Rubber compound containing functionalized conjugated diene polymer, natural rubber, and reinforcing filler

Abstract

Embodiments of the present disclosure are directed to a rubber compound comprising a functionalized conjugated diene polymer, natural rubber, and a reinforcing filler comprising at least one of silica and carbon black. The functionalized conjugated diene polymer has a functional group, a vinyl content of 50% or more, and a weight average molecular weight M of about 75,000 g / mol to about 1,000,000 g / mol. w has.

Description

[Technical field]

[0001] FIELD OF THE DISCLOSURE Embodiments of the present disclosure relate generally to functionalized conjugated diene polymers, and specifically to rubber compounds comprising a functionalized conjugated diene polymer, natural rubber, and a reinforcing filler having improved filler dispersion. [Background technology]

[0002] Rubber compounds containing natural rubber, butadiene rubber, and reinforcing fillers such as silica and carbon black are commonly used in tire applications, such as tire treads. However, sufficient dispersion of the silica and / or carbon black in the natural rubber can be difficult due to poor interaction between the natural rubber and the silica and / or carbon black, leading to increased rolling resistance.

[0003] Thus, there is a continuing need for improved rubber compounds that have improved filler dispersion, thereby providing reduced rolling resistance. Summary of the Invention

[0004] The embodiments of the present disclosure are directed to rubber compounds of functionalized conjugated diene polymer and natural rubber with improved rolling resistance due to improved filler dispersion. Specifically, high cis 1,4-polybutadiene rubber has low miscibility with natural rubber. The rubber compounds disclosed herein replace the natural rubber with a functionalized conjugated diene polymer that is preferentially miscible with natural rubber and favors the natural rubber phase over another diene polymer phase that is not miscible with natural rubber, such as a high cis 1,4-polybutadiene rubber phase. The functional groups of the functionalized conjugated diene polymer may react with silica or carbon black to improve the dispersion of the silica or carbon black in the natural rubber phase.

[0005] According to one embodiment, a rubber formulation is provided. The rubber formulation includes a functionalized conjugated diene polymer, natural rubber, and a reinforcing filler including at least one of silica and carbon black. The functionalized conjugated diene polymer has a functional group, a vinyl content of about 50% or more, and a weight average molecular weight M of about 75,000 g / mol to about 1,000,000 g / mol. w has.

[0006] Additional features and advantages of the embodiments described herein are set forth in the Detailed Description below, and, in part, will be readily apparent to those skilled in the art from this description or will be recognized by the practice of the embodiments described herein, including the Detailed Description and Claims below. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] DETAILED DESCRIPTION OF THE DISCLOSURE Embodiments of the present disclosure are directed to a rubber formulation comprising a functionalized conjugated diene polymer, natural rubber, and a reinforcing filler comprising at least one of silica and carbon black. The functionalized conjugated diene polymer has a functional group, a vinyl content of about 50% or greater, and a weight average molecular weight M of about 75,000 g / mol to about 1,000,000 g / mol. w This disclosure should not be construed as being limited to the embodiments described herein. 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.

[0008] definition 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 present disclosure herein is for describing particular embodiments only and is not intended to be limiting.

[0009] 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.

[0010] Unless expressly stated otherwise, it is never intended that any method described herein be interpreted as requiring that its steps be performed in a particular order, or that any apparatus requires a particular orientation. Thus, where a method claim does not actually recite an order that its steps should be followed, or where any apparatus claim does not actually recite an order or orientation for individual components, or where it is otherwise specifically stated in the claim or description that the steps are to be limited to a particular order, or that no particular order or orientation for the apparatus components is recited, no order or orientation is ever intended to be inferred in any respect. This applies to any possible implicit basis for interpretation, including questions of logic regarding the arrangement of steps, operational flow, order of components, or orientation of components, the plain meaning derived from grammatical construction or punctuation, and the number or type of embodiments described herein.

[0011] As used in this specification and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms unless the context clearly dictates otherwise. Thus, for example, reference to "a" element includes aspects having two or more such elements unless the context clearly dictates otherwise.

[0012] The term "phr" as used herein refers to parts by weight of a specified component per 100 parts of rubber.

[0013] The term "rubber compound" as used herein refers to rubber (i.e., functionalized conjugated diene polymer, natural rubber, and optionally high cis 1,4-polybutadiene rubber) and additional fillers and additives blended therewith in tire and non-tire applications.

[0014] The term "vinyl content," as used herein, refers to the percentage of vinyl 1,2 bonds in a polydiene, such as a functionalized conjugated diene polymer. "Vinyl content" is determined by 400 MHz nuclear magnetic resonance using CDCl3 as the solvent.

[0015] The term "high vinyl", as used herein, means that the vinyl 1,2 bond content in the functionalized conjugated diene polymer is 50% or greater.

[0016] The term "cis content," as used herein, refers to the percentage of cis 1,4 bonds in a polydiene.

[0017] The term "high cis" as used herein means that the cis-1,4 bond content in the resulting polydiene is 85% or greater.

[0018] The term "non-sulfur," as used herein, refers to a moiety that does not contain a sulfur atom.

[0019] The term "control rubber compound," as used herein, refers to a rubber compound that contains natural rubber, high cis 1,4-polybutadiene rubber, and silica and / or carbon black, and does not contain a synthetic conjugated diene polymer that is miscible with natural rubber.

[0020] The number average molecular weight M n , weight average molecular weight M w , and peak molecular weight M p is determined by gel permeation chromatography.

[0021] Glass transition temperature T g As described herein, is measured by differential scanning calorimetry.

[0022] Mooney viscosity, as described herein, is determined using a Monsanto Mooney viscometer.

[0023] The tensile mechanical properties such as modulus of elasticity at 100% strain M100, modulus of elasticity at 300% strain M300, stress at break (Tb), and maximum strain (Eb) described herein are determined according to ASTM D412.

[0024] The viscoelastic properties described herein, such as loss tangent tan δ(2%), loss tangent tan δ(5%), loss tangent tan δ(10%), and change in storage modulus ΔG'(0.25-10%), were measured by strain sweep tests performed using an Advanced Rheometric Expansion System from TA Instruments.

[0025] The viscoelastic property, loss modulus G", as described herein, was measured by a temperature sweep test performed using an Advanced Rheometric Expansion System from TA Instruments.

[0026] The viscoelastic properties described herein, such as loss tangent tan δ(0° C.), loss tangent tan δ(60° C.), and storage modulus E′ at 30° C., were measured by temperature sweep tests conducted at various temperatures at 2% strain using a GABO Eplexor.

[0027] As mentioned above, natural and butadiene rubber blends containing silica and / or carbon black are commonly used in tire tread applications. However, the natural rubber may react poorly with the silica and / or carbon black, resulting in poor dispersion of the silica and / or carbon black in the natural rubber and increased rolling resistance.

