Modified high cis polydiene polymers, related methods and rubber compositions

Abstract

Disclosed herein is a modified high cis polydiene polymer, a method for preparing the modified high cis polydiene polymer, and a tire rubber composition comprising the modified high cis polydiene polymer. The method utilizes a functionalized compound of formula I or formula II and a coupling agent to prepare a modified high cis polydiene polymer from a certain amount of conjugated diene monomers polymerized using a lanthanide-based catalyst system. The modified high cis polydiene polymer comprises at least one polymer chain having a residue from the functionalized compound and a residue from the coupling agent, and can be used in a tire rubber composition in combination with other ingredients such as fillers.

Description

Technical Field

[0001] The present application relates to modified high-cis polydiene polymers, related methods and tire rubber compositions. Background Art

[0002] High cis polydiene polymers have many uses in industry, including use in tire rubber compositions for tire components such as tire treads. Modification of such high cis polydiene polymers by certain functionalizing compounds to increase filler-polymer interactions can result in polymers having desirable Mooney viscosities, but also undesirable increases in cold flow, creating challenges in storing the modified polymers. Summary of the invention

[0003] Disclosed herein are a modified high-cis polydiene polymer, a method for preparing the modified high-cis polydiene polymer, and a tire rubber composition comprising the modified high-cis polydiene polymer.

[0004] In a first embodiment, a method for preparing a modified high cis polydiene polymer is provided. According to a first embodiment, the method comprises: (a) providing a lanthanide-based catalyst system, the lanthanide-based catalyst system comprising (i) a lanthanide compound, (ii) an alkylating agent and (iii) a halogen source, wherein (iii) may be optionally provided by (i), (ii), or both (i) and (ii); b. polymerizing a certain amount of conjugated diene monomers using the catalyst system of (a) to produce polymer chains having active ends; (c) reacting the active end polymer chains from (b) with a functionalizing compound selected from Formula I or Formula II, thereby producing an intermediate product comprising a polymer chain terminally functionalized with a residue from a first functionalizing compound; (d) coupling the intermediate product from (c) using a coupling agent selected from silicon halides, thereby producing a modified high cis polydiene polymer having a cis 1,4-bond content of at least 92%, preferably at least 94%, and a Mooney viscosity ML of at least 40, preferably 45 to 80 at 100°C. 1+4 .

[0005] In a second embodiment, a modified high cis polydiene polymer is provided. According to the second embodiment, the modified high cis polydiene polymer comprises: (a) at least one polymer chain produced by polymerization of a certain amount of conjugated diene monomers and having a residue from a functionalized compound selected from Formula I or Formula II, and (b) a residue from a coupling agent having at least one polymer chain of (a) bonded thereto, wherein the coupling agent is selected from silicon halides, and the residue from the coupling agent has at least one halide replaced by the polymer chain of (a), wherein the modified high cis polydiene has a cis 1,4-bond content of at least 92%, preferably at least 94%, and a Mooney viscosity ML of at least 40, preferably 45 to 80 at 100°C. 1+4 .

[0006] In a third embodiment, a tire rubber composition is provided. According to the third embodiment, the tire rubber composition comprises: (a) 10-100 phr, preferably 30-80 phr of a modified high cis polydiene according to the second embodiment or as produced according to the first embodiment; (b) 0 phr to 90 phr, preferably 20 phr to 70 phr of at least one polymer containing a diene monomer selected from natural rubber, polyisoprene, styrene-butadiene copolymer, styrene-butadiene-isoprene rubber, isoprene-butadiene rubber, and combinations thereof; and (c) 10 phr to 100 phr of at least one carbon black filler and 0 phr to 100 phr of at least one silica filler. According to the third embodiment, the tire rubber composition is preferably contained in a tire component, more preferably in a tire tread. DETAILED DESCRIPTION

[0007] Disclosed herein are a modified high-cis polydiene polymer, a method for preparing the modified high-cis polydiene polymer, and a tire rubber composition comprising the modified high-cis polydiene polymer.

[0008] In a first embodiment, a method for preparing a modified high cis polydiene polymer is provided. According to a first embodiment, the method comprises: (a) providing a lanthanide-based catalyst system, the lanthanide-based catalyst system comprising (i) a lanthanide compound, (ii) an alkylating agent and (iii) a halogen source, wherein (iii) may be optionally provided by (i), (ii), or both (i) and (ii); b. polymerizing a certain amount of conjugated diene monomers using the catalyst system of (a) to produce polymer chains having active ends; (c) reacting the active end polymer chains from (b) with a functionalizing compound selected from Formula I or Formula II, thereby producing an intermediate product comprising a polymer chain terminally functionalized with a residue from a first functionalizing compound; (d) coupling the intermediate product from (c) using a coupling agent selected from silicon halides, thereby producing a modified high cis polydiene polymer having a cis 1,4-bond content of at least 92%, preferably at least 94%, and a Mooney viscosity ML of at least 40, preferably 45 to 80 at 100°C. 1+4 .

[0009] In a second embodiment, a modified high cis polydiene polymer is provided. According to the second embodiment, the modified high cis polydiene polymer comprises: (a) at least one polymer chain produced by polymerization of a certain amount of conjugated diene monomers and having a residue from a functionalized compound selected from Formula I or Formula II, and (b) a residue from a coupling agent having at least one polymer chain of (a) bonded thereto, wherein the coupling agent is selected from silicon halides, and the residue from the coupling agent has at least one halide replaced by the polymer chain of (a), wherein the modified high cis polydiene has a cis 1,4-bond content of at least 92%, preferably at least 94%, and a Mooney viscosity ML of at least 40, preferably 45 to 80 at 100°C. 1+4 .

[0010] In a third embodiment, a tire rubber composition is provided. According to the third embodiment, the tire rubber composition comprises: (a) 10-100 phr, preferably 30-80 phr of a modified high cis polydiene according to the second embodiment or as produced according to the first embodiment; (b) 0 phr to 90 phr, preferably 20 phr to 70 phr of at least one polymer containing a diene monomer selected from natural rubber, polyisoprene, styrene-butadiene copolymer, styrene-butadiene-isoprene rubber, isoprene-butadiene rubber, and combinations thereof; and (c) 10 phr to 100 phr of at least one carbon black filler and 0 phr to 100 phr of at least one silica filler. According to the third embodiment, the tire rubber composition is preferably contained in a tire component, more preferably in a tire tread.

[0011] definition

[0012] The terms described herein are used only to describe the embodiments and should not be construed to limit the invention as a whole.

[0013] As used herein, the term "living end" (eg, the living end of a polymer chain) is used to refer to a polymeric species having a living end that has not been capped. The living end is capable of reacting with a functionalizing compound and, therefore, can be described as reactive.

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

[0015] As used herein, the abbreviation Mw is used for weight average molecular weight.

[0016] Unless otherwise specified herein, the term "Mooney viscosity" refers to the Mooney viscosity ML 1+4 As will be appreciated by those skilled in the art, the Mooney viscosity of a rubber composition is measured prior to vulcanization or curing.

[0017] As used herein, the term "natural rubber" refers to naturally occurring rubber, such as rubber that can be harvested from sources such as the Hevea rubber tree and non-Hevea sources (e.g., guayule shrubs and dandelions such as TKS). In other words, the term "natural rubber" should be interpreted as not including synthetic polyisoprene.

[0018] As used herein, the term "phr" means parts per hundred parts of rubber. One hundred parts of rubber may also be referred to herein as 100 parts of the elastomeric component.

[0019] As used herein, the term "polyisoprene" refers to synthetic polyisoprene. In other words, the term is used to refer to polymers made from isoprene monomers and should not be interpreted to include naturally occurring rubbers (e.g., Hevea natural rubber, guayule-derived natural rubber, or dandelion-derived natural rubber). However, the term "polyisoprene" should be interpreted to include polyisoprene made from natural sources of isoprene monomers.

[0020] As used herein, the term "tread" refers to both that portion of the tire that comes in contact with the road when normally inflated and loaded, and any subtread.

[0021] Method for preparing modified high cis polydiene polymers

[0022] Generally speaking, the method of the first embodiment described herein can be regarded as a solution polymerization method. In this type of polymerization method, the polymerization reaction occurs in a solution based on an organic solvent. Here, the solution based on an organic solvent initially contains a certain amount of conjugated diene monomers and a lanthanide-based catalyst system. Generally speaking, according to the method of the first embodiment, the solution based on an organic solvent contains 20-90 weight % (wt %) of organic solvent based on the total weight of monomers, organic solvents and polydienes in the solution. Preferably, the organic solvent comprises the main component of the solution, i.e., 50-90 weight % of organic solvent based on the total weight of monomers, organic solvents and polydienes, and more preferably 70 weight % to 90 weight % of organic solvents. The solution polymerization method disclosed herein can be contrasted with gas-type or bulk-type polymerization, wherein the polymerization is carried out in the absence of any organic solvent or in the presence of less than 20 weight % of organic solvent based on the total weight of monomers, organic solvents and polydienes.

[0023] Organic solvents suitable for the solution polymerization method according to the first embodiment described herein are those solvents that are inert to the polymerization reaction so that the solvent is not a reactant in the polymerization reaction. Suitable organic solvents include aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons. Examples of suitable aromatic hydrocarbon solvents include, but are not limited to, benzene, toluene, ethylbenzene, diethylbenzene, naphthalene, mesitylene, xylene, etc. Examples of suitable aliphatic hydrocarbon solvents include, but are not limited to, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, isopentane, hexane, isohexane, isopentane, isooctane, 2,2-dimethylbutane, petroleum ether, kerosene, petroleum spirit, etc. Non-limiting examples of suitable alicyclic hydrocarbon solvents include cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, etc. Mixtures of the above-mentioned aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents and alicyclic hydrocarbon solvents may also be used. In certain embodiments of the first embodiment, preferred organic solvents include aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, or mixtures thereof. Additional available organic solvents suitable for the method of the first embodiment are known to those skilled in the art.

[0024] The solution polymerization process according to the first embodiment disclosed herein is preferably carried out under anaerobic conditions under a blanket of inert gas such as nitrogen, argon or helium. The polymerization temperature can vary widely, ranging from -50°C to 150°C, with a preferred temperature range of 50°C to 120°C. The polymerization pressure can also vary widely, ranging from 1 atmosphere (atm) to 30 atm, preferably 1 atm to 10 atm.

[0025] The solution polymerization process according to the first embodiment disclosed herein can be carried out in a continuous, semi-continuous or batch process. In a semi-continuous process, monomer is intermittently charged to replace the monomer that has been polymerized. When the monomer and the lanthanide-based catalyst system are all present in an organic solvent-based solution, the polymerization of conjugated diene monomers to high cis-polydienes occurs according to the process described herein.

[0026] Generally speaking, the polymerization method of the first embodiment as disclosed herein can be stopped by adding any suitable terminator. Non-limiting examples of suitable terminators include protic compounds, such as alcohols, carboxylic acids, mineral acids, water, and mixtures thereof. Other suitable terminators are known to those skilled in the art. In addition, once the polymerization is stopped, the resulting high cis polydiene can be recovered from the solution using conventional methods known to those skilled in the art (e.g., steam desolventizing, condensing with alcohol, filtering, purifying, drying, etc.).

[0027] Lanthanide-based catalyst systems

[0028] As described above, the method of the first embodiment includes using (providing) a lanthanide-based catalyst system, the lanthanide-based catalyst system comprising: (i) a lanthanide compound, (ii) an alkylating agent, and (iii) a halogen source, wherein (iii) may be optionally provided by (i), (ii), or both (i) and (ii). The lanthanide-based catalyst system is used to polymerize a certain amount of conjugated diene monomers (discussed in more detail below) to produce a polymer chain having an active end. Preferably, according to the method of the first embodiment, the lanthanide-based catalyst system is preformed prior to addition to any solution of conjugated diene monomer (although in certain preferred embodiments, a small amount of 1,3-butadiene is added to the mixture of catalyst ingredients during formation of the catalyst system, e.g., in a molar ratio of about 1:5 to about 1:100 (e.g., 1:5, 1:10, 1:20, 1:30, 1:40, 1:50, 1:60, 1:70, 1:80, 1:90, or 1:100), preferably about 1:10 to about 1:25 (e.g., 1:10, 1:15, 1:20, or 1:25), wherein the ratio is based on moles of lanthanide:moles of 1,3-butadiene).

[0029] As described above, the lanthanide-based catalyst system used in the method of the first embodiment includes lanthanide compounds. The lanthanide compounds that can be used in the method of the first embodiment are those compounds that contain at least one atom of a lanthanide. As used herein, "lanthanide" refers to the elements present in the lanthanide series (i.e., element numbers 57-71) of the periodic table and didymium, which is a mixture of rare earth elements obtained from monazite sand. Specifically, the lanthanides as disclosed herein include lanthanum, neodymium, cerium, praseodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium and didymium. Preferably, the lanthanide compound contains at least one atom of neodymium, gadolinium, samarium or a combination thereof. Most preferably, the lanthanide compound contains at least one neodymium atom.

[0030] The lanthanide atom in the lanthanide compound can be in various oxidation states, including but not limited to 0, +2, +3 and +4 oxidation states. According to certain embodiments of the method of the first embodiment, a trivalent lanthanide compound is used, wherein the lanthanide atom is in the +3 oxidation state. Generally speaking, suitable lanthanide compounds for the method of the first embodiment include but are not limited to lanthanide carboxylates, lanthanide organophosphates, lanthanide organophosphonates, lanthanide organophosphinates, lanthanide carbamates, lanthanide dithiocarbamates, lanthanide xanthates, lanthanide β-diketonates, lanthanide alkoxides or phenolates, lanthanide halides, lanthanide pseudohalides, lanthanide oxyhalides and organolanthanide compounds. Preferably, the lanthanide compound is a lanthanide carboxylate or a lanthanide organophosphonate, more preferably a neodymium carboxylate, and most preferably neodymium versatate.

