Hydrogenated, functionalized polymers, and rubber compositions incorporating same having improved processability and maintained wear resistance

Abstract

Embodiments of the present disclosure are directed to functionalized copolymers produced by copolymerization of at least one conjugated diolefin monomer and at least one vinyl monomer, the functionalized copolymer comprising at least one alkoxysilyl functional group, wherein the functionalized copolymer has a degree of hydrogenation from 40 mol% to 75 mol%, as measured using proton nuclear magnetic resonance spectroscopy (1H NMR).

Description

Docket No. BDGP21138WO-P21138WO1A1 of 41HYDROGENATED, FUNCTIONALIZED POLYMERS, AND RUBBER COMPOSITIONS INCORPORATING SAME HAVING IMPROVED PROCESSABILITY AND MAINTAINED WEAR RESISTANCECROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Application Serial No.63 / 751,503, filed January 30, 2025, the contents of which are incorporated in their entirety herein.TECHNICAL FIELD

[0002] Embodiments of the present disclosure are generally related to hydrogenated copolymers, and are specifically related to hydrogenated, functionalized copolymers having improved processability and maintained wear resistance.BACKGROUND

[0003] Rubber tires employing tire treads have been used for more than a century. Because the tire tread provides the interface between the tire and the road surface, the tire tread performance correlates to the drivability of the vehicle. The performance of the tire tread, such as wear performance may be improved by increasing the degree of hydrogenation of the functionalized copolymer therein. However, as the degree of hydrogenation increases, viscosity increases, leading to decreased processability.

[0004] Accordingly, a continual need exists for improved rubber compositions with decreased viscosity and maintained wear resistance.SUMMARY

[0005] Embodiments of the present disclosure are directed to rubber compositions comprising hydrogenated, functionalized copolymers, which provide improved processability and maintained wear resistance, especially in tread tire applications. Specifically, by utilizing a hydrogenated, functionalized copolymer comprising a relatively low degree of hydrogenation (e.g., less than or equal to 75 mol%), the rubber composition has a lower viscosity and maintained wear resistance (i.e., within 15%) as compared to a similar rubber composition including a hydrogenated copolymer having a degree of hydrogenation greater than 75 mol%. Lower viscosity may beDocket No. BDGP21138WO-P21138WO1A2 of 41important for compound processability in tire plant mixing and extrusion equipment. Moreover, while the present disclosure may focus on the utilization of the present rubber compositions in tire tread applications, the present compositions may also be suitable for tire sidewalls, inner liners and bladders, because the hydrogenated, functionalized copolymers have good ozone resistance properties (due to minimal double bonds) and good gas permeability (due to minimal solubility of gases within the polymer).

[0006] One embodiment of the present disclosure is directed to a polymer. The polymer comprises a functionalized copolymer produced by copolymerization of at least one conjugated diolefin monomer and at least one vinyl monomer, the functionalized copolymer comprising at least one functional group, wherein the functionalized copolymer has a degree of hydrogenation from 40 mol% to 75 mol%, as measured using proton nuclear magnetic resonance spectroscopy

[0007] Another embodiment of the present disclosure is directed to a method of making a hydrogenated, functionalized copolymer. The method comprises the steps of: introducing an anionic polymerization initiator, at least one conjugated diolefin monomer, at least one vinyl monomer, and solvent to a reactor to produce a living copolymer via anionic polymerization; reacting at least one functional group with the living copolymer to produce a functionalized copolymer; and hydrogenating the functionalized copolymer by mixing the functionalized copolymer with solvent and a hydrogenation catalyst in a hydrogen stream, wherein the hydrogenated, functionalized copolymer has a degree of hydrogenation from 40 mol% to 75 mol%, as measured using

[0008] Additional features and advantages of the embodiments described herein will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the embodiments described herein, including the detailed description which follows, and the claims.DETAILED DESCRIPTION

[0009] The present disclosure will now be described by reference to more detailed embodiments, but the disclosure should not be construed as limited to the embodiments set forthDocket No. BDGP21138WO-P21138WO1A3 of 41herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the subject matter to those skilled in the art.

[0010] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used in the disclosure herein is for describing particular embodiments only and is not intended to be limiting. As used in the specification and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. All publications, patent applications, patents, and other references mentioned herein are expressly incorporated by reference in their entirety.

[0011] Definitions

[0012] The terminology as set forth herein is for description of the embodiments only and should not be construed as limiting the scope of the disclosure as a whole.

[0013] Ranges may be expressed herein as from “about” one particular value, and / or to “about” another particular value. When such a range is expressed, another embodiment includes from the one particular value and / or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another embodiment. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.

[0014] As used herein, the term "phr" means the parts by weight of rubber. If the rubber composition comprises more than one rubber, "phr" means the parts by weight per hundred parts of the sum of all rubbers.

[0015] As used herein, the term "polybutadiene" is used to indicate a polymer that is manufactured from 1,3 -butadiene monomers. The term polybutadiene is also used interchangeably with the phrase "polybutadiene rubber" and the abbreviation "BR."

[0016] As used herein, the term "styrene-butadiene copolymer", “styrene-butadiene rubber” or "SBR" means a copolymer manufactured from styrene and 1,3-butadiene monomers.Docket No. BDGP21138WO-P21138WO1A4 of 41

[0017] As used herein, the term "natural rubber" or "NR" means naturally occurring rubber such as can be harvested from sources such as Hevea rubber trees, and non-Hevea source (e.g., guayule shrubs).

[0018] As used herein, the term “copolymer” refers to a polymer produced from two or more monomers, and thus could encompass polymers produced from two monomers or more than two monomers, such as terpolymers.

[0019] As used herein, “rubber composition” refers to the copolymer (e.g., the functionalized, hydrogenated copolymer) and the additional fdlers and additives blended therewith for use in tire and non-tire applications.

[0020] As used herein, "vinyl content" refers to the percentage of 1,2-vinyl double bonds in the polymer (e.g., the functionalized, hydrogenated copolymer).

[0021] As used herein, “base,” such as in “base weight average molecular weight (Mw),” refers to a property of the copolymer (i.e., base copolymer) prior to being functionalized.

[0022] As used herein, “maintained wear resistance” refers to a wear resistance of a rubber composition disclosed herein that is within 15% of the wear resistance of a similar rubber composition including a hydrogenated copolymer having a degree of hydrogenation greater than 75 mol%.

[0023] As discussed hereinabove, increasing the degree of hydrogenation of a functionalized copolymer included in a rubber composition may decrease the wear resistance of the rubber composition. However, increasing hydrogenation content also increases viscosity, leading to decreased processability.

[0024] Disclosed herein are hydrogenated, functionalized copolymers and rubber compositions comprising same which mitigate the aforementioned problems. Specifically, the hydrogenated, functionalized copolymers disclosed herein have a degree of hydrogenation from 40 mol% to 75 mol%, as measured using proton nuclear magnetic resonance spectroscopy (XH NMR). This relatively lower degree of hydrogenation results in a rubber composition having a lower viscosity, thereby improving processability, while maintaining wear resistance (e.g., withinDocket No. BDGP21138WO-P21138WO1A5 of 4115%) as compared to a similar rubber composition including a hydrogenated copolymer having a degree of hydrogenation greater than 75 mol%.

[0025] Monomers

[0026] Various monomers are contemplated for the conjugated diolefin monomers and the vinyl monomers.

[0027] The conjugated diolefin monomers may include various hydrocarbon compositions. For example, the conjugated diolefins include those having from about 4 to about 12 carbon atoms such as 1,3 -butadiene, 1,3 -cyclohexadiene, isoprene, 1,3 -pentadiene, 1,3 -hexadiene, 2,3-dimethyl- 1,3 -butadiene, 2-ethyl- 1,3 -butadiene, 2-methyl-l,3 pentadiene, 3-methyl-l,3-pentadiene, 4-methyl- 1,3 -pentadiene, and 2,4-hexadiene, or combinations thereof. The conjugated diolefins also may encompass trienes such as myrcene.

[0028] The vinyl monomers may copolymerize with the conjugated diolefin monomers to produce a copolymer or terpolymers. The vinyl aromatic monomers may comprise hydrocarbons having from about 8 to about 20 carbon atoms or from about 8 to 10 carbon atoms. These vinyl aromatic monomers may include vinyl aromatic monomers, for example, monovinyl aromatic hydrocarbons. In one or more embodiments, the vinyl monomers may comprise styrene, alphamethyl styrene, 1 -vinylnaphthalene, 2-vinylnaphthalene, 1 -alpha-methylvinylnaphthalene, 2-alphamethyl-vinylnaphthalene, and mixtures of these as well as halo, alkoxy, alkyl, cycloalkyl, aryl, alkaryl and aralkyl derivatives thereof in which the total number of carbon atoms in the combined hydrocarbon is generally not greater than 12. Examples of these latter compounds include 4-methylstyrene, vinyl toluene, 3,5-diethylstyrene, 2-ethyl-4-benzylstyrene, 4-phenylstyrene, 4-para-tolylstyrene, and 4,5-dimethyl-l -vinylnaphthalene, or mixtures thereof.

[0029] The copolymers may comprise from 20 to 100 % by weight, or about 40 to 80 % by weight of the conjugated diolefin monomers. Conversely, the copolymers may comprise from 0 to about 80 % by weight or about 10 to about 50 % by weight of vinyl aromatic monomers. The copolymers may be random copolymers or block copolymers. In one embodiment, the conjugated diolefin monomer is 1,3 -butadiene and the vinyl aromatic monomer is styrene, which copolymerize to produce styrene butadiene copolymers. In specific embodiments, the copolymer is a random styrene butadiene copolymer.Docket No. BDGP21138WO-P21138WO1A6 of 41

[0030] Solvents

[0031] The polymerizations of the present disclosure may be conducted in the presence of solvent, for example, inert solvent. The term "inert solvent" means that the solvent does not enter into the structure of the resulting polymer, does not adversely affect the properties of the resulting polymer, and does not adversely affect the activity of the catalyst employed. Suitable inert solvents include hydrocarbon solvents which may contain aliphatic, aromatic, or cycloaliphatic hydrocarbons such as hexane, pentane, toluene, benzene, cyclohexane and the like. Ethers such as tetrahydro furan and tertiary amines such as triethylamine and tributylamine may also be used as solvents, but these may modify the polymerization as to styrene distribution, vinyl content and rate of reaction. In one or more embodiments, the solvents may comprise hexane, or blends and mixtures of hexanes (e.g., linear and branched), for example, cyclohexane alone or mixed with other forms of hexane.

