COMPOSITIONS COMPRISING FUNCTIONALIZED SILYLATED POLYMERS, CURING COMPOSITIONS, AND METHODS - Patent application

Abstract

A polymer composition comprising a silylated polymer derived from a polydiene polymer modified with a grafting agent containing a silyl group and a functional group. The polymer composition is a curable rubber blend, which serves to provide its cured products, such as tires, with improved properties. Methods for preparing the composition and the cured products, such as tire components.

Description

[Technical field]

[0001] The present invention relates to a polymer composition comprising a silylated polymer derived from a polydiene polymer modified with a grafting agent containing a silyl group and a functional group. The polymer composition is preferably a curable rubber blend in which the silylated polymer helps provide its cured product, such as a tire, with improved properties including filler dispersion, lower rolling resistance, and improved snow traction. Methods for preparing the composition and the cured product, such as a tire component, are disclosed. [Background technology]

[0002] Hydrosilylation as a functionalization methodology has been very well studied and has found widespread industrial application. It provides a facile method for incorporating silane functional groups onto polymers. Silylated polymers have been utilized to produce cured polymer and rubber compositions.

[0003] WO 2015 / 091020 relates to a method for synthesizing modified polymers containing epoxide groups along the polymer chain by hydrosilylation reaction of hydrosilanes bearing unsaturation and epoxide functional groups in the presence of a suitable catalyst. Functional polymers and crosslinkable compositions containing same are also described.

[0004] No. 9,315,600 relates to a method for producing a modified conjugated diene polymer, comprising a polymerization step of obtaining a conjugated diene polymer containing a nitrogen atom and an active end in the polymer chain by copolymerizing a conjugated diene compound and a nitrogen atom-containing vinyl compound, or a conjugated diene compound, an aromatic vinyl compound, and a nitrogen atom-containing vinyl compound, using an alkali metal compound and / or an alkaline earth metal compound as a polymerization initiator, and a modification step of reacting a modifying agent.

[0005] US Patent Application Publication No. 2016 / 0369015 relates to backbone modified elastomeric polymers, polymer compositions containing such modified polymers, the use of such compositions in the preparation of vulcanized polymer compositions, and articles prepared therefrom. The modified polymers are reportedly useful in the preparation of vulcanized, i.e. crosslinked, elastomeric compositions with relatively low hysteresis loss. Such vulcanized compositions are reportedly useful in many articles, including tire treads, with low heat build-up, low rolling resistance, good wet and ice grip, along with other physical and chemical properties such as abrasion resistance and tensile strength. Furthermore, the unvulcanized polymer compositions are reported to exhibit processability.

[0006] EP 3394119 relates to diene elastomers, characterized in that they contain units derived from dienes distributed along the chain carrying pendant groups of the following formula (I): *-SiR1R2-AB, where A and B are such that the melting point of the non-hydrosilylated analogue HAB is below 70° C., and contain 10 to 40% by weight of pendant groups of formula (I) relative to the total weight of the elastomer. A process for preparing such diene elastomers, compositions containing them, in particular rubber compositions for tires, are disclosed. Summary of the Invention

[0007] In view of the above, there remains a need in the art for a curable polymer composition comprising a silylated polydiene polymer containing multiple functional groups incorporated into the polymer backbone. When the composition cures, it provides improved properties such as filler dispersion, lower rolling resistance, and improved snow traction. It provides a template for a cured composition with improved compound performance.

[0008] In a preferred embodiment, the composition of the present invention comprises a polymer blend comprising a silylated polydiene polymer and at least one non-silylated polydiene polymer. In another embodiment, the silylated polydiene polymer and the at least one non-silylated polydiene polymer are derived from the same monomer. For example, in one embodiment, the silylated polydiene polymer comprises repeat units derived from styrene and butadiene. Similarly, the non-silylated polydiene polymer also comprises repeat units derived from styrene and butadiene.

[0009] In one embodiment, the silylated polydiene polymer is present in a minor amount (by weight) based on the total weight of the silylated polydiene polymer and the non-silylated polydiene polymer. In another embodiment, the reverse is true, and the non-silylated polydiene polymer is present in a minor amount compared to the silylated polydiene polymer derived from the same monomeric unit as the non-silylated polydiene polymer. In yet another embodiment, the polymer composition comprises equal amounts of silylated polydiene polymer and non-silylated polydiene polymer derived from the same monomeric unit.

[0010] In additional embodiments, the polymer composition of the present invention and the cured product comprising the same are derived from a blend of different polymers, such as two or more polymers or three or more polymers, at least one of the polymers being a silylated polydiene polymer. The silylated polydiene polymer carries pendant functional groups, in some embodiments, pendant functional groups that are preferably polar, resulting in improved filler dispersion for the composition compared to the same composition without the silylated polydiene polymer. Each of the polymers utilized imparts desirable properties to the cured product, such as lower rolling resistance and improved snow traction, as mentioned above, for example, when the cured product comprises a tire tread. In some preferred embodiments, the polymer composition comprises natural rubber, poly(butadiene), a copolymer of isobutene and isoprene (butyl rubber), and a styrene-butadiene copolymer, at least one of the polymers comprising at least a portion thereof that is silylated.

[0011] After curing, products comprising the inventive polymer composition comprising a silylated polydiene polymer exhibit one or more of the following properties compared to cured polymer compositions not comprising a silylated polydiene polymer: improved Payne effect (ΔG′) for samples aged 1 day at 100° C., Tan δ at 60° C., and improved M300 at room temperature and at 100° C. The noted performance improvements are enhanced when the polymer composition comprises a filler that is one or more of carbon black and silica.

[0012] According to one embodiment of the present invention, a silylated polydiene polymer comprising the reaction product of i) a polydiene and ii) a silylated grafting agent having the formula: [ka] wherein n is an integer from 0 to 8, 25, or 150; each R is individually a hydrogen atom, a halogen atom, Fg, or a monovalent organic group, or two or more R groups together form a bond or a polyvalent organic group, provided that at least one R is a hydrogen atom; Fg is derived from a compound having the formula CH2=C(R1(R2), where at least one of R1 and R2 has a functional group that can participate in hydrogen bonding, chemical reaction with a filler, or grafting of a polymer, and one of R1 and R2 can be a hydrogen atom or an organic group; in a preferred embodiment, the compound has the formula CH2=CHCH2X-R, where X is O, S, or N, and R is a polyethylene oxide having 3 to 100 repeating groups, or derived from piperidine when X is N, or derived from bis(trimethylsilyl)amine when X is N; or [ka] (In the formula, R is a hydrogen atom, a halogen atom, Fg, or a monovalent organic group, Fg is as defined above, and n is 2 to 5.) A curable polymer composition is disclosed that includes a non-silylated polydiene polymer that includes natural rubber and a filler that includes one or more of carbon black and silica. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The curable polymer composition, the cured composition, and the cured product formed using the curable polymer composition comprise a silylated polydiene polymer comprising the reaction product of i) a polydiene and ii) a silylated grafting agent having the formula: [ka] wherein n is an integer from 0 to 8, 25, or 150, each R is individually a hydrogen atom, a halogen atom, Fg, or a monovalent organic group, or two or more R groups together form a bond or a polyvalent organic group, with the proviso that at least one R is a hydrogen atom, and Fg is derived from a compound having the formula CH2=C(R1)(R2), where at least one of R1 and R2 has a functional group that can participate in hydrogen bonding, chemical reaction with a filler, or grafting of a polymer, and one of R and R2 can be a hydrogen atom or an organic group; in a preferred embodiment, the compound has the formula CH2=CHCH2X-R, where X is O, S, or N, and R is a polyethylene oxide having 3 to 100 repeating groups, or is derived from piperidine when X is N, or is derived from bis(trimethylsilyl)amine when X is N; or [ka] (In the formula, R is a hydrogen atom, a halogen atom, Fg, or a monovalent organic group, Fg is as defined above, and n is 2 to 5.) a non-silylated polydiene polymer comprising one or more of natural rubber, styrene-butadiene copolymer, and poly(1,3-butadiene); and a filler; The grafting agents that are grafted to the polydiene polymer to produce the silylated polydiene polymer, in addition to having a silicon atom, contain a functional group, in one embodiment a functional group that is preferably polar, which can improve filler interaction within the composition blend and improve properties in the cured composition.