[0028] Disclosed herein is a rubber compound that alleviates the aforementioned problems. Specifically, high cis 1,4-polybutadiene rubber has low miscibility with natural rubber. Disclosed herein is a rubber compound that replaces natural rubber with a functionalized conjugated diene polymer that is preferentially miscible with natural rubber and favors the natural rubber phase over another diene polymer phase that is not miscible with natural rubber, such as a high cis 1,4-polybutadiene rubber phase. The functional groups of the functionalized conjugated diene polymer can react with silica or carbon black to improve the dispersion of the silica or carbon black in the natural rubber phase. Improved filler dispersion due to polymer-filler interactions is manifested in improved rheological properties, such as a reduced change in storage modulus ΔG', which correlates with improved filler dispersion, and a reduced loss tangent tan δ at 60° C., which correlates with reduced rolling resistance, compared to a control rubber compound having natural rubber and high cis 1,4-polybutadiene rubber. Additionally, replacing natural rubber with the functionalized conjugated diene polymer has minimal or no effect on tensile properties (e.g., modulus at 300% strain M300, stress at break Tb, and maximum strain Eb), wet traction (as indicated by loss tangent tan δ at 0°C), and cornering coefficient as indicated by storage modulus E' at 30°C.

[0029] The rubber compounds disclosed herein can be generally described as comprising a functionalized conjugated diene polymer, natural rubber, and a reinforcing filler comprising silica and / or carbon black.

[0030] As used herein, the term "natural rubber" refers to naturally occurring rubber, such as that which can be harvested from sources such as Hevea rubber trees, and from non-Hevea sources (e.g., guayule and dandelion, such as TKS). In other words, the term "natural rubber" should be interpreted to exclude synthetic polyisoprene.

[0031] As used herein, the term "polyisoprene" means synthetic polyisoprene. In other words, the term is used to indicate a polymer made from isoprene monomers and should not be construed to include naturally occurring rubber (e.g., Hevea natural rubber, natural rubber of guayule origin, or natural rubber of dandelion origin). However, the term "polyisoprene" should be construed to include polyisoprene made from natural sources of isoprene monomers.

[0032] Functionalized Conjugated Diene Polymers As mentioned above, replacing natural rubber with a functionalized conjugated diene polymer improves the dispersion of silica or carbon black in the natural rubber, resulting in reduced rolling resistance.

[0033] The described functionalized conjugated diene polymers may have functional groups that react with silica to improve silica dispersion in the natural rubber phase. For example, in embodiments, the functional groups of the functionalized conjugated diene polymers include non-sulfur alkoxysilane groups. In embodiments, the non-sulfur alkoxysilane groups may have at least one alkoxysilane terminal moiety, and in further embodiments, may have two or three alkoxysilane terminal moieties. The alkoxysilane terminal moieties may include C1-C6 alkoxy groups, and in certain embodiments, may include methoxysilane or ethoxysilane.

[0034] More generally, in embodiments, the functional group has the general formula (I): R 1 ZYSi(OR 2 ) n X (3-n) (I) It can be expressed as:

[0035] In the formula, R 1 is C1~C 20 Aliphatic hydrocarbon groups, C1-C 20 Alicyclic hydrocarbon groups, C1-C 20C1-C having an aromatic hydrocarbon group and one or more heteroatoms selected from O, N, and Si 20 In one or more embodiments, the substituent is selected from a heterohydrocarbon group. 20 The heterohydrocarbon group may contain an unsaturated carbonyl, an alkylsilyl group (eg, trimethylsilyl), an epoxy group, or a glycidoxy group.

[0036] X represents an alkyl group (1 to 20 carbon atoms) or a halogen atom; R 2 and Y independently represent a group selected from aliphatic, alicyclic and aromatic hydrocarbon groups having 1 to 20 carbon atoms, or even 1 to 13 carbon atoms. Considering reactivity with silica, an alkyl group having 1 to 3 carbon atoms may be desirable. The aromatic hydrocarbon group may be, for example, phenyl, naphthyl, biphenyl, anthryl, or phenanthryl.

[0037] In addition, Z is an O atom, an N atom, or a bond, and n is an integer of 1 to 3.

[0038] In a further embodiment, R 1 may represent a group selected from the group consisting of γ-glycidoxyethyl, γ-glycidoxypropyl, γ-glycidoxybutyl, γ-methacryloxymethyl, γ-methacryloxyethyl, γ-methacryloxypropyl, β-(3,4-epoxycyclohexyl)ethyl, and β-(3,4-epoxycyclohexyl)propyl.

[0039] Examples of the functional group represented by the general formula (I) include γ-glycidoxyethyl trimethoxysilane, γ-glycidoxypropyl trimethoxysilane, γ-glycidoxybutyl trimethoxysilane, γ-glycidoxypropyl triethoxysilane, γ-glycidoxypropyl tripropoxysilane, γ-glycidoxypropyl tributoxysilane, γ-glycidoxypropyl triphenoxysilane, γ-glycidoxypropyl methyl dimethoxysilane, γ-glycidoxypropyl ethyl dimethoxysilane, γ-glycidoxypropyl ethyl Diethoxysilane, gamma-glycidoxypropyl methyldiethoxysilane, gamma-glycidoxypropyl methyldipropoxysilane, gamma-glycidoxypropyl methyldibutoxysilane, gamma-glycidoxypropyl methyldiphenoxysilane, gamma-glycidoxypropyl dimethylmethoxysilane, gamma-glycidoxypropyl diethylethoxysilane, gamma-glycidoxypropyl dimethylethoxysilane, gamma-glycidoxypropyl dimethylphenoxysilane, gamma-glycidoxypropyl diethylmethoxysilane, gamma-glycidoxypropyl methyldi Isopropenoxysilane, bis(γ-glycidoxypropyl)dimethoxysilane, bis(γ-glycidoxypropyl)diethoxysilane, bis(γ-glycidoxypropyl)dipropoxysilane, bis(γ-glycidoxypropyl)dibutoxysilane, bis(γ-glycidoxypropyl)diphenoxysilane, bis(γ-glycidoxypropyl)methylmethoxysilane, bis(γ-glycidoxypropyl)methylethoxysilane, bis(γ-glycidoxypropyl)methylpropoxysilane, bis(γ-glycidoxypropyl)methylbutoxy Silane, bis(γ-glycidoxypropyl)methylphenoxysilane, tris(γ-glycidoxypropyl)methoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxymethyltrimethoxysilane, γ-methacryloxyethyltriethoxysilane, bis(γ-methacryloxypropyl)dimethoxysilane, tris(γ-methacryloxypropyl)methoxysilane, β-(3,4-epoxycyclohexyl)ethyl-trimethoxysilane, β-(3,4-Epoxycyclohexyl)ethyl-triethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-tripropoxysilane, β-(3,4-epoxycyclohexyl)ethyl-tributoxysilane, β-(3,4-epoxycyclohexyl)ethyl-triphenoxysilane, β-(3,4-epoxycyclohexyl)propyl-trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-methyldimethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-ethyldimethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-ethyldiethoxysilane, β-(3,4-epoxycycloexyl)ethyl-methyldiethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-methyldipropoxysilane, β-(3,4-epoxycyclohexyl)ethyl-methyldipropoxysilane, Examples of the epoxycyclohexyl ethyl silane include β-(3,4-epoxycyclohexyl)ethyl-methyldibutoxysilane, β-(3,4-epoxycyclohexyl)ethyl-methyldiphenoxysilane, β-(3,4-epoxycyclohexyl)ethyl-dimethylmethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-diethylethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-dimethylethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-dimethylpropoxysilane, β-(3,4-epoxycyclohexyl)ethyl-dimethylbutoxysilane, β-(3,4-epoxycyclohexyl)ethyl-dimethylphenoxysilane, β-(3,4-epoxycyclohexyl)ethyl-diethylmethoxysilane, and β-(3,4-epoxycyclohexyl)ethyl-methyldiisopropenoxysilane.