[0031] According to certain embodiments of the method of the first embodiment, the lanthanide compound can be soluble in a hydrocarbon solvent, such as an aromatic hydrocarbon solvent, an aliphatic hydrocarbon solvent, or an alicyclic hydrocarbon solvent disclosed herein. However, lanthanide compounds that are insoluble in hydrocarbons can also be used in the method of the first embodiment because they can be suspended in the polymerization medium to form a catalytically active species.

[0032] For ease of illustration, further discussion of lanthanide compounds useful in the process of the first embodiment will focus on neodymium compounds, but one skilled in the art will be able to select similar compounds based on other lanthanide metals disclosed herein.

[0033] Examples of suitable neodymium carboxylates for use as lanthanide compounds in the method of the first embodiment include, but are not limited to, neodymium formate, neodymium acetate, neodymium acrylate, neodymium methacrylate, neodymium valerate, neodymium gluconate, neodymium citrate, neodymium fumarate, neodymium lactate, neodymium maleate, neodymium oxalate, neodymium 2-ethylhexanoate, neodymium neodecanoate (i.e., neodymium versatate or NdV3), neodymium cyclohexaneate, neodymium stearate, neodymium oleate, neodymium benzoate, and neodymium picolinate.

[0034] Examples of suitable neodymium organophosphates for use as the lanthanide compound in the method of the first embodiment include, but are not limited to, dibutyl neodymium phosphate, diamyl neodymium phosphate, dihexyl neodymium phosphate, diheptyl neodymium phosphate, dioctyl neodymium phosphate, bis(1-methylheptyl) neodymium phosphate, bis(2-ethylhexyl) neodymium phosphate, didecyl neodymium phosphate, didodecyl neodymium phosphate, dioctadecyl neodymium phosphate, dioleyl neodymium phosphate, diphenyl neodymium phosphate, bis(p-nonylphenyl) neodymium phosphate, butyl(2-ethylhexyl) neodymium phosphate, (1-methylheptyl)(2-ethylhexyl) neodymium phosphate, and (2-ethylhexyl)(p-nonylphenyl) neodymium phosphate.

[0035] Examples of suitable neodymium organophosphonates for use as the lanthanide compound in the process of the first embodiment include, but are not limited to, neodymium butylphosphonate, neodymium pentylphosphonate, neodymium hexylphosphonate, neodymium heptylphosphonate, neodymium octylphosphonate, neodymium (1-methylheptyl)phosphonate, neodymium (2-ethylhexyl)phosphonate, neodymium decylphosphonate, neodymium dodecylphosphonate, neodymium octadecylphosphonate, neodymium oleylphosphonate, neodymium phenylphosphonate, neodymium (p-nonylphenyl)phosphonate, neodymium butylbutylphosphonate, neodymium pentylpentylphosphonate, neodymium hexylhexylphosphonate, neodymium heptylheptylphosphonate, neodymium octyloctylphosphonate, neodymium (1-methylheptyl)(1-methylheptyl)phosphonate , (2-ethylhexyl)(2-ethylhexyl)phosphonate neodymium, decyldecylphosphonate neodymium, dodecyldodecylphosphonate neodymium, octadecyloctadecylphosphonate neodymium, oleyloleylphosphonate neodymium, phenylphenylphosphonate neodymium, (p-nonylphenyl)(p-nonylphenyl)phosphonate neodymium, butyl(2-ethylhexyl)phosphonate neodymium, (2-ethylhexyl)butylphosphonate neodymium, (1-methylheptyl)(2-ethylhexyl)phosphonate neodymium, (2-ethylhexyl)(1-methylheptyl)phosphonate neodymium, (2-ethylhexyl)(p-nonylphenyl)phosphonate neodymium and (p-nonylphenyl)(2-ethylhexyl)phosphonate neodymium.

[0036] Examples of suitable neodymium organophosphites for use as the lanthanide compound in the method of the first embodiment include, but are not limited to, neodymium butylphosphite, neodymium amylphosphite, neodymium hexylphosphite, neodymium heptylphosphite, neodymium octylphosphite, neodymium (1-methylheptyl)phosphite, neodymium (2-ethylhexyl)phosphite, neodymium decylphosphite, neodymium dodecylphosphite, neodymium octadecylphosphite, neodymium oleylphosphite, neodymium phenylphosphite, neodymium (p-nonylphenyl)phosphite, neodymium dibutylphosphite, neodymium dipentylphosphite. , neodymium dihexylphosphite, neodymium diheptylphosphite, neodymium dioctylphosphite, neodymium bis(1-methylheptyl)phosphite, neodymium bis(2-ethylhexyl)phosphite, neodymium didecylphosphite, neodymium didodecylphosphite, neodymium dioctadecylphosphite, neodymium dioleylphosphite, neodymium diphenylphosphite, neodymium bis(p-nonylphenyl)phosphite, neodymium butyl(2-ethylhexyl)phosphite, (1-methylheptyl)(2-ethylhexyl)phosphite, and neodymium (2-ethylhexyl)(p-nonylphenyl)phosphite.

[0037] Examples of suitable neodymium carbamates for use as the lanthanide compound in the method of the first embodiment include, but are not limited to, neodymium dimethylcarbamate, neodymium diethylcarbamate, neodymium diisopropylcarbamate, neodymium dibutylcarbamate, and neodymium dibenzylcarbamate.

[0038] Examples of suitable neodymium dithiocarbamates for use as the lanthanide compound in the method of the first embodiment include, but are not limited to, neodymium dimethyldithiocarbamate, neodymium diethyldithiocarbamate, neodymium diisopropyldithiocarbamate, neodymium dibutyldithiocarbamate, and neodymium dibenzyldithiocarbamate.

[0039] Examples of suitable neodymium xanthates for use as the lanthanide compound in the method of the first embodiment include, but are not limited to, neodymium methyl xanthate, neodymium ethyl xanthate, neodymium isopropyl xanthate, neodymium butyl xanthate, and neodymium benzyl xanthate.

[0040] Examples of suitable neodymium beta-diketonates for use as the lanthanide compound in the method of the first embodiment include, but are not limited to, neodymium acetylacetonate, neodymium trifluoroacetylacetonate, neodymium hexafluoroacetylacetonate, neodymium benzoylacetonate, and neodymium 2,2,6,6-tetramethyl-3,5-heptanedione.

[0041] Examples of suitable neodymium alkoxides or phenoxides for use as the lanthanide compound in the method of the first embodiment include, but are not limited to, neodymium methoxide, neodymium ethoxide, neodymium isopropoxide, neodymium 2-ethylhexoxide, neodymium phenoxide, nonylbenzene neodymium oxide, and neodymium naphthalene oxide.

[0042] Examples of suitable neodymium halides for use as lanthanide compounds in the method of the first embodiment include, but are not limited to, neodymium fluoride, neodymium chloride, neodymium bromide, and neodymium iodide. Suitable neodymium pseudohalides include, but are not limited to, neodymium cyanide, neodymium cyanate, neodymium thiocyanate, neodymium azide, and neodymium ferrocyanide. Suitable neodymium oxyhalides include, but are not limited to, neodymium oxyfluoride, neodymium oxychloride, and neodymium oxybromide. Lewis bases, such as tetrahydrofuran ("THF"), may be used as an auxiliary agent to dissolve such neodymium compounds in an inert organic solvent. In the case of using lanthanide halides, lanthanide oxyhalides, or other lanthanide compounds containing halogen atoms, the lanthanide compound may also optionally provide all or part of the halogen source in the lanthanide-based catalyst system.

[0043] As used herein, the term "organolanthate compound" refers to any lanthanide compound containing at least one lanthanide-carbon bond. These compounds are primarily, but not exclusively, those containing cyclopentadienyl ("Cp"), substituted cyclopentadienyl, allyl, and substituted allyl ligands. Suitable organolanthate compounds for use as lanthanide compounds in the method of the first embodiment include, but are not limited to, Cp3Ln, Cp2LnR, Cp2LnCl, CpLnCl2, CpLn(cyclooctatetraene), (C5Me5)2LnR, LnR3, Ln(allyl)3, and Ln(allyl)2Cl, where Ln represents a lanthanide atom and R represents a hydrocarbyl group or a substituted hydrocarbyl group. In one or more embodiments, the hydrocarbyl group or substituted hydrocarbyl group useful in the method of the first embodiment may contain heteroatoms, such as, for example, nitrogen, oxygen, boron, silicon, sulfur, and phosphorus atoms.

[0044] As mentioned above, the lanthanide-based catalyst system employed in the method of the first embodiment comprises an alkylating agent. According to one or more embodiments of the method of the first embodiment, the alkylating agent (also referred to as a hydrocarbylating agent) comprises an organometallic compound that can transfer one or more hydrocarbyl groups to another metal. Generally speaking, these agents include electropositive metals, such as organometallic compounds of Group 1, Group 2, and Group 3 metals (Group IA, IIA, and IIIA metals). Alkylating agents useful in the method of the first embodiment include, but are not limited to, organoaluminum and organomagnesium compounds. As used herein, the term "organoaluminum compound" refers to any aluminum-containing compound having at least one aluminum-carbon bond. In one or more embodiments, an organoaluminum compound soluble in a hydrocarbon solvent may be used. As used herein, the term "organomagnesium compound" refers to any magnesium-containing compound having at least one magnesium-carbon bond. In one or more embodiments, an organomagnesium compound soluble in hydrocarbons may be used. As will be described in more detail below, certain suitable alkylating agents may be in the form of halogenated compounds. In the case where the alkylating agent comprises a halogen atom, the alkylating agent may also optionally provide all or part of the halogen source in the lanthanide-based catalyst system.

[0045] In one or more embodiments of the method of the first embodiment, the organoaluminum compound utilized comprises a compound of the general formula AlR a n X 3-n Those represented by each R a is independently a monovalent organic group connected to the aluminum atom via a carbon atom; wherein each X is independently a hydrogen atom, a halogen atom, a carboxylate group, an alkoxide group, or an aryloxide group; and wherein n is an integer in the range of 1 to 3. In one or more embodiments, each R a Independently, a hydrocarbyl group or a substituted hydrocarbyl group includes, but is not limited to, alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, aralkyl, alkaryl, allyl, and alkynyl groups, each of which contains 1 carbon atom or the appropriate minimum number of atoms to form the group, up to 20 carbon atoms (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms). These hydrocarbyl groups or substituted hydrocarbyl groups may optionally contain heteroatoms, including, but not limited to, nitrogen, oxygen, boron, silicon, sulfur, and phosphorus atoms.

[0046] In the process of the first embodiment, the alkylating agent used is a compound of the general formula AlR a n X 3-nExamples of the types of organoaluminum compounds represented include, but are not limited to, trialkylaluminum, dialkylaluminum hydride, alkylaluminum dihydride, dialkylaluminum carboxylate, alkylaluminum bis(carboxylate), dialkylaluminum alkoxide, alkylaluminum dialkoxide, dialkylaluminum halide, alkylaluminum dihalide, dialkylaluminum phenolate, and alkylaluminum diphenolate compounds.

[0047] Examples of suitable trihydrocarbyl aluminum compounds for use as the alkylating agent in the process of the first embodiment include, but are not limited to, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tri-n-propyl aluminum, triisopropyl aluminum, tri-n-butyl aluminum, tri-tert-butyl aluminum, tri-n-pentyl aluminum, triphenopenty aluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tri(2-ethylhexyl)aluminum, tricyclohexyl aluminum, tri(1-methylcyclopentyl)aluminum, triphenyl aluminum, tri-p-tolylaluminum, tris(2,6-dimethylphenyl)aluminum, tribenzyl aluminum, diethylphenyl aluminum, diethyl-p-tolylaluminum, diethylbenzyl aluminum, ethyldiphenyl aluminum, ethyldi-p-tolylaluminum, and ethyldibenzyl aluminum.

[0048] Examples of suitable dihydrocarbyl aluminum hydride compounds for use as the alkylating agent in the process of the first embodiment include, but are not limited to, diethylaluminum hydride, di-n-propylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, di-n-octylaluminum hydride, diphenylaluminum hydride, di-p-tolylaluminum hydride, dibenzylaluminum hydride, phenylethylaluminum hydride, phenyl-n-propylaluminum hydride, phenylisopropylaluminum hydride, phenyl-n-butylaluminum hydride, Aluminum hydride, phenyl isobutyl aluminum hydride, phenyl-n-octyl aluminum hydride, p-tolyl ethyl aluminum hydride, p-tolyl-n-propyl aluminum hydride, p-tolyl isopropyl aluminum hydride, p-tolyl-n-butyl aluminum hydride, p-tolyl isobutyl aluminum hydride, p-tolyl-n-octyl aluminum hydride, benzyl ethyl aluminum hydride, benzyl-n-propyl aluminum hydride, benzyl isopropyl aluminum hydride, benzyl-n-butyl aluminum hydride, benzyl isobutyl aluminum hydride and benzyl-n-octyl aluminum hydride.

[0049] Examples of suitable hydrocarbyl aluminum hydrides for use as the alkylating agent in this process include, but are not limited to, ethylaluminum dihydride, n-propylaluminum dihydride, isopropylaluminum dihydride, n-butylaluminum dihydride, isobutylaluminum dihydride, and n-octylaluminum dihydride.