[0032] Anionic Polymerization Initiator

[0033] Various anionic polymerization initiators are contemplated for the anionic polymerization processes of the present disclosure. The anionic polymerization initiator may comprises a lithium catalyst, specifically, an organolithium anionic initiator catalyst. The organolithium initiator employed may be any anionic organolithium initiators useful in the polymerization of conjugated diolefin monomers (e.g., 1,3-butadiene monomers). In general, the organolithium compounds include hydrocarbon containing lithium compounds of the formula R(Li)xwherein R represents hydrocarbon groups containing from one to about 20 carbon atoms, and preferably from about 2 to about 8 carbon atoms, and x is an integer from 1 to 2. Although the hydrocarbon group is preferably an aliphatic group, the hydrocarbon group may also be cycloaliphatic or aromatic. The aliphatic groups may be primary, secondary, or tertiary groups although the primary and secondary groups are preferred. Examples of aliphatic hydrocarbyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, n- amyl, sec-amyl, n-hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-dodecyl, and octa-decyl. The aliphatic groups may contain some unsaturation such as allyl, 2-butenyl, and the like. Cycloalkyl groups are exemplified by cyclohexyl, methylcyclohexyl, ethylcyclohexyl, cycloheptyl, cyclopentylmethyl, and methylcyclopentylethyl. Examples of aromatic hydrocarbyl groups include phenyl, tolyl, phenylethyl, benzyl, naphthyl, phenyl cyclohexyl, and the like. Mixtures of different lithium initiator compounds also can be employed such as those containing one or more lithiumDocket No. BDGP21138WO-P21138WO1A7 of 41compounds such as R(Li)x, R and x as defined above. Other lithium catalysts which can be employed alone or in combination with the hydrocarbyl lithium initiators are tributyl tin lithium, lithium dialkyl amines, lithium dialkyl phosphines, lithium alkyl aryl phosphines and lithium diaryl phosphines. In one embodiment, the organolithium initiator is n-butyl lithium.

[0034] The amount of initiator required to effect the desired polymerization may be varied over a wide range depending upon a number of factors such as the desired polymer molecular weight, the desired 1,2- and 1,4-content of the conjugated diene, and the desired physical properties for the polymer produced. In general, the amount of initiator utilized may vary from as little as 0.2 millimole of lithium per 100 grams of monomers up to about 100 millimoles of lithium per 100 grams of monomers, depending upon the desired polymer molecular weight.

[0035] Polymerization is begun by introducing the monomer(s) and solvent to a suitable reaction vessel, followed by the addition of the anionic polymerization initiator. The polymerization reaction may be carried out in a batch polymerization reactor system or a continuous polymerization reactor system. Polymerization conditions such as temperature, pressure, and time are well known in the art for polymerizing the monomers as described with the anionic polymerization initiator as described. For example, for illustrative purposes only, the temperature employed in the polymerization is generally not critical and may range from about -60° C to about 150° C. Exemplary polymerization temperatures may range from about 25° C to about 130° C for a polymerization time of a few minutes to up to 24 hours or more, and employing pressures generally sufficient to maintain polymerization admixtures substantially in the liquid phase, for example, at or near atmospheric pressure, depending on the temperature and other reaction parameters. The procedure may be carried out under anhydrous, anaerobic conditions. Polymerization of any of the above-identified monomers in the presence of an organolithium initiator results in the formation of a "living" polymer. The lithium proceeds to move down the growing chain as polymerization continues. Throughout formation or propagation of the polymer, the polymeric structure may be anionic and living. In other words, a carbon anion is present. A new batch of monomer subsequently added to the reaction can add to the living ends of the existing chains and increase the degree of polymerization. A living polymer or copolymer, therefore, may include a polymeric segment having an anionic reactive end.

[0036] Functional GroupsDocket No. BDGP21138WO-P21138WO1A8 of 41

[0037] Functional groups may then be applied to the anionic reactive end of the living polymer to cap or terminate the living polymer. For the present functional copolymers, the functional groups may be silica-reactive. The silica-reactive moieties encompass one or more reactive groups that will react with silica reinforcing fdler to form an ionic or covalent bond. Useful functional groups that react with silica typically are electron donors or are capable of reacting with a proton.

[0038] Non-limiting examples of nitrogen-containing functional groups that can be utilized include, but are not limited to, a substituted or unsubstituted amino group, an amide residue, an isocyanate group, an imidazolyl group, an indolyl group, an imino group, a nitrile group, a pyridyl group, and a ketimine group. The foregoing substituted or unsubstituted amino group should be understood to include a primary alkylamine, a secondary alkylamine, or a cyclic amine, and an amino group derived from a substituted or unsubstituted imine.

[0039] In embodiments, the functional group may be from a compound which includes nitrogen in the form of an imino group. Such an imino-containing functional group may be added by reacting the active terminal of a polymer chain with a compound having the following formula (I):wherein R, R’, R”, and R’” each independently are selected from a group having 1 to 18 carbon""atoms (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms) selected from the group consisting of an alkyl group, an allyl group, and an aryl group; m and n are integers of 1 to 20 (e.g, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20) and 1 to 3 (1, 2, or 3), respectively. Each of R, R’, R”, and R’” may be hydrocarbyl and contain no heteroatoms. In embodiments, each R and R’ may be independently selected from an alkyl group having 1 to 6 carbon atoms (e.g, 1, 2, 3, 4, 5, or 6 carbon atoms. In some embodiments, m may be an integer of 2 to 6 (e.g, 2, 3, 4, 5, or 6). In embodiments, R’” may be selected from an alkyl group having 1 to 6 carbon atoms (e.g, 1, 2, 3, 4, 5, or 6 carbon atoms). In some embodiments, R” may be selected from an alkyl group having 1 to 6 carbon atoms (e.g, 1, 2, 3, 4, 5, or 6 carbon atoms). In embodiments, n may be 3 resulting in a compound with a trihydrocarboxysilane moietyDocket No. BDGP21138WO-P21138WO1A9 of 41such as a trialkoxysilane moiety. Non-limiting examples of compounds having an imino group and meeting formula (I) above, which are suitable for providing the silica-reactive functional group for the styrene-butadiene rubber of (i) include, but are not limited to, N-(l,3-dimethylbutylidene)-3 -(triethoxysilyl)- 1 -propaneamine, N-(l-methylethylidene)-3- (triethoxysilyl)-l -propaneamine, N-ethylidene-3-(triethoxysilyl)-l -propaneamine, N-(l-methylpropylidene)-3 -(triethoxysilyl)- 1 -propaneamine, and N-(4-N,N-dimethylaminobenzylidene )-3-( triethoxysilyl)-l -propaneamine.

[0040] Non-limiting examples of silicon-containing functional groups that can be utilized include, but are not limited to, an organic silyl or siloxy group, and more precisely, such a functional group may be selected from an alkoxysilyl group, an alkylhalosilyl group, a siloxy group, an alkylaminosilyl group, and an alkoxyhalosilyl group. Optionally, the organic silyl or siloxy group may also contain one or more nitrogens. Suitable silicon-containing functional groups for use in functionalizing diene-based elastomers also include those disclosed in U.S. Patent No. 6,369,167, the entire disclosure of which is herein incorporated by reference. .

[0041] In some embodiments, the functional group may include a silicon-containing functional group having a siloxy group (e.g., a hydrocarbyloxysilane-containing compound), wherein the compound optionally includes a monovalent group having at least one functional group. Such a silicon-containing functional group may be added by reacting the active terminal of a polymer chain with a compound having the following formula (II):wherein A1represents a monovalent group having at least one functional group selected from epoxy, isocyanate, imine, cyano, carboxylic ester, carboxylic anhydride, cyclic tertiary amine, non-cyclic tertiary amine, pyridine, silazane and sulfide; Rcrepresents a single bond or a divalent hydrocarbon group having from 1 to 20 carbon atoms (e.g, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms); Rdrepresents a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms (e.g, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms), a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms (e.g, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms) or areactive group; RerepresentsDocket No. BDGP21138WO-P21138WO1A10 of 41a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms) or a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms (e.g, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms); b is an integer of 0 to 2; when more than one Rdor OReare present, each Rdand / or ORemay be the same as or different from each other; and an active proton is not contained in a molecule) and / or a partial condensation product thereof. As used herein, a partial condensation product refers to a product in which a part (not all) of a SiOR group in the hydrocarbyloxysilane compound is turned into a SiOSi bond by condensation. In embodiments, at least one of the following is met: (a) Rcrepresents a divalent hydrocarbon group having 1 to 12 carbon atoms (e.g, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms), 2 to 6 carbon atoms (e.g, 2, 3, 4, 5, or 6 carbon atoms), or 2 to 3 carbon atoms (e.g, 2 or 3 carbon atoms); (b) Rerepresents a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms (e.g, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms), 2 to 6 carbon atoms (e.g, 2, 3, 4, 5, or 6 carbon atoms), or 1 to 2 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 8 carbon atoms; (c) Rdrepresents a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms(e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms), 2 to 6 carbon atoms (e.g, 2, 3, 4, 5, or 6 carbon atoms), or 1 to 2 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 8 carbon atoms; in certain such embodiments, each of (a), (b) and (c) are met and Rc, Reand Rdare selected from one of the foregoing groups.

[0042] In some embodiments, the functional group results from a compound represented by Formula (II) wherein A1has at least one epoxy group. Non-limiting specific examples of such compounds include 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, (2-gly cidoxy ethyl)methyldimethoxy silane, 3 -gly cidoxypropyltrimethoxy silane, y_glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, (3-glycidoxypropyl)-methyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyl(methyl)dimethoxysilane and the like.

[0043] In some embodiments, the functional group results from a compound represented by Formula (II) wherein A1has at least one isocyanate group. Non-limiting specific examples of such compounds include 3 -isocyanatopropyltrimethoxy silane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 3-isocyanatopropyltriisopropoxysilane and the like.Docket No. BDGP21138WO-P21138WO1A11 of 41

[0044] In some embodiments, the functional group results from a compound represented by Formula (II) wherein A1has at least one imine group. Non-limiting specific examples of such compounds include N-(l,3-dimethylbutylidene)-3-(triethoxysilyl)-l-propaneamine, N-(l-methylethylidene)-3-(triethoxysilyl)-l -propaneamine, N-ethylidene-3-(triethoxysilyl)-l-propaneamine, N-(l-methylpropylidene)-3 -(triethoxysilyl)- 1 -propaneamine, N-(4-N,N-dimethylaminobenzylidene)-3-(triethoxysilyl)-l -propaneamine, N-(cyclohexylidene)-3- (triethoxysilyl)-l -propaneamine and trimethoxysilyl compounds, methyldiethoxysilyl compounds, ethyldimethoxysilyl compounds and the like each corresponding to the above triethoxysilyl compounds. Also, the imine(amidine) group-containing compounds may include 1-[3-trimethoxysilyl]propyl]-4,5-dihydroimidazole, 3-(l-hexamethyleneimino)propyl(triethoxy)silane, (l-hexamethyleneimino)methyl(trimethoxy)silane, N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole, N-(3-isopropoxysilylpropyl)-4,5-dihydroimidazole, N-(3-methyldiethoxysilylpropyl)-4,5-dihydroimidazole and the like.

