Use of aging hydrogenation catalysts and hydrogenation-functionalized polymers in their preparation

Abstract

Embodiments of this disclosure relate to a method for producing a hydrogenated functionalized polymer, comprising: aging a hydrogenation catalyst for about one day or more to form an aged hydrogenation catalyst; introducing an anionic polymerization initiator, a conjugated diolefin monomer, and a solvent into a reactor to produce a living polymer by anionic polymerization; reacting at least one silane modifier with the living polymer to produce a functionalized polymer; and hydrogenating the functionalized polymer by mixing the functionalized polymer in a solvent and an aged hydrogenation catalyst and introducing a hydrogen stream. The aged hydrogenation catalyst has a degree of retained activity compared to a hydrogenation catalyst.

Description

[Technical Field]

[0001] Embodiments of this disclosure generally relate to aging hydrogenation catalysts, and more specifically to the use of aging hydrogenation catalysts in the preparation of hydrogenation-functionalized polymers. [Background technology]

[0002] Rubber compositions containing hydrogenated polymers are commonly used in tire applications, such as tire treads, due to their improved wear performance and tensile strength. In certain cases, it may be desirable to store and / or transport the hydrogenation catalyst before use for hydrogenating the polymer. However, various storage conditions can lead to catalyst decomposition, thereby affecting the amount of hydrogenation achieved.

[0003] Therefore, there is a continuous need for improved methods to produce hydrogenated polymers using aging hydrogenation catalysts without performing hydrogenation. [Overview of the project]

[0004] Embodiments of this disclosure relate to a method for producing hydrogenation-functionalized polymers using an aging hydrogenation catalyst having a degree of activity that is retained compared to a hydrogenation catalyst.

[0005] According to one embodiment, a method for producing a hydrogenated functionalized polymer is provided. This method includes aging a hydrogenation catalyst for about one day or more to form an aged hydrogenation catalyst; introducing an anionic polymerization initiator, a conjugated diolefin monomer, and a solvent into a reactor to produce a living polymer by anionic polymerization; reacting at least one silane modifier with the living polymer to produce a functionalized polymer; and hydrogenating the functionalized polymer by mixing the functionalized polymer in a solvent and an aged hydrogenation catalyst and introducing a hydrogen stream. The aged hydrogenation catalyst has a degree of retained activity compared to a hydrogenation catalyst.

[0006] Further features and advantages of the embodiments described herein are described in the following “Modes for Carrying Out the Invention,” which will be readily apparent to a certain extent from this specification or by implementing the embodiments described herein, including the following “Modes for Carrying Out the Invention” and “Claims.” [Modes for carrying out the invention]

[0007] Embodiments of this disclosure relate to a method for producing a hydrogenated functionalized polymer, comprising: aging a hydrogenation catalyst for about one day or more to form an aged hydrogenation catalyst; introducing an anionic polymerization initiator, a conjugated diolefin monomer, and a solvent into a reactor to produce a living polymer by anionic polymerization; reacting at least one silane modifier with the living polymer to produce a functionalized polymer; and hydrogenating the functionalized polymer by mixing the functionalized polymer in a solvent and an aged hydrogenation catalyst and introducing a hydrogen stream. The aged hydrogenation catalyst has a degree of retained activity compared to a hydrogenation catalyst.

[0008] The present disclosure will be described below with reference to more detailed embodiments, but this disclosure should not be construed as being limited to the embodiments described herein. Rather, these embodiments are provided to ensure that this disclosure is thorough and complete and to fully convey the subject matter to those skilled in the art.

[0009] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art. The technical terms used herein are for the purpose of describing specific embodiments only and are not intended to limit them.

[0010] definition A range may be expressed herein as "about" one particular value and / or "about" another particular value. Where such a range is expressed, another embodiment includes one particular value and / or another particular value. Similarly, where a value is expressed as an approximation by the use of the antecedent "about", it will be understood that a particular value forms another embodiment. It will be further understood that each endpoint of a range is important both with respect to the other endpoints and independently of the other endpoints.

[0011] Unless otherwise explicitly stated, no method described herein is ever intended to be construed as requiring its steps to be performed in a specific order, or as requiring a specific orientation for any physical entity. Therefore, if a claim for a method does not actually enumerate the order in which its steps should be followed, or if a claim relating to any physical entity does not actually enumerate the order or orientation for its individual components, or if it is not otherwise specifically stated in the claims or specification that the steps should be limited to a specific order, or that no specific order or orientation for the components of a physical entity is enumerated, then no order or orientation is ever intended to be inferred in any respect. This applies to any possible implicit criteria for interpretation, including logical issues relating to the arrangement of steps, the flow of operation, the order of components, or the orientation of components; plain meanings arising from grammatical construction or punctuation; and the number or type of embodiments described herein.

[0012] As used herein and in the appended claims, the singular forms “a,” “an,” and “the” are intended to also include the plural form unless the context clearly indicates otherwise. Therefore, for example, a reference to an “a” component includes embodiments having two or more such components unless the context clearly indicates otherwise.

[0013] As used herein, the term "phr" means parts by weight of a specified component per 100 parts of rubber. If the rubber composition contains two or more types of rubber, "phr" means parts by weight per 100 parts of all rubbers combined.

[0014] As used herein, the term "polybutadiene" is used to refer to a polymer produced from 1,3-butadiene monomer. The term polybutadiene is also used interchangeably with the phrase "polybutadiene rubber" and the abbreviation "BR".

[0015] As used herein, the terms “styrene-butadiene copolymer,” “styrene-butadiene rubber,” or “SBR” mean copolymers produced from styrene and 1,3-butadiene monomer.

[0016] In the present invention, the terms "natural rubber" or "NR" refer to natural rubber, including rubber trees of the genus Hevea, and rubber that can be harvested from non-Hevea species (e.g., guayule shrub).

[0017] As used herein, the term “homopolymer” refers to a polymer produced from a single monomer.

[0018] As used herein, the term "copolymer" refers to a polymer produced from two or more monomers, and therefore may include polymers produced from two monomers or three or more monomers, such as a terpolymer.

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

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

[0021] As used herein, the term "room temperature" refers to 20°C to 25°C.

[0022] As used herein, the term "aged hydrogenation catalyst" refers to a hydrogenation catalyst that has been stored for a given period of time under given conditions (e.g., temperature and environment).

[0023] As used herein, the term "retains a degree of activity", when describing an aged hydrogenation catalyst, means that the aged hydrogenation catalyst has a degree of hydrogenation within 5% of the degree of hydrogenation achieved by the original (i.e., unaged) hydrogenation catalyst.

[0024] As mentioned above, hydrogenated polymers are commonly used in tire applications such as tire treads due to their improved wear performance and tensile strength. In certain cases, it may be desirable to store and / or transport the hydrogenation catalyst prior to use for hydrogenating the polymer. However, various storage conditions can lead to degradation of the catalyst, thereby affecting the amount of hydrogenation achieved.