[0050] Examples of suitable dihydrocarbyl aluminum halide compounds for use as the alkylating agent in the process of the first embodiment include, but are not limited to, diethylaluminum chloride, di-n-propylaluminum chloride, diisopropylaluminum chloride, di-n-butylaluminum chloride, diisobutylaluminum chloride, di-n-octylaluminum chloride, diphenylaluminum chloride, di-p-tolylaluminum chloride, dibenzylaluminum chloride, phenylethylaluminum chloride, phenyl-n-propylaluminum chloride, phenylisopropylaluminum chloride, phenyl-n-butylaluminum chloride, phenylisobutylaluminum chloride, phenyl-n-octylaluminum chloride, p-tolylethylaluminum chloride, p-tolyl-n-propylaluminum chloride, p-tolylisopropylaluminum chloride, p-tolyl-n-butylaluminum chloride, p-tolylisobutylaluminum chloride, p-tolyl-n-octylaluminum chloride, benzylethylaluminum chloride, benzyl-n-propylaluminum chloride, benzylisopropylaluminum chloride, benzyl-n-butylaluminum chloride, benzylisobutylaluminum chloride, and benzyl-n-octylaluminum chloride.

[0051] Examples of suitable hydrocarbyl aluminum dihalide compounds for use as the alkylating agent in the process of the first embodiment include, but are not limited to, ethylaluminum dichloride, n-propylaluminum dichloride, isopropylaluminum dichloride, n-butylaluminum dichloride, isobutylaluminum dichloride, and n-octylaluminum dichloride.

[0052] In the process of the first embodiment, the alkylating agent used is a compound of the general formula AlR a n X 3-n Examples of other suitable organoaluminum compounds include, but are not limited to, dimethylaluminum hexanoate, diethylaluminum octoate, diisobutylaluminum 2-ethylhexanoate, dimethylaluminum neodecanoate, diethylaluminum stearate, diisobutylaluminum oleate, methylaluminum bis(hexanoate), ethylaluminum bis(octoate), isobutylaluminum bis(2-ethylhexanoate), methylaluminum bis(neodecanoate), ethylaluminum bis(stearate), isobutylaluminum bis(oleate), dimethylaluminum methoxide, diethylaluminum methoxide, diisobutylaluminum methoxide, dimethylaluminum ethoxide, diethylaluminum ethoxide, diisobutylaluminum ethoxide, dimethylbenzenealuminum oxide, diethylbenzenealuminum oxide, diisobutylbenzenealuminum oxide, methylaluminum dimethanol, ethylaluminum dimethanol, isobutylaluminum dimethanol, methylaluminum diethoxide, ethylaluminum diethoxide, isobutylaluminum diethoxide, methyldiphenylaluminum oxide, ethyldiphenylaluminum oxide, and isobutyldiphenylaluminum oxide.

[0053] Another class of organoaluminum compounds suitable for use as alkylating agents in the process of the first embodiment is aluminoxanes. Suitable aluminoxanes include oligomeric linear aluminoxanes, which can be represented by the following general formula:

[0054]

[0055] and oligomeric cyclic aluminoxanes, which can be represented by the following general formula:

[0056]

[0057] wherein x is an integer in the range of 1 to 100 (e.g., 1, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100) or 10 to 50 (e.g., 10, 15, 20, 25, 30, 35, 40, 45, or 50); y is an integer in the range of 2 to 100 (e.g., 2, 10, 20, 30, 40, 50, 60, 70, 80, 90, or 100) or 3 to 20 (e.g., 3, 5, 10, 15, or 20); and wherein each R is independently a monovalent organic group attached to the aluminum atom via a carbon atom. In one embodiment of the method of the first embodiment, each R is independently a hydrocarbyl group or a substituted hydrocarbyl group, including but not limited to alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl, aryl, substituted aryl, aralkyl, alkaryl, allyl, and alkynyl groups, wherein each group preferably contains 1 carbon atom or the appropriate minimum number of atoms to form the group, up to 20 carbon atoms (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms). These hydrocarbyl groups or substituted hydrocarbyl groups may also contain heteroatoms, including but not limited to nitrogen, oxygen, boron, silicon, sulfur, and phosphorus atoms. As used herein, the number of moles of aluminoxane refers to the number of moles of aluminum atoms, not the number of moles of oligomeric aluminoxane molecules. This convention is commonly used in the field of catalyst systems utilizing aluminoxanes.

[0058] Aluminoxane can be prepared by reacting a trihydrocarbylaluminum compound with water. The reaction can be carried out according to a known method, such as, for example, (1) a method in which a trihydrocarbylaluminum compound is dissolved in an organic solvent and then contacted with water, (2) a method in which a trihydrocarbylaluminum compound is reacted with, for example, crystal water contained in a metal salt or water adsorbed in an inorganic or organic compound, or (3) a method in which a trihydrocarbylaluminum compound is reacted with water in the presence of a monomer to be polymerized or a monomer solution.

[0059] Examples of suitable aluminoxane compounds for use as the alkylating agent in the process of the first embodiment include, but are not limited to, methylaluminoxane ("MAO"), modified methylaluminoxane ("MMAO"), ethylaluminoxane, n-propylaluminoxane, isopropylaluminoxane, butylaluminoxane, isobutylaluminoxane, n-pentylaluminoxane, neopentylaluminoxane, n-hexylaluminoxane, n-octylaluminoxane, 2-ethylhexylaluminoxane, cyclohexylaluminoxane, 1-methylcyclopentylaluminoxane, phenylaluminoxane, and 2,6-dimethylphenylaluminoxane. In certain preferred embodiments of the process of the first embodiment, the alkylating agent comprises MAO. The modified methylaluminoxane may be prepared by using techniques known to those skilled in the art with C2 to C 12Hydrocarbyl groups (e.g., C2, C3, C4, C5, C6, C7, C8, C9, C 10 , C 11 or C 12 ), preferably by substituting 5% to 80% (e.g., 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70% or 80%) of the methyl groups of the methylaluminoxane with isobutyl groups.

[0060] According to certain embodiments of the method of the first embodiment, aluminoxane can be used alone or in combination with other organoaluminum compounds. In one embodiment, methylaluminoxane and at least one organoaluminum compound other than aluminoxane (e.g., AlR a n X 3-n ) is used as an alkylating agent in combination with an organoaluminum compound represented by . According to this embodiment and other embodiments, the alkylating agent includes a dihydrocarbyl aluminum hydride, a dihydrocarbyl aluminum halide, an aluminoxane, or a combination thereof. For example, according to one embodiment, the alkylating agent includes diisobutyl aluminum hydride, diethyl aluminum chloride, methylaluminoxane, or a combination thereof. U.S. Pat. No. 8,017,695 (the entire text of which is incorporated herein by reference) provides other examples in which aluminoxane and an organoaluminum compound can be used in combination.

[0061] As described above, suitable alkylating agents for use in the method of the first embodiment include organomagnesium compounds. According to one or more embodiments of the method of the first embodiment, suitable organomagnesium compounds include compounds of the general formula MgR b 2 represents those where each R b is independently a monovalent organic group connected to the magnesium atom via a carbon atom. In one or more embodiments, each R b Independently, a hydrocarbyl group or a substituted hydrocarbyl group includes, but is not limited to, an alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl, aryl, allyl, substituted aryl, aralkyl, alkaryl, and alkynyl group, each of which preferably contains 1 carbon atom or the appropriate minimum number of atoms to form the group, up to 20 carbon atoms (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms). These hydrocarbyl groups or substituted hydrocarbyl groups may also optionally contain heteroatoms, including, but not limited to, nitrogen, oxygen, silicon, sulfur, and phosphorus atoms.

[0062] In the process of the first embodiment, the alkylating agent used is a sulfhydryl group having the general formula MgR b Examples of suitable organomagnesium compounds represented by 2 include, but are not limited to, diethylmagnesium, di-n-propylmagnesium, diisopropylmagnesium, dibutylmagnesium, dihexylmagnesium, diphenylmagnesium, and dibenzylmagnesium.

[0063] Another class of organomagnesium compounds suitable for use as alkylating agents according to an embodiment of the method of the first embodiment is composed of the general formula R c MgX c Indicates that R c is a monovalent organic group connected to the magnesium atom via a carbon atom, and X is a hydrogen atom, a halogen atom, a carboxylate group, an alkoxide group, or an aryloxy group. c is a hydrocarbyl group or a substituted hydrocarbyl group, including, but not limited to, alkyl, cycloalkyl, substituted cycloalkyl, alkenyl, cycloalkenyl, substituted cycloalkenyl, aryl, allyl, substituted aryl, aralkyl, alkaryl, and alkynyl groups, each of which contains 1 carbon atom or the appropriate minimum number of atoms to form the group, up to 20 carbon atoms (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms). These hydrocarbyl groups or substituted hydrocarbyl groups may also contain heteroatoms, including, but not limited to, nitrogen, oxygen, boron, silicon, sulfur, and phosphorus atoms. In one embodiment, X c is a carboxylate group, an alkoxide group, or an aryloxy group, wherein each group contains 1 carbon atom up to 20 carbon atoms (e.g., 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms).

[0064] In the process of the first embodiment, the alkylating agent used is a c MgX c Examples of suitable types of organomagnesium compounds include, but are not limited to, hydrocarbylmagnesium hydrides, hydrocarbylmagnesium halides, hydrocarbylmagnesium carboxylates, hydrocarbylmagnesium alkoxides, and hydrocarbylmagnesium aryloxides.

[0065] In the process of the first embodiment, the alkylating agent used is a c MgX c Examples of suitable organomagnesium compounds include, but are not limited to, methylmagnesium hydride, ethylmagnesium hydride, butylmagnesium hydride, hexylmagnesium hydride, phenylmagnesium hydride, benzylmagnesium hydride, methylmagnesium chloride, ethylmagnesium chloride, butylmagnesium chloride, hexylmagnesium chloride, phenylmagnesium chloride, benzylmagnesium chloride, methylmagnesium bromide, ethylmagnesium bromide, butylmagnesium bromide, hexylmagnesium bromide, phenylmagnesium bromide, benzylmagnesium bromide, methylmagnesium hexanoate, ethylmagnesium hexanoate, butylmagnesium hexanoate, hexylmagnesium hexanoate, phenylmagnesium hexanoate, benzylmagnesium hexanoate, methylmagnesium ethoxide, ethylmagnesium ethoxide, butylmagnesium ethoxide, hexylmagnesium ethoxide, phenylmagnesium ethoxide, benzylmagnesium ethoxide, methylmagnesium oxide, ethylmagnesium oxide, butylmagnesium oxide, hexylmagnesium oxide, phenylmagnesium oxide, and benzylmagnesium oxide.

[0066] As described above, the lanthanide-based catalyst system employed in the method of the first embodiment comprises a halogen source. As used herein, the term "halogen source" refers to any substance comprising at least one halogen atom. According to one or more embodiments of the method of the first embodiment, all or part of the halogen source may optionally be provided by a lanthanide compound, an alkylating agent, or both a lanthanide compound and an alkylating agent. In other words, the lanthanide compound can be used as both the lanthanide compound and all or at least a portion of the halogen source. Similarly, the alkylating agent can be used as both the alkylating agent and all or at least a portion of the halogen source.

[0067] According to certain embodiments of the method of the first embodiment, at least a portion of the halogen source can be present in the catalyst system in the form of separate and different halogen-containing compounds. Various compounds containing one or more halogen atoms or mixtures thereof can be used as halogen sources. Examples of halogen atoms include, but are not limited to, fluorine, chlorine, bromine and iodine. Combinations of two or more halogen atoms can also be used. Halogen-containing compounds soluble in organic solvents (such as aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbon solvents disclosed herein) are suitable for use as halogen sources in the method of the first embodiment. In addition, hydrocarbon-insoluble halogen-containing compounds that can be suspended in the polymerization system to form catalytically active substances can also be used in certain embodiments of the method of the first embodiment.

[0068] Examples of suitable types of halogen-containing compounds used in the method of the first embodiment include, but are not limited to, elemental halogens, mixed halogens, hydrogen halides, organic halides, inorganic halides, metal halides, and organometallic halides. In certain preferred embodiments of the method of the first embodiment, the halogen-containing compound comprises an organometallic halide.

[0069] Examples of elemental halogens suitable for use as halogen sources in the method of the first embodiment include, but are not limited to, fluorine, chlorine, bromine, and iodine. Some specific examples of suitable mixed halogens include, but are not limited to, iodine monochloride, iodine monobromide, iodine trichloride, and iodine pentafluoride.

[0070] Examples of suitable hydrogen halides for use as a halogen source in the disclosed methods include, but are not limited to, hydrogen fluoride, hydrogen chloride, hydrogen bromide, and hydrogen iodide.

[0071] Examples of suitable organic halides for use as a halogen source in the method of the first embodiment include, but are not limited to, tert-butyl chloride, tert-butyl bromide, allyl chloride, allyl bromide, benzyl chloride, benzyl bromide, chloro-diphenylmethane, bromo-diphenylmethane, triphenylmethyl chloride, triphenylmethyl bromide, benzal chloride, benzal bromide, methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, trimethylchlorosilane, benzoyl chloride, benzoyl bromide, propionyl chloride, propionyl bromide, methyl chloroformate, and methyl bromoformate.