[0040] In embodiments, the non-sulfur alkoxysilane group is an aminoalkylalkoxysilane, such as 3-(1,3-dimethylbutylidene)aminopropylmethyldiethoxysilane, 3-(1,3-dimethylbutylidene)aminopropylmethyldimethoxysilane, 3-(1,3-dimethylbutylidene)aminopropyltriethoxysilane, 3-(1,3-dimethylbutylidene)aminopropyltrimethoxysilane, 3-(1,3-dimethylbutylidene)aminoethylmethyldiethoxysilane, 3-(1,3-dimethylbutylidene)aminoethylmethyldimethoxysilane, 3-(1,3-dimethylbutylidene)aminoethyltriethoxysilane, 3-(1,3-dimethylbutylidene)aminoethyltrimethoxysilane, 3-(1,3-dimethylbutylidene)aminobutylmethyldiethoxysilane, 3-(1,3-dimethylbutylidene)aminobutylmethyldimethoxysilane, 3-(1,3-dimethylbutylidene)aminobutyltriethoxysilane, 3-(1,3-dimethylbutylidene N,N-bis(trimethylsilyl)-aminopropyltrimethoxysilane, N,N-bis(trimethylsilyl)-aminopropylmethyldiethoxysilane, N,N-bis(trimethylsilyl)-aminopropylmethyldimethoxysilane, N,N-bis(trimethylsilyl)-aminopropyltriethoxysilane, N,N-bis(trimethylsilyl)-aminopropyltrimethoxysilane, N,N-bis(trimethylsilyl)-aminoethylmethyldiethoxysilane, N,N-bis(trimethylsilyl)-aminoethylmethyl It may be dimethoxysilane, N,N-bis(trimethylsilyl)-aminoethyltriethoxysilane, N,N-bis(trimethylsilyl)-aminoethyltrimethoxysilane, N,N-bis(trimethylsilyl)-aminobutylmethyldiethoxysilane, N,N-bis(trimethylsilyl)-aminobutylmethyldimethoxysilane, N,N-bis(trimethylsilyl)-aminobutyltriethoxysilane, or N,N-bis(trimethylsilyl)-aminobutyltrimethoxysilane.

[0041] In some embodiments, the functionalized conjugated diene polymers described herein may have functional groups that react with carbon black to improve carbon black dispersion in the natural rubber phase. For example, in embodiments, the functionalized conjugated diene polymer functional groups include tin-based groups, amine groups, or combinations thereof. Functionalization can be introduced as either an initiator or a terminator of the polymerization.

[0042] In embodiments, the tin-based group may include tin halides (e.g., chloride, bromide, iodide, and fluoride). For example, in embodiments, the tin halides may include tin tetrahalides, (R1)3SnX, (R1)2SnX2, R1SnX3, or combinations thereof, where X is Cl, Br, I, or F, and R1 is an alkyl, cycloalkyl, or aralkyl having 1 to about 20 carbon atoms. By way of example, and not limitation, the tin halides may include tin tetrachlorides, (R1)3SnCl, (R1)2SnCl2, R1SnCl3, or combinations thereof, where R1 is an alkyl, cycloalkyl, or aralkyl having 1 to about 20 carbon atoms.

[0043] In embodiments, the amine group has the general formula:

[0044] [ka] or a dialkyl or dicycloalkylamine radical having the general formula:

[0045] [ka] It may also be a cyclic amine radical having the formula:

[0046] In these formulas, R1 is an alkyl, cycloalkyl, or aralkyl having 1 to about 20 carbon atoms, both R1 groups may be the same or different, and R2 is an alkylene-substituted, oxy-, or N-alkylamino-alkylene group having about 3 to about 16 methylene groups. The amino-alkylene group may be an N-alkylamino alkylene. By "substituted alkylene," it is understood that the alkylene has a substituent thereon. Substituted alkylene may include mono- to octa-substituted alkylene. In embodiments, the substituent may be a straight or branched alkyl, cycloalkyl, bicycloalkyl, aryl, and aralkyl having 1 to about 12 carbon atoms.

[0047] Exemplary R groups can include methyl, ethyl, butyl, octyl, cyclohexyl, 3-phenyl-1-propyl, isobutyl, etc. Exemplary R groups can include tetramethylene, hexamethylene, oxydiethylene, N-alkylazadiethylene, dodecamethylene, hexadecamethylene, etc.

[0048] For example, the amine group may be a derivative or radical of pyrrolidine; piperidine; monoalkyl-piperazines; perhydroazepines such as 3,3,5-trimethylhexahydroazepine and hexamethyleneimine; 1-azacyclooctane; azacyclotridecane, also known as dodecamethyleneimine; azacycloheptadecane, also known as hexadecamethyleneimine; 1-azacycloheptadec-9-ene; or 1-azacycloheptadec-8-ene, including bicyclic compounds such as perhydroisoquinoline, perhydroindole, 1,3,3-trimethyl-6-azabicyclo[3.2.1]octane, and the like.

[0049] There are many useful examples of alkyl, cycloalkyl, aryl and aralkyl substituents on the cyclic and bicyclic amines of the present invention, including but not limited to, 2-(2-ethylhexyl)pyrrolidine; 3-(2-propyl)pyrrolidine; 3,5-bis(2-ethylhexyl)piperidine; 4-phenylpiperidine; 7-decyl-1-azacyclotridecane; 3,3-dimethyl-1-azacyclotetradecane; 4-dodecyl-1-azacyclooctane; 4-(2-phenylbutyl)-1-azacyclooctane; 3-ethyl-5-cyclohexyl-1-azacycloheptane; 4-hexyl-1-azacycloheptane; 9-isoamyl-1-azacyclo 2-methyl-1-azacycloheptadecane; 3-isobutyl-1-azacyclododecane; 2-methyl-7-t-butyl-1-azacyclododecane; 5-nonyl-1-azacyclodecane; 8-(4'-methylphenyl)-5-pentyl-3-azabicyclo[5.4.0]undecane; 1-butyl-6-azabicyclo[3.2.1]octane; 8-ethyl-3-azabicyclo[3.2.1.]octane; 1-propyl-3-azabicyclo[3.2.2]nonane; 3-t-butyl)-7-azabicyclo[4.3.0]nonane; 1,5,5-trimethyl-3-azabicyclo[4.4.0]decane, and the like.