[0025] Disclosed herein is a method of making a hydrogenated functionalized polymer that mitigates the aforementioned problems. Specifically, the method herein comprises aging a hydrogenation catalyst for one or more days, thereby forming an aged hydrogenation catalyst. The aged hydrogenation catalyst has a retained degree of activity compared to the original hydrogenation catalyst.

[0026] Hydrogenation Catalyst Various catalysts can be considered as hydrogenation catalysts. In one embodiment, the hydrogenation catalyst may contain nickel. In further embodiments, the hydrogenation catalyst may contain at least one nickel-containing composition, such as nickel octoate. In some embodiments, the hydrogenation catalyst may contain at least one nickel compound and at least one aluminum compound. In one or more embodiments, the nickel in the hydrogenation catalyst may include organonicickel compounds, such as nickel carboxylane complexes, such as nickel octanoate. With respect to hydrogenation catalysts containing nickel and aluminum, aluminum may also include organoaluminum compounds. Additional nickel-containing compounds include, but are not limited to, nickel alkoxides, nickel aryl oxides, nickel halides, and nickel β-diketonates, and are intended for use in hydrogenation catalysts. In one embodiment, the organoaluminum compound may be triethylaluminum. Nickel and aluminum may be included in various amounts. For example, aluminum and nickel may be added in Al / Ni molar ratios of 1:1 to 5:1, or 2:1 to 4:1.

[0027] In additional embodiments, the hydrogenation catalyst may contain one or more of ruthenium (Ru), rhodium (Rh), palladium (Pd), iridium (Ir), or platinum (Pt). Various ligands containing these intended catalytic materials can be intended as hydrogenation catalysts. However, in some embodiments, the hydrogenation catalyst may not contain titanium (Ti). While not limited to any particular theory, it is considered that Ti may be undesirable as a hydrogenation catalyst if an oxygen heteroatom is present in a functional group that can react with a living polymer to produce a functionalized copolymer. For example, a functional group containing an oxygen heteroatom indirectly bonded to the silicon of a silane, including a silane modifier, may react with the Ti catalyst to inhibit hydrogenation, alter the desirable chemical properties of the functionalized copolymer, or both. Hydrogenation catalysts containing nickel have been observed to provide excellent catalytic performance when such functional groups are utilized. Additionally, other non-Ti hydrogenation catalysts may offer enhanced functionality compared to Ti hydrogenation catalysts.

[0028] The hydrogenation catalysts disclosed herein are aged for about one day or longer, thereby forming aged hydrogenation catalysts. Aged hydrogenation catalysts have a degree of retained activity compared to hydrogenation catalysts. Therefore, the hydrogenation catalysts disclosed herein can be stored and / or transported for about one day or longer before use in hydrogenating polymers, while achieving a degree of retained activity.

[0029] In the embodiment, the hydrogenation catalyst can be aged for about 1 day or more, about 5 days or more, about 10 days or more, about 30 days or more, about 60 days or more, 90 days or more, more than 120 days, or even more than 150 days.

[0030] In embodiments, the hydrogenation catalyst may be aged by storing it at temperatures of approximately -20°C to approximately 100°C, approximately -20°C to approximately 75°C, approximately -20°C to approximately 50°C, approximately -20°C to approximately 25°C, approximately -10°C to approximately 100°C, approximately -10°C to approximately 75°C, approximately -10°C to approximately 50°C, approximately -10°C to approximately 25°C, approximately 0°C to approximately 100°C, approximately 0°C to approximately 75°C, approximately 0°C to approximately 50°C, approximately 0°C to approximately 25°C, approximately 10°C to approximately 100°C, approximately 10°C to approximately 75°C, approximately 10°C to approximately 50°C, or approximately 10°C to approximately 25°C. In embodiments, the hydrogenation catalyst may be aged by storing it at room temperature.

[0031] In embodiments, the hydrogenation catalyst may be aged by storing it in an environment having an oxygen concentration of less than about 2.5 ppm, less than about 2 ppm, less than about 1.5 ppm, or less than about 1 ppm. In embodiments, the hydrogenation catalyst may be aged by storing it in an oxygen-free environment (i.e., an oxygen concentration of 0 ppm).

[0032] In some embodiments, the hydrogenation catalyst may be aged by storing it in a gas containing nitrogen, argon, or a combination thereof.

[0033] In some embodiments, the hydrogenation catalyst may be aged by storing it in a glove box or cabinet (e.g., a standard flammable cabinet). In some embodiments, the hydrogenation catalyst may be placed in a glass container, such as a bottle, before being stored in the glove box or cabinet. In some embodiments, the glass container may be sealed and stored under gas.

[0034] In embodiments, the amount of aging hydrogenation catalyst used to hydrogenate the polymer may be about 0.2 mmol (mmol phgm) to about 0.8 mmol phgm, about 0.2 mmol phgm to about 0.6 mmol phgm, about 0.4 mmol phgm to about 0.8 mmol phgm, or about 0.4 mmol phgm to about 0.6 mmol phgm per 100 grams of monomer.

[0035] monomer Various monomers are intended for use as conjugated diolefin monomers and vinyl aromatic monomers.

[0036] Conjugated diolefin monomers can include a variety of hydrocarbon compositions. For example, in embodiments, conjugated diolefins may include those having 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-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, and 2,4-hexadiene, or combinations thereof. Conjugated diolefins can also include trienes such as myrcene. At least two conjugated diolefin monomers can polymerize to produce a homopolymer, such as polybutadiene.

[0037] Vinyl aromatic monomers can copolymerize with conjugated diolefin monomers to produce copolymers or terpolymers. In embodiments, vinyl aromatic monomers may include hydrocarbons having about 8 to about 20 carbon atoms, or about 8 to about 10 carbon atoms. These vinyl aromatic monomers may include, for example, monovinyl aromatic hydrocarbons. In one or more embodiments, vinyl aromatic monomers may include styrene, α-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 1-α-methylvinylnaphthalene, 2-α-methyl-vinylnaphthalene, mixtures thereof, and halo, alkoxy, alkyl, cycloalkyl, aryl, alkaryl and aralkyl derivatives, the total number of carbon atoms is generally 12 or more for synthetic hydrocarbons. Examples of these latter compounds include 4-methylstyrene, vinyltoluene, 3,5-diethylstyrene, 2-ethyl-4-benzylstyrene, 4-phenylstyrene, 4-para-tolylstyrene, and 4,5-dimethyl-1-vinylnaphthalene, or mixtures thereof.

