Amino and Siloxane Functionalized Polymers

Abstract

1. A process for producing a functionalized diene polymer, comprising: (i) preparing a diene polymer by a polymerization reaction to produce a reaction mixture comprising a diene polymer having reactive polymer chain ends; (ii) reacting a diene polymer represented by formula (I) (iii) reacting a reaction mixture containing the first reaction product with a first functionalizing reagent according to formula (II): to produce a functionalized diene polymer having at least one amino group and at least one siloxane group, wherein the diene polymer comprises at least 51 wt. % of units derived from 1,3-butadiene, based on the total weight of the polymer; in formula (I), R1 and R2, independently of each other and of each unit n, represent hydrogen or an organic residue having a hydrogen atom and 1 to 24 carbon atoms, the organic residue optionally further comprising one or more heteroatoms selected from O, S, N, Si, and combinations thereof; and in formula (II), R' A process in which R1, R'2, and R3, independently of one another, represent a hydrogen atom and an organic residue having 1 to 24 carbon atoms, the organic residue optionally further comprising one or more heteroatoms selected from O, S, N, Si, and combinations thereof; A represents a divalent alkylene unit having 1 to 6 carbon atoms in the alkylene unit, the alkylene group being unsubstituted or substituted, in which case at least one hydrogen atom of the alkylene unit is replaced with a hydrogen atom and an organic residue having 1 to 24 carbon atoms, the organic residue optionally further comprising one or more heteroatoms selected from O, S, N, Si, and combinations thereof. Also provided are polymers obtainable by the process and articles containing the polymers or cured versions thereof, as well as methods for making such articles.

Description

[Background technology]

[0001] Diene-based polymers are widely used commercially as rubber components in rubber compositions, such as tires and other articles. These polymers reduce rolling resistance due to their excellent dynamic mechanical properties. It is known that the rolling resistance of rubber articles can be further reduced by improving the interaction between diene polymers and fillers typically present in such articles. Modifying the polymer to create functional groups can improve the interaction between the polymer and filler. Many methods are known for modifying diene rubbers with various chemically distinct modifiers. For example, diene polymers with aminosiloxane end groups are reported in EP 1 457 501 and WO 2006 / 076629. The polymer is functionalized by reacting the polymer chain with a cyclic silane amino-functionalizing agent. Nevertheless, there is a continuing need for improved or alternative functionalized diene polymers. [Prior art documents] [Patent documents]

[0002] [Patent Document 1] European Patent No. 1457501 [Patent Document 2] International Publication No. 2006 / 076629 Summary of the Invention [Means for solving the problem]

[0003] In one aspect, there is provided a process for producing a functionalized diene polymer, comprising: (i) preparing a diene polymer by a polymerization reaction to produce a reaction mixture comprising a diene polymer having reactive polymer chain ends; (ii) Formula (I) [ka] reacting a first functionalizing reagent according to formula (I) with a reactive polymer chain end to obtain a first reaction product; (iii) reacting the reaction mixture containing the first reaction product with a compound represented by formula (II) [ka] to form a functionalized diene polymer having at least one amino group and at least one siloxane group. Including, the diene polymer comprises at least 51 wt. % of units derived from 1,3-butadiene, based on the total weight of the polymer; In formula (I), R1 and R2, independently of each other and of each unit n, represent hydrogen or an organic residue having a hydrogen atom and 1 to 24 carbon atoms, the organic residue optionally further comprising one or more heteroatoms selected from O, S, N, Si, and combinations thereof, and n represents 3, 4, 5, 6, 7, or 8; In formula (II), R'1, R'2 and R3 each independently represent an organic residue containing a hydrogen atom and 1 to 24 carbon atoms, and the organic residue optionally further contains one or more heteroatoms selected from O, S, N, Si and combinations thereof; A represents a divalent alkylene unit having 1 to 6 carbon atoms in the alkylene unit, the alkylene group can be unsubstituted or substituted, wherein at least one of the hydrogen atoms of the alkylene unit is replaced with a hydrogen atom and an organic residue comprising 1 to 24 carbon atoms, the organic residue optionally further comprising one or more heteroatoms selected from O, S, N, Si, and combinations thereof.

[0004] In another aspect of the present disclosure, there is provided a functionalized diene polymer obtainable by this process.

[0005] In yet another aspect of the present disclosure, there is provided a curable compound comprising a functionalized diene polymer and at least one curative for curing the functionalized diene polymer, optionally further comprising at least one rubber other than the functionalized polymer, at least one filler, or a combination thereof.

[0006] In a further aspect of the present disclosure, there is provided a method of making a curable rubber compound, the method comprising combining at least one functionalized diene polymer with at least one rubber component selected from at least one curative for curing the functionalized diene polymer, at least one filler, at least one rubber other than the functionalized diene polymer, or combinations thereof.

[0007] In yet another aspect of the present disclosure, an article is provided comprising the reaction product of a curing reaction, the curing reaction comprising curing a composition comprising a functionalized diene polymer and at least one curing agent.

[0008] In a further aspect of the present disclosure, there is provided a method of making an article, comprising subjecting a functionalized diene polymer to curing and shaping, wherein shaping can occur before, after, or during curing. DETAILED DESCRIPTION OF THE INVENTION

[0009] This disclosure is further illustrated in the detailed description below. In the description below, reference may be made to specific standards (e.g., ASTM, DIN, ISO, etc.). Unless otherwise specified, the standards will be used in the version that came into effect on October 1, 2020. If a version was not valid on that date, for example, if the standard has expired, the version that came into effect closest to October 1, 2020 will be referenced.

[0010] In the following description, the amounts of components of a composition or polymer may be referred to interchangeably by "weight percent," "wt%," or "% by weight." The terms "weight percent," "wt%," or "% by weight" are based on the total weight of the composition or polymer, respectively, which total weight corresponds to 100% unless otherwise specified. The term "phr" means "parts by weight per 100 parts by weight of rubber." This term is used in rubber compounding such that the amounts of components of a rubber composition are based on the total amount of rubber in the rubber compound. The amounts of one or more components of a composition (parts by weight of one or more components) are based on 100 parts by weight of rubber.

[0011] Ranges identified in this disclosure are meant to include and disclose all values ​​between the endpoints of the range, as well as the endpoints, unless otherwise specified.

