Patent Description:
High-cis polybutadiene polymers have numerous uses in industry, including use in tire rubber compositions for use in tire components such as tire treads. Modification of such high-cis polybutadiene polymers by certain functionalizing compounds to increase filler-polymer interactions may lead to a polymer with a desirable initial Mooney viscosity, but such polymers may be prone to Mooney viscosity growth upon aging creating challenges with storage of the modified polymer. <CIT> discloses a modified high-cis polybutadiene that exhibits low heat build-up.

Disclosed herein are a modified high-cis polybutadiene polymer, and a process for preparing the modified high-cis polybutadiene polymer.

In a first embodiment, a process is provided for preparing a modified high-cis polybutadiene polymer. According to the first embodiment, the process comprises: (A) providing a catalyst system comprising (a) a lanthanide-based catalyst system comprising (i) a lanthanide compound, (ii) an alkylating agent, and (iii) a halogen source, where (iii) may optionally be provided by (i), (ii), or both (i) and (ii); (b) a nickel-based catalyst system comprising (i) a nickel compound, optionally in combination with an alcohol, (ii) an organoaluminum, organomagnesium, organozinc compound, or a combination thereof, and (iii) a fluorine-containing compound or a complex thereof; or (c) a cobalt-based catalyst system, comprising (i) a cobalt compound, (ii) an organo aluminum halide, and (iii) optionally water; (B) using the catalyst system of (A) to polymerize <NUM>,<NUM>-butadiene to produce polymer chains with a living end; (C) reacting the living end polymer chains from (B) with a functionalizing compound having formula (I) as follows
<CHM>
where X is a group reactive with the living end polymer chains and is selected from the group consisting of cyano, epoxy, ketone, aldehyde, ester, and acid anhydrides, R<NUM> is selected from hydrocarbylene of C<NUM>-C<NUM>, wherein each of the foregoing optionally contain one unsaturated carbon-carbon bond, each R' is selected from alkoxy of C<NUM>-C<NUM>, and R" is selected from alkyl of C<NUM>-C<NUM> or aryl of C<NUM>-C<NUM>, thereby producing a modified high-cis polybutadiene having a cis <NUM>,<NUM>-bond content of <NUM>-<NUM>%; (D) isolating the modified high-cis polybutadiene of (C) to produce a final modified high-cis polybutadiene having, an initial Mooney viscosity ML<NUM>+<NUM> at <NUM> of <NUM>-<NUM>, and an aged Mooney viscosity ML<NUM>+<NUM> at <NUM> of no more than <NUM>.

In a second embodiment, a modified high-cis polybutadiene polymer is provided. According to the second embodiment, the modified high-cis polybutadiene polymer has polymer chains bonded to a residue of a functionalizing compound having formula (I) as follows
<CHM>
where X is a group reactive with the living end polymer chains and is selected from the group consisting of cyano, epoxy, ketone, aldehyde, ester, and acid anhydrides, R<NUM> is selected from hydrocarbylene of C<NUM>-C<NUM>, wherein each of the foregoing optionally contain one unsaturated carbon-carbon bond, R' is selected from alkoxy of C<NUM>-C<NUM>, and R" is selected from alkyl of C<NUM>-C<NUM> or aryl of C<NUM>-C<NUM>, and wherein each polymer chain is bonded to the residue of the functionalizing compound through the X group, and the polymer has an initial Mooney viscosity ML<NUM>+<NUM> at <NUM> of <NUM>-<NUM>, and an aged Mooney viscosity ML<NUM>+<NUM> at <NUM> of no more than <NUM>.

Disclosed herein are a modified high-cis polybutadiene polymer, processes for preparing the modified high-cis polybutadiene polymer, and tire rubber compositions containing the modified high-cis polybutadiene polymer.

In a first embodiment, a process is provided for preparing a modified high cis polybutadiene polymer. According to the first embodiment, the process comprises: (A) providing a catalyst system comprising (a) a lanthanide-based catalyst system comprising (i) a lanthanide compound, (ii) an alkylating agent, and (iii) a halogen source, where (iii) may optionally be provided by (i), (ii), or both (i) and (ii); (b) a nickel-based catalyst system comprising (i) a nickel compound, optionally in combination with an alcohol, (ii) an organoaluminum, organomagnesium, organozinc compound, or a combination thereof, and (iii) a fluorine-containing compound or a complex thereof; or (c) a cobalt-based catalyst system, comprising (i) a cobalt compound, (ii) an organo aluminum halide, and (iii) optionally water; (B) using the catalyst system of (A) to polymerize <NUM>,<NUM>-butadiene to produce polymer chains with a living end; (C) reacting the living end polymer chains from (B) with a functionalizing compound having formula (I) as follows
<CHM>
where X is a group reactive with the living end polymer chains and is selected from the group consisting of cyano, epoxy, ketone, aldehyde, ester, and acid anhydrides, R<NUM> is selected from hydrocarbylene of C<NUM>-C<NUM>, preferably C<NUM>-C<NUM>, more preferably C<NUM>-C<NUM>, wherein each of the foregoing optionally contain one unsaturated carbon-carbon bond, each R' is selected from alkoxy of C<NUM>-C<NUM>, preferably alkoxy of C<NUM>-C<NUM>, more preferably alkoxy of C<NUM>-C<NUM>, most preferably alkoxy of C<NUM> or C<NUM>, and R" is selected from alkyl of C<NUM>-C<NUM> or aryl of C<NUM>-C<NUM>, preferably alkyl of C<NUM>-C<NUM> or aryl of C<NUM>-C<NUM>, more preferably alkyl of C<NUM>-C<NUM> or aryl of C<NUM>, thereby producing a modified high-cis polybutadiene having a cis <NUM>,<NUM>-bond content of at least <NUM>%, preferably at least <NUM>%; (D) isolating the modified high-cis polybutadiene of (C), wherein the isolating preferably takes place by steam distillation, to produce a final modified high-cis polybutadiene having, an initial Mooney viscosity ML<NUM>+<NUM> at <NUM> of <NUM>-<NUM>, preferably <NUM>-<NUM>, and an aged Mooney viscosity ML<NUM>+<NUM> at <NUM> of no more than <NUM>, preferably no more than <NUM>.

In a second embodiment, a modified high-cis polybutadiene polymer is provided. According to the second embodiment, the modified high-cis polybutadiene polymer has polymer chains bonded to a residue of a functionalizing compound having formula (I) as follows
<CHM>
where X is a group reactive with the living end polymer chains and is selected from the group consisting of cyano, epoxy, ketone, aldehyde, ester, and acid anhydrides, R<NUM> is selected from hydrocarbylene of C<NUM>-C<NUM>, preferably C<NUM>-C<NUM>, more preferably C<NUM>-C<NUM>, wherein each of the foregoing optionally contain one unsaturated carbon-carbon bond, R' is selected from alkoxy of C<NUM>-C<NUM>, preferably alkoxy of C<NUM>-C<NUM>, more preferably alkoxy of C<NUM>-C<NUM>, most preferably alkoxy of C<NUM> or C<NUM>, and R" is selected from alkyl of C<NUM>-C<NUM> r aryl of C<NUM>-C<NUM>, preferably alkyl of C<NUM>-C<NUM> or aryl of C<NUM>-C<NUM>, more preferably alkyl of C<NUM>-C<NUM> or aryl of C<NUM>, and wherein each polymer chain is bonded to the residue of the functionalizing compound through the X group, and the polymer has an initial Mooney viscosity ML<NUM>+<NUM> at <NUM> of <NUM>-<NUM>, preferably <NUM>-<NUM>, and an aged Mooney viscosity ML<NUM>+<NUM> at <NUM> of no more than <NUM>, preferably no more than <NUM>.

The terminology as set forth herein is for description of the embodiments only and should not be construed as limiting the invention as a whole.

As used herein, the term "living end" (e.g., living end of a polymer chain) is used to refer to a polymer species having a living end that has not yet been terminated; the living end is capable of reacting with a functionalizing compound and, thus, can be described as reactive.

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

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

Unless otherwise indicated herein, the term "Mooney viscosity" refers to the Mooney viscosity, ML<NUM>+<NUM>. As those of skill in the art will understand, a polymer or rubber composition's Mooney viscosity is measured prior to vulcanization or curing.

As used herein, the term "natural rubber" means naturally occurring rubber such as can be harvested from sources such as Hevea rubber trees and non-Hevea sources (e.g., guayule shrubs and dandelions such as TKS). In other words, the term "natural rubber" should be construed so as to exclude synthetic polyisoprene.

As used herein, the term "phr" means parts per one hundred parts rubber. The one hundred parts rubber may also be referred to herein as <NUM> parts of an elastomer component.

As used herein the term "polyisoprene" means synthetic polyisoprene. In other words, the term is used to indicate a polymer that is manufactured from isoprene monomers, and should not be construed as including naturally occurring rubber (e.g., Hevea natural rubber, guayule-sourced natural rubber, or dandelion-sourced natural rubber). However, the term polyisoprene should be construed as including polyisoprenes manufactured from natural sources of isoprene monomer.

As used herein, the term "tread," refers to both the portion of a tire that comes into contact with the road under normal inflation and load as well as any subtread.

Generally, process of the first embodiment described herein can be considered to be solution polymerization processes. In this type of polymerization process, the polymerization reaction takes place in organic solvent-based solution. Here, that organic solvent-based solution initially contains a quantity of conjugated diene monomer and one of the specified catalyst systems. Generally, according to the processes of the first embodiment, the organic solvent-based solution comprises <NUM>-<NUM>% by weight (wt%) organic solvent based on the total weight of the monomer, organic solvent, and polybutadiene in the solution. Preferably, the organic solvent comprises the predominant component of the solution, i.e., <NUM>-<NUM> wt% organic solvent, and more preferably <NUM> wt% to <NUM> wt% organic solvent based on the total weight of the monomer, organic solvent, and polybutadiene. The solution polymerization processes disclosed herein can be contrasted with gas-type or bulk-type polymerizations, where polymerization is carried out in the absence of any organic solvent or where there is less than <NUM> wt% organic solvent present based on the total weight of the monomer, organic solvent, and polybutadiene.

Suitable organic solvents for use in solution polymerization processes according to the first embodiment described herein are those solvents that are inert to the polymerization reaction such that the solvent is not a reactant in the polymerization reaction. Suitable organic solvents include aromatic hydrocarbons, aliphatic hydrocarbons, and cycloaliphatic hydrocarbons. Examples of suitable aromatic hydrocarbon solvents include, but are not limited to benzene, toluene, ethylbenzene, diethylbenzene, naphthalenes, mesitylene, xylenes, and the like. Examples of suitable aliphatic hydrocarbon solvents include, but are not limited to, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, isopentane, hexanes, isohexanes, isopentanes, isooctanes, <NUM>,<NUM>-dimethylbutane, petroleum ether, kerosene, petroleum spirits, and the like. Non-limiting examples of suitable cycloaliphatic hydrocarbon solvents include cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, and the like. Mixtures of the foregoing aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, and cycloaliphatic hydrocarbon solvents can also be used. In certain embodiments of the first embodiment, the preferred organic solvent includes an aliphatic hydrocarbon solvent, a cycloaliphatic hydrocarbon solvent, or mixtures thereof. Additional useful organic solvents suitable for use in the processes of the first embodiment are known to those skilled in the art.

Solution polymerization processes according to the first embodiment disclosed herein are preferably conducted under anaerobic conditions under a blanket of inert gas, such as nitrogen, argon, or helium. The polymerization temperature may vary widely, ranging from -<NUM> to <NUM>, with the preferred temperature range being <NUM> to <NUM>. The polymerization pressure may also vary widely, ranging from <NUM> atmosphere (atm) to <NUM> atm, preferably <NUM> atm to <NUM> atm (e.g., <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, or <NUM> atm).

