Process for producing polydienes

(54) Title: POLIDIENE PRODUCTION PROCESS (30) Unionist Priority: 12/31/2007 us 11 / 967,549 (73) Owner (s): Bridgestone Corporation (72) Inventor (s): Jason T. Poulton, Kevin M. Mccauley, Steven Luo (57) Abstract: process for the production of POLIDIENES. A process for preparing a polydiene, the process comprising the step of polymerizing conjugated diene monomer in the presence of a dihydrocarbyl ether, where the polymerization step employs a lanthanide-based catalytic system.

FIELD OF

PROCESS FOR THE PRODUCTION OF POLIDIENES INVENTION

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

BACKGROUND OF THE INVENTION

Polydienes can be produced by polymerization of solution, where conjugated diene monomer is polymerized in a diluent or inert solvent. The solvent serves to solubilize the reagents and products, act as a diluent for the reagents and product, assist in the transfer of the polymerization heat, and help to moderate the polymerization rate. The solvent also allows for easier stirring and transfer of the polymerization mixture (also called cement), since the viscosity of the cement is decreased in the presence of the solvent. However, the presence of solvent presents several difficulties. The solvent must be separated from the polymer and then recycled for reuse or otherwise disposed of as waste. 0 The cost of recovering and recycling the solvent greatly increases the cost of the polymer in production, and there is always a 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 raise environmental concerns. In addition, 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

2/46 polymerized 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. Mass polymerization offers several economic advantages including lower capital cost for new plant capacity, lower energy cost for operation, and fewer people for operation. The solvent-free feature also provides environmental advantages, with reduced emissions and wastewater pollution.

Despite its many advantages, mass polymerization requires very careful temperature control, and there is also a need for elaborate and strong stirring equipment since the viscosity of the polymerization mixture can become very high. In the absence of added diluent, the high cement viscosity and exothermic effects can make temperature control very difficult. Consequently, local hot spots can occur, resulting in degradation, freezing and / or

<td>in</td><td>polymer.</td><td colspan="2">In the extreme case,</td>

<td>gives</td><td>rate of</td><td>polymerization</td><td>can</td>

<td>in</td><td>control</td><td>disastrous.</td><td>For</td>

lead to outside reactions to facilitate temperature control during mass polymerization, it is desirable for a catalyst to provide a reaction rate that is fast enough for economic reasons but is slow enough to allow removal of heat from exothermic polymerization to ensure the process safety.

Lanthanide-based catalyst systems that comprise a lanthanide compound, an alkylating agent, and a halogen source are known as

3/46 useful for the production of conjugated diene polymer having high levels of cis-1,4 binding. However, when applied to the mass polymerization of conjugated dienes, lanthanide-based catalyst systems, especially those that comprise an aluminoxane compound as a catalyst component, often provide excessively fast polymerization rates, which makes it very difficult to control temperature and compromises process security. Therefore, it is desirable to develop a method of moderating the mass polymerization of conjugated dienes catalyzed by lanthanide based catalysts.

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

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, where 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 of 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 polydiene prepared by a process comprising the step of polymerizing diene monomer conjugated to a lanthanide-based catalytic system including the combination of or reaction 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

According to 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. It has been found that the presence of a dihydrocarbyl ether offers 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 resulting polydiene's cis-1,4 bond content compared to polydienes produced in the absence of a dihydrocarbyl ether. The presence of a dihydrocarbyl ether is particularly advantageous in bulk polymerization systems because it has been found that the presence of a dihydrocarbyl ether modulates the rate of polymerization and thereby facilitates temperature control and reduces the risk of out-of-control reactions in mass polymerization.

The practice of one or more modalities of the present invention is not limited by the selection of any

5/46 catalyst based on specific lanthanide. 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 does not need to include a separate halogen-containing compound; for example, the catalyst includes an alkylating agent compound.

can simply halogenated and a modalities, lanthanide aluminoxane

Certain alkylating agents may include at least one other organoaluminium compound. In still other embodiments, a compound containing an uncoordinated anion, or an uncoordinated anion precursor, that is, a compound that can be subjected to a chemical reaction to form an uncoordinated anion, can be used in place of a compound containing halogen. In one embodiment, where the alkylating agent includes an organoaluminum hydride compound, the halogen-containing compound 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 can be employed in addition to the ingredients or components set out above. For example, in one embodiment, a nickel-containing compound can 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 according to the present invention by introducing (a) conjugated diene monomer, (b) a lanthanide compound, (c) an alkylating agent, (d) a compound

6/46 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 or reaction product of a lanthanide compound, an alkylating agent, a halogen-containing compound and a dihydrocarbyl ether .

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

Various lanthanide compounds or mixtures thereof can be employed. In one or more embodiments, these compounds can 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 lanthanum atom, neodymium, cerium, praseodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium and didymium. Didymium may include a commercial blend of rare earth elements obtained from monazitic sand.