[0038] In an embodiment, the polymer may contain conjugated diolefin monomers in amounts of about 60% to about 100% by weight, or about 60% to about 95% by weight, or about 60% to about 90% by weight, or about 70% to about 100% by weight, or about 70% to about 95% by weight, or about 70% to about 90% by weight, or about 80% to about 100% by weight, or about 80% to about 95% by weight, or about 80% to about 90% by weight. Conversely, the polymer may contain vinyl aromatic monomers in amounts of about 0% to about 40% by weight, or about 0% to about 30% by weight, or about 0% to about 20% by weight, or about 5% to about 40% by weight, or about 5% to about 20% by weight, or about 5% to about 20% by weight, or about 10% to about 40% by weight, or about 10% to about 30% by weight, or about 10% to about 20% by weight. The polymer may be a random copolymer or a block copolymer. In one embodiment, the conjugated diolefin monomer may be 1,3-butadiene, and the vinyl aromatic monomer may be styrene, which copolymerizes to produce a styrene-butadiene copolymer. In some embodiments, the copolymer may be a random styrene-butadiene copolymer.

[0039] solvent The polymerization of the present disclosure is carried out in the presence of a solvent, such as an inert solvent. The term "inert solvent" means a solvent that 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 used. Suitable inert solvents include hydrocarbon solvents that may contain aliphatic, aromatic, or alicyclic hydrocarbons such as hexane, pentane, toluene, benzene, and cyclohexane. Ethers such as tetrahydrofuran, and tertiary amines such as triethylamine and tributylamine can also be used as solvents, but these may alter the polymerization depending on the styrene distribution, vinyl content, and reaction rate. In one or more embodiments, the solvent may include hexane or blends and mixtures of hexanes (e.g., linear and branched chains), for example, cyclohexane mixed with hexane alone or in other forms.

[0040] Anionic polymerization initiator Various anionic polymerization initiators are intended for the anionic polymerization process of this disclosure. In embodiments, the anionic polymerization initiator may include a lithium catalyst, such as an organolithium anionic initiator catalyst. The organolithium initiator used may be any anionic organolithium initiator useful for the polymerization of conjugated diolefin monomers (e.g., 1,3-butadiene monomers). Generally, the organolithium compound may include a hydrocarbon-containing lithium compound of the formula R(Li)x, where R represents a hydrocarbon group containing about 1 to about 20 carbon atoms, for example, about 2 to about 8 carbon atoms, and x is an integer from 1 to 2. The hydrocarbon group may be an aliphatic group, but in other embodiments, the hydrocarbon group may be alicyclic or aromatic. In embodiments, the aliphatic group may be a primary, secondary, or tertiary group. 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 octadecyl. The aliphatic groups may include several unsaturated groups such as allyl and 2-butenyl. Cycloalkyl groups can be exemplified by cyclohexyl, methylcyclohexyl, ethylcyclohexyl, cycloheptyl, cyclopentylmethyl, and methylcyclopentylethyl. Examples of aromatic hydrocarbyl groups include phenyl, tolyl, phenylethyl, benzyl, naphthyl, and phenylcyclohexyl. Mixtures of different lithium initiator compounds can also be used, such as those containing one or more lithium compounds as defined above, such as R(Li)x, R, and x. Other lithium catalysts that can be used alone or in combination with a lithium hydrocarbyl initiator may include lithium tributyltin, lithium dialkylamine, lithium dialkylphosphine, lithium alkylarylphosphine, and lithium diarylphosphine. In one embodiment, the organolithium initiator may be n-butyllithium.

[0041] The amount of initiator required to bring about the desired polymerization can vary widely depending on numerous factors, including the desired polymer molecular weight, the desired 1,2- and 1,4-contents of the conjugated diene, and the desired physical properties of the resulting polymer. Generally, the amount of initiator used can vary from a minimum of about 0.2 mmol of lithium lithium per 100 grams of monomer to a maximum of about 100 mmol per 100 grams of monomer, depending on the desired polymer molecular weight (typically 1,000 to 10,000,000 grams / mol average molecular weight).

[0042] Polymerization is initiated by introducing the monomer and solvent into a suitable reaction vessel, followed by the addition of an anionic polymerization initiator. The polymerization reaction can 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 monomers using the anionic polymerization initiators described above. For example, for illustrative purposes only, the temperature used for 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 polymerization times ranging from a few minutes to more than 24 hours, using a pressure generally sufficient to maintain the polymerization mixture in a substantially liquid phase, for example, at or near atmospheric pressure, depending on temperature and other reaction parameters. This procedure may be carried out under anhydrous anaerobic conditions. In the presence of an organolithium initiator, polymerization of any of the monomers identified above results in the formation of a “living” polymer. Lithium migrates into the growing chain as polymerization continues. Throughout the formation or growth of the polymer, the polymer structure is anionic and can be living. In other words, carbon anions are present. A new batch of monomers subsequently added to the reaction may be added to the living ends of the existing chain, increasing the degree of polymerization. Thus, the living polymer or copolymer may contain polymeric moieties having anionically reactive ends.

[0043] functional group Next, functional groups may be applied to the anionic reactive ends of the living polymer to cap or terminate the living polymer. With respect to this functionalized polymer, the functional groups can be silica-reactive and, optionally, carbon black-reactive. The silica-reactive moiety comprises one or more reactive groups that react with a silica-reinforced filler to form ionic or covalent bonds. While the focus is on the reactivity of many functional groups with silica, it is intended that functional groups may be reactive with both silica and carbon black. Useful functional groups that react with silica are electron donors or can react with protons. Exemplary groups include one or a combination of alkoxysilyl, hydroxyl, polyalkylene glycol, silanol, silyl halide, anhydride, organic acid, amine, heterocyclic, and epoxy groups. Useful silica-reactive compounds containing one or more of these functional groups include functionalized elastomers, silica coupling agents, and silica-reactive dispersants.

[0044] In one or more embodiments, the functional group may be a silane modifier. The silane modifier may contain silica atoms bonded to hydrocarbon groups that may contain heteroatoms (silica atoms are typically bonded to four hydrocarbon groups). The hydrocarbon groups bonded to silica may contain cyclic portions and may be branched or linear. For example, various alkoxysilyl compositions are intended, for example, alkoxysilane compounds, aralkyloxysilane compounds, tetraalkoxysilane compounds, alkylalkoxysilane compounds, alkenylalkoxysilane compounds, halogenoalkoxysilane compounds, or combinations thereof. These include one or more dimethoxysilanes and trimethoxysilanes.

[0045] Examples of tetraalkoxysilane compounds include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra(2-ethylhexaneoxy)silane, tetraphenoxysilane, tetratoluyloxysilane, and combinations thereof.

[0046] Examples of alkylalkoxysilane compounds include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-n-butoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltritri-n-butoxysilane, ethyltriphenoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldi-n-butoxysilane, dimethyldiphenoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane (GPMOS), γ-methacrylateoxypropyltrimethoxysilane, and combinations thereof.