[0045] In embodiments, the functional group results from a compound represented by Formula (II) wherein A1has at least one carboxylic ester group. Non-limiting specific examples of such compounds include 3 -methacryloyloxypropyltriethoxy silane, 3-methacryloyloxypropyltrimethoxy silane, 3 -methacryloyloxypropylmethyldiethoxy silane, 3 -methacryloyloxypropyltriisopropoxysilane and the like.

[0046] In some embodiments, the functional group results from a compound represented by Formula (II) wherein A1has at least one carboxylic anhydride group. Non-limiting specific examples of such compounds include 3 -trimethoxy silylpropylsuccinic anhydride, 3-triethoxysilylpropylsuccinic anhydride, 3-methyldiethoxysilylpropylsuccinic anhydride and the like.

[0047] In some embodiments, the functional group results from a compound represented by Formula (II) wherein A1has at least one cyano group. Non-limiting specific examples of such compounds include 2-cyanoethylpropyltriethoxysilane and the like.

[0048] In embodiments, the functional group results from a compound represented by Formula (II) wherein A1has at least one cyclic tertiary amine group. Non-limiting specific examples of such compounds include 3 -(l-hexamethyleneimino)propyltriethoxy silane, 3-(l-hexamethyleneimino)propyltrimethoxy silane, (1 -hexamethyleneimino)methyltriethoxy silane, (1 -Docket No. BDGP21138WO-P21138WO1A12 of 41 hexamethyleneimino)methyltrimethoxy silane, 2-(l -hexamethyleneimino)ethyltriethoxysilane, 3-(1 -hexamethyleneimino)ethyltrimethoxysilane, 3-(l -pyrrolidinyl)propyltrimethoxysilane, 3-(l -pyrrolidinyl)propyltriethoxysilane, 3-(l -heptamethyleneimino)propyltriethoxysilane, 3-(l-dodecamethyleneimino)propyltri ethoxy silane, 3-(l-hexamethyleneimino)propyldiethoxymethylsilane, 3 -( 1 -hexamethyleneimino)propyldiethoxyethylsilane, 3-[10-(triethoxysilyl)decyl]-4-oxazoline and the like.

[0049] In some embodiments, the functional group results from a compound represented by Formula (II) wherein A1has at least one non-cyclic tertiary amine group. Non-limiting specific examples of such compounds include 3 -dimethylaminopropyltri ethoxy silane, 3-dimethylaminopropyltrimethoxy silane, 3 -diethylaminopropyltriethoxy silane, 3 -dimethylaminopropyltrimethoxysilane, 2-dimethylaminoethyltriethoxysilane, 2-dimethylaminoethyltrimethoxy silane, 3-dimethylaminopropyldiethoxymethylsilane, 3-dibutylaminopropyltriethoxy silane and the like, and among them, 3-dimethylaminopropyltriethoxysilane and 3 -diethylaminopropyltri ethoxysilane are suited.

[0050] In embodiments, the functional group results from a compound represented by Formula (II) wherein A1has at least one pyridine group. Non-limiting specific examples of such compounds include 2-trimethoxysilylethylpyridine and the like.

[0051] In some embodiments, the functional group results from a compound represented by Formula (II) wherein A1has at least one silazane group. Non-limiting specific examples of such compounds include N,N-bis(trimethylsilyl)-aminopropylmethyldimethoxysilane, 1-trimethylsilyl-2,2-dimethoxy-l -aza-2-silacyclopentane, N,N-bis(trimethylsilyl)aminopropyltrimethoxysilane, N,N-bis(trimethylsilyl)aminopropyltriethoxysilane, N,N-bis(trimethylsilyl)aminopropylmethyldiethoxysilane, N,N-bis(trimethylsilyl)aminoethyltrimethoxysilane,N,N-bis(trimethylsilyl)aminoethyltriethoxysilane, N,N-bis(trimethylsilyl)aminoethylmethyldimethoxysilane, N,N-bis(trimethylsilyl)aminoethylmethyldiethoxysilane and the like.

[0052] Non-limiting examples of oxygen- or sulfur-containing functional groups that can be utilized include, but are not limited to, a hydroxyl group, a carboxyl group, an epoxy group, aDocket No. BDGP21138WO-P21138WO1A13 of 41glycidoxy group, a diglycidylamino group, a cyclic dithiane-derived functional group, an ester group, an aldehyde group, an alkoxy group, a ketone group, a thiocarboxyl group, a thioepoxy group, a thioglycidoxy group, a thiodiglycidylamino group, a thioester group, a thioaldehyde group, a thioalkoxy group, and a thioketone group. In some embodiments, the foregoing alkoxy group may be an alcohol-derived alkoxy group derived from a benzophenone.

[0053] The alkoxysilyl functional group may be derived from an alkoxysilane compound selected from the group consisting of 2-(3,4 epoxycyclohexyl)ethyltrimethoxysilane, 3-gly cidylpropyltrimethoxy silane, y-g lyc i doxy propy I tri methoxy s i I ane, 3 -glycidylpropylmethyldimethoxysilane, or combinations thereof.

[0054] The polymerization conditions and reactants may dictate how much of the functional group is added. In one or more embodiments, the functional group may be present in a molar ratio (to initiator) of about 0.25 to 2, or about 0.5 to 1.

[0055] Functionalized Copolymer

[0056] In embodiments, the functionalized copolymer may be an alkoxysilane functionalized styrene butadiene copolymer.

[0057] The functionalized copolymer may have a minimum base weight average molecular weight (Mw) (e.g., greater than or equal to 50,000 g / mol) to ensure a rubber composition having a maintained wear resistance is achieved. The base weight average molecular weight (Mw) of the functionalized copolymer may be limited (e.g., less than or equal to 500,000 g / mol) to ensure improved processability. Accordingly, in embodiments, the functionalized copolymer may have a base weight average molecular weight (Mw) from 50,000 g / mol to 500,000 g / mol. In embodiments, the functionalized copolymer may have a base weight average molecular weight (Mw) greater than or equal to 50,000 g / mol; greater than or equal to 75,000 g / mol; greater than or equal to 100,000 g / mol; greater than or equal to 125,000 g / mol; or even greater than or equal to 150,000 g / mol. In embodiments, the functionalized copolymer may have a base weight average molecular weight (Mw) less than or equal to 500,000 g / mol; less than or equal to 450,000 g / mol; less than or equal to 400,000 g / mol; less than or equal to 350,000 g / mol; less than or equal to 300,000 g / mol; less than or equal to 250,000 g / mol; or even less than or equal to 200,000 g / mol. In embodiments, the functionalized copolymer may have a base weight average molecular weightDocket No. BDGP21138WO-P21138WO1A14 of 41(Mw) from 50,000 g / mol to 500,000 g / mol;, from 50,000 g / mol to 450,000 g / mol; from 50,000 g / mol to 400,000 g / mol; from 50,000 g / mol to 350,000 g / mol; from 50,000 g / mol to 300,000 g / mol; from 50,000 g / mol to 250,000 g / mol; from 50,000 g / mol to 200,000 g / mol; from 75,000 g / mol to 500,000 g / mol; from 75,000 g / mol to 450,000 g / mol; from 75,000 g / mol to 400,000 g / mol; from 75,000 g / mol to 350,000 g / mol; from 75,000 g / mol to 300,000 g / mol; from 75,000 g / mol to 250,000 g / mol; from 75,000 g / mol to 200,000 g / mol; from 100,000 g / mol to 500,000 g / mol; from 100,000 g / mol to 450,000 g / mol; from 100,000 g / mol to 400,000 g / mol; from 100,000 g / mol to 350,000 g / mol; from 100,000 g / mol to 300,000 g / mol; from 100,000 g / mol to 250,000 g / mol; from 100,000 g / mol to 200,000 g / mol; from 125,000 g / mol to 500,000 g / mol; from 125,000 g / mol to 450,000 g / mol; from 125,000 g / mol to 400,000 g / mol; from 125,000 g / mol to 350,000 g / mol; from 125,000 g / mol to 300,000 g / mol; from 125,000 g / mol to 250,000 g / mol; from 125,000 g / mol to 200,000 g / mol; from 150,000 g / mol to 500,000 g / mol; from 150,000 g / mol to 450,000 g / mol; from 150,000 g / mol to 400,000 g / mol; from 150,000 g / mol to 350,000 g / mol; from 150,000 g / mol to 300,000 g / mol; from 150,000 g / mol to 250,000 g / mol; or even from 150,000 g / mol to 200,000 g / mol; or any and all sub-ranges formed from any of these endpoints.

[0058] The functionalized copolymer may have a minimum base number average molecular weight (Mn) (e.g., greater than or equal to 25,000 g / mol) to ensure a rubber composition having a maintained wear resistance is achieved. The base number average molecular weight (Mn) of the functionalized copolymer may be limited (e.g., less than or equal to 500,000 g / mol) to ensure improved processability. In embodiments, the functionalized copolymer may have a base number average molecular weight (Mn) from 25,000 g / mol to 500,000 g / mol. In embodiments, the functionalized copolymer may have a base number average molecular weight (Mn) greater than or equal to 25,000 g / mol; greater than or equal to 50,000 g / mol; greater than or equal to 75,000 g / mol, greater than or equal to 100,000 g / mol; greater than or equal to 125,000 g / mol; or even greater than or equal to 150,000 g / mol. In embodiments, the functionalized copolymer may have a base number average molecular weight (Mn) less than or equal to 500,000 g / mol; less than or equal to 400,000 g / mol; less than or equal to 300,000 g / mol; less than or equal to 200,000 g / mol; or even less than or equal to 100,000 g / mol. In embodiments, the functionalized copolymer may have a base number average molecular weight (Mn) from 25,000 g / mol to 500,000 g / mol; from 25,000 g / mol to 400,000 g / mol; from 25,000 g / mol to 300,000 g / mol; from 25,000 g / mol to 200,000 g / mol; from 25,000 g / mol to 100,000 g / mol; from 50,000 g / mol to 500,000 g / mol; from 50,000 g / mol to 400,000 g / mol; from 50,000 g / mol to 300,000 g / mol; from 50,000 g / mol to 200,000Docket No. BDGP21138WO-P21138WO1A15 of 41g / mol; from 50,000 g / mol to 100,000 g / mol; from 75,000 g / mol to 500,000 g / mol; from 75,000 g / mol to 400,000 g / mol; from 75,000 g / mol to 300,000 g / mol; from 75,000 g / mol to 200,000 g / mol; from 75,000 g / mol to 100,000 g / mol; from 100,000 g / mol to 500,000 g / mol; from 100,000 g / mol to 400,000 g / mol; from 100,000 g / mol to 300,000 g / mol; from 100,000 g / mol to 200,000 g / mol; from 125,000 g / mol to 500,000 g / mol; from 125,000 g / mol to 400,000 g / mol; from 125,000 g / mol to 300,000 g / mol; from 125,000 g / mol to 200,000 g / mol; from 150,000 g / mol to 500,000 g / mol; from 150,000 g / mol to 400,000 g / mol; from 150,000 g / mol to 300,000 g / mol; or even from 150,000 g / mol to 200,000 g / mol, or any and all sub-ranges formed from any of these endpoints.