[0072] Examples of suitable inorganic halides for use as a halogen source in the method of the first embodiment include, but are not limited to, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride, phosphorus oxybromide, boron trifluoride, boron trichloride, boron tribromide, silicon tetrafluoride, silicon tetrachloride, silicon tetrabromide, silicon tetraiodide, arsenic trichloride, arsenic tribromide, arsenic triiodide, selenium tetrachloride, selenium tetrabromide, tellurium tetrachloride, tellurium tetrabromide, and tellurium tetraiodide.

[0073] Examples of suitable metal halides for use as a halogen source in the method of the first embodiment include, but are not limited to, tin tetrachloride, tin tetrabromide, aluminum trichloride, aluminum tribromide, antimony trichloride, antimony pentachloride, antimony tribromide, aluminum triiodide, aluminum trifluoride, gallium trichloride, gallium tribromide, gallium triiodide, gallium trifluoride, indium trichloride, indium tribromide, indium triiodide, indium trifluoride, titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, zinc dichloride, zinc dibromide, zinc diiodide, and zinc difluoride.

[0074] Examples of suitable organometallic halides for use as a halogen source in the process of the first embodiment include, but are not limited to, dimethylaluminum chloride, diethylaluminum chloride, dimethylaluminum bromide, diethylaluminum bromide, dimethylaluminum fluoride, diethylaluminum fluoride, methylaluminum dichloride, ethylaluminum dichloride, methylaluminum dibromide, ethylaluminum dibromide, methylaluminum difluoride, ethylaluminum difluoride, sesquimethylaluminum chloride, sesquiethylaluminum chloride, sesquiisobutylaluminum chloride, methylmagnesium chloride, methylmagnesium bromide, methylmagnesium iodide, ethylmagnesium chloride, ethylmagnesium bromide, butylmagnesium chloride, butylmagnesium bromide, phenylmagnesium chloride, phenylmagnesium bromide, benzylmagnesium chloride, trimethyltin chloride, trimethyltin bromide, triethyltin chloride, triethyltin bromide, di-tert-butyltin dichloride, di-tert-butyltin dibromide, dibutyltin dichloride, dibutyltin dibromide, tributyltin chloride, and tributyltin bromide. According to one embodiment, the halogen source comprises an organometallic halide. For example, according to certain embodiments, the halogen source includes diethylaluminum chloride, which, as described above, can also be used as an alkylating agent in a lanthanide-based catalyst system. Thus, according to certain embodiments of the method of the first embodiment, the halogen source can be provided in whole or in part by an alkylating agent in the catalyst system disclosed herein.

[0075] The lanthanide-based catalyst system used in the method of the first embodiment can be formed by combining or mixing the above-mentioned catalyst components. As referred to herein, the terms "catalyst composition" and "catalyst system" encompass simple mixtures of the components, complexes of the various components caused by physical or chemical attraction, chemical reaction products of the components, or combinations of the above-mentioned components. The terms "catalyst composition" and "catalyst system" are used interchangeably herein.

[0076] Conjugated diene monomer

[0077] As described above, according to the method of the first embodiment, a certain amount of conjugated diene monomer is polymerized as part of a method for producing a modified high-cis polydiene polymer. A conjugated diene is a compound having two carbon-carbon double bonds (i.e., two -C=C- bonds) separated by a single bond (i.e., -CC-); therefore, the conjugated diene will contain at least one -C=CC=C- portion. The specific structure of the conjugated diene monomer used in the method of the first embodiment, present in the polymer chain, or in the modified high-cis polydiene polymer included in the first to third embodiments disclosed herein may vary. Preferably, according to the first to third embodiments, the conjugated diene monomer is a 1,3-conjugated diene, and in a preferred embodiment, at least 99% by weight of the conjugated diene monomer is a 1,3-conjugated diene monomer. According to the first to third embodiments, one or more than one type of conjugated diene monomer may be used (thereby present in the resulting polymer). The reference to one or more than one type of conjugated diene monomer herein means that the conjugated diene monomer may include all one (type) formula or a mixture of multiple (types) formulas. As a non-limiting example, a certain amount of conjugated diene monomers containing two types of conjugated diene monomers may include a combination of 1,3-butadiene and isoprene. In certain embodiments of the first embodiment to the third embodiment disclosed herein, the conjugated diene monomer includes at least one of the following: 1,3-butadiene; isoprene; 1-3-pentadiene; 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; 2,4-hexadiene; 1,3-hexadiene; 1,3-cyclopentadiene; 1,3-cyclohexadiene; 1,3-cycloheptadiene; or 1,3-cyclooctadiene. In certain preferred embodiments of the first embodiment to the third embodiment, the conjugated diene monomer includes 1,3-butadiene or isoprene, more preferably 1,3-butadiene. In certain embodiments of the first through third embodiments, the conjugated diene monomer comprises 1,3-butadiene in combination with isoprene. In certain particularly preferred embodiments of the first through third embodiments, the only conjugated diene monomer utilized is 1,3-butadiene.

[0078] Functionalized compounds

[0079] As discussed above, the method of the first embodiment comprises reacting an active terminal polymer chain with a functionalized compound selected from Formula I or Formula II. Also as discussed above, according to the second and third embodiments, the modified high cis polydiene comprises at least one polymer chain produced by polymerization of a conjugated diene monomer bearing a residue from a functionalized compound of Formula I or Formula II. Reference to a residue from a functionalized compound is intended to indicate that the polymer chain has been bonded to the functionalized compound (the bonding point or connection point between the polymer chain and the functionalized compound is discussed in more detail below).

[0080] According to the first to third embodiments, structure I is as follows:

[0081]

[0082] wherein n is an integer from 0 to 16 (e.g., 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16). In certain embodiments of the first to third embodiments, wherein a functionalized compound having structure I is utilized, n is preferably an integer from 1 to 10, more preferably from 1 to 3. Exemplary compounds having structure I include, but are not limited to, N-vinyl caprolactam, N-vinyl pyrrolidinedione (also known as N-vinyl pyrrolidinedione, 1-vinyl-2-pyrrolidinedione, and N-vinyl pyrrolidone), N-vinyl piperidone (also known as N-vinyl-2-piperidone or 1-vinyl-2-piperidone), N-vinyl-4-butyl pyrrolidone, N-vinyl-4-propyl pyrrolidone, N-vinyl-4-methyl caprolactam, N-vinyl-6-methyl caprolactam, and N-vinyl-7-butyl caprolactam.

[0083] According to the first to third embodiments, structure II is as follows

[0084]

[0085] Where R 1 Selected from H and C1-C 20 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C 10 , C 11 , C 12 , C 13 , C 14 , C 15 , C 16 , C 17 , C 18 , C 19 or C 20 ) and R 2 Selected from H and C1-C20 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C 10 , C 11 , C 12 , C 13 , C 14 , C 15 , C 16 , C 17 , C 18 , C 19 or C 20 In certain preferred embodiments of the first to third embodiments, wherein the functionalized compound has the structure, R 1 , R 2 or two selected from C1-C 10 According to the first to third embodiments, when R 1 and / or R 2 When a hydrocarbon group, the hydrocarbon group is preferably an alkyl group and may be linear or branched.

[0086] In those embodiments of the first through third embodiments, wherein the functionalized compound has structure I, one or more polymer chains may be bonded to the beta-carbon from the vinyl group that is connected to the nitrogen (in which case the alpha and beta carbons from the vinyl group will no longer be double bonded) and / or to the carbon of the carbonyl group (in which case the carbon will no longer be double bonded to the oxygen). Such points of attachment of polymer chains are shown below in structures IA and IB, where * indicates the point of attachment of the polymer chain to the functionalized compound of structure I.

[0087]

[0088] It is worth noting that when one or more polymer chains are bonded to a functionalized compound as shown in IA, the ring can open, resulting in structures I-A1 or I-A2 as shown below (which shows cisBR as a polymer chain, where the rest of the structure is the residue of the functionalized compound). It should also be noted that when the point of attachment is as indicated in IA, more than one polymer chain can be bonded to the functionalized compound, as shown below in I-A2, where two polymer chains are bonded to the residue of the functionalized compound.

[0089]

[0090]

[0091] In those embodiments of the first through third embodiments, wherein the functionalized compound has structure II, the polymer chain can be bonded to the beta-carbon from the vinyl group that is connected to the nitrogen (in which case the alpha and beta carbons from the vinyl group will no longer be double bonded) or to the carbon of the carbonyl group (in which case the carbon will no longer be double bonded to the oxygen). The above points of attachment of the polymer chain are shown below in Structure II-A and Structure II-B, where * represents the point of attachment of the polymer chain to the first functionalized group resulting from the first functionalized compound of Structure II.

[0092]

[0093] According to the first to third embodiments, the amount of the functionalized compound of formula I or II used to modify the active terminal polymer chain (i.e., according to the method of the first embodiment) or present as a residue in the modified high cis polydiene polymer (i.e., according to the second and third embodiments) can vary. In certain embodiments of the first to third embodiments, the functionalized compound is present in an amount of 10:1 to 100:1 (e.g., 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, 50:1, 55:1, 60:1, 65:1, 70:1, 75:1, 80:1, 85:1, 90:1, 95:1 or 100:1), preferably 20:1 to 80:1 (e.g., 20:1, 25:1, 30:1, 35:1, 40:1, 45:1 1, 50:1, 55:1, 60:1, 65:1, 70:1, 75:1, 80:1), more preferably 30:1 to 60:1 (e.g., 30:1, 32:1, 34:1, 35:1, 36:1, 38:1, 40:1, 42:1, 44:1, 45:1, 46:1, 48:1, 50:1, 52:1, 54:1, 55:1, 56:1, 58:1 or 60:1) are used in a molar ratio based on moles of functionalized compound: moles of lanthanide in the lanthanide compound.

[0094] Coupling agent

[0095] As discussed above, the method of the first embodiment includes a coupling intermediate product, which is produced by reacting an active terminal polymer chain with a functionalized compound of formula I or formula II using a coupling agent selected from a silicon halide. According to the second embodiment and the third embodiment, the modified high-cis polydiene polymer comprises a residue from a coupling agent. More specifically, in the modified high-cis polydiene polymer according to the first embodiment and the second embodiment, the residue from the coupling agent has at least one polymer chain bonded thereto (polymer chain refers to a polymer chain produced by reacting with a functionalized compound of formula I or formula II), wherein the coupling agent is selected from a silicon halide, and the residue from the coupling agent has at least one halide replaced by a polymer chain of (a). Preferably, according to the first embodiment to the third embodiment, the coupling agent is a silicon halide.

[0096] According to the method of the first embodiment, the coupling agent is added to the polymerization system after the conjugated diene monomer is polymerized to produce a polymer chain with an active end. Therefore, according to such a method, the coupling agent is not added to the monomer solution before the lanthanide catalyst system or its components are added.

[0097] According to the first to third embodiments, the specific structure of the halogenated silicon coupling agent may vary. In certain preferred embodiments of the first to third embodiments, the coupling agent has the formula III: Si(R*) n (Y) 4-n Or Formula IV: R**[SiY3]2. According to Formula III, each R * independently selected from a group consisting of 1 to 20 carbon atoms (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C 10 , C 11 , C 12 , C 13 , C 14 , C 15 , C 16 , C 17 , C 18 , C 19 or C 20 ), preferably a monovalent organic group having 1 to 10 carbon atoms, more preferably 1-6 carbon atoms. According to Formula IV, R** is a monovalent organic group having 1 to 20 carbon atoms (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, C 10 , C 11 , C 12 , C 13 , C 14 , C 15 , C 16 , C 17 , C 18 , C 19or C 20 ), preferably 1 to 10 carbon atoms, more preferably 1-6 carbon atoms of the alkylene group. In certain preferred embodiments, when the coupling agent has formula IV, the SiY3 group is not bonded to the same carbon atom of R**, which is required to have at least 2 carbon atoms (e.g., 2-20 carbon atoms, preferably 2-10 carbon atoms, more preferably 2-6 carbon atoms). The alkylene group R** may be saturated or unsaturated (i.e., may contain one or more double bonds), and may be aliphatic or aromatic. The alkylene group R** may be straight chain or branched. According to formula III and formula IV, the coupling agent contains at least one silicon atom (Si); each Y is a halogen atom or a C1-C 10 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, or C 10 ), preferably C1-C6, more preferably C1-C2 alkoxy, and n is an integer of 0-3, preferably 0-2. In preferred embodiments of the first embodiment to the third embodiment, each Y is a halogen. As will be appreciated by those skilled in the art, when n of formula III is 0 and Y is a halogen, the coupling agent contains four halogens and can be referred to as a metal tetrahalide. According to formula III, R* can be selected from alkyl groups and aryl organic groups having a plurality of carbon atoms as shown above. Preferably, the halogen in formula III or IV is chlorine or bromine, most preferably chlorine.

[0098] In those of the first to third embodiments wherein the coupling agent has Formula III and is a silicon halide, non-limiting examples of suitable coupling agents include diphenyldichlorosilane, dihexyldichlorosilane, dioctyldichlorosilane, dibutyldichlorosilane, dimethyldichlorosilane, methyltrichlorosilane, phenyltrichlorosilane, hexyltrichlorosilane, octyltrichlorosilane, butyltrichlorosilane, methyltrichlorosilane, and the like.