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

7/46

Lanthanide compounds include, but are not limited to, lanthanide carboxylates, lanthanide organophosphates, lanthanide organophosphates, lanthanide organophosphinates, lanthanide carbamates, lanthanide dithiocarbamates, lanthanide xanthanates, lanthanide alkanides, lanthanide oxides, lanthanides , lanthanide halides, lanthanide pseudohalides, lanthanide oxalides 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 format, neodymium acetate, neodymium acrylate, neodymium methacrylate, neodymium valerate, neodymium gluconate,. neodymium citrate, neodymium fumarate, neodymium lactate, neodymium maleate, neodymium oxalate, neodymium 2-ethyl hexanoate, neodymium neodecaonate (known as neodymium versatate), neodymium naphthenate, neodymium stearate, neodymium benzoate and neodymium picolinate.

Neodymium and neodymium organophosphates, dipentyl phosphine and neodymium, neodymium phosphates diepty, bis (l-methyl) bis (2-ethyl hexyl) phosphate neodymium phosphate, neodymium diodetyl phosphate didodecyl phosphate, diole neodymium phosphate, bis (p-nonylphenyl)

<td>LO</td><td>include</td><td>dibutil</td>

<td>is from</td><td>neodymium,</td><td>diexil</td>

<td>in</td><td>neodymium,</td><td>dioctyl</td>

<td colspan="3">heptyl) phosphate</td>

<td>in</td><td>neodymium,</td><td>didecil</td>

<td>phosphate</td><td>neodymium</td><td>butyl</td><td>(2-ethyl</td><td>hexyl)</td><td>phosphate</td><td>in</td>

<td>neodymium,</td><td>(1-methyl</td><td>heptil)</td><td>(2-ethyl</td><td>hexyl)</td><td>phosphate</td><td>in</td>

<td>neodymium and</td><td>(2-ethyl</td><td>hexyl)</td><td>(p-nonil</td><td>phenyl)</td><td>phosphate</td><td>in</td>

8/46 neodymium.

Organophosphonates of. neodymium include neodymium butyl phosphonate, neodymium pentyl phosphonate, neodymium hexyl phosphonate, neodymium hepty phosphonate, neodymium octyl phosphonate, neodymium (1-methyl heptyl) neodymium phosphonate, (2-ethyl hexyl) phosphonate neodymium phosphonate neodymium, neodymium dodecyl phosphonate, neodymium octadecyl phosphonate, neodymium oleyl phosphonate, neodymium phenyl phosphonate, neodymium phosphonate (p-nonyl phenyl), neodymium butyl phosphonate, neodymium pentyl pentylphosphonate, neodymium hexyl hexylphosphonate, neodymium heptyl heptyphosphonate, octyl neodymium octylphosphonate, (1-methyl heptyl) (1-methyl heptyl) neodymium phosphonate, (2-ethylhexylate) (2-ethylhexyl) (2 neodymium ,. decyl decyl neodymium phosphonate, neodymium dodecyl dodecyl phosphonate, neodymium octadecyl octadecyl phosphonate, neodymium oleyl oleylphosphonate, neodymium phenylphenyl (hexyl-phenyl) (p-nonylphenyl) (p-nonylphenyl) (p-nonyl) neodymium, (2-ethylhexyl) (2-ethylhexyl) (2-ethylhexyl) (1-methylhexyl) (1-methylhexyl) (2-ethylhexyl) (2-ethylhexyl) (p-nonylphenyl) neodymium, neodymium, neodymium, neodymium, neodymium.

and (p-nonylphenyl) (2-ethyl hexyl)

Neodymium phosphonate phosphonate organophosphinates include neodymium butylphosfinate ,. neodymium pentylphosphinate, neodymium hexylphosfinate, neodymium heptylphosfinate, neodymium octylphosphinate, (1-methyl heptyl) neodymium phosphinate, (2-ethyl hexyl) neodymium phosphate, neodymium diodylate, neodymium phosphate, dodion neodymium, neodymium phenyl phosphinate, (p-nonylphenyl)

9/46 neodymium phosphinate, neodymium dibutyl phosphinate, neodymium dipentyl phosphinate, neodymium diexyl phosphinate, neodymium diepty phosphinate, neodymium phosphate, bis (l-methyl hepty) neodymium phosphinate, bis (2-ethyl hex) neodymium phosphinate, didecyl neodymium phosphinate, didodecyl · neodymium phosphinate, neodymium difinetecyl phosphinate, neodymium dioleyl phosphinate, neodymium diphenyl phosphinate, neodymium phosphinate bis, (p-nonylphenyl) phosphinate, neodymium butyl (2-ethyl hexyl) phosphinate, neodymium (2-ethyl hexyl) (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 dithiocarbamate, neodymium dithiocarbamate, neodymium diisopropyl dithiocarbamate, neodymium dibutyl dithiocarbamate and neodymium dibenzyldiocarbamate.

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-3,5 heptanedionate.