[0012] The term "comprising" is used in an open, non-limiting sense. The phrase "a composition comprising components A and B" means to include components A and B, but the composition may also have additional components. In contrast to the use of "comprising," the word "consisting of" is used in a narrow, restrictive sense. The phrase "a composition consisting of components A and B" is meant to describe a composition that contains components A and B but does not contain additional components.

[0013] Functionalized Diene Polymers The diene polymers according to the present disclosure are functionalized to have at least one amino group and at least one siloxane group.

[0014] The diene polymers according to the present disclosure are curable and can be cured to make articles or components of articles. Articles made with diene rubbers typically contain functionalized diene polymers in their cured state.

[0015] The diene polymer is preferably a butadiene polymer, including homopolymers and copolymers of 1,3-butadiene. Preferably, the diene polymer according to the present disclosure comprises at least 51 wt%, preferably at least 60 wt%, of units derived from 1,3-butadiene, based on the weight of the polymer. In one embodiment of the present disclosure, the diene polymer comprises at least 60 wt%, or at least 75 wt%, of units derived from 1,3-butadiene, based on the total weight of the polymer.

[0016] In one embodiment of the present disclosure, the diene polymer comprises from 0 wt % or 1 wt % up to 49 wt %, or from 0 wt % or 1 wt % up to 40 wt %, of units derived from one or more comonomers, based on the total weight of the polymer.

[0017] In one embodiment of the present disclosure, the diene polymer comprises at least 60 wt % or at least 70 wt % of units derived from 1,3-butadiene and 0 wt % or 1 wt % up to 40 wt %, or 0 wt % or 1 wt % up to 30 wt % of units derived from one or more comonomers, based on the total weight of the polymer.

[0018] Suitable comonomers include, but are not limited to, conjugated dienes preferably having 5 to 24 carbon atoms, more preferably 5 to 20. Specific examples of conjugated dienes include, but are not limited to, isoprene, 1,3-pentadiene, 2,3-dimethyl-butadiene, 1-phenyl-1,3-butadiene, 1,3-hexadiene, myrcene, ocimene, farnesene, and combinations thereof.

[0019] In one embodiment of the present disclosure, the diene polymer contains 0 wt. % or 1 wt. % to a maximum of 20 wt. % of units derived from one or more conjugated dienes other than 1,3-butadiene. Suitable comonomers also include vinyl aromatic comonomers, preferably vinyl aromatic comonomers having 8 to 30 carbon atoms. Specific examples of vinyl aromatic comonomers include, but are not limited to, styrene, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, para-butylstyrene, vinylnaphthalene, divinylbenzene, trivinylbenzene, divinylnaphthalene, 4-ethenyl-N,N-dimethylbenzylamine, 3-ethenyl-N,N-dimethylbenzylamine, 2-ethenyl-N,N-dimethylbenzylamine, 1-[(4-ethenylphenyl)methyl]pyrrolidine, 1-[(3-ethenylphenyl)methyl]pyrrolidine, 1-[(2-ethenylphenyl)methyl]pyrrolidine, and combinations thereof.

[0020] In one embodiment of the present disclosure, the diene polymer comprises up to 49 wt.%, preferably 5-40 wt.%, of units derived from one or more vinyl aromatic comonomers. Preferably, the diene polymer of the present disclosure comprises up to 49 wt.%, or 0-40 wt.%, of units derived from styrene, based on the weight of the polymer.

[0021] Suitable comonomers further include one or more α-olefins such as ethene, propene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and combinations thereof.

[0022] In one embodiment of the present disclosure, the diene polymer comprises 0% or 1% up to 20% by weight of units derived from ethene, propene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and combinations thereof.

[0023] Suitable comonomers also include, but are not limited to, one or more other copolymerizable comonomers that introduce functional groups, including crosslinking sites, branching sites, branching, or functionalizing groups. In one embodiment of the present disclosure, the diene polymer comprises 0% or 0.1% up to 10% or 0% or 0.1% up to 5% by weight, based on the weight of the polymer, of units derived from one or more of such other comonomers.

[0024] Combinations of one or more comonomers of the same chemical type as those mentioned above and combinations of one or more comonomers of different chemical types may be used.

[0025] The diene polymers according to the present disclosure preferably have a Mooney viscosity ML1+4 at 100° C. of from 10 to 200 Mooney units, for example from 30 to 150 or from 35 to 85 Mooney units.

[0026] The diene polymers according to the present disclosure preferably have a number average molecular weight (Mn) of 10,000 to 2,000,000 g / mol or 100,000 to 1,000,000 g / mol, for example, 100,000 to 400,000 g / mol or 200,000 to 300,000 g / mol. In one embodiment of the present disclosure, the polymer has a Mn of 150 to 320 kg / mol.

[0027] The diene polymers according to the present disclosure preferably have a molecular weight distribution (MWD) of 1.0 to 15, for example, 1.0 to 5. In one embodiment of the present disclosure, the polymers have an MWD of 1.0 to 3.5 or 1.0 to 2.0. MWD is the ratio of the weight average molecular weight (Mw) to the number average molecular weight Mn, i.e., MWD is equal to Mw / Mn.

[0028] Typically, the diene polymers according to the present disclosure are rubbers. Rubbers typically have a glass transition temperature of less than 20°C. The diene polymers according to the present disclosure preferably have a glass transition temperature (Tg) of from -120 to less than 20°C. In preferred embodiments of the present disclosure, the polymers have a Tg of from 0 to -110°C or from -10 to -80°C. In one embodiment of the present disclosure, the butadiene polymers have a glass transition temperature of about -10 to -70°C.

[0029] In one embodiment of the present disclosure, the diene polymer has a number average molecular weight of 100,000 to 1,000,000, a Mooney viscosity ML1+4 at 100°C of 30 to 150 units, and a glass transition temperature of -110°C to 0°C.

[0030] In one embodiment, the diene polymer according to the present disclosure has a Mooney viscosity ML1+4 at 100°C of 30 to 150 units, a molecular weight of 100,000 to 400,000 g / mol, a glass transition temperature of -110°C to 0°C, and a molecular weight distribution (MWD) of 1.0 to 20.

[0031] Process for producing functionalized diene polymers The functionalized diene polymers according to the present invention are obtained by polymerization of butadiene, with or without comonomers, and reaction with first and second functionalizing reagents.

[0032] The diene polymers according to the present disclosure can be obtained by anionic polymerization or polymerization using a coordination catalyst. Coordination catalysts in this context include Ziegler-Natta catalysts and single-metal catalyst systems. Preferred coordination catalysts include catalysts based on Ni, Co, Ti, Zr, Nd, Gd, V, Cr, Mo, W, or Fe. Preferably, the diene polymers are obtained by polymerization, including anionic polymerization.