[0050] When R1 and R2 are each branched at the alkyl position, such as di-t-butyl, diisopropyl, tertiary butyl, etc., the resulting polymerization is slow, likely due to interference around the nitrogen at the initiation site. Thus, in embodiments, the carbon atoms in R1 and R2 that are bonded to the nitrogen in the amine may be bonded to a total of at least three hydrogen atoms.

[0051] In embodiments, the functionalized conjugated diene polymer may have a vinyl content of about 50% or more. In embodiments, the functionalized conjugated diene may have a vinyl content of about 50% or more, about 55% or more, about 60% or more, about 63% or more, about 65% or more, or even about 67% or more. In embodiments, the functionalized conjugated diene may have a vinyl content of about 90% or less, about 85% or less, about 80% or less, about 77% or less, about 75% or less, or even about 73% or less. In embodiments, the functionalized conjugated diene polymer is from about 50% to about 90%, from about 50% to about 85%, from about 50% to about 80%, from about 50% to about 77%, from about 50% to about 75%, from about 50% to about 73%, from about 55% to about 90%, from about 55% to about 85%, from about 55% to about 80%, from about 55% to about 77%, from about 55% to about 75%, from about 55% to about 73%, from about 60% to about 90%, from about 60% to about 85%, from about 60% to about 80%, from about 60% to about 77%, from about 60% to about 75%, from about 60% to about 73%, from about 63% to about 90%, from about 63% up to about 85%, about 63% to about 80%, about 63% to about 77%, about 63% to about 75%, about 63% to about 73%, about 65% to about 90%, about 65% to about 85%, about 65% to about 80%, about 65% to about 77%, about 65% to about 75%, about 65% to about 73%, about 67% to about 90%, about 67% to about 85%, about 67% to about 80%, about 67% to about 77%, about 67% to about 75%, or even about 67% to about 73%, or any and all subranges formed from any of these endpoints.

[0052] In embodiments, the functionalized conjugated diene polymer has a weight average molecular weight M of about 75,000 g / mol to about 1,000,000 g / mol. w In embodiments, the functionalized conjugated diene may have a weight average molecular weight M of 75,000 g / mol or more, 100,000 g / mol or more, 200,000 g / mol or more, or even 300,000 g / mol or more. w In embodiments, the functionalized conjugated diene may have a weight average molecular weight M of 1,000,000 g / mol or less, 800,000 g / mol or less, 600,000 g / mol or less, or even 400,000 g / mol or less. wIn embodiments, the functionalized conjugated diene polymer may have a molecular weight of about 75,000 g / mol to about 1,000,000 g / mol, about 75,000 g / mol to about 800,000 g / mol, about 75,000 g / mol to about 600,000 g / mol, about 75,000 g / mol to about 400,000 g / mol, about 100,000 g / mol to about 1,000,000 g / mol, about 100,000 g / mol to about 800,000 g / mol, about 100,000 g / mol to about 600,000 g / mol, about 100,000 g / mol to about 400,000 g / mol, about 200,000 g / mol, or about 300,000 g / mol. mol to about 1,000,000 g / mol, about 200,000 g / mol to about 800,000 g / mol, about 200,000 g / mol to about 600,000 g / mol, about 200,000 g / mol to about 400,000 g / mol, about 300,000 g / mol to about 1,000,000 g / mol, about 300,000 g / mol to about 800,000 g / mol, about 300,000 g / mol to about 600,000 g / mol, or even about 300,000 g / mol to about 400,000 g / mol, or any and all subranges formed from any of these endpoints. w

[0043]

[0053] In embodiments, the functionalized conjugated diene polymer has a number average molecular weight M of about 75,000 g / mol to about 1,000,000 g / mol. n In embodiments, the functionalized conjugated diene may have a number average molecular weight M of 75,000 g / mol or more, 100,000 g / mol or more, 200,000 g / mol or more, or even 300,000 g / mol or more. n In embodiments, the functionalized conjugated diene may have a number average molecular weight M of 1,000,000 g / mol or less, 800,000 g / mol or less, 600,000 g / mol or less, or even 400,000 g / mol or less. nIn embodiments, the functionalized conjugated diene polymer may have a molecular weight of about 75,000 g / mol to about 1,000,000 g / mol, about 75,000 g / mol to about 800,000 g / mol, about 75,000 g / mol to about 600,000 g / mol, about 75,000 g / mol to about 400,000 g / mol, about 100,000 g / mol to about 1,000,000 g / mol, about 100,000 g / mol to about 800,000 g / mol, about 100,000 g / mol to about 600,000 g / mol, about 100,000 g / mol to about 400,000 g / mol, about 200,000 g / mol, or about 300,000 g / mol. mol to about 1,000,000 g / mol, about 200,000 g / mol to about 800,000 g / mol, about 200,000 g / mol to about 600,000 g / mol, about 200,000 g / mol to about 400,000 g / mol, about 300,000 g / mol to about 1,000,000 g / mol, about 300,000 g / mol to about 800,000 g / mol, about 300,000 g / mol to about 600,000 g / mol, or even about 300,000 g / mol to about 400,000 g / mol, or any and all subranges formed from any of these endpoints. n

[0043]

[0054] In embodiments, the functionalized conjugated diene polymer has a peak molecular weight M of about 75,000 g / mol to about 1,000,000 g / mol. p In embodiments, the functionalized conjugated diene may have a peak molecular weight M of 75,000 g / mol or greater, 100,000 g / mol or greater, 200,000 g / mol or greater, or even 300,000 g / mol or greater. p In embodiments, the functionalized conjugated diene may have a peak molecular weight M of 1,000,000 g / mol or less, 800,000 g / mol or less, 600,000 g / mol or less, or even 400,000 g / mol or less. pIn embodiments, the functionalized conjugated diene polymer may have a molecular weight of about 75,000 g / mol to about 1,000,000 g / mol, about 75,000 g / mol to about 800,000 g / mol, about 75,000 g / mol to about 600,000 g / mol, about 75,000 g / mol to about 400,000 g / mol, about 100,000 g / mol to about 1,000,000 g / mol, about 100,000 g / mol to about 800,000 g / mol, about 100,000 g / mol to about 600,000 g / mol, about 100,000 g / mol to about 400,000 g / mol, about 200,000 g / mol and a peak molecular weight M of about 1 to about 1,000,000 g / mol, about 200,000 g / mol to about 800,000 g / mol, about 200,000 g / mol to about 600,000 g / mol, about 200,000 g / mol to about 400,000 g / mol, about 300,000 g / mol to about 1,000,000 g / mol, about 300,000 g / mol to about 800,000 g / mol, about 300,000 g / mol to about 600,000 g / mol, or even about 300,000 g / mol to about 400,000 g / mol, or any and all subranges formed from any of these endpoints. p

[0043]

[0055] In embodiments, the functionalized conjugated diene polymer may comprise a polymerization reaction product of 1,3 butadiene monomer. In embodiments, the functionalized conjugated diene polymer may comprise polybutadiene. In embodiments, the functionalized conjugated diene polymer may comprise high vinyl polybutadiene rubber.