[0059] In embodiments, the functionalized copolymer may have a base peak molecular weight (Mp) greater than or equal to 50,000 g / mol; greater than or equal to 75,000 g / mol; greater than or equal to 100,000 g / mol; greater than or equal to 125,000 g / mol; or even greater than or equal to 150,000 g / mol. In embodiments, the functionalized copolymer may have a base peak molecular weight (Mp) less than or equal to 500,000 g / mol; less than or equal to 450,000 g / mol; less than or equal to 400,000 g / mol; less than or equal to 350,000 g / mol; less than or equal to 300,000 g / mol; less than or equal to 250,000 g / mol; or even less than or equal to 200,000 g / mol. In embodiments, the functionalized copolymer may have a base peak molecular weight (Mp) from 50,000 g / mol to 500,000 g / mol;, from 50,000 g / mol to 450,000 g / mol; from 50,000 g / mol to 400,000 g / mol; from 50,000 g / mol to 350,000 g / mol; from 50,000 g / mol to 300,000 g / mol; from 50,000 g / mol to 250,000 g / mol; from 50,000 g / mol to 200,000 g / mol; from 75,000 g / mol to 500,000 g / mol; from 75,000 g / mol to 450,000 g / mol; from 75,000 g / mol to 400,000 g / mol; from 75,000 g / mol to 350,000 g / mol; from 75,000 g / mol to 300,000 g / mol; from 75,000 g / mol to 250,000 g / mol; from 75,000 g / mol to 200,000 g / mol; from 100,000 g / mol to 500,000 g / mol; from 100,000 g / mol to 450,000 g / mol; from 100,000 g / mol to 400,000 g / mol; from 100,000 g / mol to 350,000 g / mol; from 100,000 g / mol to 300,000 g / mol; from 100,000 g / mol to 250,000 g / mol; from 100,000 g / mol to 200,000 g / mol; from 125,000 g / mol to 500,000 g / mol; from 125,000 g / mol to 450,000 g / mol; from 125,000 g / mol to 400,000 g / mol; from 125,000 g / mol to 350,000 g / mol; from 125,000 g / mol to 300,000 g / mol; from 125,000 g / mol to 250,000 g / mol; from 125,000 g / mol to 200,000 g / mol; from 150,000 g / mol to 500,000 g / mol; from 150,000 g / mol to 450,000 g / mol; from 150,000 g / mol to 400,000 g / mol; from 150,000 g / mol to 350,000 g / mol; from 150,000 g / mol to 300,000 g / mol; from 150,000 g / mol to 250,000 g / mol; or even from 150,000 g / mol to 200,000 g / mol; or any and all sub-ranges formed from any of these endpoints.Docket No. BDGP21138WO-P21138WO1A16 of 41

[0060] In embodiments, a ratio of a base weight average molecular weight (Mw) of the functionalized copolymer to a base number average molecular weight (Mn) of the functionalized copolymer is from 1 to 2 to ensure a rubber composition having a maintained wear resistance is achieved. In embodiments, a ratio of a base weight average molecular weight (Mw) of the functionalized copolymer to a base number average molecular weight (Mn) of the functionalized copolymer may be greater than or equal to 1, greater than or equal to 1.25, or even greater than or equal to 1.5. In embodiments, a ratio of a base weight average molecular weight (Mw) of the functionalized copolymer to a base number average molecular weight (Mn) of the functionalized copolymer may be less than or equal to 2, less than or equal to 1.75, less than or equal to 1.5, or even less than or equal to 1.25. In embodiments, a ratio of a base weight average molecular weight (Mw) of the functionalized copolymer to a base number average molecular weight (Mn) of the functionalized copolymer may be from 1 to 2, from 1 to 1.75, from 1 to 1.5, from 1 to 1.25, from 1.25 to 2, from 1.25 to 1.75, from 1.25 to 1.5, from 1.5 to 2, or even from 1.5 to 1.75, or any and all sub-ranges formed from any of these endpoints.

[0061] Additional Polymerization Ingredients

[0062] Additionally, in order to promote randomization in copolymerization and to control vinyl content, one or more polymeric modifiers may optionally be added to the polymerization ingredients. Amounts of polymeric modifier may range from 0 to about 90 or more equivalents per equivalent of initiator (e.g., lithium catalyst). Compounds useful as polymeric modifiers are typically organic and include those having an oxygen or nitrogen hetero-atom and a non-bonded pair of electrons. Examples include dialkyl ethers of mono and oligo alkylene glycols, “crown” ethers, tertiary amines such as tetramethyethylene diamine (TMEDA), tetrahydrofuran (THF), 2,2-bis(2’ -tetrahydro furyl)propane, THF oligomers linear and cyclic oligomeric oxolanyl alkanes (e.g., cyclic oligomeric oxolanyl propanes), potassium / -amylate (KTA), or combinations thereof.

[0063] The process of the present disclosure may optionally also include a stabilizing agent, for example, a silane stabilizing agent. One suitable silane stabilizing agent is octyltriethoxysilane. Moreover, an antioxidant such as 2,6-di-t-butyl-4-methylphenol (also called butylated hydoxytoluene (BHT)) may be added to reduce the likelihood of Mooney viscosity instability due to oxidative coupling. The stabilizing agent may be added to the reactor or another mixer downstream of the reactor. Similarly, the antioxidant may be added to the reactor or another mixer downstream of the reactor.Docket No. BDGP21138WO-P21138WO1A17 of 41

[0064] Optionally, upon termination, the functionalized terminated polymer may be quenched, if necessary, and dried. Quenching may be conducted by contacting the functionalized copolymer with a quenching agent for about 0.05 to about 2 hours at temperatures of from about 30° C to about 120° C to insure complete reaction. Suitable well known quenching agents include alcohols, water, carboxylic acids such 2-ethyl hexanoic acid (EHA), acetic acid and the like. Coagulation is typically done with alcohols such as methanol or isopropanol. Alternative to, or in combination with, the step of quenching, the functionalized polymer may be drum dried as known in the art. The use of steam or high heat to remove solvent is also considered suitable.

[0065] Hydrogenation

[0066] After production of the functionalized copolymer, the functionalized copolymer is hydrogenated by mixing the functionalized copolymer with a solvent and a hydrogenation catalyst in the presence of a hydrogen stream. The solvent may include one or more of the solvents described above. In one embodiment, the hydrogenation catalyst comprises nickel. In further embodiments, the hydrogenation catalyst comprises nickel and aluminum. In one or more embodiments, the nickel of the hydrogenation catalyst comprises an organic nickel compound such as nickel octoate. For hydrogenation catalysts including nickel and aluminum, the aluminum may also include an organic aluminum compound. In one embodiment, the organic aluminum compound is triethylaluminum. The nickel and aluminum may be included in various amounts. For example, the aluminum and nickel may be added at an Al / Ni molar ratio from 1:1 to 5:1 or from 2:1 to 4:1.

[0067] In the hydrogenation process, pressurized hydrogen may be added at a pressure from 1 atm to 100 atm. Like the above polymerization, additional components, such as the quenching agents and antioxidants, may be added to the reactor.

[0068] The following exemplary reaction depicted in Formula 1 below illustrates the hydrogenation of a styrene-butadiene copolymer.Docket No. BDGP21138WO-P21138WO1A18 of 41SBRFormula 1

[0069] While not shown in Formula 1 above, the styrene butadiene copolymer may be functionalized with a functional group comprising silica reactive moieties prior to hydrogenation.

[0070] As described herein, in embodiments, the functionalized copolymer may have a degree of hydrogenation from 40 mol% to 75 mol%, as measured using proton nuclear magnetic resonance spectroscopy (1H NMR), such that the rubber composition including the functionalized copolymer has a lower viscosity and maintained wear resistance (i.e., within 15%) as compared to a similar rubber composition including a hydrogenated copolymer having a degree of hydrogenation greater than 75 mol%. In embodiments, the functionalized copolymer may have a degree of hydrogenation from 50 mol% to 75 mol%, as measured usingNMR. In embodiments, the functionalized copolymer may have a degree of hydrogenation greater than or equal to 40 mol%, greater than or equal to 45 mol%, greater than or equal to 50 mol%, greater than or equal to 55 mol%, greater than or equal to 60 mol%, greater than or equal to 65 mol%, or even greater than or equal to 70 mol%, as measured usingNMR. In embodiments, the functionalized copolymer may have a degree of hydrogenation less than or equal to 75 mol% or even less than or equal to 70 mol%, as measured using NMR. In embodiments, theDocket No. BDGP21138WO-P21138WO1A19 of 41functionalized copolymer may have a degree of hydrogenation from 40 mol% to 75 mol%, from 40 mol% to 70 mol%, from 45 mol% to 75 mol%, from 45 mol% to 70 mol%, from 50 mol% to 75 mol%, from 50 mol% to 70 mol%, from 55 mol% to 75 mol%, from 55 mol% to 70 mol%, from 60 mol% to 75 mol%, from 60 mol% to 70 mol%, from 65 mol% to 75 mol%, from 65 mol% to 70 mol%, or even from 70 mol% to 75 mol%, or any and all sub-ranges formed from any of these endpoints, as measured using