[0014] Silylated Polydiene Polymer

[0015] Synthesis of silylated grafting agents

[0016] The silylated grafting agents are derived from siloxanes and compounds having a vinyl group substituted on one carbon atom of the double bond, and in some embodiments polar compounds containing an allyl group, which react preferably in an inert atmosphere in the presence of a metal catalyst.

[0017] Siloxane

[0018] Siloxanes suitable for use in the present invention are characterized by comprising at least two hydrogen atoms covalently bonded to different silicon atoms. The first hydrogen atom participates in a reaction with a compound having a vinyl group in which one carbon atom of the double bond is substituted, in some embodiments preferably a polar compound containing an allyl group, and the second hydrogen atom participates in a hydrosilylation reaction with a polymer. In one or more embodiments, the siloxane is defined by the following formula: [ka] wherein n is an integer from 0 to 8, 25, or 150; each R is individually a hydrogen atom, a halogen atom, or a monovalent organic group, or two or more R groups together form a bond or a polyvalent organic group, provided that each siloxane contains at least two R groups that are hydrogen atoms bonded to different silicon atoms. In a preferred embodiment, n is 0. In one or more embodiments, n is 1 to 4; or [ka] (In the formula, R is a hydrogen atom, a halogen atom, or a monovalent organic group, and n is an integer of 2 to 5).

[0019] Non-limiting examples of specific siloxanes include 1,1,3,3-tetramethyldisiloxane (TMDS), 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane, 1,1,1,3,5,7,7,7-octaalkyltetrasiloxane, 1,1,3,3-tetraethyldisiloxane, 1,1,3,3,5,5-hexaethyltrisiloxane, 1,1,3,3,5,5,7,7-octaethyltetrasiloxane, 1,1,1,3,5,7,7,7-octaalkyltetrasiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, and 2,4,6-trimethylcyclotrisiloxane.

[0020] Compounds containing vinyl groups

[0021] To synthesize the grafting agent, a compound having a vinyl group substituted at one carbon atom of the double bond is utilized. In one embodiment, the compound is a polar compound containing an allyl group that reacts with siloxane under reaction conditions. In one embodiment, the compound has the formula CH2=C(R1)(R2), where at least one of R1 and R2 has a functional group that can participate in hydrogen bonding, chemical reaction with a filler, or grafting of a polymer, and one of R1 and R2 can be a hydrogen atom or an organic group. In a preferred embodiment, the polar compound has the formula: CH2=CHCH2-XR, where X is O, S, or N, and R is a polyethylene oxide having 3 to 100 repeating groups. In another preferred embodiment, the polar compound is derived from piperidine. In yet another preferred embodiment, the polar compound is derived from bis(trimethylsilyl)amine.

[0022] Grafting Agent Catalyst

[0023] The catalyst utilized in the hydrosilylation reaction is selected from organometallic compounds, salts, or metals, such as Ni, Ir, Rh, Ru, Os, Pd, and Pt compounds, as taught in U.S. Pat. No. 3,159,601, U.S. Pat. No. 3,159,662, U.S. Pat. No. 3,419,593, U.S. Pat. No. 3,715,334, U.S. Pat. No. 3,775,452, and U.S. Pat. No. 3,814,730, which are incorporated herein by reference in their entirety. In a preferred embodiment, the catalyst is chloro(1,5-cyclooctadiene)rhodium(I). The catalyst may be added to the reaction mixture in any conventional form, but is preferably in the form of a solution in a solvent.

[0024] solvent

[0025] The reaction to form the grafting agent may be carried out in a suitable solvent(s). Suitable organic solvents include aromatic, aliphatic, and cycloaliphatic hydrocarbons. Examples of suitable aromatic hydrocarbon solvents include, but are not limited to, benzene, toluene, ethylbenzene, diethylbenzene, naphthalene, mesitylene, xylene, and the like. Examples of suitable aliphatic hydrocarbon solvents include, but are not limited to, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, isopentane, hexane, isohexane, isopentane, isooctane, 2,2-dimethylbutane, petroleum ether, kerosene, petroleum spirits, and the like. Non-limiting examples of suitable cycloaliphatic hydrocarbon solvents include cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, and the like. Still other suitable solvents include polar aprotic solvents such as tetrahydrofuran. Mixtures of the aforementioned aromatic, aliphatic, and cycloaliphatic hydrocarbon solvents and polar aprotic solvents may be used. In certain embodiments, preferred organic solvents include aliphatic hydrocarbon solvents, cycloaliphatic hydrocarbon solvents, or mixtures thereof. Additional useful organic solvents suitable for use in forming the grafting agent are known to those skilled in the art.

[0026] Synthesis of the grafting agent

[0027] A suitable reaction vessel is charged with the desired amount of siloxane and a compound having a vinyl group substituted at one carbon atom of the double bond. In one or more embodiments, the siloxane is generally used in a molar ratio to the polar compound ranging from greater than 1:1 to about 5:1, desirably greater than 1.25:1 to about 4:1, preferably from about 1.5:1 to about 2.5:1, with 2:1 being most preferred. In one or more embodiments, the reaction vessel is cooled since the reaction is exothermic in nature. Thereafter, a catalyst, preferably dissolved in a suitable solvent in one embodiment, is added to the vessel. In one or more embodiments, an inert atmosphere is utilized. Preferably, the reaction mixture is stirred or otherwise mixed during the reaction. The reaction mixture is warmed to a temperature such as room temperature or to a temperature of about 25°C to about 100°C over a period of time such as about 3 to about 5 hours. The reaction vessel is vented during the reaction to prevent excessive accumulation of H2 gas.

