Process for producing polydienes

PROCESS FOR THE PRODUCTION OF POLYDIENES

FIELD OF

INVENTION

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One or more embodiments of the present invention is directed to a process for producing polydienes, the process comprising polymerizing diene monomer conjugated to a lanthanide-based catalyst system in the presence of a dihydrocarbyl ether.

BACKGROUND OF THE INVENTION

Polydienes can be produced by solution polymerization, where conjugated diene monomer is polymerized in an inert diluent or solvent. The solvent serves to solubilize the reactants and products, act as a diluent for the reactants and product, aid in heat transfer of polymerization, and help moderate the rate of polymerization. 0 Solvent also allows for easier agitation and transfer of the polymerization mixture (also called cement), as the viscosity of the cement is lowered in the presence of the solvent. However, the presence of solvent presents several difficulties. The solvent 20 must be separated from the polymer and then recycled for reuse or otherwise disposed of as waste. The cost of recovering and recycling the solvent greatly increases the cost of the polymer in production, and there is always the risk that the recycled solvent, after purification, may still retain some impurities that will poison the polymerization catalyst. In addition, some solvents such as aromatic hydrocarbons can give rise to environmental concerns. Additionally, the purity of the polymer product can be affected if there are difficulties in removing the solvent.

Polydienes can also be produced by mass polymerization, where conjugated diene monomer is in the absence or substantial absence of any solvent, and in reality, the monomer itself acts as a diluent. Since bulk polymerization is essentially solvent-free, there is less risk of contamination, and product separation is simplified.

Bulk polymerization offers several economic advantages including lower capital cost for new plant capacity, lower energy cost to operate, and fewer people to operate. 10 The solvent-free feature also provides environmental benefits, with reduced emissions and wastewater pollution.

Despite its many advantages, bulk polymerization requires very careful temperature control, and there is also a need for elaborate and strong stirring equipment as the viscosity of the polymerization mixture can become very high. In the absence of added diluent, high cement viscosity and exothermic effects can make temperature control very difficult. Consequently, local hot spots can occur, resulting in degradation, freezing and/or discoloration of the polymer product. In the extreme case, uncontrolled acceleration of the polymerization rate can lead to disastrous out-of-control reactions. To facilitate temperature control during bulk polymerization, it is desirable for a catalyst to provide a reaction rate that is fast enough for economic reasons but slow enough to allow removal of heat from the exothermic polymerization to ensure process safety. .

Lanthanide-based catalyst systems comprising a lanthanide compound, an alkylating agent, and a halogen source are known as 'τ

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useful for producing conjugated diene polymer having high contents of cis-1,4 bond. Nevertheless, when applied to the bulk polymerization of conjugated dienes, lanthanide-based catalyst systems, especially those comprising an aluminoxane compound as a catalyst component, often provide excessively rapid polymerization rates, which makes temperature control very difficult and compromises process safety. Therefore, it is desirable to develop a method of moderating the bulk polymerization of conjugated dienes catalyzed by lanthanide based catalysts.

It is also known that cis-1,4 polydienes having higher content of cis-1,4 bond exhibit the increased ability to undergo stress-induced crystallization and thereby provide superior physical properties such as higher tensile strength and resistance to wear. higher abrasion. Therefore, it is desirable to develop a method for producing cis-1,4 polydienes having higher content of cis-1,4 bond in both solution and bulk polymerization systems.

SUMMARY OF THE INVENTION

One or more embodiments of the present invention provide a process for preparing a polydiene, the process comprising the step of polymerizing conjugated diene monomer in the presence of a dihydrocarbyl ether, wherein the polymerization step employs a lanthanide based catalyst system.

Other embodiments provide a process for preparing a polydiene, the process comprising the step of introducing (a) conjugated diene monomer, (b) a lanthanide compound, (c) an alkylating agent, (d) a halogen-containing compound, and (e) a dihydrocarbyl ether.

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Other embodiments provide a catalyst system comprising the combination or reaction product of (a) a lanthanide compound, (b) an alkylating agent, (c) a halogen-containing compound, (d) a dihydrocarbyl ether, and optionally (e) conjugated diene monomer.

Still other embodiments provide a cis-1,4 polyidene prepared by a process comprising the step of polymerizing diene monomer conjugated to a lanthanide-based catalytic system including combining or reacting product of (a) a lanthanide compound, ( b) an alkylating agent, (c) a halogen-containing compound, and (d) a dihydrocarbyl ether.

DETAILED DESCRIPTION OF ILLUSTRATIVE MODALITIES

In accordance with one or more embodiments of the present invention, polydienes are produced by polymerizing conjugated diene monomer with a lanthanide based catalyst system in the presence of dihydrocarbyl ether. The presence of a dihydrocarbyl ether has been found to offer several advantages. Where a lanthanide-based catalyst system is designed to provide cis-1,4 polydienes, the presence of a dihydrocarbyl ether advantageously increases the cis-1,4 bond content of the resulting polydiene compared to 25 polydienes produced in the absence of a dihydrocarbyl ether. The presence of a dihydrocarbyl ether is particularly advantageous in bulk polymerization systems because the presence of a dihydrocarbyl ether has been found to modulate the rate of polymerization and thereby facilitate temperature control and reduce the risk of runaway reactions. in bulk polymerization.

The practice of one or more embodiments of the present invention is not limited by the selection of any specific lanthanide-based catalyst. In one or more embodiments, the catalyst composition can include a lanthanide compound, an alkylating agent, and a halogen-containing compound that includes one or more unstable halogen atoms. Where the lanthanide compound and/or alkylating agent includes one or more unstable halogen atoms, the catalyst need not include a separate halogen-containing compound; for example, the catalyst may simply include a halogenated lanthanide compound and an alkylating agent. In certain embodiments, the alkylating agent may include an aluminoxane and at least one other organoaluminium compound. In still other embodiments, a compound containing an uncoordinated anion, or an uncoordinated anion precursor, i.e., a compound that can undergo a chemical reaction to form an uncoordinated anion, can be employed in place of a compound containing halogen. In one embodiment, where the alkylating agent includes an organoaluminum hydride compound, the halogen-containing compound 20 may be a tin halide, as disclosed in US Patent Number 7,008,899, which is incorporated herein by reference. In these or other embodiments, other organometallic compounds, Lewis bases and/or catalyst modifiers may be employed in addition to the ingredients or components set out above. For example, in one embodiment, a nickel-containing compound may be employed as a molecular weight regulator, as disclosed in US Patent Number 6,699,813, which is incorporated herein by reference.

In one or more embodiments, polydienes are produced in accordance with the present invention by introducing (a) conjugated diene monomer, (b) a lanthanide compound, (c) an alkylating agent, (d) a compound

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containing halogen, and (e) a dihydrocarbyl ether. In certain embodiments, the dihydrocarbyl ether can be combined with the other catalyst components to form a catalytic system that includes the combination of the reaction product of a lanthanide compound, an alkylating agent, a halogen-containing compound, and a hydrogen ether. dihydrocarbyl.

In one or more embodiments, examples of conjugated diene monomer that can be polymerized in accordance with the present invention include 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl — T,3-butadiene, 2-ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene and 2,4hexadiene. Mixtures of two or more conjugated dienes 15 can also be used in copolymerization.

Various lanthanide compounds or mixtures thereof may be employed. In one or more embodiments, these compounds may be soluble in hydrocarbon solvents such as aromatic hydrocarbons, aliphatic hydrocarbons, or cycloaliphatic hydrocarbons. In other embodiments, hydrocarbon-insoluble lanthanide compounds, which can be suspended in the polymerization medium to form the catalytically active species, are also useful.

Lanthanide compounds can include at least one atom of lanthanum, neodymium, cerium, praseodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium and didymium. Didymium may include a commercial mixture of rare earth elements obtained from monazite sand.

The lanthanide atom in lanthanide compounds can be in various oxidation states including, but not limited to, the 0, +2, +3, and +4 oxidation states.

1!^

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Lanthanide compounds include, but are not limited to, lanthanide carboxylates, lanthanide organophosphates, lanthanide organophosphonates, lanthanide organophosphinates, lanthanide carbamates, 5-lanthanide dithiocarbamates, lanthanide xanthanides, lanthanide β-diketonates, alkoxides or aryloxides of lanthanide, lanthanide halides, lanthanide pseudohalides, lanthanide oxyaldehydes and organolanthanide compounds.

Without wishing to limit the practice of the present invention, further discussion will focus on neodymium compounds, although those skilled in the art are able to select similar compounds that are based on other lanthanide metals.

Neodymium carboxylates include neodymium formate, neodymium acetate, neodymium acrylate, neodymium methacrylate, neodymium valerate, neodymium gluconate, neodymium citrate, neodymium fumarate, neodymium lactate, neodymium maleate, neodymium oxalate, 2 -neodymium ethyl hexanoate, neodymium neodecaonate (known as neodymium versatate), neodymium naphthenate, neodymium stearate, neodymium oleate, neodymium benzoate and neodymium picolinate.