[0047] Examples of arylalkoxysilane compounds include phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltri-n-butoxysilane, phenyltriphenoxysilane, and combinations thereof.

[0048] Examples of alkenylalkoxysilane compounds include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propoxysilane, vinyltri-n-butoxysilane, vinyltriphenoxysilane, allyltrimethoxysilane, octenyltrimethoxysilane, divinyldimethoxysilane, styryltrimethoxysilane, and combinations thereof.

[0049] Examples of halogenoalkoxysilane compounds include trimethoxychlorosilane, triethoxychlorosilane, tri-n-propoxychlorosilane, tri-n-butoxychlorosilane, triphenoxychlorosilane, dimethoxydichlorosilane, diethoxydichlorosilane, di-n-propoxydichlorosilane, diphenoxydichlorosilane, methoxytrichlorosilane, ethoxytrichlorosilane, n-propoxytrichlorosilane, phenoxytrichlorosilane, trimethoxybromosilane, triethoxybromosilane, tri-n-propoxybromosilane, triphenoxybromosilane, and dimethoxydibromosilane. Examples include diethoxydibromosilane, di-n-propoxydibromosilane, diphenoxydibromosilane, methoxytribromosilane, ethoxytribromosilane, n-propoxytribromosilane, phenoxytribromosilane, trimethoxyiodosilane, triethoxyiodosilane, tri-n-propoxyiodosilane, triphenoxyiodosilane, dimethoxydiiodosilane, di-n-propoxydiiodosilane, diphenoxydiiodosilane, methoxytriiodosilane, ethoxytriiodosilane, n-propoxytriiodosilane, phenoxytriiodosilane, and combinations thereof.

[0050] Additionally, examples of alkoxysilyl compositions include trimethoxysilane compositions such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (ECETMOS), methyltrimethoxysilane (MeSi(OMe)3), 3-glycidylpropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, or 3-(1,3-dimethylbutylidene)aminopropyltriethoxysilane. Furthermore, examples of alkoxysilyl compositions include tetraethyl orthosilicate, 3-glycidylpropylmethyldimethoxysilane, or combinations thereof.

[0051] According to one or more embodiments, the silane modifier may contain an oxygen-containing moiety, and the oxygen atoms of the oxygen-containing moiety do not have to be directly bonded to the silicon atoms of the silane modifier. For example, the oxygen-containing moiety may be bonded to the silicon atoms of the silane modifier with carbon molecules. In such embodiments, it should be understood that other moieties bonded to the silica atom may be bonded to oxygen atoms such as alkoxy groups. However, at least one group (for example, one of four groups bonded to the silica atom) may contain an oxygen atom that is not directly bonded to the central silicon atom.

[0052] In additional embodiments described herein, the oxygen-containing moiety may include an oxygen heteroatom in the ring structure. For example, the oxygen-containing moiety may include a hexacarbon ring structure having an oxygen atom bonded to any two carbons (possibly adjacent carbons) in the hexacarbon ring. The hexacarbon ring may be bonded to the silicon atom of the silane modifier, for example, by an alkyl carbon chain.

[0053] In further embodiments, the oxygen-containing portion may include an oxygen heteroatom that is a terminal oxygen atom. As described herein, the terminal atom may include the atom furthest from the silicon molecule of the silane modifier (e.g., terminating the hydrocarbon chain), and additionally, the terminal molecule may be included on the branch of a branched hydrocarbon portion. The terminal atom may also include a heteroatom that is bonded to or included in a cyclic functional group at the end of the hydrocarbon chain. For example, an oxygen-containing portion bonded to an adjacent carbon molecule in a six-carbon ring portion terminating a carbon chain may be considered a terminal atom.

[0054] In additional embodiments, the silane modifier may not contain one or more of sulfur, phosphorus, or nitrogen. For example, in some embodiments, the silane modifier may not contain any of sulfur, phosphorus, and nitrogen. In further embodiments, the silane modifier may not contain one or two of sulfur, phosphorus, or nitrogen, but may contain a third (in any combination).

[0055] In further embodiments, the functional group may include a carbon black reactive moiety. The carbon reactive moiety may include an amine functional group. Various amines, such as primary amines (e.g., NH2), secondary amines, or tertiary amines, are intended. Furthermore, the amine functional group may include an aliphatic or aromatic moiety. In other embodiments, the functional group may include a tin compound for making the functionalized polymer carbon black reactive. Various tin compounds are intended, but are not limited to, butyltin tris-(2-ethylhexanoate), butyltin chloride dihydroxyl, butyltin hydroxyhydrate, dibutyltin dilaurate, and dibutyltin dimaleate. Mixtures of monofunctional alkyltin compounds can also be used. Furthermore, inorganic tin functional groups such as tin tetrachloride (SnCl4) are intended.

[0056] Polymerization conditions and reagents can determine the amount of functional group added. In one or more embodiments, the functional group may be present in a molar ratio of about 0.25 to 2, or about 0.5 to 1 (relative to the initiator).

[0057] Additional polymerization components In addition, to promote randomization in copolymerization and to control the vinyl content, one or more polymer modifiers may be optionally added to the polymerization components. The amount of polymer modifier may range from 0 to about 90 equivalents or more per equivalent of the initiator (e.g., lithium catalyst). Compounds useful as polymer modifiers may be organic and may include those having oxygen or nitrogen heteroatoms and non-bonding electron pairs. Examples include dialkyl ethers of mono and oligoalkylene glycols, "crown" ethers, tertiary amines such as tetramethylethylenediamine (TMEDA), tetrahydrofuran (THF), 2,2-bis(2'-tetrahydrofuryl)propane, THF oligomers, linear and cyclic oligomer oxolanyl alkanes (e.g., cyclic oligomer oxolanylpropane), potassium t-amilate (KTA), or combinations thereof.

[0058] The method of this disclosure may optionally include a stabilizer, such as a silane stabilizer. One suitable silane stabilizer may be octyltriethoxysilane. Furthermore, to reduce the possibility of Mooney viscosity instability due to oxidative coupling, an antioxidant such as 2,6-di-t-butyl-4-methylphenol (also known as butylated hydroxytoluene (BHT)) may be added. The stabilizer may be added to the reactor or to another mixer downstream of the reactor. Similarly, the antioxidant may be added to the reactor or to another mixer downstream of the reactor.

[0059] Optionally, at the point of termination, the stopped functional polymer may be quenched and dried as needed. Quenching can be carried out by contacting the functional copolymer with a quenching agent at a temperature of about 30°C to about 120°C for about 0.05 to about 2 hours to ensure completion of the reaction. Suitable and well-known quenching agents include alcohols, water, carboxylic acids such as 2-ethylhexanoic acid (EHA) and acetic acid. Coagulation is usually carried out using alcohols such as methanol or isopropanol. Instead of, or in combination with, the functional polymer may be subjected to drum drying as is well known in the art. The use of steam or high heat to remove the solvent may also be considered suitable.