A solution polymerization process according to the first embodiment disclosed herein may be conducted as a continuous, a semi-continuous, or a batch process. In a semi-continuous process, the monomer is intermittingly charged to replace the monomer that has already polymerized. The polymerization of <NUM>,<NUM>-butadiene monomer into a high-cis polybutadiene in accordance with the processes described herein occurs when the monomer and the lanthanide-based catalyst system are all present in the organic solvent-based solution. The order of addition of the monomer and catalyst to the organic solvent does not matter.

Generally, the polymerization process of the first embodiment as disclosed herein can be stopped by adding any suitable terminating agent. Non-limiting examples of suitable terminating agents include protic compounds, such as alcohols, carboxylic acids, inorganic acids, water, and mixtures thereof. Other suitable terminating agents are known to those skilled in the art. Furthermore, once the polymerization has been stopped, the resulting high-cis polydiene can be recovered (or isolated) from the solution using conventional methods, e.g., steam desolventization or steam distillation, coagulation with an alcohol, filtration, purification, drying, etc., known to those skilled in the art. In preferred embodiments of the first embodiment, the high-cis polybutadiene polymer is isolated by the use of steam distillation.

As mentioned above, according to the process of the first embodiment, the catalyst system is selected from one of (a) a lanthanide-based catalyst system, (b) a nickel-based catalyst system, or (c) a cobalt-based catalyst system. Preferably, a lanthanide-based catalyst system is used. Use of one of the specified catalyst systems in the process of the first embodiment provides advantages in modifying the living end of the polymer chains with a functionalizing compound, as discussed further infra. According to the process of the first embodiment, the catalyst system that is used avoids the use of anionic initiator (e.g., an organolithium compound such as n-butyl lithium).

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

As mentioned above, the lanthanide-based catalyst system employed in the processes of the first embodiment includes a lanthanide compound. Lanthanide compounds useful in the processes of the first embodiment are those compounds that include at least one atom of a lanthanide element. As used herein, "lanthanide element" refers to the elements found in the lanthanide series of the Periodic Table (i.e., element numbers <NUM>-<NUM>) as well as didymium, which is a mixture of rare-earth elements obtained from monazite sand. In particular, the lanthanide elements 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 includes at least one atom of neodymium, gadolinium, samarium, or combinations thereof. Most preferably, the lanthanide compound includes at least one atom of neodymium.

The lanthanide atom in the lanthanide compound can be in various oxidation states including, but not limited to, the <NUM>, +<NUM>, +<NUM>, and +<NUM> oxidation states. In accordance with certain preferred embodiments of the processes of the first embodiment, a trivalent lanthanide compound, where the lanthanide atom is in the +<NUM> oxidation state, is used. Generally, suitable lanthanide compounds for use in the processes of the first embodiment include, but are not limited to, lanthanide carboxylates, lanthanide organophosphates, lanthanide organophosphonates, lanthanide organophosphinates, lanthanide carbamates, lanthanide dithiocarbamates, lanthanide xanthates, lanthanide β-diketonates, lanthanide alkoxides or aryloxides, lanthanide halides, lanthanide pseudo-halides, lanthanide oxyhalides, and organolanthanide compounds. Preferably, the lanthanide compound is a lanthanide carboxylate, more preferably a neodymium carboxylate and most preferably neodymium versatate.

In accordance with certain embodiments of the processes of the first embodiment, the lanthanide compound(s) may be soluble in hydrocarbon solvents such as the aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, or cycloaliphatic hydrocarbon solvents disclosed herein. Hydrocarbon-insoluble lanthanide compounds, however, can also be useful in the process of the first embodiment, as they can be suspended in the polymerization medium to form the catalytically active species.

For ease of illustration, further discussion of useful lanthanide compounds for use in the processes of the first embodiment will focus on neodymium compounds, although those skilled in the art will be able to select similar compounds that are based upon the other lanthanide metals disclosed herein.

Examples of suitable neodymium carboxylates for use as the lanthanide compound in the processes 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 <NUM>-ethylhexanoate, neodymium neodecanoate (i.e., neodymium versatate or NdV<NUM>), neodymium naphthenate, neodymium stearate, neodymium oleate, neodymium benzoate, and neodymium picolinate.

Examples of suitable neodymium organophosphates for use as the lanthanide compound in the processes of the first embodiment include, but are not limited to, neodymium dibutyl phosphate, neodymium dipentyl phosphate, neodymium dihexyl phosphate, neodymium diheptyl phosphate, neodymium dioctyl phosphate, neodymium bis(<NUM>-methylheptyl)phosphate, neodymium bis(<NUM>-ethylhexyl)phosphate, neodymium didecyl phosphate, neodymium didodecyl phosphate, neodymium dioctadecyl phosphate, neodymium dioleyl phosphate, neodymium diphenyl phosphate, neodymium bis(p-nonylphenyl)phosphate, neodymium butyl (<NUM>-ethylhexyl)phosphate, neodymium (<NUM>-methylheptyl) (<NUM>-ethylhexyl)phosphate, and neodymium (<NUM>-ethylhexyl) (p-nonylphenyl)phosphate.

Examples of suitable neodymium organophosphonates for use as the lanthanide compound in processes of the first embodiment include, but are not limited to, neodymium butyl phosphonate, neodymium pentyl phosphonate, neodymium hexyl phosphonate, neodymium heptyl phosphonate, neodymium octyl phosphonate, neodymium (<NUM>-methylheptyl)phosphonate, neodymium (<NUM>-ethylhexyl)phosphonate, neodymium decyl phosphonate, neodymium dodecyl phosphonate, neodymium octadecyl phosphonate, neodymium oleyl phosphonate, neodymium phenyl phosphonate, neodymium (p-nonylphenyl)phosphonate, neodymium butyl butylphosphonate, neodymium pentyl pentylphosphonate, neodymium hexyl hexylphosphonate, neodymium heptyl heptylphosphonate, neodymium octyl octylphosphonate, neodymium (<NUM>-methylheptyl) (<NUM>-methylheptyl)phosphonate, neodymium (<NUM>-ethylhexyl) (<NUM>-ethylhexyl)phosphonate, neodymium decyl decylphosphonate, neodymium dodecyl dodecylphosphonate, neodymium octadecyl octadecylphosphonate, neodymium oleyl oleylphosphonate, neodymium phenyl phenylphosphonate, neodymium (p-nonylphenyl) (p-nonylphenyl)phosphonate, neodymium butyl (<NUM>-ethylhexyl)phosphonate, neodymium (<NUM>-ethylhexyl)butylphosphonate, neodymium (<NUM>-methylheptyl) (<NUM>-ethylhexyl)phosphonate, neodymium (<NUM>-ethylhexyl) (<NUM>-methylheptyl)phosphonate, neodymium (<NUM>-ethylhexyl) (p-nonylphenyl)phosphonate, and neodymium (p-nonylphenyl) (<NUM>-ethylhexyl)phosphonate.

Examples of suitable neodymium organophosphinates for use as the lanthanide compound in the processes of the first embodiment include, but are not limited to, neodymium butylphosphinate, neodymium pentylphosphinate, neodymium hexylphosphinate, neodymium heptylphosphinate, neodymium octylphosphinate, neodymium (<NUM>-methylheptyl)phosphinate, neodymium (<NUM>-ethylhexyl)phosphinate, neodymium decylphosphinate, neodymium dodecylphosphinate, neodymium octadecylphosphinate, neodymium oleylphosphinate, neodymium phenylphosphinate, neodymium (p-nonylphenyl)phosphinate, neodymium dibutylphosphinate, neodymium dipentylphosphinate, neodymium dihexylphosphinate, neodymium diheptylphosphinate, neodymium dioctylphosphinate, neodymium bis(<NUM>-methylheptyl)phosphinate, neodymium bis(<NUM>-ethylhexyl)phosphinate, neodymium didecylphosphinate, neodymium didodecylphosphinate, neodymium dioctadecylphosphinate, neodymium dioleylphosphinate, neodymium diphenylphosphinate, neodymium bis(p-nonylphenyl)phosphinate, neodymium butyl (<NUM>-ethylhexyl)phosphinate, neodymium (<NUM>-methylheptyl)(<NUM>-ethylhexyl)phosphinate, and neodymium (<NUM>-ethylhexyl)(p-nonylphenyl)phosphinate.

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

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

Examples of suitable neodymium xanthates for use as the lanthanide compound in the processes of the first embodiment include, but are not limited to, neodymium methylxanthate, neodymium ethylxanthate, neodymium isopropylxanthate, neodymium butylxanthate, and neodymium benzylxanthate.

Examples of suitable neodymium β-diketonates for use as the lanthanide compound in the processes of the first embodiment include, but are not limited to, neodymium acetylacetonate, neodymium trifluoroacetylacetonate, neodymium hexafluoroacetylacetonate, neodymium benzoylacetonate, and neodymium <NUM>,<NUM>,<NUM>,<NUM>-tetramethyl-<NUM>,<NUM>-heptanedionate.

Examples of suitable neodymium alkoxides or aryloxides for use as the lanthanide compound in the processes of the first embodiment include, but are not limited to, neodymium methoxide, neodymium ethoxide, neodymium isopropoxide, neodymium <NUM>-ethylhexoxide, neodymium phenoxide, neodymium nonylphenoxide, and neodymium naphthoxide.

Examples of suitable neodymium halides for use as the lanthanide compound in the processes of the first embodiment include, but are not limited to, neodymium fluoride, neodymium chloride, neodymium bromide, and neodymium iodide. Suitable neodymium pseudo-halides include, but are not limited to, neodymium cyanide, neodymium cyanate, neodymium thiocyanate, neodymium azide, and neodymium ferrocyanide. Suitable neodymium oxyhalides include, but are not limited to, neodymium oxyfluoride, neodymium oxychloride, and neodymium oxybromide. A Lewis base, such as tetrahydrofuran ("THF"), can be employed as an aid for solubilizing this class of neodymium compounds in inert organic solvents. Where lanthanide halides, lanthanide oxyhalides, or other lanthanide compounds containing a halogen atom are used, the lanthanide compound may optionally also provide all or part of the halogen source in the lanthanide-based catalyst system.

As used herein, the term "organolanthanide compound" refers to any lanthanide compound containing at least one lanthanide-carbon bond. These compounds are predominantly, though not exclusively, those containing cyclopentadienyl ("Cp"), substituted cyclopentadienyl, allyl, and substituted allyl ligands. Suitable organolanthanide compounds for use as the lanthanide compound in the processes of the first embodiment include, but are not limited to, Cp<NUM>Ln, Cp<NUM>LnR, Cp<NUM>LnCl, CpLnCl<NUM>, CpLn(cyclooctatetraene), (C<NUM>Me<NUM>)<NUM>LnR, LnR<NUM>, Ln(allyl)<NUM>, and Ln(allyl)<NUM>Cl, where Ln represents a lanthanide atom, and R represents a hydrocarbyl group or a substituted hydrocarbyl group. In one or more embodiments, hydrocarbyl groups or substituted hydrocarbyl groups useful in the processes of the first embodiment may contain heteroatoms such as, for example, nitrogen, oxygen, boron, silicon, sulfur, and phosphorus atoms.

As mentioned above, the lanthanide-based catalyst system employed in the processes of the first embodiment includes an alkylating agent. In accordance with one or more embodiments of the processes of the first embodiment, alkylating agents, which may also be referred to as hydrocarbylating agents, include organometallic compounds that can transfer one or more hydrocarbyl groups to another metal. Generally, these agents include organometallic compounds of electropositive metals such as Groups <NUM>, <NUM>, and <NUM> metals (Groups IA, IIA, and IIIA metals). Alkylating agents useful in the processes 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, organoaluminum compounds that are soluble in a hydrocarbon solvent can be used. As used herein, the term "organomagnesium compound" refers to any magnesium-containing compound having at least one magnesium-carbon bond. In one or more embodiments, organomagnesium compounds that are soluble in a hydrocarbon can be used. As will be described in more detail below, certain suitable alkylating agents may be in the form of a halide compound. Where the alkylating agent includes a halogen atom, the alkylating agent may optionally also provide all or part of the halogen source in the lanthanide-based catalyst system.