[0033] Anionic polymerization of diene polymers is known in the art. Suitable initiators for anionic solution polymerization include organic alkali metal compounds and organic alkaline earth metal compounds. Specific examples of initiators include methyllithium, ethyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, pentyllithium, n-hexyllithium, cyclohexyllithium, octyllithium, decyllithium, 2-(6-lisio-n-hexyloxy)tetrahydropyran, 3-(tert-butyldimethylsiloxy)-1-propyllithium, phenyllithium, 4-butylphenyllithium, 1-naphthyllithium, p-toluyllithium and allyllithium compounds, initiators derived from tertiary N-allylamine, such as [1-(dimethylamino)-2- Examples of suitable initiators include [1-[bis(phenyl-methyl)amino]-2-propenyl]lithium, [1-(diphenylamino)-2-propenyl]lithium, [1-(1-pyrrolidinyl)-2-propenyl]lithium, lithium amides of secondary amines, such as lithium pyrrolidide, lithium piperidide, lithium hexamethyleneimide, lithium 1-methylimidazolidide, lithium 1-methylpiperazide, lithium 4-methylpiperidide, lithium 3-methylpiperidide, lithium morpholide, lithium dicyclohexylamide, lithium dibenzylamide, and lithium diphenylamide. Bifunctional and polyfunctional organolithium compounds, such as 1,4-dilithiobutane and dilithium piperazide, can also be used. Preferred initiators include n-butyllithium and sec-butyllithium.

[0034] Regulators known in the art for regulating the microstructure of the polymer, for example its content of vinyl units, can be used in the polymerization.Such regulators include, for example, diethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol di-n-butyl ether, ethylene glycol di-tert-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-butyl ether, diethylene glycol di-tert-butyl ether, 2-(2-ethoxyethoxy)-2-methyl-propane. , triethylene glycol dimethyl ether, tetrahydrofuran, ethyl tetrahydrofurfuryl ether, hexyl tetrahydrofurfuryl ether, 2,2-bis(2-tetrahydrofuryl)propane, dioxane, trimethylamine, triethylamine, N,N,N',N'-tetramethyl-ethylenediamine, N-methylmorpholine, N-ethylmorpholine, 1,2-dipiperidinoethane, 1,2-dipyrrolidinoethane, 1,2-dimorpholinoethane, and potassium and sodium salts of alcohols, phenols, carboxylic acids, and sulfonic acids.

[0035] Preferably, the polymerization is carried out in a solution, preferably using an inert aprotic solvent. Suitable inert aprotic solvents include saturated aliphatic hydrocarbons, alkenes, and aromatic hydrocarbons. Specific examples of saturated aliphatic hydrocarbons include butane, pentane, hexane, heptane, octane, decane, and cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, and 1,4-dimethylcyclohexane. Specific examples of suitable alkenes include 1-butene. Specific examples of suitable aromatic hydrocarbons include benzene, toluene, ethylbenzene, xylene, diethylbenzene, or propylbenzene. Solvents can also be used in combination with each other or with one or more polar solvents. Preferred solvents include cyclohexane, methylcyclopentane, and n-hexane.

[0036] Generally, the solvent can be used in an amount of about 100 to about 1000 g, preferably 200 to 700 g, per 100 g of monomer.

[0037] Preferably, the polymerization is carried out by introducing the monomer and solvent, followed by adding a polymerization initiator or initiator system to initiate the polymerization and optionally activating it. Other known methods of carrying out polymerization, such as continuously feeding at least one feed stream containing solvent, monomer, and initiator, and feeding at least one product stream from a reaction vessel, can also be used. The polymerization can be carried out as a batch polymerization or a continuous polymerization.

[0038] The reaction is usually carried out at a pressure of 1 to 10 bar. Typical reaction pressures include 3 to 8 bar.

[0039] The molecular weight, molecular weight distribution, and Mooney viscosity of the polymer can be controlled, as known in the art, for example, by using chain transfer agents or by adjusting the monomer feed, amount of initiator, and reaction rate. The glass transition temperature of the polymer can be controlled, for example, by the composition and amount of monomers and comonomers.

[0040] The polymerization reaction forms reactive polymer chain ends. At least one first functionalizing reagent is added to react with the reactive chain ends of the polymer to provide a first functionalized polymer as the reaction product. At least one second functionalizing reagent is added to and reacts with the reaction product.

[0041] The first functionalizing reagent is preferably a cyclosiloxane. Suitable cyclosiloxanes have the general formula (I): [ka] wherein n represents 3, 4, 5, 6, 7, or 8; R1 and R2, independently of each other and of each n unit, represent hydrogen or an organic residue containing hydrogen atoms and 1 to 24 carbon atoms, which organic residue may contain, in addition to carbon and hydrogen atoms, one or more heteroatoms selected from O, S, N, Si, and -Si-O-.

[0042] Preferably, in formula (I), R1 and R2, independently of each other and of each n unit, represent hydrogen, an alkyl group, an alkenyl group, or a C6-C20 aryl group, i.e., an aryl group having 6 to 20 carbon atoms. The alkyl preferably has 1 to 20 carbon atoms, more preferably 1 to 6 carbon atoms. The alkenyl group preferably has 2 to 20 carbon atoms, preferably 2 to 6 carbon atoms. The alkyl, aryl, and alkenyl residues may be unsubstituted or substituted, in which case at least one hydrogen atom of the residue is substituted with a substituent selected from halogen (preferably Cl or F), alkylamino, alkylphosphino, alkylsilyl, n(alkylamino)alkyl, (alkylphosphino)alkyl, (alkylsilyl)alkyl groups, and combinations thereof. Each substituent other than the halogen preferably has 1 to 19 carbon atoms and may be unsubstituted or substituted, in which case at least one hydrogen atom of the substituent is replaced by another substituent, which is preferably selected from the halogens, preferably Cl or F.

[0043] In certain embodiments of the present disclosure, in formula (I), R1 is selected from methyl, ethyl, or phenyl, independently of n. In preferred embodiments, R1 is the same for each unit n and is selected from methyl, ethyl, or phenyl. Preferably, R2 is selected from hydrogen, methyl, ethyl, phenyl, diphenylphosphinomethyl, diphenylphosphinoethyl, and vinyl (-CH=CH2), and n is 3, 4, or 5. In another specific embodiment of the present disclosure, R1 and R2 are both methyl, and n is 3, 4, or 5.