Neodymium organophosphates include neodymium dibutyl phosphate, neodymium dipentyl phosphate, neodymium dihexyl phosphate, neodymium dieptyl phosphate, neodymium dioctyl phosphate, neodymium bis(1-methyl heptyl) phosphate, bis(2-ethyl hexyl) phosphate neodymium, neodymium didecyl phosphate, neodymium didodecyl phosphate, neodymium dioctadecyl phosphate, neodymium dioleyl phosphate, neodymium diphenyl phosphate, neodymium bis(p-nonylphenyl) phosphate, neodymium butyl(2-ethyl hexyl) phosphate, (1-methyl heptyl) (2-ethyl hexyl) neodymium phosphate and (2-ethyl hexyl) (p-nonyl phenyl) phosphate

8/46 neodymium.

Organophosphonates of. neodymium include neodymium butyl phosphonate, neodymium pentyl phosphonate, neodymium hexyl phosphonate, neodymium heptyl phosphonate, neodymium octyl phosphonate, neodymium (1-methyl heptyl) phosphonate, neodymium (2-ethyl hexyl) phosphonate, decyl phosphonate neodymium, neodymium dodecyl phosphonate, neodymium octadecyl phosphonate, neodymium oleyl phosphonate, neodymium phenyl phosphonate, (p—nonyl phenyl) neodymium phosphonate, neodymium butyl butyl phosphonate, neodymium pentyl pentyl phosphonate, neodymium hexyl hexyl phosphonate, neodymium heptyl heptyl phosphonate, neodymium octyl octyl phosphonate, neodymium (1-methyl heptyl) (1-methyl heptyl) phosphonate, neodymium (2-ethyl hexyl) (2-ethyl hexyl) phosphonate neodymium,. neodymium decyl decyl phosphonate, neodymium dodecyl dodecyl phosphonate, neodymium octadecyl octadecyl phosphonate, neodymium oleyl oleyl phosphonate, neodymium phenyl phenyl phosphonate, (p-nonylphenyl) (p-nonylphenyl) neodymium phosphonate, butyl (2-ethyl hexyl) phosphonate neodymium (2-ethyl hexyl) butyl phosphonate neodymium (1-methyl heptyl) (2-ethyl hexyl) phosphonate neodymium (2-ethyl hexyl) (1-methyl heptyl) phosphonate neodymium (2-ethyl hexyl) ) (p-nonylphenyl) neodymium phosphonate, and neodymium (p-nonylphenyl)(2-ethyl hexyl)phosphonate.

Neodymium organophosphinates include neodymium butylphosphinate4. neodymium pentylphosphinate, neodymium hexylphosphinate, neodymium heptylphosphinate, neodymium octylphosphinate, neodymium (1-methyl heptyl)phosphinate, neodymium (2-ethyl hexyl)phosphinate, neodymium decylphosphinate, neodymium dodecylphosphinate, neodymium octadecyl phosphinate, oleylphosphinate neodymium, neodymium phenyl phosphinate, (p-nonylphenyl)

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neodymium phosphinate, neodymium dibutyl phosphinate, neodymium dipentyl phosphinate, neodymium dihexyl phosphinate, neodymium dieptyl phosphinate, neodymium dioctyl phosphinate, neodymium bis(1-methyl heptyl) phosphinate, 5-bis(2-ethyl hexyl) neodymium phosphinate, neodymium didecyl phosphinate, neodymium didodecyl phosphinate, neodymium dioctadecyl phosphinate, neodymium dioleyl phosphinate, neodymium diphenyl phosphinate, neodymium bis(p-nonylphenyl) phosphinate, neodymium butyl(2-ethyl hexyl) phosphinate, neodymium (ΙΙΟ methyl heptyl) (2-ethyl hexyl) phosphinate, and neodymium (2-ethyl hexyl) (p-nonyl phenyl) phosphinate.

Neodymium carbamates include neodymium dimethyl carbamate, neodymium diethyl carbamate, neodymium diisopropyl carbamate, neodymium dibutyl carbamate and neodymium dibenzyl carbamate.

Neodymium dithiocarbamates include neodymium dimethyl ditipcarbamate, neodymium diethyl dithiocarbamate, neodymium diisopropyl dithiocarbamate, neodymium dibutyl dithiocarbamate, and neodymium dibenzyldithiocarbamate.

Neodymium xanthates include neodymium methyl xanthate, neodymium ethyl xanthate, neodymium isopropyl xanthate, neodymium butyl xanthate, and neodymium benzyl xanthate.

Neodymium β-diketonates include neodymium acetyl acetonate, neodymium trifluoroacetyl acetonate, neodymium hexafluoroacetonate, neodymium benzoyl acetonate, and neodymium 2,2,6,6-tetramethyl-3,5heptanedionate.

Neodymium alkoxides or aryloxides include neodymium methoxide, neodymium ethoxide, neodymium isopropoxide, neodymium 2-ethylhexoxide, neodymium phenoxide, neodymium nonylphenoxide and neodymium naphthoxide.

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Neodymium halides include neodymium fluoride, neodymium chloride, neodymium bromide and neodymium iodide. Suitable neodymium pseudohalides include neodymium cyanide, neodymium cyanate, neodymium thiocyanate, neodymium azide and neodymium ferrocyanide.

Suitable neodymium oxylides include neodymium oxyfluoride, neodymium oxychloride, and neodymium oxybromide. Where neodymium halides, neodymium oxylides or other neodymium compounds containing unstable halogen atoms are employed, the neodymium-containing compound can also serve as the halogen-containing compound.

The term organolanthanide compound may refer to any lanthanide compound containing at least one carbon-lanthanide bond. These compounds 15 are predominantly, though not exclusively, those containing cyclopentadienyl (Cp), substituted cyclopentadienyl, allyl, and substituted allyl ligands. Suitable organolanthanide compounds include Cp₃Ln, Cp₂LnR, Cp₂LnCl, CpLnCl₂, CpLn (cyclooctatetraene), 20 (C₅Me₅)₂LnR, LnR₃, Ln(alila)₃ and Ln(alila)₂C1, where Ln represents lanthanide atom, and R represents a hydrocarbyl group.

Various alkylating agents, or mixtures thereof, may be used. In one or more embodiments, alkylating agents which may also be mentioned as hydrocarbylating agents include organometallic compounds which can transfer hydrocarbyl groups to another metal. Typically, such agents include organometallic compounds of electropositive metals such as Groups 1, 2, and 3 metals (Group IA, IIA, and IIIA metals). In one or more embodiments, alkylating agents include organoaluminum and organomagnesium compounds. Where the alkylating agent includes a halogen atom

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unstable, the alkylating agent can also serve as the halogen-containing compound.

The term organoaluminium composite can be

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refer to any aluminum compound containing at least one aluminum-carbon bond. In one or more embodiments, organoaluminium compounds may be soluble in a hydrocarbon solvent.

In one or more embodiments, organoaluminium compounds include those represented by the formula

AlR_noX3-nz where each R, which may be the same or different, is a monovalent organic group that is attached to the aluminum atom through a carbon atom, where each X, which may be the same or different, is a hydrogen atom, a halogen atom, a carboxylate group, an alkoxy group, or an aryloxy group and where n is an integer from 1 to 3. In one or more embodiments, 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. These hydrocarbyl groups may contain heteroatoms such as, but not limited to, nitrogen, oxygen, boron, silicon, sulfur, and phosphorus atoms.

Organoaluminium compounds include, but are not limited to, trihydrocarbylaluminum compounds, dihydrocarbylaluminum hydride, hydrocarbylaluminum dihydride, dihydrocarbylaluminum carboxylate, hydrocarbylaluminum bis(carboxylate), dihydrocarbylaluminum alkoxide, hydrocarbylaluminum dialkoxide, dihydrocarbylaluminum halide, hydrocarbylaluminum dialect , dihydrocarbylaluminum aryloxide and hydrocarbylaluminum diaryloxide.

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Trihydrocarbylaluminum compounds include trimethylaluminium, triethylaluminium, triisobutylaluminium, tri-n-propylaluminium, triisopropylaluminium, tri-n-butylaluminium, tri-t-butylaluminium, tri-n-pentylaluminium, trineopentylaluminium, tri-n-hexyl aluminum, tri-n-octyl aluminum, tris(2-ethyl hexyl) aluminum, tricyclohexyl aluminum, tris(1-methyl cyclopentyl) aluminum, triphenyl aluminum, tri-p-tolyl aluminum, tris(2,6-dimethyl phenyl) aluminum , aluminum tribenzyl, aluminum diethyl phenyl, diethyl-p-tolyl aluminum, diethyl benzyl aluminum, ethyl diphenyl aluminum, ethyl di-p-tolyl aluminum, and ethyl dibenzyl aluminum.

Dihydrocarbyl aluminum hydride compounds include diethyl aluminum hydride, di-n-propyl aluminum hydride, diisopropyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, di-n-octyl aluminum hydride, diphenyl hydride aluminum, di-p-tolyl aluminum hydride, dibenzyl aluminum hydride, phenyl ethyl aluminum hydride, phenyl-n-propyl aluminum hydride, phenyl isopropyl aluminum hydride, phenyl-n-butyl aluminum hydride, phenyl isobutyl aluminum hydride, phenyl-n-octyl aluminum hydride, p-tolyl ethyl aluminum hydride, p-tolyl-n-propyl aluminum hydride, p-tolyl isopropyl aluminum hydride, p-tolyl-n- butyl aluminum, p-tolyl hydride. isobutyl aluminum, p-tolyl-n-octyl aluminum hydride, benzyl ethyl aluminum hydride, benzyl-n-propyl aluminum hydride, benzylisopropyl aluminum hydride, benzyl-n-butyl aluminum hydride, benzyl isobutyl aluminum hydride of benzyl-n-octyl aluminum.