[0099] In those of the first to third embodiments in which the coupling agent has Formula IV and M is silicon, non-limiting examples of suitable coupling agents include 1,1-bis(trichlorosilylmethyl)ethylene, 1,1-bis(trimethoxysilylmethyl)ethylene, 1,3-bis(trichlorosilyl)propane, bis(trichlorosilyl)methane, 1,2-bis(trichlorosilyl)ethane, 1,6-bis(trichlorosilylmethyl)hexane, 1,6-bis(trichlorosilyl)hexane, 1,10-bis(trichlorosilyl)decane, 1,2-bis(trichlorosilyl)decane, 1,2-bis(trichlorosilyl)ethane, 1,4-bis(trichlorosilyl)benzene, 1,4-bis(trichlorosilylethyl)benzene, 1,4-bis(trichlorosilylmethyl)benzene, 1,4-bis(trichlorosilylpropyl)benzene, and the like. Certain suitable coupling agents are available from Gelest, Inc., Morrisville, Pennsylvania.

[0100] According to the first to third embodiments, the amount of coupling agent used for coupling the intermediate product produced by reacting the active terminal polymer chain with the functionalized compound of formula I or formula II (i.e., according to the method of the first embodiment) or present as a residue in the modified high-cis polydiene polymer (i.e., according to the second and third embodiments) using a coupling agent selected from silicon halides can vary. In certain embodiments of the first to third embodiments, the coupling agent is used in a molar ratio of 0.2:1 to 10:1 (e.g., 0.2:1, 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1, or 10:1), preferably 1:1 to 5:1 (e.g., 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1), the molar ratio being based on moles of coupling agent:moles of lanthanide in the lanthanide compound.

[0101] Properties of Modified High Cis Polydiene Polymers

[0102] As mentioned above, the process of the first embodiment produces a modified high cis polydiene polymer having a cis 1,4-linkage content of at least 92%, preferably at least 94%, and a Mooney viscosity ML at least 40, preferably 45 to 80 at 100°C. 1+4 As also mentioned above, the modified high cis polydiene polymer of the second embodiment has a cis 1,4-linkage content of at least 92%, preferably at least 94%, and a Mooney viscosity ML of at least 40, preferably 45 to 80 at 100°C.1+4 . The modified high-cis polydiene polymer of the second embodiment can be prepared using the method of the first embodiment. Therefore, the above discussion of certain embodiments of the first embodiment should be understood to be applicable as completely as possible to the polymers of the second embodiment and the polymers used in the composition of the third embodiment. Since the tire rubber composition of the third embodiment utilizes the modified high-cis polydiene polymer of the second embodiment or the modified high-cis polydiene polymer prepared by the method according to the first embodiment, the modified high-cis polydiene polymer of the third embodiment can also be understood to have a cis 1,4-bond content of at least 92%, preferably at least 94%, and a Mooney viscosity ML of at least 40, preferably 45 to 80 at 100°C. 1+4 By a cis 1,4-linkage content of at least 92% is meant that it is 92% or higher (e.g., 92%, 93%, 94%, 95%, 96%, 97%, 98%, 98.5%, 99% or higher), which should be understood to include ranges such as 92%-99%, 92%-98%, 92%-97%, 92%-96%, 92%-95%, etc. In preferred embodiments of the first to third embodiments, the modified high cis polydiene polymer has a cis 1,4-linkage content of at least 94%. The so-called cis 1,4-bond content of at least 94% means 94% or higher (e.g., 94%, 95%, 96%, 97%, 98%, 98.5%, 99% or higher), which should be understood to include ranges such as 94%-99%, 94%-98%, 94%-97%, 94%-96%, 94%-95%, etc. The cis 1,4-bond content referred to herein is measured by FTIR (Fourier transform infrared spectroscopy). Specifically, a polymer sample is dissolved in CS2 and then subjected to FTIR. The so-called Mooney viscosity ML at 100°C 1+4 At least 40 means that it is 40 or higher (e.g., 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100 or higher). Preferably, according to the first to third embodiments, the Mooney viscosity ML at 100°C is 1+4 The amount of the present invention is not more than 100, preferably 45 to 80 (e.g., 45, 46, 48, 50, 52, 54, 55, 56, 58, 60, 62, 64, 65, 68, 70, 72, 74, 75, 76, 78 or 80) or 40 to 80 (e.g., 40, 42, 44, 45, 46, 48, 50, 52, 54, 55, 56, 58, 60, 62, 64, 65, 68, 70, 72, 74, 75, 76, 78 or 80).

[0103] According to the first to third embodiments, other characteristics of the modified high cis polydiene polymer may vary. For example, the polymer may have various Mw, Mn and Mw / Mn values. In certain embodiments of the first to third embodiments, the modified high cis polydiene polymer satisfies at least one of the following: (a) having 150,000 g / mol to 400,000 g / mol (e.g., 150,000 g / mol, 175,000 g / mol, 200,000 g / mol, 225,000 g / mol, 250,000 g / mol, 275,000 g / mol, 300,000 g / mol, 325,000 g / mol, 350,000 g / mol, 375,000 g / mol, or 400,000 g / mol), preferably 200,000 g / mol to 350,000 g / mol. / mol (e.g., 200,000 g / mol, 225,000 g / mol, 250,000 g / mol, 275,000 g / mol, 300,000 g / mol, 325,000 g / mol, or 350,000 g / mol), more preferably 220,000 g / mol to 300,000 g / mol (e.g., 220,000 g / mol, 225,000 g / mol, 250,000 g / mol, 275,000 g / mol, or 300,000 g / mol); (b) has an Mw of 80,000 g / mol to 250,000 g / mol (e.g., 80,000 g / mol, 90,000 g / mol, The present invention relates to an aqueous solution of at least 200 g / mol and a polyol of at least 200 g / mol, preferably 90,000 g / mol to 200,000 g / mol (e.g., 90,000 g / mol, 100,000 g / mol, 110,000 g / mol, 120,000 g / mol, 130,000 g / mol, 140,000 g / mol, 150,000 g / mol, 160,000 g / mol, 170,000 g / mol, 180,000 g / mol, 190,000 g / mol, or 200,000 g / mol), preferably 90,000 g / mol to 200,000 g / mol (e.g., 90,000 g / mol, 100,000 g / mol, 110,000 g / mol, 120,000 g / mol, 130,000 g / mol, 140,000 g / mol 0 g / mol, 150,000 g / mol, 160,000 g / mol, 170,000 g / mol, 180,000 g / mol, 190,000 g / mol, or 200,000 g / mol), more preferably 100,000 g / mol to 150,000 g / mol (e.g., 100,000 g / mol, 110,000 g / mol, 120,000 g / mol, 130,000 g / mol, 140,000 g / mol, 150,000 g / mol, 160,000 g / mol, 170,000 g / mol, or 180,000 g / mol); (c) having an Mn of 1.5 to 3.5.or (d) having a Mooney viscosity ML of 40 to 80 (e.g., 40, 45, 50, 55, 60, 65, 70, 75 or 80) at 100°C. 1+4 . In certain embodiments of the first to third embodiments, the modified high cis polydiene polymer satisfies each of (a) to (d). In certain embodiments of the first to third embodiments, the modified high cis polydiene polymer satisfies the preferred range of each of (a) to (d). In certain embodiments of the first to third embodiments, the modified high cis polydiene polymer satisfies the more preferred range of each of (a) to (d). Mn represents the number average molecular weight in grams per mole (determined by GPC), Mw represents the weight average molecular weight in grams per mole (determined by GPC), and Mw / Mn represents the molecular weight distribution or polydispersity of the polymer. Typically, the Mn and Mw of these polymers can be determined by using gel permeation chromatography (GPC), which is calibrated with polystyrene standards and the Mark-Hauwink constant of the polymer under consideration.

[0104] Tire rubber composition

[0105] As discussed above, the third embodiment disclosed herein relates to a tire rubber composition comprising the modified high cis polydiene polymer of the second embodiment or the modified high cis polydiene polymer produced by the method of the first embodiment. More specifically, the tire rubber composition of the third embodiment comprises: (a) 10 to 100 phr, preferably 30-80 phr of the modified high cis polydiene according to the second embodiment or as produced according to the first embodiment; (b) 0 to 90 phr, preferably 20 to 70 phr of at least one polymer containing a diene monomer selected from natural rubber, polyisoprene, styrene-butadiene copolymer, styrene-butadiene-isoprene rubber, isoprene-butadiene rubber, and combinations thereof; and (c) 10 to 100 phr of at least one carbon black filler and 0 to 100 phr of at least one silica filler. According to the third embodiment, the tire rubber composition is preferably contained in a tire component, more preferably in a tire tread. Therefore, also disclosed herein is a tire tread made from the rubber composition according to the third embodiment.

[0106] As mentioned above, according to the third embodiment, the amount of the modified high cis polydiene (a) present in the rubber composition may vary from 10 to 100 phr (e.g., 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100 phr). In certain preferred embodiments of the third embodiment, the amount of the modified high cis polydiene (a) present in the rubber composition is from 30 to 80 phr (e.g., 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80 phr). An amount of (a) within the aforementioned range may also be used in the rubber composition of the third embodiment, for example, 40 to 80 phr, 50 to 80 phr, 40 to 70 phr, 40 to 60 phr, and the like.

[0107] Other rubbers for tire rubber compositions

[0108] As also mentioned above, according to the third embodiment, the rubber composition may include 0 to 80 phr (e.g., 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80 phr) of at least one polymer containing a diene monomer selected from natural rubber, polyisoprene, styrene-butadiene copolymer, styrene-butadiene-isoprene rubber, isoprene-butadiene rubber, and combinations thereof. In a preferred embodiment of the third embodiment, at least one polymer containing a diene monomer (b) is selected from styrene-butadiene copolymer, natural rubber, polyisoprene, or combinations thereof. In certain preferred embodiments of the third embodiment, the amount of at least one polymer (b) containing a diene monomer is 20 phr to 70 phr (e.g., 20 phr, 25 phr, 30 phr, 35 phr, 40 phr, 45 phr, 50 phr, 55 phr, 60 phr, 65 phr or 70 phr). The amount of (b) within the aforementioned range can also be used in the rubber composition of the third embodiment, for example, 20 to 60, 20 to 50, 30 to 60, 40 to 60, etc. In certain embodiments of the third embodiment, for example, in addition to (a) and (b), the rubber composition also includes one or more other rubbers. In a preferred embodiment of the third embodiment, the entire 100 phr elastomer component of the rubber composition is composed of a combination of (a) and (b). In other words, in such embodiments, in addition to (a) and (b), there are no other rubbers. In certain embodiments of the third embodiment, the rubber composition does not contain polyisoprene (i.e., 0 phr of polyisoprene). In certain embodiments of the third embodiment, the rubber composition contains no polybutadiene, except the modified high-cis polybutadiene according to (a). In certain embodiments of the third embodiment, the rubber composition contains no natural rubber and no polyisoprene.

[0109] Fillers for tire rubber compositions

[0110] As discussed above, according to the third embodiment, the tire rubber composition further comprises, as a filler component, 10 to 100 phr (e.g., 10 phr, 15 phr, 20 phr, 25 phr, 30 phr, 35 phr, 40 phr, 45 phr, 50 phr, 55 phr, 60 phr, 65 phr, 70 phr, 75 phr, 80 phr, 85 phr, 90 phr, 95 phr, or 100 phr). The present invention also provides a plurality of carbon black fillers, wherein the carbon black filler is present in an amount of at least one carbon black filler (e.g., 0.00 phr) and at least one silica filler of 0 to 100 phr (e.g., 10 phr, 15 phr, 20 phr, 25 phr, 30 phr, 35 phr, 40 phr, 45 phr, 50 phr, 55 phr, 60 phr, 65 phr, 70 phr, 75 phr, 80 phr, 85 phr, 90 phr, 95 phr, or 100 phr). In other words, according to the foregoing, the carbon black filler can be considered to be always present, while the silica filler is optionally present. According to a preferred embodiment of the third embodiment, both the carbon black filler and any silica filler present are reinforcing fillers. In certain embodiments of the third embodiment, the silica filler is present in an amount of at least 5 phr, 5 phr to 200 phr, 5 phr to 150 phr, 5 phr to 100 phr, at least 20 phr, 20 phr to 200 phr, 20 phr to 150 phr, 20 phr to 100 phr, at least 50 phr, 50 phr to 200 phr, 50 phr to 150 phr, 50 phr to 100 phr, or an amount within one of the foregoing ranges.

[0111] As used herein, the term "reinforcing" with respect to "reinforcing carbon black filler," "reinforcing silica filler," and "reinforcing filler" should generally be understood to include fillers conventionally described as reinforcing and fillers conventionally described as semi-reinforcing. Traditionally, the term "reinforcing filler" is used to refer to a carbon black filler having a carbon black content greater than about 100 m 2 / g, and in some cases, greater than 100m 2 / g, greater than about 125m 2 / g, greater than 125m 2 / g, or even greater than about 150m 2 / g or greater than 150m 2 / g of nitrogen absorption specific surface area (N2SA). Alternatively (or additionally), the traditional use of the term "reinforcing filler" can also be used to refer to particulate matter having a particle size of about 10nm to about 50nm (including 10nm to 50nm). Traditionally, the term "semi-reinforcing filler" is used to refer to fillers whose particle size, surface area (N2SA), or both are between non-reinforcing fillers (as discussed below) and reinforcing fillers. In certain embodiments of the third embodiment disclosed herein, the term "reinforcing filler" is used to refer to a particulate material having a particle size of about 20nm to about 50nm. 2 / g or greater, including 20m 2 / g or more, greater than about 50m 2 / g, greater than 50m 2 / g, greater than about 100m 2 / g, greater than 100m 2 / g, greater than about 125m 2 / g, and greater than 125m 2 / g of nitrogen absorption specific surface area (N2SA) of particulate matter. In certain embodiments of the third embodiment disclosed herein, the term "reinforcing filler" is used to refer to particulate matter having a particle size of about 10 nm to about 1000 nm, including 10 nm to 1000 nm, about 10 nm to about 50 nm, and 10 nm to 50 nm.