[0056] In embodiments, the amount of functionalized conjugated diene polymer in the rubber formulation may be greater than about 3 phr, greater than or equal to about 6 phr, greater than or equal to about 9 phr, or even greater than or equal to about 12 phr. In embodiments, the amount of functionalized conjugated diene polymer in the rubber formulation may be less than or equal to about 30 phr, less than or equal to about 25 phr, less than or equal to about 20 phr, or even less than or equal to about 15 phr. In embodiments, the amount of functionalized conjugated diene polymer in the rubber compound may be from about 3 phr to about 30 phr, from about 3 phr to about 25 phr, from about 3 phr to about 20 phr, from about 3 phr to about 15 phr, from about 6 phr to about 30 phr, from about 6 phr to about 25 phr, from about 6 phr to about 20 phr, from about 6 phr to about 15 phr, from about 9 phr to about 30 phr, from about 9 phr to about 25 phr, from about 9 phr to about 20 phr, from about 9 phr to about 15 phr, from about 12 phr to about 30 phr, from about 12 phr to about 25 phr, from about 12 phr to about 20 phr, or even from about 12 phr to about 15 phr, or any and all subranges formed from any of these endpoints.

[0057] In embodiments, the amount of functionalized conjugated diene polymer in the rubber formulation may be about 3 phr or more, about 5 phr or more, about 10 phr or more, about 15 phr or more, or even about 20 phr or more. In embodiments, the amount of functionalized conjugated diene polymer in the rubber formulation may be about 50 phr or less, about 40 phr or less, about 30 phr or less, or even about 20 phr or less. In embodiments, the amount of functionalized conjugated diene polymer in the rubber formulation may be about 3 phr to about 50 phr, about 3 phr to about 40 phr, about 3 phr to about 30 phr, about 3 phr to about 20 phr, about 5 phr to about 50 phr, about 5 phr to about 40 phr, about 5 phr to about 30 phr, about 5 phr to about 20 phr, about 10 phr to about 50 phr, about 10 phr to about 4 ... It may be from 0 phr to about 30 phr, from about 10 phr to about 20 phr, from about 15 phr to about 50 phr, from about 15 phr to about 40 phr, from about 15 phr to about 30 phr, from about 15 phr to about 20 phr, from about 20 phr to about 50 phr, from about 20 phr to about 40 phr, or even from about 20 phr to about 30 phr, or any and all subranges formed from any of these endpoints.

[0058] Natural rubber As mentioned above, replacing natural rubber with a functionalized conjugated diene polymer improves the dispersion of silica or carbon black in the natural rubber, resulting in reduced rolling resistance.

[0059] In embodiments, the amount of natural rubber in the rubber formulation may be about 10 phr or more, about 20 phr or more, about 30 phr or more, about 40 phr or more, or even about 50 phr or more. In embodiments, the amount of natural rubber in the rubber formulation may be about 100 phr or less, about 90 phr or less, or even about 80 phr or less. In embodiments, the amount of natural rubber in the rubber compound may be from about 10 phr to about 100 phr, from about 10 phr to about 90 phr, from about 10 phr to about 80 phr, 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 30 phr to about 100 phr, from about 30 phr to about 90 phr, from about 30 phr to about 80 phr, from about 40 phr to about 100 phr, from about 40 phr to about 90 phr, from about 40 phr to about 80 phr, from about 50 phr to about 100 phr, from about 50 phr to about 90 phr, or even from about 10 phr to about 50 phr, or any and all subranges formed from any of these endpoints.

[0060] In embodiments, the amount of natural rubber in the rubber formulation may be greater than about 0 phr, greater than or equal to about 15 phr, or even greater than or equal to about 30 phr. In embodiments, the amount of natural rubber in the rubber formulation may be less than or equal to 85 phr, less than or equal to about 75 phr, or even less than or equal to about 60 phr. In embodiments, the amount of natural rubber in the rubber formulation may be greater than or equal to about 0 phr to about 85 phr, greater than or equal to about 0 phr to about 75 phr, greater than or equal to about 0 phr to about 60 phr, from about 15 phr to about 85 phr, from about 15 phr to about 75 phr, from about 15 phr to about 60 phr, from about 30 phr to about 85 phr, from about 30 phr to about 75 phr, or even from about 30 phr to about 60 phr, or any and all subranges formed from any of these endpoints.

[0061] In embodiments, in addition to natural rubber, the rubber formulation may include high cis 1,4-polybutadiene rubber. In embodiments, the amount of high cis 1,4-polybutadiene rubber in the rubber formulation may be from about 15 phr to about 45 phr, from about 15 phr, to about 35 phr, from about 25 phr to about 45 phr, or even from about 25 phr to about 30 phr, or any and all subranges formed from any of these endpoints.

[0062] Reinforcing Fillers Silica and / or carbon black, when dispersed within the natural rubber in the rubber compounds described herein, provide a reinforcing effect and reduce rolling resistance.

[0063] In embodiments, the silica may include silicon compounds such as wet silica (hydrated silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, or combinations thereof.

[0064] In embodiments, the amount of silica in the rubber formulation may be about 8 phr or more, about 12 phr or more, about 16 phr or more, or even about 20 phr or more. In embodiments, the amount of silica in the rubber formulation may be about 40 phr or less, about 36 phr or less, about 32 phr or less, or even about 28 phr or less. In embodiments, the amount of silica in the rubber compound may be from about 8 phr to about 40 phr, from about 8 phr to about 36 phr, from about 8 phr to about 32 phr, from about 8 phr to about 28 phr, from about 12 phr to about 40 phr, from about 12 phr to about 36 phr, from about 12 phr to about 32 phr, from about 12 phr to about 28 phr, from about 16 phr to about 40 phr, from about 16 phr to about 36 phr, from about 16 phr to about 32 phr, from about 16 phr to about 28 phr, from about 20 phr to about 40 phr, from about 20 phr to about 36 phr, from about 20 phr to about 32 phr, or even from about 20 phr to about 28 phr, or any and all subranges formed from any of these endpoints.