Hydrocarbyl aluminum dihydrides include ethyl aluminum dihydride, n-propyl aluminum dihydride, isopropyl aluminum dihydride, n-butyl dihydride

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aluminum, isobutyl aluminum dihydride and noctyl aluminum dihydride.

Dihydrocarbyl aluminum chloride compounds include diethyl aluminum chloride, di-n-propyl aluminum chloride, diisopropyl aluminum chloride, di-n-butyl aluminum chloride, diisobutyl aluminum chloride, di-n-octyl aluminum chloride, diphenyl aluminum chloride, di-p-tolyl aluminum chloride, dibenzyl aluminum chloride, phenyl ethyl aluminum chloride, phenyl-n-propyl aluminum chloride, phenyl isopropyl aluminum chloride, phenyl-n-butyl aluminum chloride, phenyl isobutyl aluminum chloride, phenyl-n-octyl aluminum chloride, p-tolyl ethyl aluminum chloride, p-tolyl-n-propyl aluminum chloride, p-tolyl isopropyl aluminum chloride, p-tolyl-n- butyl aluminum, p-tolyl isobutyl aluminum chloride, p-tolyl-n-octyl aluminum chloride, benzyl ethyl aluminum chloride, benzyl-n-propyl aluminum chloride, benzyl isopropyl aluminum chloride, benzyl-n- butyl aluminum, benzyl isobutyl aluminum chloride and benzyl-n20 octyl aluminum chloride.

Hydrocarbyl aluminum dichloride includes ethyl aluminum dichloride, n-propyl aluminum dichloride, isopropyl aluminum dichloride, n-butyl aluminum dichloride, isobutyl aluminum dichloride and n25 octyl aluminum dichloride.

Other organoaluminium compounds include dimethyl aluminum hexanoate, diethyl aluminum octoate, diisobutyl aluminum 2-ethyl hexanoate, dimethyl aluminum neodecanoate, diethyl aluminum stearate, diisobutyl aluminum oleate, methyl aluminum bis(hexanoate), bis( ethyl aluminum octoate, isobutyl aluminum bis(2-ethyl hexanoate), methyl aluminum bis(neodecanoate), ethyl aluminum bis(stearate), isobutyl bis(oleate)

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aluminum, dimethyl aluminum methoxide, diethyl aluminum methoxide, diisobutyl aluminum methoxide, dimethyl aluminum ethoxide, diethyl aluminum ethoxide, diisobutyl aluminum ethoxide, dimethyl aluminum phenoxide, diethyl aluminum phenoxide 5, diisobutyl aluminum phenoxide, aluminum dimethoxide methyl aluminum, ethyl aluminum dimethoxide, isobutyl aluminum dimethoxide, methyl aluminum dietoxide, ethyl aluminum dietoxide, isobutyl aluminum dietoxide, methyl aluminum diphenoxide, ethyl aluminum diphenoxide, isobutyl aluminum diphenoxide and the like and mixtures thereof.

Another class of organoaluminium compounds includes aluminoxanes. Aluminoxanes include oligomeric linear aluminoxanes which can be represented by the general formula:

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and oligomeric cyclic aluminoxanes that can be represented by the general formula:

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where x can be an integer from 1 to about 100, and in other embodiments from about 10 to about 50; y may be an integer from 2 to approximately 100, and in other embodiments from approximately 3 to approximately 20; and where each R¹ which can be the same or different, can be a group

15/46 monovalent organic compound that is attached to the aluminum atom via a carbon atom. In one or more modalities, each R¹ is 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. These hydrocarbyl groups may contain heteroatoms such as, but not limited to, nitrogen, oxygen, boron, silicon, sulfur, and phosphorus atoms. It should be noted that the number of moles of aluminoxane, as used in this application, refers to the number of moles of aluminum atoms rather than the number of moles of oligomeric aluminoxane molecules. This convention is commonly employed in the catalysis technique using aluminoxanes.

Aluminoxanes can be prepared by reacting aluminum trihydrocarbyl compounds with water. This reaction can be carried out according to known methods, such as (1) a method in which the trihydrocarbyl aluminum compound can be dissolved in an organic solvent and then contacted with water, (2) a method in which the trihydrocarbyl compound aluminum can be reacted with water of crystallization contained, for example, in metal salts, or water adsorbed on inorganic or organic compounds, and (3) a method in which the aluminum trihydrocarbyl compound can be reacted with water in the presence of the monomer or monomer solution that is to be polymerized.

Aluminoxane compounds include methyl aluminoxane (MAO), modified methyl aluminoxane (MMAO), ethyl aluminoxane, n-propyl aluminoxane, isopropyl aluminoxane, butyl aluminoxane, isobutyl aluminoxane, npentyl aluminoxane, neopentyl aluminoxane, n-hexyl aluminoxane, n-octyl aluminoxane, 2-ethyl hexyl aluminoxane, cyclohexyl aluminoxane, 1-methyl cyclopentyl aluminoxane,

16/46 phenyl. aluminoxane,

2,6-dimethyl phenyl aluminoxane and

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similar and mixtures thereof. Modified methyl aluminoxane can be formed by replacing approximately 20-80% of the methyl groups of methyl aluminoxane with C2 to C12 hydrocarbyl groups, preferably with isobutyl groups, using techniques known to those skilled in the art.

Aluminoxanes can be used alone or in combination with other organoaluminium compounds. In one embodiment, methyl aluminoxane and at least one other organa aluminum compound (e.g., AlR_noX3-_no), such as diisobutyl aluminum hydride, are used in combination. US serial number 60/877,535, which is incorporated herein by reference, provides further examples where aluminoxanes and organoaluminium compounds are employed in combination.

The term organomagnesium compound can refer to any magnesium compound that contains at least one carbon-magnesium bond. Organomagnesium compounds may be soluble in a hydrocarbon solvent. One class of organomagnesium compounds that can be used can be represented by the formula MgR2 / where each R, which may be the same or different, is a monovalent organic group, with the proviso that the group is attached to the magnesium atom via. carbon atom. In one or more embodiments, each R may be a hydrocarbyl group, and the resulting organomagnesium compounds are dihydrocarbyl magnesium compounds. Examples of hydrocarbyl groups include, but are not limited to, alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl, aryl, allyl, substituted aryl, aralkyl, alkaryl, and alkynyl groups. These hydrocarbyl groups may contain

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heteroatoms such as, but not limited to, nitrogen, oxygen, silicon, sulfur and phosphorus.

Examples of suitable dihydrocarbyl magnesium compounds include diethyl magnesium, di-n-propyl magnesium, diisopropyl magnesium, dibutyl magnesium, dihexyl magnesium, diphenyl magnesium, dibenzyl magnesium and mixtures thereof.

Another class of organomagnesium compounds that can be used includes those that can be represented by the formula RMgX, where R is a monovalent organic group, with the proviso that the group 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 aryloxy group. In one or more embodiments, R may be a hydrocarbyl group such as, but not limited to, alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl, aryl, allyl, substituted aryl, aralkyl, alkaryl, and alkynyl groups. These hydrocarbyl groups may contain heteroatoms such as, but not limited to, nitrogen, oxygen, boron, atoms. silicon, sulfur and phosphorus. In one or more embodiments, X is a carboxylate group, an alkoxy group, or an aryloxy group.

Exemplary types of organomagnesium compounds that may be represented by the formula RMgX include, but are not limited to, hydrocarbyl magnesium hydride, hydrocarbyl magnesium haleph, hydrocarbyl magnesium carboxylate, hydrocarbyl magnesium alkoxide, hydrocarbyl magnesium aryloxide and mixtures thereof.

