphonate, nickel octylphosphonate, nickel octylphosphonate, nickel octylphosphonate, nickel octylphosphonate, nickel Nickel butyl (2-ethylhexyl) phosphonate, nickel (2-ethylhexyl) phosphonate, nickel butyl (2-ethylhexyl) phosphonate, nickel (1-methylheptyl) (2-ethylhexyl) phosphonate, nickel (2-ethylhexyl) (1-methylheptyl) phosphonate, nickel (2-ethylhexyl) (p-nonylphenyl) phosphonate, and nickel (p-nonylphenyl) (2-ethylhexyl) phosphonate.

[0101] Suitable nickel organic phosphinates may include nickel butylphosphinate, nickel amylphosphinate, 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 diamylphosphinate, nickel dihexylphosphinate, nickel diheptylphosphinate The invention also includes nickel bis(butyl)phosphinate, nickel bis(2-ethylhexyl)phosphinate, 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.

[0102] Suitable nickel carbamates may include nickel dimethyl carbamate, nickel diethyl carbamate, nickel diisopropyl carbamate, nickel dibutyl carbamate, and nickel dibenzyl carbamate.

[0103] Suitable nickel dithiocarbamates may include nickel dimethyldithiocarbamate, nickel diethyldithiocarbamate, nickel diisopropyldithiocarbamate, nickel dibutyldithiocarbamate, and nickel dibenzyldithiocarbamate.

[0104] Suitable nickel xanthates include nickel methyl xanthate, nickel ethyl xanthate, nickel isopropyl xanthate, nickel butyl xanthate and nickel benzyl xanthate.

[0105] Suitable nickel beta-diketonates may include nickel acetylacetonate, nickel trifluoroacetylacetonate, nickel hexafluoroacetylacetonate, nickel benzoylacetonate, and nickel 2,2,6,6-tetramethyl-3,5-heptanedione.

[0106] Suitable nickel alkoxides or nickel aryloxides may include nickel methoxide, nickel ethoxide, nickel isopropoxide, nickel 2-ethylhexoxide, nickel phenoxide, nickel nonylphenoxide, and nickel naphthoxide.

[0107] Suitable nickel halides may include nickel fluoride, nickel chloride, nickel bromide and nickel iodide. Pseudo-nickel halides include nickel cyanide, nickel cyanate, nickel thiocyanate, nickel azide and nickel ferrocyanide. Nickel oxyhalides include nickel oxyfluoride, nickel oxychloride and nickel oxybromide. In the case where nickel halides, nickel oxyhalides or other nickel-containing compounds contain unstable fluorine or chlorine atoms, nickel-containing compounds may also be used as fluorine-containing compounds or chlorine-containing compounds. Lewis bases such as alcohols may be used as dissolution aids for such compounds.

[0108] The term organonickel compound may refer to any nickel compound containing at least one nickel-carbon bond. Organonickel compounds include bis(cyclopentadienyl)nickel (also known as nickelocene), bis(pentamethylcyclopentadienyl)nickel (also known as decamethylnickelocene), bis(tetramethylcyclopentadienyl)nickel, bis(ethylcyclopentadienyl)nickel, bis(isopropylcyclopentadienyl)nickel, bis(pentadienyl)nickel, bis(2,4-dimethylpentadienyl)nickel, (cyclopentadienyl)(pentadienyl)nickel, bis(1,5-cyclooctadienyl)nickel, bis(allyl)nickel, bis(methallyl)nickel, and bis(crotonyl)nickel.

[0109] According to the method of the first embodiment, the organoaluminum, organomagnesium compound, organozinc compound or combination thereof used for the (ii) component of the nickel-based catalyst system may vary. In a preferred embodiment, when the method of the first embodiment utilizes a nickel-based catalyst system, component (ii) is an organoaluminum or organomagnesium compound, more preferably an organoaluminum compound. When the organoaluminum, organomagnesium or organozinc compound includes unstable fluorine, it may also be used as a fluorine-containing compound (no separate fluorine-containing compound is required). In certain embodiments, the organoaluminum, organomagnesium or organozinc compound does not contain chlorine or bromine atoms.

[0110] Suitable compounds for use as the organoaluminum compound or the organomagnesium compound in the nickel-based catalyst system are discussed above in the section regarding the lanthanide-based catalyst system.

[0111] According to the method of the first embodiment, the fluorine-containing compound used in the nickel-based catalyst system can vary. Suitable fluorine-containing compounds can include various compounds containing one or more unstable fluorine atoms or their mixtures. In one or more embodiments, the fluorine-containing compound is soluble in a hydrocarbon solvent. In other embodiments, it may be useful to suspend in the polymerization medium to form a catalytically active material that is insoluble in hydrocarbons.

[0112] 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 employed. Specific examples of these complexes include complexes of boron trifluoride and hydrogen fluoride with Lewis bases.

[0113] The halogenated fluoride may include iodine monofluoride, iodine trifluoride, and iodine pentafluoride.

[0114] The organic fluoride may include tert-butyl fluoride, allyl fluoride, benzyl fluoride, fluorodiphenylmethane, triphenylmethyl fluoride, benzal fluoride, methyltrifluorosilane, phenyltrifluorosilane, dimethyldifluorosilane, diphenyldifluorosilane, trimethylfluorosilane, benzoyl fluoride, propionyl fluoride, and methylfluoroformate.

[0115] The inorganic fluoride may include phosphorus trifluoride, phosphorus pentafluoride, phosphorus oxyfluoride, boron trifluoride, silicon tetrafluoride, arsenic trifluoride, selenium tetrafluoride, and tellurium tetrafluoride.

[0116] The metal fluorides may include tin tetrafluoride, aluminum trifluoride, antimony trifluoride, antimony pentafluoride, gallium trifluoride, indium trifluoride, titanium tetrafluoride, and zinc difluoride.

[0117] The organometallic fluoride may 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-tert-butyltin difluoride, dibutyltin difluoride, and tributyltin fluoride.

[0118] As mentioned above, when the method of the first embodiment utilizes a nickel-based catalyst system, the nickel compound can be used in combination with an alcohol. Various alcohols and their mixtures can be used. In one or more embodiments, the alcohol includes a monohydric alcohol (that is, those comprising a hydroxyl group), and in other embodiments, the alcohol includes a polyhydric alcohol (that is, those comprising two or more hydroxyl groups), including a dihydric alcohol (which can be referred to as a glycol or a dihydric alcohol), a trihydric alcohol (which can be referred to as glycerol) and a polyhydric alcohol. In one or more embodiments, the alcohol includes a primary alcohol and / or a secondary alcohol. Primary alcohols and secondary alcohols include those alcohols in which the α-carbon (that is, the carbon adjacent to the carbon comprising the hydroxyl group) is a primary carbon or a secondary carbon. In certain preferred embodiments, when using a nickel-based catalyst system, a monohydric alcohol is used, preferably hexanol.

[0119] The alcohol may include aliphatic alcohols, including straight or branched chain alcohols. In other embodiments, the alcohol may include cyclic alcohols, in other embodiments may include aromatic alcohols, in other embodiments may include heterocyclic alcohols, and in other embodiments may include polycyclic alcohols.

[0120] 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 occurs.

[0121] In one or more embodiments, available alcohol can be represented by the formula R-OH, wherein R is a monovalent organic group, and-OH is a hydroxyl group. The monovalent organic group can include a hydrocarbyl group or a substituted hydrocarbyl group, such as but not limited to: alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl, aryl, allyl, substituted aryl, aralkyl, alkaryl and alkynyl groups. The substituted group includes those groups in which the hydrogen atom of the group itself is replaced by a monovalent organic group. These hydrocarbyl groups may include heteroatoms, such as but not limited to nitrogen, oxygen, silicon, tin, sulfur, boron and phosphorus atoms. In certain embodiments, the hydrocarbyl group may not contain halogen atoms, such as chlorine or bromine atoms. In certain embodiments, the monovalent organic group may contain one or more hydroxyl groups connected thereto. Therefore, alcohol may include two or more hydroxyl groups. In other embodiments, the hydrocarbyl group does not contain heteroatoms.

[0122] In one or more embodiments, useful alcohols include hydrocarbon groups of 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.

[0123] Exemplary aliphatic alcohols include methanol, ethanol, propanol, isopropanol, n-butanol, tert-butanol, isobutanol, n-pentanol, n-hexanol, 2-ethylhexanol, n-heptanol, octanol, decanol, and mixtures thereof.

[0124] Exemplary cyclic alcohols include cyclohexanol, methanol, tert-butyl cyclohexanol, cyclopentanol, cycloheptanol, cyclooctanol, and mixtures thereof.

[0125] Exemplary unsaturated alcohols include allyl alcohol and mixtures thereof.

[0126] Exemplary aromatic alcohols include substituted phenols, phenol, benzyl alcohol, and mixtures thereof.

[0127] Exemplary heterocyclic alcohols include furanol and mixtures thereof.

[0128] Exemplary polycyclic alcohols include sterols and mixtures thereof.

[0129] The aforementioned catalyst composition can have high catalytic activity to polymerize conjugated dienes into stereospecific polydienes over a wide range of catalyst concentrations and catalyst component ratios. It is believed that the catalyst components can interact with each other to form active catalyst species. It is also believed that the optimal concentration of any one catalyst component may depend on the concentration of the other catalyst components.

[0130] In one or more embodiments, the molar ratio of the (ii) component to the nickel-containing compound may vary from about 1:1 to about 200:1, in other embodiments from about 3:1 to about 30:1, and in other embodiments from about 5:1 to about 15:1. As used herein, the term molar ratio refers to the ratio of equivalents of the relevant components of the ingredients, for example, 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, where difunctional or multifunctional compounds (e.g., those compounds containing two or more carboxylic acid groups) are employed, fewer moles of the compound are required to achieve the desired equivalent ratio.

[0131] 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.

[0132] 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 relevant components of the ingredients, for example, the ratio of equivalents of chlorine atoms on the chlorine-containing compound to equivalents of nickel atoms on the nickel-containing compound.

[0133] Generally speaking, nickel-based catalyst systems can be formed by combining or mixing catalyst ingredients. Although it is believed that active catalyst species are produced by such combination, the extent of interaction or reaction between the various ingredients or components is not clear. Therefore, the term "catalyst system" has been used to cover a simple mixture of the ingredients, a complex of the ingredients caused by physical or chemical attraction, a chemical reaction product of the ingredients, or a combination of the above.

