Highly functionalized and stable dihydrocarbyloxysilyl polydienes and polydiene copolymers

Abstract

1. A polymeric composition comprising a plurality of hydrocarbyloxysilyl-terminated polydienes or polydiene copolymers, wherein the polymeric composition has a Mooney viscosity (ML @ 100°C) after aging of from about 40 to about 105. 1+4 ), wherein the polymer composition comprises from about 10 to about 95 mole percent of said hydrocarbyloxysilyl terminated polydiene or polydiene copolymer, said hydrocarbyloxysilyl terminated polydiene or polydiene copolymer being formed by reacting a reactive polydiene or polydiene copolymer with a dihydrocarbyloxysilyl endstopper.

Description

[Technical field]

[0001] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention is directed to dihydrocarbyloxysilyl-functionalized polydienes and polydiene copolymers that are characterized by high functionality and long-term stability against deleterious Mooney growth. [Background technology]

[0002] In the manufacture of tires, particularly tire treads, it is known to use modified polymers, such as those containing terminal functionalization. Rubber vulcanizates prepared with these modified polymers have been observed to exhibit reduced hysteresis loss and reduced Payne effect, which is the loss of mechanical energy due to deagglomeration of fillers.

[0003] Polymer modification is often accomplished by reacting a living polymer species with a compound capable of imparting functional groups to the ends of the polymer chain. For example, U.S. Patent No. 6,369,167 teaches preparing diene polymers, such as random copolymers of butadiene and styrene, by anionic polymerization techniques and then terminating the polymer with an imine-containing hydrocarbyloxysilane compound. The terminating compound, also referred to as a terminal modifier, is used in an amount of 0.25 to 3 moles per mole of organolithium compound used to initiate the anionic polymerization.

[0004] A similar end-modifier is disclosed in U.S. Patent No. 7,683,151, which teaches the use of 0.3 molar equivalents or more based on apparent active sites. Following the modification reaction, the patent teaches the addition of a condensation promoter (e.g., tin carboxylate) to condense the hydrocarbyloxysilane residues at the polymer chain ends, thereby resulting in polymer coupling. Upon completion, the resulting modified polymer has a Mooney viscosity (ML at 100°C) of 10 to 150. 1+4 ).

[0005] Hydrocarbyloxysilane residues have been found to increase the Mooney viscosity after aging, and this increase is believed to be due to coupling occurring between functional polymers in the presence of water. This coupling is believed to be initiated when water hydrolyzes the hydrocarbyloxysilane substituents to form siloxy substituents, which then condense and couple with the siloxy substituents of each polymer. U.S. Pat. No. 6,255,404 teaches a remedy for this increase in Mooney viscosity by treating the modified polymer with an alkylalkoxysilane (e.g., octyltriethoxysilane), thereby stabilizing the hydrocarbyloxysilane end groups. The alkylalkoxysilane may be added in amounts of 1 to 20 moles per mole of initiator, but if present in an amount greater than the equivalent amount of alkoxysilane functionality, a decrease in polymer viscosity is observed due to the plasticizing effect of the alkylalkoxysilane (i.e., excess alkylalkoxysilane acts as an oil). Summary of the Invention

[0006] One or more embodiments of the present invention provide a polymeric composition comprising a plurality of hydrocarbyloxysilyl terminated polydienes or polydiene copolymers, the polymeric composition having an aged Mooney (ML @ 100° C.) of from about 40 to about 105. 1+4 ), the polymer composition comprising from about 10 to about 95 mole percent of said hydrocarbyloxysilyl terminated polydiene or polydiene copolymer, said hydrocarbyloxysilyl terminated polydiene or polydiene copolymer being a reactive polydiene or polydiene copolymer having the formula:

[0007] [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , and R 5 are each independently a hydrocarbyl group; R 6is a dihydrocarbyl group),

[0008] Another embodiment of the present invention is a method for preparing a functionalized polydiene or polydiene copolymer polymer composition, comprising: reacting a reactive polydiene or polydiene copolymer with a compound having the formula:

[0009] [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , and R 5 are each independently a hydrocarbyl group; R 6 is a dihydrocarbyl group), thereby forming a functionalized polydiene or polydiene copolymer.

[0010] Yet another embodiment of the present invention is a vulcanizable rubber composition comprising: (i) a reactive polydiene or polydiene copolymer having the formula:

[0011] [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , and R 5 are each independently a hydrocarbyl group; R 6 is a dihydrocarbyl group), (ii) a silica filler, and (iii) a curing agent.

[0012] Yet another embodiment of the present invention is a vulcanizate comprising: (i) a reactive polydiene or polydiene copolymer having the formula:

[0013] [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , and R 5 are each independently a hydrocarbyl group; R 6 is a dihydrocarbyl group), (ii) a silica filler, and (iii) a curing agent. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] The present invention is based, at least in part, on the discovery of a process for producing hydrocarbyloxysilyl-functionalized polydienes and polydiene copolymers that are characterized by desirable rheological properties (e.g., Mooney viscosity) and result in rubber vulcanizates with advantageous dynamic properties. Although the prior art contemplates hydrocarbyloxysilyl-functionalized polydienes and polydiene copolymers and their use in rubber vulcanizates, the usefulness of these functionalized polymers has been hindered by their time-dependent rheological properties, necessitating the use of stabilizers. It has been observed that the degree of functionalization (e.g., using imine-containing hydrocarbyloxysilanes) is directly proportional to the amount of stabilizer required (e.g., using octyltriethoxysilane), and that the tradeoff between functionalization and stabilization use leans toward lowering the level of functionalization from a polymer processing perspective. However, it is believed that at lower levels of functionalization, potential benefits in vulcanizate properties are lost. The present invention provides the unexpected advantage of desirable rheological properties and improved dynamic properties over previously used techniques.

[0015] Preparation of dihydrocarbyloxysilyl-functionalized polydienes. In one or more embodiments, hydrocarbyloxysilyl-functionalized polydienes and polydiene copolymers, which may also be referred to as functionalized hydrocarbyloxysilyl polydienes and polydiene copolymers, are prepared by (i) anionic synthesis of reactive polydienes and / or polydiene copolymers, (ii) reacting the reactive polydienes and / or polydiene copolymers with a dihydrocarbyloxysilyl functionalizing agent to thereby form functionalized hydrocarbyloxysilyl polydiene and / or polydiene copolymers, (iii) optionally treating the functionalized hydrocarbyloxysilyl polydiene and / or polydiene copolymer with a stabilizing agent, and (iv) isolating the functionalized hydrocarbyloxysilyl polydiene and / or polydiene copolymer. As used herein, hydrocarbyloxysilyl-functionalized polydienes or hydrocarbyloxysilyl-terminated polydienes or copolymers refer to polydienes and / or copolymers functionalized with a dihydrocarbyloxysilyl functionalizing agent.

[0016] Anionic synthesis of reactive polydienes. In one or more embodiments, the reactive polydienes and polydiene copolymers are prepared by anionically polymerizing a diene monomer, optionally together with a monomer copolymerizable therewith. In one or more embodiments, the polymerization comprises anionically polymerizing a conjugated diene monomer (e.g., butadiene) and a vinyl aromatic monomer (e.g., styrene) in solution to provide a polymerization mixture comprising polydiene polymers and copolymers having reactive polymer chain ends.

[0017] The preparation of polymers by using anionic polymerization techniques is generally known. The important mechanistic features of anionic polymerization are described in books (e.g., Hsieh, HL; Quirk, RP Anionic Polymerization: Principles and Practical Applications; Marcel Dekker: New York, 1996) and articles (e.g., Hadjichristidis, N.; Pitsikalis, M.; Pispas, S.; Iatrou, H.; Chem. Rev. 2001, 101(12), 3747-3792). Anionic initiators can advantageously produce polymers with reactive chain ends (e.g., living polymers) that can be reacted with additional monomers for further chain growth or reacted with certain functionalizing agents to give functionalized polymers before quenching. Polymers with reactive polymer chain ends are sometimes simply referred to as reactive polymers. As will be appreciated by those skilled in the art, these reactive polymers contain reactive chain ends, which are believed to be ionic, at which a reaction occurs between a functionalizing agent and the reactive chain end of the polymer, thereby imparting functionality or functional groups to the polymer chain end, or allowing multiple polymers to be coupled together.

[0018] Monomers that can be anionically polymerized to form these polymers include conjugated diene monomers, which can optionally be copolymerized with other monomers, such as vinyl-substituted aromatic monomers. Examples of conjugated diene monomers include 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, and 2,4-hexadiene. Mixtures of two or more conjugated dienes may also be utilized in the copolymerization. Examples of monomers that can be copolymerized with conjugated diene monomers include vinyl-substituted aromatic compounds, such as styrene, p-methylstyrene, α-methylstyrene, and vinylnaphthalene.

[0019] The practice of the present invention is not limited by the selection of any particular anionic initiator. Exemplary anionic initiators include organolithium compounds. In one or more embodiments, the organolithium compounds may include a heteroatom. In these or other embodiments, the organolithium compounds may include one or more heterocyclic groups. Types of organolithium compounds include alkyllithium compounds, aryllithium compounds, and cycloalkyllithium compounds. Specific examples of organolithium compounds include ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, n-amyllithium, isoamyllithium, and phenyllithium. Still other anionic initiators include organosodium compounds such as phenylsodium and 2,4,6-trimethylphenylsodium.

[0020] Anionic polymerization may be carried out in polar solvents, non-polar solvents, and mixtures thereof. In one or more embodiments, a solvent may be used as a carrier to dissolve or suspend the initiator to facilitate delivery of the initiator to the polymerization system.

[0021] In one or more embodiments, suitable solvents include organic compounds that do not undergo polymerization or incorporation into the propagating polymer chain during polymerization of monomers in the presence of a catalyst. In one or more embodiments, these organic species are liquid at ambient temperature and pressure. In one or more embodiments, these organic solvents are inert to the catalyst. Exemplary organic solvents include hydrocarbons with low or relatively low boiling points, such as aromatic, aliphatic, and cycloaliphatic hydrocarbons. Non-limiting examples of aromatic hydrocarbons include benzene, toluene, xylene, ethylbenzene, diethylbenzene, and mesitylene. Non-limiting examples of aliphatic hydrocarbons include n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, isopentane, isohexane, isopentane, isooctane, 2,2-dimethylbutane, petroleum ether, kerosene, and mineral spirits. Non-limiting examples of cycloaliphatic hydrocarbons include cyclopentane, cyclohexane, methylcyclopentane, and methylcyclohexane. Mixtures of the above hydrocarbons can also be used. The low boiling point hydrocarbon solvent is typically separated from the polymer when the polymerization is completed. Other examples of organic solvents include high molecular weight, high boiling point hydrocarbons, such as paraffinic oils, aromatic oils, or other hydrocarbon oils that are commonly used in oil-extending polymers. Because these hydrocarbons are non-volatile, they typically do not need to be separated and remain entrapped within the polymer.