In one or more embodiments of the processes of the first embodiment, organoaluminum compounds that are utilized include those represented by the general formula AlRanX<NUM>-n, where each Ra independently is a monovalent organic group that is attached to the aluminum atom via a carbon atom; where each X independently is a hydrogen atom, a halogen atom, a carboxylate group, an alkoxide group, or an aryloxide group; and where n is an integer in the range of from <NUM> to <NUM>. In one or more embodiments, each Ra independently is 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, with each group containing from <NUM> carbon atom, or the appropriate minimum number of atoms to form the group, up to <NUM> carbon atoms (e.g., <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM> or <NUM> 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.

Examples of types of organoaluminum compounds for use as the alkylating agent in the processes of the first embodiment that are represented by the general formula AlRanX<NUM>-n include, but are not limited to, trihydrocarbylaluminum, dihydrocarbylaluminum hydride, hydrocarbylaluminum dihydride, dihydrocarbylaluminum carboxylate, hydrocarbylaluminum bis(carboxylate), dihydrocarbylaluminum alkoxide, hydrocarbylaluminum dialkoxide, dihydrocarbylaluminum halide, hydrocarbylaluminum dihalide, dihydrocarbylaluminum aryloxide, and hydrocarbylaluminum diaryloxide compounds.

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

Examples of suitable dihydrocarbylaluminum hydride compounds for use as the alkylating agent in the processes 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, phenylisobutylaluminum hydride, phenyl-n-octylaluminum hydride, p-tolylethylaluminum hydride, p-tolyl-n-propylaluminum hydride, p-tolylisopropylaluminum hydride, p-tolyl-n-butylaluminum hydride, p-tolylisobutylaluminum hydride, p-tolyl-n-octylaluminum hydride, benzylethylaluminum hydride, benzyl-n-propylaluminum hydride, benzylisopropylaluminum hydride, benzyl-n-butylaluminum hydride, benzylisobutylaluminum hydride, and benzyl-n-octylaluminum hydride.

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

Examples of suitable dihydrocarbylaluminum halide compounds for use as the alkylating agent in the processes 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.

Examples of suitable hydrocarbylaluminum dihalide compounds for use as the alkylating agent in the processes 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.

Examples of other suitable organoaluminum compounds for use as the alkylating agent in the processes of the first embodiment that are represented by the general formula AlRanX<NUM>-n include, but are not limited to, dimethylaluminum hexanoate, diethylaluminum octoate, diisobutylaluminum <NUM>-ethylhexanoate, dimethylaluminum neodecanoate, diethylaluminum stearate, diisobutylaluminum oleate, methylaluminum bis(hexanoate), ethylaluminum bis(octoate), isobutylaluminum bis(<NUM>-ethylhexanoate), methylaluminum bis(neodecanoate), ethylaluminum bis(stearate), isobutylaluminum bis(oleate), dimethylaluminum methoxide, diethylaluminum methoxide, diisobutylaluminum methoxide, dimethylaluminum ethoxide, diethylaluminum ethoxide, diisobutylaluminum ethoxide, dimethylaluminum phenoxide, diethylaluminum phenoxide, diisobutylaluminum phenoxide, methylaluminum dimethoxide, ethylaluminum dimethoxide, isobutylaluminum dimethoxide, methylaluminum diethoxide, ethylaluminum diethoxide, isobutylaluminum diethoxide, methylaluminum diphenoxide, ethylaluminum diphenoxide, and isobutylaluminum diphenoxide.

Another class of organoaluminum compounds suitable for use as an alkylating agent in the processes of the first embodiment is aluminoxanes. Suitable aluminoxanes include oligomeric linear aluminoxanes, which can be represented by the general formula:
<CHM>
and oligomeric cyclic aluminoxanes, which can be represented by the general formula:
<CHM>
where x is an integer in the range of from <NUM> to <NUM> (e.g., <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, or <NUM>), or <NUM> to <NUM> (e.g., <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, or <NUM>); y is an integer in the range of from <NUM> to <NUM> (e.g., <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM> or <NUM>), or <NUM> to <NUM> (e.g., <NUM>, <NUM>, <NUM>, <NUM>, or <NUM>); and where each R independently is a monovalent organic group that is attached to the aluminum atom via a carbon atom. In one embodiment of the processes of the first embodiment, each R independently is 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, with each group preferably containing from <NUM> carbon atom, or the appropriate minimum number of atoms to form the group, up to <NUM> carbon atoms (e.g., <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM> or <NUM> 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 the aluminoxane refers to the number of moles of the aluminum atoms rather than the number of moles of the oligomeric aluminoxane molecules. This convention is commonly employed in the art of catalyst systems utilizing aluminoxanes.

Aluminoxanes can be prepared by reacting trihydrocarbylaluminum compounds with water. This reaction can be performed according to known methods, such as, for example, (<NUM>) a method in which the trihydrocarbylaluminum compound is dissolved in an organic solvent and then contacted with water, (<NUM>) a method in which the trihydrocarbylaluminum compound is reacted with water of crystallization contained in, for example, metal salts, or water adsorbed in inorganic or organic compounds, or (<NUM>) a method in which the trihydrocarbylaluminum compound is reacted with water in the presence of the monomer or monomer solution that is to be polymerized.

Examples of suitable aluminoxane compounds for use as the alkylating agent in the processes 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, <NUM>-ethylhexylaluminoxane, cyclohexylaluminoxane, <NUM>-methylcyclopentylaluminoxane, phenylaluminoxane, and <NUM>,<NUM>-dimethylphenylaluminoxane. In certain preferred embodiments of the processes of the first embodiment, the alkylating agent includes MAO. Modified methylaluminoxane can be formed by substituting from <NUM> to <NUM> percent of the methyl groups of methylaluminoxane with C<NUM> to C<NUM> hydrocarbyl groups (e.g., C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM> or C<NUM>), preferably with isobutyl groups, by using techniques known to those skilled in the art.

In accordance with certain embodiments of the processes of the first embodiment, aluminoxanes 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., an organoaluminum compound represented by AlRanX<NUM>-n, are used in combination as the alkylating agent. In accordance with this and other embodiments, the alkylating agent comprises a dihydrocarbylaluminum hydride, a dihydrocarbylaluminum halide, an aluminoxane, or combinations thereof. For example, in accordance with one embodiment, the alkylating agent comprises diisobutylaluminum hydride, diethylaluminum chloride, methylaluminoxane, or combinations thereof. <CIT>, which is incorporated herein by reference in its entirety, provides other examples where aluminoxanes and organoaluminum compounds can be employed in combination.

As mentioned above, suitable alkylating agents used in the processes of the first embodiment include organomagnesium compounds. In accordance with one or more embodiments, of the processes of the first embodiment, suitable organomagnesium compounds include those represented by the general formula MgRb<NUM>, where each Rb independently is a monovalent organic group that is attached to the magnesium atom via a carbon atom. In one or more embodiments, each Rb independently 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, with each group preferably containing from <NUM> carbon atom, or the appropriate minimum number of atoms to form the group, up to <NUM> carbon atoms (e.g., <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM> or <NUM> 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.

Examples of suitable organomagnesium compounds for use as the alkylating agent in the processes of the first embodiment hat are represented by the general formula MgRb<NUM> include, but are not limited to, diethylmagnesium, di-n-propylmagnesium, diisopropylmagnesium, dibutylmagnesium, dihexylmagnesium, diphenylmagnesium, and dibenzylmagnesium.

Another class of organomagnesium compounds suitable for use as an alkylating agent in accordance with embodiments of the processes of the first embodiment is represented by the general formula RcMgXc, where Rc is a monovalent organic group that is attached 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 aryloxide group. In one or more embodiments, Rc 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, with each group containing from <NUM> carbon atom, or the appropriate minimum number of atoms to form the group, up to <NUM> carbon atoms (e.g., <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM> or <NUM> 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, Xc is a carboxylate group, an alkoxide group, or an aryloxide group, with each group containing from <NUM> carbon atom up to <NUM> carbon atoms (e.g., <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM> or <NUM> carbon atoms).

Examples of suitable types of organomagnesium compounds for use as the alkylating agent in the processes of the first embodiment that are represented by the general formula RcMgXc include, but are not limited to, hydrocarbylmagnesium hydride, hydrocarbylmagnesium halide, hydrocarbylmagnesium carboxylate, hydrocarbylmagnesium alkoxide, and hydrocarbylmagnesium aryloxide.

Examples of suitable organomagnesium compounds for use as the alkylating agent in the processes of the first embodiment represented by the general formula RcMgXc 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 phenoxide, ethylmagnesium phenoxide, butylmagnesium phenoxide, hexylmagnesium phenoxide, phenylmagnesium phenoxide, and benzylmagnesium phenoxide.

As mentioned above, the lanthanide-based catalyst systems employed in the processes of the first embodiment include a halogen source. As used herein, the term "halogen source" refers to any substance including at least one halogen atom. In accordance with one or more embodiments of the processes of the first embodiment, all or part of the halogen source may optionally be provided by the lanthanide compound, the alkylating agent, or both the lanthanide compound and the alkylating agent. In other words, the lanthanide compound may serve as both the lanthanide compound and all or at least a portion of the halogen source. Similarly, the alkylating agent may serve as both the alkylating agent and all or at least a portion of the halogen source.

In accordance with certain embodiments of the processes of the first embodiment, at least a portion of the halogen source may be present in the catalyst system in the form of a separate and distinct halogen-containing compound. Various compounds, or mixtures thereof, that contain one or more halogen atoms can be used as the halogen source. Examples of halogen atoms include, but are not limited to, fluorine, chlorine, bromine, and iodine. A combination of two or more halogen atoms can also be utilized. Halogen-containing compounds that are soluble in an organic solvent, such as the aromatic hydrocarbon, aliphatic hydrocarbon, and cycloaliphatic hydrocarbon solvents disclosed herein, are suitable for use as the halogen source in the processes of the first embodiment. In addition, hydrocarbon-insoluble halogen-containing compounds that can be suspended in a polymerization system to form the catalytically active species are also useful in certain embodiments of the processes of the first embodiment.

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

Examples of elemental halogens suitable for use as the halogen source in the processes 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.

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

Examples of suitable organic halides for use as the halogen source in the processes of the first embodiment include, but are not limited to, t-butyl chloride, t-butyl bromide, allyl chloride, allyl bromide, benzyl chloride, benzyl bromide, chloro-di-phenylmethane, bromo-di-phenylmethane, triphenylmethyl chloride, triphenylmethyl bromide, benzylidene chloride, benzylidene bromide, methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, trimethylchlorosilane, benzoyl chloride, benzoyl bromide, propionyl chloride, propionyl bromide, methyl chloroformate, and methyl bromoformate.

Examples of suitable inorganic halides for use as the halogen source in the processes 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.

Examples of suitable metallic halides for use as the halogen source in the processes 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.

Examples of suitable organometallic halides for use as the halogen source in the processes 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, methylaluminum sesquichloride, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, 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-t-butyltin dichloride, di-t-butyltin dibromide, dibutyltin dichloride, dibutyltin dibromide, tributyltin chloride, and tributyltin bromide. In accordance with one embodiment, the halogen source comprises an organometallic halide. For example, in accordance with certain embodiments, the halogen source comprises diethylaluminum chloride, which as mentioned above can also serve as an alkylating agent in the lanthanide-based catalyst system. Thus, in accordance with certain embodiments of the processes of the first embodiment, the halogen source may be provided in all or in part by the alkylating agent in the catalyst systems disclosed herein.