[0028] If desired, additional steps can be carried out to remove the metal catalyst and purify the crude product. For example, after the reaction, activated carbon can be added to the reaction mixture and stirred for a period of time, for example, about 1 hour in some embodiments. The mixture can then be passed through a pad of basic alumina using a hydrocarbon solvent, for example, anhydrous pentane, as the eluent. The eluent can be further processed and concentrated under vacuum to obtain the silylated grafting agent.

[0029] Silylated Grafting Agent

[0030] The resulting silylated grafting agent has the formula: [ka] wherein each R and n are as defined above, with the proviso that at least one R is a hydrogen atom, and Fg is derived from a compound having the formula CH2=C(R1)(R2), where at least one of R1 and R2 has a functional group that can participate in hydrogen bonding, chemical reaction with a filler, or grafting of a polymer, and one of R and R2 can be a hydrogen atom or an organic group, and in a preferred embodiment the compound has the formula CH2=CHCH2X-R, where X is O, S, or N, and R is a polyethylene oxide having 3 to 100 repeating groups, or derived from piperidine when X is N, or derived from bis(trimethylsilyl)amine when X is N, or b)

[0031] (wherein R is a hydrogen atom, a halogen atom, or a monovalent organic group, Fg is as defined above, and n is 2 to 5).

[0032] Hydrosilylation of polymers with grafting agents

[0033] The grafted polymers of the present invention are the reaction product of a polydiene polymer and a silylated grafting agent as described herein. In addition to adding pendant silicon atoms to the polymer, the grafting agent also contains functional groups as described herein.

[0034] The polymer contains pendant groups or unsaturation at one or more locations on the polymer backbone. As used herein, terms such as "grafted" should be understood to mean pendant or side groups fixed to the polymer backbone resulting from grafting by hydrosilylation of the grafting agent. Thus, according to the present invention, the hydrosilane of the grafting agent reacts with the unsaturation of the polydiene polymer by hydrosilylation.

[0035] Polydiene Polymer

[0036] As used herein, the term "polymer" is defined as a homopolymer, ie, a polymer formed from the same monomers, and a copolymer, ie, a polymer formed from two or more different monomers.

[0037] The non-grafted polymers subjected to backbone modification in the present invention are homopolymers of dienes or copolymers of a first diene monomer with one or more second comonomers selected from a second diene monomer and an aromatic vinyl compound.

[0038] Examples of suitable dienes include, but are not limited to, (1,3-butadiene); 2-(C1-C5 alkyl)-1,3-butadiene such as isoprene (2-methyl-1,3-butadiene); 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene, 1,3-hexadiene, 1,3-heptadiene, 1,3-octadiene, 2-methyl-2,4-pentadiene, cyclopentadiene, 2,4-hexadiene, 1,3-cyclohexadiene, and 1,3-cyclooctadiene. As noted above, two or more conjugated dienes can be used together to form a polymer. In one or more embodiments, butadiene is present in a polydiene.

[0039] Examples of aromatic vinyl compounds suitable for use in the polymer include monovinyl aromatic compounds, i.e. compounds having one vinyl group attached to an aromatic group, and di- or higher vinyl aromatic compounds having two or more vinyls attached to an aromatic group. Exemplary aromatic vinyl compounds include styrene; C1-C4 alkyl-substituted styrenes such as 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,4,6-trimethylstyrene, α-methylstyrene, 2,4-diisopropylstyrene, and 4-tert-butylstyrene; stilbene, vinylbenzyldimethylamine, (4-vinylbenzyl)dimethylaminoethyl ether, N,N-dimethylaminoethylstyrene, tert-butoxystyrene, vinylpyridine; and divinylaromatic compounds such as 1,2-divinylbenzene, 1,3-divinylbenzene, and 1,4-divinylbenzene. Two or more aromatic vinyl compounds may be used in combination. A preferred aromatic vinyl compound is a monovinyl aromatic compound, more preferably styrene.

[0040] In some embodiments, the aromatic vinyl compound comprises from 5% to 50% by weight, preferably from 10% to 45% by weight, of the total monomer content of the polymer.

[0041] Preferred polydiene polymers include styrene-butadiene rubber (SBR), poly(butadiene), butyl rubber (BR), and isoprene rubber (IR).

[0042] Polymers suitable for use in the present invention can be obtained according to conventional polymerization techniques utilizing conventional additives well known to those skilled in the art. The polymers can be, for example, block, random, sequential or microsequential, and can be prepared, for example, in dispersion, emulsion or solution.

[0043] The polymerization can be carried out under batch, continuous, or semi-continuous conditions. The polymerization process is preferably carried out as a solution polymerization, where the resulting polymer is substantially soluble in the reaction mixture, or as a suspension / slurry polymerization, where the polymer is substantially insoluble in the reaction medium. As the polymerization solvent, any hydrocarbon solvent that does not deactivate the initiator, catalyst, or active polymer chains is conventionally used.

[0044] Polymer hydrosilylation

[0045] In an important aspect of the present invention, the grafting agent can be grafted onto the polymer in the polymerization solvent utilized to prepare the polymer, which saves both time and money by eliminating the need to dry and subsequently resolvate the polymer prior to reaction with the grafting agent.

[0046] Preferably, the majority of the polymer chain ends, i.e. more than 50%, in particular at least 70%, preferably at least 80%, are terminated before the addition of the grafting agent, i.e. living polymer chain ends are preferably absent and cannot react with the graft. The termination of the polymer chain ends can be influenced by the action of coupling agents, quenching agents or chain terminators, by functionalization of the chain ends, or by other means such as impurities in the polymerization process, or by inter- or intra-chain reactions.

[0047] In one or more embodiments, the quenching agent can protonate the chain ends of the living polymer. The quenching agent can include a protic compound, including, but not limited to, an alcohol, a carboxylic acid, an inorganic acid, water, or a mixture thereof. An antioxidant, such as 2,6-di-tert-butyl-4-methylphenol, can be added together with, before, or after the addition of the quenching agent. In certain embodiments, the quenching agent and / or antioxidant is selected to limit interference with the hydrosilylation reaction. The amount of antioxidant used can range from 0.2% to 1% by weight based on the weight of the polymer.

[0048] In one or more embodiments, a living polymer can be terminated with a compound that imparts a functional group to the end of the polymer, thereby causing the resulting polymer to bear at least one additional functional group.