[0022] Anionic polymerization may be carried out in the presence of a randomizer (sometimes referred to as a polar coordinator) or vinyl modifier. As will be appreciated by those skilled in the art, these compounds may play a dual role, aiding in the randomization of comonomers throughout the polymer chain and / or modulating the vinyl content of diene-derived mer units. Compounds useful as randomizers include those with oxygen or nitrogen heteroatoms and non-bonding electron pairs. Examples include linear and cyclic oligomeric oxolanyl alkanes; dialkyl ethers of mono- and oligoalkylene glycols (also known as glyme ethers); "crown" ethers; tertiary amines; linear THF oligomers; and the like. Linear and cyclic oligomeric oxolanyl alkanes are described in U.S. Pat. Nos. 4,429,091 and 9,868,795, which are incorporated herein by reference. Specific examples of compounds useful as randomizers include 2,2-bis(2'-tetrahydrofuryl)propane, 1,2-dimethoxyethane, N,N,N',N'-tetramethylethylenediamine (TMEDA), tetrahydrofuran (THF), 1,2-dipiperidylethane, dipiperidylmethane, hexamethylphosphoramide, N-N'-dimethylpiperazine, diazabicyclooctane, dimethyl ether, diethyl ether, tri-n-butylamine, and mixtures thereof. In other embodiments, potassium alkoxides can be used to randomize the styrene distribution.

[0023] The amount of randomizer to be used may depend on a variety of factors, such as the desired polymer microstructure, the monomer to comonomer ratio, the polymerization temperature, and the nature of the particular randomizer used, In one or more embodiments, the amount of randomizer used may range from 0.01 to 100 moles per mole of anionic initiator.

[0024] The introduction of the anionic initiator and the randomizer into the polymerization system can be accomplished by a variety of methods. In one or more embodiments, the anionic initiator and the randomizer can be added separately to the monomer to be polymerized, either stepwise or simultaneously.

[0025] As discussed above, reactive polymers are produced by polymerizing a conjugated diene monomer together with a monomer copolymerizable therewith in the presence of an effective amount of an initiator. Introduction of the initiator, conjugated diene monomer, comonomer, and solvent forms a polymerization mixture in which the reactive polymer is formed. Polymerization in a solvent produces a polymerization mixture in which the polymer product is dissolved or suspended in the solvent. This polymerization mixture is sometimes referred to as a polymer cement.

[0026] The amount of initiator to be used may depend on the interplay of various factors, such as the type of initiator used, the purity of the components, the polymerization temperature, the desired polymerization rate and conversion, the desired molecular weight, and many other factors. In one or more embodiments, the amount of initiator used may be expressed as millimoles of initiator per weight of monomer. In one or more embodiments, the initiator loading may vary from about 0.05 to about 50 millimoles, in other embodiments from about 0.1 to about 25 millimoles, in still other embodiments from about 0.2 to about 2.5 millimoles, and in other embodiments from about 0.4 to about 0.7 millimoles of initiator per 100 grams of monomer.

[0027] In one or more embodiments, the polymerization may take place in any conventional polymerization vessel known in the art. For example, the polymerization may take place in a conventional stirred tank reactor. In one or more embodiments, all of the ingredients used for the polymerization may be mixed in a single vessel (e.g., a conventional stirred tank reactor) and all steps of the polymerization process may take place in this vessel. In other embodiments, two or more of the ingredients may be pre-combined in one vessel and then transferred to another vessel where the polymerization of the monomer (or at least a majority of it) takes place. Since various embodiments of the present invention include the use of multiple reactors or reaction zones, the vessel in which the polymerization takes place (e.g., a tank reactor) may be referred to as the first vessel or first reaction zone.

[0028] The polymerization can be carried out as a batch, continuous, or semi-continuous process. In a semi-continuous process, monomer is intermittently charged as needed to replace already polymerized monomer. In one or more embodiments, the heat of polymerization can be removed by external cooling through a thermally controlled reactor jacket, internal cooling by vaporizing and condensing the monomer using a reflux condenser connected to the reactor, or a combination of the two methods. Conditions can also be controlled to carry out the polymerization under pressures of about 0.1 atm to about 50 atm, in other embodiments about 0.5 atm to about 20 atm, and in other embodiments about 1 atm to about 10 atm. In one or more embodiments, pressures at which the polymerization may be carried out include those that ensure that the majority of the monomer is in the liquid phase. In these or other embodiments, the polymerization mixture can be maintained under anaerobic conditions.

[0029] Polymerization temperature In one or more embodiments, the conditions under which the polymerization proceeds may be controlled to maintain a peak polymerization temperature of the polymerization mixture above 30° C., in other embodiments above 50° C., and in other embodiments above 70° C. In these or other embodiments, the conditions under which the polymerization proceeds may be controlled to maintain a peak polymerization temperature of the polymerization mixture below 120° C., in other embodiments below 110° C., and in other embodiments below 100° C. In one or more embodiments, the conditions under which the polymerization proceeds may be controlled to maintain the temperature of the polymerization mixture within the range of about −10° C. to about 200° C., in other embodiments from about 0° C. to about 150° C., and in other embodiments from about 20° C. to about 110° C.

[0030] Polymer properties before modification Reactive polymers may be characterized by their molecular weight, which may include number average molecular weight (Mn), weight average molecular weight (Mw), and peak molecular weight (Mp). As one skilled in the art will appreciate, molecular weight may be determined by using gel permeation chromatography (GPC) using appropriate calibration standards with suitable detectors, such as refractive index and / or ultraviolet detectors. For purposes of this specification, GPC measurements use polystyrene standards and polystyrene Mark-Hwink constants unless otherwise specified. Percent coupling may also be determined by GPC by measuring the area under the base peak (A) and the total area under the GPC curve (B). Percent coupling is then calculated as percent coupling=(BA) / A×100%.

[0031] In accordance with embodiments of the present invention, the molecular weight of the base polymer can be increased while remaining within the desired rheological properties (e.g., Mooney viscosity) given that it has been observed that the functionalizing agents of the present invention result in less coupling, particularly the coupling of three or more chains together.

[0032] In one or more embodiments, the reactive polymer has an Mp, which may also be referred to as the base Mp, greater than 160 kg / mol, in other embodiments greater than 180 kg / mol, in other embodiments greater than 200 kg / mol, in other embodiments greater than 215 kg / mol, in other embodiments greater than 230 kg / mol, in other embodiments greater than 240 kg / mol, in other embodiments greater than 250 kg / mol, in other embodiments greater than 260 kg / mol, and in other embodiments greater than 270 kg / mol. In these or other embodiments, the reactive polymer has an Mp less than 370 kg / mol, in other embodiments less than 360 kg / mol, in other embodiments less than 350 kg / mol, in other embodiments less than 330 kg / mol, in other embodiments less than 310 kg / mol, in other and other embodiments less than 280 kg / mol, and in other embodiments less than 250 kg / mol. In one or more embodiments, the reactive polymer has an Mp of about 160 to about 280 kg / mol, in other embodiments about 170 to about 260 kg / mol, in other embodiments about 200 to about 370 kg / mol, in other embodiments about 215 to about 360 kg / mol, in other embodiments about 230 to about 350 kg / mol, and in other embodiments about 180 to about 250 kg / mol.

[0033] In one or more embodiments, the reactive polymer has a Mn, which may also be referred to as base Mn, greater than 130 kg / mol, in other embodiments greater than 140 kg / mol, in other embodiments greater than 150 kg / mol, in other embodiments greater than 170 kg / mol, in other embodiments greater than 200 kg / mol, in other embodiments greater than 210 kg / mol, in other embodiments greater than 220 kg / mol, and in other embodiments greater than 230 kg / mol. In these or other embodiments, the reactive polymer has a Mn less than 350 kg / mol, in other embodiments less than 340 kg / mol, in other embodiments less than 330 kg / mol, in other embodiments less than 320 kg / mol, in other embodiments less than 300 kg / mol, in other embodiments less than 280 kg / mol, and in other embodiments less than 260 kg / mol. In one or more embodiments, the reactive polymer has a Mn of about 130 to about 300 kg / mol, in other embodiments about 140 to about 280 kg / mol, in other embodiments about 170 to about 350 kg / mol, in other embodiments about 200 to about 340 kg / mol, in other embodiments about 210 to about 330 kg / mol, and in other embodiments about 150 to about 260 kg / mol.

[0034] In one or more embodiments, the reactive polymer has a Mw, which may also be referred to as base Mw, greater than 180 kg / mol, in other embodiments greater than 190 kg / mol, in other embodiments greater than 200 kg / mol, in other embodiments greater than 230 kg / mol, in other embodiments greater than 245 kg / mol, in other embodiments greater than 260 kg / mol, in other embodiments greater than 275 kg / mol, and in other embodiments greater than 285 kg / mol. In these or other embodiments, the reactive polymer has a Mw less than 650 kg / mol, in other embodiments less than 600 kg / mol, in other embodiments less than 550 kg / mol, in other embodiments less than 500 kg / mol, and in other embodiments less than 450 kg / mol. In one or more embodiments, the reactive polymer has a Mw of about 180 to about 650 kg / mol, in other embodiments about 190 to about 600 kg / mol, in other embodiments about 200 to about 550 kg / mol, in other embodiments about 230 to about 500 kg / mol, in other embodiments about 250 to about 500 kg / mol, and in other embodiments about 200 to about 400 kg / mol.

[0035] The reactive polymers produced according to aspects of the invention can be characterized by their vinyl content, which can be described as the number of unsaturations in the 1,2-microstructure relative to the total unsaturation in the polymer chain. As will be appreciated by those skilled in the art, vinyl content can be determined by FTIR analysis. In one or more embodiments, the reactive polymer comprises greater than 10% by weight, in other embodiments greater than 20% by weight, and in other embodiments greater than 35% by weight vinyl. In these or other embodiments, the reactive polymer comprises less than 80% by weight, in other embodiments less than 60% by weight, and in other embodiments less than 46% by weight. In one or more embodiments, the reactive polymer comprises from about 10 to about 80% by weight, in other embodiments from about 20 to about 60% by weight, and in other embodiments from about 35 to about 46% by weight vinyl.

[0036] Reactive polymers may be characterized by a relatively high live (also referred to as reactive) end content, which refers to the mole percent of the polymer that has a reactive chain end and can react with a functionalizing agent. In one or more embodiments, greater than 60%, in other embodiments greater than 70%, in other embodiments greater than 80%, in other embodiments greater than 85%, in other embodiments greater than 90%, and in other embodiments greater than 90% of the polymer in the polymerization mixture contains live or reactive chain ends.

[0037] Polymer Modification As mentioned above, following polymerization, the reactive polymer undergoes modification, which may also be referred to as functionalization. That is, the reactive end of the polymer is modified by introducing an imine-containing dihydrocarbyloxysilane compound into the polymerization mixture, which may also be referred to as functionalization. It is believed that the polymer chain end reacts with the imine-containing hydrocarbyloxysilane (which may also be referred to as a functionalizing agent or modifying agent for the purposes of this specification) to provide a residue of the functionalizing agent at the polymer chain end. In particular, it is believed that a significant portion of the functionalization reaction occurs at the silicon atom, thereby replacing the hydrocarbyloxy group on the imine-containing dihydrocarbyloxysilane compound. Thus, the reaction between the polymer and the functionalizing agent produces a polymer composition that includes one or more polymer chains that include end groups derived from the imine-containing dihydrocarbyloxysilane. It should be understood that polymer coupling may also result from the reaction between the functionalizing agent and the reactive polymer. In either case, both the polymer with the chain end functional group and the polymer coupled with the residue of the functionalizing agent are referred to as modified or functionalized polymers, unless otherwise specified.