[0060] Hydrogenation After the functionalized polymer is produced, the functionalized polymer is hydrogenated by mixing it with an aging hydrogenation catalyst in a solvent and introducing a hydrogen stream.

[0061] In the hydrogenation method, pressurized hydrogen at a pressure of 1 to 100 atm may be added. As with the polymerization described above, additional components such as quenching agents and oxidizing agents may be added to the reactor.

[0062] In the hydrogenation method, pressurized hydrogen at a pressure of 1 to 100 atm may be added. As with the polymerization described above, additional components such as quenching agents and oxidizing agents may be added to the reactor.

[0063] The following exemplary reaction, illustrated in Equation 1 below, illustrates the hydrogenation of a styrene-butadiene copolymer.

[0064] [ka]

[0065] Although not shown in Formula 1 above, styrene-butadiene copolymers can be functionalized with functional groups containing silica-reactive moieties before hydrogenation.

[0066] As described herein, the aging hydration catalyst has a retained degree of activity compared to the original hydrogenation catalyst. In embodiments, the functionalized polymer may have a degree of hydrogenation of about 75 mol% to about 99 mol%, about 75 mol% to about 97 mol%, about 75 mol% to about 95 mol%, about 80 mol% to about 99 mol%, about 80 mol% to about 97 mol%, about 80 mol% to about 95 mol%, about 85 mol% to about 99 mol%, about 85 mol% to about 97 mol%, about 85 mol% to about 95 mol%, about 90 mol% to about 99 mol%, about 90 mol% to about 97 mol%, or about 90 mol% to about 95 mol%. Although not limited to theory, such high levels of hydrogenation in the functionalized polymer have correlated with improved mechanical performance.

[0067] While hydrogenation reduces the number of double bonds, functionalized polymers may, in one or more embodiments, have an initial vinyl content of approximately 10% to 60%, 10% to 50%, 10% to 40%, 10% to 30%, 15% to 60%, 15% to 50%, 15% to 40%, 15% to 30%, 20% to 60%, 20% to 50%, 20% to 40%, 20% to 30%, 25% to 60%, 25% to 50%, 25% to 40%, or 25% to 30% before hydrogenation. Although not constrained by theory, controlling the initial vinyl content can maintain the amorphous nature of the functionalized polymer, thereby reducing crystal formation that could degrade tire tread performance.

[0068] rubber composition As already stated, the hydrogenated functionalized polymers detailed above can be incorporated into rubber compositions for tire and non-tire applications. The rubber composition may also include at least one curing agent and at least one reinforcing filler.

[0069] hardening agent As used herein, a curing agent is a vulcanizing agent used for vulcanizing a functionalized polymer. In one or more embodiments, the curing agent may include a sulfur-based curing agent or a peroxide-based curing agent. Examples of specific suitable sulfur curing agents include "rubbermaker's" soluble sulfur, disulfide amines, polymeric polysulfides, or sulfur olefin adducts, as well as insoluble polymeric sulfur. In one embodiment, the sulfur curing agent may include soluble sulfur or a mixture of soluble and insoluble polymeric sulfur. Suitable curing agents used for curing For general disclosures of and other compositions (e.g., vulcanization inhibitors, scorch inhibitors), one can refer to Kirk-Othmer, "Encyclopedia of Chemical Technology," 3rd Edition, Wiley Interscience, NY, 1982, Vol. 20, pp. 365-468, in particular Vulcanization Agents and Auxiliary Materials, pp. 390-402, or Vulcanization by AYCoran (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 intended, the curing agent may be used in amounts ranging from about 0.1 phr to about 10 phr, including about 1 phr to about 7.5 phr (including about 1 phr to about 5 phr, preferably about 1 phr to about 3.5 phr).

[0070] Reinforcing filler As used herein, the term "reinforcement filler" refers to a filler with a nitrogen absorption specific surface area (N2SA) of approximately 100 m².2 If the amount exceeds / g, in certain cases, 100m 2 / g, about 125m 2 / g, 125m 2 / g or more, or approximately 150m 2 / g or more, or 150m 2 It can refer to particulate materials with a particle size greater than / g. Alternatively, "reinforcement filler" can also be used to refer to particulate materials with particle sizes ranging from approximately 10 nm to approximately 50 nm.

[0071] In one or more embodiments, the reinforcing filler may include silica, carbon black, or a combination thereof.

[0072] Various carbon black compositions are considered suitable. Useful carbon blacks include furnace black, channel black, and lamp black. More specifically, examples of useful carbon blacks include super abrasion furnace (SAF) black, high abrasion furnace (HAF) black, fast extrusion furnace (FEF) black, fine furnace (FF) black, intermediate super abrasion furnace (ISAF) black, semi-reinforcing furnace (SRF) black, moderately processable channel black, difficult-to-process channel black, and conductive channel black. Another carbon black that can be used is acetylene black. In certain embodiments, the rubber composition may contain a mixture of two or more of the above carbon blacks.

[0073] Various amounts of carbon black are intended. In one or more embodiments, the total amount of reinforcing carbon black filler is approximately 5 phr to 175 phr, approximately 5 phr to 150 phr, approximately 5 phr to 100 phr, approximately 5 phr to 80 phr, approximately 10 phr to 200 phr, approximately 10 phr to 175 phr, approximately 10 phr to 150 phr, approximately 10 phr to 100 phr, approximately 10 phr to 80 phr, approximately 20 phr to 200 phr, approximately 20 phr to 175 phr, approximately 20 phr to 150 phr, approximately 20 phr to 100 phr, approximately 20 phr to 80 phr, and approximately 25 phr. The carbon black used may range from approximately 5 phr to approximately 200 phr, including approximately 25 phr to approximately 175 phr, approximately 25 phr to approximately 150 phr, approximately 25 phr to approximately 100 phr, approximately 25 phr to approximately 80 phr, approximately 30 phr to approximately 200 phr, approximately 30 phr to approximately 175 phr, approximately 30 phr to approximately 150 phr, approximately 30 phr to approximately 100 phr, approximately 30 phr to approximately 80 phr, approximately 35 phr to approximately 200 phr, approximately 35 phr to approximately 175 phr, approximately 35 phr to approximately 150 phr, approximately 35 phr to approximately 100 phr, or approximately 35 phr to approximately 80 phr. The carbon black used may be in pelletized form or in unpelletized aggregate form. For more uniform mixing in the rubber composition, unpelletized carbon black may be used in some embodiments.

[0074] Furthermore, silica fillers may also be used as reinforcing fillers. Suitable examples of reinforcing silica fillers include, but are not limited to, precipitated amorphous silica, wet silica (hydrated silicic acid), dry silica (anhydrous silicic acid), fumed silica, and calcium silicate. Other suitable silica fillers for use in the rubber compositions of the specific embodiments disclosed herein include, but are not limited to, aluminum silicate, magnesium silicate (e.g., Mg2SiO4, MgSiO3), calcium magnesium silicate (CaMgSiO4), and calcium aluminum silicate (e.g., Al2O3,CaO2SiO2).