[0071] While the hydrogenation reduces the number of double bonds, the functionalized copolymer may, in one or more embodiments, have an initial vinyl content prior to hydrogenation from 10 % to 50 %. Without being bound by theory, controlling the initial vinyl content can maintain the amorphous nature of the functionalized copolymer, thereby reducing crystal formation that can degrade performance of the tire tread. In embodiments, the initial vinyl content of the functionalized copolymer may be from 15 wt% to 30 wt%. In embodiments, the functionalized copolymer may have an initial vinyl content greater than or equal to 10 wt%, greater than or equal to 15 wt%, greater than or equal to 20 wt%, greater than or equal to 25 wt%, or even greater than or equal to 30 wt%.. In embodiments, the functionalized copolymer may have an initial vinyl content less than or equal to 50 wt%, less than or equal to 45 wt%, less than or equal to 40 wt%, less than or equal to 35 wt%, or even less than or equal to 30 wt%. In embodiments, the functionalized copolymer may have an initial vinyl content from 10 wt% to 50 wt%, from 10 wt% to 45 wt%, from 10 wt% to 40 wt%, from 10 wt% to 35 wt%, from 10 wt% to 30 wt%, from 15 wt% to 50 wt%, from 15 wt% to 45 wt%, from 15 wt% to 40 wt%, from 15 wt% to 35 wt%, from 15 wt% to 30 wt%, from 20 wt% to 50 wt%, from 20 wt% to 45 wt%, from 20 wt% to 40 wt%, from 20 wt% to 35 wt%, from 20 wt% to 30 wt%, from 25 wt% to 50 wt%, from 25 wt% to 45 wt%, from 25 wt% to 40 wt%, from 25 wt% to 35 wt%, from 25 wt% to 30 wt%, from 30 wt% to 50 wt%, from 30 wt% to 45 wt%, from 30 wt% to 40 wt%, or even from 30 wt% to 35 wt%, or any and all sub-ranges formed from any of these endpoints.

[0072] In embodiments, the hydrogenated, functionalized copolymer may comprise a glass transition temperature Tgfrom -80 °C to -50 °C, from -80 °C to -55 °C, from -80 °C to -60 °C, from -80 °C to -65 °C, from -75 °C to -50 °C, from -75 °C to -55 °C, from -75 °C to -60 °C, from -75 °C to -65 °C, from -70 °C to -50 °C, from -70 °C to -55 °C, from -70 °C to -60 °C, or even from -70 °C to -65 °C, or any and all sub-ranges formed from any of these endpoints.

[0073] Rubber CompositionsDocket No. BDGP21138WO-P21138WO1A20 of 41

[0074] As stated previously, the hydrogenated, functionalized copolymers detailed above, may be included in rubber compositions for tire and non-tire applications. The rubber composition may also include at least one curative, and at least one reinforcing fdler.

[0075] Curative

[0076] As used herein, curatives are vulcanizing agents used in the vulcanization of the functionalized copolymer. In one or more embodiments, the curative includes a sulfur-based curative or a peroxide-based curative. Examples of specific suitable sulfur curatives include "rubbermaker's" soluble sulfur; sulfur donating curing agents, such as an amine disulfide, polymeric polysulfide, or sulfur olefin adducts; and insoluble polymeric sulfur. In one embodiment, the sulfur curative comprises soluble sulfur or a mixture of soluble and insoluble polymeric sulfur. For a general disclosure of suitable curatives and other components used in curing, e.g., vulcanizing inhibitor and anti-scorching agents, one can refer to Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd ed., Wiley Interscience, N.Y. 1982, Vol. 20, pp. 365 to 468, particularly Vulcanization Agents and Auxiliary Materials, pp. 390 to 402, or Vulcanization by A. Y. Coran, Encyclopedia of Polymer Science and Engineering, Second Edition (1989 John Wiley & Sons, Inc.), both of which are incorporated herein by reference. While various amounts are contemplated, the curatives may be used in an amount ranging from 0.1 to 10 phr, including from 1 to 7.5 phr, including from 1 to 5 phr, and preferably from 1 to 3.5 phr.

[0077] Reinforcing Filler

[0078] As used herein, “reinforcing fdler” may refer particulate material that has a nitrogen absorption specific surface area (N2SA) of more than about 100 m2 / g, and in certain instances more than 100 m2 / g, more than about 125 m2 / g, more than 125 m2 / g, or even more than about 150 m2 / g or more than 150 m2 / g. Alternatively, “reinforcing filler” can also be used to refer to a particulate material that has a particle size of about 10 nm to about 50 nm.

[0079] In one or more embodiments, the reinforcing filler may comprise silica, carbon black, or combinations thereof.

[0080] Examples of reinforcing silica fillers suitable for use include, but are not limited to, precipitated amorphous silica, wet silica (hydrated silicic acid), dry silica (anhydrous silicic acid), fumed silica, calcium silicate and the like. Other suitable silica fillers for use in rubberDocket No. BDGP21138WO-P21138WO1A21 of 41compositions of certain embodiments of the first-third embodiments disclosed herein include, but are not limited to, aluminum silicate, magnesium silicate (e.g., Mg?SiO4, MgSiCh), magnesium calcium silicate (CaMgSiCM), aluminum calcium silicate (e.g., AhOs.CaChSiCh), and the like.

[0081] Like the carbon black, various amounts of silica are contemplated for use as reinforcing filler. In one or more embodiments, the total amount of the reinforcing silica filler or silica filler may be from about 5 to about 200 phr, including from about 5 to about 150 phr, from about 5 to about 100 phr, from about 5 to about 75 phr, from about 10 to about 200 phr, from about 10 to about 150 phr, from about 10 to about 100 phr, from about 10 to about 75 phr, from about 25 to about 200 phr, from about 25 to about 150 phr, from about 25 to about 100 phr, from about 25 to about 75 phr, from about 50 to about 200 phr, from about 50 to about 150 phr, from about 50 to about 100 phr, or even from about 50 to about 75 phr, or any and all sub-ranges formed from any of these endpoints.

[0082] Moreover, carbon black filler may also be used as reinforcing filler. Various carbon black compositions are considered suitable. Among the useful carbon blacks are furnace black, channel blacks, and lamp blacks. More specifically, examples of useful carbon blacks include super abrasion furnace (SAF) blacks, high abrasion furnace (HAF) blacks, fast extrusion furnace (FEF) blacks, fine furnace (FF) blacks, intermediate super abrasion furnace (ISAF) blacks, semireinforcing furnace (SRF) blacks, medium processing channel blacks, hard processing channel blacks and conducting channel blacks. Other carbon blacks which can be utilized include acetylene blacks. In certain embodiments, the rubber composition includes a mixture of two or more of the foregoing carbon blacks. The carbon blacks utilized can be in pelletized form or an unpelletized flocculent mass.

[0083] In one or more embodiments, carbon black can be sourced from a recycled material. Such recycled material can include reclaimed or recycled vulcanized rubber, whereby the vulcanized rubber is typically reclaimed from manufactured articles such as a pneumatic tire, an industrial conveyor belt, a power transmission belt, and a rubber hose. The recycled carbon black may be obtained by a pyrolysis process or other methods known for obtaining recycled carbon black. In an aspect, a recycled carbon black can be formed from incomplete combustion of recycled rubber feedstock or rubber articles. In another aspect, the recycled carbon black can be formed from the incomplete combustion of feedstock including oil resulting from the tire pyrolysisDocket No. BDGP21138WO-P21138WO1A22 of 41process. The carbon blacks utilized in the preparation of the vulcanizable elastomeric compositions can be in pelletized form or an unpelletized flocculent mass.

[0084] Various amounts of carbon black are contemplated. In one or more embodiments, the total amount of the reinforcing carbon black fdler may be from about 1 phr to about 100 phr, including from about 1 phr to about 75 phr, from about 1 phr to about 50 phr, from about 1 phr to about 25 phr, from about 1 phr to about 10 phr, from about 5 phr to about 100 phr, from about 5 phr to about 75 phr, from about 5 phr to about 50 phr, from about 5 phr to about 25 phr, or even from about 5 phr to about 10 phr, or any and all sub-ranges formed from any of these endpoints.

[0085] In other embodiments, the rubber composition may comprise at least one reinforcing fdler other than silica or carbon black, or alternatively in addition to reinforcing silica and reinforcing carbon black fdlers. Non-limiting examples of suitable such reinforcing fdlers for use in the rubber compositions disclosed herein include, but are not limited to, aluminum hydroxide, talc, alumina (AI2O3), aluminum hydrate (AI2O3H2O), aluminum hydroxide (A1(OH)3), aluminum carbonate (Ah(CO3)2), aluminum magnesium oxide (MgOAhCh), pyrofdite (AhC SiCh.IbO), bentonite (Al2O3.4SiO2.2H2O), mica, kaolin, glass balloon, glass beads, calcium oxide (CaO), calcium hydroxide (Ca(OH)2), calcium carbonate (CaCCh), magnesium carbonate, magnesium hydroxide (Mg(OH)2), magnesium oxide (MgO), magnesium carbonate (MgCCh), potassium titanate, barium sulfate, zirconium oxide (ZrO2), zirconium hydroxide [Zr(OH)2.nH2O], zirconium carbonate [Zr(CO3)2], crystalline aluminosilicates, reinforcing grades of zinc oxide (i.e., reinforcing zinc oxide), and combinations thereof.

[0086] The rubber composition can further include fdler in the form of one or more recycled rubbers in a particulate form. Recycled particulate rubber is typically broken down and reclaimed (or recycled) by any of a plurality of processes, which can include physical breakdown, grinding, chemical breakdown, devulcanization, cryogenic grinding, a combination thereof, etc. The term recycled particulate rubber can relate to both vulcanized and devulcanized rubber, where devulcanized recycle or recycled rubber (reclaim rubber) relates to rubber which has been vulcanized, ground into particulates and may have further undergone substantial or partial devulcanization. In an example, the recycled particulate rubber used in the rubber composition is essentially free of recycled rubber resulting from devulcanization. In a situation where the vulcanized rubber contains wire or textile fiber reinforcement, such wire or fiber reinforcement can be removed by any suitable process such as magnetic separation, air aspiration and / or airDocket No. BDGP21138WO-P21138WO1A23 of 41flotation step. In certain embodiments, the "recycled particulate rubber" comprises cured, i.e., vulcanized (crosslinked) rubber that has been ground or pulverized into particulate matter having a mean average particle size as discussed below.