[0049] Useful terminating agents include those that are conventionally used in the art.Non-limiting examples of compounds that are used for the end-functionalization of living polymers include carbon dioxide, benzophenone, benzaldehyde, imidazolidone, pyrrolidinone, carbodiimide, urea, isocyanate, and Schiff base, including those disclosed in U.S. Patent Nos. 3,109,871, 3,135,716, 5,332,810, 5,109,907, 5,210,145, 5,227,431, 5,329,005, and 5,935,893, which are incorporated herein by reference. Additional examples include trialkyltin halides such as tributyltin chloride, as disclosed in U.S. Patent Nos. 4,519,431, 4,540,744, 4,603,722, 5,248,722, 5,349,024, 5,502,129, and 5,877,336, which are incorporated herein by reference. Other examples include cyclic amino compounds such as hexamethyleneimine alkyl chlorides, as disclosed in U.S. Patent Nos. 5,786,441, 5,916,976, and 5,552,473, which are incorporated herein by reference. Other examples include N-substituted aminoketones, N-substituted thioaminoketones, N-substituted aminoaldehydes, and N-substituted thioaminoaldehydes, including N-methyl-2-pyrrolidone or dimethylimidazolidinone (i.e., 1,3-dimethylethyleneurea), as disclosed in U.S. Pat. Nos. 4,677,165, 5,219,942, 5,902,856, 4,616,069, 4,929,679, 5,115,035, and 6,359,167, which are incorporated herein by reference. Additional examples include cyclic sulfur- or oxygen-containing azaheterocycles such as those disclosed in U.S. Patent Publication Nos. 2006 / 0074197(A1), 2006 / 0178467(A1), and U.S. Patent No. 6,596,798, which are incorporated herein by reference. Other examples include boron-containing terminators such as those disclosed in U.S. Patent No. 7,598,322, which are incorporated herein by reference.Still other examples include cyclic siloxanes such as hexamethylcyclotrisiloxane, including those disclosed in co-pending US Patent Publication No. 2007 / 0149744(A1), which is incorporated herein by reference. Still other examples include α-halo-ω-aminoalkanes such as 1-(3-bromopropyl)-2,2,5,5-tetramethyl-1-aza-2,5-disilacyclopentane, including those disclosed in co-pending US Patent Publication No. 2007 / 0293620(A1) and US Patent Publication No. 2007 / 0293620(A1), which is incorporated herein by reference. Further examples include γ-mercapto-propyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, and vinylmethyldimethoxysilane. Still further examples include 3-bis(trimethylsilyl)aminopropyl-methyldiethoxysilane and 3-(1,3-dimethylbutylidene)aminopropyltriethoxysilane. Additional terminating agents include trialkylsilyl halides, such as but not limited to trimethylsilyl chloride (TMSCI), triarylsilyl halides, such as but not limited to triphenylsilyl chloride, and mixtures of alkyl-arylsilyl halides, such as tert-butyldiphenylsilyl chloride, tris(dimethylamino)chlorosilane, and 3-cyanopropylaminodimethylchlorosilane. The foregoing list of terminating agents should not be construed as limiting, but rather as possible. Although terminating agents can be used, the practice of the present invention is not limited to a specific agent or class of such compounds.

[0050] In one or more embodiments, living polymers can be coupled to link two or more living polymer chains together. In certain embodiments, living polymers can be treated with both coupling and terminating agents, which act to couple some chains and terminate the polymerization of others. Combinations of coupling and terminating agents can be used in various molar ratios. Although the terms coupling and terminating agents have been used herein, those skilled in the art will understand that certain compounds can serve both functions. That is, certain compounds can both link polymer chains and provide polymer chains with functional groups. Those skilled in the art will also understand that the ability to link polymer chains can depend on the amount of coupling agent reacted with the polymer chains. For example, advantageous linking can be achieved when the coupling agent is added in a 1:1 ratio of equivalents of a metal, such as lithium, in the initiator to equivalents of a leaving group (e.g., halogen atom) in the coupling agent. Non-limiting examples of coupling agents include metal halides, metalloid halides, alkoxysilanes, and alkoxystannanes.

[0051] In one or more embodiments, the metal halide or metalloid halide has the formula (1) R* n M 1 Y (4-n) , Equation (2)M 1 Y4, and formula (3)M 2 Y3 (wherein each R* is independently a monovalent organic group having 1 to 20 carbon atoms; M 1 is a tin atom, a silicon atom, or a germanium atom, M 2 is a phosphorus atom, Y is a halogen atom, and n is an integer of 0 to 3.

[0052] Representative compounds represented by formula (1) include organometallic halogenated compounds, and compounds represented by formulas (2) and (3) include metal halide compounds.

[0053] M 1When represents a silicon atom, the compound represented by formula (1) may be, for example, triphenylchlorosilane, trihexylchlorosilane, trioctylchlorosilane, tributylchlorosilane, trimethylchlorosilane, diphenyldichlorosilane, dihexyldichlorosilane, dioctyldichlorosilane, dibutyldichlorosilane, dimethyldichlorosilane, methyltrichlorosilane, phenyltrichlorosilane, hexyltrichlorosilane, octyltrichlorosilane, butyltrichlorosilane, methyltrichlorosilane, etc. Furthermore, examples of the compound represented by formula (2) include silicon tetrachloride, silicon tetrabromide, etc.

[0054] M 1 When represents a germanium atom, the compound represented by formula (1) may be, for example, triphenylgermanium chloride, dibutylgermanium dichloride, diphenylgermanium dichloride, butylgermanium trichloride, etc. Further, examples of the compound represented by formula (2) include germanium tetrachloride, germanium tetrabromide, etc. Examples of the compound represented by formula (3) include phosphorous trichloride, phosphorous tribromide, etc. In one or more embodiments, a mixture of metal halides and / or semimetal halides may be used.

[0055] In one or more embodiments, the alkoxysilane or alkoxystannane is represented by the formula (4) R* n M 1 (OR^) 4-n (wherein each R* is independently a monovalent organic group having 1 to 20 carbon atoms; M 1 is a tin atom, a silicon atom, or a germanium atom, OR^ is an alkoxy group, R^ is a monovalent organic group, and n is an integer of 0 to 3.

[0056] Representative compounds represented by formula (4) include tetraethyl orthosilicate, tetramethyl orthosilicate, tetrapropyl orthosilicate, tetraethoxytin, tetramethoxytin, and tetrapropoxytin.

[0057] The addition of the grafting agent may occur before, after, or during the addition of the coupling agent (if used), and before, after, or during the addition of the chain end modifying agent (if used), and before, after, or during the addition of the chain terminator (if used). Preferably, the grafting agent is added after the addition of any of the coupling agent, chain end modifying agent, and chain terminator.

[0058] The grafting agent can be added directly to the polymer solution (polymerization solution) without dilution (undiluted), but it may be beneficial to add the grafting agent in solution. The amount of grafting agent added varies depending on the monomer species, grafting agent species, reaction conditions, and the desired final properties, but is generally about 1% to about 30% by weight, desirably about 2.5% to 20% by weight, and preferably about 5% to about 15% by weight, based on the weight of the polymer without any solvent (i.e., the unmodified polymer (homopolymer or copolymer)).

[0059] The hydrosilylation can generally be carried out at a temperature range of 50°C to 120°C, desirably 50°C to 100°C, and preferably 50°C to 80°C.

[0060] Generally, there is no limit to the duration and timing of the functionalization reaction. The polymer is reacted with the grafting agent for a suitable period of time, generally ranging from about 0.5 hours to about 10 hours, as can be readily established by one skilled in the art.