[0134] 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 can be formed in situ by adding each catalyst component to a solution containing monomer and solvent in a stepwise or simultaneous manner or adding to a simple bulk monomer. In one embodiment, a mixture of (ii) component, nickel-containing compound and alcohol (when present) is formed. The mixture can be formed in a solvent. The mixture and fluorine-containing compound can then be added to the monomer to be polymerized.

[0135] In one or more embodiments, the selected catalyst components of the nickel-based catalyst system can be premixed outside the polymerization system at an appropriate temperature, which can be from about -20°C to about 80°C, and the resulting catalyst system can be aged for a period of time ranging from a few seconds to a few days before adding to the monomer.

[0136] In one or more embodiments, (ii) component, nickel-containing compound and alcohol (when present) mixture is formed in the presence of a small amount of monomer and optional solvent. That is, the selected catalyst component can be formed in the presence of a small amount of conjugated diene monomer at an appropriate temperature, which can be about -20 ° C to about 80 ° C. The amount of conjugated diene monomer that can be used to form the mixture can be from about 1 mol / mol nickel-containing compound to about 500 mol / mol nickel-containing compound, from about 5 mol / mol nickel-containing compound to about 250 mol / mol nickel-containing compound in other embodiments, and from about 10 mol / mol nickel-containing compound to about 100 mol / mol nickel-containing compound in other embodiments. The resulting composition can be aged for a period of time in the range of a few seconds to a few days, and then added to the remainder of the conjugated diene monomer to be polymerized with the fluorine-containing compound.

[0137] When a solution of a nickel-based catalyst system or one or more catalyst components thereof is prepared outside a polymerization system as shown in the above method, an organic solvent or carrier may be used. An organic solvent may be used to dissolve the catalyst composition or component, or the solvent may simply be used as a carrier in which the catalyst composition or component may be suspended. The organic solvent may be inert to the catalyst composition. Available solvents include hydrocarbon solvents, such as aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic 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, petroleum spirit, etc. Moreover, non-limiting examples of alicyclic hydrocarbon solvents include cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, etc. Commercial mixtures of the above hydrocarbons may also be used.

[0138] Cobalt-based catalyst systems

[0139] As mentioned above, the process of the first embodiment can utilize a cobalt-based catalyst system comprising: (i) a cobalt compound, (ii) an organic aluminum halide, and (iii) optionally water. The specific compounds used for each of (i) and (ii) can vary.

[0140] Suitable cobalt compounds for the cobalt-based catalyst system include, but are not limited to, cobalt benzoate, cobalt acetate, cobalt borate, cobalt naphthenate, bis(α-furanyldioxime)cobalt, cobalt hexanoate, cobalt octoate, cobalt oxalate, cobalt tartrate, cobalt sorbate, cobalt adipate, cobalt palmitate, cobalt stearate, cobalt acetylacetonate, bis(salicylic aldehyde ethylene diimide)cobalt, salicylaldehyde cobalt, octacarbonyl dicobalt, and mixtures thereof. According to a preferred embodiment, when the method of the first embodiment uses a cobalt-based catalyst system, the cobalt compound is a cobalt salt (the cobalt salt contains two monovalent anions or one divalent anion). The anion in the cobalt salt is preferably derived from C6-C 20 Organic acid.

[0141] Suitable organoaluminum halide compounds for cobalt-based catalyst systems include, but are not limited to, those discussed above for lanthanide-based catalyst systems. Suitable examples of organoaluminum halide compounds as discussed above include dihydrocarbyl aluminum halides and hydrocarbyl aluminum dihalides.

[0142] Preferably, the organoaluminum halide compound comprises a compound having the formula:

[0143] R 5 p AlX q

[0144] Where: R5 C2-C 12 An alkyl group, X is halogen, and p+q is 3.

[0145] More preferably, the organoaluminum halide compound is selected from the group consisting of diorgano (preferably dialkyl)aluminum chloride compounds, alkylaluminum sesquichloride compounds and mixtures thereof.

[0146] Even more preferably, the organoaluminum halide compound is selected from: (I) a mixture of: (a) an alkylaluminum chloride selected from diethylaluminum chloride and ethylaluminum sesquichloride (this can be achieved by including a mixture of diethylaluminum chloride and ethylaluminum dichloride in approximately equimolar amounts), and (b) an organoaluminum compound of formula R3Al, wherein R is C8-C 12 an alkyl group (eg, trioctylaluminum, tridecylaluminum, etc.); and (II) an alkylaluminum chloride, wherein the alkyl group has 8 to 12 carbon atoms (eg, dioctylaluminum chloride, didecylaluminum chloride, etc.).

[0147] Embodiment (I) is more preferred. In this preferred embodiment, it is particularly preferred to use an organoaluminum compound of formula R3Al, which is present in an amount of 0 wt % to 1 wt % of the mixture of (I) and (II). Particularly preferred organoaluminum compounds of formula R3Al include trioctyl aluminum.

[0148] The preferred catalyst system for the process of the present invention comprises a cobalt salt selected from cobalt octoate and cobalt naphthenate, and an organoaluminum halide compound selected from the group consisting of: (i) a mixture of diethylaluminum chloride and one or more of trioctylaluminum, tridecylaluminum and tridodecylaluminum, and (ii) one or more of dioctylaluminum chloride, didecylaluminum chloride and docosylaluminum chloride.

[0149] When a cobalt-based catalyst system is used in the process of the first embodiment, the ratio of components (i), (ii) and (iii) may vary. In certain embodiments, the molar ratio of the cobalt compound to the total organoaluminum halide (e.g., diethylaluminum chloride to trioctylaluminum) is from about 1:15 to about 1:30 (e.g., 1:15, 1:20, 1:25 or 1:30), preferably from about 1:15 to about 1:20 (e.g., 1:15, 1:16, 1:17, 1:18, 1:19 or 1:20), and the halide (e.g., chlorine in diethylaluminum chloride) to the organoaluminum halide is about 1:15 to about 1:20 (e.g., 1:15, 1:16, 1:17, 1:18, 1:19 or 1:20). The molar ratio of the total metal content in the aluminum halide (e.g., diethylaluminum chloride plus aluminum in trioctylaluminum) is from 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 from 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 from about 0.3 to about 0.8 (e.g., 0.4:1, 0.5:1, 0.6, 0.7, or 0.8), preferably from about 0.5 to about 0.65 (e.g., 0.5, 0.55, 0.6, or 0.65) millimoles per millimole of the organic aluminum halide used.

[0150] Functionalized compounds

[0151] As discussed above, the method of the first embodiment includes reacting an active terminal polymer chain with a functionalized compound of formula (I). Also as discussed above, according to the second and third embodiments, the modified high cis polybutadiene polymer comprises a polymer chain produced by the polymerization of 1,3-butadiene, which is bonded to a residue of a functionalized compound having formula (I), wherein each polymer chain is bonded to the residue of the functionalized compound through an X group. In preferred embodiments of the first to third embodiments, the only functionalized compound used to prepare the modified high cis polybutadiene is a functionalized compound of formula (I). It is noteworthy that in such embodiments, no dialkoxysilane compound or monoalkoxysilane compound (e.g., no cyano-alkylene-alkyl-dialkoxysilane and no cyano-alkylene-dialkylmonoalkoxysilane) is used as a functionalized compound for polybutadiene or otherwise present as a residue on the modified high cis polybutadiene.

[0152] According to the first to third embodiments, formula (I) is as follows:

[0153]

[0154] Where X is a cyano group, R 1 Independently selected from C1-C 20 , preferably C1-C10 , more preferably C1-C3 alkylene, wherein each of the foregoing optionally contains an unsaturated carbon-carbon bond, each R' is independently selected from C1-C 20 Alkoxy, preferably C1-C 10 In certain embodiments of the first to third embodiments, the functionalized compound of formula (I) has a 1 and R' are both selected from the structure of the group as described in the preferred embodiment. In other embodiments of the first embodiment to the third embodiment, the functionalized compound of formula (I) has a structure in which R 1 and R' are both selected from the structure of the group as described in the preferred embodiment. Since the functionalized compound of formula (I) has three alkoxy groups on Si, the compound can be referred to as trialkoxysilane. 1 Being a hydrocarbylene group means that it is bonded to two other elements (i.e., the X group and Si). In certain preferred embodiments of the first to third embodiments, R 1 Is aliphatic and unsaturated. In other embodiments of the first to third embodiments, R 1 is aliphatic and may include one unsaturated carbon-carbon bond. Generally speaking, according to the first to third embodiments, R 1 The carbons in the group may be positioned in a straight chain configuration or may be branched.

[0155] As mentioned above, according to the first to third embodiments, X (or a residue produced therefrom) of the functionalized compound of formula (I) is a cyano group. According to certain embodiments of the first to third embodiments, non-limiting examples of suitable cyano groups that can be used as X in formula (I) include compounds in which the cyano group and Si are separated by a hydrocarbylene group having 1-20 carbons, preferably 1-10 carbons, and more preferably 1-3 carbons. According to certain embodiments of the first to third embodiments, non-limiting examples of suitable cyano groups that can be used as X in formula (I) include 2-cyanoethyltriethoxysilane (CETEOS), 2-cyanoethyltrimethoxysilane (CETMOS), 3-cyanopropyltriethoxysilane (CPTEOS) and 3-cyanopropyltrimethoxysilane (CPTMOS).

[0156] According to the first to third embodiments, the polymer chain (which is produced by the polymerization of 1,3-butadiene using one of the defined catalyst systems) is bonded to the functionalized compound through the X group. Since the structure of the functionalized compound will change to some extent when the polymer chain is bonded to the X group, the portion to which the polymer chain is bonded is described as the residue of the functionalized compound. Generally speaking, one polymer chain will be bonded to the residue of the functionalized compound through the X group of each molecule of the functionalized compound. More than one polymer chain may be bonded to the residue of the functionalized compound. The position at which the polymer chain is bonded to the functionalized compound according to the method of the first embodiment (i.e., using one of the defined catalyst systems) can be contrasted with the position at which the polymer chain will be bonded to the functionalized compound if 1,3-butadiene is polymerized using an anionic initiator (e.g., n-butyllithium). More specifically, if an anionic initiator is used, the polymer chain can be bonded to the functionalized compound via the alkoxy group on Si (OR replacing the OR alkoxy group and directly bonded to Si) and through the X group. When one of the defined catalyst systems is used to polymerize 1,3-butadiene and produce living terminal polymer chains, the polymer chains are bonded to the functionalized compound (only) via the X group.