[0087] Additional Rubber

[0088] In further embodiments, the rubber composition may comprise an additional rubber component comprising natural rubber, synthetic rubber, or combinations thereof. For example, and not by way of limitation, the synthetic rubber may comprise synthetic polyisoprene, polyisobutylene-co-isoprene, neoprene, poly(ethylene-co-propylene), poly(styrene-co-butadiene), poly(styrene-co-isoprene), and poly(styrene-co-isoprene-co-butadiene), poly(isoprene-co-butadiene), poly(ethylene-co-propylene-co-diene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, or combinations thereof.

[0089] Additional Additives

[0090] Optionally, a silane coupling agent may be blended with the silica reinforcing filler further improve the reinforcing properties. For example, the silane coupling agent may include bis(3 -triethoxy silylpropyl) tetrasulfide, bis(3-triethoxysilylpropyl) trisulfide, bis(3-triethoxysilylpropyl) disulfide, bis(2-triethoxysilylethyl) tetrasulfide, bis(3-trimethoxy silylpropyl) tetrasulfide, bis(2-trimethoxy silylethyl) tetrasulfide, 3-mercaptopropyltrimethoxy silane, 3 -mercaptopropyltriethoxy silane, 2-mercaptoethyltrimethoxy silane, 2-mercaptoethyltri ethoxy silane, 3 -trimetho xysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3 -trimethoxysilylpropyl benzothiazole tetrasulfide, 3 -triethoxy silylpropyl benzothiazole tetrasulfide, 3-tri ethoxy silylpropyl methacrylate monosulfide, 3 -trimethoxy silylpropyl methacrylate monosulfide, bis(3-diethoxymethylsilylpropyl) tetrasulfide, 3 -mercaptopropyl dimethoxymethyl silane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, dimethoxymethylsilylpropyl benzothiazole tetrasulfide, 3 -hexanoy Ithiopropyltriethoxysilane, 3-octanoylthiopropyltriethoxysilane, 3 -decanoy Ithiopropyltriethoxysilane, 3-lauroylthiopropyltriethosysilane, 2-hexanoylthioethyltriethoxysilane, 2-octanoylthioethyltriethoxysilane, 2-decanoylthioethyltriethoxysilane, 2-lauroylthioethyltriethoxy silane, 3 -hexanoy Ithiopropyltrimethoxy silane, 3 -Docket No. BDGP21138WO-P21138WO1A24 of 41octanoy Ithiopropyltrimethoxy silane, 3 -decanoy Ithi op ropy Itrimethoxy silane, 3 -lauroylthiopropyltrimethoxysilane, 2-hexanoylthioethyltrimethoxysilane, 2-octanoylthioethyltrimethoxysilane, 2-decanoylthioethyltrimethoxysilane and 2-lauroylthioethyltrimethoxysilane, and the like. These silane coupling agents may be used alone or in a combination of two or more.

[0091] Useful processing or extender oils may also be included. Such oils include those that are commercially available as paraffinic, aromatic, or naphthenic oils. In one or more embodiments, the major constituent of the oil is naphthenic. The rubber compositions may also include other additives such as anti-ozonants, waxes, scorch inhibiting agents, processing aids, zinc oxide, tackifying resins, reinforcing resins, fatty acids such as stearic acid, peptizers, and one or accelerators.

[0092] The anti-ozonants may comprise N,N'disubstituted-p- phenylenediamines, such as N-1,3-dimethylbutyl-N'phenyl-p-phenylenediamine (6PPD), N,N'-Bis(l,4-dimethylpently)-p-phenylenediamine (77PD), N-phenyl-N-isopropyl-p- phenylenediamine (IPPD), and N-phenyl-N'-(l,3-dimethylbutyl)-p-phenylenediamine (HPPD). Other examples of anti-ozonants include, Acetone diphenylamine condensation product (Alchem BL), 2,4-Trimethyl-l,2-dihydroquinoline (TMQ), Octylated Diphenylamine (ODPA), and 2,6-di-t-butyl-4-methyl phenol (BHT).

[0093] The curing accelerators may include, but are not limited to, guanidine-type accelerators, such as diphenylguanidine (DPG), dithiocarbamate accelerators, including the metal dialkyldithiocarbamates such as, for example, zinc dibutyldithiocarbamate (ZDBDC), zinc diethyldithiocarbamate, zinc dimethyldithiocarbamate, and ferric dimethyldithiocarbamate; thiazole accelerators including 2-mercaptobenzothiazole, the benzothiazole disulfides such as, for example, mercaptobenzothiazole disulfide (MBTS); the benzothiazole sulfenamides, such as, for example, «-cyclohexyl-2-benzothiazole sulfenamide; and sulfenamide accelerators such as, for example, t-butyl-2-benzothiazyl sulfenamide (TBBS).

[0094] In embodiments, the amount of the hydrogenated, functionalized copolymer in the rubber composition may be from about 20 phr to about 100 phr, from about 20 phr to about 90 phr, from about 20 phr to about 80 phr, from about 20 phr to about 70 phr, from about 20 phr to about 60 phr, from about 40 phr to about 100 phr, from about 40 phr to about 90 phr, from aboutDocketNo. BDGP21138WO-P21138WO1A25 of 4140 phr to about 80 phr, from about 40 phr to about 70 phr, or even from about 40 phr to about 60 phr, or any and all sub-ranges formed from any of these endpoints.

[0095] The rubber composition may be obtained by milling with a milling machine such as rolls, an internal mixer or the like, which can be shaped and vulcanized for use in tire applications such as a tread, an under tread, a carcass, a sidewall, a bead and the like as well as a rubber cushion, a belt, a hose and other industrial products, but it is particularly suitable for use in the tire tread.

[0096] As described herein, by utilizing a hydrogenated, functionalized copolymer comprising a relatively low degree of hydrogenation (e.g., less than or equal to 75 mol%), the rubber compositions have a lower viscosity, thereby improving processability, while maintaining wear resistance (i.e., within 15%) as compared to a similar rubber composition including a hydrogenated copolymer having a degree of hydrogenation greater than 75 mol%.

[0097] In embodiments, the rubber composition may have a lower viscosity as compared to a similar rubber composition including a hydrogenated copolymer having a degree of hydrogenation greater than 75 mol%. In embodiments, the rubber composition comprise a Mooney viscosity less than or equal to 110, less than or equal to 100, less than or equal to 90, less than or equal to 80, less than or equal to 70, or even less than or equal to 60.

[0098] In embodiments, the rubber composition may comprise a wear resistance within 15%, within 12%, within 10%, within 7%, or even within 5% of the wear resistance of a similar rubber composition including a hydrogenated copolymer having a degree of hydrogenation greater than 75 mol%.

[0099] In embodiments, the rubber composition may comprise a wear resistance from 100 to 150, from 100 to 140, from 100 to 130, from 100 to 120, from 110 to 150, from 110 to 140, from 110 to 130, or even from 110 to 120, or any and all sub-ranges formed from any of these endpoints.

[0100] TESTING METHODS

[0101] Gel Permeation Chromatography (GPC)

[0102] The base molecular weight (Mn, Mwand Mp(i.e., peak Mnof GPC curve)) and base molecular weight distribution (Mw / Mn) of the polymers were determined by gel permeation chromatography (GPC) using a Tosoh Ecosec HLC-8320GPC system and Tosoh TSKgel GMHxl-Docket No. BDGP21138WO-P21138WO1A26 of 41BS columns with THF as a solvent. The system was calibrated using a series of polystyrene standards.

[0103] 'H-NMR Spectroscopy

[0104] The styrene, vinyl, and hydrogenation contents of the polymer samples were determined by 'H-NMR spectroscopy in chloroform-d.

[0105] Differential Scanning Calorimetry (DSC)

[0106] Glass transition temperature (Tg) was determined using DSC. DSC measurements were made on a TA Instruments Q2000 with helium purge gas and a Liquid Nitrogen Cooling System (LNCS) accessory for cooling. The sample was prepared in a TZero aluminum pan and scanned at 10°C / min over the temperature range of interest.

[0107] Wear Resistance

[0108] The wear resistance of the test samples was evaluated using an abrasion test. Test specimens were rubber wheels of about 70 mm in outside diameter, about 30 mm in inside diameter and about 20 mm in thickness. The test specimens were placed on an axle and run at various slip ratios against a driven abrasive surface for various amounts of time. The abrading surface used was 240 grit sandpaper. A load of about 35 N was applied to the rubber wheel during testing. A linear, least squares curve-fit was applied to the weight loss data as a function of time. The slope of the line is the abrasion rate. The reported wear index is one-hundred multiplied by the control compound abrasion rate divided by the subject compound abrasion rate. Thus, a wear index greater than 100 indicates that the subject composition is better (abrades at a lower rate) than its respective control composition.

[0109] Mooney Viscosity

[0110] The Mooney viscosities of polymers disclosed herein were determined at 130 °C using an Alpha Technologies Mooney viscometer with a large rotor, a one minute warm-up time, and a four minute running time. More specifically, the Mooney viscosity was measured by preheating each polymer to 130 °C for one minute before the rotor starts. The Mooney viscosity was recorded for each sample as the torque at four minutes after the rotor started. Torque relaxation wasDocket No. BDGP21138WO-P21138WO1A27 of 41recorded after completing the four minutes of measurement. The tso values represent the time required for decaying 80% of the torque of each polymer.

[0111] The embodiments of the present disclosure are further illustrated by reference to the following examples.

[0112] EXAMPLES

[0113] Example 1 Synthesis of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (hereinafter “Agent A ”) Functionalized SBR

[0114] Agent A functionalized styrene-butadiene copolymer (SBR) was prepared according to the following process. To a five-gallon (approximately 18.9 liter) N2 purged reactor equipped with a stirrer was added 3.358 kilograms of hexane, 0.266 kilograms of 32.2 weight % styrene in hexane, and 7.756 kilograms of 21.0 weight % 1,3-butadiene in hexane. The reactor was charged with 1.97 milliliters of 2,2-bis(2’-tetrahydrofuryl)propane (OOPS, 1.60 Molar in hexane), followed by 5.72 milliliters of n-butyllithium (BuLi, 2.50 Molar in hexane), and the reactor jacket was heated to 50 °C. After 46 minutes, the batch temperature peaked at 82 °C. After an additional 40 minutes, the anionic polymerization reaction was terminated by adding 3.31 milliliters of Agent A. After an additional 30 minutes, 1.09 milliliters of isopropyl alcohol was added. After an additional 10 minutes, a sample of polymer cement was collected for characterization and the remaining cement was transferred to a storage vessel in preparation for transfer to a hydrogenation reactor. Polymer characterization data of the non-hydrogenated, functionalized SBR intermediate is summarized in Table 1.