[0061] Hydrosilylation Catalyst

[0062] The hydrosilylation reaction can be carried out as known in the art, and is usually carried out in the presence of a hydrosilylation catalyst. Two or more catalyst compounds can be used in combination. The catalysts described above for the production of the grafting agent can be utilized, which are incorporated herein by reference. In one or more embodiments, the preferred catalyst includes Karstedt's catalyst. The catalyst can be added before, after, or simultaneously with the addition of the grafting agent. The total amount of hydrosilylation catalyst depends on the amount of the grafting agent. A low amount of hydrosilylation catalyst may result in too low a conversion of the grafting agent, and a high amount may be economically disadvantageous.

[0063] Polymerization / Hydrosilylation Solvents

[0064] As described herein, the polymerization of the monomers utilized to form the polydiene polymer is preferably carried out in a solvent. In one or more embodiments, the hydrosilylation reaction is carried out directly in the polymerization solvent. In other embodiments, a solvent other than or in addition to the polymerization solvent can be utilized.

[0065] Examples of solvents include, but are not limited to, those described above with respect to the preparation of the grafting agent, which are incorporated herein by reference.

[0066] Grafted Polymer

[0067] The degree of grafting can be adjusted in a manner known to those skilled in the art by varying various operating conditions, such as the amount of molecules to be grafted, the reaction temperature, and the reaction time.

[0068] The reaction of the grafting agent with the polydiene polymer results in pendant grafts having functional groups attached to the silicon atoms derived from the siloxane, for example TDMS.

[0069] More specifically, the pendant groups attached to the backbone of the polymer have the formula: [ka] [ka] [ka] [ka] [ka] where R and Fg are as defined above and the * indicates the point of attachment to the polymer chain.

[0070] Generally, the average number of grafted units per chain is from about 0.25 to about 15, alternatively from about 2 to about 8. When the functional group comprises ethylene oxide units, the grafting of ethylene oxide units onto the backbone has generally been found to be in the range of from about 0.5% to about 10% by weight, preferably from about 0.6% to about 4.5% by weight.

[0071] In embodiments where the functional group contains a nitrogen atom, the grafting of the nitrogen-containing functional group onto the backbone generally varies from about 50 ppm to about 2200 ppm N / chain.

[0072] In embodiments, the hydrosilyl-functionalized polydiene polymer may have a weight average molecular weight Mw of about 75,000 g / mol to about 1,000,000 g / mol. In embodiments, the functionalized conjugated diene may have a weight average molecular weight Mw 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. In embodiments, the functionalized conjugated diene may have a weight average molecular weight Mw 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. In an embodiment, the functionalized conjugated diene polymer may be from about 75,000 g / mol to about 1,000,000 g / mol, from about 75,000 g / mol to about 800,000 g / mol, from about 75,000 g / mol to about 600,000 g / mol, from about 75,000 g / mol to about 400,000 g / mol, from about 100,000 g / mol to about 1,000,000 g / mol, from about 100,000 g / mol to about 800,000 g / mol, from about 100,000 g / mol to about 600,000 g / mol, from about 100,000 g / mol to about 400,000 g / mol, from about 200,000 g / mol to about The copolymer may have a molecular weight Mw of 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. Weight average molecular weights Mw are determined by gel permeation chromatography using a Tosoh Ecosec HLC-8320 GPC system and a Tosoh TSKgel GMHxl-BS column with THF as the solvent, calibrated and referenced to PS.

[0073] In embodiments, the hydrosilyl-functionalized polydiene polymer may have a number average molecular weight Mn of about 75,000 g / mol to about 1,000,000 g / mol. In embodiments, the functionalized conjugated diene may have a number average molecular weight Mn 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. In embodiments, the functionalized conjugated diene may have a number average molecular weight Mn 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. In an embodiment, the functionalized conjugated diene polymer may be from about 75,000 g / mol to about 1,000,000 g / mol, from about 75,000 g / mol to about 800,000 g / mol, from about 75,000 g / mol to about 600,000 g / mol, from about 75,000 g / mol to about 400,000 g / mol, from about 100,000 g / mol to about 1,000,000 g / mol, from about 100,000 g / mol to about 800,000 g / mol, from about 100,000 g / mol to about 600,000 g / mol, from about 100,000 g / mol to about 400,000 g / mol, from about 200,000 g / mol to about The molecular weight Mn may be from about 1,000,000 g / mol, from about 200,000 g / mol to about 800,000 g / mol, from about 200,000 g / mol to about 600,000 g / mol, from about 200,000 g / mol to about 400,000 g / mol, from about 300,000 g / mol to about 1,000,000 g / mol, from about 300,000 g / mol to about 800,000 g / mol, from about 300,000 g / mol to about 600,000 g / mol, or even from about 300,000 g / mol to about 400,000 g / mol, or any and all subranges formed from any of these endpoints. Number average molecular weights Mn are determined by gel permeation chromatography using a Tosoh Ecosec HLC-8320 GPC system and a Tosoh TSKgel GMHxl-BS column with THF as the solvent, calibrated and referenced to PS.

[0074] Non-silylated polydiene polymers.

[0075] The polymer compositions of the present invention utilize one or more non-silylated or non-grafted polydiene polymers. Polydienes contain carbon-carbon double bonds and are therefore unsaturated and can be cured or vulcanized as known in the art.

[0076] The non-silylated polydiene polymers may be derived at least in part from conjugated or non-conjugated diene monomers. The amount of unsaturation along the chain will, of course, vary depending on the particular polymer utilized.

[0077] Non-limiting examples of non-silylated polydiene polymers suitable for use in the present invention include, but are not limited to, the following:

[0078] (a) a homopolymer obtained by polymerization of a conjugated diene monomer having from 4 to 12 carbon atoms;

[0079] (b) a copolymer obtained by copolymerization of a first conjugated diene monomer with one or more of a second different conjugated diene monomer and one or more ethylenically unsaturated monomers;

[0080] (c) homopolymers obtained by polymerization of non-conjugated diene monomers having 5 to 12 carbon atoms;

[0081] (d) a copolymer obtained by copolymerization of a first non-conjugated diene with one or more of a second, different non-conjugated diene and one or more ethylenically unsaturated monomers;

[0082] (e) terpolymers obtained by copolymerization of ethylene, an alpha-olefin having from 3 to 6 carbon atoms, and a non-conjugated diene monomer having from 6 to 12 carbon atoms;

[0083] (f) optionally halogenated copolymers of isobutylene and isoprene;

[0084] (g) natural rubber,

[0085] (h) unsaturated olefinic copolymers, the chains of which contain at least olefinic monomer units and diene units derived from at least one conjugated diene, or

[0086] (i) A mixture of two or more of (a) to (h).

[0087] Examples of suitable conjugated diene monomers useful in synthesizing polymers (a), (b), and (h) include, but are not limited to, 1,3-butadiene, 2-methyl-1,3-butadiene; 2,3-di(C1-C5 alkyl)-1,3-butadiene, such as 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, or 2-methyl-3-isopropyl-1,3-butadiene; aryl-1,3-butadienes, 1,3-pentadiene, or 2,4-hexadiene.