[0075] Like carbon black, various amounts of silica are intended for use as a reinforcing filler. In one or more embodiments, the total amount of reinforcing silica filler or silica filler may be about 5 to about 175 phr, about 5 phr to about 150 phr, about 5 phr to about 125 phr, about 5 phr to about 100 phr, about 5 phr to about 80 phr, about 10 phr to about 175 phr, about 10 phr to about 150 phr, about 10 phr to about 125 phr, about 10 phr to about 100 phr, about 10 phr to about 80 phr, about 20 phr to about 175 phr, about 20 phr to about 150 phr, about 20 phr to about 125 phr, about 20 phr to about 100 phr, Includes approximately 20 phr to 80 phr, approximately 25 phr to 175 phr, approximately 25 phr to 150 phr, approximately 25 phr to 125 phr, approximately 25 phr to 100 phr, approximately 25 phr to 80 phr, approximately 30 phr to 175 phr, approximately 30 phr to 150 phr, approximately 30 phr to 125 phr, approximately 30 phr to 100 phr, approximately 30 phr to 80 phr, approximately 35 phr to 175 phr, approximately 35 phr to 150 phr, approximately 35 phr to 125 phr, approximately 35 phr to 100 phr, or approximately 35 phr to 80 phr.

[0076] In other embodiments, the rubber composition may include, or alternatively, at least one reinforcing filler in addition to, carbon black and silica. Non-limiting examples of such reinforcing fillers suitable for use in the rubber compositions disclosed herein include aluminum hydroxide, talc, alumina (Al2O3), aluminum hydrate (Al2O3H2O), aluminum hydroxide (Al(OH)3), aluminum carbonate (Al2(CO3)2), aluminum magnesium oxide (MgOAl2O3), pyrophyllite (Al2O34SiO2H2O), bentonite (Al2O34SiO22H2O), mica, kaolin, glass balloons, glass beads, and calcium oxide. This includes, but is not limited to, um (CaO), calcium hydroxide (Ca(OH)2), calcium carbonate (CaCO3), magnesium carbonate, magnesium hydroxide (Mg(OH)2), magnesium oxide (MgO), magnesium carbonate (MgCO3), potassium titanate, barium sulfate, zirconium oxide (ZrO2), zirconium hydroxide [Zr(OH)2.nH2O], zirconium carbonate [Zr(CO3)2], crystalline aluminosilicate, reinforcing grade zinc oxide (i.e., reinforcing zinc oxide), and combinations thereof. If at least one reinforcing filler is present in addition to or alternatively to the reinforcing carbon black filler and reinforcing silica filler, the total amount of all reinforcing fillers may be about 5 to about 200 phr. In other words, if at least one reinforcing filler is present in addition to or alternatively to carbon black silica, the amounts of reinforcing carbon black filler and reinforcing silica filler are adjusted so that the total amount of reinforcing fillers is about 5 to about 200 phr.

[0077] additional rubber In further embodiments, the rubber composition may include additional rubber components, including natural rubber, synthetic rubber, or combinations thereof. For example, but not limited to, synthetic rubbers may include 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.

[0078] Additional additives Optionally, silane coupling agents can be blended with silica-reinforced fillers to further improve reinforcement properties. For example, silane coupling agents include bis(3-triethoxysilylpropyl)tetrasulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, and 3-trimethoxysilylpropyl-N,N-dimethylthio Carbamoyl tetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropyl benzothiazole tetrasulfide, 3-triethoxysilylpropyl benzothiazole tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis(3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyl dimethoxymethylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, dimethoxymethylsilylpropylbenzothiazole tetrasulfide, 3-hexanoylthiopropyltriethoxysilane, 3-octanoylthiopropyltriethoxysilane, 3-decanoylthiopropyltriethoxysilane, 3-lauroylthiopropyltriethosylsilane, 2-hexanoylthioethyltriethoxysilane, 2-octanoylthioethyltriethoxysilane, 2-decanoylthioethyltriethoxysilane, 2 Examples include lauroylthioethyltriethoxysilane, 3-hexanoylthiopropyltrimethoxysilane, 3-octanoylthiopropyltrimethoxysilane, 3-decanoylthiopropyltrimethoxysilane, 3-lauroylthiopropyltrimethoxysilane, 2-hexanoylthioethyltrimethoxysilane, 2-octanoylthioethyltrimethoxysilane, 2-decanoylthioethyltrimethoxysilane, and 2-lauroylthioethyltrimethoxysilane. These silane coupling agents may be used alone or in combination of two or more.

[0079] Furthermore, useful processing oils or drawer oils may be included. Examples of such oils include commercially available paraffinic, aromatic, or naphthenic oils. In one or more embodiments, the main component of the oil may be naphthenic. The rubber component may also include other additives such as anti-ozone agents, waxes, scorch inhibitors, processing aids, zinc oxide, adhesive resins, reinforcing resins, fatty acids such as stearic acid, peptidizing agents, and one or more accelerators.

[0080] The anti-ozone agent may include N,N'-disubstituted-p-phenylenediamines, such as N-1,3-dimethylbutyl-N'phenyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine, N-phenyl-N-isopropyl-p-phenylenediamine, and N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine. Other examples of ozone degradation inhibitors include acetone diphenylamine condensation products, 2,4-trimethyl-1,2-dihydroquinoline, octylated diphenylamine, and 2,6-di-t-butyl-4-methylphenol.

[0081] Examples of curing accelerators include, but are not limited to, dithiocarbamate accelerators containing metal dialkyldithiocarbamates such as zinc dibutyldithiocarbamate, zinc diethyldithiocarbamate, zinc dimethyldithiocarbamate, and iron dimethyldithiocarbamate; thiazole accelerators containing benzothiazole disulfides such as 2-mercaptobenzothiazole, for example, mercaptobenzothiazole disulfide; benzothiazole sulfenamides such as n-cyclohexyl-2-benzothiazole sulfenamide; and sulfenamide accelerators such as t-butyl-2-benzothiadiyl sulfenamide.

[0082] The rubber composition may contain at least 3 parts by weight (phr), or about 5 to about 1000 phr, or about 20 to about 80 phr, or about 30 to about 50 phr, of filler per 1000 parts by weight of rubber. The rubber composition may also contain about 0 to about 80 parts, or about 5 to about 50 phr, or about 10 to about 30 phr, of processing oil or draw oil per 100 parts by weight of rubber.

[0083] The functional polymer may comprise approximately 20 to 100 parts of the total 100 parts of rubber, or approximately 25 to 75 parts of the total 100 parts, or approximately 30 to 60 parts of the total 100 parts.