The lanthanide-based catalyst system used in the process of the first embodiment may be formed by combining or mixing the foregoing catalyst ingredients. The terms "catalyst composition" and "catalyst system," as referred to herein, encompass a simple mixture of the ingredients, a complex of the various ingredients that is caused by physical or chemical forces of attraction, a chemical reaction product of the ingredients, or a combination of the foregoing. The terms "catalyst composition" and "catalyst system" can be used interchangeably herein.

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

According to the processes of the first embodiment, the nickel compound that is used in the nickel-based catalyst system may vary. The nickel atom in the nickel-containing compound can be in various oxidation states including but not limited to the <NUM>, +<NUM>, +<NUM>, and +<NUM> oxidation states. Suitable nickel-containing compounds for use in a nickel-based catalyst system according to the process of the first embodiment include, but are not limited to, nickel carboxylates, nickel carboxylate borates, nickel organophosphates, nickel organophosphonates, nickel organophosphinates, nickel carbamates, nickel dithiocarbamates, nickel xanthates, nickel β-diketonates, nickel alkoxides or aryloxides, nickel halides, nickel pseudo-halides, nickel oxyhalides, and organonickel compounds. In preferred embodiments of the process of the first embodiment, when a nickel-based catalyst system is used, the nickel compound is a nickel carboxylate.

Suitable nickel carboxylates can include nickel formate, nickel acetate, nickel acrylate, nickel methacrylate, nickel valerate, nickel gluconate, nickel citrate, nickel fumarate, nickel lactate, nickel maleate, nickel oxalate, nickel <NUM>-ethylhexanoate, nickel neodecanoate, nickel naphthenate, nickel stearate, nickel oleate, nickel benzoate, and nickel picolinate.

Suitable nickel carboxylate borates may include compounds defined by the formulae (RCOONiO)<NUM>B or (RCOONiO)<NUM>B(OR), where each R, which may be the same or different, is a hydrogen atom or a mono-valent organic group. In one embodiment, each R may be a hydrocarbyl group such as, but not limited to, alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, aralkyl, alkaryl, allyl, and alkynyl groups, with each group preferably containing from <NUM> carbon atom, or the appropriate minimum number of carbon atoms to form the group, up to about <NUM> carbon atoms. These hydrocarbyl groups may contain heteroatoms such as, but not limited to, nitrogen, oxygen, silicon, sulfur, and phosphorus atoms. Nickel carboxylate borate may include those disclosed in <CIT>, which is incorporated herein by reference. Specific examples of nickel carboxylate borate include nickel(II) neodecanoate borate, nickel(II) hexanoate borate, nickel(II) naphthenate borate, nickel(II) stearate borate, nickel(II) octoate borate, nickel(II) <NUM>-ethylhexanoate borate, and mixtures thereof.

Suitable nickel organophosphates can include nickel dibutyl phosphate, nickel dipentyl phosphate, nickel dihexyl phosphate, nickel diheptyl phosphate, nickel dioctyl phosphate, nickel bis(<NUM>-methylheptyl)phosphate, nickel bis(<NUM>-ethylhexyl)phosphate, nickel didecyl phosphate, nickel didodecyl phosphate, nickel dioctadecyl phosphate, nickel dioleyl phosphate, nickel diphenyl phosphate, nickel bis(p-nonylphenyl)phosphate, nickel butyl(<NUM>-ethylhexyl)phosphate, nickel (<NUM>-methylheptyl) (<NUM>-ethylhexyl)phosphate, and nickel (<NUM>-ethylhexyl) (p-nonylphenyl)phosphate.

Suitable nickel organophosphonates can include nickel butyl phosphonate, nickel pentyl phosphonate, nickel hexyl phosphonate, nickel heptyl phosphonate, nickel octyl phosphonate, nickel (<NUM>-methylheptyl)phosphonate, nickel (<NUM>-ethylhexyl)phosphonate, nickel decyl phosphonate, nickel dodecyl phosphonate, nickel octadecyl phosphonate, nickel oleyl phosphonate, nickel phenyl phosphonate, nickel (p-nonylphenyl)phosphonate, nickel butyl butylphosphonate, nickel pentyl pentylphosphonate, nickel hexyl hexylphosphonate, nickel heptyl heptylphosphonate, nickel octyl octylphosphonate, nickel (<NUM>-methylheptyl) (<NUM>-methylheptyl)phosphonate, nickel (<NUM>-ethylhexyl) (<NUM>-ethylhexyl)phosphonate, nickel decyl decylphosphonate, nickel dodecyl dodecylphosphonate, nickel octadecyl octadecylphosphonate, nickel oleyl oleylphosphonate, nickel phenyl phenylphosphonate, nickel (p-nonylphenyl) (p-nonylphenyl)phosphonate, nickel butyl(<NUM>-ethylhexyl)phosphonate, nickel (<NUM>-ethylhexyl)butylphosphonate, nickel (<NUM>-methylheptyl) (<NUM>-ethylhexyl)phosphonate, nickel (<NUM>-ethylhexyl) (<NUM>-methylheptyl)phosphonate, nickel (<NUM>-ethylhexyl) (p-nonylphenyl)phosphonate, and nickel (p-nonylphenyl) (<NUM>-ethylhexyl)phosphonate.

Suitable nickel organophosphinates can include nickel butylphosphinate, nickel pentylphosphinate, nickel hexylphosphinate, nickel heptylphosphinate, nickel octylphosphinate, nickel (<NUM>-methylheptyl)phosphinate, nickel (<NUM>-ethylhexyl)phosphinate, nickel decylphosphinate, nickel dodecylphosphinate, nickel octadecylphosphinate, nickel oleylphosphinate, nickel phenylphosphinate, nickel (p-nonylphenyl)phosphinate, nickel dibutylphosphinate, nickel dipentylphosphinate, nickel dihexylphosphinate, nickel diheptylphosphinate, nickel dioctylphosphinate, nickel bis(<NUM>-methylheptyl)phosphinate, nickel bis(<NUM>-ethylhexyl)phosphinate, nickel didecylphosphinate, nickel didodecylphosphinate, nickel dioctadecylphosphinate, nickel dioleylphosphinate, nickel diphenylphosphinate, nickel bis(p-nonylphenyl)phosphinate, nickel butyl(<NUM>-ethylhexyl)phosphinate, nickel (<NUM>-methylheptyl)(<NUM>-ethylhexyl)phosphinate, and nickel (<NUM>-ethylhexyl) (p-nonylphenyl)phosphinate.

Suitable nickel carbamates can include nickel dimethylcarbamate, nickel diethylcarbamate, nickel diisopropylcarbamate, nickel dibutylcarbamate, and nickel dibenzylcarbamate.

Suitable nickel dithiocarbamates can include nickel dimethyldithiocarbamate, nickel diethyldithiocarbamate, nickel diisopropyldithiocarbamate, nickel dibutyldithiocarbamate, and nickel dibenzyldithiocarbamate.

Suitable nickel xanthates include nickel methylxanthate, nickel ethylxanthate, nickel isopropylxanthate, nickel butylxanthate, and nickel benzylxanthate.

Suitable nickel β-diketonates can include nickel acetylacetonate, nickel trifluoroacetylacetonate, nickel hexafluoroacetylacetonate, nickel benzoylacetonate, and nickel <NUM>,<NUM>,<NUM>,<NUM>-tetramethyl-<NUM>,<NUM>-heptanedionate.

Suitable nickel alkoxides or aryloxides can include nickel methoxide, nickel ethoxide, nickel isopropoxide, nickel <NUM>-ethylhexoxide, nickel phenoxide, nickel nonylphenoxide, and nickel naphthoxide.

Suitable nickel halides can include nickel fluoride, nickel chloride, nickel bromide, and nickel iodide. Nickel pseudo-halides include nickel cyanide, nickel cyanate, nickel thiocyanate, nickel azide, and nickel ferrocyanide. Nickel oxyhalides include nickel oxyfluoride, nickel oxychloride and nickel oxybromide. Where the nickel halides, nickel oxyhalides or other nickel-containing compounds contain labile fluorine or chlorine atoms, the nickel-containing compounds can also serve as the fluorine-containing compound or the chlorine-containing compound. A Lewis base such as an alcohol can be used as a solubility aid for this class of compounds.

The term organonickel compound may refer to any nickel compound containing at least one nickel-carbon bond. Organonickel compounds include bis(cyclopentadienyl) nickel (also called nickelocene), bis(pentamethylcyclopentadienyl) nickel (also called decamethylnickelocene), bis(tetramethylcyclopentadienyl) nickel, bis(ethylcyclopentadienyl) nickel, bis(isopropylcyclopentadienyl) nickel, bis(pentadienyl)nickel, bis(<NUM>,<NUM>-dimethylpentadienyl)nickel, (cyclopentadienyl) (pentadienyl) nickel, bis(<NUM>,<NUM>-cyclooctadiene)nickel, bis(allyl)nickel, bis(methallyl)nickel, and bis(crotyl)nickel.

According to the processes of the first embodiment, the organoaluminum, organomagnesium compound, organozinc compound, or a combination thereof that is used for the (ii) component of the nickel-based catalyst system may vary. In preferred embodiments, when the process of the first embodiment utilizes a nickel-based catalyst system, the component (ii) is an organoaluminum or organomagnesium compound, more preferably an organoaluminum compound. When the organoaluminum, organomagnesium, or organozinc compound includes labile fluorine it may also serve as the fluorine-containing compound (with no need for a separate fluorine-containing compound). In certain embodiments, the organoaluminum, organomagnesium or organozinc compound is devoid of chlorine or bromine atoms.

Suitable compounds for use as an organoaluminum compound or organomagnesium compound in a nickel-based catalyst system are discussed above in the section on lanthanide-based catalyst systems.

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

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

Halogen fluorides may include iodine monofluoride, iodine trifluoride, and iodine pentafluoride.

Organic fluorides may include t-butyl fluoride, allyl fluoride, benzyl fluoride, fluoro-di-phenylmethane, triphenylmethyl fluoride, benzylidene fluoride, methyltrifluorosilane, phenyltrifluorosilane, dimethyldifluorosilane, diphenyldifluorosilane, trimethylfluorosilane, benzoyl fluoride, propionyl fluoride, and methyl fluoroformate.

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

Metallic fluorides may include tin tetrafluoride, aluminum trifluoride, antimony trifluoride, antimony pentafluoride, gallium trifluoride, indium trifluoride, titanium tetrafluoride, and zinc difluoride.

Organometallic fluorides 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-t-butyltin difluoride, dibutyltin difluoride, and tributyltin fluoride.

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

The alcohols may include aliphatic alcohols, which include straight chain or branched alcohols. In other embodiments, the alcohols may include cyclic alcohols, in other embodiments aromatic alcohols, in other embodiments heterocyclic alcohols, and in other embodiments polycyclic alcohols.

In these or other embodiments, the alcohols may be saturated, and in other embodiments they may unsaturated. In certain embodiments, useful alcohols include those alcohols that are soluble, or at least partially soluble, within the reaction medium in which the polymerization takes place.

In one or more embodiments, useful alcohols may be defined by the formula R-OH, where R is a monovalent organic group, and -OH is a hydroxyl group. Monovalent organic groups may include hydrocarbyl groups or substituted hydrocarbyl groups such as, but not limited to alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl, aryl, allyl, substituted aryl, aralkyl, alkaryl, and alkynyl groups. Substituted groups include those groups where a hydrogen atom of the group is itself replaced by a monovalent organic group. These hydrocarbyl groups may contain heteroatoms such as, but not limited to, nitrogen, oxygen, silicon, tin, sulfur, boron, and phosphorous atoms. In certain embodiments, the hydrocarbyl group may be devoid of halogen atoms such as a chlorine or bromine atom. In certain embodiments, the monovalent organic group may contain one or more hydroxyl groups attached thereto. As a result, the alcohol may contain two or more hydroxyl groups. In other embodiments, the hydrocarbyl groups are devoid of heteroatoms.