[0044] Specific examples of suitable cyclosiloxanes according to formula (I) include, but are not limited to, 2,2,4,4,6,6-hexamethylcyclotrisiloxane, 2,2,4,4,6,6,8,8-octamethyl-cyclotetrasiloxane, 2,2,4,4,6,6,8,8,10,10-decamethylcyclopentasiloxane, 2,2,4,4,6,6,8,8,10,10,12,12-dodecamethylcyclohexasiloxane, 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane, 2,4,6-trimethyl-2,4,6-triphenylcyclotrisiloxane, 2,4,6-trimethylcyclotrisiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetramethylcyclotrisiloxane, vinylcyclotetrasiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetraphenylcyclotetrasiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, 2,2,4,4,6,6-hexaphenylcyclotrisiloxane, 2,2,4,4,6,6,8,8-octaphenylcyclotetrasiloxane, 2,4,6,8,10-pentamethylcyclopentasiloxane, 2,4,6,8,10-pentamethyl-2,4,6,8,10-pentavinylcyclopentasiloxane, 2,4,6,8-tetraethylcyclotetrasiloxane, and 2,4,6,8-tetramethyl-2,4,6,8-tetrakis(2-diphenylphosphinoethyl)cyclotetrasiloxane. Preferred examples include, but are not limited to, 2,2,4,4,6,6-hexamethylcyclotrisiloxane and 2,2,4,4,6,6,8,8-octamethylcyclotetrasiloxane.

[0045] The first functionalizing reagent itself can be added as a solution or suspension. Two or more different functionalizing reagents according to general formula (I) can be added simultaneously or sequentially, for example. When the polymer chain ends are still reactive, for example, when at least 90% of the monomers have been consumed, preferably after 99% of the monomers have been consumed, the first functionalizing reagent is preferably added toward the end of the polymerization reaction. Preferably, the functionalizing reagent is added to the polymerization reaction mixture. If necessary, the temperature of the reaction mixture can be lowered or raised before, during, or after the addition, but the reaction of at least one first functionalizing reagent with the reactive polymer chain ends can be carried out at the same temperature as used for the polymerization reaction. The temperature of the reaction mixture can be lowered or raised as needed, for example, to increase, decrease, or control the rate of reaction with the first functionalizing reagent.

[0046] Preferably, the first functionalizing reagent is added in an amount sufficient to allow all reactive polymer chain ends to react, although in some cases, for example, when a high degree of variation in the different chain ends is to be maintained, it may be desirable to add the reagent in a smaller amount. Typical amounts include 0.2 to 2 molar equivalents of the functionalizing reagent based on the total molar amount of initiator used in the polymerization. Preferably, the total amount of cyclosiloxane according to formula (I) corresponds to 0.1 to 1.5 molar equivalents of the total molar amount of initiator used in the polymerization.

[0047] At least one second functionalizing reagent is added. Preferably, the second functionalizing reagent is added to the reaction mixture after the reaction of the polymer chain ends with the first reactant is complete, but its addition can begin earlier and overlap with the addition of the first functionalizing reagent. Preferably, the second functionalizing reagent is added directly to the reaction mixture.

[0048] Typically, the second functionalizing reagent is a compound of the general formula (II): [ka] Corresponding to, wherein R'1, R'2 and R3 each independently represent an organic residue containing a hydrogen atom and 1 to 24 carbon atoms, and optionally further containing one or more heteroatoms selected from O, S, N, Si and combinations thereof; A represents a divalent alkylene unit having 1 to 6 carbon atoms in the alkylene unit, the alkylene group can be unsubstituted or substituted, in which case at least one of the hydrogen atoms can be replaced by a substituent selected from halogen, preferably Cl and F, and an organic residue containing a hydrogen atom and 1 to 24 carbon atoms, the organic residue optionally further containing one or more heteroatoms selected from O, S, N, Si, and combinations thereof.

[0049] Preferably, in formula (II), R3 represents a linear or branched C1-C12 alkyl group, i.e., an alkyl group having 1 to 12 carbon atoms. The C1-C12 alkyl group may be unsubstituted or substituted, in which case at least one hydrogen atom of the group is substituted with a substituent selected from halogen, alkoxy group, alkoxysilyl group, (alkoxysilyl)alkyl group, alkylsilyl group, (alkylsilyl)alkyl group, (alkylamino)alkyl group, alkylamino group, and combinations thereof, and each substituent other than the halogen may include another substituent selected from halogen, phenyl, benzyl, alkylphenyl, and alkylbenzyl. Preferably, the halogen is selected from Cl and F. Typically, each substituent other than the halogen has 1 to 20 carbon atoms. More preferably, R3 represents a trialkoxysilylalkyl, for example selected from trialkoxybutyl, trialkoxypropyl, trialkoxyethyl and trialkoxymethyl, and preferably the trialkoxy residue is selected from trimethyloxy-, triethyloxy-, tripropyloxy-, tributyloxy-, tripentyloxy- and trihexyloxy-.

[0050] Preferably, in formula (II), R'1 and R'2 independently represent a C1-C12 alkyl residue, which may be linear or branched. More preferably, R'1 and R'2 independently represent a C1-C6 alkyl residue, more preferably a C1-C3 alkyl residue.

[0051] Preferably, in formula (II), A represents ethylene, propylene, or butylene, so that the resulting molecule is respectively azasilacyclobutane, azasilacyclopentane, or azasilacycloheptane. The ethylene, propylene, or butylene residue may be substituted, in which case at least one hydrogen atom of the residue is replaced by a halogen, preferably Cl or F, a C1-C7 alkyl group, preferably methyl or ethyl, or an aryl group (preferably a phenyl group) or an alkylaryl group (preferably an alkylphenyl group), an (alkylaryl)alkyl group, or an arylalkyl group (preferably a benzyl group), each of the alkyl or aryl residues of the substituents may carry one or more further substituents selected from a halogen, preferably Cl or F. Preferably, A is selected from ethylene, propylene and substituted propylenes, including but not limited to propylene substituted once or twice with C1-C6 alkyl groups, including but not limited to 2-methylpropylene, 2,2-dimethylpropylene, 1,2-dimethylpropylene, 1,3-dimethylpropylene, 2-ethyl-propylene, 2,2-diethylpropylene, 1,2-diethylpropylene, 2-propyl-propylene, 2,2-dipropylpropylene and 1,2-dipropylpropylene.