Neodymium alkoxides or aryloxides include neodymium methoxide, neodymium ethoxide, neodymium isopropoxide, neodymium 2-ethylexoxide, 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 oxyhalides include neodymium oxyfluoride, neodymium oxychloride, and neodymium oxybromide. Where neodymium halides, neodymium oxyhalides 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 can refer to any lanthanide compound containing at least one carbon-lanthanide bond. These compounds are predominantly, though not exclusively, those containing cyclopentadienyl (Cp), substituted cyclopentadienyl, allyl, and substituted allyl ligands. Suitable organolanthanide compounds include Cp₃Ln, CpsLnR, CpzLnCÍ, CpLnCl₂, CpLn (cyclooctatetraene), (CsMesULnR, LnR₃, Ln (alila) ₃ and Ln (alila) ₂C1, where Ln represents a lanthanide atom, and R represents a hydrocarbyl group.

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

11/46 unstable, the alkylating agent can also serve as the halogen-containing compound.

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

In one or more modalities, organoaluminium compounds include those represented by the formula AlR_nX3-nr where each R, which can 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 can be the same or different, is a hydrogen atom, a halogen atom, a carboxylate group, an alkoxide group, or an aryloxide group and where n is an integer from 1 to 3. In one or more modalities, each R can be a hydrocarbyl group such as, but not limited to, alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, aralkyl, alkyl, alyl and alquinyl groups. These hydrocarbyl groups may contain hetero atoms 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, hydrocarbylaluminium dihydride, dihydrocarbylaluminium bis (carboxylate), hydrocarbylaluminum alkoxide, dihydrocarbylaluminium dihydrocarbylaluminium, hydrocarbylaluminium dialkoxide, halocarbonaluminium, dihydrocarbylaluminium, halocarbonaluminium, hydrocarbylaluminium, hydrocarbonaluminium. dihydrocarbilaluminium aryloxide and hydrocarbilaluminium diaryloxide.

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Trihydrocarbilalumin compounds include trimethylaluminum, triethyl aluminum, triisobutyl aluminum, tri-n-propylaluminum, triisopropyl aluminum, tri-n-butyl aluminum, tri-t-butyl aluminum, tri-n-pentyl aluminum, trineopentyl aluminum, tri-n-hexyl aluminum aluminum, tri-n-octyl aluminum, tris (2-ethyl aluminum, tris (l-methyl aluminum, aluminum, hexyl) aluminum, tricyclohexyl cyclopentyl) aluminum, triphenyl tri-p-tolyl aluminum, tris (2,6-dimethyl phenyl ) aluminum tribenyl, diethyl phenyl aluminum, diethyl-p-tolyl aluminum, diethyl benzyl aluminum, ethyl diphenyl aluminum, ethildi-p-tolyl aluminum, and ethyl dibenzyl aluminum.

Dihydrocarbyl aluminum hydride compounds include diethyl aluminum hydride, di-n-propyl aluminum hydride, diisopropyl aluminum hydride, aluminum di-n-butyl hydride, aluminum diisobutyl hydride, aluminum di-n-octyl hydride diphenyl 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- hydride aluminum butyl, p-tolyl · isobutyl aluminum hydride, p-tolyl-n-octyl aluminum hydride, benzyl ethyl aluminum hydride, benzyl-n-propyl aluminum hydride, benzylisopropyl aluminum, aluminum hydride, aluminum isobutyl benzyl hydride and benzyl-n-octyl aluminum hydride.

Hydrocarbon aluminum dihydrides include ethyl aluminum dihydride, n-propyl aluminum dihydride, isopropyl aluminum dihydride, benzyl n-butyl n-butyl hydride

13/46 aluminum, aluminum isobutyl dihydride and aluminum noctil 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 chloride aluminum, di-p-tolyl aluminum chloride, aluminum dibenzyl 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- chloride 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 chloride aluminum, benzyl chloride isobutyl aluminum and benzyl chloride-noctyl aluminum.

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

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

14/46 aluminum, dimethyl aluminum methoxide, aluminum diethyl methoxide, aluminum diisobutyl methoxide, aluminum dimethyl ethoxide, aluminum diethyl ethoxide, aluminum diisobutyl ethoxide, aluminum dimethyl phenoxide, aluminum diethyl phenoxide, aluminum diisobutyl phenoxide, methyl aluminum dimethoxide, ethyl aluminum dimethoxide, aluminum isobutyl dimethoxide, methyl aluminum diethoxide, ethyl aluminum dioxide, aluminum isobutyl dioxide, methyl aluminum diphenoxide, ethyl aluminum diphenoxide, aluminum isobutyl diphenoxide and the like and mixtures thereof.

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

<img file="BRPI0806041A2_D0001.tif" />

cyclic formula and aluminoxanes represented by the general oligmerics:

<img file="BRPI0806041A2_D0002.tif" />

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

15/46 monovalent organic which 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, alcaryl, allyl and alkynyl groups. These hydrocarbyl groups may contain hetero atoms 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 instead of the number of moles of oligomeric aluminoxane molecules. This convention is commonly used in the catalysis technique using aluminoxanes.