[0157] According to the first to third embodiments, the amount of the functionalized compound of formula (I) used to react with the active terminal polymer chain (i.e., according to the method of the first embodiment) or to be 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 functionalized compound is in an amount 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, 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, 2:1, 1:1, 0.5:1), preferably 50:1 to 1:1 (e.g., 1, 6:1, 4:1, 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) molar ratio based on the number of moles of functionalized compound to the number of moles of primary metal in the catalyst system (the number of moles of lanthanide for a lanthanide-based catalyst system, the number of moles of nickel for a nickel-based catalyst system, or the number of moles of cobalt for a cobalt-based catalyst system).

[0158] Stabilizer

[0159] As mentioned above, according to the process of the first embodiment, the modified high-cis polybutadiene (from step C) is reacted with a stabilizer of formula (II) as follows:

[0160] R 2 n Si(OR 3 ) 4-n

[0161] Where R 2 Choose from C1 to C 20 Alkyl, C4 to C 10 Cycloalkyl or C5 to C 20 The group consisting of aromatic groups; preferably selected from C1 to C 10 Alkyl, C4 to C6 cycloalkyl or C6 to C 14 and more preferably selected from the group consisting of C1 to C6 alkyl, C4 to C6 cycloalkyl or C6 aromatic groups, wherein R 3 Can be used with R 2 The same or different and selected from C1 to C 20 Alkyl, C4 to C 10 Cycloalkyl or C5 to C 20 Aromatic group; preferably selected from C1 to C 10 Alkyl, C4 to C6 cycloalkyl or C6 to C 14 and more preferably selected from the group consisting of C1 to C6 alkyl, C4 to C6 cycloalkyl or C6 aromatic groups, and n is an integer from 1 to 3, preferably from 2 to 3, more preferably 3. In certain embodiments of the method of the first embodiment, the stabilizer of formula (II) has R selected from the aforementioned preferred groups or values 2 , R 3 In other embodiments of the method of the first embodiment, the stabilizer of formula (II) has R selected from the aforementioned more preferred groups or values 2 , R 3 In a particularly preferred embodiment of the method of the first embodiment, the stabilizer is a trialkoxy(alkyl)silane (ie, n is 3 and R 2 is an alkyl group, as described above), wherein octyltriethoxysilane is particularly preferred. According to the method of the first embodiment, a stabilizer of formula (II) is added after (C) but before (E), i.e., before separating the modified high cis polybutadiene. The use of a stabilizer can be advantageous in preparing a modified high cis polybutadiene polymer that produces improved snow or ice performance in a tire tread comprising the modified high cis polybutadiene polymer. As will be appreciated by those skilled in the art, the snow or ice performance of the 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 preferred performance.

[0162] According to the method of the first embodiment, the amount of stabilizer used in the method can vary. In certain embodiments of the first embodiment, the stabilizer is used in an amount 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 1, 4:1, 4.5:1 or 5:1), more preferably 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) molar ratio based on the number of moles of stabilizer: the number of moles of functionalized compound.

[0163] Quencher

[0164] As mentioned above, according to the method of the first embodiment, a quencher of formula (III) is used in combination with a stabilizer of formula (II). According to the method of the first embodiment, the formula (III) of the quencher is as follows:

[0165] R 4 COOH

[0166] Where R 4 Selected from H and C1 to C 18 The group consisting of alkyl groups is preferably selected from H and C1 to C 10 In certain preferred embodiments of the first embodiment, the quencher comprises 2-ethylhexanoic acid or acetic acid, more preferably 2-ethylhexanoic acid; in certain such embodiments, the quencher consists of 2-ethylhexanoic acid.

[0167] Properties of modified high cis polybutadiene polymers

[0168] As mentioned above, the process of the first embodiment produces 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 at least 20-100, preferably 30-80 or 40-80, more preferably 40 to 70 at 100°C. 1+4and an aged Mooney viscosity ML of no more than 120 (e.g., 120, 110, 100, 90, 80, 70, 60, 50 or less), preferably no more than 105 (e.g., 105, 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50 or less) at 100°C 1+4 In certain embodiments, the modified high cis polybutadiene polymer has an aged Mooney viscosity ML at 100° C. of 120 to 50, 120 to 80, 120 to 100, 105 to 50, 105 to 80, or 105 to 100. 1+4 As also mentioned above, the modified high cis polybutadiene polymer of the second embodiment has a cis 1,4-linkage content of at least 92%, preferably at least 94%; and an initial Mooney viscosity ML of at least 20-100, preferably 30-80 or 40-80, more preferably 40 to 70 at 100°C. 1+4 Since the tire of the third embodiment has a component comprising a rubber composition comprising the modified high cis polydiene polymer of the second embodiment or the modified high cis polydiene polymer prepared by the method according to the first embodiment, the modified high cis polydiene polymer of the third embodiment can also be understood to have a cis 1,4-bond content of at least 92%, preferably at least 94%; an initial Mooney viscosity ML of at least 20-100, preferably 30-80 or 40-80, more preferably 40 to 70 at 100°C; 1+4 By a cis 1,4-bond content of at least 92% is meant that it is 92% or higher (e.g., 92%, 93%, 94%, 95%, 96%, 97%, 98%, 98.5%, 99% or higher), which should be understood to include ranges such as 92%-99%, 92%-98%, 92%-97%, 92%-96%, 92%-95%, etc. In preferred embodiments of the first to third embodiments, the modified high cis polybutadiene polymer has a cis 1,4-bond content of at least 94%. The so-called cis 1,4-bond content of at least 94% means 94% or higher (e.g., 94%, 95%, 96%, 97%, 98%, 98.5%, 99% or higher), which should be understood to include ranges such as 94%-99%, 94%-98%, 94%-97%, 94%-96%, 94%-95%, etc. The cis 1,4-bond content referred to herein is measured by FTIR (Fourier transform infrared spectroscopy). Specifically, a polymer sample is dissolved in CS2 and then subjected to FTIR.

[0169] Initial Mooney viscosity ML at 100°C 1+4The initial Mooney viscosity ML at 100°C is the Mooney viscosity measurement (described below) made on the final modified high cis polybutadiene polymer (which has been isolated and dried, for example, by steam distillation) prior to heat aging. 1+4 20-100 means that it may vary between 20-100 (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 1+4 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) or 40 to 80, or more preferably 40 to 70 at 100°C. Aged Mooney viscosity ML at 100°C 1+4 Refers to the Mooney viscosity measurement performed on a sample of a high cis polybutadiene polymer that has been heat aged. More specifically, the polymer sample has been aged at 100°C for at least 2 days (more preferably 2 days). Generally speaking, the aged Mooney viscosity of the modified high cis polybutadiene polymer will be somewhat higher than the initial viscosity of the polymer.

[0170] According to the first to third embodiments, other characteristics of the modified high cis polybutadiene polymer may vary. For example, the polymer may have various Mw, Mn and Mw / Mn values. In certain embodiments of the first to third embodiments, the modified high cis polybutadiene polymer satisfies at least one of the following: (a) having 150,000 g / mol to 2,000,000 g / mol (e.g., 150,000 g / mol, 200,000 g / mol, 250,000 g / mol, 300,000 g / mol, 350,000 g / mol, 400,000 g / mol, 450,000 g / mol, 500,000 g / mol, 600,000 g / mol, 700,000 g / mol, 800,000 g / mol, 900,000 g / mol, 1000,000 g / mol, 1100,000 g / mol, 1200,000 g / mol, 1300,000 g / mol, 1400,000 g / mol, 1500,000 g / mol, 1600,000 g / mol, 1700,000 g / mol, 1800,000 g / mol, 1900,000 g / mol, 2000,000 g / mol, 2100,000 g / mol, 2200,000 g / mol, 2300,000 g / mol, 2400,000 g / mol, 2500,000 g / mol, 2600,000 g / mol, 2700,000 g / mol, 2800,000 g / mol, 2900,0 , 1,200,000 g / mol, 1,300,000 g / mol, 1,400,000 g / mol, 1,500,000 g / mol, 1,600,000 g / mol, 1,700,000 g / mol, 1,800,000 g / mol, 1,900,000 g / mol, or 2,000,000 g / mol), preferably 90,000 g / mol to 1,000,000 g / mol (e.g., 90,000 g / mol, 150,000 g / mol, 200,000 g / mol, 250,000 g / mol, 300,000 g / mol, 350,000 g / mol, 400,000 g / mol, 450,000 g / mol, 500,000 g / mol, 600,000 g / mol, 700,000 g / mol, 800,000 g / mol, 900,000 g / mol, or 1,000,000 g / mol), more preferably 250,000 g / mol to 750,000 g / mol (e.g., 250,000 g / mol, 275 ... / mol, 300,000 g / mol, 325,000 g / mol, 350,000 g / mol, 375,000 g / mol, 400,000 g / mol, 425,000 g / mol, 450,000 g / mol, 475,000 g / mol, 500,000 g / mol, 550,000 g / mol, 600,000 g / mol, 650,000 g / mol, 700,000 g / mol, or 750,000 g / mol, or 300,000 g / mol to 800,000 g / mol (e.g., 300,000 g / mol);325,000 g / mol, 350,000 g / mol, 375,000 g / mol, 400,000 g / mol, 425,000 g / mol, 450,000 g / mol, 475,000 g / mol, 500,000 g / mol, 550,000 g / mol, 600,000 g / mol, 650,000 g / mol, 700,000 g / mol, 750,000 g / mol, or 800,000 g / mol); (b) having an Mw of 80,000 g / mol to 800,000 g / mol (e.g., 80,000 g / mol, 100,000 g / mol, 120,000 g / mol, 140,000 g / mol); , 150,000 g / mol, 160,000 g / mol, 180,000 g / mol, 200,000 g / mol, 250,000 g / mol, 300,000 g / mol, 350,000 g / mol, 400,000 g / mol, 450,000 g / mol, 500,000 g / mol, 550,000 g / mol, 600,000 g / mol, 650,000 g / mol, 700,000 g / mol, 750,000 g / mol, or 800,000 g / mol), preferably 90,000 g / mol to 500,000 g / mol (e.g., 90,000 g / mol, 110,000 g / mol, 130,000 g / mol, 1 , 50,000 g / mol, 50,000 g / mol, 170,000 g / mol, 190,000 g / mol, 210,000 g / mol, 230,000 g / mol, 250,000 g / mol, 270,000 g / mol, 290,000 g / mol, 310,000 g / mol, 330,000 g / mol, 350,000 g / mol, 370,000 g / mol, 390,000 g / mol, 410,000 g / mol, 430,000 g / mol, 450,000 g / mol, 470,000 g / mol, 490,000 g / mol, or 500,000 g / mol), more preferably 100,000 g / mol to 350, , 150,000 g / mol; 170,000 g / mol; 190,000 g / mol; 200,000 g / mol; 250,000 g / mol; 300,000 g / mol; 350,000 g / mol; or 400,000 g / mol of Mn;(c) having an Mw / Mn of 1.5 to 3.5 (e.g., 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) having an initial Mooney viscosity ML at 100° C. of 40 to 80 (e.g., 40, 42, 44, 45, 46, 48, 50, 52, 54, 55, 56, 58, 60, 62, 64, 65, 66, 68 or 70), more preferably 40 to 70; 1+4 . In certain embodiments of the first embodiment to the third embodiment, the modified high cis polybutadiene polymer satisfies each of (a)-(d). In certain embodiments of the first embodiment to the third embodiment, the modified high cis polybutadiene polymer satisfies the preferred range of each of (a)-(d). In certain embodiments of the first embodiment to the third embodiment, the modified high cis polybutadiene polymer satisfies the more preferred range of each of (a)-(d). Mn represents the number average molecular weight in grams per mole (determined by GPC), Mw represents the weight average molecular weight in grams per mole (determined by GPC), and Mw / Mn represents the molecular weight dispersion or polydispersity of the polymer. Typically, the Mn and Mw of these polymers can be determined by using gel permeation chromatography (GPC), which is calibrated with polystyrene standards.