[0052] Specific examples of functionalizing reagents according to formula (II) include, but are not limited to, 2,2-diethoxy-1-[3-(triethoxysilyl)propyl]-1-aza-2-silacyclopentane and 1-ethyl-2,2-dimethoxy-4-methyl-1-aza-2-silacyclopentane.

[0053] The second functionalizing reagent can be added in solution or suspension by itself. Two or more different second functionalizing reagents can be added simultaneously or sequentially. The reaction of the second functionalizing reagent with the polymer functionalized by the first functionalizing reagent can be carried out at the same temperature used for the polymerization reaction, but if necessary, the temperature can be increased or decreased before, during, or after the addition of the second functionalizing reagent. If necessary, the temperature can be increased or decreased, for example, to increase, decrease, or control the rate of reaction with the first functionalizing reagent.

[0054] The second functionalizing reagent can be added in an amount effective to convert all of the first end groups, i.e., an equimolar amount or a molar excess. However, it may be desirable not to convert all of the end groups and to add the second functionalizing reagent in a less equimolar amount. Typically, the total amount of the second functionalizing reagent added can be in the range of 0.2 to 2 molar equivalents, preferably 0.6 to 1.5 molar equivalents, based on the molar amount of the first functionalizing reagent used.

[0055] Reaction of the second functionalizing reagent with the polymer chain and the reaction product of the first functionalizing reagent produces a functionalized polymer having at least one amino group and at least one siloxane group. Preferably, the polymer has the formula (III): [ka] wherein R1, R2, R'1, R'2, R3, A and n have the same meanings as above for formulas (I) and (II).

[0056] One or more coupling reagents known in the art for anionic or catalytic diene polymerization may be added to the reaction mixture. Examples of such coupling reagents include silicon tetrachloride, tin tetrachloride, tetraalkoxysilane, 2,2-dimethoxy-1-thia-2-silacyclopentane, (3-glycidoxypropyl)trimethoxysilane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, and N,N,N',N'-tetraglycidyl-1,3-bis(aminomethyl)cyclohexane. The coupling reagent may be added before, after, or simultaneously with the addition of the compound of formula (II).

[0057] The functionalized polymer can be isolated by methods known in the art. The solvent can be removed from the reaction mixture by, for example, distillation, steam stripping, or application of vacuum, as known in the art. For example, an antioxidant known in the art can be added before or during the work-up process, preferably before solvent removal. Examples of suitable antioxidants include sterically hindered phenols, aromatic amines, phosphites, and thioethers. Extender oils known in the rubber processing and compounding art can be added to the reaction mixture, preferably before solvent removal, to provide, for example, an oil-extended functionalized diene polymer. Suitable extender oils include TDAE (treated distilled aromatic extract) oil, MES (mild extractive solvate) oil, RAE (residual aromatic extract) oil, TRAE (treated residual aromatic extract) oil, naphthenic oil, or vegetable-based oil.

[0058] The functionalized polymers according to the present disclosure can be shaped for storage or handling or further processing into compounds or articles. The polymers can be shaped into forms such as bales, pellets, powders, sheets, or granules.

[0059] The diene polymers according to the present disclosure are curable. The polymers can be crosslinked (cured), for example, by reaction or activation of one or more curatives, to produce a "vulcanizate," i.e., a crosslinked rubber article. However, the polymers according to the present disclosure can also be provided in an uncured or partially crosslinked form, meaning that they have been crosslinked to some extent but can still be further crosslinked.

[0060] In one aspect of the present disclosure, a composition is provided comprising at least one functionalized diene polymer of the present disclosure. Such a composition may comprise at least 90 wt. %, preferably at least 96 wt. %, of one or more butadiene polymers according to the present disclosure, based on the total weight of the composition. Such a composition may be in the form of a powder, granules, extruded pellets or strands, or in the form of a sheet or bale. In one embodiment, the composition contains at least 90 wt. % or at least 96 wt. % of one or more curable polymers according to the present disclosure, and the composition does not contain a curative. Such a composition may be used, for example, to produce a rubber compound.

[0061] Compound The rubber compound typically comprises at least 5 wt. % of at least one functionalized diene polymer according to the present disclosure, based on the weight of the compound, and at least one component for making a rubber composition, typically including at least one curative, at least one filler, or a combination thereof.

[0062] Thus, in another aspect of the present disclosure, there is provided a rubber composition comprising at least one diene polymer according to the present disclosure, at least one curative, at least one filler, or a combination thereof. The rubber composition (also referred to in the art as a "compound") may be in the form of, for example, powder, granules, extruded pellets or strands, or in the form of a sheet or bale.

[0063] Filler Conventional fillers known in the art may be used. Preferably, the rubber composition comprises at least one filler, preferably a filler suitable for application in tires, tire components, and materials for manufacturing tires. Preferably, the filler comprises one or more silicon oxides, one or more carbon blacks, or a combination of one or more silicon oxides and one or more carbon blacks. Preferably, the filler has a viscosity of 5 to 1,000 m. 2 / g, preferably 20 to 400m 2 The fillers preferably include silica-containing particles having a BET surface area (nitrogen absorption) of 1000 nm / g. Such fillers can be obtained, for example, by precipitation from a solution of silicate salts or by flame hydrolysis of silicon halides. The silica filler particles can have a particle size of 10 to 400 nm. The silica-containing filler can also contain oxides of Al, Mg, Ca, Ba, Zn, Zr, or Ti. Other examples of silicon oxide-based fillers include aluminum silicate, 20 to 400 nm. 2 Examples of fillers include alkaline earth metal silicates, such as magnesium silicate or calcium silicate, preferably having a BET surface area of ​​1 / g and a primary particle size of 10-400 nm, natural silicates such as kaolin, and other natural silicates (layered silica), including clays. Further examples of fillers include glass particle-based fillers such as glass beads, microspheres, glass fibers, and glass fiber products (mats, strands). Polar fillers, such as silica-containing fillers, can be modified to increase hydrophobicity. Suitable modifiers include silanes or silane-based compounds. Common examples of such modifiers include, but are not limited to, compounds represented by the general formula (V): (R 1 R 2 R 3 O)3Si-R 4 -X (V) and compounds corresponding to the formula: 1 , R 2 , R 3 are each independently an alkyl group, preferably R 1 , R 2 , R 3 are all methyl or all ethyl, and R 4is an aliphatic or aromatic linking group having 1 to 20 carbon atoms, and X is a sulfur-containing functional group and is selected from -SH, -SCN, -C(=O)S, or a polysulfide group.