[0112] According to the third embodiment, the specific type or types of carbon black utilized may vary. Generally speaking, suitable carbon blacks for use as reinforcing fillers in the rubber composition of the third embodiment include any of the commonly available, commercially produced carbon blacks, including those having at least about 20 m 2 / g(including at least 20m 2 / g), more preferably at least about 35 m 2 / g up to about 200m 2 / g or higher (including 35m 2 / g up to 200m 2 / g) of those carbon blacks. The surface area values ​​for carbon black herein are determined by ASTM D-1765 using hexadecyltrimethylammonium bromide (CTAB) technology. Wherein available carbon black is furnace black, channel black and lamp black. More specifically, the example of available carbon black includes super wear-resistant furnace (SAF) black, high wear-resistant furnace (HAF) black, fast pressed furnace (FEF) black, fine furnace (FF) black, medium super wear-resistant furnace (ISAF) black, semi-reinforced furnace (SRF) black, medium processing channel black, difficult processing channel black and conductive channel black. Available other carbon black includes acetylene black. In certain embodiments of the third embodiment, the rubber composition includes a mixture of two or more of the above blacks. Preferably, according to the third embodiment, if there is a carbon black filler, it is only composed of one type (or grade) of reinforcing carbon black. Typical carbon blacks suitable for use in certain embodiments of the third embodiment are N-110, N-220, N-339, N-330, N-351, N-550 and N-660 specified by ASTM D-1765-82a. The carbon black used can be in granular form or in non-granular flocculated masses. Preferably, non-granular carbon blacks are preferred for more uniform mixing.

[0113] When reinforcing silica fillers are used in the tire rubber composition of the third embodiment, the specific type of silica used for at least one reinforcing silica filler can vary. Non-limiting examples of reinforcing silica fillers suitable for use in certain embodiments of the third embodiment include, but are not limited to, precipitated amorphous silica, wet silica (hydrated silicic acid), dry silica (anhydrous silicic acid), pyrogenic silica, calcium silicate, and the like. Other reinforcing silica fillers suitable for use in certain embodiments of the third embodiment include, but are not limited to, aluminum silicate, magnesium silicate (Mg2SiO4, MgSiO3, etc.), calcium magnesium silicate (CaMgSiO4), calcium silicate (Ca2SiO4, etc.), aluminum silicate (Al2SiO5, Al4.3SiO4.5H2O, etc.), aluminum calcium silicate (Al2O3.CaO2SiO2, etc.), and the like. Among the reinforcing silica fillers listed, precipitated amorphous wet, hydrated silica fillers are preferred. Such reinforcing silica fillers are produced by a chemical reaction in water, whereby they precipitate as ultrafine spherical particles, wherein the primary particles strongly associate into aggregates, which in turn are less strongly combined into agglomerates. The surface area as measured by the BET method is a preferred measurement for characterizing the reinforcing properties of different reinforcing silica fillers. In certain embodiments of the third embodiment disclosed herein, the rubber composition comprises a reinforcing silica filler having a surface area of ​​100 m 2 / g to 400m 2 / g (e.g., 100m 2 / g, 110m 2 / g, 120m 2 / g, 130m 2 / g, 140m 2 / g, 150m 2 / g, 160m 2 / g, 170m 2 / g, 180m 2 / g, 190m 2 / g, 200m 2 / g, 210m 2 / g, 220m 2 / g, 230m 2 / g, 240m 2 / g, 250m 2 / g, 260m 2 / g, 270m 2 / g, 280m 2 / g, 290m 2 / g、300m 2 / g, 310m 2 / g, 320m 2 / g, 330m 2 / g, 340m 2 / g, 350m 2 / g, 360m 2 / g, 370m 2 / g、380m 2 / g, 390m 2 / g, or 400m 2 / g)、150m 2 / g to 350m 2 / g, 200m 2 / g to 300m 2 / g, or 150m 2 / g to 250m 2 / g of surface area (as measured by the BET method).

[0114] In certain embodiments of the third embodiment disclosed herein, the rubber composition comprises a reinforcing silica filler having a pH of 5.5 to 8 (e.g., 5.5, 5.7, 5.9, 6.1, 6.3, 6.5, 6.7, 6.9, 7.1, 7.3, 7.5, 7.7, 7.9, or 8), 6 to 8 (e.g., 6, 6.2, 6.4, 6.6, 6.8, 7, 7.2, 7.4, 7.6, 7.8, or 8), 6 to 7.5, 6.5 to 8, 6.5 to 7.5, or 5.5 to 6.8. Some commercially available reinforcing silica fillers that can be used in certain embodiments of the third embodiment include, but are not limited to EZ120G, EZ120G-D, 134G, 160G, 160G-D, EZ 200G, EZ 200G-D, 210, 233. 243LD, 255CG-D, 315-D, 315G-D, HDP320G, etc., are produced by PPG Industries (Pittsburgh, Pa.) in Pittsburgh, Pennsylvania. Similarly, a variety of commercial grades of different reinforcing silica fillers are also available from Evonik Corporation (e.g., 320GR, 5000GR, 5500GR, 7000GR, VN2 GR, VN2, VN3, VN3 GR, GR 7005, 7500GR, 7800GR, 9500GR, 9000G, 9100GR) and Solvay (e.g. 1115MP, 1085GR, 1165MP, 1200MP, Premium, 195HR, 195GR, 185GR, 175GR and 165GR).

[0115] In certain embodiments of the third embodiment, one or more than one silica coupling agent may also be (optionally) utilized. Silica coupling agents may be used to prevent or reduce the aggregation of silica fillers in the rubber composition. It is believed that the aggregates of silica filler particles increase the viscosity of the rubber composition, and therefore, preventing the aggregation will reduce viscosity and improve the processability and miscibility of the rubber composition.

[0116] Generally, any conventional type of silica coupling agent can be used, such as those having silane and constituent components or parts that can react with polymers, particularly vulcanizable polymers. The silica coupling agent acts as a connecting bridge between silica and polymers. The silica coupling agent suitable for use in certain embodiments of the third embodiment includes those containing the following groups: such as alkyl alkoxy, thiol, end-capped thiol, sulfide-containing groups (e.g., containing alkoxy based on monosulfide, containing alkoxy based on disulfide, containing alkoxy based on tetrasulfide), amino, vinyl, epoxy, and combinations thereof. In certain embodiments, the silica coupling agent can be added to the rubber composition as a pre-treated silica; the pre-treated silica has been surface pre-treated with silane before being added to the rubber composition. The use of pre-treated silica allows two components (i.e., silica and silica coupling agent) to be added as one component, which usually makes rubber easier to compound.

[0117] When a silica coupling agent is utilized in the tire rubber composition according to the third embodiment, the amount used may vary. In certain embodiments of the third embodiment, the rubber composition does not contain any silica coupling agent. In other embodiments of the third embodiment, the silica coupling agent is present in an amount sufficient to provide a ratio of the total amount of silica coupling agent to the silica filler of 0.1:100 to 1:5 (i.e., 0.1 to 20 parts by weight per 100 parts of silica), 1:100 to 1:10, 1:100 to 1:20, and 1:100 to 1:25, and about 1:100 to about 0:100 and 1:100 to 0:100. In certain embodiments according to the third embodiment, the tire rubber composition comprises an amount of 0.1 phr to 15 phr (e.g., 0.1 phr, 0.5 phr, 1 phr, 2 phr, 3 phr, 4 phr, 5 phr, 6 phr, 7 phr, 8 phr, 9 phr, 10 phr, 11 phr, 12 phr, 13 phr, 14 phr or 15 phr), 0.1 phr to 12 phr, 0.1 phr to 10 phr, 0.1 phr to 5 phr, 1 phr to 15 phr (e.g., 1 phr, 2 phr, 3 phr, 4 phr, 5 phr, 6 phr, 7 phr, 8 phr, 9 phr, 10 phr, 11 phr, 12 phr, 13 phr, 14 phr or 15 phr). 5 phr, 9 phr, 10 phr, 11 phr, 12 phr, 13 phr, 14 phr or 15 phr), 1 phr to 10 phr (e.g., 1 phr, 1.5 phr, 2 phr, 2.5 phr, 3 phr, 3.5 phr, 4 phr, 4.5 phr, 5 phr, 5.5 phr, 6 phr, 6.5 phr, 7 phr, 7.5 phr, 8 phr, 8.5 phr, 9 phr, 9.5 phr or 10 phr), 1 phr to 5 phr, or 1 phr to 3 phr of a silica coupling agent.

[0118] Plasticizers for tire rubber compositions

[0119] In certain embodiments of the third embodiment, the tire rubber composition further comprises (also includes) a plasticizing system comprising at least one of a hydrocarbon resin and an oil.

[0120] Various types of oil can be used, including but not limited to aromatic oils, naphthenic oils and low PCA oils. Suitable low PCA oils include those having a polycyclic aromatic hydrocarbon content of less than 3 % by weight as determined by the IP346 method. The procedure of the IP346 method can be found in Standard Methods for Analysis & Testing of Petroleum and Related Products (Standard Methods for Analysis and Testing of Petroleum and Related Products) and British Standard 2000 Parts (British Standard 2000 Parts) the 62nd edition published by the Institute of Petroleum, United Kingdom in 2003. Suitable low PCA oils include mild extraction solvates (MES), treated distillate aromatic extracts (TDAE), TRAE and heavy naphthenes. Suitable MES oils are commercially available from SHELL as CATENEX SNR, from EXXONMOBIL as PROREX 15 and FLEXON 683, from BP as VIVATEC 200, from TOTAL FINA ELF as PLAXOLENE MS, from DAHLEKE as TUDALEN 4160 / 4225, from REPSOL as MES-H, from Z8 as MES, and from AGIP as OLIO MES S201. Suitable TDAE oils are commercially available from EXXONMOBIL as TYREX 20, from BP as VIVATEC 500, VIVATEC 180 and ENERTHENE 1849, and from REPSOL as EXTENSOIL 1996. Suitable heavy naphthenic oils can be obtained as SHELLFLEX 794, ERGON BLACK OIL, ERGON H2000, CROSS C2000, CROSS C2400 and SAN JOAQUIN 2000L. Suitable low PCA oils also include oils from various plant sources, such as oils harvested from vegetables, nuts and seeds. Non-limiting examples include, but are not limited to, soybean oil or soybean oil, sunflower oil (including high oleic sunflower oil with an oleic acid content of at least 60%, at least 70% or at least 80%), safflower oil, corn oil, linseed oil, cottonseed oil, rapeseed oil, cashew nut oil, sesame oil, camellia oil, jojoba oil, macadamia oil, coconut oil and palm oil.Generally speaking, for most applications, the total amount of oil used in the tire rubber composition is in the range of 1 phr to 70 phr (e.g., 1 phr, 2 phr, 3 phr, 4 phr, 5 phr, 10 phr, 15 phr, 20 phr, 25 phr, 30 phr, 35 phr, 40 phr, 45 phr, 50 phr, 55 phr, 60 phr, 65 phr or 70 phr), 2 phr to 60 phr, 3 phr to 50 phr. In certain embodiments of the third embodiment, the tire rubber composition contains only a limited amount of oil, such as less than 10 phr (e.g., 9 phr, 8 phr, 7 phr, 6 phr, 5 phr, 4 phr, 3 phr, 2 phr, 1 phr or 0 phr), less than 5 phr, 1 phr to 5 phr, or even 0 phr.

[0121] Various types of hydrocarbon resins can be used, including plasticizing resins. As used herein, the term plasticizing resin refers to a compound that is solid at room temperature (23°C) and is miscible in a rubber composition in an amount of generally at least 5 phr. In certain embodiments of the third embodiment, the rubber composition comprises at least one resin of about 5 phr to about 60 phr (e.g., 5 phr, 10 phr, 15 phr, 20 phr, 25 phr, 30 phr, 35 phr, 40 phr, 45 phr, 50 phr, 55 phr or 60 phr), 5 phr to 60 phr, 5 phr to 20 phr, about 25 phr to about 60 phr, 25 phr to 60 phr, or 30 phr to 50 phr; in certain such embodiments, at least one hydrocarbon resin is a plasticizing resin. Generally speaking, a plasticizing resin will be used as a diluent and can be contrasted with a generally immiscible tackifying resin, and can migrate to the surface of a rubber composition providing tack. In certain embodiments of the third embodiment, a plasticizing resin is used, which includes a hydrocarbon resin and can be aliphatic, aromatic or aliphatic / aromatic, depending on the monomers contained therein. Examples of plasticizing resins suitable for the rubber composition of the third embodiment include, but are not limited to, cyclopentadiene (abbreviated as CPD) or dicyclopentadiene (abbreviated as DCPD) homopolymer or copolymer resins, terpene homopolymer or copolymer resins and C5 fraction homopolymer or copolymer resins. Such resins can be used, for example, alone or in combination. In certain embodiments of the third embodiment, a plasticizing resin that satisfies at least one of the following can be used: Tg greater than 30°C (preferably greater than 40°C and / or not greater than 120°C or not greater than 100°C), a number average molecular weight (Mn) between 400 g / mol and 2000 g / mol (preferably 500 g / mol-2000 g / mol), and a polydispersity index (PI) less than 3 (preferably less than 2), wherein PI=Mvv / Mn, and Mvv is the weight average molecular weight of the resin. The Tg of the resin can be measured by DSC (differential scanning calorimetry) according to ASTM D3418 (1999). The Mw, Mn and PI of the resin can be determined by size exclusion chromatography (SEC), which uses THF (35°C; concentration 1 g / l; flow rate 1 ml / min; solution filtered through a filter with a porosity of 0.45 μm before injection; molar calibration using polystyrene standards; 3 "Waters" column sets ("Styragel" HR4E, HR1 and HR0.5) in series; detected by a differential spectrometer ("Waters 2410") and its associated operating software ("Waters Empower").