[0038] In one or more embodiments, greater than 10 mol %, in other embodiments greater than 30 mol %, in other embodiments greater than 35 mol %, and in other embodiments greater than 40 mol % of the polymer chains in the polymer composition comprise a terminal functional group. In these or other embodiments, less than 95 mol %, in other embodiments less than 90 mol %, and in other embodiments less than 85 mol % of the polymer chains in the polymer composition comprise a terminal functional group. In one or more embodiments, from about 10 to about 95 mol %, in other embodiments from about 30 to about 90 mol %, and in other embodiments from about 35 to about 85 mol % of the polymer chains in the polymer composition comprise a terminal functional group.

[0039] Dihydrocarbyloxy Functionalizing Agents As mentioned above, the anionically synthesized reactive polydienes are functionalized with imine-containing dihydrocarbyloxysilanes, which may also be referred to as imine-containing dihydrocarbyloxysilyl functionalizing agents, iminodihydrocarbyloxysilanes, or simply dihydrocarbyloxysilanes or dihydrocarbyloxysilyl functionalizing agents. Because the most common hydrocarbyloxy groups are alkoxy groups, the functionalizing agents used in the present invention may also be generally referred to using the alkoxy name (e.g., imine-containing dialkoxysilanes).

[0040] In one or more embodiments, the imine-containing dihydrocarbyloxysilane functionalizing agent has the formula:

[0041] [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , and R 5 are each independently a hydrocarbyl group; R 6 is a dihydrocarbyl group.

[0042] Examples of such imino group-containing alkoxysilane compounds include 3-(1-hexamethyleneimino)propyl(diethoxy)methylsilane, 3-(1-hexamethyleneimino)propyl(dimethoxy)methylsilane, (1-hexamethyleneimino)methyl(dimethoxy)methylsilane, (1-hexamethyleneimino)methyl(diethoxy)methylsilane, 2-(1-hexamethyleneimino)ethyl(diethoxy)methylsilane, 2-(1-hexamethyleneimino)ethyl(dimethoxy)methylsilane, 3-(1-pyrrolidinyl)propyl(diethoxy)methylsilane, 3-(1-pyrrolidinyl)propyl(dimethoxy)methylsilane, 3-(1-heptamethyleneimino)propyl(diethoxy)methylsilane, 3-(1-dodecamethyleneimino)propyl(diethoxy)methylsilane, 3-(1-hexamethyleneimino)propyl(dimethoxy)methylsilane, 3-(1-hexam ...dimethoxy)methylsilane, 3-(1-hexamethyleneimino)propyl(dimethoxy)methylsilane, 3-(1- N-(1,3-dimethylbutylidene)-3-(diethoxysilyl)methyl-1-propanamine, N-(1-methylethylidene)-3-(diethoxysilyl)methyl-1-propanamine, N-ethylidene-3-(diethoxysilyl)methyl-1-propanamine, N-(1-methylpropylidene)-3-(diethoxysilyl)methyl-1-propanamine, N-(4-N,N-dimethylaminobenzylidene)-3-(diethoxysilyl)methyl-1-propanamine, N-(cyclohexylidene)-3-(diethoxysilyl)methyl 1-propanamine, (dimethoxy)propylsilyl compounds, (diethoxy)propylsilyl compounds, (diethoxy)ethylsilyl compounds, (dimethoxy)methylsilyl compounds, and (dimethoxy)butylsilyl compounds corresponding to these triethoxysilyl compounds, 1-[3-(diethoxymethylsilyl)propyl]-4,5-dihydroimidazole, 1-[3-(dimethoxymethylsilyl)propyl]-4,5-dihydroimidazole, 3-[10-(diethoxymethylsilyl)decyl]-4-oxazoline, 3-(1-hexamethyleneimino)propyl(diethoxy)methylsilane, (1-hexamethyleneimino)methyl(dimethoxy)methylsilane, N-(3-(diethoxy)methylsilylpropyl)-4,5-dihydroimidazole, N-(3-isopropoxysilylpropyl)-4,5-dihydroimidazole, and N-(3-methyldiethoxysilylpropyl)-4,5-dihydroimidazole.

[0043] Amount of Dialkoxy Functionalizing Agent Used The amount of functionalizing agent (i.e., imine-containing hydrocarbyloxysilane) used in the practice of the invention may be described in terms of the lithium or metal cation associated with the initiator. In one or more embodiments, the amount of functionalizing agent introduced into the polymerization mixture is greater than 0.40, in other embodiments greater than 0.50, in other embodiments greater than 0.60, in other embodiments greater than 0.65, in other embodiments greater than 0.70, and in other embodiments greater than 0.75 moles of functionalizing agent per mole of lithium in the initiator. In these or other embodiments, less than 0.98, in other embodiments less than 0.95, in other embodiments less than 0.90, in other embodiments less than 0.85, in other embodiments less than 0.80, in other embodiments less than 0.75, and in other embodiments less than 0.70 moles of functionalizing agent per mole of lithium are introduced into the polymerization mixture. In one or more embodiments, from about 0.60 to about 0.90, in other embodiments from about 0.65 to about 0.85, and in other embodiments from about 0.70 to about 0.80 moles of functionalizing agent per mole of lithium are introduced into the polymerization mixture.

[0044] In one or more embodiments, the amount of functionalizing agent (i.e., imine-containing hydrocarbyloxysilane) used in the practice of the present invention can be described relative to moles of reactive polymer. In one or more embodiments, the molar ratio of functionalizing agent to reactive polymer (i.e., polydiene or polydiene copolymer) is greater than 0.50:1, in other embodiments greater than 0.60:1, in other embodiments greater than 0.65:1, in other embodiments greater than 0.70:1, and in other embodiments greater than 0.75:1 moles of functionalizing agent per mole of lithium in the initiator. In these or other embodiments, the molar ratio of functionalizing agent to reactive polymer is less than 1:1, in other embodiments less than 0.98, in other embodiments less than 0.95, in other embodiments less than 0.90, and in other embodiments less than 0.88. In one or more embodiments, the molar ratio of functionalizing agent to reactive polymer is from about 0.60:1 to about 1:1, in other embodiments from about 0.7:1 to about 0.98:1, and in other embodiments from about 0.75:1 to 0.95:1.

[0045] In one or more embodiments, the reaction between the functionalizing agent and the reactive polymer may be carried out at a temperature of about 10° C. to about 150° C., and in other embodiments, about 20° C. to about 100° C. The time required for the reaction between the functionalizing agent and the reactive polymer to be completed depends on a variety of factors, including the type and amount of catalyst or initiator used in the preparation of the reactive polymer, the type and amount of functionalizing agent, and the temperature at which the functionalization reaction is carried out. In one or more embodiments, the reaction between the functionalizing agent and the reactive polymer may be carried out for about 10 to 60 minutes.

[0046] In one or more embodiments, the functionalizing agent is introduced into the polymer cement (i.e., polymerization mixture) while the polymer is dissolved or suspended in the solvent. As will be appreciated by those skilled in the art, this solution may also be referred to as the polymer cement. In one or more embodiments, the characteristics of the polymer cement, such as its concentration, are the same or similar to the characteristics of the cement prior to functionalization.

[0047] In one or more embodiments, the modification of the polymer (i.e., the introduction of the functionalizing agent into the polymer cement) occurs in the same vessel in which the polymerization occurs. In other embodiments, the modification of the polymer occurs outside of the reaction vessel in which the polymerization occurs. For example, the functionalizing agent can be introduced into the polymerization mixture (i.e., the polymer cement) in a downstream vessel or downstream transfer conduit.

[0048] Polymer Stabilization As described above, following modification, the modified polymer may be stabilized. In one or more embodiments, stabilizers known in the art may be used. For example, the stabilizer may include an alkyl hydrocarbyloxy silane (e.g., an alkyl alkoxy silane) as disclosed in U.S. Pat. No. 6,255,404, which is incorporated herein by reference. An exemplary alkyl alkoxy silane includes octyl triethoxy silane. In other embodiments, the stabilizer may include a long chain alcohol as disclosed in U.S. Pat. No. 6,279,632, which is incorporated herein by reference. An exemplary long chain alcohol includes sorbitan stearate or sorbitan monooleate. In still other embodiments, the polymer may be stabilized by treating with an alkyl alkoxy silane, as disclosed in U.S. Pat. No. 9,546,237, which is incorporated herein by reference, followed by treatment with a silane containing a hydrolyzable group that forms an acidic species upon hydrolysis, such as methyltrichlorosilane.

[0049] In one or more embodiments, the modified polymer can be stabilized by introducing an alkylhydrocarbyloxysilane into the polymerization mixture containing the modified polymer. The alkylhydrocarbyloxysilane is believed to react with the terminal functional group. It is also believed that the reaction between the chain end functional group and the alkylhydrocarbyloxysilane occurs upon introduction of the two molecules or after aging of the composition. The reaction between the alkylhydrocarbyloxysilane and the terminal group produces a polymer composition that includes one or more polymer chains that include terminal groups derived from the reaction of the imine-containing dihydrocarbyloxysilane and the subsequent alkylhydrocarbyloxysilane.

[0050] In one or more embodiments, the stabilizer has Formula I:

[0051] [ka] (In the formula, R 2 is a hydrocarbyl group, R 3 , R 4 , and R 5 are hydrocarbyloxy silanes (i.e., stabilizers) that may be defined by: 3 , R 4 , and R 5 is a hydrocarbyl group. In other embodiments, R 3 and R 4 is a hydrocarbyl group, R 5 is a hydrocarbyloxy group. In other embodiments, R 3 is a hydrocarbyl group, R 4 and R 5 is a hydrocarbyloxy group. In certain embodiments, R 3 , R 4 , and R 5 are all hydrocarbyloxy groups.

[0052] In one or more embodiments, the hydrocarbyl group of the hydrocarbyl hydrocarbyloxysilane includes, but is not limited to, alkyl groups, cycloalkyl groups, substituted cycloalkyl groups, alkenyl groups, cycloalkenyl groups, substituted cycloalkenyl groups, aryl groups, allyl groups, substituted aryl groups, aralkyl groups, alkaryl groups, or alkynyl groups. Substituted hydrocarbyl groups include hydrocarbyl groups in which one or more hydrogen atoms are replaced with a substituent such as an alkyl group. In one or more embodiments, the hydrocarbyl group may contain one or the minimum number of carbon atoms suitable for forming a group up to 20 carbon atoms. These hydrocarbyl groups may contain heteroatoms such as, but not limited to, nitrogen, boron, oxygen, silicon, sulfur, and phosphorus atoms.

[0053] In one or more embodiments, the hydrocarbyloxy group of the hydrocarbyl hydrocarbyloxy silane includes, but is not limited to, alkoxy, cycloalkoxy, substituted cycloalkoxy, alkenyloxy, cycloalkenyloxy, substituted cycloalkenyloxy, aryloxy, allyloxy, substituted aryloxy, aralkyloxy, alkaryloxy, or alkynyloxy. Substituted hydrocarbyloxy groups include hydrocarbyloxy groups in which one or more hydrogen atoms bonded to a carbon atom are replaced with a substituent such as an alkyl group. In one or more embodiments, the hydrocarbyloxy group may contain one or the minimum number of carbon atoms suitable for forming a group up to 20 carbon atoms. The hydrocarbyloxy group may contain heteroatoms such as, but not limited to, nitrogen, boron, oxygen, silicon, sulfur, and phosphorus atoms.