[0065] In embodiments, the amount of silica in the rubber compound may be about 0 phr or more, about 5 phr or more, about 10 phr or more, 15 phr or more, or even about 20 phr or more. In embodiments, the amount of silica in the rubber compound may be about 60 phr or less, about 50 phr or less, about 40 phr or less, 30 phr or less, or even about 30 phr or less. In embodiments, the amount of silica in the rubber compound may be about 0 phr to about 60 phr, about 0 phr to about 50 phr, about 0 phr to about 40 phr, about 0 phr to about 30 phr, about 5 phr to about 60 phr, about 5 phr to about 50 phr, about 5 phr to about 40 phr, about 5 phr to about 30 phr, about 10 phr to about 60 phr, about 10 phr to about 50 phr, about 10 phr to about 40 phr, It may be from about 10 phr to about 30 phr, from about 15 phr to about 60 phr, from about 15 phr to about 50 phr, from about 15 phr to about 40 phr, from about 15 phr to about 30 phr, from about 20 phr to about 60 phr, from about 20 phr to about 50 phr, from about 20 phr to about 40 phr, or even from about 20 phr to about 30 phr, or any and all subranges formed from any of these endpoints.

[0066] In embodiments, the carbon black may include high speed extrusion furnace black, semi-reinforcement furnace black, high abrasive furnace black, medium super abrasive furnace black, super abrasive furnace black, etc. In embodiments, the carbon black may have an iodine absorption of about 60 mg / g or greater and a dibutyl phthalate oil absorption value of about 80 mL / 100 g or greater.

[0067] In embodiments, the amount of carbon black in the rubber formulation may be about 4 phr or more, about 8 phr or more, or even about 12 phr or more. In embodiments, the amount of carbon black in the rubber formulation may be 32 phr or less, 28 phr or less, 24 phr or less, or even 20 phr or less. In embodiments, the amount of carbon black in the rubber formulation may be from about 4 phr to about 32 phr, from about 4 phr to about 28 phr, from about 4 phr to about 24 phr, from about 4 phr to about 20 phr, from about 8 phr to about 32 phr, from about 8 phr to about 28 phr, from about 8 phr to about 24 phr, from about 8 phr to about 20 phr, from about 12 phr to about 32 phr, from about 12 phr to about 28 phr, from about 12 phr to about 24 phr, or even from about 12 phr to about 20 phr, or any and all subranges formed from any of these endpoints.

[0068] In embodiments, the amount of carbon black in the rubber formulation may be about 0 phr or more, about 4 phr or more, about 8 phr or more, 12 phr or more, 16 phr or more, or even about 20 phr or more. In embodiments, the amount of carbon black in the rubber formulation may be 70 phr or less, 60 phr or less, 50 phr or less, 46 phr or less, 42 phr or less, 38 phr or less, 34 phr or less, 30 phr or less, 26 phr or less, or even 22 phr or less. In embodiments, the amount of carbon black in the rubber compound ranges from about 0 phr to about 70 phr, from about 0 phr to about 60 phr, from about 0 phr to about 50 phr, from about 0 phr to about 46 phr, from about 0 phr to about 42 phr, from about 0 phr to about 38 phr, from about 0 phr to about 34 phr, from about 0 phr to about 30 phr, from about 0 phr to about 26 phr, from about 0 phr to about 22 phr, from about 4 phr to about 70 phr, from about 4 phr to about 60 phr, from about 4 phr to about 50 phr, from about 4 phr to about 46 phr, from about 4 phr to about 42 phr, from about 4 phr to about 38 phr, from about 4 phr to about 34 phr, from about 4 phr to about 30 phr, from about 4 phr to about 26 phr, from about 4 phr to about 22 phr, from about 8 phr to about 70 phr. , about 8 phr to about 60 phr, about 8 phr to about 50 phr, about 8 phr to about 46 phr, about 8 phr to about 42 phr, about 8 phr to about 38 phr, about 8 phr to about 34 phr, about 8 phr to about 30 phr, about 8 phr to about 26 phr, about 8 phr to about 22 phr, about 12 phr to about 70 phr, about 12 phr to about 60 phr, about 12 phr to about 50 phr, about 12 phr to about 46 phr, about 12 phr to about 42 phr, about 12 phr to about 38 phr, about 12 phr to about 34 phr, about 12 phr to about 30 phr, about 12 phr to about 26 phr, or even about 12 phr to about 22 phr, or any and all subranges formed from any of these endpoints.

[0069] In embodiments, the reinforcing filler may include at least one of silica and carbon black. In some embodiments, the rubber compound may include silica and not include carbon black. In other embodiments, the rubber compound may include carbon black and not include silica. In certain embodiments, the rubber compound may include both carbon black and silica to achieve a balance of desired properties. Carbon black is typically used for wear performance, but may exhibit deficiencies in rolling resistance. Silica is typically used for rolling resistance and sometimes tear, but may exhibit deficiencies in wear performance. Both types of fillers may be used simultaneously to balance the benefits and tradeoffs and achieve the desired performance for the rubber compound.

[0070] In embodiments, the reinforcing filler can include about 30% to about 70% by weight silica and about 30% to 70% by weight carbon black, about 35% to about 65% by weight silica and about 35% to about 65% by weight carbon black, or even about 40% to about 60% by weight silica and about 40% to about 60% by weight carbon black.

[0071] In embodiments, in addition to silica and carbon black, other fillers may be included in the rubber compound, including those conventionally used in tire manufacturing, including starch, aluminum hydroxide, magnesium hydroxide, clay (hydrated aluminum silicate), and combinations thereof.

[0072] Rubber Compounds As described herein, the rubber formulations disclosed herein replace natural rubber with functionalized conjugated diene polymers. Miscibility is measured using the T predicted for the control composition. g The transition temperature T of the rubber composition from g The transition temperature T of natural rubber compared to a control rubber compound is measured by the deviation of gThe functionalized conjugated diene polymer is preferentially miscible with natural rubber, as indicated by a shift in the loss modulus G″ peak of the rubber compound in favor of a natural rubber phase over a high cis-butadiene rubber phase.

[0073] The functionalized conjugated diene polymer may be preferentially miscible with natural rubber while reacting with the silica or carbon black to improve dispersion of the silica or carbon black in the natural rubber phase, as indicated by a reduced change in storage modulus ΔG' compared to a control rubber compound measured in a strain sweep from 0.25% to 10% strain performed at 60° C. and 10 Hz. In embodiments, the rubber compound may have a change in storage modulus ΔG' of 0.950 or less, as measured in a strain sweep from 0.25% to 10% strain performed at 60° C. and 10 Hz.

[0074] The rubber compounds disclosed herein have a reduced loss tangent tan δ at 60° C. compared to a control rubber compound, which correlates with reduced rolling resistance. In embodiments, the rubber compounds may have a tan δ at 60° C. of 0.110 or less.

[0075] Additionally, the replacement of natural rubber with the functionalized conjugated diene polymer has minimal or no effect on tensile properties (e.g., modulus at 300% strain M300, stress at break Tb, and maximum strain Eb), wet traction as indicated by loss tangent tan δ at 0°C, and cornering coefficient as indicated by storage modulus E' at 30°C, compared to the control rubber compound.