[0064] Instead of or in addition to the silica modified as described above, when preparing a rubber compound, such modification can also be carried out in situ, for example, during compounding or during the process of manufacturing the tire or component, by adding, for example, a modifier, preferably a silane or silane-based modifier, such as a modifier according to formula (V).

[0065] Fillers based on metal oxides other than silicon oxide include, but are not limited to, zinc oxide, calcium oxide, magnesium oxide, aluminum oxide, and combinations thereof. Other fillers include metal carbonates such as magnesium carbonate, calcium carbonate, zinc carbonate, and combinations thereof, metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and combinations thereof, α-β-unsaturated fatty acids, and salts of acrylic or methacrylic acids having 3 to 8 carbon atoms, such as zinc acrylate, zinc diacrylate, zinc methacrylate, zinc dimethacrylate, and mixtures thereof.

[0066] In another embodiment of the present disclosure, the rubber compound includes one or more carbon-based fillers, such as one or more carbon blacks. The carbon blacks may be produced, for example, by the lamp black process, the furnace black process, or the gas black process. Preferably, the carbon black has a viscosity of 20 to 200 mPa. 2 / g BET surface area (nitrogen adsorption). Suitable examples include, but are not limited to, SAF, ISAF, HAF, FEF, and GPF black. Other examples of suitable fillers include carbon-silica dual-phase fillers, lignin or lignin-based materials, starch or starch-based materials, and combinations thereof.

[0067] In a preferred embodiment, the filler comprises one or more silicon oxides, carbon black, or a combination thereof.

[0068] Typical amounts of filler include 5 to 200 parts per 100 parts of rubber, such as 10 to 150 parts by weight or 10 to 95 parts by weight per 100 parts by weight of rubber.

[0069] Hardener: Conventional curing agents known in the art may be used. The curing agent is capable of crosslinking (curing) the diene polymer and is also referred to herein as a "crosslinking agent," a "vulcanizing agent," or a "curing agent." Suitable curing agents include, but are not limited to, sulfur, sulfur-based compounds, and organic or inorganic peroxides.

[0070] In a preferred embodiment of the present disclosure, the curing agent comprises sulfur. Instead of a single curing agent, a combination of one or more curing agents may be used, or one or more curing agents may be used in combination with one or more cure accelerators or catalysts. Examples of sulfur-containing compounds that act as sulfur donors include, but are not limited to, sulfur, sulfur halides, dithiodimorpholine (DTDM), tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), and dipentamethylenethiuram tetrasulfide (DPTT). Examples of cure accelerators include, but are not limited to, amine derivatives, guanidine derivatives, aldehyde-amine condensation products, thiazoles, thiuram sulfides, dithiocarbamates, and thiophosphates.

[0071] In another embodiment of the present disclosure, the curing agent may include a peroxide. Examples of peroxides used as vulcanizing agents include, but are not limited to, di-tert-butyl peroxide, di-(tert-butyl-peroxy-trimethyl-cyclohexane), di-(tert-butyl-peroxy-isopropyl-)benzene, dichlorobenzoyl peroxide, dicumyl peroxide, tert-butyl-cumyl peroxide, dimethyl-di(tert-butyl-peroxy)hexane, dimethyl-di(tert-butyl-peroxy)hexyne, and butyl-di(tert-butyl-peroxy)valerate. Sulfenamide-, guanidine-, or thiuram-type vulcanization accelerators may be used in conjunction with the required vulcanizing agent. When added, the vulcanizing agent is typically present in an amount of 0.5 to 10 parts by weight, preferably 1 to 6 parts by weight, per 100 parts by weight of the functionalized diene polymer.

[0072] Other rubber Rubber compounds and compositions according to the present disclosure may contain one or more additional rubbers other than the functionalized diene polymers according to the present disclosure (also referred to herein as "other rubbers"), examples include unfunctionalized or differently functionalized functionalized diene rubbers of the present disclosure and butadiene rubbers of the same or different composition.

[0073] Further examples include copolymers of one or more butadienes with C1-C4 alkyl acrylates, copolymers having an acrylonitrile content of 10 to 40 wt. %, partially or fully hydrogenated acrylonitrile rubber, ethylene-propylene-diene copolymers, natural rubber, and combinations thereof. Typical amounts of the one or more other rubbers in the compound may include, for example, 5 to 500 parts per 100 parts of the functionalized butadiene rubber according to the present disclosure.

[0074] In a preferred embodiment of the present disclosure, the compound comprises at least one butadiene polymer having a cis unit content of at least 90% by weight. Such polymers are also referred to in the art as "high cis butadiene." Such butadiene polymers are generally obtained using polymerization catalysts based on gadolinium, neodymium, titanium, nickel, or cobalt. Butadiene polymers obtained by anionic polymerization are diene polymers according to the present disclosure that typically have a high vinyl content, for example, a vinyl group content of at least 10% by weight based on the weight of the polymer. The high cis-butadiene polymer may be (partially) hydrogenated or not hydrogenated. Suitable examples include rubbers commercially available under the trade name BUNA from ARLANXEO Deutschland GmbH, such as, for example, BUNA CB22, BUNA CB24, BUNA CB25, BUNA CB29, BUNA CB29 TSAED, BUNA CB 29MES, and also cobalt BR and Li BR grades, such as BUNA CB1203, BUNA CB1220 AO, BUNA CB1221, and combinations thereof.

[0075] In one embodiment of the present disclosure, the rubber compound contains one or more of the following rubbers: at least one natural rubber, at least one polybutadiene having a cis content greater than 90% by weight, or a combination thereof.

[0076] Rubber Auxiliaries Compositions and rubber compounds containing one or more diene polymers according to the present disclosure may contain one or more rubber auxiliaries known in the art of rubber compounding and processing. Such additional rubber auxiliaries include, but are not limited to, cure accelerators, antioxidants, heat stabilizers, light stabilizers, processing aids, plasticizers, tackifiers, blowing agents, and colorants. Processing aids include organic acids, waxes, and process oils. Examples of oils include, but are not limited to, MES (Mild Extraction Solvates), TDAE (Treated Distillate Aromatic Extracts), RAE (Residual Aromatic Extracts), and naphthenic and vegetable oils. Specific examples of commercially available oils include those with the trade names Nytex 4700, Nytex 8450, Nytex 5450, Nytex 832, Tufflo 2000, and Tufflo 1200. Examples of oils include functionalized oils, partially epoxidized oils, and hydroxylated oils.