[0054] In one or more embodiments, types of hydrocarbyl hydrocarbyloxy silanes include trihydrocarbyl hydrocarbyloxy silanes, dihydrocarbyl dihydrocarbyloxy silanes, hydrocarbyl trihydrocarbyloxy silanes, and tetrahydrocarbyloxy silanes.

[0055] Specific examples of hydrocarbyloxysilanes include methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, phenyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, phenyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, methyltriphenoxysilane, ethyltriphenoxysilane, propyltriphenoxysilane, octyltriphenoxysilane, Phenyltriphenoxysilane, Decyltriphenoxysilane, Methyldiethoxymethoxysilane, Ethyldiethoxymethoxysilane, Propyldiethoxymethoxysilane, Phenyldiethoxymethoxysilane, Octyldiethoxymethoxysilane, Decyldiethoxymethoxysilane, Methyldiphenoxymethoxysilane, Ethyldiphenoxymethoxysilane, Propyldiphenoxymethoxysilane, Phenyldiphenoxymethoxysilane, Octyldiphenoxymethoxysilane, Decyldiphenoxymethoxysilane, Methyldimethoxyethoxysilane, Ethyl Tyl dimethoxyethoxysilane, propyl dimethoxyethoxysilane, phenyl dimethoxyethoxysilane, octyl dimethoxyethoxysilane, decyl dimethoxyethoxysilane, methyl diphenoxyethoxysilane, ethyl diphenoxyethoxysilane, propyl diphenoxyethoxysilane, phenyl diphenoxyethoxysilane, octyl diphenoxyethoxysilane, decyl diphenoxyethoxysilane, methyl dimethoxyphenoxysilane, ethyl dimethoxyphenoxysilane, propyl dimethoxyphenoxysilane, phenyl dimethoxyphenoxy Noxylsilane, octyldimethoxyphenoxysilane, decyldimethoxyphenoxysilane, methyldiethoxyphenoxysilane, ethyldiethoxyphenoxysilane, propyldiethoxyphenoxysilane, phenyldiethoxyphenoxysilane, octyldiethoxyphenoxysilane, decyldiethoxyphenoxysilane, methylmethoxyethoxyphenoxysilane, ethylmethoxyethoxyphenoxysilane, propylmethoxyethoxyphenoxysilane, phenylmethoxyethoxyphenoxysilane, octylmethoxyethoxyphenoxysilane,and decyl methoxy ethoxy phenoxy silane.

[0056] In one or more embodiments, the stabilizing agent is added to the polymer cement after sufficient time has been provided to complete the reaction between the reactive polymer and the functionalizing agent, in one or more embodiments, the stabilizing agent is introduced to the polymer cement 30 minutes, in other embodiments 15 minutes, and in other embodiments 10 minutes after the time the functionalizing agent is introduced to the polymer cement.

[0057] The amount of stabilizer (i.e., hydrocarbyl hydrocarbyloxysilane) used in the practice of the invention may be described in terms of moles of lithium relative to the initiator. In one or more embodiments, greater than 0.5 moles, in other embodiments greater than 1 mole, in other embodiments greater than 2 moles, and in other embodiments greater than 3 moles of stabilizer are introduced to the polymerization mixture per mole of lithium in the initiator. In these or other embodiments, less than 8, in other embodiments less than 7, in other embodiments less than 6, in other embodiments less than 5, in other embodiments less than 4.5, in other embodiments less than 4, and in other embodiments less than 3.5 moles of stabilizer are introduced to the polymerization mixture per mole of lithium. In one or more embodiments, from about 0 to about 7, in other embodiments from about 2 to about 6, and in other embodiments from about 3 to about 5 moles of stabilizer are introduced to the polymerization mixture per mole of lithium. In one or more embodiments, no stabilizer (e.g., hydrocarbyl hydrocarbyloxysilane) is used.

[0058] In other embodiments, the amount of stabilizer (i.e., hydrocarbyl hydrocarbyloxysilane) used in the practice of the invention can be described as a molar ratio to the moles of functionalizing agent used. In one or more embodiments, the ratio of moles of stabilizer to moles of functionalizing agent used is from about 0:1 to about 16:1, in other embodiments from about 0.5:1 to about 10:1, and in other embodiments from about 2:1 to about 8:1. In these or other embodiments, the ratio of moles of stabilizer to moles of functionalizing agent used is less than 16:1, in other embodiments less than 10:1, in other embodiments less than 8:1, in other embodiments less than 5:1, and in other embodiments less than 4.5:1.

[0059] In one or more embodiments, the stabilization of the polymer (i.e., introduction of the stabilizing agent) is performed in the same vessel in which the polymerization was performed. In these embodiments, this includes the same vessel in which the modification was performed. In other embodiments, the stabilization of the polymer (i.e., introduction of the stabilizing agent) is performed outside the vessel in which the polymerization was performed. Similarly, in one or more embodiments, the stabilization of the polymer is performed outside the vessel in which the modification of the polymer was performed. For example, in one or more embodiments, the stabilizing agent can be added to the polymerization mixture (i.e., polymer cement) in a vessel or transfer line that is downstream of the vessel in which the polymerization was performed and downstream of the vessel in which the polymer modification was performed. For purposes of this specification, the vessel or conduit in which the stabilizing agent is introduced relative to the polymerization vessel may also be referred to as a second vessel or second reaction zone. In other embodiments, the stabilizing agent can be introduced to the polymer while it is suspended or dissolved in the monomer.

[0060] Antioxidants In one or more embodiments, an antioxidant may be added to the polymerization mixture after the functionalizing agent is introduced into the reactive polymer, optionally after the addition of a quenching agent and / or an antioxidant, optionally after or together with a stabilizing agent, and optionally after recovery or isolation of the functionalized polymer. An exemplary antioxidant includes 2,6-di-tert-butyl-4-methylphenol.

[0061] In one or more embodiments, after the polymer is formed, processing aids and other optional additives, such as oils, may be added to the polymer cement.

[0062] Optional Quenching In one or more embodiments, after the reaction between the reactive polymer and the functionalizing agent is achieved or completed, a quenching agent may be added to the polymerization mixture to deactivate any remaining reactive polymer chains and catalyst or catalyst components. The quenching agent may include a protic compound, including, but not limited to, an alcohol, a carboxylic acid, an inorganic acid, water, or a mixture thereof. The amount of quenching agent used may range from 0.5 to 10 moles of quenching agent per mole of lithium used to initiate the polymerization.

[0063] Condensation promoter In one or more embodiments, a condensation promoter may be added to the polymerization mixture after the functionalizing agent is introduced into the reactive polymer, optionally after the addition of a quenching agent and / or antioxidant, optionally after or together with the stabilizing agent, and optionally after recovery or isolation of the functionalized polymer. Useful condensation promoters include tin and / or titanium carboxylates and tin and / or titanium alkoxides. One specific example is titanium 2-ethylhexyl oxide. Useful condensation catalysts and their uses are disclosed in U.S. Patent Application Publication No. 2005 / 0159554 (U.S. Patent No. 7,683,151), which is incorporated herein by reference. In other embodiments, organic acids may be used as condensation promoters. Useful types of organic acids include aliphatic, alicyclic, and aromatic mono-, di-, tri-, and tetra-carboxylic acids. Specific examples of useful organic acids include, but are not limited to, acetic acid, propionic acid, butyric acid, hexanoic acid, 2-methylhexanoic acid, 2-ethylhexanoic acid, cyclohexanoic acid, and benzoic acid.

[0064] The amount of condensation promoter used in the practice of the invention can be described in terms of the moles of lithium relative to the initiator. In one or more embodiments, the amount of condensation promoter per mole of lithium is greater than 1.0, in other embodiments greater than 1.5, and in other embodiments greater than 1.8 moles of condensation promoter per mole of lithium in the initiator. In these or other embodiments, less than 4.0, in other embodiments less than 3.3, and in other embodiments less than 3.0 moles of condensation promoter per mole of lithium are introduced to the polymerization mixture. In one or more embodiments, from about 1.0 to about 4.0, in other embodiments from about 1.5 to about 3.3, and in other embodiments from about 1.8 to about 3.0 moles of condensation promoter per mole of lithium are introduced to the polymerization mixture.

[0065] Polymer desolvation As described above, following optional stabilization and following the introduction of optional condensation promoters and / or antioxidants, the polymer product (e.g., stabilized functionalized polymer) undergoes separation from the solvent, which may be referred to as desolvation. In other words, as described above, the polymer is synthesized in an organic solvent, and during the desolvation step, the organic solvent is separated from the polymer.

[0066] In certain embodiments, the desolventization involves hot water and / or steam coagulation. For example, the polymerization mixture containing the modified polymer can be combined with steam or hot water flow. The heat associated with the steam or hot water flow volatilizes the solvent and any unreacted monomers. The polymer product is then dispersed within the aqueous phase, for example in the form of polymer crumbs. The nature and size of the polymer crumbs can generally be manipulated by the introduction of mechanical energy (e.g., in the form of a mixer).

[0067] In one or more embodiments, the polymer crumbs are temporarily stored as a crumb dispersion in water until the subsequent drying step described below. The crumb dispersion is generally a mixture of polymer particles or crumbs and water. The polymer particles, sometimes referred to as coagulated polymer, are generally macro-scale and have dimensions at least greater than 1 mm. The crumb dispersion can be contained in a vessel, such as a conventional reactor vessel, such as a continuous stirred tank reactor.

[0068] In one or more embodiments, the polymer crumbs may be further processed to remove residual solvent and dry the polymer (i.e., separate the polymer from the water). In the practice of the present invention, the polymer may be dried using conventional techniques that may include one or more of filtering, squeezing, and heating. After desolventization and drying, the volatile content of the dried polymer may be less than 2.0% by weight of the polymer, in other embodiments less than 1.0% by weight, and in other embodiments less than 0.5% by weight.

[0069] In other embodiments, the polymer product may be desolvated by using a devolatilizer, which is an extruder-type device that may operate in conjunction with heat and / or vacuum, hi yet other embodiments, the polymerization mixture may be directly drum dried.

[0070] Regardless of the method used to desolvent and dry the polymer, the finished polymer product may be referred to as a dried polymer. The dried polymer may be shaped or otherwise manipulated into bales using conventional techniques.

[0071] Polymer properties of dry polymer In one or more embodiments, the dried, unaged functionalized polymers of the present invention have advantageous Mooney Viscosity (ML at 100° C.) 1+4 Specifically, in one or more embodiments, the polymer has a Mooney viscosity (ML at 100° C.) of less than 95, in other embodiments less than 90, and in other embodiments less than 85, within 24 hours of desolvation and drying. 1+4In these or other embodiments, the polymer has a Mooney viscosity (ML at 100° C.) within 24 hours of desolvation and drying of from about 35 to about 120, in other embodiments from about 55 to about 95, in other embodiments from about 60 to about 90, and in other embodiments from about 65 to about 85. 1+4 For purposes of this specification, the dry, unaged Mooney viscosity (ML at 100° C.) is used. 1+4 ) may be referred to as the Beer Mooney viscosity.