[0171] The method of the first embodiment can result in (and the polymer of the second embodiment can be and the tire / tire component of the third embodiment can utilize) a polymer of a modified high cis-polybutadiene polymer product, which contains a small portion of high molecular weight polymer material. Generally speaking, if necessary, such high molecular weight materials can be filtered out before using the polymer (e.g., in a rubber composition) or selling the polymer. The amount of high molecular weight material will generally be less than about 10 weight %, sometimes less than about 5 weight %. The Mw, Mn and Mw / Mn values ​​provided in the preceding paragraphs refer to values ​​that can be measured via GPC for a material sample prepared by the first embodiment and / or according to the method of the second embodiment or the third embodiment, and encompass the Mw and Mn values ​​of the high molecular weight material that can be filtered out. The Mw and Mn values ​​provided for the working examples are measured by GPC for samples that have been filtered to remove high molecular weight materials and gels to avoid potential damage to the GPC. Also disclosed herein is a polymer product prepared by the process of the first embodiment (as well as polymers of the second embodiment and polymers useful in the third embodiment), wherein at least 90 wt %, preferably at least 95 wt %, or even at least 98 wt % of the polymer in the polymer product has an Mw of 150,000 to 800,000 g / mole, preferably 250,000 to 600,000 g / mole, more preferably 300,000 to 500,000 g / mole and an Mn of 80,000 to 400,000 g / mole, preferably 90,000 to 300,000 g / mole, more preferably 150,000 to 300,000 g / mole.

[0172] Tire having a component comprising a modified high-cis polybutadiene polymer

[0173] As mentioned above, the modified high cis polybutadiene prepared according to the method of the first embodiment and the modified high cis polybutadiene of the second embodiment are particularly useful in rubber compositions for tire components. Therefore, the third embodiment disclosed herein relates to a tire having a component comprising a rubber composition, the rubber composition comprising the modified high cis polybutadiene prepared according to the method of the first embodiment or the modified high cis polybutadiene of the second embodiment. Generally speaking, according to the third embodiment, the rubber composition of the tire component comprises: (a) an elastomeric component, (b) a reinforcing filler component, (c) a plasticizing component, and (d) a curing package. More specifically, according to the third embodiment, the rubber composition of the tire component comprises: (a) an elastomer component comprising: (i) 10 phr to 100 phr of the high cis-modified polybutadiene polymer according to the second embodiment or the high cis-modified polybutadiene polymer produced by the method of the first embodiment, and (ii) 0 phr to 90 phr of at least one additional polymer selected from the group consisting of unmodified polybutadiene, styrene-butadiene, natural rubber, and polyisoprene; (b) a reinforcing filler The invention relates to a plasticizing component, wherein the reinforcing filler component comprises: (i) 10 phr to 200 phr of a reinforcing silica filler, and (ii) 0 phr to 50 phr of a reinforcing carbon black filler, wherein the reinforcing carbon black filler is present in an amount not exceeding 20% ​​by weight of the reinforcing silica filler; (c) a plasticizing component, wherein the plasticizing component comprises: (i) 0 phr to 50 phr of at least one plasticizing oil, and (ii) 0 phr to 60 phr of at least one hydrocarbon resin having a Tg of at least 30° C.; and (d) a curing package.

[0174] As mentioned above, according to the third embodiment, the amount of modified high cis polybutadiene polymer (a)(i) present in the rubber composition can generally vary between 10 phr and 100 phr (e.g., 10 phr, 15 phr, 20 phr, 25 phr, 30 phr, 35 phr, 40 phr, 45 phr, 50 phr, 55 phr, 60 phr, 65 phr, 70 phr, 75 phr, 80 phr, 85 phr, 90 phr, 95 phr 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) or more preferably 30 to 60 phr (e.g., 30, 35, 40, 45, 50, 55, or 60 phr). Amounts of (a)(i) within the foregoing ranges may also be used in the rubber composition of the third embodiment, for example, 40 to 80 phr, 50 to 80 phr, 40 to 70 phr, 40 to 60 phr, etc.

[0175] Other rubber

[0176] As also mentioned above, according to the third embodiment, the rubber composition may include 0 phr-90 phr (e.g., 0 phr, 5 phr, 10 phr, 15 phr, 20 phr, 25 phr, 30 phr, 35 phr, 40 phr, 45 phr, 50 phr, 55 phr, 60 phr, 65 phr, 70 phr, 75 phr, 80 phr, 85 phr 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 phr-80 phr (e.g., 20 phr, 25 phr, 30 phr, 35 phr, 40 phr, 45 phr, 50 phr, 55 phr, 60 phr, 65 phr, 70 phr, 75 phr, or 80 phr) or 40 phr-60 phr (e.g., 40 phr, 45 phr, 50 phr, 55 phr, or 60 phr), such as to make up 100 phr or 100 parts of the total amount of (a)(i) and (a)(ii) polymers. Amounts of (b)(ii) within the foregoing ranges may also be used in the rubber composition of the third embodiment, for example, 20 to 60, 20 to 50, 30 to 60, 40 to 60, etc. In certain embodiments of the third embodiment, that is, in addition to (a) and (b), the rubber composition also includes one or more additional rubbers. In a preferred embodiment of the third embodiment, the entire 100phr elastomer component of the rubber composition is composed of a combination of (a) (i) and (a) (ii). In other words, in such embodiments, except the rubber of (a) (i) and (a) (ii), there are no other rubbers. In certain embodiments of the third embodiment, the rubber composition does not contain polyisoprene (that is, 0phr polyisoprene). In certain embodiments of the third embodiment, the rubber composition does not contain polybutadiene except the modified high cis-polybutadiene according to (a) (i). In certain embodiments of the third embodiment, the rubber composition does not include natural rubber and does not include polyisoprene.

[0177] filler

[0178] As discussed above, according to a third embodiment, the rubber composition further comprises 10 phr to 200 phr of a reinforcing silica filler (e.g., 10 phr, 15 phr, 20 phr, 25 phr, 30 phr, 35 phr, 40 phr, 45 phr, 50 phr, 55 phr, 60 phr, 65 phr, 70 phr, 75 phr, 80 phr, 85 phr, 90 phr, 95 phr, 100 phr, 105 phr, 110 phr, 115 phr, 120 phr, 125 phr). , 130 phr, 135 phr, 140 phr, 145 phr, 150 phr, 155 phr, 160 phr, 165 phr, 170 phr, 175 phr, 180 phr, 185 phr, 190 phr, 195 phr or 200 phr) and 0 phr-50 phr (e.g., 0 phr, 5 phr, 10 phr, 15 phr, 20 phr, 25 phr, 30 phr, 35 phr, 40 phr, 45 phr or 50 phr) of reinforcing carbon black filler as filler component. In other words, according to the foregoing, silica filler can be considered to be always present, while carbon black filler is optionally present. In a preferred embodiment of the third embodiment, the rubber composition comprises 30 phr to 200 phr (e.g., 30 phr, 35 phr, 40 phr, 45 phr, 50 phr, 55 phr, 60 phr, 65 phr, 70 phr, 75 phr, 80 phr, 85 phr, 90 phr, 95 phr, 100 phr, 105 phr, 110 phr, 115 phr, 120 phr, 125 phr, 130 phr, 135 phr, 140 phr, 145 phr, 150 phr, 155 phr, 160 phr, 165 phr). The reinforcing silica filler may be present in an amount of 1-20 phr, 1-30 phr, 1-40 phr, 1-60 phr, 1-80 phr, 1-90 phr, 2-100 phr, 2-25 phr, 2-30 phr, 2-40 phr, 2-50 phr, 2-60 phr, 2-70 phr, 2-80 phr, 2-90 phr, 3-100 phr, 3-150 phr, 3-150 phr, 4-150 phr, 4-150 phr, 5-100 phr, 5-150 phr, 6-100 phr, 6-150 phr, 7-150 phr, 7-150 phr, 8 ...In a preferred embodiment of the third embodiment, the rubber composition comprises a reinforcing carbon black filler in an amount of 1 phr to 20 phr (e.g., 1 phr, 2 phr, 3 phr, 4 phr, 5 phr, 6 phr, 7 phr, 8 phr, 9 phr, 10 phr, 12 phr, 14 phr, 16 phr, 18 phr or 20 phr), more preferably 1 phr to 10 phr (e.g., 1 phr, 2 phr, 3 phr, 4 phr, 5 phr, 6 phr, 7 phr, 8 phr, 9 phr or 10 phr). In certain embodiments of the third embodiment, both the amount of reinforcing silica filler and the amount of reinforcing carbon black filler are within the aforementioned preferred amounts. In certain preferred embodiments of the third embodiment, the reinforcing carbon black filler is present in an amount not exceeding 20% ​​by weight of the reinforcing silica filler (for example, if 100 phr of silica filler is used, the amount of reinforcing carbon black filler will be 20 phr or less), preferably not exceeding 10% by weight of the reinforcing silica filler; non-limiting examples of the foregoing amounts of reinforcing carbon black filler include 20 wt % to 1 wt %, 20 wt % to 5 wt %, 15 wt % to 1 wt %, 15 wt % to 5 wt %, 10 wt % to 1 wt %, 10 wt % to 5 wt %, and 5 wt % to 1 wt % of reinforcing silica filler.