[0122] Curing package for tire rubber composition

[0123] In some embodiments of the third embodiment, the tire rubber composition further comprises (also comprises) a curing package. Generally speaking, the curing package will comprise at least one of the following: a vulcanizing agent, a vulcanization accelerator, a vulcanization activator (e.g., zinc oxide, stearic acid, etc.), a vulcanization inhibitor, and a scorch retarder. In certain embodiments, the curing package comprises at least one vulcanizing agent, at least one vulcanization accelerator, at least one vulcanization activator, and optionally a vulcanization inhibitor and / or a scorch retarder. Vulcanization accelerators and vulcanization activators are used as catalysts for vulcanizing agents. Various vulcanization inhibitors and scorch retarders are known in the art and can be selected by those skilled in the art based on desired vulcanization characteristics.

[0124] Examples of suitable types of vulcanizing agents used in some embodiments of the first embodiment to the fourth embodiment include, but are not limited to, sulfur or peroxide-based curing components. Examples of specific suitable sulfur-based vulcanizing agents include soluble sulfur for "rubber maker"; sulfur-supplying curing agents such as disulfide amines, polymerized polysulfides or sulfur olefin adducts; and insoluble polymerized sulfur. Preferably, the sulfur-based vulcanizing agent is a mixture of soluble sulfur or soluble and insoluble polymerized sulfur. Generally speaking, the vulcanizing agent can be used in an amount within the range of 0.1phr to 10phr, including 1phr to 7.5phr, including 1phr to 5phr, and preferably 1phr to 3.5phr.

[0125] Vulcanization accelerators are used to control the time and / or temperature required for vulcanization and improve the properties of the vulcanized rubber. Examples of suitable vulcanization accelerators include, but are not limited to, thiazole vulcanization accelerators, such as 2-mercaptobenzothiazole, 2,2'-dithiobis(benzothiazole) (MBTS), N-cyclohexyl-2-benzothiazole-sulfenamide (CBS), N-tert-butyl-2-benzothiazole-sulfenamide (TBBS), etc.; guanidine vulcanization accelerators, such as diphenylguanidine (DPG), etc.; thiuram vulcanization accelerators; carbamate vulcanization accelerators; etc. Typically, the amount of vulcanization accelerator used is in the range of 0.1phr to 10phr, preferably 0.5phr to 5phr.

[0126] Vulcanization activator is an additive for supporting vulcanization. Conventionally, vulcanization activator comprises both inorganic component and organic component. Zinc oxide is the most widely used inorganic vulcanization activator. Conventionally, various organic vulcanization activators are used, including zinc salts of stearic acid, palmitic acid, lauric acid and the above. Generally speaking, the consumption of vulcanization activator is 0.1phr to 6phr (for example, 0.1phr, 0.5phr, 1phr, 1.5phr, 2phr, 2.5phr, 3phr, 3.5phr, 4phr, 4.5phr, 5phr, 5.5phr or 6phr), preferably in the scope of 0.5phr to 4phr (for example, 0.5phr, 1phr, 1.5phr, 2phr, 2.5phr, 3phr, 3.5phr or 4phr).

[0127] Vulcanization inhibitors are used to control the vulcanization process and usually delay or inhibit vulcanization until the desired time and / or temperature is reached. Common vulcanization inhibitors include, but are not limited to, PVI (cyclohexylthiophthalimide) from Santogard. Generally speaking, the amount of vulcanization inhibitor is 0.1 phr to 3 phr, preferably 0.5 phr to 2 phr.

[0128] Other ingredients for tire rubber compositions

[0129] Various other ingredients that may be optionally added to the tire rubber composition of the third embodiment disclosed herein include waxes, processing aids, tackifying resins, reinforcing resins and peptizers, and antioxidants.

[0130] In certain preferred embodiments of the third embodiment, the tire rubber composition is free of (i.e., contains less than 0.1 phr or more preferably 0 phr) metal salts of fatty acids having 1 to 36 carbon atoms (or 5 to 25 or 10 to 20 carbon atoms). Exemplary such fatty acid salts include salts of the following fatty acids: formic acid, acetic acid, propionic acid, butyric acid, valeric acid, octanoic acid, dodecanoic acid, octanoic acid, stearic acid, lauric acid, oleic acid, and eicosanoids. Exemplary such fatty acids include those having alkali metals, alkaline earth metals, or transition metals, such as the following: lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, and barium.

[0131] In certain preferred embodiments of the third embodiment, the tire rubber composition does not contain (i.e., contains less than 0.1 phr or more preferably 0 phr) aliphatic primary amine or alicyclic primary amine compounds. Such amine compounds are known to be used in rubber compositions to produce improved elongation at break properties. Exemplary such amines include heptylamine, stearylamine, dodecylamine, cyclohexylamine and 2-ethylhexylamine.

[0132] In certain particularly preferred embodiments of the third embodiment, the tire rubber composition does not contain both the metal salt of the above-mentioned fatty acid and the primary aliphatic amine / alicyclic primary amine compound.

[0133] Method for preparing a rubber composition

[0134] The rubber composition according to the third embodiment disclosed herein can generally be formed in the following manner: by methods known in the art, such as, for example, by kneading the ingredients together in a Banbury mixer or on a grinding roller, the ingredients of the rubber composition (as disclosed above) are mixed together. These methods generally include at least one non-productive masterbatch mixing stage and a final productive mixing stage. The term "non-productive masterbatch stage" is known to those skilled in the art, and is generally understood to be a mixing stage in which no vulcanizing agent or vulcanization accelerator is added. The term final productive mixing stage is also known to those skilled in the art, and is generally understood to be a mixing stage in which a vulcanizing agent and a vulcanization accelerator are added to the rubber composition. In certain embodiments of the third embodiment, a non-productive masterbatch mixing stage can be used in the preparation of the rubber composition. In certain embodiments of the third embodiment, more than one non-productive masterbatch mixing stage is used. In certain embodiments of the third embodiment utilizing silica and a silica coupling agent, more than one non-productive masterbatch mixing stage is used, and at least a portion of the silica filler is added to a second non-productive masterbatch mixing stage (also referred to as a regrind stage); in certain such embodiments, all of the silica coupling agent (along with at least a portion of the silica filler) is added only in the second non-productive masterbatch mixing stage, and no silica coupling agent is added in the initial non-productive masterbatch mixing stage.

[0135] In certain embodiments of the third embodiment, the masterbatch mixing stage includes at least one of series mixing or intermeshing mixing. In-line mixing can be understood to include the use of a mixer with two mixing chambers, each of which has a set of mixing rotors; typically, the two mixing chambers are stacked together, wherein the upper mixing is the main mixer, and the lower mixer receives the batch material from the upper or main mixer. In certain embodiments, the main mixer utilizes an intermeshing rotor, and in other embodiments, the main mixer utilizes a tangential rotor. Preferably, the lower mixer utilizes an intermeshing rotor. Intermeshing mixing can be understood to include the use of a mixer with an intermeshing rotor. An intermeshing rotor refers to a group of rotors in which the large diameter of one rotor in a group interacts with the small diameter of the opposite rotor in the group so that the rotors intermesh with each other. Due to the interaction between the rotors, the intermeshing rotor must be driven at a uniform speed. In contrast to the intermeshing rotor, the tangential rotor refers to a group of rotors in which each rotor rotates independently of the other in a cavity (which may be referred to as a side). Typically, a mixer with a tangential-type rotor will include a plunger, whereas a plunger is not necessary in a mixer with an intermeshing-type rotor.

[0136] In certain embodiments of the third embodiment, the rubber composition is prepared by a method having a non-productive masterbatch mixing stage at a temperature of about 130°C to about 200°C. In certain embodiments of the third embodiment, the rubber composition is prepared by a method of a final productive mixing stage performed at a temperature below the vulcanization temperature to avoid undesired pre-curing of the rubber composition. Therefore, the temperature of the productive mixing stage should not exceed about 120°C, and is typically about 40°C to about 120°C, or about 60°C to about 110°C, and in particular about 75°C to about 100°C.

[0137] Example

[0138] The following examples illustrate specific and exemplary embodiments and / or features in the embodiments of the present disclosure. These embodiments are provided for illustrative purposes only and should not be construed as limitations of the present disclosure. Without departing from the essence and scope of the embodiments disclosed herein, multiple modifications to these specific embodiments are possible. It should be particularly understood that modified high-cis polydiene polymers prepared using different conjugated diene monomers, using / having different functional compounds (i.e., according to Structure I or Structure II, as discussed above), and using / having different coupling agents (as discussed above), or using / having different functional compounds and coupling agents can be prepared and used in rubber compositions. It should also be understood that high-cis polydiene polymers or other such polymers (as mentioned above) can be used in rubber compositions together with ingredients (e.g., additional rubber, filler, curing package ingredients) that are different from those used in the examples in relative amounts, composition, or both (i.e., as fully disclosed in the preceding paragraphs).

[0139] As explained in detail below, high cis polydiene polymers were produced in Examples 1-4. Example 4 can be considered as an exemplary of the second embodiment and a modified high cis polydiene polymer produced according to a method that is exemplary of the first embodiment, while Examples 1-3 should be considered as comparative or control examples. The polymers produced in Examples 1-4 were then used to prepare the rubber composition in Example 5. Rubber composition 5-4 can be considered as an example of the third embodiment disclosed herein, while Examples 5-1, 5-2, and 5-3 should be considered as comparative or control examples.

[0140] General polymerization process

[0141] Example 1: To a dry 2 gallon reactor purged with nitrogen was added 1184 grams of hexane and 2893 grams of a 21.4 wt % 1,3-butadiene (Bd) in hexane to give a 15.0 wt % Bd in hexane solution (4128 grams or 11.45 moles Bd). The solution was maintained at 22°C. The preformed catalyst was prepared by mixing 7.17 milliliters of a 4.32 mole (M) methylaluminoxane in toluene solution, 1.7 grams of a 21.4 wt % 1,3-butadiene in hexane solution, 0.61 milliliters of a 0.508 M versatate neodymium carbonate in cyclohexane solution, 6.31 milliliters of a 1.03 M diisobutylaluminum hydride in hexane solution, and 1.16 milliliters of a 1.07 M diethylaluminum chloride in hexane solution. The catalyst was aged for 20 minutes and loaded into the reactor. The reactor jacket was then set to 65°C. About 60 minutes after the addition of the catalyst, the polymerization mixture was cooled to room temperature. The resulting polymer cement was quenched and coagulated with 12 liters of isopropanol containing 5 grams of 2,6-di-tert-butyl-4-methylphenol and then drum dried. The Mooney viscosity (ML) of the resulting polymer was determined at 100°C using an Alpha Technologies Mooney viscometer with a large rotor, a one-minute preheat time, and a four-minute run time. 1+4 ). Molecular weight and polydispersity were determined by gel permeation chromatography (GPC). The polymer microstructure of the polymers was measured by infrared spectroscopy. The properties of the resulting polymers are summarized in Table 1.

[0142] Example 2 : To a dry 2 gallon reactor purged with nitrogen was added 1294 grams of hexane and 2695 grams of a 21.8 wt % hexane solution of 1,3-butadiene (Bd) to give a 15.0 wt % hexane solution of Bd (4309 grams or 11.95 moles Bd). The solution was maintained at 22°C. The preformed catalyst was prepared by mixing 5.69 milliliters of a 4.32M toluene solution of methylaluminoxane, 1.5 grams of a 21.8 wt % hexane solution of 1,3-butadiene, 0.48 milliliters of a 0.508M versatate neodymium cyclohexane solution, 5.01 milliliters of a 1.03M hexane solution of diisobutylaluminum hydride, and 0.92 milliliters of a 1.07M hexane solution of diethylaluminum chloride. The catalyst was aged for 20 minutes and loaded into the reactor. The reactor jacket was then set to 65°C. About 60 minutes after the addition of the catalyst, the polymerization mixture was cooled to room temperature. The resulting polymer cement was quenched and coagulated with 12 liters of isopropanol containing 5 grams of 2,6-di-tert-butyl-4-methylphenol and then drum dried. The properties of the resulting polymer are summarized in Table 1.