Aluminoxanes can be prepared by reacting trihydrocarbyl aluminum compounds with water. This reaction can be carried out according to known methods, such as (1) a method in which the aluminum trihydrocarb compound can be dissolved in an organic solvent and then contacted with water, (2) a method in which the aluminum trihydrocarb compound 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 must 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, alopinoalane 2-ethyl hexyl aluminoxane, hexyl aluminoxane cycle, 1-methyl pentyl aluminoxane,

16/46 phenyl aluminoxane, 2,6-dimethyl phenyl aluminoxane and the like and mixtures thereof. Modified methyl aluminoxane can be formed by replacing approximately 20-80% of the methyl aluminoxane methyl groups with C2 to C hydrocarbyl groups_X2, preferably with isobutyl groups, using techniques known to those skilled in the art.

Aluminoxanes can be used individually or in combination with other organoaluminium compounds. In one embodiment, methyl aluminoxane and at least one other organo aluminum compound (for example, AlR_nX₃-_n), as diisobutyl aluminum hydride, are used in combination. US serial number 60 / 877,535, which is hereby incorporated by reference, provides other examples where aluminoxanes and organoaluminium compounds are used in combination.

The term organomagnesium compound can refer to any magnesium compound that contains at least one carbon-magnesium bond. Organomagnesium compounds can be soluble in a hydrocarbon solvent. A class of organomagnesium compounds that can be used can be represented by the formula MgR2, where each R, which can 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 can be a hydrocarbyl group, and the resulting organomagnesium compounds are dihydrocarbium magnesium compounds. Examples of hydrocarbyl groups include, but are not limited to, alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl, aryl, ally, substituted aryl, aralkyl, alkaryl and alkynyl groups. These hydrocarbyl groups may contain

17/46 heteroatoms such as, but not limited to, nitrogen atom, oxygen, silicon, sulfur and phosphorus.

Examples of suitable magnesium dihydrocarbyl compounds include diethyl magnesium, di-n-propyl magnesium, diisopropyl magnesium, dibutyl magnesium, diexyl 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 aryloxide group. In one or more embodiments, R can 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 hetero atoms such as, but not limited to, nitrogen, oxygen, boron, silicon, sulfur and phosphorus atoms. In one or more embodiments, X is a carboxylate group, an alkoxide group or an aryloxide group.

Exemplary types of organomagnesium compounds that can be represented by the formula RMgX include, but are not limited to, hydrocarbium magnesium hydride, hydrocarbium magnesium halide, hydrocarbium magnesium carboxylate, hydrocarbium magnesium alkoxide, magnesium hydrocarbyl 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>magnesium,</td><td>hydride</td><td>in</td><td>phenyl</td><td>magnesium,</td><td>hydride</td><td>in</td><td>benzyl</td>

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

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

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

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

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

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

<td>magnesium,</td><td>hexanoate</td><td>in</td><td>methyl</td><td>magnesium,</td><td colspan="3">ethyl hexanoate</td>

<td>magnesium,</td><td>hexanoate</td><td>in</td><td>butt</td><td>magnesium,</td><td>hexanoatc</td><td>) in</td><td>hexyl</td>

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

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

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

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

<td>magnesium,</td><td>phenoxide</td><td>in</td><td>methyl</td><td>magnesium,</td><td colspan="3">ethyl phenoxide</td>

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

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

<td>magnesium</td><td colspan="2">and the like, and</td><td colspan="3">mixtures thereof.</td><td></td><td></td>

Various compounds containing halogen, or mixtures thereof, which contain one or more unstable halogen atoms can be employed. Examples of halogen atoms include, but are not limited to, fluorine, chlorine, bromine and iodine. A combination of two or more halogen-containing compounds having different halogen atoms can also be used. In one or more embodiments, the halogen-containing compounds can be soluble in a hydrocarbon solvent. In other embodiments, compounds containing hydrocarbon-insoluble halogen, which can be suspended in the polymerization medium to form the catalytically active species, may be useful.

Suitable types of halogen-containing compounds include, but are not limited to, elemental halogens, mixed halogens, hydrogen halides, organic halides, inorganic halides, metal halides, halides

19/46 organometallic and mixtures thereof.

Elementary 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 triphenyl methyl, benzylidene chloride, benzylidene bromide, methyl trichlorosilane, phenyl trichlorosilane, dimethyl dichlorosilane, diphenyl dichlorosilane, trimethyl chlorosilane, benzoyl chloride, benzoyl bromide, propionyl chloride, 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 tetrachloride, silicon tetrachetride , arsenic trichloride, arsenic tribromide, arsenic triiodide, selenium tetrachloride, selenium tetrabromide, tellurium tetrachloride, tellurium tetrabromide and tellurium tetraiodide.

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

20/46 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, aluminum dimethyl fluoride, aluminum diethyl fluoride, methyl aluminum dichloride, ethyl aluminum dichloride, methyl aluminum dibromide ethyl aluminum, methyl aluminum difluoride, ethyl aluminum difluoride, methyl aluminum sesquichloride, ethyl aluminum sesquichloride,

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

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

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

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

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

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

tin, trimethyl tin bromide, triethyl tin chloride, trietid bromide. tin, di-t-butyl tin dichloride, di-t-butyl tin dibromide, dibutyl tin dichloride, dibutyl tin dibromide, tributyltin chloride and tributyltin bromide.