[0179] As used herein, the term "reinforcing" with respect to "reinforcing carbon black filler," "reinforcing silica filler," and "reinforcing filler" should generally be understood to include fillers conventionally described as reinforcing and fillers conventionally described as semi-reinforcing. Traditionally, the term "reinforcing filler" is used to refer to a carbon black filler having a carbon black content greater than about 100 m 2 / g, and in some cases, greater than 100m 2 / g, greater than about 125m 2 / g, greater than 125m 2 / g, or even greater than about 150m 2 / g or greater than 150m 2 / g of nitrogen absorption specific surface area (N2SA). Alternatively (or additionally), the traditional use of the term "reinforcing filler" can also be used to refer to particulate matter having a particle size of about 10nm to about 50nm (including 10nm to 50nm). Traditionally, the term "semi-reinforcing filler" is used to refer to fillers whose particle size, surface area (N2SA), or both are between non-reinforcing fillers (as discussed below) and reinforcing fillers. 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 about 20nm to about 50nm. 2 / g or greater, including 20m 2 / g or more, greater than about 50m 2 / g, greater than 50m 2 / g, greater than about 100m2 / g, greater than 100m 2 / g, greater than about 125m 2 / g, and greater than 125m 2 / g of nitrogen absorption specific surface area (N2SA) of particulate matter. In certain embodiments of the third embodiment disclosed herein, the term "reinforcing filler" is used to refer to particulate matter having a particle size of about 10 nm to about 1000 nm, including 10 nm to 1000 nm, about 10 nm to about 50 nm, and 10 nm to 50 nm.

[0180] According to the third embodiment, the specific type or types of carbon black utilized may vary. Generally speaking, suitable carbon blacks for use as reinforcing fillers in the rubber composition of the third embodiment include any of the commonly available, commercially produced carbon blacks, including those having at least about 20 m 2 / g(including at least 20m 2 / g), more preferably at least about 35 m 2 / g up to about 200m 2 / g or higher (including 35m 2 / g up to 200m 2 / g) of those carbon blacks. The surface area values ​​for carbon black herein are determined by ASTM D-1765 using hexadecyltrimethylammonium bromide (CTAB) technology. Wherein available carbon black is furnace black, channel black and lamp black. More specifically, the example of available carbon black includes super wear-resistant furnace (SAF) black, high wear-resistant furnace (HAF) black, fast pressed furnace (FEF) black, fine furnace (FF) black, medium super wear-resistant furnace (ISAF) black, semi-reinforced furnace (SRF) black, medium processing channel black, difficult processing channel black and conductive channel black. Available other carbon black includes acetylene black. In certain embodiments of the third embodiment, the rubber composition includes a mixture of two or more of the above blacks. Preferably, according to the third embodiment, if there is a carbon black filler, it is only composed of one type (or grade) of reinforcing carbon black. Typical carbon blacks suitable for use in certain embodiments of the third embodiment are N-110, N-220, N-339, N-330, N-351, N-550 and N-660 specified by ASTM D-1765-82a. The carbon black used can be in granular form or in non-granular flocculated masses. Preferably, non-granular carbon blacks are preferred for more uniform mixing.

[0181] The specific type of reinforcing silica filler used in the rubber composition of the third embodiment can 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), pyrogenic silica, calcium silicate, etc. 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.), calcium magnesium silicate (CaMgSiO4), calcium silicate (Ca2SiO4, etc.), aluminum silicate (Al2SiO5, Al4.3SiO4.5H2O, etc.), calcium aluminum silicate (Al2O3.CaO2SiO2, etc.), etc. Among the reinforcing silica fillers listed, precipitated amorphous wet, hydrated silica fillers are preferred. Such reinforcing silica fillers are produced by a chemical reaction in water, whereby they precipitate as ultrafine spherical particles, wherein the primary particles strongly associate into aggregates, which in turn are less strongly combined into agglomerates. The surface area as measured by the BET method is a preferred measurement for characterizing the reinforcing properties of different reinforcing silica fillers. In certain embodiments of the third embodiment disclosed herein, the rubber composition comprises a reinforcing silica filler having a surface area of ​​100 m 2 / g to 400m 2 / g (e.g., 100m 2 / g, 110m 2 / g, 120m 2 / g, 130m 2 / g, 140m 2 / g, 150m 2 / g, 160m 2 / g, 170m 2 / g, 180m 2 / g, 190m 2 / g, 200m 2 / g, 210m 2 / g, 220m 2 / g, 230m 2 / g, 240m 2 / g, 250m 2 / g, 260m 2 / g, 270m 2 / g, 280m 2 / g, 290m 2 / g、300m 2 / g, 310m 2 / g, 320m 2 / g, 330m 2 / g, 340m 2 / g, 350m2 / g, 360m 2 / g, 370m 2 / g, 380m 2 / g, 390m 2 / g, or 400m 2 / g)、150m 2 / g to 350m 2 / g, 200m 2 / g to 300m 2 / g, or 150m 2 / g to 250m 2 / g of surface area (as measured by the BET method).

[0182] 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, but are not limited to EZ120G, EZ120G-D, 134G, 160G, 160G-D, 190, 190G-D, EZ 200G, EZ 200G-D, 210, 233. 243LD, 255CG-D, 315-D, 315G-D, HDP320G, etc., are produced by PPG Industries (Pittsburgh, Pa.) in Pittsburgh, Pennsylvania. Similarly, a variety of commercial grades of different reinforcing silica fillers are also available from Evonik Corporation (e.g., 320GR, 5000GR, 5500GR, 7000GR, VN2 GR, VN2, VN3, VN3 GR, 7000GR, 7005, 7500GR, 7800GR, 9500GR, 9000G, 9100GR) and Solvay (e.g. 1115MP, 1085GR, 1165MP, 1200MP, Premium, 195HR, 195GR, 185GR, 175GR and 165GR).

[0183] In certain embodiments of the third embodiment, one or more than one silica coupling agent may also be (optionally) utilized. Silica coupling agents may be used to prevent or reduce the aggregation of silica fillers in the rubber composition. It is believed that the aggregates of silica filler particles increase the viscosity of the rubber composition, and therefore, preventing the aggregation will reduce viscosity and improve the processability and miscibility of the rubber composition.

[0184] Generally, any conventional type of silica coupling agent can be used, such as those having silane and constituent components or parts that can react with polymers, particularly vulcanizable polymers. The silica coupling agent acts as a connecting bridge between silica and polymers. The silica coupling agent suitable for use in certain embodiments of the third embodiment includes those containing the following groups: such as alkyl alkoxy, thiol, end-capped thiol, sulfide-containing groups (e.g., containing alkoxy based on monosulfide, containing alkoxy based on disulfide, containing alkoxy based on tetrasulfide), amino, vinyl, epoxy, and combinations thereof. In certain embodiments, the silica coupling agent can be added to the rubber composition as a pre-treated silica; the pre-treated silica has been surface pre-treated with silane before being added to the rubber composition. The use of pre-treated silica allows two components (i.e., silica and silica coupling agent) to be added as one component, which usually makes rubber easier to compound.

[0185] When a silica coupling agent is utilized in the rubber composition according to the third embodiment, the amount used may vary. In certain embodiments of the third embodiment, the rubber composition does not contain 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 the 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 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 an amount of 0.1 phr to 15 phr (e.g., 0.1 phr, 0.5 phr, 1 phr, 2 phr, 3 phr, 4 phr, 5 phr, 6 phr, 7 phr, 8 phr, 9 phr, 10 phr, 11 phr, 12 phr, 13 phr, 14 phr or 15 phr), 0.1 phr to 12 phr, 0.1 phr to 10 phr, 0.1 phr to 5 phr, 1 phr to 15 phr (e.g., 1 phr, 2 phr, 3 phr, 4 phr, 5 phr, 6 phr, 7 phr, 8 phr, 9 phr, 10 phr, 11 phr, 12 phr, 13 phr, 14 phr or 15 phr). 5 phr, 9 phr, 10 phr, 11 phr, 12 phr, 13 phr, 14 phr or 15 phr), 1 phr to 10 phr (e.g., 1 phr, 1.5 phr, 2 phr, 2.5 phr, 3 phr, 3.5 phr, 4 phr, 4.5 phr, 5 phr, 5.5 phr, 6 phr, 6.5 phr, 7 phr, 7.5 phr, 8 phr, 8.5 phr, 9 phr, 9.5 phr or 10 phr), 1 phr to 5 phr, or 1 phr to 3 phr of a silica coupling agent.

[0186] Plasticizers

[0187] As mentioned above, according to the third embodiment, the rubber composition comprises a plasticizing component comprising 0phr-50phr (e.g., 0phr, 5phr, 10phr, 15phr, 20phr, 25phr, 30phr, 35phr, 40phr, 45phr or 50phr) of at least one plasticizing oil and 0phr-60phr (e.g., 0phr, 5phr, 10phr, 15phr, 20phr, 25phr, 30phr, 35phr, 40phr, 45phr, 50phr, 55phr or 60phr) 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 0phr-30phr of a plasticizing oil and 5phr-60phr of a hydrocarbon resin. In a more preferred embodiment of the 3rd embodiment, the plasticizing component comprises a plasticizing oil of 0phr-15phr and a hydrocarbon resin of 5phr-50phr. In certain embodiments of the 3rd embodiment, the plasticizing oil exists in an amount of at least 1phr (e.g., 1phr-50phr, 1phr-30phr, 1phr-15phr, 1phr-10phr, 1phr-5phr etc.). In certain embodiments of the third embodiment, the total amount of plasticizing components does not exceed 65 phr (e.g., 65 phr, 60 phr, 55 phr, 50 phr, 45 phr, 40 phr, 35 phr, 30 phr, 25 phr, 20 phr, 15 phr, 10 phr, 5 phr or 1 phr), preferably 5 phr to 65 phr, more preferably 10 phr to 55 phr or 15 phr to 50 phr; in certain such embodiments, the hydrocarbon resin accounts for at least 50%, at least 60%, at least 70%, 50% to 100%, 50% to 90%, 60% to 100%, 60% to 90%, 70% to 100% or 70 to 90% of the total amount of plasticizing components.