[0088] Examples of non-conjugated diene monomers suitable for synthesizing polymers (c), (d), and (e) include, but are not limited to, 1,4-pentadiene, 1,4-hexadiene, ethylidenenorbornene, and dicyclopentadiene.

[0089] Ethylenically unsaturated monomers that can be used for copolymerization with one or more conjugated or non-conjugated diene monomers to synthesize copolymers (b) or (d) include, but are not limited to, vinyl aromatic compounds having 8 to 20 carbon atoms, such as styrene, ortho-, meth-, or para-methylstyrene, vinyl mesitylene, divinylbenzene, and vinyl naphthalene; vinyl nitrile monomers having 3 to 12 carbon atoms, such as acrylonitrile and methacrylonitrile; acrylic acid ester monomers derived from acrylic acid or methacrylic acid and alcohols having 1 to 12 carbon atoms, such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate acrylate, and isobutyl methacrylate.

[0090] Copolymer (b) or (d) may contain from 99% to 1% by weight of diene units and from 1% to 99% by weight of vinyl aromatic, vinyl nitride, and / or acrylate units.

[0091] Suitable monoolefin monomers for synthesizing polymer (h) include, but are not limited to, ethylene or α-olefins having 3 to 6 carbon atoms, such as propylene, butylene, or isobutylene. Preferably, the monoolefin monomer is ethylene, butylene, and / or isobutylene.

[0092] According to certain embodiments, the olefin copolymers (h) that can be used in the present invention are copolymers whose chains comprise olefin monomer units, i.e. units resulting from the insertion of at least one monoolefin, and diene units resulting from at least one conjugated diene. According to other embodiments, the units are not entirely units resulting from diene monomers and monoolefin monomers. According to these embodiments, other units resulting from ethylenically unsaturated monomers, for example as explained above, are present in the carbon-based chain. In some embodiments, the olefin monomer units and copolymers (h) predominate, i.e. are present in a molar content of 50% or more relative to the polymer.

[0093] Based on the above description, examples of suitable non-silylated polydiene polymers include polybutadiene, polyisoprene, or polychloroprene, and hydrogenated versions thereof; block copolymers of polyisobutylene, butadiene, and isoprene with styrene, and hydrogenated versions thereof, such as poly(styrene-b-butadiene) (SB), poly(styrene-b-butadiene-b-styrene) (SBS), poly(styrene-b-isoprene-b-styrene) (SIS), poly[styrene-b-(isoprene-stat-butadiene)-b-styrene], or poly(styrene-b-isoprene-b-butadiene-b-styrene) (SIBS), hydrogenated S Examples of rubbers that may be used include, but are not limited to, BS (SEBS), poly(styrene-b-butadiene-b-methyl methacrylate) (SBM) and hydrogenated versions thereof (SEBM); random copolymers of butadiene with styrene and acrylonitrile (NBR) (SBR) and hydrogenated versions thereof; random copolymers of isoprene with styrene (SIR) and hydrogenated versions thereof; random copolymers of isoprene with butadiene and styrene (SBIR) and hydrogenated versions thereof; butyl or halogenated rubber, ethylene-propylene-diene terpolymer (EPDM), ethylene-diene copolymers, and mixtures thereof.

[0094] In various preferred embodiments, the polydiene polymer is preferably, alone or in combination, polybutadiene (abbreviated as "BR"), synthetic polyisoprene (IR), natural rubber (NR), butadiene copolymer, isoprene copolymer, ethylene-diene copolymer, and mixtures of these polymers. Such copolymers are more preferably selected from the group consisting of butadiene-styrene copolymer (SBR), isoprene-butadiene copolymer (BIR), isoprene-styrene copolymer (SIR), isoprene-butadiene-styrene copolymer (SBIR), and ethylene-butadiene copolymer (EBR).

[0095] The polymers suitable for use in the present invention can be obtained according to conventional polymerization techniques utilizing conventional additives well known to those skilled in the art. The polymers can have any microstructure that is a function of the polymerization conditions used. The polymers can be, for example, block, random, sequential or microsequential, and can be prepared, for example, in dispersion, emulsion or solution. The polymerization can be carried out under batch, continuous or semi-continuous conditions.

[0096] The amount of non-silylated polydiene polymer relative to the silylated polydiene polymer can vary depending on the end use of the composition containing it. However, in one or more embodiments, the curable polymer composition comprises a majority amount of non-silylated polydiene polymer based on the total amount of non-silylated polydiene polymer and silylated polydiene polymer. In further embodiments, the non-silylated polydiene polymer is generally present in an amount greater than 50 parts by weight, preferably greater than 60 parts by weight, based on 100 parts by weight of the total polymer. In further embodiments, the silylated polydiene polymer is present in an amount of about 10 parts by weight to about 50 or 75 parts by weight, based on 100 parts by weight of the silylated polydiene polymer and the non-silylated polydiene polymer, or the silylated polydiene polymer is present in an amount of about 15 parts by weight to about 35 parts by weight, based on 100 parts by weight of the silylated polydiene polymer and the non-silylated polydiene polymer.

[0097] Filler

[0098] In a preferred embodiment, the curable polymer composition of the present invention comprises one or more fillers that function as reinforcing agents in the polymer composition and include, but are not limited to, carbon black, silica, carbon nanotubes, starch, aluminum hydroxide, magnesium hydroxide, clay, calcium carbonate, magnesium carbonate, layered silicates, and glass.

[0099] Carbon black includes furnace black, channel black, and lamp black. More specific examples of carbon black include super abrasion furnace black, medium super abrasion furnace black, high abrasion furnace black, high speed extrusion furnace black, fine furnace black, semi-reinforced furnace black, medium processed channel black, hard processed channel black, conductive channel black, and acetylene black.

[0100] If utilized, carbon black is generally added in an amount of from about 1 to about 40, 75, 100, or 110 parts by weight, desirably from about 5 to about 38 parts by weight, and preferably from about 10 to about 35 parts by weight, based on 100 parts by weight of total polymer.

[0101] Non-limiting examples of silica fillers include, but are not limited to, wet-process silica, dry-process silica, synthetic silicate-type silica, and combinations thereof. Silica with small particle size and large surface area exhibits high reinforcing effect. Small diameter, highly aggregated silica (i.e., with large surface area and high oil absorption) exhibits excellent dispersibility in polymer compositions, which represents desirable properties and excellent processability. The average particle size of the silica, in terms of primary particle size, is 5-60 nm in some embodiments, and 10-35 nm in some embodiments. Furthermore, the specific surface area of ​​the silica particles (N2A, measured by BET method) is 35-300 m in some embodiments. 2 In some embodiments, the silica is 150 to 300 m 2 / g surface area. Lower N2A values ​​can undesirably lead to lower reinforcing effect, while higher N2A values ​​can provide increased viscosity and worse processability to the rubber compound. For examples of suitable silica filler diameters, particle sizes, and BET surface areas, see WO 2009 / 148932.