[0077] Activators include triethanolamine, polyethylene glycol, hexanetriol. Colorants include dyes and pigments and can be organic or inorganic, such as zinc white and titanium dioxide.

[0078] The additional rubber auxiliaries may be used in an appropriate amount depending on the intended use as known in the art. Typical amounts of the auxiliaries, individually or in total, include 0.1 to 50 wt. % based on the total weight of rubber in the compound.

[0079] To produce a rubber compound, the diene polymer according to the present disclosure may be combined with one or more of the components for producing the rubber compound by blending as known in the art of rubber processing. Blending may be carried out, for example, by using a roller, kneader, internal mixer, and mixing extruder. The filler is preferably incorporated into the solid diene polymer or its mixture with other rubbers known in the art, for example, using a kneader. The filler may be added as a solid or a slurry or in another form known in the art. The curative and accelerator are preferably added separately in the final mixing stage.

[0080] vulcanizate Rubber vulcanizates according to the present disclosure are obtained by subjecting the rubber compounds of the present disclosure to one or more curing steps. Curing can be carried out as known in the art. Curing is typically carried out at temperatures of 100 to 200°C, e.g., 130 to 180°C. Curing can be carried out in a mold under pressure. Typical pressures include pressures of 10 to 200 bar. Curing times and conditions vary depending on the actual composition of the rubber compound and the amount and type of curatives and curative components.

[0081] Goods The diene polymers according to the present disclosure can be used to manufacture articles, and are particularly suitable for manufacturing tires or tire components such as tire treads. Tires include pneumatic tires. Tires include automobiles, aircraft, and electric and hybrid vehicles, i.e., vehicles that can be powered by combustion engines or electric engines or batteries. Typical tire components include innerliners, treads, undertreads, carcasses, and sidewalls. The polydienes according to the present disclosure can also be used to manufacture other articles, particularly those in which reduced rolling resistance is desired or useful. Examples include, but are not limited to, bearings and balls, such as golf balls.

[0082] In one embodiment, the diene polymer, composition or compound according to the present disclosure is used in a sealant, for example to make an O-ring, a gasket or any other seal or component of a seal.

[0083] In one embodiment, diene polymers according to the present disclosure are used as impact modifiers for thermoplastic resins such as polystyrene and styrene-acrylonitrile. In another embodiment, diene polymers according to the present disclosure are used in the manufacture of golf balls or components thereof. In another embodiment, diene polymers according to the present disclosure are used to manufacture molded articles selected from profiles, membranes, damping elements, and hoses.

[0084] In another embodiment, the diene polymers according to the present disclosure are used in the manufacture of shoe soles, cable sheathing, hoses, linings such as roll linings or belts such as conveyor belts, escalator belts and power transmission belts.

[0085] Articles are obtained by subjecting a curable rubber compound containing at least one diene polymer according to the present disclosure to curing and molding. The molding step can occur during or after the curing step, or even before the curing step. A single curing and / or molding step can be used, or multiple curing and / or molding steps can also be used. During curing or molding to form an article, the compositions and compounds of the present disclosure can be combined with one or more additional components required to produce the article.

[0086] Below, the present disclosure is further illustrated by specific embodiments and examples, but it is not intended that the present disclosure be limited to these specific embodiments and examples. [Example]

[0087] The weight-average molecular weight (Mw), number-average molecular weight (Mn), polydispersity (Mw / Mn), and coupling degree of the polymers were determined using GPC (PS (polystyrene) calibration). A modular system (available from Agilent, Santa Clara, CA, USA) was used, equipped with an Agilent 1260 refractive index detector, an Agilent 1260 variable wavelength detector, an Agilent 1260ALS autosampler, a column oven (Agilent 1260TCC), an Agilent 1200 degasser, an Agilent 1100 Iso pump, and a column combination of a 3PLgel 10 μm Mixed B 300 × 7.5 mm column from Agilent. Tetrahydrofuran (THF) was used as the solvent. Polystyrene standards were used from PSS Polymer Standards Service GmbH (Maiz, Germany). Polymer samples dissolved in THF were filtered through a syringe filter (0.45 μm PTFE membrane, 25 mm diameter). Measurements were performed at 40°C using a flow rate of 1 mL / min.

[0088] The Mooney viscosity ML(1+4) at 100°C was measured in accordance with DIN 53523 or ISO 296.

[0089] The comonomer content can be determined for rubber films by FTIR spectroscopy. The content of vinyl, cis and trans units in polymers can be determined by Fourier transform infrared spectroscopy (FT-IR spectroscopy) using absorbance and absorbance ratio as described in the ISO12965:2000(E) standard.

[0090] The glass transition temperature (Tg) was determined using DSC (differential scanning calorimetry) from the second heating curve at a heating rate of 20 K / min.

[0091] Compound characteristics The loss factor (tanδ) was measured at 0°C and 60°C to determine the temperature-dependent dynamic mechanical properties. An Eplexor 500N instrument (available from GABO) was used for this purpose. Measurements were performed on Ares strips at 10 Hz in accordance with DIN 53513 in the temperature range of -100 to 100°C. To determine the strain-dependent dynamic mechanical properties, ΔG' and the maximum loss factor (tanδmax) were determined as the difference between the shear modulus at 0.5% strain and the shear modulus at 15% strain. These measurements were performed on cylindrical specimens (20 mm x 6 mm) in accordance with DIN 53513-1990 using a 2 mm compression at 60°C and a measurement frequency of 10 Hz in the strain range of 0.1 to 40%.

[0092] Example 1 (Comparative): Synthesis of Styrene-Butadiene Copolymer An inert 20-L steel reactor was charged with 8.5 kg of hexane, 5.5 mmol of 2,2-bis(2-tetrahydrofuryl)-propane, and 10.1 mmol of n-butyllithium (as a 23 wt. % solution in hexane) and heated to 38°C. The heating circuit was closed, and 1,185 g of 1,3-butadiene and 315 g of styrene were added simultaneously. Polymerization was carried out under stirring for a total of 40 minutes, during which a peak temperature of 61°C was reached. Ten minutes after reaching the peak temperature, monomer consumption was considered complete. The anionic polymer chain ends were quenched by the addition of 10.1 mmol of n-octanol. The rubber solution was discharged into a separate vessel and stabilized by the addition of 3 g of IRGANOX 1520 (2,4-bis(octylthiomethyl)-6-methylphenol). The solvent was removed by steam stripping. The rubber crumbs were dried in a vacuum drying oven at 65°C for 16 hours.