[0084] The present rubber composition can be obtained by milling with a milling machine such as a roll or a closed mixer that can be molded and vulcanized for use in tire applications such as treads, undertreads, carcasses, sidewalls, and beads, as well as rubber cushions, belts, hoses and other industrial products, and is particularly suitable for use in tire treads.

Examples

[0085] The hydrogenated functionalized polymers described herein are further described in the following examples, which are not intended to limit the polymers.

[0086] Measurement Number average molecular weight (M n n), weight average molecular weight (M w w), peak molecular weight (M p p) were determined by gel permeation chromatography using a TOSOH Esosec HLC-8320 GPC system and a TOSOH TSKgel GMHxl-BS column, with THF as the solvent. The system was calibrated using polystyrene standards.

[0087] The cis content, vinyl content, and hydrogenation level were determined in chloroform-d1 at room temperature by 1 1H-nuclear magnetic resonance spectroscopy.

[0088] Example 1: Synthesis of ECETMOS-functionalized BR ECETMOS [2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane]-functionalized butadiene polymer (BR) was prepared according to the following method. 3.515 kg of hexane and 21.8 wt% of 1,3-butadiene in 7.865 kg of hexane were added to a 5-gallon (approximately 18.9 liters) N2-purge reactor equipped with a stirrer. 0.893 ml of 2,2-bis(2'-tetrahydrofuryl)propane (OOPS, 1.60 mol in hexane), followed by 5.72 ml of n-butyllithium (BuLi, 2.50 mol in hexane), were added to the reactor, and the reactor jacket was heated to 50°C. After 46 minutes, the batch temperature peaked at 95°C. After an additional 40 minutes, the anionic polymerization reaction was stopped by adding 3.31 ml of ECETMOS. After a further 30 minutes, 1.31 ml of isopropyl alcohol was added. After another 10 minutes, a 550 mL sample of polymer cement was collected for use in high-throughput hydrogenation. The remaining cement was transferred to a storage container and then prepared for transfer to the hydrogenation reactor. The property data of the non-hydrogenated functionalized BR intermediate polymer are summarized in Table 1.

[0089] [Table 1]

[0090] Example 2: Preparation of Ni catalyst 400 mL of hexane and 22 mL of 1 M triethylaluminum were added to a nitrogen-purged dry bottle, and 4.0 mL of nickel octanoate (10 wt% Ni in hexane, 0.40 mmol Ni phgm) was added dropwise to obtain a Ni / Al catalyst (Al / Ni = 3.3 / 1.0). A portion of the catalyst was divided into two glass bottles, catalyst A and catalyst B, sealed, and stored under nitrogen. The glass bottle containing catalyst A was stored at room temperature (RT) in a nitrogen-filled glove box. The glass bottle containing catalyst B was immediately stored in a freezer at -30°C in the dark.

[0091] Example 3: Hydrogenation of functionalized BR from Example 1 A hexane solution of the functionalized BR from Example 1 was introduced into a reactor under a nitrogen atmosphere, and the reactor was sealed. The reactor was purged three times with hydrogen at 50 psi, and the reactor jacket was heated to 50°C. The reactor was immediately pressurized to 150 psi with hydrogen, and 0.75 mL each of catalyst A and catalyst B were transferred to each reactor using an OSR tip, as shown in Table 2. After 120 minutes of the hydrogenation reaction, hydrogen was released from the reactor to solidify the polymer cement, and it was drum-dried at 120°C. The polymer properties data of the hydrogenated functionalized BR are summarized in Table 2.

[0092] [Table 2]

[0093] Catalysts A and B began to precipitate over time. Catalyst A had a small amount of precipitate, but still visually resembled the freshly prepared (i.e., original) catalyst mixture. Catalyst B was visibly precipitated, and nickel was beginning to deposit on the walls of the vial. After vigorously shaking the vials containing catalysts A and B, the polymer was hydrogenated.

[0094] As shown in Table 2, catalyst A produced a degree of hydrogenation of 96 mol% in sample 3-1. Catalyst B produced a degree of hydrogenation of 22.8 mol% in sample 3-2. Although we do not wish to be constrained by theory, it is thought that storage of catalyst B at relatively low temperatures would result in a greater degree of precipitation, which would ultimately deactivate the catalyst. Furthermore, since both glass bottles containing the catalysts were sealed and stored under nitrogen, it is thought that the atmosphere in which the glass bottles containing the catalysts were stored did not affect the catalysts in this example.

[0095] As illustrated in Table 2, catalyst storage is possible for up to 6 days while achieving a relatively high level of hydrogenation.

[0096] Example 4: Hydrogenation of functionalized BR from Example 1 using catalyst A from Example 3 A hexane solution of the functionalized BR from Example 1 was introduced into a reactor under a nitrogen atmosphere, and the reactor was sealed. The reactor was purged three times with hydrogen at 50 psi, and the reactor jacket was heated to 50°C. The reactor was immediately pressurized to 100 psi with hydrogen, and 0.75 mL of catalyst A was transferred to the reactor as shown in Table 3. After 60 minutes of the hydrogenation reaction, hydrogen was released from the reactor to solidify the polymer cement, which was then drum-dried at 120°C. The polymer properties data of the hydrogenated functionalized BR are summarized in Table 2.

[0097] [Table 3]

[0098] As shown in Table 3, samples 4-2 to 4-16, which were hydrogenation catalysts aged for more than one day, had a degree of hydrogenation of 5 mol% or less of that of the original hydrogenation catalyst (i.e., the unaged hydrogenation catalyst) sample 4-1. As illustrated in Table 3, hydrogenation catalysts can be aged for about one day or more to form aged hydrogenation catalysts that retain a degree of activity compared to the unaged hydrogenation catalyst.