[0102] Silica, when utilized, in some embodiments is generally added in an amount of from about 1 to about 30, 40, 100, or 120 parts by weight, in some embodiments desirably from about 10 to about 28 parts by weight, and in some embodiments preferably from about 12 to about 25 parts by weight, based on 100 parts by weight of total polymer.

[0103] In some preferred embodiments, multiple different fillers, such as both carbon black and silica, are added together to the composition, in which case the total amount of filler generally ranges from about 1 to about 40, 75, 100, or 110 parts by weight, preferably from about 10 to about 35 parts by weight, based on 100 parts by weight of total polymer. Optional Ingredients

[0104] Other ingredients or components that may be used in the polymer compositions of the present invention include, but are not limited to, oils, waxes, scorch inhibitors, processing aids, zinc oxide, tackifying resins, reinforcing resins, fatty acids such as stearic acid, peptizers, coupling agents, stabilizers, and combinations thereof.

[0105] Hardener

[0106] A number of rubber curatives may be used, including sulfur or peroxide based cure systems. Curatives are well known in the art and are described, by way of non-limiting example, in many volumes of the various editions of the Kirk-Othmer Encyclopedia of Chemical Technology and Vulcanization in Encyclopedia of Polymer Science and Engineering, which are incorporated herein by reference. Curatives may be used alone or in combination.

[0107] Cured Polymer Composition

[0108] The cured polymer compositions of the present invention are obtained by curing or vulcanizing the uncured polymer compositions described herein that contain one or more curing agents under conditions and using machinery conventionally known in the art.

[0109] When the curable polymer compositions are used in the manufacture of tires, they can be processed into tire components according to conventional tire manufacturing techniques, including standard rubber molding, molding, and curing techniques. Typically, curing can be accomplished by heating the composition in a mold, for example, to about 40 to about 180°C. The cured or crosslinked polymer composition may also be referred to as a vulcanizate, which generally contains a thermoset three-dimensional polymer network. Other components of the composition, such as fillers and processing aids, are preferably uniformly dispersed throughout the matrix or network.

[0110] Articles Comprising Cured Polymer Compositions

[0111] The cured polymer compositions of the present invention exhibit properties including one or more of improved filler dispersion, low rolling resistance, and improved snow traction and are therefore well suited for use in the manufacture of, for example, tires or components thereof including, for example, tire treads, sidewalls, and other components of tires, as well as other industrial products such as belts, hoses, vibration dampers, and footwear components.

[0112] Thus, an article of the invention includes at least one component formed from the cured polymer composition of the invention. The article can be, for example, a tire, a tire tread, a tire sidewall, a tire carcass, a belt, a gasket, a seal, a hose, a vibration damper, a golf ball, or a footwear component such as a shoe sole.

[0113] Working Example

[0114] The following examples are provided to illustrate the silylated grafting agents, methods of synthesis thereof, polymers grafted therewith, compositions comprising silylated polymers, and methods of production thereof, and are not intended to limit the scope of the invention.

[0115] The following test protocol was used for the study: [Table 1]

[0116] Synthesis of TMDS-propylpiperidine

[0117] A 100 mL oven-dried three-neck flask was charged with 1-allylpiperidine (5 g, 0.04 mol), 1,1,3,3-tetramethyldisiloxane (10.7 g, 0.08 mol), chloro(1,5-cyclooctadiene)rhodium(I) (5 mg, 0.01 mol) dissolved in anhydrous toluene (1 mL) under an inert atmosphere, and a stir bar. The flask was vented during the reaction to prevent accumulation of H2 gas. As the reaction proceeded, the color of the reaction mixture changed from light yellow to reddish orange. After 5 h, activated charcoal (5 g) was added and the reaction mixture was stirred for an additional 1 h. The black heterogeneous mixture was then passed through a pad of basic alumina using anhydrous pentane (500 mL) as the eluent. The colorless eluent was concentrated under vacuum to give a colorless liquid as the pure product (4.58 g, 44%). The reaction product was eluted with 100% CO.sub.2 (1H, ... 1H NMR(400 MHz,CDCl3):4.66(1H,Si-H),2.37(4H,br),2.27(2H,triplet),1.64-1.38(9H,multiplet),0.48(2H,triplet),0.16(6H,doublet),0.08(6H,doublet).

[0118] Example 1-1. Synthesis of a Control SBR-Based Polymer Containing 40% Styrene

[0119] A nitrogen purged jacketed steel reactor was charged with 3.53 pounds of anhydrous hexane, 1.68 pounds of 32.2 wt% styrene in hexane, and 4.57 pounds of 21.0 wt% butadiene in hexane. The reactor jacket temperature was set to 145° F. and then the reactor was charged with a mixture of n-butyllithium (3.49 mL, 1.6 M in hexane, 0.820 mmol per 100 grams of monomer) and hexamethyleneimine (HMI) (1.67 mL, 3.0 M in cyclohexane, 0.9 equivalents relative to Li), followed by 2,2-bis(2′-tetrahydrofuryl)propane (0.14 mL, 1.6 M in hexane, 0.04 equivalents relative to Li) and potassium tert-amylate (0.39 mL, 0.90 M in cyclohexane, 0.078 equivalents relative to Li). The batch temperature peaked at about 177.1° F. after about 38 minutes. Tin tetrachloride (0.91 mL, 1.0 M in heptane, 0.163 equivalents relative to Li) was charged to the reactor at the peak temperature. After an additional 30 minutes, the polymerization reaction was quenched by dropping the polymer cement into a bucket containing about 8 L of isopropyl alcohol and 15 g of 2,6-di-tert-butyl-4-methylphenol. The polymer was coagulated and drum-dried. The polymer was analyzed by GPC, NMR, DSC, and TN analysis, and the values ​​are reported in Table 2.

[0120] Example 1-2. Synthesis of SBR-g-TMDS propylpiperidine in THF To SBR (50 g) dissolved in THF to a total volume of 600 mL was added silylating agent (5 wt%, 2.5 g, 9.63 mmol) and a solution of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in xylene Pt approx. 2% (1 mL). The bottle was stirred in a 50°C water bath for 8 hours, and the bottle was quenched with 3 mL of IPA / BHT solution (approx. 0.1 g BHT / mL IPA solution), poured into a bucket of IPA / BHT solution, coagulated, and drum-dried. The polymer was analyzed by GPC, NMR, DSC, and TN techniques and the values ​​are reported in Table 2.

[0121] Example 1-3. Synthesis of SBR-g-TMDS propylpiperidine in hexane

[0122] To SBR (50 g) dissolved in hexane to a total volume of 600 mL was added silylating agent (5 wt%, 2.5 g, 9.63 mmol) and a solution of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in xylene Pt approx. 2% (1 mL). The bottle was stirred overnight in a water bath at 80° C., the bottle was quenched with 3 mL of IPA / BHT solution (approx. 0.1 g BHT / mL IPA solution), poured into a bucket of IPA / BHT solution, coagulated, and drum-dried. The polymer was analyzed by GPC, NMR, DSC, and TN techniques and the values ​​are reported in Table 2.