In one or more embodiments, useful alcohols include from <NUM> to about <NUM> carbon atoms, in other embodiments from about <NUM> to about <NUM> carbon atoms, in other embodiments from about <NUM> to about <NUM> carbon atoms, and in other embodiments from about <NUM> to about <NUM> carbon atoms.

Exemplary aliphatic alcohols include methanol, ethanol, propanol, isopropanol, n-butanol, t-butanol, isobutanol, n-pentanol, n-hexanol, <NUM>-ethyl hexanol, n-heptanol, octanol, decanol, and mixtures thereof.

Exemplary cyclic alcohols include cyclohexanol, methanol, t-butyl cyclohexanol, cyclopentanol, cycloheptanol, cyclooctanol, and mixtures thereof.

Exemplary unsaturated alcohols include allyl alcohol, and mixtures thereof.

Exemplary aromatic alcohols include substituted phenol, phenol, benzyl alcohol, and mixtures thereof.

Exemplary heterocyclic alcohols include furfuryl alcohol, and mixtures thereof.

Exemplary polycyclic alcohols include sterols, and mixtures thereof.

The foregoing catalyst compositions may have high catalytic activity for polymerizing conjugated dienes into stereospecific polydienes over a wide range of catalyst concentrations and catalyst ingredient ratios. It is believed that the catalyst ingredients may interact to form an active catalyst species. It is also believed that the optimum concentration for any one catalyst ingredient may be dependent upon the concentration of the other catalyst ingredients.

In one or more embodiments, the molar ratio of the (ii) component to the nickel-containing compound can be varied from about <NUM>:<NUM> to about <NUM>:<NUM>, in other embodiments from about <NUM>:<NUM> to about <NUM>:<NUM>, and in other embodiments from about <NUM>:<NUM> to about <NUM>:<NUM>. The term molar ratio, as used herein, refers to the equivalent ratio of relevant components of the ingredients, e.g., the ratio of equivalents of aluminum atoms on the aluminum-containing compound to equivalents of nickel atoms on the nickel-containing compound. In other words, where difunctional or polyfunctional compounds (e.g., those compounds including two or more carboxylic acid groups) are employed, fewer moles of the compound are required to achieve the desired equivalent ratio.

In one or more embodiments, the molar ratio of the fluorine-containing compound to the nickel-containing compound (F/Ni) can be varied from about <NUM>:<NUM> to about <NUM>:<NUM>, in other embodiments from about <NUM>:<NUM> to about <NUM>:<NUM>, and in other embodiments from about <NUM>:<NUM> to about <NUM>:<NUM>.

In one or more embodiments, the molar ratio of the alcohol to the nickel-containing compound (-OH/Ni) can be varied from about <NUM>:<NUM> to about <NUM>:<NUM>, in other embodiments from about <NUM>:<NUM> to about <NUM>:<NUM>, and in other embodiments from about <NUM>:<NUM> to about <NUM>:<NUM>. The term molar ratio, as used herein, refers to the equivalent ratio of relevant components of the ingredients, e.g., the ratio of equivalents of chlorine atoms on the chlorine-containing compound to equivalents of nickel atoms on the nickel-containing compound.

Generally, the nickel-based catalyst system may be formed by combining or mixing the catalyst ingredients. Although an active catalyst species is believed to result from this combination, the degree of interaction or reaction between the various ingredients or components is not known with any great degree of certainty. Therefore, the term "catalyst system " has been employed to encompass a simple mixture of the ingredients, a complex of the various ingredients that is caused by physical or chemical forces of attraction, a chemical reaction product of the ingredients, or a combination of the foregoing.

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

In one or more embodiments, the selected catalyst ingredients of the nickel-based catalyst system may be pre-mixed outside the polymerization system at an appropriate temperature, which may be from about -<NUM>° C. to about <NUM>° C. , and the resulting catalyst system may be aged for a period of time ranging from a few seconds to a few days and then added to the monomer.

In one or more embodiments, the mixture of the (ii) component, nickel-containing compound, and alcohol (when present) is formed in the presence of a small amount of monomer and optionally a solvent. That is, the selected catalyst ingredients may be formed in the presence of a small amount of conjugated diene monomer at an appropriate temperature, which may be from about -<NUM>° C. to about <NUM>° C. The amount of conjugated diene monomer that may be used to form this mixture can range from about <NUM> to about <NUM> moles per mole, in other embodiments from about <NUM> to about <NUM> moles per mole, and in other embodiments from about <NUM> to about <NUM> moles per mole of the nickel-containing compound. The resulting composition may be aged for a period of time ranging from a few seconds to a few days and then added to the remainder of the conjugated diene monomer that is to be polymerized together with the fluorine-containing compound.

When a solution of the nickel-based catalyst system or one or more of the catalyst ingredients thereof is prepared outside the polymerization system as set forth in the foregoing methods, an organic solvent or carrier may be employed. The organic solvent may serve to dissolve the catalyst composition or ingredients, or the solvent may simply serve as a carrier in which the catalyst composition or ingredients may be suspended. The organic solvent may be inert to the catalyst composition. Useful solvents include hydrocarbon solvents such as aromatic hydrocarbons, aliphatic hydrocarbons, cycloaliphatic hydrocarbons and/or a mixture of two or more thereof. Non-limiting examples of aromatic hydrocarbon solvents include benzene, toluene, xylenes, ethylbenzene, diethylbenzene, mesitylene, and the like. Non-limiting examples of aliphatic hydrocarbon solvents include n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, isopentane, isohexanes, isopentanes, isooctanes, <NUM>,<NUM>-dimethylbutane, petroleum ether, kerosene, petroleum spirits, and the like. And, non-limiting examples of cycloaliphatic hydrocarbon solvents include cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, and the like. Commercial mixtures of the above hydrocarbons may also be used.

As mentioned above, the process of the first embodiment may utilize a cobalt-based catalyst system which comprises: (i) a cobalt compound, (ii) an organo aluminum halide, and (iii) optionally water. The particular compounds used for each of (i) and (ii) may vary.

Suitable cobalt compounds for use in the cobalt-based catalyst system include, but are not limited to, cobalt benzoate, cobalt acetate, cobalt boroacylate, cobalt naphthenate, bis(. -furyl dioxime) cobalt, cobalt hexanoate, cobalt octanoate, cobalt oxalate, cobalt tartrate, cobalt sorbate, cobalt adipate, cobalt palmitate, cobalt stearate, cobalt acetylacetonate, bis(salicylaldehyde ethylene diimine)cobalt, cobalt salicylaldehyde, dicobalt octacarbonyl and mixtures thereof. According to preferred embodiments, when the process of the first embodiment uses a cobalt-based catalyst system, the cobalt compound is a cobalt salt (the cobalt salt includes either two monovalent anions or one divalent anion). The anion in a cobalt salt is preferably derived from a C<NUM>-C<NUM> organic acid.

Suitable organo aluminum halide compounds for use in the cobalt-based catalyst system include, but are not limited to, those discussed above for the lanthanide-based catalyst system. Suitable examples of organo aluminum halide compounds as discussed above include dihydrocarbyl aluminum halides and hydrocarbyl aluminum dihalides.

Preferably, the organo aluminum halide compound comprises a compound having the formula:.

wherein: R<NUM> is a C<NUM>-C<NUM> alkyl group, X is a halogen and p+q is <NUM>.

More preferably, the organo aluminum halide compound is selected from the group comprising a diorgano (preferably dialkyl) aluminum chloride compound, an alkyl aluminum sesquichoride compound and mixtures thereof.

Even more preferably, the organo aluminum halide compound is selected from: (I) a mixture of: (a) an alkyl aluminum chloride selected from diethyl aluminum chloride and ethyl aluminum sesquichloride (this may be achieved by a mixture containing approximately equimolar amounts of diethyl aluminum chloride and ethyl aluminum dichloride), and (b) an organoaluminum compound of formula R<NUM>Al wherein R is C<NUM>-C<NUM> alkyl group (e.g., trioctyl aluminum, tridecyl aluminum and the like); and (II) an alkyl aluminum chloride wherein the alkyl group has <NUM> to <NUM> carbon atoms (e.g., dioctyl aluminum chloride, didecyl aluminum chloride and the like).

Embodiment (I) is more preferred. In this preferred embodiment, it is especially preferred to use the organoaluminum compound of formula R<NUM>Al is present in an amount of <NUM> to <NUM> percent by weight of the mixture of (I) and (II). A particularly preferred organoaluminum compound of formula R<NUM>Al comprises tri-octyl aluminum.

A preferred catalyst system for use in the present process comprises a cobalt salt selected from cobalt octoate and cobalt naphthenate, and an organo aluminum halide compound selected from: (i) a mixture of diethyl aluminum chloride and one or more of trioctyl aluminum, tridecyl aluminum and tridodecyl aluminum, and (ii) one or more of dioctyl aluminum chloride, didecyl aluminum chloride and didodecyl aluminum chloride.

When a cobalt-based catalyst system is used in the process of the first embodiment, the ratios of components (i), (ii) and (iii) may vary. In certain embodiments, the molar ratio of cobalt compound to the total organo aluminum halide (e.g., diethyl aluminum chloride with trioctyl aluminum) is from about <NUM>:<NUM> to about <NUM>:<NUM> (e. g, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, or <NUM>:<NUM>), preferably from about <NUM>:<NUM> to about <NUM>:<NUM> (e.g., <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, or <NUM>:<NUM>) and the molar ratio of halide (e.g., chlorine in the diethyl aluminum chloride) to the total metal content in the organo aluminum halide (e.g., aluminum in the diethyl aluminum chloride plus trioctyl aluminum) is from about <NUM>:<NUM> to about <NUM>: <NUM> (e.g., <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, or <NUM>:<NUM>) preferably from about <NUM>:<NUM> to about <NUM>:<NUM> (e.g., <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, or <NUM>:<NUM>). In certain embodiments, the amount of water is from about <NUM> to about <NUM> (e.g., <NUM>:<NUM>, <NUM>:<NUM>, <NUM>, <NUM>, or <NUM>), preferably from about <NUM> to about <NUM> (e.g., <NUM>, <NUM>, <NUM>, or <NUM>), millimols per millimol of the organo aluminum halide used (e.g., alkyl aluminum chloride).

As discussed above, the process of the first embodiment includes reacting the living end polymer chains with a functionalizing compound of formula (I). As also discussed above, according to the second embodiment, the modified high-cis polybutadiene polymer includes polymer chains resulting from polymerization of <NUM>,<NUM>-butadiene which are bonded to a residue of the functionalizing compound having formula (I), wherein each polymer chain is bonded to the residue of the functionalizing compound through the X group.