Specific examples of organomagnesium compounds that can be represented by the formula RMgX include methyl magnesium hydride, ethyl magnesium hydride, butyl magnesium hydride, hexyl hydride

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<td></td><td>2 T</td>

<td>magnesium.</td><td>phenyl magnesium hydride, benzyl hydride</td>

<td>magnesium,</td><td>methyl magnesium chloride, ethyl chloride</td>

<td>magnesium,</td><td>butyl magnesium chloride, hexyl chloride ·,</td>

<td>magnesium,</td><td>phenyl magnesium chloride, benzyl chloride</td>

<td>magnesium,</td><td>methyl magnesium bromide, ethyl bromide</td>

<td>magnesium,</td><td>butyl magnesium bromide, hexyl bromide</td>

<td>magnesium,</td><td>phenyl magnesium bromide, benzyl bromide</td>

<td>magnesium,</td><td>methyl magnesium hexanoate, ethyl hexanoate</td>

<td>magnesium,</td><td>butyl magnesium hexanoate, hexyl hexanoate</td>

<td>magnesium,</td><td>phenyl magnesium hexanoate, benzyl hexanoate</td>

<td>magnesium,</td><td>methyl magnesium ethoxide, ethyl ethoxide</td>

<td>magnesium,</td><td>butyl magnesium ethoxide, hexyl ethoxide</td>

<td>magnesium,</td><td>phenyl magnesium ethoxide, benzyl ethoxide</td>

<td>magnesium.</td><td>Methyl Magnesium Phenoxide, Ethyl Phenoxide</td>

<td>magnesium,</td><td>butyl magnesium phenoxide, hexyl phenoxide</td>

<td>magnesium,</td><td>magnesium phenyl phenoxide, benzyl phenoxide</td>

<td>magnesium</td><td>and the like, and mixtures thereof.</td>

<td></td><td>Various halogen-containing compounds, or mixtures</td>

<td colspan="2">of the same, which contain one or more halogen atoms</td>

<td>unstable</td><td>can be employed. Examples of atoms of</td>

<td>halogen</td><td>include, but are not limited to, fluorine, chlorine,</td>

<td>bromine and</td><td>iodine. A combination of two or more compounds</td>

<td>containing</td><td>halogen having different halogen atoms</td>

<td colspan="2">can also be used. In one or more modes, the</td>

<td>compounds</td><td>containing halogen may be soluble in a</td>

<td>solvent</td><td>of hydrocarbon. In other modalities,</td>

<td>compounds</td><td>containing halogen insoluble hydrocarbons,</td>

<td colspan="2">that can be suspended in the polymerization medium to</td>

<td>form the</td><td>catalytically active species, may be useful.</td>

<td></td><td>Appropriate types of halogen-containing compounds</td>

<td>include,</td><td>but are not limited to elemental halogens,</td>

<td colspan="2">mixed halogens, hydrogen halides, halides</td>

<td>organic</td><td>, inorganic halides, metal halides, halides</td>

%

19/46

<img file="BRPI0806041B1_D0025.tif" />

<img file="BRPI0806041B1_D0026.tif" />

organometallics and mixtures thereof.

Elemental halogens include fluorine, chlorine, bromine and iodine. Mixed halogens include iodine monochloride, iodine monobromide, iodine trichloride and iodine pentafluoride.

Hydrogen halides include hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide.

Organic halides include t-butyl chloride, t-butyl bromides, allyl chloride, allyl bromide, benzyl chloride, benzyl bromide, chloro-d-phenyl methane, bromo-di-phenyl methane, triphenyl methyl chloride, bromide of triphenyl methyl, benzylidene chloride, benzylidene bromide, methyl trichlorosilane, phenyl trichlorosilane, dimethyl dichlorosilane, diphenyl dichlorosilane, trimethyl chlorosilane, benzoyl chloride, benzoyl bromide, propionyl chloride, propionyl bromide, methyl chloroformate and methyl bromoformate.

Inorganic halides include phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride, phosphorus oxybromide, boron trifluoride, boron trichloride, boron tribromide, silicon tetrafluoride, silicon tetrachloride, silicon tetrabromide, silicon, arsenic trichloride, arsenic tribromide, arsenic triiodide, selenium tetrachloride, selenium tetrabromide, tellurium tetrachloride, tellurium tetrabromide and tellurium tetraiodide.

Metal halides include 30 tin tetrachloride, tin tetrabromide, aluminum trichloride, aluminum tribromide, antimony trichloride, antimony pentachloride, antimony tribromide, aluminum triiodide, aluminum trifluoride, trichloride

20/46

<img file="BRPI0806041B1_D0027.tif" />

of gallium, 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.

Organometallic halides include dimethyl aluminum chloride, diethyl aluminum chloride, dimethyl aluminum bromide, diethyl aluminum bromide, dimethyl aluminum fluoride, diethyl aluminum fluoride, methyl aluminum dichloride, ethyl aluminum dichloride, methyl aluminum dibromide, aluminum dibromide ethyl aluminum, methyl aluminum difluoride, ethyl aluminum difluoride, sesquichloride

<td>of methyl</td><td colspan="2">aluminum,</td><td colspan="2">ethyl sesquichloride</td><td colspan="2">aluminum,</td>

<td colspan="2">sesquichloride of</td><td colspan="2">isobutyl</td><td>aluminum chloride</td><td>in</td><td>methyl</td>

<td>magnesium,</td><td>bromide</td><td>in</td><td>methyl</td><td>magnesium, iodide</td><td>in</td><td>methyl</td>

<td>magnesium,</td><td>chloride</td><td>in</td><td>ethyl</td><td>magnesium bromide</td><td>in</td><td>ethyl</td>

<td>magnesium,</td><td>chloride</td><td>in</td><td>butyl</td><td>magnesium bromide</td><td>in</td><td>butyl</td>

<td>magnesium,</td><td>chloride</td><td>in</td><td>phenyl</td><td>magnesium bromide</td><td>in</td><td>phenyl</td>

<td>magnesium,</td><td>chloride</td><td colspan="2">of benzyl</td><td>magnesium chloride</td><td colspan="2">: trimethyl</td>

tin, trimethyl tin bromide, triethyl tin chloride, triethyl tin bromide, di-t-butyl tin dichloride, di-t-butyl tin dibromide, dibutyl tin dichloride, dibutyl tin dibromide, tributyl tin chloride and bromide of tributyl tin.

In still other embodiments, a compound containing an uncoordinated anion, or an uncoordinated anion precursor, that is, a compound that can undergo a chemical reaction to form an uncoordinated anion, can be employed in place of a compound containing halogen. Compounds containing uncoordinated anions are known in the art. In general, uncoordinated anions are sterically bulky anions that do not form bonds.

21/46

<img file="BRPI0806041B1_D0028.tif" />

coordinates, for example, with the active center of a catalytic system due to steric hindrance. Exemplary uncoordinated anions include fluorinated tetraaryl borate anions and fluorinated tetraaryl borate anions. Compounds 5 containing an uncoordinated anion also contain a counter cation such as a carbon, ammonium, or phosphonium cation. Exemplary counter cations include triaryl carbonium cations and Ν,Ν-dialkylanilinium cations. Examples of compounds containing one uncoordinated anion and one against 10 cation include triphenyl carbonium tetrakis (pentafluorophenyl) borate, Ν,Ν-dimethyl anilinium tetrakis (pentafluorophenyl) borate, triphenyl carbonium tetrakis[3,5bis(trifluoromethyl)phenyl]borate, and Ν ,Ν-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl] borate.

Uncoordinated anion precursors include compounds that can form an uncoordinated anion under reaction conditions. Exemplary uncoordinated anion precursors include triaryl boron compounds, BRs, where R is a strong electron-withdrawing aryl group such as a pentafluorophenyl or 3,5-bis(trifluoromethyl)phenyl group.

In one or more embodiments, dihydrocarbyl ethers include those compounds represented by the formula ROR, where each R, which may be the same or different, is a hydrocarbyl group or substituted hydrocarbyl group. The hydrocarbyl group may contain heteroatoms such as, but not limited to, nitrogen, oxygen, silicon, tin, sulfur, boron, and phosphorus atoms. Examples of hydrocarbyl groups or substituted hydrocarbyl groups include, but are not limited to, alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, cycloalkenyl, aryl, substituted aryl, and heterocyclic groups.

22/46

<img file="BRPI0806041B1_D0029.tif" />

<img file="BRPI0806041B1_D0030.tif" />

Exemplary alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, nheptyl, 2-ethyl hexyl, n-octyl, n-nonyl and n-decyl.

Exemplary cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 2-methyl cyclohexyl, 2-t-butyl cyclohexyl and 4-t-butyl cyclohexyl groups.

Exemplary aryl groups include phenyl, substituted phenyl, biphenyl, substituted biphenyl, bicyclic aryl, substituted bicyclic aryl, polycyclic aryl, and substituted polycyclic aryl groups. Substituted aryl groups include those where a hydrogen atom is replaced by a monovalent organic group 15 such as a hydrocarbyl group.

Exemplary substituted phenyl groups include 2-methyl phenyl, 3-methyl phenyl, 4-methyl phenyl, 2,3-dimethyl phenyl, 3,4-dimethyl phenyl, 2,5-dimethyl phenyl, 2,6-dimethyl phenyl groups , and 2,4,6-trimethyl phenyl (also called mesityl).

Exemplary bicyclic or polycyclic aryl groups include 1-naphthyl, 2-naphthyl, 9-anthryl, 9-phenanthryl, 2-benzo[b]thienyl, 3-benzo[b]thienyl, 2-naphtho[2,3-b]thienyl, 2-thianthrenyl, 125 isobenzofuranyl, 2-xanthenyl, 2-phenoxathiinyl,2indolizinyl, N-methyl-2-indolyl, N-methyl-indazol-3-yl, Nmethyl-8-purinyl, 3-isoquinolyl, 2-quinolyl,3-cinolinyl , 2-pteridinyl, N-methyl-2-carbazolyl, N-methylp-carbolin-3-yl, 3-phenanthridinyl, 2-acridinyl,130-phthalazinyl, 1,8-naphthyridine-2-yl, 2-quinoxalinyl, 2quinazolinyl, 1,7-phenanthrolin-3-yl, 1-phenazinyl, N-methyl-2-phenothiazinyl, 2-phenarsazinyl and N-methyl-2-phenoxazinyl.