[0123] Example 1-4. Synthesis of SBR-g-TMDS propylpiperidine in toluene

[0124] To SBR dissolved in toluene to a total volume of 600 mL was added silylating agent (5 wt%, 2.5 g, 9.63 mmol) and a solution of platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in xylene Pt approx. 2% (1 mL). The bottle was stirred overnight in a water bath at 80° C., the bottle was quenched with 3 mL of IPA / BHT solution (approx. 0.1 g BHT / mL IPA solution), poured into a bucket of IPA / BHT solution, coagulated, and drum-dried. The polymer was analyzed by GPC, NMR, DSC, and TN methods, and the values ​​are reported in Table 2.

[0125] [Table 2] Table 2 shows the analytical results characterized by GPC, NMR, DSC, and TN test methods. Example 1-1 represents the base SBR used as a control for comparison with the hydrosilylated SBRs (Examples 1-2, 1-3, and 1-4).

[0126] Compositions Comprising Silylated Polymers

[0127] The polymer composition was mixed in a 65g Brabender mixer using natural rubber (NR), BR, and the SBR polymers mentioned above. The masterbatch and remill stages were mixed for 6 and 5 minutes, respectively, at 60 rpm with a starting temperature of 125°C. All stocks were mixed into the masterbatch for approximately 2-3 minutes at 150°C-160°C to achieve the silanization step. The final stage was mixed for 2 minutes at 50 rpm with a starting temperature of 90°C. The green rubber was cured for 33 minutes at 145°C based on MDR torque measurements.

[0128] In accordance with the patent statutes, the best mode and preferred embodiment have been described, and the scope of the invention is not limited thereto, but rather by the appended claims.

Claims

1. 1. A curable polymer composition comprising:

1. A silylated polydiene polymer comprising: i) a polydiene; and ii) a silylated polydiene polymer having the following formula: 【Chemistry 1】 wherein n is an integer from 0 to 150; each R is individually a hydrogen atom, a halogen atom, Fg, or a monovalent organic group, or two or more R groups together form a bond or a polyvalent organic group, provided that at least one R is a hydrogen atom; Fg is a compound of the formula CH ２ = C(R １ ) (R ２ ) (wherein, R １ and R ２ At least one of R and R has a functional group that can participate in hydrogen bonding, chemical reaction with a filler, or grafting of a polymer; ２ one of which may be a hydrogen atom or an organic group), or 【Chemistry 2】 (wherein R is a hydrogen atom, a halogen atom, Fg, or a monovalent organic group, Fg is as defined above, and n is 2 to 5); and a silylated polydiene polymer comprising the reaction product of a non-silylated polydiene polymer comprising one or more of natural rubber, styrene-butadiene copolymer, and poly(1,3-butadiene); and a filler comprising one or more of carbon black and silica.

2. 2. The composition of claim 1, wherein the silylated polydiene polymer comprises one or more of: a) a copolymer of butadiene and a comonomer that is one or more of an aromatic vinyl compound and a conjugated diene; and b) poly(1,3-butadiene).

3. The aromatic vinyl compound is selected from the group consisting of styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-dimethylstyrene, 2,4,6-trimethylstyrene, α-methylstyrene, 2,4-diisopropylstyrene, 4-tert-butylstyrene, stilbene, vinylbenzyldimethylamine, (4-vinylbenzyl)dimethylaminoethyl ether, N,N-dimethylaminoethylstyrene, tert-butoxystyrene, vinylpyridine, 1,2-divinylbenzene, 1,3-divinylbenzene, and 1,4-divinylbenzene.

3. The composition of claim 2, wherein the aromatic vinyl compound comprises 0 to 50 weight percent of the total monomer content of the copolymer, and the conjugated diene is isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene, 1,3-hexadiene, 1,3-heptadiene, 1,3-octadiene, 2-methyl-2,4-pentadiene, cyclopentadiene, 2,4-hexadiene, 1,3-cyclohexadiene, or 1,3-cyclooctadiene, or a combination thereof.

4. 4. The composition of claim 2 or 3, wherein the copolymer is a styrene-butadiene copolymer, a poly(butadiene) homopolymer, a butadiene-isoprene copolymer, or a styrene-isoprene-butadiene copolymer, and the styrene content is from 5 to 50 weight percent of the total monomer content of the copolymer.

5. 5. The composition of claim 1, wherein the filler is present in an amount of about 1 part by weight to about 110 parts by weight, based on 100 parts by weight of the combined total of the silylated polydiene polymer and the non-silylated polydiene polymer.

6. 6. The composition of any one of claims 1 to 5, wherein the non-silylated polydiene polymer further comprises one or more of butyl rubber, polybutadiene, synthetic polyisoprene, polyisoprene and ethylene-diene copolymers, styrene-butadiene copolymers, butadiene-isoprene copolymers, styrene-isoprene copolymers, styrene-isoprene-butadiene copolymers, and ethylene-butadiene copolymers.

7. 7. The composition of any one of claims 1 to 6, wherein the silylated polydiene polymer is present in an amount of about 10 parts by weight to about 75 parts by weight, based on 100 parts by weight of the combined total of the silylated polydiene polymer and the non-silylated polydiene polymer.

8. The composition of any one of claims 1 to 7, wherein the non-silylated polydiene polymer comprises two or more different polymers.

9. The composition of claim 8, wherein the non-silylated polydiene polymers include butyl rubber, poly(butadiene), natural rubber, and styrene-butadiene copolymers.

10. 10. The composition of any one of claims 1 to 9, wherein the silylated polydiene polymer is present in an amount of about 15 parts by weight to about 50 parts by weight, based on 100 parts by weight of the combined total of the silylated polydiene polymer and the non-silylated polydiene polymer.

11. The composition of any one of claims 1 to 10, wherein the silylated polydiene polymer has a backbone grafted nitrogen-containing functional group concentration ranging from about 50 ppm to about 2000 ppm.

12. The composition of any one of claims 1 to 11, wherein the filler comprises silica in an amount of about 1 part by weight to about 120 parts by weight based on 100 parts by weight of total polymer.

13. The composition of any one of claims 1 to 12, wherein the polymer has a weight average molecular weight of about 75,000 g / mol to about 1,000,000 g / mol.

14. The composition of any one of claims 1 to 12, wherein the polymer has a number average molecular weight of about 75,000 g / mol to about 1,000,000 g / mol.

15. A tire comprising the composition of any one of claims 1 to 14.

16. A cured polymer composition obtainable by curing the polymer composition according to any one of claims 1 to 14.

17. 20. An article comprising at least one component formed from the vulcanized polymer composition of claim 16.

18. A method for curing the curable polymer composition according to any one of claims 1 to 14, comprising the steps of: obtaining said polymer composition; and curing the polymer composition utilizing a curing agent.

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