[0188] Various types of plasticizing oils can be used, including but not limited to aromatic oils, naphthenic oils and low PCA oils. Preferably, the plasticizing oil is liquid (pourable) at 25°C. Suitable low PCA oils include those having a polycyclic aromatic hydrocarbon content of less than 3% by weight as determined by the IP346 method. The procedure of the IP346 method can be found in the Standard Methods for Analysis & Testing of Petroleum and Related Products (Standard Methods for Analysis and Testing of Petroleum and Related Products) and British Standard 2000 Parts (British Standard 2000 Part) 62nd edition published by the Institute of Petroleum, United Kingdom in 2003. Suitable low PCA oils include mild extraction solvates (MES), treated distillate aromatic extracts (TDAE), TRAE and heavy naphthenes. Suitable MES oils are commercially available from SHELL as CATENEX SNR, from EXXONMOBIL as PROREX 15 and FLEXON 683, from BP as VIVATEC 200, from TOTAL FINA ELF as PLAXOLENE MS, from DAHLEKE as TUDALEN 4160 / 4225, from REPSOL as MES-H, from Z8 as MES, and from AGIP as OLIO MES S201. Suitable TDAE oils are commercially available from EXXONMOBIL as TYREX 20, from BP as VIVATEC 500, VIVATEC 180 and ENERTHENE 1849, and from REPSOL as EXTENSOIL 1996. Suitable heavy naphthenic oils can be obtained as SHELLFLEX 794, ERGON BLACK OIL, ERGON H2000, CROSS C2000, CROSS C2400 and SANJOAQUIN 2000L. Suitable low PCA oils also include oils from various plant sources, such as oils harvested from vegetables, nuts and seeds. Non-limiting examples include, but are not limited to, soybean or soya oil, sunflower oil (including high oleic sunflower oil with 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 nut oil, sesame oil, camellia oil, jojoba oil, macadamia oil, coconut oil and palm oil.In certain embodiments of the third embodiment, the tire rubber composition contains only limited amounts of oil, such as less than 10 phr (e.g., 9 phr, 8 phr, 7 phr, 6 phr, 5 phr, 4 phr, 3 phr, 2 phr, 1 phr or 0 phr), less than 5 phr, 1 phr to 5 phr, or even 0 phr.

[0189] Various types of hydrocarbon resins, including plasticizing resins, can be utilized in the plasticizing component. As used herein, the term plasticizing resin refers to a compound that is solid at room temperature (23°C) and is miscible in a rubber composition in an amount that is usually at least 5phr. Generally speaking, the plasticizing resin will be used as a diluent and can be contrasted with a generally immiscible tackifying resin, and can migrate to the surface of the rubber composition providing viscosity. In certain embodiments of the third embodiment, a plasticizing resin is utilized, which comprises a hydrocarbon resin and can be aliphatic, aromatic, or aliphatic / aromatic, depending on the monomers contained therein. Examples of plasticizing resins suitable for the rubber composition of the third embodiment include, but are not limited to, cyclopentadiene (abbreviated as CPD) or dicyclopentadiene (abbreviated as DCPD) homopolymers or copolymer resins, terpene homopolymers or copolymer resins, and C5 fraction homopolymers or copolymer resins. Such resins can be used, for example, alone or in combination. In certain embodiments of the third embodiment, a plasticizing resin that satisfies at least one of the following can be used: a Tg greater than 30°C (preferably greater than 40°C and / or not greater than 120°C or not greater than 100°C), a number average molecular weight (Mn) between 400 g / mol and 2000 g / mol (preferably 500 g / mol-2000 g / mol), and a polydispersity index (PI) less than 3 (preferably less than 2), wherein PI=Mvv / Mn, and Mvv is the weight average molecular weight of the resin. The Tg of the resin can be measured by DSC (differential scanning calorimetry) according to ASTM D3418 (1999). The Mw, Mn and PI of the resin can be determined by size exclusion chromatography (SEC) using THF (35°C; concentration 1 g / l; flow rate 1 ml / min; filtration of the solution through a filter with a porosity of 0.45 μm before injection; molar calibration using polystyrene standards; a set of 3 "Waters" columns in series ("Styragel" HR4E, HR1 and HR0.5); detection by a differential spectrometer ("Waters 2410") and its associated operating software ("Waters Empower").

[0190] Curing package

[0191] As mentioned above, according to the third embodiment, the rubber composition includes a curing package. Generally speaking, the curing package will include at least one of the following: vulcanizing agent, vulcanization accelerator, vulcanization activator (for example, zinc oxide, stearic acid, etc.), vulcanization inhibitor and scorch retarder. In certain embodiments, the curing package includes at least one vulcanizing agent, at least one vulcanization accelerator, at least one vulcanization activator and optionally vulcanization inhibitor and / or scorch retarder. Vulcanization accelerator and vulcanization activator are used as the catalyst of vulcanizing agent. Various vulcanization inhibitors and scorch retarder are known in the art, and can be selected by those skilled in the art based on required vulcanization characteristics.

[0192] Examples of suitable types of vulcanizing agents used in certain embodiments of the third embodiment include, but are not limited to, sulfur-based curing components or peroxide-based curing components. Examples of specific suitable sulfur-based vulcanizing agents include soluble sulfur for "rubber maker"; sulfur-supplying curing agents such as disulfide amines, polymerized polysulfides or sulfur olefin adducts; and insoluble polymerized sulfur. Preferably, the sulfur-based vulcanizing agent is a mixture of soluble sulfur or soluble and insoluble polymerized sulfur. Generally speaking, the vulcanizing agent can be used in an amount within the range of 0.1phr to 10phr, including 1phr to 7.5phr, including 1phr to 5phr, and preferably 1phr to 3.5phr.

[0193] Vulcanization accelerators are used to control the time and / or temperature required for vulcanization and improve the properties of the vulcanized rubber. 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), etc.; guanidine vulcanization accelerators such as diphenylguanidine (DPG), etc.; thiuram vulcanization accelerators; carbamate vulcanization accelerators; etc. Generally speaking, the amount of vulcanization accelerator used is in the range of 0.1 phr to 10 phr (e.g., 0.1 phr, 0.5 phr, 1 phr, 2 phr, 3 phr, 4 phr, 5 phr, 6 phr, 7 phr, 8 phr, 9 phr or 10 phr), preferably 0.5 phr to 5 phr (e.g., 0.5 phr, 1 phr, 1.5 phr, 2 phr, 2.5 phr, 3 phr, 3.5 phr, 4 phr, 4.5 phr or 5 phr).

[0194] Vulcanization activator is an additive for supporting vulcanization. Conventionally, vulcanization activator comprises both inorganic component and organic component. Zinc oxide is the most widely used inorganic vulcanization activator. Conventionally, various organic vulcanization activators are used, including zinc salts of stearic acid, palmitic acid, lauric acid and the above. Generally speaking, the consumption of vulcanization activator is in the range of 0.1phr to 6phr (for example, 0.1phr, 0.5phr, 1phr, 1.5phr, 2phr, 2.5phr, 3phr, 3.5phr, 4phr, 4.5phr, 5phr, 5.5phr or 6phr), preferably in the range of 0.5phr to 4phr (for example, 0.5phr, 1phr, 1.5phr, 2phr, 2.5phr, 3phr, 3.5phr or 4phr).

[0195] Vulcanization inhibitors are used to control the vulcanization process and usually delay or inhibit vulcanization until the desired time and / or temperature is reached. Common vulcanization inhibitors include, but are not limited to, PVI (cyclohexylthiophthalimide) from Santogard. Generally speaking, the amount of vulcanization inhibitor is 0.1 phr to 3 phr (e.g., 0.1 phr, 0.5 phr, 1 phr, 1.5 phr, 2 phr, 2.5 phr or 3 phr), preferably 0.5 phr to 2 phr (e.g., 0.5 phr, 1 phr, 1.5 phr or 2 phr).

[0196] Other ingredients

[0197] Various other ingredients that may be optionally added to the tire rubber composition of the third embodiment disclosed herein include waxes, processing aids, tackifying resins, reinforcing resins and peptizers, and antioxidants.

[0198] Method for preparing a rubber composition

[0199] The rubber composition according to the third embodiment disclosed herein can generally be formed in the following manner: by methods known in the art, such as, for example, by kneading the ingredients together in a Banbury mixer or on a grinding roller, the ingredients of the rubber composition (as disclosed above) are mixed together. These methods generally include at least one non-productive masterbatch mixing stage and a final productive mixing stage. The term "non-productive masterbatch stage" is known to those skilled in the art, and is generally understood to be a mixing stage in which no vulcanizing agent or vulcanization accelerator is added. The term final productive mixing stage is also known to those skilled in the art, and is generally understood to be a mixing stage in which a vulcanizing agent and a vulcanization accelerator are added to the rubber composition. In certain embodiments of the third embodiment, a non-productive masterbatch mixing stage can be used in the preparation of the rubber composition. In certain embodiments of the third embodiment, more than one non-productive masterbatch mixing stage is used. In certain embodiments of the third embodiment utilizing silica and a silica coupling agent, more than one non-productive masterbatch mixing stage is used, and at least a portion of the silica filler is added to a second non-productive masterbatch mixing stage (also referred to as a regrind stage); in certain such embodiments, all of the silica coupling agent (along with at least a portion of the silica filler) is added only in the second non-productive masterbatch mixing stage, and no silica coupling agent is added in the initial non-productive masterbatch mixing stage.

[0200] In certain embodiments of the third embodiment, the masterbatch mixing stage includes at least one of series mixing or intermeshing mixing. In-line mixing can be understood to include the use of a mixer with two mixing chambers, each of which has a set of mixing rotors; typically, the two mixing chambers are stacked together, wherein the upper mixing is the main mixer, and the lower mixer receives the batch material from the upper or main mixer. In certain embodiments, the main mixer utilizes an intermeshing rotor, and in other embodiments, the main mixer utilizes a tangential rotor. Preferably, the lower mixer utilizes an intermeshing rotor. Intermeshing mixing can be understood to include the use of a mixer with an intermeshing rotor. An intermeshing rotor refers to a group of rotors in which the large diameter of one rotor in a group interacts with the small diameter of the opposite rotor in the group so that the rotors intermesh with each other. Due to the interaction between the rotors, the intermeshing rotor must be driven at a uniform speed. In contrast to the intermeshing rotor, the tangential rotor refers to a group of rotors in which each rotor rotates independently of the other in a cavity (which may be referred to as a side). Typically, a mixer with a tangential-type rotor will include a plunger, whereas a plunger is not necessary in a mixer with an intermeshing-type rotor.