According to the first-second embodiments, formula (I) is as follows:
<CHM>
where X is a group reactive with the living end polymer chains and is selected from the group consisting of cyano, epoxy, ketone, aldehyde, ester, and acid anhydrides, each R<NUM> is selected from hydrocarbylene of C<NUM>-C<NUM> (e.g., C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, or C<NUM>), preferably C<NUM>-C<NUM> (e.g., C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, or C<NUM>), more preferably C<NUM>-C<NUM> (e.g., C<NUM>, C<NUM>, or C<NUM>), wherein each of the foregoing optionally contain one unsaturated carbon-carbon bond, R' is selected from alkoxy of C<NUM>-C<NUM> (e.g., C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, or C<NUM>), preferably alkoxy of C<NUM>-C<NUM> (e.g., C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, or C<NUM>), more preferably alkoxy of C<NUM>-C<NUM> (e.g., C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, or C<NUM>), most preferably alkoxy of C<NUM> or C<NUM>, and R" is selected from alkyl of C<NUM>-C<NUM> or aryl of C<NUM>-C<NUM>(e.g., C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, or C<NUM>), preferably alkyl of C<NUM>-C<NUM> (e.g., C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, or C<NUM>), or aryl of C<NUM>-C<NUM> (e.g., C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, C<NUM>, or C<NUM>), more preferably alkyl of C<NUM>-C<NUM> or aryl of C<NUM>. Formula (I) can also be represented as: X-R<NUM>-Si(R')<NUM>(R"). In certain embodiments of the first-second embodiments, the functionalizing compound of formula (I) has a structure wherein R<NUM>, R' and R" are all selected from the groups described as preferred. In other embodiments of the first-second embodiments, the functionalizing compound of formula (I) has a structure wherein R<NUM>, R' and R" are all selected from the groups described as preferred. Since the functionalizing compound of formula (I) has two alkoxy groups on the Si, the compound can be referred to a dialkoxysilane (more specifically an alkyldialkoxysilane or aryldialkoxysilane due to the presence of the R" group). By stating that R<NUM> is a hydrocarbylene group is meant that that it is bonded to two other constituents (i.e., the X group and the Si). In certain preferred embodiments of the first-second embodiments, R<NUM> is aliphatic and unsaturated. In other embodiments of the first-second embodiment, R<NUM> is aliphatic and can include one unsaturated carbon-carbon bond. Generally, according to the first-second embodiments, the carbons in the R<NUM> group can be positioned in a linear configuration or may be branched.

In certain preferred embodiments of the first-second embodiments, X is a cyano group or an epoxy group, more preferably an epoxy group. According to the first-second embodiments, when X is a cyano group, its particular structure may vary, such as is discussed in more detail below. According to the first-second embodiments, when X is an epoxy group, it preferably has <NUM>-<NUM> carbon atoms (e.g., <NUM>, <NUM>, or <NUM> carbon atoms) in the epoxy ring.

As mentioned above, according to the first-second embodiments, the X of the functionalizing compound of formula (I) (or the residue resulting therefrom) is preferably selected from an epoxy group, more preferably the epoxy group is a glycidoxy group. Suitable compounds for use as the functionalizing compound of formula (I) wherein X is an epoxy group include, but are not limited to, (<NUM>-glycidoxyethyl)methyldimethoxysilane, (<NUM>-glycidoxyethyl)methyldiethoxysilane, (<NUM>-glycidoxyethyl)ethyldimethoxysilane, (<NUM>-glycidoxyethyl)ethyldiethoxysilane, (<NUM>-glycidoxypropyl)methyldimethoxysilane, (<NUM>-glycidoxypropyl)methyldiethoxysilane, (<NUM>-glycidoxypropyl)ethyldimethoxysilane, (<NUM>-glycidoxypropyl)ethyldiethoxysilane, <NUM>-(<NUM>,<NUM>-epoxycyclohexyl)ethyl(methyldimethoxy)silane, <NUM>-(<NUM>,<NUM>-epoxycyclohexyl)ethyl(methyldiethoxy)silane, <NUM>-(<NUM>,<NUM>-epoxycyclohexyl)ethyl(ethyldimethoxy)silane, and <NUM>-(<NUM>,<NUM>-epoxycyclohexyl)ethyl(ethyldiethoxy)silane. Among the foregoing, (<NUM>-glycidoxypropyl)methyldimethoxysilane and (<NUM>-glycidoxypropyl)methyldiethoxysilane are particularly preferred.

As mentioned above, according to the first-second embodiments, the X of the functionalizing compound of formula (I) (or the residue resulting therefrom) is preferably selected from a cyano group. Non-limiting examples of suitable cyano groups that may be used as X in formula (I) according to certain embodiments of the first-second embodiments include compounds where the cyano group and the Si are separated by a hydrocarbylene group having <NUM>-<NUM> carbons, preferably <NUM>-<NUM> carbons. Non-limiting examples of suitable cyano groups that may be used as X in formula (I) according to certain embodiments of the first-second embodiments include <NUM>-cyanoethylmethyldiethoxysilane and <NUM>-cyanopropylmethyldiethoxysilane. In those embodiments of the first-second embodiments, wherein the X of the functionalizing compound of formula (I) (or the residue resulting therefrom) is selected from a ketone group, various compounds may be suitable as the functionalizing compound.

In those embodiments of the first-second embodiments, wherein the X of the functionalizing compound of formula (I) (or the residue resulting therefrom) is selected from a ketone group, various compounds may be suitable as the functionalizing compound. A non-limiting example of such a compound is p-(methyldiethoxysilyl)acetophenone.

In those embodiments of the first-second embodiments, wherein the X of the functionalizing compound of formula (I) (or the residue resulting therefrom) is selected from an aldehyde group, various compounds may be suitable as the functionalizing compound. A non-limiting example of such a compound is (methyldiethoxysilyl)undecanal.

In those embodiments of the first-second embodiments, wherein the X of the functionalizing compound of formula (I) (or the residue resulting therefrom) is selected from an ester group, various compounds may be suitable as the functionalizing compound. Non-limiting examples of suitable such compounds include hydrocarbyloxysilane compounds having a carboxylic acid hydrocarbyl ester residue. Particular examples of such compounds include, but are not limited to, <NUM>-methacryloyloxypropylmethyldiethoxysilane, <NUM>-methacryloyloxypropylmethyldimethoxysilane, <NUM>-methacryloyloxypropylethyldimethoxysilane, <NUM>-methacryloyloxypropylethyldiethoxysilane, and <NUM>-methacryloyloxypropylmethyldiisopropoxysilane. Among the foregoing, <NUM>-methacryloyloxypropylmethyldimethoxysilane and <NUM>-methacryloyloxypropylmethyldiethoxysilane are preferred.

In those embodiments of the first-second embodiments, wherein the X of the functionalizing compound of formula (I) (or the residue resulting therefrom) is selected from an acid anhydride group, various compounds may be suitable as the functionalizing compound. Non-limiting examples of suitable such compounds include hydrocarbyloxysilane compounds having a carboxylic anhydride residue. Particular examples of such compounds include, but are not limited to, <NUM>-(methyldiethoxysilyl)propylsuccinic anhydride and <NUM>-(methyldimethoxysilyl)propylsuccinic anhydride. Among them, <NUM>-(methyldiethoxysilyl)propylsuccinic anhydride is preferred.

According to the first-second embodiments, polymer chains (which result from polymerization of <NUM>,<NUM>-butadiene using one of the defined catalyst systems) are bonded to a functionalizing compound through the X group. Since the structure of the functionalizing compound will change somewhat upon bonding of a polymer chain to the X group, the moiety to which the polymer chain is bonded is described as a residue of a functionalizing compound. Generally, one polymer chain will bond to the residue of the functionalizing compound through the X group of each molecule of functionalizing compound. However, depending upon the structure of the X group, it is possible for more than one polymer chain to bond to the residue of the functionalizing compound. The location upon the functionalizing compound where the polymer chain bonds according to the process of the first embodiment (i.e., using one of the defined catalyst systems) can be contrasted with the location upon the functionalizing compound where the polymer chain would bond if an anionic initiator (e.g., n-butyl lithium) was used to polymerize <NUM>,<NUM>-butadiene. More specifically, if an anionic initiator was used, polymer chains may bond to the functionalizing compound via an alkoxy group on the Si (replacing the OR of an OR alkoxy group and bonding directly to the Si) as well as through the X group. When one of the defined catalyst systems is used to polymerize <NUM>,<NUM>-butadiene and produce living end polymer chains, the polymer chain bonds (only) to the functionalizing compound through the X group. As a non-limiting example, when the X of the functionalizing compound is an epoxy group, a polymer chain would bond to one of the carbons alpha to the oxygen of the epoxy ring. More specifically, according to such a bonding reaction, one polymer chain would bond to one of the carbon atoms alpha to the oxygen of the epoxy ring and the bonding would cause ring opening with conversion of the oxygen atom to OH.

According to the first-second embodiments, the amount of functionalizing compound of formula (I) that is used to react with the living end polymer chains (i.e., according to the process of the first embodiment) or that is present in the modified high-cis polybutadiene polymer as a residue (i.e., according to the second embodiment) may vary. In certain embodiments of the first-second embodiments, the functionalizing compound is used in a molar ratio of <NUM>:<NUM> to <NUM>:<NUM> (e.g., <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>), preferably <NUM>:<NUM> to <NUM>:<NUM> (e.g., <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, or <NUM>:<NUM>), more preferably <NUM>:<NUM> to <NUM>:<NUM> (e.g., <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, or <NUM>:<NUM>), the molar ratio based upon the moles of functionalizing compound to moles of primary metal in the catalyst system (i.e., moles of lanthanide for a lanthanide-based catalyst system, moles of nickel for a nickel-based catalyst system, or moles of cobalt for a cobalt-based catalyst system).

In certain embodiments of the process of the first embodiment, the process for preparing the modified high-cis polybutadiene polymer further comprises (also includes) a step of reacting the modified high-cis polybutadiene (from step C) with a stabilizing agent of formula (II) as follows:.

wherein R<NUM> is selected from the group consisting of C<NUM> to C<NUM> alkyl, C<NUM> to C<NUM> cycloalkyl, or C<NUM> to C<NUM> aromatic groups; preferably from the group consisting of C<NUM> to C<NUM> alkyl, C<NUM> to C<NUM> cycloalkyl, or C<NUM> to C<NUM> aromatic groups; and more preferably from C<NUM> to C<NUM> alkyl, C<NUM> to C<NUM> cycloalkyl, or C<NUM> aromatic groups, wherein R<NUM> may be the same as or different from R<NUM> and is selected from C<NUM> to C<NUM> alkyl, C<NUM> to C<NUM> cycloalkyl, or C<NUM> to C<NUM> aromatic groups; preferably from the group consisting of C<NUM> to C<NUM> alkyl, C<NUM> to C<NUM> cycloalkyl, or C<NUM> to C<NUM> aromatic groups; and more preferably from C<NUM> to C<NUM> alkyl, C<NUM> to C<NUM> cycloalkyl, or C<NUM> aromatic groups, and n is an integer of <NUM> to <NUM>, preferably <NUM> to <NUM>, more preferably <NUM>. In certain embodiments of the process of the first embodiment, the stabilizing agent of formula (II) has R<NUM>, R<NUM> and n selected from the foregoing preferred groups or values. In other embodiments of the process of the first embodiment, the stabilizing agent of formula (II) has R<NUM>, R<NUM> and n selected from the foregoing more preferred groups or values. In particularly preferred embodiments of the process of the first embodiment, the stabilizing agent trialkoxy(alkyl)silane (i.e., n is <NUM> and R<NUM> is alkyl, as described above), with octyl triethoxy silane being especially preferred. In those embodiments of the first embodiment wherein the stabilizing agent is utilized, it is added after (C) but prior to (D), i.e., prior to isolating the modified high-cis polybutadiene. The use of a stabilizing agent may be beneficial in producing a modified high-cis polybutadiene polymer which produces improved snow or ice performance in a tire tread which incorporates the modified high-cis polybutadiene polymer. As those of skill in the art will understand, snow or ice performance of a rubber composition upon its incorporation into a tire tread can be predicted by measuring the value of G' at -<NUM> for the rubber composition, with higher values indicating preferred performance.

In certain embodiments of the first embodiment, no stabilizing agent is utilized in the process. Avoiding the use of a stabilizing agent can lead to an overall cost savings in production of the modified high-cis polybutadiene polymer due the use of one less raw material and elimination of a step in the overall process.