In still other embodiments, a compound containing an uncoordinated anion, or an uncoordinated anion precursor, that is, a compound that can be subjected to a chemical reaction to form an uncoordinated anion, can be used 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 coordinates, for example, with the active center of a catalytic system due to steric impediment. Exemplary uncoordinated anions include tetra-aryl borate anions and fluorinated tetra-aryl anions. Compounds containing an uncoordinated anion also contain a counter cation such as a carbon, ammonium or phosphonium cation. Exemplary cations include triaryl carbon dioxide and Ν, Ν-dialkyl anilinium cations. Examples of compounds containing an uncoordinated anion and a counter cation include triphenyl carbonium tetrakis (pentafluorophenyl) borate, Ν, Ν-dimethyl anilinium tetrakis (pentafluorophenyl) borate, triphenyl carbonium tetrakis [3,5 bis (trifluoromethyl) phenyl] borate and Ν, Ν-dimethyl anilinium 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, BR₃, 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-substituted hydrocarbyl group or group of

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 groups, heterocyclic groups.

arila arila substituted and

22/46

Exemplary alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, nheptila, 2-ethyl hexyl, n-octyl, n-nonila and n-decila.

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

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

Exemplary substituted phenyl groups include groups of 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, and 2,4,6-trimethyl phenyl (also called mesity).

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

23/46

Exemplary heterocyclic groups include groups of 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, 2-pyridyl, 3-pyridyl, '4-pyridyl, pyrazinyl, 2-pyrimidinyl, 3-pyridazinyl, 3-isothiazolyl, 3isoxazolyl, 3-furazanil, 2-triazinyl, morpholinyl, pyridinyl, pimple , 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 include dimethyl ether, diethyl ether, di-propyl ether, diisopropyl ether, di-n-butyl ether, diisobutyl ether, di-t-butyl ether, di-n ether -pentyl, diisopentyl ether, dineopentyl ether, di-nhexyl ether, di-n-heptyl ether, · di-2-ethyl hexyl ether, di-n-octyl ether, di-n- ether nonila, di-ndecyl ether and dibenzyl ether.

Specific examples of dicycloalkyl ethers include dicyclopropyl ether, dicyclobutyl ether, dicyclopentyl ether, dicyclohexyl ether, di-2-methyl cyclohexyl 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 include n-butyl methyl ether, methyl isobutyl ether, sec-butyl methyl ether, t-butyl methyl ether, n-butyl ethyl ether, ethyl isobutyl ether, ethyl secbutyl ether , t-butyl ethyl ether, t-amyl methyl ether,

24/46 t-amyl ethyl ether, phenyl ethyl ether, phenyl npropyl ether, phenyl isopropyl ether, phenyl n-butyl ether, phenyl isobutyl ether, n-octyl phenyl ether, ethyl ptolyl ether, ether p-tolyl n-propyl ether, p-tolyl isopropyl ether, p-tolyl n-butyl ether, p-tolyl isobutyl ether, p-tolyl t-butyl ether, noctila p-tolyl ether, benzyl ether n-ethyl, benzyl ether n-propyl, benzyl isopropyl ether, benzyl n-butyl ether, benzyl isobutyl ether, t-butyl benzyl ether and n-octyl benzyl ether.

In one or more embodiments, one or both of the hydrocarbyl (R) groups in the dihydrocarbyl ether may contain one or more additional ether bonds (i.e., COC). These ether compounds can 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), diethylene glycol ether, di-n-butyl diethyl ether glycol, dimethyl triethylene glycol ether, (also called triglyme), diethyl triethylene glycol ether, dimethyl tetraethylene glycol ether (also called tetraglime), 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

25/46 conventionally referred to as a catalyst system or catalyst composition. Dihydrocarbyl ether, as used here, can be mentioned as a component of that system or as a modifier for that system. In this respect, reference to catalyst ingredients refers to the lanthanide compound, alkylating agent, compound containing halogen and dihydrocarbyl ether. The term composition of modified catalyst or modified catalytic system can 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 for polymerizing 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 catalyst ingredients. For example, since the 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 the alkylating agent to the 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 500 : 1, and in other modalities from approximately 5: 1 to approximately 200: 1.

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

26/46 as alkylating agents, the molar ratio of the aluminoxane to the lanthanide compound (aluminoxane / Ln) can be varied from 5: 1 to approximately 1,000: 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 modalities from approximately 2: 1 to approximately 150: 1, and in other modalities 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 modalities, the molar ratio of halogen / Ln can be varied from approximately 0.5: 1 to approximately 20: 1, in other modalities from approximately 1: 1 to approximately 10: 1, and in other modalities from approximately 2 : 1 to approximately 6: 1.

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

In one or more embodiments, the molar ratio of dihydrocarbyl ether to the lanthanide compound (ether / Ln) can be varied from approximately 0.5: 1 to approximately 1,000: 1, in other embodiments from approximately 1: 1 to approximately 700 : 1, and in other modalities from approximately 5: 1 to approximately 500: 1.