[0072] Polymer properties after aging As mentioned above, the functionalized polymers of the present invention have advantageous Mooney viscosity after aging (ML at 100° C.). 1+4 Specifically, in one or more embodiments, the polymer has a Mooney viscosity (ML at 100° C.) of less than 120, in other embodiments less than 105, and in other embodiments less than 95, when aged for 2 years after desolvation and drying. 1+4 In one or more embodiments, the polymer has a Mooney viscosity (ML at 100° C.) of from about 70 to about 120, in other embodiments from about 80 to about 105, and in other embodiments from about 85 to about 95, when aged for 2 years after desolvation and drying. 1+4 ) For purposes herein, specifically, two days of accelerated aging at 100°C may be used instead of two years of room temperature aging, compared to the Mooney viscosity after two years of aging. In other words, for purposes herein, the two aging methods are treated equally with respect to the resulting viscosity.

[0073] Industrial Applicability In one or more embodiments, the functionalized polydienes and polydiene copolymers of the present invention may be used in compounding vulcanizable rubber compositions that may be useful, for example, in preparing tire components. Rubber compounding techniques and additives used therein are generally described in detail in Rubber Technology (2002) 14:131-135. nd This is disclosed in The Compounding and Vulcanization of Rubber, Ed. 1973.

[0074] Generally speaking, these vulcanizable rubber compositions include a vulcanizable rubber component, a reinforcing filler, and a curative or curative system. These compositions may also optionally include metal activators, resins, and processing oils, as well as various other ingredients that may conventionally be included in these vulcanizable rubber compositions.

[0075] Components of the Vulcanizable Composition In one or more embodiments, the stabilized functionalized polydienes or polydiene copolymers of the present invention may form all or a portion of the rubber component of the vulcanizable composition, i.e., the rubber component may include other vulcanizable rubbers, which may also be referred to as elastomeric polymers or simply elastomers.

[0076] Rubber compositions can be prepared by using the polymers of the present invention alone or with other elastomers (i.e., polymers that can be vulcanized to form compositions having rubbery or elastomeric properties). Other elastomers that may be used include natural and synthetic rubbers. Synthetic rubbers are typically derived from the polymerization of conjugated diene monomers, the copolymerization of conjugated diene monomers with other monomers such as vinyl substituted aromatic monomers, or the copolymerization of ethylene with one or more α-olefins and optionally one or more diene monomers.

[0077] Exemplary elastomers include natural rubber, synthetic polyisoprene, polybutadiene, polyisobutylene-co-isoprene, neoprene, poly(ethylene-co-propylene), poly(styrene-co-butadiene), poly(styrene-co-isoprene), poly(styrene-co-isoprene-co-butadiene), poly(isoprene-co-butadiene), poly(ethylene-co-propylene-co-diene), polysulfide rubbers, acrylic rubbers, urethane rubbers, silicone rubbers, epichlorohydrin rubbers, and mixtures thereof. These elastomers can have a myriad of macromolecular structures, including linear, branched, and star structures.

[0078] The rubber composition may include fillers, such as inorganic and organic fillers. Examples of organic fillers include carbon black and starch. Examples of inorganic fillers include silica, aluminum hydroxide, magnesium hydroxide, mica, talc (hydrated magnesium silicate), and clay (hydrated aluminum silicate). Carbon black and silica are the most common fillers used in the manufacture of tires. In certain embodiments, a mixture of different fillers may be used to advantage.

[0079] In one or more embodiments, carbon blacks include furnace blacks, channel blacks, and lamp blacks. More specific examples of carbon blacks include super abrasion furnace blacks, medium super abrasion furnace blacks, high abrasion furnace blacks, high speed extrusion furnace blacks, fine furnace blacks, semi-reinforced furnace blacks, medium processed channel blacks, hard processed channel blacks, conductive channel blacks, and acetylene blacks.

[0080] In certain embodiments, the carbon black has a surface area (EMSA) of at least 20 m 2 / g, and in other embodiments, at least 35m 2 The surface area may be expressed in terms of surface area per gram and may be determined using the cetyltrimethylammonium bromide (CTAB) technique per ASTM standard D-1765. The carbon black may be in pelletized or non-pelletized flocculent form. The preferred form of the carbon black may depend on the type of mixing equipment used to mix the rubber compound.

[0081] Some commercially available silicas that can be used include Hi-Sil™ 215, Hi-Sil™ 233, and Hi-Sil™ 190 (PPG Industries, Inc.; Pittsburgh, PA). Other suppliers of commercially available silica include Grace Davison (Baltimore, MD), Degussa Corp. (Parsippany, NJ), Rhodia Silica Systems (Cranbury, NJ), and JM Huber Corp. (Edison, NJ).

[0082] In one or more embodiments, silica can be characterized by its surface area, which is a measure of its reinforcing properties. The Brunauer, Emmet and Teller ("BET") method (described in J. Am. Chem. Soc., 1939, vol. 60, 2 p. 309-319) is an accepted method for determining surface area. The BET surface area of ​​silica is generally about 450 m 2 / g. A useful range of surface area is from about 32 to about 400 m 2 / g, about 100~250m 2 / g, and about 150 to about 220 m 2 / g are examples.

[0083] The pH of the silica generally ranges from about 5 to about 7, or slightly above 7, or in other embodiments, from about 5.5 to about 6.8.

[0084] In one or more embodiments, when silica is used as a filler (alone or in combination with other fillers), a coupling agent and / or shielding agent may be added to the rubber composition during mixing to enhance the interaction of the silica with the elastomer. Useful coupling agents and shielding agents are disclosed in U.S. Patents 3,842,111, 3,873,489, 3,978,103, 3,997,581, 4,002,594, 5,580,919, 5,583,245, 5,663,396, 5,674,932, 5,71 ... Nos. 6,684,171, 5,684,172, 5,696,197, 6,608,145, 6,667,362, 6,579,949, 6,590,017, 6,525,118, 6,342,552, and 6,683,135, which are incorporated herein by reference.

[0085] In one or more embodiments, the vulcanizable composition of the present invention may include one or more resins. As will be understood by those skilled in the art, the resins may include plasticizing resins and curable or thermosetting resins. Useful plasticizing resins include hydrocarbon resins such as cycloaliphatic resins, aliphatic resins, aromatic resins, terpene resins, and combinations thereof. Useful resins are commercially available under various trade names from a variety of companies, including, for example, Chemfax, Dow Chemical Company, Eastman Chemical Company, Idemitsu, Neville Chemical Company, Nippon, Polysat Inc., Resinall Corp., Pinova Inc., Yasuhara Chemical Co., Ltd., Arizona Chemical, and SI Group Inc., and Zeon.

[0086] In one or more embodiments, useful hydrocarbon resins may be characterized by a glass transition temperature (Tg) of from about 30 to about 160° C., from about 35 to about 60° C. in other embodiments, and from about 70 to about 110° C. in other embodiments. In one or more embodiments, useful hydrocarbon resins may also be characterized by their softening point being higher than their glass transition temperature (Tg). In certain embodiments, useful hydrocarbon resins have a softening point of from about 70 to about 160° C., from about 75 to about 120° C. in other embodiments, and from about 120 to about 160° C. in other embodiments.

[0087] In certain embodiments, one or more cycloaliphatic resins are used in combination with one or more of an aliphatic resin, an aromatic resin, and a terpene resin. In one or more embodiments, one or more cycloaliphatic resins are used as the major weight component (e.g., greater than 50% by weight) based on the total amount of resin. For example, the resin used comprises at least 55% by weight, in other embodiments at least 80% by weight, and in other embodiments at least 99% by weight of one or more cycloaliphatic resins.

[0088] In one or more embodiments, cycloaliphatic resins include both cycloaliphatic homopolymer resins and cycloaliphatic copolymer resins, including those derived from cycloaliphatic monomers, optionally in combination with one or more other (non-cycloaliphatic) monomers (although the majority of all monomers are cycloaliphatic). Non-limiting examples of suitable useful cycloaliphatic resins include cyclopentadiene ("cyclopentadiene, CPD") homopolymer or copolymer resins, and dicyclopentadiene ("dicyclopentadiene, DCPD") homopolymer or copolymer resins, and combinations thereof. Non-limiting examples of cycloaliphatic copolymer resins include CPD / vinyl aromatic copolymer resins, DCPD / vinyl aromatic copolymer resins, CPD / terpene copolymer resins, DCPD / terpene copolymer resins, CPD / aliphatic copolymer resins (e.g., CPD / C5 fraction copolymer resins), DCPD / aliphatic copolymer resins (e.g., DCPD / C5 fraction copolymer resins), CPD / aromatic copolymer resins (e.g., CPD / C9 fraction copolymer resins), DCPD / aromatic copolymer resins (e.g., DCPD / C9 fraction copolymer resins), C ... -aliphatic copolymer resins (e.g., CPD / C5 and C9 fraction copolymer resins), DCPD / aromatic-aliphatic copolymer resins (e.g., DCPD / C5 and C9 fraction copolymer resins), CPD / vinyl aromatic copolymer resins (e.g., CPD / styrene copolymer resins), DCPD / vinyl aromatic copolymer resins (e.g., DCPD / styrene copolymer resins), CPD / terpene copolymer resins (e.g., limonene / CPD copolymer resins), and DCPD / terpene copolymer resins (e.g., limonene / DCPD copolymer resins). In certain embodiments, the cycloaliphatic resin may include a hydrogenated form of one of the above cycloaliphatic resins (i.e., a hydrogenated cycloaliphatic resin). In other embodiments, the cycloaliphatic resin excludes any hydrogenated cycloaliphatic resin. In other words, the cycloaliphatic resin is not hydrogenated.

[0089] In certain embodiments, one or more aromatic resins are used in combination with one or more of an aliphatic resin, a cycloaliphatic resin, and a terpene resin. In one or more embodiments, one or more aromatic resins are used as the major weight component (e.g., greater than 50% by weight) based on the total amount of resin. For example, the resin used comprises at least 55% by weight, in other embodiments at least 80% by weight, and in other embodiments at least 99% by weight of one or more aromatic resins.

[0090] In one or more embodiments, aromatic resins include both aromatic homopolymer resins and aromatic copolymer resins, including those derived from one or more aromatic monomers in combination with one or more other (non-aromatic) monomers, provided that the majority of any type of monomer is aromatic. Non-limiting examples of useful aromatic resins include coumarone-indene resins and alkyl-phenol resins, as well as vinyl aromatic homopolymer or copolymer resins, such as those derived from one or more of alpha-methylstyrene, styrene, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, vinyltoluene, para(tert-butyl)styrene, methoxystyrene, chlorostyrene, hydroxystyrene, vinylmesitylene, divinylbenzene, vinylnaphthalene, or vinyl aromatic monomers obtained from the C9 or C8-C10 fractions. Non-limiting examples of vinyl aromatic copolymer resins include vinyl aromatic / terpene copolymer resins (e.g., limonene / styrene copolymer resins), vinyl aromatic / C5 fraction resins (e.g., C5 fraction / styrene copolymer resins), vinyl aromatic / aliphatic copolymer resins (e.g., CPD / styrene copolymer resins, and DCPD / styrene copolymer resins). Non-limiting examples of alkyl-phenol resins include alkylphenol-acetylene resins, such as p-tert-butylphenol-acetylene resins, alkylphenol-formaldehyde resins (e.g., resins with low polymerization degrees). In certain embodiments, the aromatic resin may include a hydrogenated form of one of the above aromatic resins (i.e., a hydrogenated aromatic resin). In other embodiments, the aromatic resin excludes any hydrogenated aromatic resin. In other words, the aromatic resin is not hydrogenated.