23/46

Exemplary heterocyclic groups include 2-thienyl, 3-thienyl, 2-furyl, 3-furyl, N-methyl-2-pyrrolyl, N-methyl-3-pyrrolyl, N-methyl-2-imidazolyl, 1-pyrazolyl, N-methyl- 3-pyrazolyl, N-methyl-4-pyrazolyl, pyridyl, 3-pyridyl, '4-pyridyl, pyrazinyl, 2-pyrimidinyl, 3-pyridazinyl, 3-isothiazolyl, 3-isoxazolyl, 3-furazanyl, 2-triazinyl, morpholinyl, thiomorpholinyl, piperidinyl, piperazinyl, pyrrolidinyl, pyrrolinyl, imidazolidinyl and imidazolinyl.

Suitable types of hydrocarbyl ethers include, but are not limited to, dialkyl ethers, dicycloalkyl ethers, diaryl ethers and mixed dihydrocarbyl ethers.

Specific examples of dialkyl ethers 15 include dimethyl ether, diethyl ether, di-npropyl ether, diisopropyl ether, di-n-butyl ether, diisobutyl ether, di-t-butyl ether, di- n-pentyl, diisopentyl ether, dineopentyl ether, dihexyl ether, di-n-heptyl ether, di-2-ethyl hexyl ether, di-n-octyl ether, di- n-nonyl, di-ndecyl ether and dibenzyl ether.

Specific examples of dicycloalkyl ethers include dicyclopropyl ether, dicyclobutyl ether, dicyclopentyl ether, dicyclohexyl ether, di-225 cyclohexyl methyl ether and di-2-t-butyl cyclohexyl ether.

Specific examples of diaryl ethers include diphenyl ether, di-o-tolyl ether, di-m-tolyl ether and di-p-tolyl ether.

Specific examples of mixed dihydrocarbyl ethers 30 include n-butyl methyl ether, isobutyl methyl ether, sec-butyl methyl ether, t-butyl methyl ether, n-butyl ethyl ether, isobutyl ethyl ether, sec-butyl ether ethyl, t-butyl ethyl ether, t-amyl methyl ether,

24/46 -/A

A &gt;3#

---m, H**^Γ*·&gt; &lt;S?

t-amyl ethyl ether, phenyl ethyl ether, n-phenyl ether. propyl, phenyl isopropyl ether, phenyl n-butyl ether, phenyl isobutyl ether, phenyl n-octyl ether, ptolyl ethyl ether, p-tolyl n-propyl ether, p-tolyl isopropyl ether, p -tolyl n-butyl ether, p-tolyl isobutyl ether, p-tolyl t-butyl ether, p-tolyl noctyl ether, benzyl n-ethyl ether, benzyl n-propyl ether, benzyl isopropyl ether, benzyl n-butyl, isobutyl benzyl ether, benzyl t-butyl ether and benzyl n-octyl ether.

In one or more embodiments, one or both of the hydrocarbyl groups (R) on the dihydrocarbyl ether may contain one or more additional ether (i.e., COC) bonds. Such ether compounds may be referred to as polyethers. Specific examples of polyethers include glyme ethers such as dimethyl ethylene glycol ether (also called monoglyme), diethyl ethylene glycol ether, dimethyl diethylene glycol ether (also called diglyme), diethyl diethylene glycol ether, di-n-butyl diethylene ether glycol, dimethyl triethylene glycol ether (also called triglyme), diethyl triethylene glycol ether, dimethyl tetraethylene glycol ether (also called tetraglyme), and diethyl tetraethylene glycol ether.

The catalyst composition of the present invention can be formed by combining or mixing the above catalyst ingredients. Although it is believed that one or more species of active catalyst results from the combination of the catalyst ingredients, the degree of interaction or reaction between the various catalyst ingredients or component is not known with any great degree of certainty. The combination or reaction product of the lanthanide compound, alkylating agent and halogen-containing compound is ο

25/46 conventionally referred to as catalytic system Or. catalyst composition. Dihydrocarbyl ether, as used herein, may be mentioned as a component of that system or as a modifier for that system. In this regard, reference to catalyst ingredients refers to the lanthanide compound, alkylating agent, halogen-containing compound and dihydrocarbyl ether. 0 The term modified catalyst composition or modified catalytic system may be used to encompass a simple mixture of the ingredients, a complex of the various ingredients that is caused by chemical or physical forces of attraction, a chemical reaction product of the ingredients, or a combination of the above.

The catalyst composition of the present invention advantageously has a technologically useful catalytic activity to polymerize conjugated dienes to polydienes over a wide range of catalyst concentrations and catalyst ingredient ratios. Several factors can impact the optimal concentration of any of the catalytic ingredients. For example, as catalyst ingredients can interact to form an active species, the optimal concentration for any one catalyst ingredient may be dependent on the concentrations of the other catalyst ingredients.

In one or more embodiments, the molar ratio of alkylating agent to lanthanide compound (alkylating agent/Ln) can be varied from approximately 1:1 to approximately 1,000:1, in other embodiments from approximately 2:1 to approximately 2:1 to approximately 500:1, and in other modes from approximately 5:1 to approximately 200:1.

In embodiments where both an aluminoxane and at least one other organoaluminium agent are employed

26/46' Q.

<img file="BRPI0806041B1_D0031.tif" />

as alkylating agents, a. molar ratio of aluminoxane to lanthanide compound (aluminoxane/Ln) can be varied from 5:1 to approximately 1000:1, in other embodiments from approximately 10:1 to approximately 700:1, and in other embodiments from approximately 10:1 to approximately 500:1, and the molar ratio of at least one other organoaluminium compound to the lanthanide compound (Al/Ln) can be varied from approximately 1:1 to approximately 200:1, in other embodiments from approximately 2:1 to approximately 150:1, and in other embodiments from approximately 5:1 to approximately 100:1.

The molar ratio of the halogen-containing compound to the lanthanide compound is. best described in terms of the ratio of moles of halogen atoms in the halogen-containing compound to the moles of lanthanide atoms in the lanthanide compound (halogen/Ln). In one or more embodiments, the halogen/Ln molar ratio may be varied from approximately 0.5:1 to approximately 20:1, in other embodiments from approximately 1:1 to approximately 10:1, and in other embodiments from approximately 2 :1 to approximately 6:1.

In relevant embodiments, the molar ratio of uncoordinated anion or uncoordinated anion precursor to lanthanide compound (An/Ln) can be from approximately 0.5:1 to approximately 20:1, in other embodiments from approximately 0.75 :1 to approximately 10:1, and in other embodiments from approximately 1:1 to approximately 6:1.

In one or more embodiments, the molar ratio of dihydrocarbyl ether to lanthanide compound (ether/Ln) can be varied from approximately 0.5:1 to approximately 1000:1, in other embodiments from approximately 1:1 to approximately 700: 1, and in other embodiments from approximately 5:1 to approximately 500:1.

27/46

<img file="BRPI0806041B1_D0032.tif" />

The lanthanide-based catalyst can be formed employing various techniques. For example, the catalyst may be formed by adding the catalyst components directly to the monomer to be polymerized. In this regard, the catalyst components including the dihydrocarbyl ether can be added in a stepwise or simultaneous fashion. In one embodiment, when the catalyst ingredients are added in a stepwise fashion, the dihydrocarbyl ether may be added first, followed by the alkylating agent, followed by the lanthanide compound, and finally followed by the halogen-containing compound. The addition of the catalyst components directly and individually to the monomer to be polymerized can be referred to as an in situ formation of the catalytic system.

In other embodiments, the catalyst may be preformed. That is, the catalyst ingredients including the dihydrocarbyl ether can be introduced and premixed out of the monomer to be polymerized. In specific embodiments, catalyst preformation can occur in the absence of any monomer or in the presence of a small amount of at least one conjugated diene monomer at an appropriate temperature, which is generally from approximately -20°C to approximately 80°C. . Mixtures of conjugated diene monomers can also be used. The amount of conjugated diene monomer that can be used to preform the catalyst can range from approximately 1 to approximately 500 mol, in other embodiments from approximately 5 to approximately 250 mol, and in other embodiments from approximately 10 to approximately 100 mol per mole of the lanthanide compound. The resulting preformed catalyst composition can be

<img file="BRPI0806041B1_D0033.tif" />

<img file="BRPI0806041B1_D0034.tif" />

28/46 J Λ V* 5 aged, if desired, before being added to the 2nd monomer which is to be polymerized.

In other embodiments, the catalyst may be formed using a two-stage procedure. The first stage may involve combining the lanthanide compound with the alkylating agent in the absence of any monomer or in the presence of a small amount of at least one conjugated diene monomer at an appropriate temperature (e.g. -20°C to approximately 80°C). The amount of monomer employed in the preparation of this first stage mixture can be similar to that set out above for preforming the catalyst. In the second stage, the mixture prepared in the first stage, the dihydrocarbyl ether, and the halogen-containing compound can be added in a stepwise fashion or simultaneously to the monomer which is to be polymerized. In one embodiment, the dihydrocarbyl ether may be added first, followed by the mixture prepared in the first stage, and then followed by the halogen-containing compound.