[0201] In certain embodiments of the third embodiment, the rubber composition is prepared by a method having a non-productive masterbatch mixing stage 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 method of a final productive mixing stage performed at a temperature below the vulcanization temperature to avoid undesired pre-curing of the rubber composition. Therefore, the temperature of the productive mixing 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 in particular about 75°C to about 100°C.

[0202] Example

[0203] The following examples illustrate specific and exemplary embodiments and / or features in the embodiments of the present disclosure. These embodiments are provided for illustrative purposes only and should not be construed as limitations of the present disclosure. Without departing from the essence and scope of the embodiments disclosed herein, multiple modifications to these specific embodiments are possible. It should be specifically understood that the modified high cis-polybutadiene polymer can use different functional compounds (i.e., according to formula (I), as discussed above), use different stabilizers or do not use stabilizers (as discussed above), or use / have different combinations of functional compounds and stabilizers and be used in rubber compositions to prepare. It should also be understood that the high cis-polybutadiene polymer can be used in rubber compositions together with ingredients (e.g., additional rubber, filler, curing package ingredients) that are different from those used in the examples in relative amounts, composition, or both (i.e., as fully disclosed in the preceding paragraphs).

[0204] Example 1 (Use of CPTEOS and Nd / MAO catalyst): 1209 grams of hexane and 3257 grams of a 19.5 wt% 1,3-butadiene hexane solution were added to a 2-gallon nitrogen-purged reactor equipped with a turbine agitator blade. The preformed catalyst was prepared by mixing 9.55 milliliters of a 4.32 mole solution of methylaluminoxane (MAO) in toluene, 2.03 grams of a 22.0 wt% 1,3-butadiene hexane solution, 0.77 milliliters of a 0.537 mole solution of neodymium versatate in cyclohexane, 10.32 milliliters of a 1.0 mole solution of diisobutylaluminum hydride in hexane, and 1.65 milliliters of a solution of diethylaluminum chloride in hexane. The catalyst was aged for 15 minutes and then loaded into the reactor (which already contained the solvent and the hexane solution of 1,3-butadiene). The reactor jacket was then set to 65°C. After 60 minutes of polymerization time, 1.91 ml of 4.15 mol (3-cyanopropyl) triethoxysilane (CPTEOS, 25:1 molar ratio based on moles of functionalized compound: moles of Nd in catalyst) diluted with about 20 ml of hexane was charged into the reactor. After 30 minutes, the polymerization mixture was cooled to room temperature (about 25°C).

[0205] Approximately 400 grams of the resulting modified polymer cement (approximately 4500 grams in total) was transferred (in approximately equal portions) to five bottles (labeled ae). Octyltriethoxysilane (OTES, 3.18 mol (neat)) and ethylhexanoic acid (EHA, 6.3 mol (neat)) were then added to bottle be in the amounts shown in Table 1 below. No OTES or EHA was added to bottle a, and this example is considered a control. Each bottle was tumbled in a water bath maintained at 65°C for 30 minutes. The resulting polymer cement in each bottle was quenched with 3 ml of a 12 wt % solution of 2,6-di-tert-butyl-4-methylphenol (BHT) in isopropanol, coagulated in additional isopropanol containing BHT, and drum dried. Unaged and Aged Mooney Viscosity ML 1+4 The values ​​are summarized in Table 1 below, where the aging values ​​were determined by aging the samples in an oven at 100°C for 2 days.

[0206]

[0207] 1 The first number is the amount in milliliters and the second number is the molar ratio based on moles of stabilizer: moles of functionalizing compound (eg, 1 represents a 1:1 ratio).

[0208] 2 The first number is the amount in milliliters and the second number is the molar ratio based on moles of quencher: moles of stabilizer.

[0209] As can be seen from the data in Table 1, the use of a stabilizer and a quencher in combination with a functionalized compound (i.e., CPTEOS) produces an unaged Mooney viscosity ML of less than 80. 1+4 A modified high cis polybutadiene having an aged ML not exceeding 120 1+4 In contrast, the control example (1a) without the use of stabilizer and quencher resulted in an aged ML 1+4 A modified high cis polybutadiene greater than 120 (ie, 123).

[0210] Example 2 (Use of CPTEOS and COMCAT catalysts):1209 grams of hexane and 3257 grams of a 19.5 wt% 1,3-butadiene hexane solution were added to a 2-gallon nitrogen-purged reactor equipped with a turbine agitator blade. Next, 3.13 milliliters of a 1.0 mole solution of diisobutylaluminum hydride in hexane were charged to the reactor, followed by 2.39 milliliters of 0.452 mole COMCAT catalyst (Nd-FC / SF catalyst, purchased from Comar Chemical Ltd.). The reactor jacket was then set to 65°C. After 60 minutes of polymerization time, 6.50 milliliters of 4.15 moles of (3-cyanopropyl)triethoxysilane (CPTEOS, a molar ratio of 25:1 based on the number of moles of functionalized compound: the number of moles of Nd in the catalyst) diluted with approximately 20 milliliters of hexane were charged to the reactor. After 30 minutes, the polymerization mixture was cooled to room temperature (approximately 25°C).

[0211] Approximately 400 grams of the resulting modified polymer cement was transferred (in approximately equal portions) to five bottles (labeled ae). Octyltriethoxysilane (OTES, 3.18 mol (neat)) and ethylhexanoic acid (EHA, 6.3 mol (neat)) were then added to bottle be in the amounts shown in Table 2 below. No OTES or EHA was added to bottle a, and this example is considered a control. Each bottle was tumbled in a water bath maintained at 65°C for 30 minutes. The resulting polymer cement in each bottle was quenched with 3 ml of a 12 wt % solution of 2,6-di-tert-butyl-4-methylphenol (BHT) in isopropanol, coagulated in additional isopropanol containing BHT, and drum dried. Unaged and Aged Mooney Viscosity ML 1+4 The values ​​are summarized in Table 2 below, where the aging values ​​were determined by aging the samples in an oven at 100°C for 2 days.

[0212]

[0213] 1 The first number is the amount in milliliters and the second number is the molar ratio based on moles of stabilizer: moles of functionalizing compound.

[0214] 2 The first number is the amount in milliliters and the second number is the molar ratio based on moles of quencher: moles of stabilizer.

[0215] From the data in Table 2, it can be seen that the use of a stabilizer and a quencher in combination with a functionalized compound (i.e., CPTEOS) produces an unaged Mooney ML of less than 70. 1+4 The modified high cis polybutadiene, the polymer also having an aged ML of less than 100 1+4In contrast, the control example (2a) without the use of stabilizer and quencher resulted in an aged ML 1+4 A modified high cis polybutadiene greater than 120 (ie, 140).

[0216] Example 3 (Use of CPTEOS and Nd / MAO catalyst): 1209 grams of hexane and 3257 grams of a 19.5 wt% 1,3-butadiene hexane solution were added to a 2-gallon nitrogen-purged reactor equipped with a turbine agitator blade. The preformed catalyst was prepared by mixing 9.55 milliliters of a 4.32 mole toluene solution of methylaluminoxane (MAO), 2.03 grams of a 22.0 wt% 1,3-butadiene hexane solution, 0.77 milliliters of a 0.537 mole versatate neodymium cyclohexane solution, 10.32 milliliters of a 1.0 mole diisobutylaluminum hydride hexane solution, and 1.65 milliliters of a diethylaluminum chloride hexane solution. The catalyst was aged for 15 minutes and then loaded into the reactor (which already contained a hexane solution of hexane and 1,3-butadiene). The reactor jacket was then set to 65°C. After 60 minutes of polymerization time, 1.91 ml of 4.15 mol (3-cyanopropyl) triethoxysilane (CPTEOS, 25:1 molar ratio based on moles of functionalized compound: moles of Nd in catalyst) diluted with about 20 ml of hexane was charged into the reactor. After 30 minutes, 2.50 ml of octyl triethoxysilane (OTES, 3.18 mol (pure), 1:1 molar ratio based on moles of stabilizer: moles of functionalized compound) and 0.63 ml of ethylhexanoic acid (EHA, 6.3 mol (pure), 0.5:1 molar ratio based on moles of quencher: moles of stabilizer) were charged into the reactor and reacted while the reactor was cooled to room temperature (about 25°C).

[0217] The resulting polymer cement (approximately 400 g) was coagulated in a bucket of isopropanol containing BHT and tumble dried. Unaged and Aged Mooney ML of Modified High Cis Polybutadiene 1+4 The values ​​are summarized in Table 3 below, where the aged values ​​were determined by aging the samples in an oven at 100°C for 2 days. As a control, a polymer sample not treated with any OTES or EHA was also subjected to the same aging, and the aged Mooney ML 1+4 Values ​​are expressed below as aged control Mooney.

[0218]

[0219] 1 The first number is the amount in milliliters and the second number is the molar ratio based on moles of stabilizer: moles of functionalizing compound.

[0220] 2The first number is the amount in milliliters and the second number is the molar ratio based on moles of quencher: moles of stabilizer.

[0221] From the data in Table 3, it can be seen that the unaged Mooney viscosity ML of the modified high cis-polybutadiene prepared in Example 3 is 1+4 Less than 100 (more specifically, 80), and the aged Mooney viscosity ML 1+4 It is also less than 100 (more specifically, 97).

[0222] Example 4 (Use of CPTEOS and COMCAT catalysts): 1209 grams of hexane and 3257 grams of a 19.5 wt% 1,3-butadiene hexane solution were added to a 2-gallon nitrogen-purged reactor equipped with a turbine agitator blade. Next, 3.13 milliliters of a 1.0 mole hexane solution of diisobutylaluminum hydride and 2.39 milliliters of 0.452 mole COMCAT catalyst (Nd-FC / SF catalyst, purchased from Comar Chemical Ltd.) were loaded into the reactor. The reactor jacket was then set to 65°C. After 60 minutes of polymerization time, 6.50 milliliters of 4.15 moles of (3-cyanopropyl) triethoxysilane (CPTEOS, based on a molar ratio of 25:1 based on the moles of functionalized compound: the moles of Nd in the catalyst) diluted with approximately 20 milliliters of hexane were loaded into the reactor.

[0223] After 30 minutes, 8.49 ml of octyltriethoxysilane (OTES, 3.18 mol (pure), a molar ratio of 1:1 based on the moles of stabilizer: the moles of functionalized compound) and 2.14 ml of ethylhexanoic acid (EHA, 6.3 mol (pure), a molar ratio of 0.5:1 based on the moles of quencher: the moles of stabilizer) were charged into the reactor and reacted while the reactor was cooled to room temperature (approximately 25°C).