In those embodiments of the first embodiment wherein a stabilizing agent is utilized, the amount that is utilized in the process may vary. In certain embodiments of the first embodiment, the stabilizing agent is used in a molar ratio of <NUM>:<NUM> to <NUM>:<NUM> (e.g., <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, or <NUM>:<NUM>), preferably <NUM>:<NUM> to <NUM>:<NUM> (e.g., <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, or <NUM>:<NUM>), more preferably <NUM>:<NUM> to <NUM>:<NUM> (e.g., <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, or <NUM>:<NUM>), the molar ratio based upon the moles of stabilizing agent:moles of functionalizing compound.

As mentioned above, according to process of the first embodiment, a quenching agent of formula (III) is used in combination with the stabilizing agent of formula (II). According to the process of the first embodiment, formula (III) for the quenching agent is as follows:.

wherein R<NUM> is selected from H and the group consisting of C<NUM> to C<NUM> alkyl, preferably from H and the group consisting of C<NUM> to C<NUM> alkyl, more preferably from the group consisting of C<NUM> to C<NUM> alkyl. In certain preferred embodiments of the first embodiment, the quenching agent comprises <NUM>-ethylhexanoic acid or acetic acid, more preferably <NUM>-ethylhexanoic acid; in certain such embodiments, the quenching agent consists of <NUM>-ethylhexanoic acid. In those embodiments of the first embodiment, wherein a quenching agent is utilized, the amount that is utilized in the process may vary. In certain embodiments of the first embodiment, the quenching agent is used in a molar ratio <NUM>:<NUM> to <NUM>:<NUM> (e.g., <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM> or <NUM>:<NUM>), preferably <NUM>:<NUM> to <NUM>:<NUM> (e.g., <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, or <NUM>:<NUM>), more preferably <NUM>:<NUM> to <NUM>:<NUM> (e.g., <NUM>:<NUM>, <NUM>:<NUM>, <NUM>:<NUM>, or <NUM>:<NUM>), the molar ratio based upon the moles of quenching agent:moles of stabilizing agent of formula (II).

As mentioned above, the process of the first embodiment results in a modified high-cis polybutadiene polymer having a cis <NUM>,<NUM>-bond content of <NUM>-<NUM>%, preferably at least <NUM>%, an initial Mooney viscosity ML<NUM>+<NUM> at <NUM> of <NUM>-<NUM>, preferably <NUM>-<NUM>, and an aged Mooney viscosity ML<NUM>+<NUM> at <NUM> of <NUM>-<NUM>, preferably <NUM>-<NUM>. As also mentioned above, the modified high-cis polybutadiene polymer of the second embodiment has a cis <NUM>,<NUM>-bond content of <NUM>-<NUM>%, preferably at least <NUM>%, an initial Mooney viscosity ML<NUM>+<NUM> at <NUM> of <NUM>-<NUM>, preferably <NUM>-<NUM>, and an aged Mooney viscosity ML<NUM>+<NUM> at <NUM> of <NUM>-<NUM>, preferably <NUM>-<NUM>. Since the tire rubber composition utilizes either the modified high cis polydiene polymer of the second embodiment or a modified high cis polydiene polymer made by a process according to the first embodiment, the modified high cis polydiene polymer can also be understood as having a cis <NUM>,<NUM>-bond content of <NUM>-<NUM>%, preferably at least <NUM>%, an initial Mooney viscosity ML<NUM>+<NUM> at <NUM> of <NUM>-<NUM>, preferably <NUM>-<NUM>, and an aged Mooney viscosity ML<NUM>+<NUM> at <NUM> of <NUM>-<NUM>, preferably <NUM>-<NUM>. By stating that the cis <NUM>,<NUM>-bond content is <NUM>-<NUM>% is meant that it can be e.g., <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, <NUM>%, or <NUM>%, and should be understood to include ranges such as <NUM>-<NUM>%, <NUM>-<NUM>%, and <NUM>-<NUM>%. In preferred embodiments of the first-second embodiments, the cis <NUM>,<NUM>-bond content of the modified high cis polybutadiene polymer is at least <NUM>%. By stating that the cis <NUM>,<NUM>-bond content is at least <NUM>% is meant that it is <NUM>% or higher (e.g., <NUM>%, <NUM>%, <NUM>%, <NUM>%, or <NUM>%) which should be understood to include ranges such as <NUM>-<NUM>%, <NUM>-<NUM>%, <NUM>-<NUM>%, and <NUM>-<NUM>%. The cis <NUM>,<NUM>-bond contents referred to herein are determined by FTIR (Fourier Transform Infrared Spectroscopy). In particular, a polymer sample is dissolved in CS<NUM> and then subjected to FTIR.

The initial Mooney viscosity ML<NUM>+<NUM> at <NUM> refers to a Mooney viscosity measurement that is taken upon the final modified high-cis polybutadiene polymer (the polymer has been isolated and dried, e.g., by steam distillation) before it is heat aged (as described below). By stating that the initial Mooney viscosity ML<NUM>+<NUM> at <NUM> is <NUM>-<NUM> is meant that it may vary from <NUM>-<NUM> (e.g., <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, or <NUM>). Preferably according to the first-second embodiments, the initial Mooney viscosity ML<NUM>+<NUM> at <NUM> is from <NUM> to <NUM> (e.g., <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, or <NUM>). The aged Mooney viscosity ML<NUM>+<NUM> at <NUM> refers to a Mooney viscosity measurement that is taken upon a sample of the high-cis polybutadiene polymer that has been heat aged. More specifically, the polymer sample has been aged at <NUM> for at least <NUM> days (more preferably <NUM> days). Generally, the aged Mooney viscosity of the modified high-cis polybutadiene polymer will be somewhat higher than the initial viscosity of the polymer. In certain embodiments of the first-second embodiments, in addition to meeting the aged Mooney viscosity values discussed above, the final modified high-cis polybutadiene polymer also has an aged Mooney viscosity ML<NUM>+<NUM> at <NUM> that is no more than <NUM>% higher than the initial Mooney viscosity (e.g., no more than <NUM>% higher, no more than <NUM>% higher, no more than <NUM>% higher, no more than <NUM>% higher, no more than <NUM>% higher, no more than <NUM>% higher, or less) and is no more than <NUM> (e.g., <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, or less). In preferred embodiments of the first-second embodiments, the final modified high-cis polybutadiene polymer has an aged Mooney viscosity ML<NUM>+<NUM> at <NUM> that is no more than <NUM>% higher than the initial Mooney viscosity (e.g., no more than <NUM>% higher, no more than <NUM>% higher, no more than <NUM>% higher, no more than <NUM>% higher, no more than <NUM>% higher, no more than <NUM>% higher, no more than <NUM>% higher, no more than <NUM>% higher, no more than <NUM>% higher, no more than <NUM>% higher, no more than <NUM>% higher, or less) and is no more than <NUM> (e.g., <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, or less). As a non-limiting example, if a modified high-cis polybutadiene polymer had an initial Mooney viscosity that was <NUM> and an aged Mooney viscosity that was <NUM>, the increase in Mooney viscosity would be <NUM>%.

According to the first-second embodiments, other properties 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-second embodiments, the modified high-cis polybutadiene polymer meets at least one of the following: (a) has a Mw of <NUM>,<NUM> to <NUM>,<NUM>,<NUM> grams/mole (e.g., <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>,<NUM>; <NUM>,<NUM>,<NUM>; <NUM>,<NUM>,<NUM>; <NUM>,<NUM>,<NUM>; <NUM>,<NUM>,<NUM>; <NUM>,<NUM>,<NUM>; <NUM>,<NUM>,<NUM>; <NUM>,<NUM>,<NUM>; <NUM>,<NUM>,<NUM>; <NUM>,<NUM>,<NUM>; or <NUM>,<NUM>,<NUM> grams/mole), preferably <NUM>,<NUM> to <NUM>,<NUM>,<NUM> grams/mole (e.g., <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; or <NUM>,<NUM>,<NUM> grams/mole), more preferably <NUM>,<NUM> to <NUM>,<NUM> grams/mole (e.g., <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; or <NUM>,<NUM>;grams/mole); (b) has a Mn of <NUM>,<NUM> to <NUM>,<NUM> grams/mole (e.g., <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; or <NUM>,<NUM> grams/mole), preferably <NUM>,<NUM> to <NUM>,<NUM> grams/mole (e.g., <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; or <NUM>,<NUM> grams/mole), more preferably <NUM>,<NUM> to <NUM>,<NUM> grams/mole (e.g., <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; <NUM>,<NUM>; or <NUM>,<NUM>; grams/mole); (c) has a Mw/Mn of <NUM> to <NUM> (e.g., <NUM>, <NUM>, <NUM>, <NUM>, <NUM>. , <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, or <NUM>), preferably <NUM> to <NUM> (e.g., <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, or <NUM>), more preferably <NUM> to <NUM> (e.g., <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, or <NUM>); or (d) has an initial Mooney viscosity ML<NUM>+<NUM> at <NUM> of <NUM> to <NUM> (e.g., <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, or <NUM>). In certain embodiments of the first-second embodiments, the modified high cis polybutadiene polymer meets each of (a)-(d). In certain embodiments of the first-second embodiments, the modified high cis polybutadiene polymer satisfies the preferred ranges of each of (a)-(d). In certain embodiments of the first-second embodiments, the modified high cis polybutadiene polymer satisfies the more preferred ranges of each of (a)-(d). Mn indicates the number average molecular weight in grams/mole (by GPC), Mw indicates the weight average molecular weight in grams/mole (by GPC), and Mw/Mn the molecular weight dispersion or polydispersity of the polymer. Generally, the Mn and Mw of these polymers may be determined by using gel permeation chromatography (GPC) calibrated with polystyrene standards.

The process of the first embodiment may result in (and the polymer of the second embodiment may be and a rubber composition may utilize a polymer which is) a modified high-cis polybutadiene polymer product which contains a minor portion of high molecular weight polymer material. Generally, such high molecular weight material may be filtered out, if desired, prior to use of the polymer (e.g., in a rubber composition) or sale of the polymer. The amount of the high molecular weight material will generally be less than about <NUM>%, sometimes less than about <NUM>% by weight. The Mw, Mn and Mw/Mn values that are provided in the preceding paragraph refer to values that can be determined via GPC upon a sample of material made by a process of the first embodiment and/or according to the second embodiment and encompass the Mw and Mn values for high molecular weight material that may be filtered out. The Mw and Mn values provided for the working Examples are measured by GPC upon samples that have been filtered to remove high molecular weight material and gel in order to avoid potential damage to the GPC. Also disclosed herein is a polymer product produced by the process of the first embodiment (and a polymer of the second embodiment) wherein at least <NUM>% by weight, preferably at least <NUM>% by weight or even at least <NUM>% by weight of the polymer in the polymer product has a Mw of <NUM>,<NUM> to <NUM>,<NUM> grams/mole, preferably <NUM>,<NUM> to <NUM>,<NUM> grams/mole, more preferably <NUM>,<NUM> to <NUM>,<NUM> grams/mole and a Mn of <NUM>,<NUM> to <NUM>,<NUM> grams/mole, preferably <NUM>,<NUM> to <NUM>,<NUM> grams/mole, more preferably <NUM>,<NUM> to <NUM>,<NUM> grams/mole.

As mentioned above, the modified high-cis polybutadiene produced according to the process of the first embodiment and the modified high-cis polybutadiene of the second embodiment are particularly useful in rubber compositions used for tire components.

The following examples illustrate specific and exemplary embodiments and/or features of the embodiments of the present disclosure. The examples are provided solely for the purposes of illustration and should not be construed as limitations of the present disclosure. Numerous variations over these specific examples are possible without departing from the spirit and scope of the presently disclosed embodiments. It should specifically be understood that modified high cis polybutadiene polymers can be made using different functional compounds (i.e., according to formula (I), as discussed above), using different stabilizing agents or no stabilizing agent (as discussed above), or using/having different combinations of the functional compound and stabilizing and used in rubber compositions. It should also be understood that the high cis polybutadiene polymers can be utilized in rubber compositions along with ingredients (e.g., additional rubber(s), fillers, cure package ingredients) that differ in relative amount, composition, or both from those used in the examples (i.e., as fully as disclosed in the preceding paragraphs).