[0115] Example 2 : Synthesis of Agent A Functionalized BR

[0116] Agent A functionalized polybutadiene (BR) was prepared according to the following process. To a five gallon (approximately 18.9 liter) N2 purged reactor equipped with a stirrer was added 3.479 kilograms ofhexane and 7.901 kilograms of 21.7 weight % 1,3-butadiene in hexane. The reactor was charged with 0.893 milliliters of 2,2-bis(2’-tetrahydrofuryl)propane (1.60 Molar in hexane), followed by 5.72 milliliters of n-butyllithium (2.50 Molar in hexane), and the reactor jacket was heated to 50 °C. After 52 minutes, the batch temperature peaked at 92 °C. After an additional 40 minutes, the anionic polymerization reaction was terminated by adding 3.31 milliliters of Agent A. After an additional 30 minutes, 1.09 milliliters of isopropyl alcohol wasDocket No. BDGP21138WO-P21138WO1A28 of 41added. After an additional 10 minutes, a sample of polymer cement was collected for characterization and the remaining cement was transferred to a storage vessel in preparation for transfer to a hydrogenation reactor. Polymer characterization data of the non-hydrogenated, functionalized BR intermediate is summarized in Table 1.

[0117] Example 3 : Synthesis of Azent A Functionalized BR

[0118] Agent A functionalized polybutadiene (BR) was prepared according to the following process. To a five gallon (approximately 18.9 liter) N2 purged reactor equipped with a stirrer was added 2.808 kilograms of hexane and 8.573 kilograms of 20.0 weight % 1,3-butadiene in hexane. The reactor was charged with 0.893 milliliters of 2,2-bis(2’-tetrahydrofuryl)propane (1.60 Molar in hexane), followed by 5.72 milliliters of n-butyllithium (2.50 Molar in hexane), and the reactor jacket was heated to 50 °C. After 51 minutes, the batch temperature peaked at 91 °C. After an additional 40 minutes, the anionic polymerization reaction was terminated by adding 3.31 milliliters of Agent A. After an additional 30 minutes, 1.09 milliliters of isopropyl alcohol was added. After an additional 10 minutes, a sample of polymer cement was collected for characterization and the remaining cement was transferred to a storage vessel in preparation for transfer to a hydrogenation reactor. Polymer characterization data of the non-hydrogenated, functionalized BR intermediate is summarized in Table 1.

[0119] Table 1

[0120] Example 4: Hydrogenation of Agent A Functionalized SBR from Example 1Docket No. BDGP21138WO-P21138WO1A29 of 41

[0121] To a 11.7 gallon (approximately 44.3 liter) stirred reactor under nitrogen atmosphere, 4,581 g of the Example 1 Agent A functionalized SBR solution in hexane was introduced, followed by 8,763 g of hexane, which resulted in a 5.0 wt% BR solution. The reactor was purged 3 times with 20 psi hydrogen and the reactor jacket was heated to 50 °C. To a nitrogen purged dry bottle, 250 mL of hexane and 11.01 mL of 1.0 M triethylaluminum was added, followed by 2.00 mL of nickel octoate (10 wt% Ni in hexane), resulting in a Ni / Al catalyst (Al / Ni=3.3 / 1.0). The catalyst solution was transferred into the reactor, and the reactor was immediately pressurized to 75 psi with hydrogen. After approximately 13 minutes of hydrogenation reaction, hydrogen was released from the reactor and the polymer cement was transferred to a storage vessel. The polymer cement was then transferred into 4 buckets, each containing 6.3 L of isopropanol and 11.5 g of butylated hydroxytoluene (BHT). The coagulated polymer sample was dried by a drumdrier at 120 °C. Polymer characterization data of the hydrogenated, functionalized SBR is summarized in Table 2.

[0122] Example 5 : Hydrogenation of Azent A Functionalized BR from Example 2

[0123] To a 11.7 gallon (approximately 44.3 liter) stirred reactor under nitrogen atmosphere, 4,855 g of the Example 1 Agent A functionalized BR solution in hexane was introduced, followed by 9,310 g of hexane, which resulted in a 5.0 wt% BR solution. The reactor was purged 3 times with 20 psi hydrogen and the reactor jacket was heated to 50 °C. To a nitrogen purged dry bottle, 250 mL of hexane and 11.67 mL of 1.0 M triethylaluminum was added, followed by 2.12 mL of nickel octoate (10 wt% Ni in hexane), resulting in a Ni / Al catalyst (Al / Ni=3.3 / 1.0). The catalyst solution was transferred into the reactor, and the reactor was immediately pressurized to 75 psi with hydrogen. After approximately 40 minutes of hydrogenation reaction, hydrogen was released from the reactor and the polymer cement was transferred to a storage vessel. The polymer cement was then transferred into 4 buckets, each containing 6.3 L of isopropanol and 11.5 g of butylated hydroxytoluene (BHT). The coagulated polymer sample was dried by a drum-drier at 120 °C. Polymer characterization data of the hydrogenated, functionalized BR is summarized in Table 2.

[0124] Example 6: Hydrogenation of Agent A Functionalized BR from Example 3

[0125] To a 11.7 gallon (approximately 44.3 liter) stirred reactor under nitrogen atmosphere, 5,715 g of the Example 1 Agent A functionalized BR solution in hexane was introduced, followed by 11,030 g of hexane, which resulted in a 5.0 wt% BR solution. The reactor was purged 3 timesDocket No. BDGP21138WO-P21138WO1A30 of 41with 20 psi hydrogen and the reactor jacket was heated to 50 °C. To a nitrogen purged dry bottle, 400 mL of hexane and 21.97 mL of 1.0 M triethylaluminum was added, followed by 3.99 mL of nickel octoate (10 wt% Ni in hexane), resulting in aNi / Al catalyst (Al / Ni=3.3 / 1.0). The catalyst solution was transferred into the reactor, and the reactor was immediately pressurized to 75 psi with hydrogen. After approximately 16 minutes of hydrogenation reaction, hydrogen was released from the reactor and the polymer cement was transferred to a storage vessel. The polymer cement was then transferred into 4 buckets, each containing 6.3 L of isopropanol and 11.5 g of butylated hydroxytoluene (BHT). The coagulated polymer sample was dried by a drum-drier at 120 °C. Polymer characterization data of the hydrogenated, functionalized BR is summarized in Table 2.

[0126] Table 2

[0127] Example 7 - Rubber Compositions and Properties

[0128] Referring to Table 3 below, rubber composition samples were produced from the hydrogenated polymers described in Table 2 (in phr). Control samples using commercially available non-hydrogenated polymer were also produced (Comparative Samples 1 and 2). In addition, comparative samples using H-SBR and H-BR polymers with higher levels of hydrogenation were also produced, in order to more directly evaluate the balance between wear resistance and compound viscosity. Rubber composition details can be found in Table 3 below. While the specific amounts are listed below, the rubber compositions, which were produced from mixing in a Brabender mixer, included the following components: SiCh, carbon black, silane, oil, resin, stearic acid, process aid, and antioxidant, while the cure package included sulfur, diphenylguanidine (DPG), n-tertiary butyl-2-benzothiazole sulfenamide (TBBS), mercaptobenzothiazole disulfide (MBTS), zinc oxide, and antioxidant.Docket No. BDGP21138WO-P21138WO1A31 of 41

[0129] Table 3Docket No. BDGP21138WO-P21138WO1A32 of 411The Comparative SBR is HX263 manufactured by Firestone Polymers. The SBR was obtained by solution polymerization and modified with Sn. The trade name is FS CHEMICAL HX263.284.5 mol% hydrogenation.384.8 mol% hydrogenation.4The Silica is WK023, a high surface area silica with 190 m2 / g surface area N2 absorption.

[0130] Example 8 - Wear Resistance and Viscosit

[0131] As shown in Table 4, the wear resistance and viscosity of the rubber compositions were evaluated. Because the data were collected over multiple compounding orders, the control data of Comparative Samples 1 and 2 represent an average data over three orders and four orders, respectively.

[0132] Table 41Comprative Sample 1 is the control sample with an index of 100 for wear resistance, which Comparative Sample 3 and Example 4 are compared.2Comparative Sample 2 is the control sample with an index of 100 for wear resistance, which Comparative Sample 4 and Example 6 are compared.

[0133] Referring to Table 4, comparing Comparative Sample 3 to Comparative Sample 1 and Comparative Sample 4 to Comparative Sample 2 highlights the wear resistance improvement of H-SBR as compared to SBR, but also an increase in viscosity, as measured by Mooney viscometry.

[0134] Referring again to Table 4, Example 4, a rubber composition including a hydrogenated Agent A functionalized SBR having 70.9 mol% hydrogenation, had a lower viscosity andDocket No. BDGP21138WO-P21138WO1A33 of 41maintained wear resistance as compared to Comparative Sample 3, a rubber composition including H-SBR having 84.5 mol% hydrogenation. Example 6, a rubber composition including hydrogenated Agent A functionalized BR having 72.4 mol% hydrogenation, had a lower viscosity and maintained wear resistance as compared to Comparative Sample 4, a rubber composition including H-BR having 84.8 mol% hydrogenation. As exemplified by Table 4, rubber compositions including functionalized copolymers having a degree of hydrogenation from 40 mol% to 75 mol% as described herein have a lower viscosity and maintained wear resistance as compared to a similar rubber composition including a hydrogenated copolymer having a degree of hydrogenation greater than 75 mol%.

[0135] Embodiments of the invention include but are not limited to:

[0136] 1. A polymer comprising: a functionalized copolymer produced by copolymerization of at least one conjugated diolefin monomer and at least one vinyl monomer, the functionalized copolymer comprising at least one functional group, wherein the functionalized copolymer has a degree of hydrogenation from 40 mol% to 75 mol%, as measured using proton nuclear magnetic resonance spectroscopy ('H NMR).

[0137] 2. The polymer of any preceding clause, wherein the functionalized copolymer has a degree of hydrogenation from 50 mol% to 75 mol%, as measured usingNMR.

[0138] 3. The polymer of any preceding clause, wherein the functionalized copolymer has an initial vinyl content from 10 wt% to 50 wt%.

[0139] 4. The polymer of any preceding clause, wherein the initial vinyl content of the functionalized copolymer is from 15 wt% to 30 wt%.

[0140] 5. The polymer of any preceding clause, wherein the functionalized copolymer has a base weight average molecular weight (Mw) from 50,000 g / mol to 500,000 g / mol.

[0141] 6. The polymer of any preceding clause, wherein the functionalized copolymer has a base number average molecular weight (Mn) from 25,000 g / mol to 500,000 g / mol.