27/46

The lanthanide-based catalyst can be formed using various techniques. For example, the catalyst can be formed by adding the catalyst components directly to the monomer to be polymerized. In this regard, the catalyst components including dihydrocarbyl ether can be added in a stepwise or simultaneous manner. In one embodiment, when the catalyst ingredients are added in a stepwise manner, dihydrocarbyl ether can 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 mentioned as an in situ formation of the catalytic system.

In other embodiments, the catalyst can be preformed. That is, catalyst ingredients including dihydrocarbyl ether can be introduced and premixed outside the monomer to be polymerized. In specific embodiments, catalyst pre-formation can occur in the absence of any monomer or in the presence of a small amount of at least one diene monomer conjugated at an appropriate temperature, which is generally between -20 ° C and 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 vary from approximately 1 to approximately 500 moles, in other modalities from approximately 5 to approximately 250 moles, and in other modalities from approximately 10 to approximately 100 moles per mol of the lanthanide compound. The resulting preformed catalyst composition can be

28/46 aged, if desired, before being added to the monomer to be polymerized.

In other embodiments, the catalyst can 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 diene monomer conjugated at an appropriate temperature (for example, -20 ° C to approximately 80 ° C). The amount of monomer used in the preparation of this first stage mixture can be similar to that set out above to preform 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 or simultaneous manner to the monomer that must be polymerized. In one embodiment, dihi'drocarbila ether can 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 can be employed as a diluent to dissolve or suspend the catalyst or catalyst ingredients to facilitate the 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 yet other modalities, the catalyst ingredients can be used in their pure state without any solvent.

In one or more embodiments, suitable solvents include those organic compounds that will not be subjected to polymerization or -incorporation in polymer chains being propagated during monomer polymerization in the presence of catalyst. In one or more modalities,

29/46 these organic species are liquid at ambient pressure and 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, isoexanes, 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 known in the art, and cycloaliphatic can be for environmental reasons.

aliphatic hydrocarbons desirably employed

Low-boiling hydrocarbon solvents are typically separated from the polymer after polymerization is complete.

Other examples of organic solvents include high molecular weight high boiling hydrocarbons, 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 polydenes according to the present invention can be accomplished 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 diene monomer, and any solvent, if used, forms a polymerization mixture in which the polymer product is formed. The total concentration of catalyst to be used in the polymerization mixture may depend on the interaction of several factors such as purity of the ingredients, polymerization temperature, polymerization and conversion rate, desired molecular weight, and many other factors. Therefore, a total specific catalyst concentration cannot be definitively exposed 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 can 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 according to the present invention can be carried out in a polymerization system that includes a substantial amount of solvent. In one embodiment, a solution polymerization system can 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 can 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 the preparation of the catalyst is usually added to the polymerization system. The additional solvent can be the same or different from the solvent

31/46 used in the preparation of the catalyst. Exemplary solvents have been exposed above. In one or more embodiments, the solvent content of the polymerization mixture may be greater than 20% by weight, in other embodiments greater than 50% by weight, and in other embodiments greater than 80% by weight based on the total weight of the polymerization mixture.

In other embodiments, the polymerization system employed can generally be considered to be a mass polymerization system that does not include substantially solvent or a minimum amount of solvent. Those skilled in the art will recognize the benefits of mass polymerization processes (that is, processes where the monomer acts as the solvent), and therefore the polymerization system includes less solvent than will have a detrimental impact on the benefits sought by performing mass polymerization. . 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 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 that are substantially solvent free can be mentioned as substantially not including solvent. In specific embodiments, the polymerization mixture is solvent-free.

Polymerization can be carried out in any conventional polymerization vessels known in the art.

32/46 technique. In one or more modalities, solution polymerization can be carried out in a conventional agitated tank reactor. In other embodiments, mass polymerization can be carried out in a conventional agitated tank reactor, especially if the monomer conversion is less than approximately 60%. In still other modalities, especially where the conversion of monomer in a mass polymerization process is higher than approximately 60%, which typically results in a highly viscous cement, mass 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 single-spindle or double-spindle agitator are suitable for this purpose. Examples of useful mass polymerization processes are disclosed in US publication number 2005/0197474 A1, which is incorporated herein by reference.

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

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 polymerization

33/46 proceeds can be controlled to maintain the temperature of the polymerization mixture in a range of approximately -10 ° C to approximately 200 ° C, in other embodiments of approximately 0 ° C to approximately 150 ° C, and in other modes of approximately 20 ° C to approximately 100 ° C. In one or more embodiments, the heat of polymerization can be removed by external cooling by 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 at approximately 50 atmospheres, in other modalities from approximately 0.5 to approximately 20 atmospheres, and in other modalities 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 modalities, the polymerization mixture can be maintained under anaerobic conditions.