As explained in detail below, high cis polybutadiene polymers were produced in Examples <NUM>-<NUM>. Examples <NUM>-<NUM> can be considered to be a modified high cis polybutadiene polymer exemplary of the second embodiment and produced according to processes that are exemplary of the first embodiment whereas Examples <NUM>-<NUM> should be considered as comparative or control examples (since they do not utilize a functionalizing compound meeting formula (I)). The polymers produced in Examples <NUM>-<NUM> were then used to prepare rubber compositions in Example <NUM>. Rubber compositions <NUM>-<NUM>, <NUM>-<NUM> and <NUM>-<NUM> can be considered as exemplary whereas Examples <NUM>-<NUM>, and <NUM>-<NUM> should be considered as comparative or control examples.

Example <NUM>: To a dry <NUM> liter reactor purged with nitrogen was added <NUM>,<NUM> grams of hexane and <NUM>,<NUM> grams of <NUM> weight % <NUM>,<NUM>-butadiene solution in hexane. The solution was maintained at <NUM>. <NUM> grams/<NUM> milliliters of COMCAT Nd-FC/SF catalyst (available from Comar Chemical Ltd. ) was used as a preformed catalyst. Additional diisobutylaluminum hydride was added as needed to maintain a base ML<NUM>+<NUM> in the range of <NUM> MU to <NUM> MU. The reactor jacket temperature was then set to <NUM>. The mixture was allowed to polymerize until it reached a peak temperature of <NUM>. The jacket temperature was then increased to <NUM>. After <NUM> minutes, <NUM>,<NUM> grams of hexane and <NUM> grams of neat <NUM>-cyanoethyltriethoxysilane (CETEOS) were charged to the reactor. The molar ratio of CETEOS to Nd in the neodymium versatate was <NUM>:<NUM>. After <NUM> minutes, <NUM> grams of neat triethoxy(octyl)silane was added, followed by <NUM> grams of neat ethylhexanoic acid. After about <NUM> minutes, the polymerization mixture was allowed to cool. The resulting polymer cement was quenched and coagulated using <NUM> grams of neat isopropanol followed by <NUM> grams of neat dibutylhydroxytoluene, and then steam distilled to dry. The properties of the resulting polymer are summarized below in Table <NUM>-A. The polymer of Example <NUM> can be considered a control polymer.

Example <NUM>: The polymer of Example <NUM> was made according to the procedure discussed above for Example <NUM> except that <NUM> grams of neat <NUM>-cyanopropyltriethoxysilane (CPTEOS) was used instead of the CETEOS. The polymer of Example <NUM> can be considered a control polymer.

Example <NUM>: The polymer of Example <NUM> was made according to the procedure discussed above for Example <NUM> except that <NUM> grams of neat <NUM>-<NUM>-glycidoxypropylmethyldiethoxysilane (GPMDEOS) was used instead of the CETEOS.

Example <NUM>: The polymer of Example <NUM> was made according to the procedure discussed above for Example <NUM> except that less stabilizing agent (<NUM> grams of OTES) was used.

Example <NUM>: The polymer of Example <NUM> was made according to the procedure discussed above for Example <NUM> except that no stabilizing agent (i.e., <NUM> grams of OTES) was used.

Examples <NUM>-<NUM>: High-cis polybutadiene polymers were prepared using GPTEOS/<NUM>-glycidoxypropyltriethoxysilane (Examples <NUM> and <NUM>), GPMDEOS/<NUM>-glycidoxypropylmethyldiethoxysilane (Examples <NUM> and <NUM>), or GPDMEOS/<NUM>-glycidoxydimethylethoxysilane (Examples <NUM> and <NUM>). Examples <NUM>, <NUM> and <NUM> used <NUM> equivalents of OTES (i.e., a molar ratio of OTES:Nd of <NUM>:<NUM>). Examples <NUM>, <NUM> and <NUM> used no OTES. Examples <NUM> and <NUM> are inventive and Examples <NUM>, <NUM>, <NUM> and <NUM> are control examples (which compare triethoxysilanes and monoethoxysilanes to a diethoxysilane). Generally, the same procedure as set forth in Examples <NUM>-<NUM> was used to prepare the polymers except for use of the modifiers described above (and in the amounts listed in Table <NUM>-B) and for certain of the polymers the use of a stabilizing agent (as indicated and in the amount listed in Table <NUM>-B). The properties of the resulting polymers are summarized below in Table <NUM>-B.

The Mooney viscosities disclosed in Tables <NUM>-A and <NUM>-B are polymer values (determined upon the polymers) determined at <NUM> using an Alpha Technologies Mooney viscometer with a large rotor, a one minute warm-up time, and a four minute running time, and, hence are referred to as ML<NUM>+<NUM>. More specifically, the Mooney viscosity was measured by preheating a sample from each batch to <NUM> for one minute before the rotor starts. The Mooney viscosity was recorded for each sample as the torque at four minutes after the rotor started. The initial and aged values were determined on samples as discussed, infra. The Mn, Mw, cis-<NUM>,<NUM> bond and vinyl bond contents were all determined on samples as discussed generally, infra. Gel content (in weight %) was determined by immersing a sample in toluene for <NUM> days, then capturing any gel on a mesh screen and calculating the gel content (after drying the screen under vacuum at <NUM> for <NUM> hours).

As can be seen from the data of Table <NUM>-B, the use of a functionalizing compound according to formula (I), i.e., having a diethoxysilane group) as compared to the use of a similar compound having a triethoxysilane group results in a modified high-cis polybutadiene with significantly lower insoluble content (<NUM> vs. <NUM>% or <NUM> vs. <NUM>%) regardless of whether a stabilizing agent (i.e., OTES) is used, and results in less of an increase in Mooney viscosity from initial to aged (<NUM>% vs. <NUM>) in the presence of a stabilizing agent. As discussed in more detail below, the use of the functionalizing compound according to formula (I), i.e., having a diethoxysilane group, as compared to use of a similar compound having a monoethoxysilane group resulted in improved properties when the polymer was incorporated into a rubber composition. As to the data of Table <NUM>-A, the use of a functionalizing compound according to formula (I), as compared to epoxy-containing compounds containing a triethoxysilane group, results in a modified high-cis polybutadiene with lower insoluble content, an effect that is more pronounced in the presence of increasing amounts of stabilizing agent (i.e., OTES). Additionally, the use of a functionalizing compound according to formula (I), as compared to epoxy-containing compounds containing a triethoxysilane group, results in a modified high-cis polybutadiene with both a lower initial Mooney viscosity (with values all falling within the preferred range of <NUM>-<NUM>) and a lower aged Mooney viscosity (with values all being less than <NUM>). The use of a functionalizing compound according to formula (I), as compared to epoxy-containing compounds containing a monoethoxy group results in a modified high-cis polybutadiene having a Mooney viscosity that is particularly advantageous for polymer processing. More specifically, an aged or final Mooney viscosity of at least <NUM> or at least <NUM> can be advantageous in that such polymers exhibit less stickiness.

Example <NUM>: The polymers produced according to Examples <NUM>-<NUM> were utilized to prepare rubber compositions (<NUM>-C1, <NUM>-C2 and <NUM>-<NUM> to <NUM>-<NUM>) according to the formulas provided in Table <NUM> below. The polymer of Example <NUM> was used to prepare rubber composition <NUM>-<NUM>, the polymer of Example <NUM> was used to prepare rubber composition <NUM>-<NUM>, etc. In addition to using the polymers produced according to Examples <NUM>-<NUM>, an additional control rubber composition was prepared using 140ND Diene™ polybutadiene a commercially available neodymium-catalyzed polymer from Firestone Polymers (having a cis <NUM>,<NUM> bond content of <NUM>%, a vinyl bond content of <NUM>%, a trans bond content of <NUM>%, a Tg of -<NUM>, and an initial ML<NUM>+<NUM> at <NUM> of <NUM>). Samples of the 140ND were used with OTES (<NUM>-C1) and without OTES (<NUM>-C2). The mixing procedure set forth in Table <NUM> was utilized in preparing the rubber compositions of Example <NUM>. The rubber compositions of Examples <NUM>-C1, <NUM>-C2, <NUM>-<NUM>, <NUM>-<NUM>, <NUM>-<NUM>, <NUM>-<NUM>, <NUM>-<NUM> and <NUM>-<NUM> can be considered control examples. The rubber compositions of Examples <NUM>-<NUM>, <NUM>-<NUM>, <NUM>-<NUM>, <NUM>-<NUM> and <NUM>-<NUM> can be considered inventive.

After preparation of the rubber compositions <NUM>-C and <NUM>-<NUM> to <NUM>-<NUM>, samples were taken and the properties were measured according to the following procedures. Results are reported in Tables <NUM>-A and <NUM>-B below. The compound rubber composition Mooney viscosities listed in Tables <NUM>-A and <NUM>-B were determined at <NUM> by using an Alpha Technologies Mooney viscometer with a large rotor, a one-minute warm-up time, and a four-minute running time.

Tan δ and G' values were measured using a strain sweep test conducted with an Advanced Rheometric Expansion System (ARES) from TA Instruments. The test specimen had a rectangular geometry having a length of <NUM>, a thickness of <NUM>, and a width of <NUM>. The length of specimen between the grips on the test machine, i.e., the gap, was approximately <NUM>. The test was conducted using a frequency of <NUM> rad/sec. The temperature was swept from -<NUM> to <NUM> with a strain of <NUM>% used for temperatures from -<NUM> to -<NUM> and the strain increased to <NUM>% from -<NUM> to <NUM>. A rubber composition's tan δ at <NUM> is indicative of its rolling resistance when incorporated into a tire tread, its tan G' -<NUM> is indicative of its snow performance when incorporated into a tire tread, and its tan δ at <NUM> is indicative of its wet performance when incorporated into a tire tread. The tan δ values are presented as indexed numbers (calculated by comparing the value for a given example as compared to the value for the control rubber composition) wherein a number above <NUM> is considered to be an improvement.

Claim 1:
A modified high-cis polybutadiene polymer having
polymer chains bonded to a residue of a functionalizing compound having formula (I) as follows
<CHM>
where X is a group reactive with the living end polymer chains and is selected from the group consisting of cyano, epoxy, ketone, aldehyde, ester, and acid anhydrides,
R<NUM> is selected from hydrocarbylene of C<NUM>-C<NUM>, preferably C<NUM>-C<NUM>, more preferably C<NUM>-C<NUM>, wherein each of the foregoing optionally contain one unsaturated carbon-carbon bond,
each R' is selected from alkoxy of C<NUM>-C<NUM>, preferably alkoxy of C<NUM>-C<NUM>, more preferably alkoxy of C<NUM>-C<NUM>, most preferably alkoxy of C<NUM> or C<NUM>, and
R" is selected from alkyl of C<NUM>-C<NUM> or aryl of C<NUM>-C<NUM>, preferably alkyl of C<NUM>-C<NUM> or aryl of C<NUM>-C<NUM>, more preferably alkyl of C<NUM>-C<NUM> or aryl of C<NUM>
wherein each polymer chain is bonded to the residue of the functionalizing compound through the X group, and the modified high-cis polybutadiene polymer has
a cis <NUM>,<NUM>-bond content determined by FTIR of <NUM>-<NUM>%,
an initial Mooney viscosity ML<NUM>+<NUM> at <NUM> determined using the method of the description of <NUM>-<NUM>, preferably <NUM>-<NUM>, and
an aged Mooney viscosity ML<NUM>+<NUM> at <NUM> of no more than <NUM>, preferably no more than <NUM>, wherein the aged Mooney viscosity is determined after aging at <NUM> for <NUM> days.