[0142] 7. The polymer of any preceding clause, wherein a ratio of a base weight average molecular weight (Mw) of the functionalized copolymer to a base number average molecular weight (Mn) of the functionalized copolymer is from 0.75 to 2.Docket No. BDGP21138WO-P21138WO1A34 of 41

[0143] 8. The polymer of any preceding clause, wherein the at least one functional group is derived from an alkoxysilane compound selected from the group consisting of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidylpropyltrimethoxysilane, y_glycidoxypropyltrimethoxy silane, 3 -glycidylpropylmethyldimethoxy silane, or combinations thereof.

[0144] 9. The polymer of any preceding clause, wherein the at least one functional group is derived from an imino-containing compound selected from the group consisting of N-(l,3-dimethylbutylidene)-3 -(triethoxysilyl)- 1 -propaneamine, N-(l-methylethylidene)-3- (triethoxysilyl)-l -propaneamine, N-ethylidene-3-(triethoxysilyl)-l -propaneamine, N-(l-methylpropylidene)-3-(triethoxysilyl)-l -propaneamine, N-(4-N,N-dimethylaminobenzylidene )-3-( triethoxysilyl)-l -propaneamine, or combinations thereof.

[0145] 10. The polymer of any preceding clause, wherein the conjugated diolefin monomer comprises 1,3 -butadiene, isoprene, myrcene, or combinations thereof, and wherein the vinyl monomer comprise styrene, alpha methyl styrene, or combinations thereof.

[0146] 11. The polymer of any preceding clause, wherein the functionalized copolymer is a functionalized styrene butadiene copolymer.

[0147] 12. A rubber composition comprising: the polymer of any preceding clause; at least one curative; and reinforcing fdler.

[0148] 13. The rubber composition of any preceding clause, further comprising an additional rubber, the additional rubber comprising natural rubber, synthetic rubber, or combinations thereof.

[0149] 14. The rubber composition of any preceding clause, wherein the reinforcing fdler comprises silica, carbon black, or combinations thereof, and the curative comprises sulfur.

[0150] 15. The rubber composition of any preceding clause, wherein the rubber comprises a lower viscosity as compared to a similar rubber composition including a hydrogenated copolymer having a degree of hydrogenation greater than 75 mol%.

[0151] 16. The rubber composition of any preceding clause, wherein the rubber composition comprises a wear resistance within 15% of a wear resistance of a similar rubber composition including a hydrogenated copolymer having a degree of hydrogenation greater than 75 mol%.Docket No. BDGP21138WO-P21138WO1A35 of 41

[0152] 17. A method of making a hydrogenated, functionalized copolymer comprising: introducing an anionic polymerization initiator, at least one conjugated diolefin monomer, at least one vinyl monomer, and solvent to a reactor to produce a living copolymer via anionic polymerization; reacting at least one functional group with the living copolymer to produce a functionalized copolymer; and hydrogenating the functionalized copolymer by mixing the functionalized copolymer with solvent and a hydrogenation catalyst in a hydrogen stream, wherein the hydrogenated, functionalized copolymer has a degree of hydrogenation from 40 mol% to 75 mol%, as measured using

[0153] 18. The method of any preceding clause, wherein the hydrogenation catalyst comprises nickel and aluminum, and the anionic polymerization initiator is a lithium catalyst.

[0154] 19. The method of any preceding clause, wherein the hydrogenation catalyst comprises nickel octoate.

[0155] 20. The method of any preceding clause, wherein the functionalized copolymer has an initial vinyl content from 10 wt% to 50 wt%.

[0156] 21. The method of any preceding clause, wherein the at least one functional group is derived from an alkoxysilane compound selected from the group consisting of 2-(3,4-epoxycyclohexyljethyltrimethoxysilane, 3-glycidylpropyltrimethoxysilane, y_glycidoxypropyltrimethoxy silane, 3 -glycidylpropylmethyldimethoxy silane, or combinations thereof.

[0157] 22. The method of any preceding clause, wherein the at least one functional group is derived from an imino-containing compound selected from the group consisting of N-(l,3-dimethylbutylidene)-3 -(triethoxysilyl)- 1 -propaneamine, N-(l-methylethylidene)-3- (triethoxysilyl)-l -propaneamine, N-ethylidene-3-(triethoxysilyl)-l -propaneamine, N-(l-methylpropylidene)-3-(triethoxysilyl)-l -propaneamine, N-(4-N,N-dimethylaminobenzylidene )-3-( triethoxysilyl)-l -propaneamine, or combinations thereof.

[0158] 23. The method of any preceding clause, wherein the functionalized copolymer is a functionalized styrene butadiene copolymer.Docket No. BDGP21138WO-P21138WO1A36 of 41

[0159] It will be apparent that modifications and variations are possible without departing from the scope of the disclosure defined in the appended claims. More specifically, although some aspects of the present disclosure are identified herein as preferred or particularly advantageous, it is contemplated that the present disclosure is not necessarily limited to these aspects.

Claims

Docket No. BDGP21138WO-P21138WO1A37 of 41CLAIMS1. A polymer comprising:a functionalized copolymer produced by copolymerization of at least one conjugated diolefin monomer and at least one vinyl monomer, the functionalized copolymer comprising at least one functional group,wherein the functionalized copolymer has a degree of hydrogenation from 40 mol% to 75 mol%, as measured using proton nuclear magnetic resonance spectroscopy (1H NMR).

2. The polymer of claim 1, wherein the functionalized copolymer has a degree of hydrogenation from 50 mol% to 75 mol%, as measured usingNMR.

3. The polymer of claim 1 or claim 2, wherein the functionalized copolymer has an initial vinyl content from 10 wt% to 50 wt%.

4. The polymer of claim 3, wherein the initial vinyl content of the functionalized copolymer is from 15 wt% to 30 wt%.

5. The polymer of claim 1 or claim 2, wherein the functionalized copolymer has a base weight average molecular weight (Mw) from 50,000 g / mol to 500,000 g / mol.

6. The polymer of claim 1 or claim 2, wherein the functionalized copolymer has a base number average molecular weight (Mn) from 25,000 g / mol to 500,000 g / mol.

7. The polymer of claim 1 or claim 2, wherein a ratio of a base weight average molecular weight (Mw) of the functionalized copolymer to a base number average molecular weight (Mn) of the functionalized copolymer is from 0.75 to 2.

8. The polymer of claim 1 or claim 2, wherein the at least one functional group is derived from an alkoxysilane compound selected from the group consisting of 2-(3,4-epoxycyclohexyljethyltrimethoxysilane, 3-glycidylpropyltrimethoxysilane, y_glycidoxypropyltrimethoxy silane, 3 -glycidylpropylmethyldimethoxy silane, or combinations thereof.Docket No. BDGP21138WO-P21138WO1A38 of 419. The polymer of claim 1 or claim 2, wherein the at least one functional group is derived from an imino-containing compound selected from the group consisting of N-(l,3-dimethylbutylidene)-3 -(triethoxysilyl)- 1 -propaneamine, N-(l-methylethylidene)-3- (triethoxysilyl)-l -propaneamine, N-ethylidene-3-(triethoxysilyl)-l -propaneamine, N-(l-methylpropylidene)-3-(triethoxysilyl)-l -propaneamine, N-(4-N,N-dimethylaminobenzylidene )-3-( triethoxysilyl)-l -propaneamine, or combinations thereof.

10. The polymer of claim 1 or claim 2, wherein the conjugated diolefin monomer comprises 1,3 -butadiene, isoprene, myrcene, or combinations thereof, and wherein the vinyl monomer comprise styrene, alpha methyl styrene, or combinations thereof.

11. The polymer of claim 1 or claim 2, wherein the functionalized copolymer is a functionalized styrene butadiene copolymer.

12. A rubber composition comprising:the polymer of claim 1 or claim 2;at least one curative; andreinforcing fdler.

13. The rubber composition of claim 12, further comprising an additional rubber, the additional rubber comprising natural rubber, synthetic rubber, or combinations thereof.

14. The rubber composition of claim 12, wherein the reinforcing fdler comprises silica, carbon black, or combinations thereof, and the curative comprises sulfur.

15. The rubber composition of claim 12, wherein the rubber comprises a lower viscosity as compared to a similar rubber composition including a hydrogenated copolymer having a degree of hydrogenation greater than 75 mol%.DocketNo. BDGP21138WO-P21138WO1A39 of 4116. The rubber composition of claim 12, wherein the rubber composition comprises a wear resistance within 15% of a wear resistance of a similar rubber composition including a hydrogenated copolymer having a degree of hydrogenation greater than 75 mol%.

17. A method of making a hydrogenated, functionalized copolymer comprising:introducing an anionic polymerization initiator, at least one conjugated diolefin monomer, at least one vinyl monomer, and solvent to a reactor to produce a living copolymer via anionic polymerization;reacting at least one functional group with the living copolymer to produce a functionalized copolymer; andhydrogenating the functionalized copolymer by mixing the functionalized copolymer with solvent and a hydrogenation catalyst in a hydrogen stream, wherein the hydrogenated, functionalized copolymer has a degree of hydrogenation from 40 mol% to 75 mol%, as measured using18. The method of claim 17, wherein the hydrogenation catalyst comprises nickel and aluminum, and the anionic polymerization initiator is a lithium catalyst.

19. The method of claim 17 or claim 18, wherein the hydrogenation catalyst comprises nickel octoate.

20. The method of claim 17 or claim 18, wherein the functionalized copolymer has an initial vinyl content from 10 wt% to 50 wt%.

21. The method of claim 17 or claim 18, wherein the at least one functional group is derived from an alkoxysilane compound selected from the group consisting of 2-(3,4-epoxycyclohexyljethyltrimethoxysilane, 3-glycidylpropyltrimethoxysilane, y_glycidoxypropyltrimethoxy silane, 3 -glycidylpropylmethyldimethoxy silane, or combinations thereof.

22. The method of claim 17 or claim 18, wherein the at least one functional group is derived from an imino-containing compound selected from the group consisting of N-(l,3-Docket No. BDGP21138WO-P21138WO1A40 of 41dimethylbutylidene)-3 -(triethoxysilyl)- 1 -propaneamine, N-(l-methylethylidene)-3- (triethoxysilyl)-l -propaneamine, N-ethylidene-3-(triethoxysilyl)-l -propaneamine, N-(l-methylpropylidene)-3-(triethoxysilyl)-l -propaneamine, N-(4-N,N-dimethylaminobenzylidene )-3-( triethoxysilyl)-l -propaneamine, or combinations thereof.

23. The method of claim 17 or claim 18, wherein the functionalized copolymer is a functionalized styrene butadiene copolymer.

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