[0091] In certain embodiments, one or more aliphatic resins are used in combination with one or more of cycloaliphatic resins, aromatic resins, and terpene resins. In one or more embodiments, one or more aliphatic resins are used as the major weight component (e.g., greater than 50% by weight) based on the total amount of resin. For example, the resin used comprises at least 55% by weight, in other embodiments at least 80% by weight, and in other embodiments at least 99% by weight of one or more aliphatic resins.

[0092] In one or more embodiments, aliphatic resins include both aliphatic homopolymer resins and aliphatic copolymer resins, including those derived from one or more aliphatic monomers in combination with one or more other (non-aliphatic) monomers, with the majority of any type of monomer being aliphatic. Non-limiting examples of useful aliphatic resins include C5 homopolymer or copolymer resins, C5 / C9 copolymer resins, C5 / vinyl aromatic copolymer resins (e.g., C5 / styrene copolymer resins), C5 / cycloaliphatic copolymer resins, and C5 / C9 / cycloaliphatic copolymer resins, and combinations thereof. Non-limiting examples of cyclic aliphatic monomers include, but are not limited to, cyclopentadiene ("CPD") and dicyclopentadiene ("DCPD"). In certain embodiments, the aliphatic resin may include a hydrogenated form of one of the above aliphatic resins (i.e., a hydrogenated aliphatic resin). In other embodiments, the aliphatic resin excludes any hydrogenated aliphatic resin, in other words, in such embodiments, the aliphatic resin is not hydrogenated.

[0093] In one or more embodiments, terpene resins include both terpene homopolymer resins and terpene copolymer resins, including those derived from one or more terpene monomers in combination with one or more other (non-terpene) monomers, with the majority of any type of monomer being terpenes. Non-limiting examples of useful terpene resins include alpha-pinene resins, beta-pinene resins, limonene resins (e.g., L-limonene, D-limonene, and dipentene, which is a racemic mixture of L- and D-isomers), beta-phellandrene, delta-3-carene, delta-2-carene, pinene-limonene copolymer resins, terpene phenolic resins, and aromatic modified terpene resins, and combinations thereof. In certain embodiments, the terpene resins may include a hydrogenated form of one of the above terpene resins (i.e., hydrogenated terpene resins). In other embodiments, the terpene resins exclude any hydrogenated terpene resins. In other words, in such embodiments, the terpene resin is not hydrogenated.

[0094] In one or more embodiments, the vulcanizable composition of the present invention includes a processing oil, which may also be referred to as an extender oil. In one or more embodiments, the vulcanizable composition is devoid or substantially devoid of processing oil.

[0095] In certain embodiments, the oils used include those that are traditionally used as extender oils. Useful oils or spreading agents that may be used include, but are not limited to, aromatic oils, paraffinic oils, naphthenic oils, vegetable oils (other than castor oil), low PCA oils including MES, TDAE, and SRAE, and heavy naphthenic oils. Suitable low PCA oils also include oils of various plant origins, such as those that can be obtained from vegetables, nuts, and seeds. Non-limiting examples include, but are not limited to, soybean oil, sunflower oil, safflower oil, corn oil, linseed oil, cottonseed oil, rapeseed oil, cashew oil, sesame oil, camellia oil, jojoba oil, macadamia nut oil, coconut oil, and palm oil. As is commonly understood in the art, oil refers to a compound that has a viscosity that is compared relatively to other components of the vulcanizable composition, such as resins.

[0096] In one or more embodiments, the oil comprises hydrocarbon compounds having more than 15, in other embodiments more than 20, in other embodiments more than 25, in other embodiments more than 30, in other embodiments more than 35, and in other embodiments more than 40 carbon atoms per molecule. In these or other embodiments, the oil comprises hydrocarbon compounds having less than 250, in other embodiments less than 200, in other embodiments less than 150, in other embodiments less than 120, in other embodiments less than 100, in other embodiments less than 90, in other embodiments less than 80, in other embodiments less than 70, in other embodiments less than 60, and in other embodiments less than 50 carbon atoms per molecule. In one or more embodiments, the oil comprises hydrocarbon compounds having from about 15 to about 250, in other embodiments from about 20 to about 200, in other embodiments from about 25 to about 100 carbon atoms per molecule, in other embodiments from about 25 to about 70 carbon atoms per molecule, in other embodiments from about 25 to about 70 carbon atoms per molecule, in other embodiments from about 25 to about 60 carbon atoms per molecule, and in other embodiments from about 25 to about 40 carbon atoms per molecule.

[0097] In one or more embodiments, the oil comprises a hydrocarbon compound having a dynamic viscosity at 25° C. of greater than 5, and in other embodiments greater than 10, and in other embodiments greater than 15, and in other embodiments greater than 20, and in other embodiments greater than 25, and in other embodiments greater than 30, and in other embodiments greater than 35, and in other embodiments greater than 40 mPa·s. In these or other embodiments, the oil comprises a hydrocarbon compound having a dynamic viscosity at 25° C. less than 3000, and in other embodiments less than 2500, and in other embodiments less than 2000, and in other embodiments less than 1500, and in other embodiments less than 1000, and in other embodiments less than 750, and in other embodiments less than 500, and in other embodiments less than 250, and in other embodiments less than 100, and in other embodiments less than 75 mPa·s. In one or more embodiments, the oil comprises a hydrocarbon compound having a dynamic viscosity at 25° C. of about 5 to about 3000, in other embodiments about 15 to about 2000, in other embodiments about 20 to about 1500, in other embodiments about 25 to about 1000, in other embodiments about 30 to about 750, in other embodiments about 35 to about 500, and in other embodiments about 50 to about 250 mPa·s.

[0098] A number of rubber curing agents (also called vulcanizing agents) may be used, including sulfur or peroxide based cure systems. Curing agents are described in Kirk-Othmer, Encyclopedia of Chemical Technology, Vol. 20, pgs. 365-468, (3 rd Ed.1982), especially Vulcanization Agents and Auxiliary Materials, pgs.390-402, and AYCoran, Vulcanization, Encyclopedia of Polymer Science and Engineering, (2 nd Ed. 1989), which are incorporated herein by reference. The vulcanizing agents may be used alone or in combination.

[0099] Other ingredients typically used in rubber compounding can also be added to the rubber composition. These include accelerators, accelerator activators, oils, plasticizers, waxes, antiscorch agents, processing aids, zinc oxide, tackifying resins, reinforcing resins, fatty acids such as stearic acid, deflocculants, and antidegradants such as antioxidants and antiozonants. In certain embodiments, the oils used include those traditionally used as extender oils, as previously described.

[0100] Ingredient amount As noted above, the vulcanizable composition comprises a vulcanizable rubber component. In one or more embodiments, the vulcanizable composition comprises greater than 20, in other embodiments greater than 30, and in other embodiments greater than 40 weight percent of the vulcanizable rubber component (which may be referred to simply as the rubber component), based on the total weight of the composition. In these or other embodiments, the vulcanizable composition comprises less than 90, in other embodiments less than 70, and in other embodiments less than 60 weight percent of the rubber component, based on the total weight of the vulcanizable composition. In one or more embodiments, the vulcanizable composition comprises from about 20 to about 90, in other embodiments from about 30 to about 70, and in other embodiments from about 40 to about 60 weight percent of the rubber component, based on the total weight of the vulcanizable composition.

[0101] In one or more embodiments, the rubber component of the vulcanizable composition of the present invention comprises greater than 10% by weight, in other embodiments greater than 30% by weight, and in other embodiments greater than 50% by weight of the functionalized polymer of the present invention, with the remainder comprising other vulcanizable rubbers. In these or other embodiments, the rubber component of the vulcanizable composition of the present invention comprises less than 100% by weight, in other embodiments less than 90% by weight, and in other embodiments less than 80% by weight of the functionalized polymer of the present invention, with the remainder comprising other vulcanizable rubbers. In one or more embodiments, the rubber component of the vulcanizable composition of the present invention comprises from about 10 to about 100% by weight, in other embodiments from about 30 to about 90% by weight, and in other embodiments from about 50 to about 80% by weight of the functionalized polymer of the present invention, with the remainder comprising other vulcanizable rubbers.

[0102] filling material In one or more embodiments, the vulcanizable composition comprises more than 0, in other embodiments more than 40, in other embodiments more than 60, in other embodiments more than 80, in other embodiments more than 90, in other embodiments more than 100, and in other embodiments more than 110 parts by weight (pbw) of filler per 100 parts by weight rubber (phr). In these or other embodiments, the vulcanizable composition comprises less than 200, in other embodiments less than 160, in other embodiments less than 150, and in other embodiments less than 140 pbw of filler phr. In one or more embodiments, the vulcanizable composition comprises from about 40 to about 200, in other embodiments from about 60 to about 160, and in other embodiments from about 100 to about 150 pbw of filler phr.

[0103] Carbon Black In one or more embodiments, the vulcanizable composition comprises greater than 0, in other embodiments greater than 1, in other embodiments greater than 2, in other embodiments greater than 5, in other embodiments greater than 10, and in other embodiments greater than 15 parts by weight (pbw) of carbon black per 100 parts rubber (phr). In these or other embodiments, the vulcanizable composition comprises less than 60, in other embodiments less than 40, and in other embodiments less than 30 pbw of carbon black phr. In one or more embodiments, the vulcanizable composition comprises from about 1 to about 60, in other embodiments from about 5 to about 50, and in other embodiments from about 10 to about 40 pbw of carbon black phr. In one or more embodiments, the vulcanizable composition is devoid or substantially devoid of carbon black.

[0104] silica In one or more embodiments, the vulcanizable composition comprises greater than 5, in other embodiments greater than 40, in other embodiments greater than 60, in other embodiments greater than 70, in other embodiments greater than 80, in other embodiments greater than 90, in other embodiments greater than 100, and in other embodiments greater than 110 parts by weight (pbw) of silica per 100 parts of rubber. In these or other embodiments, the vulcanizable composition comprises less than 140, in other embodiments less than 130, in other embodiments less than 120, in other embodiments less than 120, and in other embodiments less than 100 pbw of silica phr. In one or more embodiments, the vulcanizable composition comprises from about 40 to about 140, in other embodiments from about 60 to about 130, and in other embodiments from about 80 to about 120 pbw of silica phr.

[0105] Filler Ratio In one or more embodiments, the vulcanizable composition can be characterized by the ratio of silica to other filler compounds, such as carbon black. In one or more embodiments, silica is used in excess relative to other fillers, such as carbon black. In one or more embodiments, the ratio of the amount of silica to carbon black is greater than 1:1, in other embodiments greater than 2:1, in other embodiments greater than 3:1, and in other embodiments greater than 5:1, on a weight ratio basis. In one or more embodiments, the weight ratio of silica to carbon black is from about 1:1 to about 30:1, in other embodiments from about 2.1:1 to about 20:1, and in other embodiments from about 3:1 to about 10:1.