The polydenes produced by the polymerization process of the present invention may have controlled characteristics, such that some of the polymer chains in these polymers have reactive chain ends. After obtaining a desired monomer conversion, a functionalizing agent can 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 before contacting the polymerization mixture with an abrupt cooling agent. In other ways, the

34/46 functionalization can be introduced after the polymerization mixture has been partially cooled abruptly with an abrupt cooling 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 . The functional group can be reactive or interactive with other polymer chains (propagating and / or not propagating) or with other constituents such as reinforcement charges (for example, carbon black) that can be combined with the polymer. In one or more modalities, 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 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 transmit a hetero atom to the polymer chain. In particular embodiments, 'functionalizing agents include those compounds that will transmit a functional group to the polymer chain to form a functionalized polymer that reduces the loss of hysteresis by 50 ° C from a carbon black-filled vulcanisate 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 (for example, those produced according to that invention). Exemplary functionalizing agents include ketone, quinones, aldehydes, amides, esters, isocyanates, isothiocyanates, epoxides, imines, aminoketones, aminothiocetones 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, 6977,281 and 6,992,147; US patent publications 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 here by way of reference. Other examples of functionalizing agents include azine compounds, as described 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 which include, but are not limited to, metal halides such as tin tetrachloride, metalloid halides such as silicon tetrachloride, metal carboxylate-ester complexes such as dioctyl bis bis (octyl maleate),

36/46 alkoxysilanes as tetraethyl orthosilicate, and alkanoxy stananes 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 several factors including the type, and amount of catalyst used to initiate the 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 can be in a range of approximately 1 to approximately 200 moles, in other embodiments of approximately 5 to approximately 150 moles, and in other embodiments of approximately 100 to approximately 100 moles per mole of lanthanide compound.

As reactive polymer chains can end themselves slowly and at high temperatures, in one embodiment the functionalizing agent can be added to the polymerization mixture after observing the maximum polymerization temperature. In other embodiments, the functionalizing agent can be added in approximately 25 to 35 minutes after reaching the maximum polymerization temperature.

In one or more embodiments, the functionalizing agent can be introduced into the polymerization mixture after a desired monomer conversion is achieved, however, before an abrupt cooling agent 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

10%, in other modalities at least 20%, in other modalities at least 50%, and in other modalities at least 80%. In these or other modalities, the functionalizing agent is added to the polymerization mixture before a 90% monomer conversion, in other modalities before the 70% monomer conversion, in other modalities before the 50% monomer conversion, in other modalities before the conversion of 20% monomer, and in other modalities before 15%. In one or more embodiments, the functionalizing agent is added after complete conversion. In functionalization, substantially an agent can be added to the complete monomer mixture, or specific modalities, introduced polymerization immediately before, together with, or after the introduction of a Lewis base, as disclosed in copending US serial number 11 / 890,590, deposited in 7 of which is incorporated here as an August 2007 reference.

In one or more functionalization, the agent can be introduced into the polymerization mixture in a location (for example, in a container) where the polymerization (or at least a part of it) was carried out. In functionalization other .. modalities, the agent can be introduced into the polymerization mixture at a location that is distinct from where the polymerization (or at least a portion of it) occurred. For example, the functionalizing agent can be introduced into the polymerization mixture in downstream containers 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 provided, a

Blast cooling can be added to the polymerization mixture to inactivate any residual reactive polymer chains and catalyst or catalyst components. The blast cooling 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 blunt cooling agent includes a polyhydroxy compound as disclosed in copending US serial number 11 / 890,591, filed on August 7, 2007, which is hereby incorporated by reference. An antioxidant such as 2,6-di-t-butyl-4-methyl phenol can be added together with, before or - '' after the addition of the cooling agent. The amount of the -antioxidant employed can be in the range of approximately 0.2% to approximately 1% by weight of the polymer product. The blast cooling agent and antioxidant can be added as pure 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 abruptly cooled, the various constituents of the polymerization mixture can be recovered. In one or more embodiments, the unreacted monomer can 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 can be used 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 to the polymerization process.

polymer product can be recovered from the

39/46 polymerization mixture using methods known in the art. In one or more modalities, desolventization and drying techniques can be used. For example, the polymer can be. recovered by passing the polymerization mixture through a heated spindle apparatus, such as a desolventization extruder, in which volatile substances are removed by evaporation at appropriate temperatures (for example, 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 solvent. Alternatively, the polymer can also be recovered by subjecting the polymerization mixture to vapor de-solventization, followed by drying the resulting polymer fragments in a hot air tunnel. The polymer can also be recovered by directly drying the polymerization mixture in a drum dryer.

Where cis-1,4 polydienes (for example, cis-1,4 polybutadiene) are produced by one or more embodiments of the process of the present invention, cis-1,4 polydienes may advantageously have a cis-1,4 bond content 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, these polymers have excellent viscoelastic properties and are particularly useful in the manufacture of various tire components including, but not limited to, tire treads, sidewalls, tread sub-bands and bead fillings. 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

40/46 other rubbers can be natural rubber, synthetic rubbers, and mixtures thereof. Examples of synthetic rubber include polyisoprene, poly (styrene-cobutadiene), polybutadiene with a low cis1,4 content, poly (styrene-co-butadiene-co-isoprene), and mixtures thereof. Cis-1,4 polydienes can also be used in the manufacture of hoses, straps, 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, the viscosities. Mooney (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 operating time of four minutes. · The numerical average molecular weights (M_n) and mass mean (M_w) and molecular weight distributions (M „/ M_n) of the polymer samples were determined by gel permeation chromatography (GPC) calibrated with polystyrene standards and MarkHouwink constants for the polymers in question. The levels of cis-1,4, trans-1,4-binding and 1,2-binding of the polymer samples were determined by infrared spectroscopy.