[0143] Example 3: To a dry 2 gallon reactor purged with nitrogen was added 1308 grams of hexane and 2951 grams of a 21.9 wt % 1,3-butadiene (Bd) in hexane to give a 16.5 wt % Bd in hexane solution (4309 grams or 11.95 moles Bd). The solution was maintained at 22°C. The preformed catalyst was prepared by mixing 7.48 milliliters of a 4.32M methylaluminoxane solution in toluene, 1.7 grams of a 21.9 wt % 1,3-butadiene solution in hexane, 0.64 milliliters of a 0.508M versatate neodymium solution in cyclohexane, 6.59 milliliters of a 1.03M diisobutylaluminum hydride solution in hexane, and 1.21 milliliters of a 1.07M diethylaluminum chloride solution in hexane. The catalyst was aged for 20 minutes and loaded into the reactor. The reactor jacket was then set to 65°C. About 60 minutes after the addition of the catalyst, about 175 grams of the pseudo-active polymer cement was dripped into a nitrogen-purged bottle, then coagulated with isopropanol and dried on a drum dryer. The ML of the base polymer was 31.6. 18.5 milliliters of a 1.0M hexane solution of N-vinyl caprolactam (NVCL) [molar ratio of NVCL / Nd = 60] was added to the remaining polymer cement in the reactor. The mixture was further stirred at 65°C for 30 minutes. Then about 720 grams of the polymer cement was dripped into a nitrogen-purged bottle and quenched with 3 milliliters of a 12 weight percent isopropanol solution of 2,6-di-tert-butyl-4-methylphenol, coagulated with 2 liters of isopropanol containing 0.5 grams of 2,6-di-tert-butyl-4-methylphenol, and then drum dried. The properties of the resulting NVCL-modified polymer are summarized in Table 1.

[0144] Example 4: To the remainder of the NVCL-modified polymer cement synthesized in Example 3 was added 0.11 ml of pure (4.35 M) 1,1-bis(trichlorosilylmethyl)ethylene. The mixture was stirred at 65°C for another 30 minutes and then cooled to room temperature. The resulting polymer cement was quenched and coagulated with 12 liters of isopropanol containing 5 grams of 2,6-di-tert-butyl-4-methylphenol and then drum dried. The properties of the resulting polymer are summarized in Table 1.

[0145]

[0146]

[0147] 1 Functionalized compound: Neodymium molar ratio

[0148] 2 Molar ratio of coupling agent to Nd

[0149] 3 Measured by FTIR, as described above for cis-1,4 bond measurement

[0150] Example 5 : The polymers produced according to Examples 1-4 were used to prepare rubber compositions according to the formula provided in Table 2 below. The rubber composition of Example 5 was prepared using the mixing procedure set forth in Table 3.

[0151]

[0152]

[0153]

[0154] For each rubber composition of Example 5, the properties listed in Table 4 were measured as follows.

[0155] The viscosity disclosed herein is the actual dynamic viscosity measured using a rotorless Alpha Technologies RPA (Rubber Process Analyzer) instrument. The measurement was performed in accordance with the guidance of ASTM D 6204, but not strictly in accordance with ASTM D 6204. According to ASTM D 6204, a three-point frequency sweep was performed. The rubber composition was preheated at 130°C for 1 minute. According to the ASTM procedure, a strain sweep was performed at 130°C with 100% strain and 1 Hz. The recorded viscosity data is from a run performed at 266°F and G' at 0.2 minutes.

[0156] The bound rubber content test is used to determine the percentage of polymer that is bound to the filler particles in each rubber composition. The bound rubber is measured by immersing a small piece of the uncured raw material in a large excess of toluene for three days. The soluble rubber is extracted from the sample by the solvent. After three days, any excess toluene is drained off and the sample is air-dried and then dried in an oven at approximately 100°C to constant weight. The remaining pieces form a weakly cohesive gel containing the filler and some of the original rubber. The amount of rubber that remains with the filler is the bound rubber. The bound rubber content is then calculated according to the following formula:

[0157]

[0158] Where Wd is the weight of the dry gel, F is the weight of the filler in the gel or solvent insoluble material (same as the weight of filler in the original sample), and R is the weight of the polymer in the original sample. The bound rubber percentage provides a measure of the interaction between the rubber (polymer) and the filler in the rubber composition, wherein a relatively high bound rubber percentage indicates an increased and beneficial interaction between the rubber (polymer) and the filler.

[0159] · The tan δ value was measured using a strain sweep test performed with the Advanced Rheological Measurement Extension System (ARES) of TA Instruments. The specimen had a cylindrical geometry of 14.4 mm in length and 7.8 mm in diameter. The test was performed using a frequency of 10 rad / sec. The strain was scanned from 0.1% to 16%, and the temperature started at 22°C, and increased to 60°C, and maintained at 60°C. The measured values ​​of each rubber composition at 2% and 10% strain at 60°C were recorded. The tan δ of the rubber composition at 60°C indicates its rolling resistance when incorporated into the tire tread. The tan δ value is expressed as a scaled value (calculated by comparing the value of a given embodiment with the value of control polymer 1), wherein values ​​above 100 are considered to be improved. Since the lower tan δ values ​​at 60°C are considered to be improved, the scaled values ​​are calculated as (control / value) x100.

[0160]

[0161] As can be seen from the data in Table 4, rubber composition 5-4 exhibits improved properties, namely, tan δ value at 60°C, higher Mooney viscosity and higher bound rubber, compared to control example 5-1 (using the polymer of Example 1) or control example 5-2 (using the polymer of Example 2).

[0162] Although not reported in the data above, the polymer of Example 4 will have improved cold flow properties compared to the polymers of Examples 1-3. In other words, the polymer of Example 4 (compared to the polymers of Examples 1-3) will experience less cold flow. The improvement in cold flow properties can be predicted by the combination of higher Mooney viscosity and higher T80 values. It is worth noting that among the polymers produced in Examples 1-4, the polymer of Example 4 has the highest Mooney viscosity and the highest T80 value (Table 1 values). Therefore, the use of a functionalized compound of Formula I (e.g., NVCL) or a combination of Formula II and a coupling agent of Formula III or Formula IV will produce a modified high cis polybutadiene having a higher Mooney viscosity and T80 value than high cis polybutadiene prepared using only functionalized compounds of Formula I or Formula II (assuming that both polymers have the same Mw and Mn values). (The T80 stress relaxation time (T80) of the polymer samples (listed in Table 1) is measured from (at the ML of the polymer 1+4 During the Mooney viscosity test, when measuring ML 1+4 The ML at 100°C required to reduce the value by 80% 1+4The cold flow of a polymer or rubber composition sample can be measured by subjecting a sample of a given polymer / rubber composition to a compressive force and measuring the height of the sample before and after the compressive force is applied. When subjected to a compressive force, a sample that experiences less cold flow (or has improved cold flow characteristics) will keep more of its initial height. The cold flow of a polymer may be important in allowing stable storage of a polymer (and avoiding the undesirable flow of a polymer in bundle form).

[0163] The present application discloses several numerical range limitations, which support any range within the disclosed numerical range, even if the precise range limitation is not stated verbatim in the specification, because the embodiments of the compositions and methods disclosed herein can be implemented throughout the disclosed numerical range. For the use of substantially any plural or singular terminology herein, those skilled in the art can convert from the plural form to the singular form or from the singular form to the plural form, as long as it is appropriate according to the context or application. For the sake of clarity, various singular or plural arrangements can be explicitly set forth herein.

[0164] In general, those skilled in the art will understand that the terms used herein, particularly in the appended claims, are generally intended to be "open" terms. For example, the term "comprising" should be understood as "including but not limited to," the term "having" should be understood as "having at least," and the term "including" should be understood as "including but not limited to." Those skilled in the art will also understand that if a specific number of introduced claim recitations is desired, such intent will be clearly stated in the claim, and no such intent exists without such a statement. For example, for ease of understanding, the following appended claims may contain the use of the introductory phrases "at least one" and "one or more" to introduce claim recitations. However, the use of such phrases should not be construed as implying that the introduction of a claim recitation by the indefinite article "a" or "an" limits any particular claim containing such introduced claim recitation to an invention containing only one such recitation, even when the same claim includes the introductory phrase "one or more" or "at least one" and an indefinite article such as "a" or "an" (e.g., "a" or "an" should generally be understood to mean "at least one" or "one or more"); the same applies to the use of definite articles to introduce claim recitations. Furthermore, even if a specific number of introduced claim recitations is expressly stated, those skilled in the art will recognize that such recitations should generally be understood to mean at least the stated number (e.g., merely stating "two recitations" without other modifiers generally means at least two recitations, or two or more recitations). Furthermore, in those cases where a convention similar to "at least one of A, B, and C, etc." is used, such construction is generally intended to be understood by those skilled in the art (e.g., "a system having at least one of A, B, and C" will include, but is not limited to, a system having only A, a system having only B, a system having only C, a system having A and B, a system having A and C, a system having B and C, and / or a system having A, B, and C, etc.). Those skilled in the art will also understand that any transitional conjunction or phrase that actually gives two or more alternatives, whether in the specification, claims, or drawings, should be understood to contemplate the possibility of including one of these items, any of these items, or both. For example, the phrase "A or B" will be understood to include the possibility of "A" or "B" or "A and B". All references, including but not limited to patents, patent applications, and non-patent literature, are hereby incorporated by reference in their entirety. Although various aspects and embodiments of compositions and methods have been disclosed herein, other aspects and embodiments will be apparent to those skilled in the art. The various aspects and embodiments disclosed herein are for purposes of illustration and are not intended to be limiting, with the true scope and spirit being indicated by the claims.

Claims

1. A modified high-cis polydiene polymer comprising: a. at least one polymer chain produced by polymerization of a certain amount of conjugated diene monomers and bearing a residue from a functionalized compound selected from: i. wherein n is an integer from 1 to 16, or ii. Where R 1 is selected from H and a C1-C20 hydrocarbon group, and R 2 is selected from H and C1-C20 hydrocarbon groups, b. a residue from a coupling agent having at least one polymer chain of (a) bonded thereto, wherein the coupling agent is selected from a silicon halide having formula III or IV as described below Si(R*) n (Y) 4-n III wherein each R* is independently selected from a monovalent organic group having 1 to 20 carbon atoms, and each Y is a halogen atom or a C1-C 10 An alkoxy group, and n is an integer from 0 to 3, R**[SiY3]2IV wherein R** is a hydrocarbylene group having 1 to 20 carbon atoms, and each Y is a halogen atom or a C1-C 10 The alkoxy group, and said residue from said coupling agent has at least one halide which is replaced by the polymer chain of (a), The modified high cis polydiene has a cis 1,4-bond content of at least 92% and a Mooney viscosity ML of 40 to 80 at 100°C. 1+4 , and wherein the cis 1,4-bond content is determined by FTIR.

2. The modified high cis polydiene polymer of claim 1, wherein the polymer chain is based on at least 99 weight percent conjugated 1,3-diene monomers.

3. The modified high-cis polydiene polymer according to claim 1 or claim 2, wherein each of the following is satisfied: a. The polymer has a Mw of 150,000 g / mol to 375,000 g / mol; b. The polymer has an Mn of 80,000 g / mol to 250,000 g / mol; c. the polymer has a Mw / Mn of 1.5 to 3.5; and d. The polymer has a Mooney viscosity ML of 40 to 80 at 100°C 1+4 , where Mw and Mn are determined by GPC using polystyrene standards.

4. The modified high-cis polydiene polymer of claim 1 or claim 2, wherein the residue of (a) is derived from a functionalized compound of formula (I).

5. The modified high cis polydiene polymer according to claim 4, wherein the functionalized compound of formula (I) is selected from N-vinyl caprolactam, N-vinyl pyrrolidinedione (also known as N-vinyl pyrrolidinedione, 1-vinyl-2-pyrrolidinedione and N-vinyl pyrrolidone), N-vinyl piperidone (also known as N-vinyl-2-piperidone or 1-vinyl-2-piperidone), N-vinyl-4-butyl pyrrolidone, N-vinyl-4-propyl pyrrolidone, N-vinyl-4-methyl caprolactam, N-vinyl-6-methyl caprolactam, N-vinyl-7-butyl caprolactam, and combinations thereof.

6. The modified high-cis polydiene polymer of claim 1 or claim 2, wherein the residue of (a) is derived from a functionalized compound of formula (II).

7. A method for preparing a modified high-cis polydiene polymer according to any one of claims 1 to 6, the method comprising: a. providing a lanthanide-based catalyst system, the lanthanide-based catalyst system comprising (i) a lanthanide compound, (ii) an alkylating agent and (iii) a halogen source, wherein (iii) may optionally be provided by (i), (ii), or both (i) and (ii); b. polymerizing a certain amount of conjugated diene monomer using the catalyst system of (a) to produce a polymer chain having an active end; c. reacting the active terminal polymer chain from (b) with a functionalized compound selected from formula (I) or formula (II), thereby producing an intermediate product comprising a polymer chain end-functionalized with a residue from the first functionalizing compound; d. coupling the intermediate product from (c) using a coupling agent selected from silicon halides having formula III or IV, Thus, a modified high cis polydiene polymer is produced, wherein the modified high cis polydiene polymer has a cis 1,4-bond content of at least 92% and a Mooney viscosity ML of 40 to 80 at 100°C. 1+4 , and wherein the cis 1,4-bond content is determined by FTIR.

8. The method of claim 7, wherein the amount of conjugated diene monomer comprises at least 99 weight percent conjugated 1,3-diene.

9. A tire rubber composition having improved rolling resistance, comprising: a. 10 to 100 phr of a modified high cis polydiene polymer according to any one of claims 1 to 6 or produced by the process of claim 7 or claim 8, and b. 0 to 90 phr of at least one polymer containing a diene monomer selected from the group consisting of natural rubber, polyisoprene, styrene-butadiene copolymer, styrene-butadiene-isoprene rubber, isoprene-butadiene rubber, and combinations thereof; and c. 10 to 100 phr of at least one carbon black filler and 0 to 100 phr of at least one silica filler, The tire rubber composition is contained in a tire tread.

10. The rubber composition of claim 9, wherein the 10 to 100 phr of at least one carbon black filler includes 10 to 70 phr of reinforcing carbon black, and the silica filler is present in an amount of 5 to 70 phr.

Images