[0076] In embodiments, the rubber compound may have a modulus at 300% strain, M300, of about 5.0 MPa to about 6.5 MPa at room temperature. In embodiments, the rubber compound may have a stress at break of about 23.0 MPa to about 28.0 MPa at room temperature. In embodiments, the rubber compound may have a maximum strain at break of about 650% to about 725%. In embodiments, the rubber compound may have a loss tangent, tan δ, at 0°C, of ​​about 0.220 to about 0.240. In embodiments, the rubber compound may have a storage modulus, E', at 30°C, of ​​about 5.0 to about 6.0.

[0077] In embodiments, the rubber compound may have a Mooney viscosity (ML(1+4)) similar to the control rubber compound for ease of processability.

[0078] Other components In embodiments, the rubber compound may further include a silane as a coupling agent.

[0079] In some embodiments, the rubber compound may further include sulfur as a vulcanizing agent. A vulcanization accelerator may be used together with the vulcanizing agent to control the time and / or temperature required for vulcanization and improve the properties of the vulcanizate. The vulcanization accelerator suitable for use in the composition of the present disclosure is not particularly limited. The vulcanization accelerator may include, in particular, thiazole vulcanization accelerators such as 2-mercaptobenzothiazole, dibenzothiazyl disulfide, N-cyclohexyl-2-benzothiazyl-sulfenamide, N-tert-butyl-2-benzothiazyl sulfenamide, and the like; guanidine vulcanization accelerators such as diphenylguanidine, and the like; amines; disulfides; thiurams; sulfenamides; dithiocarbamates; xanthates; and thioureas.

[0080] In embodiments, useful processing or extending oils may also be included. In embodiments, the oils may include those commercially available as paraffinic, aromatic, or naphthenic oils. In embodiments, the oil may be predominantly paraffinic. In embodiments, the extending oil may be oil-extending sulfur.

[0081] The components may also include other additives such as antiozonants, waxes, scorch inhibitors, processing aids, zinc oxide, tackifying resins, reinforcing resins, fatty acids such as stearic acid, peptizing agents, and one or more accelerators.

[0082] Antiozonants 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 antiozonants may include acetone diphenylamine condensation products, 2,4-trimethyl-1,2-dihydroquinoline, octylated diphenylamine, and 2,6-di-t-butyl-4-methylphenol.

[0083] In embodiments, the rubber formulation may further include a thermosetting resin. Non-limiting examples of such resins include epoxy, urethane, and phenol-formaldehyde, although combinations of one or more of the foregoing may also be utilized. In embodiments, the rubber formulation may include a thermosetting resin, such as: (1) phenolic resins, such as phenol novolac resins, phenol-formaldehyde resins, resorcinol-formaldehyde resins, reactive resole resins (which may react with unsaturation in the elastomer or rubber contributing to crosslinking), and reactive novolac-type phenol-formaldehyde resins (which may crosslink with methylene donors); (2) aliphatic resins, such as C5 fraction homopolymer or copolymer resins, optionally combined with one or more of, for example, cycloaliphatic, aromatic, hydrogenated aromatic, or terpene resins, and / or optionally partially or fully hydrogenated; (3) cycloaliphatic resins, such as cyclopentadiene homopolymer or copolymer resins, and dicycloaliphatic resins; (4) aromatic resins (such as coumarone-indene resins and alkyl-phenol resins, as well as vinyl aromatic homopolymer or copolymer resins, such as the following monomers: alpha-methylstyrene, styrene, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, vinyltoluene, para(tert-butyl)styrene, methoxystyrene, chlorostyrene, hydroxystyrene, vinylmesitylene, divinylbenzene, vinylnaphthalene or C9 fractions or C8-C9 fractions. 10(4) aromatic resins (e.g., alpha-pinene resins, beta-pinene resins, limonene resins (e.g., L-limonene, D-limonene, dipentene which is a racemic mixture of L and D isomers), beta-phellandrene, delta-3-carene, and delta-2-carene), optionally combined with one or more of aliphatic, cycloaliphatic, aromatic, or hydrogenated aromatic resins, and / or optionally partially or fully hydrogenated; (5) terpene resins (e.g., alpha-pinene resins, beta-pinene resins, limonene resins (e.g., L-limonene, D-limonene, dipentene which is a racemic mixture of L and D isomers), beta-phellandrene, delta-3-carene, and delta-2-carene), optionally combined with one or more of aliphatic, cycloaliphatic, aromatic, or hydrogenated aromatic resins, and / or optionally partially or fully hydrogenated; The resins may include at least one of the following types of resins: (1) gum rosin, wood rosin, and tall oil rosin, glycerin ester rosin, and pentaerythritol ester rosin (optionally partially hydrogenated and / or polymerized), (2) rosin resins (e.g., gum rosin, wood rosin, and tall oil rosin, glycerin ester rosin, and pentaerythritol ester rosin (optionally partially hydrogenated and / or polymerized), optionally in combination with one or more of aliphatic, cycloaliphatic, aromatic, hydrogenated aromatic, or terpene resins, and / or optionally partially or fully hydrogenated, or (3) guayule resin. Mixtures of one or more resins may also be used.

[0084] Method of preparation In embodiments, to form a conjugated diene polymer (e.g., polybutadiene), a monomer (e.g., 1,3 butadiene monomer) may be polymerized using an organolithium initiator. In embodiments, the organolithium initiator may be an alkyllithium (e.g., n-butyllithium, sec-butyllithium, ethyllithium, propyllithium, t-butyllithium, and hexyllithium), an alkylene dilithium (e.g., 1,4-dilithiobutane), a lithiohydrocarbon (e.g., phenyllithium, stilbene dilithium, and the reaction product of butyllithium with divinylbenzene), or an organolithium metal (e.g., lithium tributyltin), a lithium amide (e.g., lithium diethylamide, N-methylbenzyllithium amide, dioctyllithium amide, lithium piperidide, lithium pyrrolidide, and lithium hexamethyleneimide), or an organolithium (e.g., a tertiary amine lithium, e.g., dimethylaminopropyllithium and diethylaminopropyllithium).

[0085] In embodiments, the conjugated diene polymer may be functionalized by reacting the active end of the polymer with a functional group (e.g., 3-(1,3-dimethylbutylidene)aminopropylmethyldiethoxysilane). After functionalization is complete, neutralization of any remaining reactive species (e.g., lithium species) can be accomplished by treatment with a proton source such as 2,5-di-tert-butyl-4-methylphenol in water or isopropyl alcohol.