In one or more embodiments, a solvent may be employed as a diluent to dissolve or suspend the catalyst or catalyst ingredients to facilitate delivery of the catalyst or catalyst ingredients to the polymerization system. In other embodiments, conjugated diene monomer can be used as the diluent catalyst. In still other embodiments, the catalyst ingredients may be used in their pure state without any solvents.

In one or more embodiments, suitable solvents 30 include those organic compounds that will not undergo polymerization or incorporation into propagating polymer chains during monomer polymerization in the presence of catalyst. In one or more modes,

29/46 these organic species are liquid

<img file="BRPI0806041B1_D0035.tif" />

room temperature. In one or more embodiments, these organic solvents are inert to the catalyst. Exemplary organic solvents include hydrocarbons with a low or relatively low boiling point such as aromatic hydrocarbons, aliphatic hydrocarbons, and cycloaliphatic hydrocarbons. Non-limiting examples of aromatic hydrocarbons include benzene, toluene, xylenes, ethyl benzene, diethyl benzene and mesitylene. Non-limiting examples of aliphatic hydrocarbons include n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, isopentane, isohexanes, isopentanes, isocotanes, 2,2-dimethyl butane, petroleum ether and kerosene. And non-limiting examples of cycloaliphatic hydrocarbons include cyclopentane, cyclohexane, methyl cyclopentane, and methyl cyclohexane. Mixtures of the above hydrocarbons can also be used. As is known in the art, aliphatic and cycloaliphatic hydrocarbons may desirably be employed for environmental reasons. Low boiling point hydrocarbon solvents are typically separated from the polymer after polymerization is complete.

Other examples of organic solvents include high-boiling hydrocarbons of high molecular weights, such as paraffinic oil, aromatic oil, or other hydrocarbon oils that are commonly used to dilute polymers in oil. Since these hydrocarbons are non-volatile, they typically do not require separation and remain embedded in the polymer.

The production of polydienes in accordance with the present invention can be carried out by polymerizing conjugated diene monomer in the presence of a catalytically effective amount of the above catalyst composition.

30/46

The introduction of the catalyst composition, the conjugated monomer diene, and any solvent, if employed, forms a polymerization mixture in which the polymer product is formed. The total concentration of catalyst to be employed in the polymerization mixture may depend on the interaction of various factors such as ingredient purity, polymerization temperature, desired polymerization and conversion rate, desired molecular weight, and many other factors. Therefore, a total specific catalyst concentration cannot be definitively stated except to say that catalytically effective amounts of the respective catalyst ingredients can be used. In one or more embodiments, the amount of the lanthanide compound used may be varied from approximately 0.01 to approximately 2 mmol, in other embodiments from approximately 0.02 to approximately 1 mmol, and in other embodiments from approximately 0.05 to approximately 0.5 mmol per 100 g of conjugated diene monomer.

In one or more embodiments, the polymerization of conjugated diene monomer in accordance with the present invention may be carried out in a polymerization system that includes a substantial amount of solvent. In one embodiment, a solution polymerization system may be employed in which both the monomer to be polymerized and the polymer formed are soluble in the solvent. In another embodiment, a precipitation polymerization system may be employed by choosing a solvent in which the polymer formed is insoluble. In both cases, an amount of solvent in addition to the amount of solvent that can be used in preparing the catalyst is normally added to the polymerization system. The additional solvent may be the same as or different from the solvent

31/46' p used in the preparation of the catalyst. Solvents „ Exemplary solvents were exposed above. In one or more embodiments, the solvent content of the polymerization mixture can be greater than 20% by weight, in other embodiments greater than 50% by weight, and in still other embodiments greater than 80% by weight based on in the total weight of the polymerization mixture.

In other embodiments, the polymerization system employed may generally be considered a bulk polymerization system that includes substantially no solvent or a minimal amount of solvent. Those skilled in the art will recognize the benefits of bulk polymerization processes (i.e., processes where the monomer acts as the solvent), and therefore the polymerization system includes less solvent than will adversely impact the benefits sought by carrying out the polymerization in bulk. pasta. In one or more embodiments, the solvent content of the polymerization mixture may be less than approximately 20% by weight, in other embodiments, less than approximately 10% by weight, and in still other embodiments, less than approximately 5% by weight. weight based on the total weight of the polymerization mixture. In yet another embodiment, the polymerization mixture is substantially solvent-free, which refers to the absence of that amount of solvent that would otherwise have an appreciable impact on the polymerization process. Polymerization systems which are substantially solvent-free may be mentioned as substantially not including solvent. In specific embodiments, the polymerization mixture is solvent-free.

The polymerization may be carried out in any conventional polymerization vessels known in the art.

<img file="BRPI0806041B1_D0036.tif" />

technique. In one or more embodiments, the solution polymerization may be carried out in a conventional stirred-tank reactor. In other embodiments, bulk polymerization can be carried out in a conventional stirred-tank reactor, especially if the monomer conversion is less than approximately 60%. In still other embodiments, especially where the monomer conversion in a bulk polymerization process is higher than approximately 60%, which typically results in a highly viscous cement, the bulk polymerization can be conducted in an elongated reactor in which the viscous cement under polymerization is driven to move by piston, or substantially by piston. For example, extruders in which the cement is pushed by a self-cleaning single-screw or twin-screw mixer are suitable for this purpose.

Examples of useful bulk polymerization processes are disclosed in US publication number 2005/0197474 A1, which is incorporated herein by reference.

In one or more embodiments, all of the ingredients used for polymerization may be combined in a single vessel (eg, a conventional stirred-tank reactor) and all steps of the polymerization process may be carried out in that vessel. In other embodiments, two or more of the ingredients may be pre-combined in one container and then transferred to another container where monomer polymerization (or at least a large portion thereof) can be carried out.

The polymerization can be carried out as a batch process, a continuous process or a semi-continuous process. In the semi-continuous process, the monomer is intermittently charged as needed to replace that already polymerized monomer. In one or more embodiments, the conditions under which the polymerization

33/46 proceeds can be controlled to maintain the temperature a of the polymerization mixture in a range of approximately -10°C to approximately 200°C, in other embodiments from approximately 0°C to approximately 150°C, and in other embodiments of approximately 20°C to approximately 100°C. In one or more embodiments, the heat of polymerization may be removed by external cooling through a thermally controlled reactor jacket, internal cooling by evaporation and condensation of the monomer through the use of a reflux condenser connected to the reactor, or a combination of the two methods. . In addition, conditions can be controlled to carry out the polymerization under a pressure of approximately 0.1 atmosphere to approximately 50 atmospheres, in other embodiments from approximately 0.5 to approximately 20 atmospheres, and in other embodiments from approximately 1 atmosphere to approximately 10 atmospheres. . In one or more embodiments, the pressures at which polymerization can be carried out include those that ensure that most of the monomer is in the liquid phase. In these or other embodiments, the polymerization mixture may be maintained under anaerobic conditions.

The polydienes produced by the polymerization process of the present invention can have controlled characteristics such that some of the polymer chains in those polymers have reactive chain ends. After achieving a desired monomer conversion, a functionalizing agent may optionally be introduced into the polymerization mixture to react with any reactive polymer chains to provide a functionalized polymer. In one or more embodiments, the functionalizing agent is introduced prior to contacting the polymerization mixture with a quenching agent. In other modalities, the agent of

34/46

<img file="BRPI0806041B1_D0037.tif" />

Functionalization can be introduced after the polymerization mixture has been partially quenched with a quenching agent.

In one or more embodiments, functionalizing agents include compounds or reagents that can react with a reactive polymer produced by the present invention and thereby provide the polymer with a functional group that is distinct from a propagating chain that has not been reacted with the functionalizing agent. . 0 functional group 10 may be reactive or interactive with other polymer chains (propagating and/or non-propagating) or with other constituents such as reinforcing fillers (eg carbon black) that can be combined with the polymer. In one or more embodiments, the reaction between the functionalizing agent and the reactive polymer proceeds via an addition or substitution reaction.

Useful functionalizing agents can include compounds that simply provide a functional group at the end of a polymer chain without joining two or more polymer chains, as well as compounds that can couple or join two or more polymer chains together via a functional bond to form a single macromolecule. The last mentioned type of functionalizing agents can also be mentioned as coupling agents.

In one or more embodiments, functionalizing agents include compounds that will add or impart a heteroatom to the polymer chain. In particular embodiments, functionalizing agents include those compounds which will impart a functional group to the polymer chain to form a functionalized polymer which reduces the hysteresis loss at 50°C of a carbon black filled vulcanizate prepared from the functionalized polymer. , as compared to vulcanized

35/46 filled with carbon black prepared from non-functionalized polymer. In one or more modalities, this reduction in hysteresis loss is at least 5%, in other modalities at least 10%, and in other modalities at least 15%.