Example 1

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

41/46

An oven-dried 800 mL glass bottle was capped with a self-sealing rubber coating and a perforated metal cap. After the bottle was completely purged with a dry nitrogen flow, the bottle was loaded with 106 g of hexanes and 227 g of a mixture of 1,3-butadiene / hexanes 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-1,4 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-Bu₂O / 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_n</td><td> 101.200</td><td> 102.600</td><td> 105.400</td><td> 105.700</td><td> 100.900</td>

<td>M „</td><td> 322.100</td><td> 291.200</td><td> 286.800</td><td> 307.400</td><td> 320.500</td>

<td>M „/ M_n</td><td> 3,2</td><td> 2,8</td><td> 2,7</td><td> 2,9</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>GO O</td><td>00 O</td><td>O 00</td><td> 0,9</td><td>O 00</td>

Examples 2-5

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

42/46 1,3-butadiene solution 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 quantities of n-Bu₂The pure ones 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 monomer solution

1.3- butadiene in bottles in the following order: (1) n-Bu₂O, (2) TIBA, (3) NdV, and (4) EADC. The properties of the resulting cis-1,4 polybutadiene 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 mass polymerization of 1,3-butadiene to form cis-1,4-polybutadiene is catalyzed by a neodymium-based catalyst system that includes nBu₂O. The polymerization reactor consisted of a one-gallon stainless cylinder equipped with a mechanical stirrer (shaft and blades) 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 inside the reactor for the duration of the polymerization. The reactor was also equipped with a cooling jacket containing cold running water. The polymerization heat was dissipated partially by internal cooling through the use of the reflux condenser system, and partially by

43/46 external cooling through thermal transfer to the cooling jacket.

The reactor was fully purged with a dry nitrogen flow, which was then replaced with

1,4-butadiene for loading 100 g of dry 1,3-butadiene monomer into the reactor, heating the reactor to 65 ° C, and then bleeding the 1,3-butadiene vapor from the top of the reflux condenser system until none liquid vapor of 1,3-butadiene liquid 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-Bu2O in hexane. After the temperature of the monomer was adjusted by a thermostat at 32 ° C, polymerization was initiated by loading a preformed catalyst into the reactor that 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 of 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 (DIBAH) in hexane, and 1.56 mL of 0.2 M diethyl aluminum chloride (DEAC) in hexane. After 13 minutes from its beginning, 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 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_n = 96,000, M_w = 363,000, M_w/ M_n = 3.8, cis1.4 bond = 99.1%, trans-1,4-bond. = 0.6% and 1.2-bond = 0.3%.

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. Polymerization was

44/46 excessively fast, and the temperature rose rapidly. In less than two minutes, the reactor was encrusted with insoluble gelled polymer. At this point, to avoid an out of control reaction, the polymerization 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 incrustation of the reactor had occurred. Specifically, the reactor wall as well as the agitator shaft and blades were covered with insoluble gelified polymer lumps. 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), indicates that the polymerization rate in example 6 is moderated by the addition of n-Bu₂0 as a catalyst component, thereby facilitating temperature control and reducing the risk of an out of control reaction in mass polymerization.

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 1,3-butadiene monomer and 14.82 ml of 0.20 M n-Bu₂0 in hexane. After the monomer temperature was adjusted by a thermostat at 32 ° C, polymerization was started by loading a preformed catalyst into the reactor that had been prepared by mixing 5.20 mL of 1.5 Μ 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 0.017 M iodoform (CHI₃) in hexane. After 7 minutes of its beginning, 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: ML₁₊₄ = 39.5, M_n = 169,000, M_w = 244,000, M_w/ M_n = 1.4, cis-1.4 link = 99.0%, trans-1.4 link = 0.7% and 1,2-link content = 0.3%.

Example 9 (example compared to example 8)

In example 9, a mass polymerization experiment similar to that described in example 8 was performed, except that no n-Bu₂Was used. After 5.2 minutes from its beginning, 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-4-methyl phenol and then drum dried. The polymer yield was 175.6 g (13.5% conversion). The resulting polymer had the following properties: ML₁₊₄ = 38.2, Mn = 171,000, M_w = 218,000 ,. M_w/ M_n = 1.3, cis-1,4 bond = 98.3%, trans-1,4-bond - 1.4% and 1,2-bond = 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-Bu₂0 as a catalyst component in example 8 increases the cis-1,4 bond content of the resulting cis-1,4-polybutadiene. In addition, the polymerization rate can be described in terms of the% monomer conversion divided by the polymerization time (ie% 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 alterations that do not depart from the scope and spirit of the present invention will become evident to those skilled in the art. This invention should not be duly limited to the illustrative modalities set out here.