[0086] 1,2-microstructure control agents or randomization modifiers are optionally used to control the 1,2-microstructure in conjugated diene contributed monomer units such as 1,3-butadiene. Suitable modifiers include hexamethylphosphoric triamide, N,N,N',N-tetramethylethylenediamine, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, 1,4-diazabicyclo[2.2.2]octane, diethyl ether, triethylamine, tri-n-butylamine, tri-n-butylphosphine, p-dioxane, 1,2-dimethoxyethane, dimethyl ether, methyl ethyl ether, ethyl propyl ether, ethyl ... Randomizing modifiers include, for example, di-n-propyl ether, di-n-octyl ether, anisole, dibenzyl ether, diphenyl ether, dimethylethylamine, bis-oxalanylpropane, tri-n-propylamine, trimethylamine, triethylamine, N,N-dimethylaniline, N-ethylpiperidine, N-methyl-N-ethylaniline, N-methylmorpholine, tetramethylenediamine, oligomeric oxanylpropane, 2,2-bis-(4-methyldioxane), bistetrahydrofurylpropane, and 2,2-di(2-tetrahydrofuryl)propane. Mixtures of one or more randomizing modifiers may also be used.

[0087] In embodiments, the functionalized conjugated diene polymer may be included in the rubber formulation by forming and mixing a masterbatch containing the functionalized conjugated diene rubber, natural rubber, silica and / or carbon black, and other ingredients. In embodiments, the masterbatch mixing step may be followed by a regrind step to incorporate additional components.

[0088] Although the above describes the use of the rubber composition in tire treads, the rubber composition of the present disclosure may be utilized in various other components or articles utilizing such rubber compositions. Typical articles may include, but are not limited to, tire sidewalls, inner tubes and tire innerliners, air cushions, pneumatic sprays, air bags, tire curing bladders, high temperature hoses and conveyor belts, damping mounts for engines, and the like.

[0089] It will be apparent that modifications and variations are possible without departing from the scope of the present disclosure, as defined in the appended claims. More specifically, although certain 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 those aspects.

Claims

1. 1. A rubber compound comprising: functional group, a vinyl content of about 50% or more, and a weight average molecular weight M of about 75,000 g / mol to about 1,000,000 g / mol. ｗ a functionalized conjugated diene polymer having Natural rubber and and a reinforcing filler comprising at least one of silica and carbon black.

2. The functionalized conjugated diene polymer has a weight average molecular weight M of from about 100,000 g / mol to about 800,000 g / mol, or from about 200,000 g / mol to about 600,000 g / mol, or from about 300,000 g / mol to about 400,000 g / mol. ｗ 2. The rubber compound of claim 1 having

3. 3. The rubber compound of claim 1 or 2, wherein the functional groups comprise non-sulfur alkoxysilane groups.

4. 4. The rubber compound of claim 3, wherein the non-sulfur alkoxysilane group has at least two alkoxysilane end moieties.

5. 5. The rubber compound of claim 3 or 4, wherein the non-sulfur alkoxysilane group comprises 3-(1,3-dimethylbutylidene aminopropylmethyldiethoxysilane, 3-(1,3-dimethylbutylidene)aminopropyltriethoxysilane, N,N-bis(trimethylsilyl)-aminopropylmethyldimethoxysilane, N,N-bis(trimethylsilyl)-aminopropylmethyldiethoxysilane, gamma-glycidoxypropylmethyldiethoxysilane, or combinations thereof.

6. The functional group has the general formula: R １ ZYSi(OR ２ ) ｎ X （３－ｎ） having In the formula, R １ But, C １ ~C ２０ Aliphatic hydrocarbon group, C １ ~C ２０ Alicyclic hydrocarbon group, C １ ~C ２０ Aromatic hydrocarbon group or C having one or more heteroatoms selected from O, N, and Si １ ~C ２０ A substituent selected from heterohydrocarbon groups, X is an alkyl group or a halogen atom, R ２ A rubber compound according to any one of claims 3 to 5, wherein Y independently represents a group selected from aliphatic, cycloaliphatic, and aromatic hydrocarbon groups of 1 to 20 carbon atoms.

7. 3. The rubber compound of claim 1 or 2, wherein the functional groups include tin-based groups, amine groups, or a combination thereof.

8. The tin-based group is a tin tetrahalide, (R １ ) ３ SnX, (R １ ) ２ SnX ２ , R １ SnX ３ or combinations thereof, X is Cl, Br, I, or F, R １ The rubber compound of claim 7, wherein is an alkyl, cycloalkyl, or aralkyl having 1 to about 20 carbon atoms.

9. The amine group has the general formula: [Formula 1] and an amine radical having the general formula: [chemical 2] and wherein the cyclic amine radical has the formula: In the formula, R １ is an alkyl, cycloalkyl, or aralkyl having 1 to about 12 carbon atoms; R ２ The rubber compound of claims 7 or 8, wherein is an alkylene, substituted alkylene, oxy- or N-alkylamino-alkylene group having from about 3 to about 16 methylene groups.

10. 10. The rubber compound of any one of claims 1 to 9, wherein the functionalized conjugated diene polymer has a vinyl content of from about 50% to about 90%, or from about 55% to about 85%, or from about 60% to about 80%.

11. The rubber compound of any one of claims 1 to 10, wherein the rubber compound comprises from about 3 phr to about 30 phr of the functionalized conjugated diene polymer.

12. The rubber compound of any one of claims 1 to 10, wherein the rubber compound comprises from about 3 phr to about 50 phr of the functionalized conjugated diene polymer.

13. The rubber compound of any one of claims 1 to 12, wherein the reinforcing filler comprises from about 8 phr to about 42 phr of silica.

14. The rubber compound of any one of claims 1 to 12, wherein the reinforcing filler comprises from greater than about 0 phr to about 85 phr of silica.

15. The rubber compound according to any one of claims 1 to 14, wherein the reinforcing filler comprises from about 4 phr to about 32 phr of carbon black.

16. 16. The rubber compound of any one of claims 1 to 15, wherein the reinforcing filler comprises from about 4 phr to about 70 phr of carbon black.

17. 17. The rubber compound according to any one of claims 1 to 16, wherein the reinforcing fillers comprise from about 30% to about 70% by weight of silica and from about 30% to 70% by weight of carbon black.

18. The rubber compound of any one of claims 1 to 17, wherein the functionalized conjugated diene polymer comprises the polymerization reaction product of 1,3-butadiene monomer.

19. The rubber compound of any one of claims 1 to 18, wherein the functionalized conjugated diene polymer comprises a polybutadiene rubber.

20. The rubber compound of any one of claims 1 to 19, wherein the rubber compound further comprises about 15 phr to 45 phr of high cis 1,4-polybutadiene.

21. The rubber compound of any one of claims 1 to 20, wherein the rubber compound further comprises from about 10 phr to about 100 phr of natural rubber.

22. The rubber compound of any one of claims 1 to 20, wherein the rubber compound further comprises from greater than about 0 phr to about 85 phr of natural rubber.

23. 22. The rubber compound of claim 21, wherein the rubber compound further comprises from about 40 phr to about 100 phr of natural rubber.

24. The rubber compound of any one of claims 21 to 23, wherein the natural rubber comprises guayule rubber.

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