[0099] The embodiments may be further described with respect to the following provisions. 1. A method for producing a hydrogenated functionalized polymer, comprising: aging a hydrogenation catalyst for about one day or more to form an aged hydrogenation catalyst such that the aged hydrogenation catalyst has a degree of activity retained compared to the hydrogenation catalyst; introducing an anionic polymerization initiator, a conjugated diolefin monomer, and a solvent into a reactor to produce a living polymer by anionic polymerization; reacting at least one silane modifier with the living polymer to produce a functionalized polymer; and hydrogenating the functionalized polymer by mixing the functionalized polymer in a solvent and an aged hydrogenation catalyst and introducing a hydrogen stream. 2. Hydrogenated functionalized polymers, proton nuclear magnetic resonance spectroscopy ( 1 The method according to Clause 1, having a degree of hydrogenation of approximately 75 mol% to approximately 99 mol% when measured using 1H NMR. 3. The method according to any one of the provisions of 1 to 2, wherein the catalyst aging process includes aging the catalyst for approximately 5 days or more. 4. The method according to any one of the clauses 1 to 3, wherein aging the hydrogenation catalyst includes storing the hydrogenation catalyst at a temperature of approximately -20°C to approximately 100°C. 5. The method according to any one of the clauses 1 to 4, wherein aging the hydrogenation catalyst includes storing the hydrogenation catalyst at room temperature. 6. The method according to any one of the clauses 1 to 5, wherein aging the hydrogenation catalyst includes storing the hydrogenation catalyst in an environment having an oxygen concentration of less than approximately 2.5 ppm. 7. The method according to any one of the clauses 1 to 6, wherein aging the hydrogenation catalyst includes storing the hydrogenation catalyst in a gas containing nitrogen, argon, or a combination thereof. 8. The method according to any one of the clauses 1 to 7, wherein aging the hydrogenation catalyst includes storing the hydrogenation catalyst in a glove box or cabinet. 9. The hydrogenation catalyst is the method described in any one of the clauses 1 to 8, comprising nickel, aluminum, ruthenium, rhodium, palladium, iridium, platinum, titanium, or a combination thereof. 10. The method according to any one of the clauses 1 to 9, wherein the hydrogenation catalyst comprises nickel and aluminum. 11. The method according to any one of the clauses 1 to 10, wherein the hydrogenation catalyst comprises nickel octanoate. 12. The method according to any one of the clauses 1 to 11, wherein the anionic polymerization initiator is a lithium catalyst. 13. The method according to any one of the claims 1 to 12, wherein the silane modifier comprises an alkoxysilyl group, a hydroxyl group, a polyalkylene glycol group, a silanol group, a halogenated silyl group, an anhydride group, an organic acid group, an epoxy group, or a combination thereof. 14. A silane modifier comprising an alkoxysilyl group, as described in any one of the claims 1 to 13. 15. The method according to any one of the claims 1 to 14, wherein the alkoxysilyl group comprises an alkoxysilane compound, an aralkyloxysilane compound, a tetraalkoxysilane compound, an alkylalkoxysilane compound, an alkenylalkoxysilane compound, a halogenoalkoxysilane compound, or a combination thereof. 16. The method according to any one of the claims 1 to 15, wherein the alkoxysilyl functional group includes trimethoxysilane, dimethoxysilane, or a combination thereof. 17. The method according to any one of the clauses 1 to 16, further comprising introducing a vinyl aromatic monomer into a reactor. 18. The method according to any one of the claims 1 to 17, wherein the conjugated diolefin monomer comprises 1,3-butadiene, isoprene, myrcene, or a combination thereof, and the vinyl aromatic monomer comprises styrene, α-methylstyrene, or a combination thereof. 19. The method according to any one of the clauses 1 to 18, wherein the polymer is a styrene-butadiene copolymer. 20. The functionalized polymer having a vinyl content of about 10% to about 60% before hydrogenation, according to any one of the methods described in Clauses 1 to 19.

[0100] It will be apparent that modifications and variations are possible without departing from the scope of this disclosure as defined in the attached "Claims." More specifically, certain aspects of this disclosure are identified herein as preferred or particularly advantageous, but it is intended that this disclosure is not necessarily limited to these aspects.

Claims

1. A method for producing hydrogenated functionalized polymers, The hydrogenation catalyst is aged for approximately one day or more, thereby forming an aged hydrogenation catalyst, wherein the aged hydrogenation catalyst retains a degree of activity compared to the original hydrogenation catalyst. An anionic polymerization initiator, a conjugated diolefin monomer, and a solvent are introduced into a reactor to produce a living polymer by anionic polymerization. The method involves reacting at least one silane modifier with the living polymer to produce a functionalized polymer, A method comprising: mixing the functionalized polymer in the solvent with the aging hydrogenation catalyst and hydrogenating the functionalized polymer by introducing a hydrogen stream.

2. The aforementioned hydrogenated functional polymer is subjected to proton nuclear magnetic resonance spectroscopy ( １ The method according to claim 1, wherein the degree of hydrogenation is approximately 75 mol% to approximately 99 mol% when measured using 1H NMR.

3. The method according to claim 1 or claim 2, wherein the step of aging the catalyst includes aging the catalyst for about 5 days or more.

4. The method according to claim 1 or claim 2, wherein aging the hydrogenation catalyst includes storing the hydrogenation catalyst at a temperature of about -20°C to about 100°C.

5. The method according to claim 1 or claim 2, wherein aging the hydrogenation catalyst includes storing the hydrogenation catalyst at room temperature.

6. The method according to claim 1 or claim 2, wherein aging the hydrogenation catalyst includes storing the hydrogenation catalyst in an environment having an oxygen concentration of less than about 2.5 ppm.

7. The method according to claim 1 or 2, wherein aging the hydrogenation catalyst includes storing the hydrogenation catalyst in a gas containing nitrogen, argon, or a combination thereof.

8. The method according to claim 1 or 2, wherein aging the hydrogenation catalyst includes storing the hydrogenation catalyst in a glove box or cabinet.

9. The method according to claim 1 or claim 2, wherein the hydrogenation catalyst comprises nickel, aluminum, ruthenium, rhodium, palladium, iridium, platinum, titanium, or a combination thereof.

10. The method according to claim 9, wherein the hydrogenation catalyst comprises nickel and aluminum.

11. The method according to claim 9, wherein the hydrogenation catalyst comprises nickel octanoate.

12. The method according to claim 1 or claim 2, wherein the anionic polymerization initiator is a lithium catalyst.

13. The method according to claim 1 or claim 2, wherein the silane modifier comprises an alkoxysilyl group, a hydroxyl group, a polyalkylene glycol group, a silanol group, a halogenated silyl group, an anhydride group, an organic acid group, an epoxy group, or a combination thereof.

14. The method according to claim 13, wherein the silane modifier comprises the alkoxysilyl group.

15. The method according to claim 14, wherein the alkoxysilyl group includes an alkoxysilane compound, an aralkyloxysilane compound, a tetraalkoxysilane compound, an alkylalkoxysilane compound, an alkenylalkoxysilane compound, a halogenoalkoxysilane compound, or a combination thereof.

16. The method according to claim 14, wherein the alkoxysilyl functional group includes trimethoxysilane, dimethoxysilane, or a combination thereof.

17. The method according to claim 1 or 2, further comprising introducing a vinyl aromatic monomer into the reactor.

18. The method according to claim 17, wherein the conjugated diolefin monomer comprises 1,3-butadiene, isoprene, myrcene, or a combination thereof, and the vinyl aromatic monomer comprises styrene, α-methylstyrene, or a combination thereof.

19. The method according to claim 1 or claim 2, wherein the polymer is a styrene-butadiene copolymer.

20. The method according to claim 1 or claim 2, wherein the functionalized polymer has a vinyl content of about 10% to about 60% before hydrogenation.

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