[0106] Silica Coupling Agent In one or more embodiments, the vulcanizable composition comprises greater than 1, in other embodiments greater than 2, and in other embodiments greater than 5 parts by weight (pbw) of silica coupling agent per 100 parts by weight of silica. In these or other embodiments, the vulcanizable composition comprises less than 20, in other embodiments less than 15, and in other embodiments less than 10 pbw of silica coupling agent per 100 parts by weight of silica. In one or more embodiments, the vulcanizable composition comprises from about 1 to about 20, in other embodiments from about 2 to about 15, and in other embodiments from about 5 to about 10 pbw of silica coupling agent per 100 parts by weight of silica. In one or more embodiments, the vulcanizable composition is devoid or substantially devoid of silica coupling agent.

[0107] plasticized resin In one or more embodiments, the vulcanizable composition comprises 0.1, in other embodiments greater than 0.5, in other embodiments greater than 1.0, in other embodiments greater than 1.5, in other embodiments greater than 15, and in other embodiments greater than 25 parts by weight (pbw) of plasticizing resin per 100 parts rubber (phr). In these or other embodiments, the vulcanizable composition comprises 150, in other embodiments less than 120, in other embodiments less than 90, in other embodiments less than 80, in other embodiments less than 60, in other embodiments less than 45, in other embodiments less than 15, in other embodiments less than 10, and in other embodiments less than 3.0 pbw (phr) of plasticizing resin (e.g., hydrocarbon resin). In one or more embodiments, the vulcanizable composition comprises from about 1 to about 150, in other embodiments from about 0.5 to about 15, in other embodiments from about 1 to about 10, in other embodiments from about 1.5 to about 3, in other embodiments from about 15 to about 100, and in other embodiments from about 25 to about 80 pbw (phr) of plasticizing resin (e.g., hydrocarbon resin). In one or more embodiments, the vulcanizable composition is devoid or substantially devoid of plasticizing resins.

[0108] Processing / Extender Oil In one or more embodiments, the vulcanizable composition comprises greater than 0.1, in other embodiments greater than 0.5, in other embodiments greater than 1, in other embodiments greater than 1.5, and in other embodiments greater than 2 pbw of processing oil (naphthenic oil) per 100 parts by weight of rubber (phr). In these or other embodiments, the vulcanizable composition comprises less than 20, in other embodiments less than 18, in other embodiments less than 15, in other embodiments less than 12, in other embodiments less than 10, and in other embodiments less than 8, in other embodiments less than 5, and in other embodiments less than 3 pbw (phr) of processing oil. In one or more embodiments, the vulcanizable composition comprises from about 0.1 to about 20, in other embodiments from about 0.5 to about 18, in other embodiments from about 0.5 to about 15, in other embodiments from about 1 to about 10, in other embodiments from about 0.5 to about 18, in other embodiments from about 1.5 to about 3.0, and in other embodiments from about 2 to about 12 pbw (phr) of oil. In one or more embodiments, the vulcanizable composition is devoid or substantially devoid of oil.

[0109] Plasticizing Additives In one or more embodiments, the plasticizing resin and the processing oil may be collectively referred to as a plasticizing additive, a plasticizing component, a plasticizing ingredient, or a plasticizing system. In one or more embodiments, the vulcanizable composition comprises greater than 0.5, in other embodiments greater than 1, and in other embodiments greater than 1.5 parts by weight (pbw) of the plasticizing additive per hundred parts by weight (phr) of rubber. In these or other embodiments, the vulcanizable composition comprises less than 15, in other embodiments less than 12, in other embodiments less than 10, in other embodiments less than 5, and in other embodiments less than 3 pbw (phr) of the plasticizing additive. In one or more embodiments, the vulcanizable composition comprises from about 0.5 to about 15, in other embodiments from about 1 to about 10, and in other embodiments from about 1.5 to about 3 pbw (phr) of the plasticizing additive.

[0110] hardening resin In one or more embodiments, the vulcanizable composition comprises less than 2, in other embodiments less than 1, and in other embodiments less than 0.5 pbw (phr) of curable resin. In one or more embodiments, the vulcanizable composition comprises from about 0.1 to about 8, in other embodiments from about 0.5 to about 6, and in other embodiments from about 2 to about 4 pbw (phr) of curable resin. In one or more embodiments, the vulcanizable composition is devoid or substantially devoid of curable resin.

[0111] sulfur In one or more embodiments, the vulcanizable composition comprises sulfur as a curative. In one or more embodiments, the vulcanizable composition comprises greater than 0.1, in other embodiments greater than 0.3, and in other embodiments greater than 0.9 parts by weight (pbw) of sulfur per hundred parts by weight of rubber (phr). In these or other embodiments, the vulcanizable composition comprises less than 6, in other embodiments less than 4, in other embodiments less than 3.0, and in other embodiments less than 2.0 pbw (phr) of sulfur. In one or more embodiments, the vulcanizable composition comprises from about 0.1 to about 5.0, in other embodiments from about 0.8 to about 2.5, in other embodiments from about 1 to about 2.0, and in other embodiments from about 1.0 to about 1.8 pbw (phr) of sulfur.

[0112] Processing of vulcanizable compositions In one or more embodiments, the vulcanizable composition is prepared by mixing the vulcanizable rubber and the filler to form a masterbatch, and then the curing agent is subsequently added to the masterbatch. The preparation of the masterbatch may be carried out using one or more auxiliary mixing steps, for example, by preparing an initial mixture by mixing two or more components, followed by sequentially adding one or more components to the composition. Additional components may also be added to the preparation of the vulcanizable composition using conventional techniques, including, but not limited to, carbon black, additional fillers, silica, silica coupling agents, silica dispersants, processing oils, processing aids such as zinc oxide and fatty acids, and anti-degradants such as antioxidants or antiozonants.

[0113] Mixing conditions In one or more embodiments, the various components of the rubber component (e.g., rubber components and fillers), optionally along with carbon black and silica fillers, are introduced to the vulcanizable rubber as initial components in the formation of a rubber masterbatch. As a result, these components undergo high shear, high temperature mixing. In one or more embodiments, this masterbatch mixing step is conducted at a minimum temperature of above 110°C, in other embodiments above 130°C, and in other embodiments above 150°C. In one or more embodiments, the high shear, high temperature mixing is conducted at a temperature of from about 110°C to about 170°C. In one or more embodiments, the masterbatch mixing step, or one or more substeps of the masterbatch mixing step, can be characterized by a peak temperature that the composition reaches during mixing. This peak temperature may also be referred to as a drop temperature. In one or more embodiments, the peak temperature of the composition during the masterbatch mixing step may be at least 140°C, in other embodiments at least 150°C, and in other embodiments at least 160°C. In these or other embodiments, the peak temperature of the composition during the masterbatch mixing step may be from about 140 to about 200°C, from about 150 to about 190°C in other embodiments, and from about 160 to about 180°C in other embodiments.

[0114] Following the initial mixing, the composition (i.e., the masterbatch) is cooled to a temperature below 100°C, or in other embodiments below 80°C, and the curative is added. In certain embodiments, mixing is continued at a temperature of about 90 to about 110°C, or in other embodiments about 95 to about 105°C, to prepare the final vulcanizable composition. Following the masterbatch mixing step, the curative or curative system is introduced to the composition and mixing is continued to ultimately form the vulcanizable composition. This mixing step may be referred to as the final mixing step, the curative mixing step, or the product mixing step. The product resulting from this mixing step may be referred to as the vulcanizable composition.

[0115] In one or more embodiments, the final mixing step can be characterized by a peak temperature that the composition reaches during final mixing. As one of ordinary skill in the art will recognize, this temperature can also be referred to as the final drop temperature. In one or more embodiments, the peak temperature of the composition during final mixing can be up to 130°C, in other embodiments up to 110°C, and in other embodiments up to 100°C. In these or other embodiments, the peak temperature of the composition during final mixing can be from about 80 to about 130°C, in other embodiments from about 90 to about 115°C, and in other embodiments from about 95 to about 105°C.

[0116] Mixing procedures and conditions particularly applicable to silica-filled tire compounds are described in U.S. Patent Nos. 5,227,425, 5,719,207, and 5,717,022, and European Patent No. 890,606, all of which are incorporated herein by reference. In one embodiment, an initial masterbatch is prepared by including the polymer and silica in the substantial absence of coupling and shielding agents.

[0117] mixing equipment All components of the vulcanizable composition can be mixed using standard mixing equipment such as built-in mixers (e.g., Banbury or Brabender mixers), extruders, kneaders, and two-roll mills. Mixing can be done singly or in parallel. As mentioned above, the components can be mixed in a single stage, or in other embodiments, in two or more stages. For example, in the first stage (i.e., mixing stage), a masterbatch (typically including rubber components and fillers) is prepared. Once the masterbatch is prepared, vulcanizing agents may be introduced and mixed into the masterbatch in a final mixing stage, which is typically performed at a relatively low temperature, thereby reducing the possibility of premature vulcanization. An additional mixing stage, sometimes called a remill, can also be employed between the masterbatch mixing stage and the final mixing stage.

[0118] According to an embodiment of the present invention, the use of the functionalized polymer of the present invention provides the unexpected advantage of reduced alcohol production (as a volatile material) during rubber processing, e.g., less ethanol is produced as a volatile material during the rubber mixing process. According to an embodiment of the present invention, the amount of alcohol (e.g., ethanol) liberated from the functionalized polymer of the present invention is less than 5.0, in other embodiments less than 4.0, in other embodiments less than 3.5, and in other embodiments less than 3.0 mmol of ethanol per kilogram of polymer processed, excluding any alcohol (e.g., ethanol) produced from the silane coupling agent. Furthermore, when considering the reduced stabilizer loading required to process the functionalized polymer of the present invention (i.e., the amount of alkoxysilane that must be introduced into the functionalized polymer as a stabilizer), the overall volatile alcohol released during polymer processing is further reduced. According to an embodiment of the present invention, the total volatile alcohol produced during rubber mixing (this volatile alcohol comes from the functionalized polymer and the stabilizer) is less than 110, in other embodiments less than 95, in other embodiments less than 80, and in other embodiments less than 70 mmol of ethanol per kilogram of polymer processed, excluding any alcohol (e.g., ethanol) produced from the silane coupling agent.

[0119] Tire Preparation The vulcanizable composition may be processed into tire components according to conventional tire manufacturing techniques, including standard rubber molding, molding, and curing techniques. Typically, vulcanization is performed by heating the vulcanizable composition in a mold, which may be heated, for example, to about 140°C to about 180°C. The cured or crosslinked rubber composition may be referred to as a vulcanizate, which generally contains a thermoset three-dimensional polymer network. Other ingredients, such as fillers and processing aids, may be uniformly dispersed throughout the crosslinked network. Pneumatic tires may be made as described in U.S. Pat. Nos. 5,866,171, 5,876,527, 5,931,211, and 5,971,046, which are incorporated herein by reference.

[0120] Industrial Applicability As mentioned above, the vulcanizable composition of the present invention can be cured to prepare various tire components, including but not limited to tire treads, tire sidewalls, belt skims, innerliners, ply skims, and bead apexes, which can be included in various vehicle tires, including passenger tires.