In one or more embodiments, suitable functionalizing agents include those compounds that contain groups that can react with controlled polymers (e.g., those produced in accordance with this invention). Exemplary functionalizing agents include ketone, quinones, aldehydes, amides, esters, isocyanates, isothiocyanates, epoxides, imines, aminoketones, aminothioketones and acid anhydrides. Examples of such compounds are disclosed in US patent numbers 4,906,706, 4,990,573, 5,064,910, 5,567,784, 5,844,050, 6838,526,

6,977,281 and 6,992,147; US patent publication numbers 2006/0004131 Al, 2006/0025539 Al, 2006/0030677 Al, and 2004/0147694 Al; Japanese patent application numbers 05051406A, 05-059103A, 10-306113A and 11-035633A; which are incorporated herein by reference. Other examples of functionalizing agents include azine compounds as disclosed in US Serial Number 11/640,711, hydrobenzamide compounds as disclosed in US Serial Number 11/710,713, nitro compounds as disclosed in US Serial Number 11/710,845, and protected oxime compounds, as disclosed in US serial number 60/875,484, all of which are incorporated herein by reference.

In specific embodiments, the functionalizing agents employed may be coupling agents that include, but are not limited to, metal A halides such as tin tetrachloride, metalloid halides such as silicon tetrachloride, carboxylate-metal ester complexes such as dioctyl tin bis(octyl maleate),

<img file="BRPI0806041B1_D0038.tif" />

<img file="BRPI0806041B1_D0039.tif" />

"The

36/4 6 ί⁹' ^Λ alkoxysilanes such as tetraethyl orthosilicate, and alkoxy stannanes such as tetraethoxy tin. Coupling agents can be used individually or in combination with other functionalizing agents. The combination of functionalizing agents can be used in any molar ratio.

The amount of functionalizing agent introduced into the polymerization mixture can depend on a number of factors including the type and amount of catalyst used to initiate polymerization, the type of functionalizing agent, the desired level of functionality, and many other factors. In one or more embodiments, the amount of functionalizing agent may range from approximately 1 to approximately 200 mol, in other embodiments from approximately 5 to approximately 150 mol, and in other embodiments from approximately 100 to approximately 100 mol per mol. of the lanthanide compound.

As reactive polymer chains can self-terminate slowly at elevated temperatures, in one embodiment the functionalizing agent can be added to the polymerization mixture after maximum polymerization temperature is observed. In other embodiments, the functionalizing agent can be added approximately 25 to 35 minutes after reaching the maximum polymerization temperature.

In one or more embodiments, the functionalizing agent may be introduced into the polymerization mixture after a desired monomer conversion is achieved but before a quenching agent 30 containing a protic hydrogen atom is added. In one or more embodiments, the functionalizing agent is added to the polymerization mixture after a monomer conversion of at least 5%, in other embodiments at least

37/46

<img file="BRPI0806041B1_D0040.tif" />

<img file="BRPI0806041B1_D0041.tif" />

10%, in other modalities at least 20%, in other modalities at least 50%, and in other modalities at least 80%. In these or other embodiments, the functionalizing agent is added to the polymerization mixture 5 prior to 90% monomer conversion, in other embodiments prior to 70% monomer conversion, in other embodiments prior to 50% monomer conversion , in other embodiments before 20% monomer conversion, and in other embodiments before 15%. In one or more • 10 embodiments, the functionalizing agent is added after complete, or substantially *-complete, monomer conversion. In specific embodiments, a functionalizing agent may be introduced into the polymerization mixture immediately before, along with, or after the introduction of a Lewis base, as disclosed in copending US Serial No. 11/890,590, filed Aug. 2007, which is incorporated herein by reference.

In one or more embodiments, the functionalizing agent may be introduced into the polymerization mixture at a location (e.g., a container) where the polymerization (or at least a portion thereof) has been carried out. In other embodiments, the functionalizing agent may be introduced into the mixture of

5 polymerization at a location that is distinct from where the polymerization (or at least a portion thereof) took place. For example, the functionalizing agent can be introduced into the polymerization mixture in downstream vessels including downstream reactors or tanks, in-line reactors or mixers, extruders or devolatilizers.

After a functionalizing agent has been introduced into the polymerization mixture and a desired reaction time has been given, a

38/46

<img file="BRPI0806041B1_D0042.tif" />

<img file="BRPI0806041B1_D0043.tif" />

Rough cooling may be added to the polymerization mixture to inactivate any residual reactive polymer chains and the catalyst or catalyst components. The quenching agent can be a protic compound, which includes, but is not limited to, an alcohol, a carboxylic acid, an inorganic acid, water, or a mixture thereof. In specific embodiments, the quenching agent includes a polyhydroxy compound as disclosed in copending US Serial No. 11/890,591, filed August 7, 2007, which is incorporated herein by reference. An antioxidant such as 2,6-di-t-butyl-4-methyl phenol can be added along with, before or * after addition of the cooling agent. The amount of the α-antioxidant employed can be in the range of from approximately 0.2% to approximately 1% by weight of the polymer product. The quenching agent and antioxidant can be added as neat materials or, if necessary, dissolved in a hydrocarbon solvent or conjugated diene monomer before being added to the polymerization mixture.

After the polymerization mixture has been quenched, the various constituents of the polymerization mixture can be recovered. In one or more embodiments, the unreacted monomer may be recovered from the polymerization mixture. For example, the monomer can be distilled from the polymerization mixture using methods known in the art. In one or more embodiments, a devolatilizer may be employed to remove the monomer from the polymerization mixture. After the monomer has been removed from the polymerization mixture, the monomer can be purified, stored and/or recycled back into the polymerization process.

The polymer product can be recovered from the

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polymerization mixture using methods known in the art. In one or more embodiments, desolventization and drying techniques may be used. For example, the polymer can be. recovered by passing the polymerization mixture through a heated screw apparatus, such as a desolventizing extruder, in which volatile substances are removed by evaporation at appropriate temperatures (e.g. approximately 100°C to approximately 170°C) and under pressure atmospheric or sub-atmospheric. This treatment serves to remove unreacted monomer as well as any low boiling solvents. Alternatively, the polymer can also be recovered by subjecting the polymerization mixture to steam desolventization, followed by drying the resulting polymer fragments in a hot air tunnel. The polymer can also be recovered by direct drying the polymerization mixture in a drum dryer.

Where cis-1,4 polydienes (e.g., cis-1,4polybutadiene) are produced by one or more process embodiments of the present invention, the cis-1,4 polydienes may advantageously have a cis-1,4-binding content in in excess of 96%, in other modalities in excess of 97%, in other modalities in excess of 98%, and in other modalities in excess of 99%. Advantageously, such polymers exhibit excellent viscoelastic properties and are particularly useful in the manufacture of various tire components including, but not limited to, tire treads, sidewalls, subtreads and bead infills. The cis-1,4 polydienes can be used as all or part of the elastomeric component of a tire material. When cis-1,4 polydienes are used in combination with other rubbers to form the elastomeric component of a tire material, these

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other rubbers may be natural rubber, synthetic rubbers, and mixtures thereof. Examples of synthetic rubber include polyisoprene, poly(styrene,^—butadiene), low cis-bonded polybutadiene5 1,4/ poly(styrene-co-butadiene-co-isoprene), and mixtures thereof. Cis-1,4 polydienes can also be used in the manufacture of hoses, belts, shoe soles, window seals, other seals, vibration dampening rubber and other industrial products.

To demonstrate the practice of the present invention, the following examples were prepared and tested. The examples should not, however, be seen as limiting the scope of the invention. The claims will serve to define the invention.

EXAMPLES

In the following examples, Mooney viscosities (MLi₊₄) of the polymer samples were determined at 100°C using a Monsanto Mooney viscometer with a large rotor, heating time of one minute, and run time of four minutes. · Numerical average molecular weights (M_no) and mass average (M_w) and molecular weight distributions (M_w/M_no) of the polymer samples were determined by gel permeation chromatography (GPC) calibrated with polystyrene standards and Mark25 Houwink constants for the polymers in question. The cis-1,4-binding, trans-1,4-binding and 1,2-binding contents of the polymer samples were determined by infrared spectroscopy.

Example 1

In example 1, which is a control experiment, the solution polymerization of 1,3-butadiene to form cis1,4-polybutadiene is catalyzed by a neodymium-based catalytic system that is free of an ether compound.

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An oven-dried 800 mL glass bottle was capped with a self-sealing rubber liner and a perforated metal cap. After the bottle was fully purged with a stream of dry nitrogen, the bottle was charged with 106 g of hexanes and 227 g of a 1,3-butadiene/hexanes mixture containing 22.1% by weight of 1,3-butadiene. The following catalyst ingredients were then loaded into the bottle in the following order: (1) 3.0 mL of 0.68 M triisobutyl aluminum (TIBA) in hexane, (2) 0.90 mL of

0.159 M neodymium(III) versatate (hereinafter NdV) in hexane, and (3) 0.80 mL of 0.159 M ethyl aluminum dichloride (EADC) in hexane. The bottle was dropped for 50 minutes in a water bath maintained at 80°C. The polymerization was terminated by the addition of 3 ml of isopropanol containing

0.30 g of 2,6-di-tert-butyl-4-methyl phenol. The resulting polymer cement was coagulated with 3 liters of isopropanol containing 0.5 g of 2,6-di-tert-butyl-4-methyl phenol, and then drum dried. The polymer yield was 48.6 g (97.2%). The properties of the resulting cis-1,420 polybutadiene are summarized in Table 1.