[0224] The resulting polymer cement (approximately 400 g) was coagulated in a bucket of isopropanol containing BHT and tumble dried. Unaged and Aged Mooney ML of Modified High Cis Polybutadiene 1+4 The values ​​are summarized in Table 4 below, where the aged values ​​were determined by aging the samples in an oven at 100°C for 2 days. As a control, a polymer sample not treated with any OTES or EHA was also subjected to the same aging, and the aged Mooney ML 1+4 Values ​​are expressed below as aged control Mooney.

[0225]

[0226] 1 The first number is the amount in milliliters and the second number is the molar ratio based on moles of stabilizer: moles of functionalizing compound.

[0227] 2 The first number is the amount in milliliters and the second number is the molar ratio based on moles of quencher: moles of stabilizer.

[0228] It can be seen from the data in Table 4 that the unaged Mooney viscosity ML of the modified high cis-polybutadiene prepared in Example 4 is 1+4 Less than 100 (more specifically, 52), and the aged Mooney viscosity ML 1+4 It is also less than 100 (more specifically, 97).

[0229] Example 5 (Use of CETEOS and Nd / MAO catalyst): Example 3 was repeated except that 1.76 ml of 4.5 moles of (2-cyanoethyl)triethoxysilane (CETEOS, 25:1 molar ratio based on moles of functionalized compound: moles of Nd in catalyst) was used instead of CPTEOS. The results are listed in Table 5.

[0230] Example 6 (Use of CETEOS and COMCAT catalysts): Example 4 was repeated except that 6.00 ml of 4.5 moles of (2-cyanoethyl)triethoxysilane (CETEOS, 25:1 molar ratio based on moles of functionalized compound: moles of Nd in catalyst) was used instead of CPTEOS. The results are listed in Table 5.

[0231]

[0232] From the data in Table 5, it can be seen that the unaged Mooney viscosity ML of the prepared modified high cis polybutadiene is 1+4 Less than 100 (more specifically, 94 and 83), and the aged Mooney viscosity ML 1+4 Less than 120 (more specifically, 112 and 99).

[0233] The present application discloses several numerical range limitations, which support any range within the disclosed numerical range, even if the precise range limitation is not stated verbatim in the specification, because the embodiments of the compositions and methods disclosed herein can be implemented throughout the disclosed numerical range. For the use of substantially any plural or singular terminology herein, those skilled in the art can convert from the plural form to the singular form or from the singular form to the plural form, as long as it is appropriate according to the context or application. For the sake of clarity, various singular or plural arrangements can be explicitly set forth herein.

[0234] In general, those skilled in the art will understand that the terms used herein, particularly in the appended claims, are generally intended to be "open" terms. For example, the term "comprising" should be understood as "including but not limited to," the term "having" should be understood as "having at least," and the term "including" should be understood as "including but not limited to." Those skilled in the art will also understand that if a specific number of introduced claim recitations is desired, such intent will be clearly stated in the claim, and no such intent exists without such a statement. For example, for ease of understanding, the following appended claims may contain the use of the introductory phrases "at least one" and "one or more" to introduce claim recitations. However, the use of such phrases should not be construed as implying that the introduction of a claim recitation by the indefinite article "a" or "an" limits any particular claim containing such introduced claim recitation to an invention containing only one such recitation, even when the same claim includes the introductory phrase "one or more" or "at least one" and an indefinite article such as "a" or "an" (e.g., "a" or "an" should generally be understood to mean "at least one" or "one or more"); the same applies to the use of definite articles to introduce claim recitations. Furthermore, even if a specific number of introduced claim recitations is expressly stated, those skilled in the art will recognize that such recitations should generally be understood to mean at least the stated number (e.g., merely stating "two recitations" without other modifiers generally means at least two recitations, or two or more recitations). Furthermore, in those cases where a convention similar to "at least one of A, B, and C, etc." is used, such construction is generally intended to be understood by those skilled in the art (e.g., "a system having at least one of A, B, and C" will include, but is not limited to, a system having only A, a system having only B, a system having only C, a system having A and B, a system having A and C, a system having B and C, and / or a system having A, B, and C, etc.). Those skilled in the art will also understand that any transitional conjunction or phrase that actually gives two or more alternatives, whether in the specification, claims, or drawings, should be understood to contemplate the possibility of including one of these items, any of these items, or both. For example, the phrase "A or B" will be understood to include the possibility of "A" or "B" or "A and B". All references, including but not limited to patents, patent applications, and non-patent literature, are hereby incorporated by reference in their entirety. Although various aspects and embodiments of 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 purposes of illustration and are not intended to be limiting, with the true scope and spirit being indicated by the claims.

Claims

1. A method for preparing a modified high-cis polybutadiene polymer, the method comprising: A. providing a catalyst system, the catalyst system comprising 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), b. a nickel-based catalyst system comprising (i) a nickel compound, the nickel compound optionally being combined 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. using the catalyst system of (A) to polymerize 1,3-butadiene to produce a polymer chain having an active terminal end, C. reacting the active terminal polymer chain from (B) with a functionalized compound having the following formula (I) Wherein X is a cyano group, R 1 Independently selected from C1-C 20 A alkylene group, which optionally contains an unsaturated carbon-carbon bond, Each R' is independently selected from C1-C 20 of alkoxy, and Thereby producing a modified high cis polybutadiene having a cis 1,4-bond content of 92-98%, D. reacting the modified high cis polybutadiene from (C) with the following substances (1) A stabilizer of formula (II) R 2 n Si(OR 3 ) 4-n Where R 2 Choose from C1 to C 20 Alkyl, C4 to C 10 Cycloalkyl or C5 to C 20 Aromatic groups consisting of groups, Where R 3 Can be used with R 2 The same or different and selected from C1 to C 20 Alkyl, C4 to C 10 Cycloalkyl or C5 to C 20 Aromatic groups, and n is an integer from 1 to 3, and (2) A quencher of formula (III) R 4 COOH Where R 4 Selected from H and C1 to C 18 The group consisting of alkyl groups, and E. separating the modified high-cis polybutadiene of (D) to produce a final modified high-cis polybutadiene having Initial Mooney viscosity ML 20-100 at 100°C 1+4 ,as well as Aged Mooney viscosity ML not exceeding 120 at 100°C 1+4 , wherein the aged Mooney viscosity is measured after aging at 100° C. for 2 days.

2. The method according to claim 1, wherein the separated modified high cis polybutadiene has an initial Mooney viscosity ML of 30-80 at 100°C. 1+4 , and an aged Mooney viscosity ML not exceeding 105 at 100°C 1+4 .

3. A method according to claim 1 or claim 2, wherein the functionalized compound of formula (I) is used in a molar ratio of 100:1 to 0.5:1, the molar ratio being based on the number of moles of the functionalized compound: the number of moles of the main metal of the catalyst system; the stabilizer of formula (II) is used in a molar ratio of 0.1:1 to 50:1, the molar ratio being based on the number of moles of the stabilizer: the number of moles of the functionalized compound; and the quencher of formula (III) is used in a molar ratio of 0.1:1 to 10:1, the molar ratio being based on the number of moles of the quencher: the number of moles of the stabilizer of formula (II).

4. The method of claim 1 or claim 2, wherein the stabilizer of formula (II) comprises octyltriethoxysilane, the quencher of formula (III) comprises 2-ethylhexanoic acid, and the catalyst system is a lanthanide-based catalyst system (a).

5. The method according to claim 1 or claim 2, wherein the modified high-cis polybutadiene satisfies at least one of the following: a. having a Mw of 150,000 g / mol to 2,000,000 g / mol; b. having a Mn of 80,000 g / mol to 800,000 g / mol; c. having a Mw / Mn of 1.5 to 4; or d. having an initial Mooney viscosity ML1+4 of 40 to 80 at 100°C, Wherein Mw and Mn are determined by GPC using polystyrene standards. The method of claim 5 , wherein each of (a)-(d) is satisfied.

7. A modified high cis polybutadiene polymer having A polymer chain bonded to a residue of a functionalized compound having the formula (I) Wherein X is a cyano group, R 1 Independently selected from C1-C 20 A alkylene group, which optionally contains an unsaturated carbon-carbon bond, Each R' is independently selected from C1-C 20 of alkoxy, and wherein each polymer chain is bonded to the residue of the functionalized compound via the X group, and the polymer has 92-98% cis 1,4-bond content, Initial Mooney viscosity ML 20-100 at 100°C 1+4 ,as well as Aged Mooney viscosity ML not exceeding 120 at 100°C 1+4 , The aged Mooney viscosity is measured after aging at 100° C. for 2 days.

8. The modified high-cis polybutadiene polymer according to claim 7, which satisfies at least one of the following: a. having a Mw of 150,000 g / mol to 2,000,000 g / mol; b. having a Mn of 80,000 g / mol to 800,000 g / mol; c. having a Mw / Mn of 1.5 to 4; or d. Having an initial Mooney viscosity ML of 40 to 70 at 100°C 1+4 , Wherein Mw and Mn are determined by GPC using polystyrene standards.

9. The modified high-cis polybutadiene polymer according to claim 8, wherein each of (a) to (d) is satisfied.

10. A tire having a component comprising a rubber composition, the rubber composition comprising: a. an elastomeric component, the elastomeric component comprising: i. 10 phr to 100 phr of the modified high cis polybutadiene polymer according to any one of claims 7 to 9 or the modified high cis polybutadiene polymer produced by the method according to any one of claims 1 to 6, and ii. 0 phr to 90 phr of at least one additional polymer selected from the group consisting of unmodified polybutadiene, styrene-butadiene, natural rubber, polyisoprene, b. A reinforcing filler component, the reinforcing filler component comprising: i. 10phr-200phr of reinforcing silica filler, and ii. 0 phr to 50 phr of a reinforcing carbon black filler, wherein the reinforcing carbon black filler is present in an amount not exceeding 20% ​​by weight of the reinforcing silica filler, c. a plasticizing component, the plasticizing component comprising: i. 0-50 phr of at least one plasticizing oil, and ii. 0 phr to 60 phr of at least one hydrocarbon resin having a Tg of at least 30°C, and d. a cure package comprising at least one vulcanizing agent, at least one vulcanization accelerator, and optionally a vulcanization activator, a vulcanization inhibitor and / or a scorch retardant.

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