[0121] Rubber compositions prepared from the polymers of the present invention are particularly useful in forming tire components such as treads, subtreads, sidewalls, body ply skims, bead fillers, etc. In one or more embodiments, these tread or sidewall compounds may contain from about 10% to about 100% by weight, in other embodiments from about 35% to about 90% by weight, and in other embodiments from about 50% to about 80% by weight of the polymers of the present invention (based on the total weight of rubber in the compound). EXAMPLES

[0122] In order to demonstrate the practice of the present invention, the following examples have been prepared and tested. However, these examples should not be construed as limiting the scope of the invention. The claims shall define the invention.

[0123] Samples were prepared in a 378.5 liter reactor equipped with a heating / cooling jacket and stirrer blade. Butyl lithium was used to anionically initiate random polymerization of butadiene and styrene with hexane in a polymerization mixture containing about 17 wt% monomer. The target base molecular weight was 215 kg / mol (polystyrene standard) and was achieved based on the butyl lithium input. The styrene to butadiene ratio was adjusted to obtain a polymer with 10 wt% styrene and the remainder butadiene. The vinyl content was targeted at 41.5 wt% of butadiene mer units, which was achieved by using 2,2-di(tetrahydrofuryl)propane as the vinyl modifier.

[0124] A reactive polymer cement was prepared by using about 64 kg of hexane, about 11 kg of styrene at about 35 wt% in hexane, and about 155 kg of butadiene at about 23 wt% in hexane, which were charged into the reactor first, and then 1.5 kg of 3 wt% butyllithium was added, followed by 0.012 kg of 2,2-di(tetrahydrofuryl)propane and 0.013 kg of potassium tert-amylate. The monomers and solvent were charged into the reactor at room temperature, stirred, and heated to a stabilization temperature of 33°C. The external heating was then discontinued, and the butyllithium initiator was charged to form a polymerization mixture. The polymerization mixture generally produced an exothermic peak about 23 minutes after the butyllithium charge, and the polymerization mixture was incubated at about 85°C using a cooling jacket. A polymer sample was withdrawn from the polymerization mixture, introduced into a 1-liter bottle, and combined with about 10 mL of isopropanol and about 10 mL of a 10% solution of butylated hydroxytoluene (BHT).

[0125] Within about 5 minutes of peak polymerization temperature, the type and amount of functionalizing agent provided in Table I was charged to the reactor. The polymerization mixture was continuously stirred for about 30 minutes, and then ethylhexanoic acid (EHA) (about 0.092 kg) was added to the reactor, followed by octyltriethoxysilane (OTES), about 4.0 equivalents of OTES per equivalent of lithium relative to the lithium initiator. Then, 0.252 kg of butylated hydroxytoluene (BHT) was charged, followed by about 0.023 kg of isopropanol. The functionalizing agents were 3-(1,3-dimethylbutylidene)aminopropyltriethoxysilane (3-EOS) and 3-(1,3-dimethylbutylidene)aminopropylmethyldiethoxysilane (2-EOS). At this point in the process, peak molecular weights were determined by GPC using polystyrene standards and polystyrene Mark Houwink constants (this analysis was also used to determine % coupling), as well as Mooney viscosity (ML at 100° C.). 1+4Samples were extracted to analyze the glass transition temperature (T) by differential scanning calorimetry (DSC) over the range of -120 °C to 23 °C at a heating rate of 10 °C / min. g ) were measured. Vinyl microstructure of butadiene content (1,2-microstructure) and vinyl microstructure of styrene content were measured by infrared. Total nitrogen analysis was performed (in triplicate) on solidified samples using a Mitsubishi Chemical Analytech NSX-2100 Elemental Analyzer System.

[0126] The polymer analyzed at this point in the process may be referred to as the "blend tank" (e.g., blend tank Mooney). For purposes of this specification and invention, blend tank Mooney and Mooney at desolventization are considered equivalent.

[0127] The polymerization mixture was then transferred to an aqueous desolventization process. Specifically, a tank containing water was heated to a temperature of about 82° C. The polymerization mixture was slowly added to the tank, the hexane was evaporated, and the volatiles were collected in a condenser. The polymer coagulated in the presence of water to form a coagulated polymer dispersion. The polymer was then dehydrated by passing the polymer-water mixture through a grinder (i.e., a single screw extruder equipped with a perforated die). The dehydrated polymer was then dried in an oven at 71° C. for 1 hour, and then heated in an oven at 60° C. until dry (e.g., less than about 0.5% by weight water content). Following drying, the polymer was baled and the Mooney viscosity (ML at 100° C.) was measured. 1+4 ) was measured to obtain the Bale Raw Mooney. Samples of the bales were aged by placing them in a 100° C. oven for 48 hours. The Mooney viscosities (ML at 100° C.) of these aged samples were then measured. 1+4 ) was measured.

[0128] Polymer Mooney viscosity was determined using a Monsanto Mooney viscometer. ML(1+4) values ​​were determined on a large rotor at 100° C. for 4 minutes with a 1 minute warm-up time.

[0129] [Table 1]

[0130] The vulcanizable compositions were prepared in a 300 g Brabender mixer by using the three-stage mixing procedure shown in Table II. The remill did not include the addition of any ingredients. The masterbatch stage was mixed starting at 50 rpm with a mixer temperature of 90° C. and mixed for 5 minutes or until the sample reached 160° C., whichever occurred first. The remill stage was mixed starting at 50 rpm with a mixer temperature of 90° C. and mixed for 3.0 minutes or until the sample reached 160° C., whichever occurred first. The final stage was mixed starting at 40 rpm with a mixer temperature of 60° C. and mixed for 2.5 minutes or until the sample reached 100° C., whichever occurred first.

[0131] [Table 2]

[0132] The vulcanizable compositions were subjected to Mooney analysis. The samples were cured at 145°C for 33 minutes and subjected to mechanical and dynamic property analysis. The mechanical properties were tested according to ASTM D412 and the dynamic properties were tested using a dynamic analyzer. The results of the analysis are listed in Table III.

[0133] [Table 3]

[0134] Various modifications and alterations that do not depart from the scope and spirit of the present invention will be apparent to those skilled in the art. This invention is not to be duly limited to the illustrative embodiments set forth herein.

Claims

1. 1. A polymer composition comprising: The polymer composition comprises a plurality of hydrocarbyloxysilyl terminated polydienes or polydiene copolymers, the polymer composition having an aged Mooney (ML at 100° C.) of about 40 to about 105. １＋４ ), said polymer composition comprising from about 10 to about 95 mole percent of said hydrocarbyloxysilyl terminated polydiene or polydiene copolymer, said hydrocarbyloxysilyl terminated polydiene or polydiene copolymer comprising a reactive polydiene or polydiene copolymer having the formula: 【Chemistry 1】 (In the formula, R １ , R ２ , R ３ , R ４ , and R ５ are each independently a hydrocarbyl group; R ６ is a dihydrocarbyl group.

2. 2. The composition of claim 1, wherein the hydrocarbyloxysilyl terminated polymer is further formed by treating the plurality of hydrocarbyloxysilyl terminated polydienes or polydiene copolymers with a stabilizing agent after the step of reacting the reactive polydiene or polydiene copolymer with a terminating agent.

3. 3. The composition of claim 1 or 2, wherein the stabilizer is an alkylhydrocarbyloxysilane.

4. 4. The composition of any one of claims 1 to 3, wherein the reactive polydiene or polydiene copolymer is prepared with a lithium-based initiator and the plurality of hydrocarbyloxysilyl-terminated polydiene or polydiene copolymers are treated with less than 6 moles of stabilizer per mole of lithium associated with the lithium initiator.

5. A method for preparing a functionalized polydiene or polydiene copolymer polymer composition comprising: reacting a reactive polydiene or polydiene copolymer with a compound of the formula: 【Chemistry 2】 (In the formula, R １ , R ２ , R ３ , R ４ , and R ５ are each independently a hydrocarbyl group; R ６ is a dihydrocarbyl group), thereby forming a functionalized polydiene or polydiene copolymer.

6. 7. The method of claim 6, wherein after the step of reacting the reactive polydiene or polydiene copolymer with an endcapping agent, the functionalized polydiene or polydiene copolymer is treated with a stabilizing agent.

7. 7. The method of any one of claims 1 to 6, wherein the reactive polydiene or polydiene copolymer is formed by anionically polymerizing 1,3-butadiene, optionally together with a monomer copolymerizable therewith, in the presence of a lithium based initiator to form the reactive polydiene or polydiene copolymer.

8. 8. The method of any one of claims 1 to 7, wherein said step of anionically polymerizing reaches a peak polymerization temperature of from about -10°C to about 200°C.

9. 9. The method of any one of claims 1 to 8, wherein the reactive polydiene or polydiene copolymer forms a polymerization mixture, the polymerization mixture comprising greater than 75 mole % of the reactive polydiene or polydiene copolymer, based on the total amount of polydiene or polydiene copolymer.

10. The method of any one of claims 1 to 9, wherein the endcapper is reacted with the reactive polydiene or polydiene copolymer in a molar ratio of from about 0.60:1 to about 1:

1.

11. The method of any one of claims 1 to 10, wherein the stabilizing agent is a low molecular weight hydrocarbyl hydrocarbyloxy silane.

12. 12. The process of any one of claims 1 to 11, wherein the molar ratio of moles of the hydrocarbylhydrocarbyloxysilane to moles of lithium associated with the lithium based initiator is less than 5:

1.

13. 13. The method of any one of claims 1 to 12, wherein the step of reacting the reactive polydiene or polydiene copolymer with an endcapping agent results in greater than 70 mole percent modification of the reactive polydiene or polydiene copolymer.

14. The polymer composition has an unaged Mooney (ML at 100° C.) of about 35 to about 120. １＋４ The method according to any one of claims 1 to 13, comprising the steps of:

15. The method of any one of claims 1 to 14, wherein the reactive polydiene or polydiene copolymer has an Mp of from about 160 to about 280 kg / mol.

16. The process according to any one of claims 1 to 15, wherein the reactive polydiene or polydiene copolymer has a Mn of more than 200 kg / mol.

17. 17. The process of any one of claims 1 to 16, wherein the amount of functionalizing agent used is greater than 0.5 moles of functionalizing agent per mole of lithium in the lithium-containing initiator.

18. 18. The method of any one of claims 1 to 17, wherein the amount of functionalizing agent used is less than 0.95 moles of functionalizing agent per mole of lithium in the lithium-containing initiator.

19. 1. A vulcanizable rubber composition comprising: (i) a functionalized polydiene or polydiene copolymer according to any one of claims 1 to 18; (ii) a silica filler; and (iii) a curing agent.

20. 20. The composition of claim 19, wherein said vulcanizable rubber composition comprises a vulcanizable rubber component, said vulcanizable rubber component comprising greater than 10 weight percent of said functionalized polydiene or polydiene copolymer.

21. The composition of any one of claims 1 to 20, wherein the vulcanizable rubber composition comprises more than 40 parts by weight of silica filler per 100 parts by weight of the rubber component.

22. 22. The composition of any one of claims 1 to 21, wherein the vulcanizable rubber composition is prepared by producing less than 110 mmol of ethanol per kilogram of rubber, excluding any alcohol produced by any silane coupling agent in the vulcanizable composition.

23. A vulcanizate prepared by vulcanizing the vulcanizable composition of any one of claims 1 to 22.

24. The vulcanizate of any one of claims 1 to 23, wherein the vulcanizate is a tire tread.

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