Table 1

<td>Example</td><td> 1</td><td> 2</td><td> 3</td><td> 4</td><td> 5</td>

<td>n-BuaO/Nd molar ratio</td><td> 0:1</td><td> 1,0:1</td><td> . 3,0:1</td><td> 5,0:1</td><td> 7,0:1</td>

<td>polymer yield</td><td> 97,2%</td><td> 96,4%</td><td> 94,4%</td><td> 89,0%</td><td> 79,2%</td>

<td>ML</td><td> 34,8</td><td> 31,7</td><td> 29,9</td><td> 30,7</td><td> 28,1</td>

<td>T80</td><td> 4,3</td><td> 4,0</td><td> 4,3</td><td> 4,0</td><td> 4,3</td>

<td>M_no</td><td> 101.200</td><td> 102.600</td><td> 105.400</td><td> 105.700</td><td> 100.900</td>

<td>M_w</td><td> 322.100</td><td> 291.200</td><td> 286.800</td><td> 307.400</td><td> 320.500</td>

<td>M„/M_no</td><td> 3,2</td><td> 2,8</td><td> 2,7</td><td>CM</td><td> 3,2</td>

<td>% cis</td><td> 97,1</td><td> 97,2</td><td> 97,5</td><td> 97,8</td><td> 98,1</td>

<td>% trans</td><td> 2,1</td><td> 2,0</td><td> 1,7</td><td> 1,3</td><td> 1,1</td>

<td>% vinyl</td><td> 0,8</td><td> | 0,8</td><td> 0,8</td><td> 0,9</td><td> 0,8</td>

Examples 2-5

In examples 2-5, which were carried out in parallel with example 1 (control), the polymerization of

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solution of 1,3-butadiene to form cis-1,4-polybutadiene is catalyzed by a neodymium-based catalytic system that includes di-n-butyl ether (N-Bu₂O) as a catalyst ingredient. The same procedure as used in example 1 was used except that n-Bu₂O was added as an additional catalyst ingredient. The amounts of n-Bu₂The pure used in Examples 2-5 were 0.0145 ml, 0.0435 ml, 0.0725 ml and 0.101 ml, respectively, to vary the molar ratio of n-Bu₂O/Nd The catalyst ingredients were added to the 1,3-butadiene monomer solution in bottles in the following order: (1) n-Bu₂0, (2) TIBA, (3) NdV, and (4) EADC. The properties of the resulting cis-1,4polybutadiene are summarized in Table 1.

A comparison of the results obtained in examples 2-5 with those obtained in example 1 (control) indicates that the addition of n-Bu₂The catalyst component in Examples 2-5 increases the cis-1,4 bond content of the resulting cis1,4-polybutadiene.

Example 6

In example 6, the bulk polymerization of 1,3butadiene to form cis-1,4-polybutadiene is catalyzed by a neodymium-based catalytic system that includes nBu₂O. The polymerization reactor consisted of a one gallon stainless cylinder equipped with a mechanical stirrer (shaft and paddles) capable of mixing high viscosity polymer cement. The top of the reactor was connected to a reflux condenser system to transport, condense and recycle the 1,3-butadiene vapor developed within the reactor for the duration of the polymerization. The reactor was also equipped with a cooling jacket containing cold running water. The heat of polymerization was dissipated partly by internal cooling through the use of a reflux condenser system, and partly by

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external cooling via heat transfer to the cooling jacket.

The reactor was fully purged with a stream of dry nitrogen, which was then replaced with 1,4-butadiene steam by loading 100 g of dry 1,3-butadiene monomer into the reactor, heating the reactor to 65°C, and then bleeding the reactor. 1,3-butadiene vapor from the top of the reflux condenser system until no liquid 1,3-butadiene vapor remained in the reactor. Cooling water was applied to the reflux condenser and reactor jacket, and 1302 g of 1,3-butadiene monomer was loaded into the reactor, followed by the addition of 19.50 mL of 0.20 M n-Bu₂0 in hexane. After the monomer temperature was thermostated to 32°C, polymerization was initiated by loading into the reactor a preformed catalyst which had been prepared by mixing 5.20 mL of 1.5 M methyl aluminoxane (MAO) in toluene. , 6.5 g of 20.6% by weight 1,3-butadiene in hexane, 1.44 mL of 0.054 M NdV in hexane, 3.12 mL of 1.0 M diisobutyl aluminum hydride 20 (DIBAH) in hexane , and 1.56 mL of 0.2 M diethyl aluminum chloride (DEAC) in hexane. After 13 minutes from the start, the polymerization was terminated by adding 4.6 ml of isopropanol dissolved in 1360 g of hexane. The polymerization mixture was coagulated with 3 gallons of isopropanol 25 containing 5 g of 2,6-di-tert-butyl-4-methyl phenol and then drum dried. The polymer yield was 130.2 g. The resulting polymer had the following properties: MLi₊₄ = 23.0, M_no - 96,000, M_w = 363,000, M_w/M_no = 3.8, cis1,4 binding = 99.1%, trans-1,4-binding 0.6% and 1,2-binding = 0.3%.

3Q Example 7 (example compared to example 6)

In example 7, a mass polymerization experiment similar to that described in example 6 was performed except that no n—Bu₂The was used. The polymerization was

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too fast, and the temperature quickly rose. In less than two minutes, the reactor was encrusted with insoluble gelled polymer. At this point, to avoid a runaway reaction, polymerization 5 was terminated by adding 4.6 mL of isopropanol dissolved in 1360 g of hexane. After the polymerization mixture was discharged from the reactor, visual inspection of the reactor interior revealed that severe reactor fouling had occurred. Specifically, the reactor wall 10 as well as the stirrer shaft and blades were coated with insoluble gelled polymer clumps. Due to fouling, the reactor had to be opened for cleaning.

A comparison of the results obtained in example 6 with those obtained in example 7 (comparative example), 15 indicates that the polymerization rate in example 6 is moderated by the addition of n-Bu₂O as a catalyst component, thereby facilitating temperature control and reducing the risk of an out-of-control reaction in bulk polymerization.

0 Example 8

In example 8, a mass polymerization experiment similar to that described in example 6 was performed except that iodoform (CHI₃) was used instead of DEAC. The reactor was charged with 1302 g of 1,325-butadiene monomer and 14.82 mL of 0.20 M n-Bu₂or in hexane. After the monomer temperature was thermostated to 32°C, polymerization was initiated by loading into the reactor a preformed catalyst that had been prepared by mixing 5.20 mL of 1.5 M MAO in toluene, 6.5 g of 20 .6% by weight of 1,3-butadiene in hexane, 1.44 mL of 0.054 M NdV in hexane, 2.34 mL of 1.0 M DIBAH in hexane, and 6.24 mL of 0.0.17 M of iodoform (CHI3) in hexane. After 7 minutes from its start, the polymerization was terminated by the addition of

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4.6 ml of isopropanol dissolved in 1360 g of hexane. The polymerization mixture was coagulated with 3 gallons of isopropanol containing 5 g of 2,6-di-tert-butyl-4-methyl phenol and then drum dried. The polymer yield was 194.5 g (14.9% conversion). The resulting polymer had the following properties: MLi₊₄ = 39.5, M_no = 169,000, M_w 244,000, M_w/M_no = 1.4, cis-1,4 binding = 99.0%, trans-1,4 binding = 0.7% and 1,2-binding content - 0.3%.

Example 9 (example compared to example 8)

In example 9, a bulk polymerization experiment similar to that described in example 8 was performed, except that no n-Bu2O was used. After 5.2 minutes from its start, the polymerization was terminated by the addition of 4.6 ml of isopropanol dissolved in 1360 g of hexane. The polymerization mixture was coagulated with 3 gallons of isopropanol containing 5 g of 2,6-di-tert-butyl-4methyl phenol and then drum dried. The polymer yield was 175.6 g (13.5% conversion). 0 resulting polymer had the following properties: : MLi₊₄ = 38.2, M_no = 171,000, M_w = 218,000.M_w/M_no = 1.3, cis-1,4 binding = 98.3%, trans-1,4-binding = 1.4% and 1,2-binding = 0.3%.

A comparison of the results obtained in example 8 with those obtained in example 9 (comparative example) indicates that the addition of n-BujO as a catalyst component in example 8 increases the cis-1,4 binding content of the cis-1,4 -resulting polybutadiene. In addition, the polymerization rate can be described in terms of % monomer conversion divided by polymerization time (i.e., % conversion/minute), with a higher value of % conversion/minute indicating a polymerization rate. higher. The % conversion/minute values ​​are 2.1 and

2.6%/minute, respectively in examples 8 and 9, indicating that the presence of n-Bu2O as a catalyst modifier in the

46/46 example 8 moderates the rate of polymerization, thereby facilitating temperature control.

Various modifications and changes which do not depart from the scope and spirit of the present invention will become apparent to those skilled in the art. This invention should not be properly limited to the illustrative embodiments set forth herein.