[0093] Example 2 (Comparative): Functionalization of Styrene-Butadiene Copolymer by Reaction with 2,2-Diethoxy-1-[3-(triethoxysilyl)propyl]-1-aza-2-silacyclopentane The procedure described in Example 1 was followed, except that the functionalizing agent 2,2-diethoxy-1-[3-(triethoxysilyl)propyl]-1-aza-2-silacyclopentane was used instead of n-octanol. The functionalizing agent was added in an amount equimolar to the amount of n-butyllithium. The contents of the reactor were stirred for 10 minutes, after which the rubber solution was discharged. 3 g of stabilizer (IRGANOX 1520 (2,4-bis(octylthiomethyl)-6-methylphenol)) was added before the solvent was stripped off with steam. The rubber crumb was dried in a vacuum drying oven at 65°C for 16 hours.

[0094] Example 3: Functionalization of styrene-butadiene copolymer by reaction with 2,2,4,4,6,6,8,8-octamethylcyclotetrasiloxane and 2,2-diethoxy-1-[3-(triethoxysilyl)propyl]-1-aza-2-silacyclopentane The procedure described in Example 2 was followed, except that 2,2,4,4,6,6,8,8-octamethylcyclotetrasiloxane was added instead of 2,2-diethoxy-1-[3-(triethoxysilyl)propyl]-1-aza-2-silacyclopentane. The functionalizing reagent was added in an equimolar amount relative to n-butyllithium. The reaction mixture was stirred for 10 minutes, after which 2,2-diethoxy-1-[3-(triethoxysilyl)propyl]-1-aza-2-silacyclopentane was added in an equimolar amount relative to n-butyllithium. The contents of the reactor were stirred for an additional 10 minutes, after which the rubber solution was discharged and stabilized by adding 3 g of Irganox® 1520 (2,4-bis(octylthiomethyl)-6-methylphenol), and the solvent was removed by steam stripping. The rubber crumb was dried in a vacuum drying oven at 65°C for 16 hours.

[0095] Example 4 (Comparative): Functionalization of Styrene-Butadiene Copolymer by Reaction with 1-Ethyl-2,2-dimethoxy-4-methyl-1-aza-2-silacyclopentane The procedure described in Example 2 was followed, except that 1-ethyl-2,2-dimethoxy-4-methyl-1-aza-2-silacyclopentane was used instead of 2,2-diethoxy-1-[3-(triethoxysilyl)propyl]-1-aza-2-silacyclopentane. The functionalizing reagent was added in an equimolar amount relative to n-butyllithium.

[0096] Example 5: Functionalization of styrene-butadiene copolymer by reaction with 2,2,4,4,6,6,8,8-octamethylcyclotetrasiloxane and 1-ethyl-2,2-dimethoxy-4-methyl-1-aza-2-silacyclopentane The procedure described in Example 3 was followed, except that instead of 2,2-diethoxy-1-[3-(triethoxysilyl)propyl]-1-aza-2-silacyclopentane, 1-ethyl-2,2-dimethoxy-4-methyl-1-aza-2-silacyclopentane was added in an amount equimolar to the amount of n-butyllithium.

[0097] The properties of the rubbers from Examples 1-5 are summarized in Table 1.

[0098] [Table 1]

[0099] rubber compound Tire tread rubber compounds containing the polymers of Examples 1-5 were prepared using the ingredients shown in Table 2. The ingredients (except for the sulfur and accelerators) were mixed in a 1.5 L kneader. The sulfur and accelerators were subsequently mixed on a roller at 40°C. The individual steps for preparing the compounds are shown in Table 3.

[0100] [Table 2]

[0101] [Table 3]

[0102] The rubber compounds were vulcanized at 160°C for 20 minutes. The physical properties of the vulcanizates are shown in Table 4. The properties of the vulcanized rubber compound of Comparative Example 6 (made with the non-functionalized polymer from Example 1) are given an index of 100. Values ​​above 100 in Table 4 indicate a percent improvement in the properties compared to Comparative Example 6.

[0103] [Table 4]

[0104] The temperature-dependent loss factor tan δ at 60°C from dynamic-mechanical measurements, tan δ maximum value, the difference in modulus between low and high strain from strain-dependent dynamic-mechanical measurements, and the rebound resilience at 60°C are all indicators of a tire's rolling resistance. The loss factor tan δ at 0°C is an indicator of a tire's wet skid resistance.

[0105] As can be seen from Table 4, functionalization of butadiene polymers with cyclic aminosilanes leads to vulcanizates with improved wet grip and rolling resistance indices. When first and second functionalizing reagents according to the present disclosure were used, the wet grip and rolling resistance indices of the vulcanizates were further improved.

Claims

1. 1. A process for producing a functionalized diene polymer, comprising: (i) preparing a diene polymer by a polymerization reaction to produce a reaction mixture comprising a diene polymer having reactive polymer chain ends; (ii) Formula (I) 【Chemical 1】 with the reactive polymer chain end to obtain a first reaction product; (iii) reacting the reaction mixture containing the first reaction product with a compound represented by formula (II) 【Chemistry 2】 to produce a functionalized diene polymer having at least one amino group and at least one siloxane group. Including, the diene polymer comprises at least 51 wt. % of units derived from 1,3-butadiene, based on the total weight of the polymer; In formula (I), R １ and R ２ represent, independently of each other and of each unit n, hydrogen or an organic residue having a hydrogen atom and 1 to 24 carbon atoms, said organic residue optionally further comprising one or more heteroatoms selected from O, S, N, Si and combinations thereof, and n represents 3, 4, 5, 6, 7 or 8; In formula (II), R' １ , R' ２ and R ３ represent, independently of each other, an organic residue comprising a hydrogen atom and 1 to 24 carbon atoms, said organic residue optionally further comprising one or more heteroatoms selected from O, S, N, Si and combinations thereof; A represents a divalent alkylene unit having 1 to 6 carbon atoms in said alkylene unit, said alkylene group can be unsubstituted or substituted, wherein at least one of the hydrogen atoms of said alkylene unit is replaced with a hydrogen atom and an organic residue comprising 1 to 24 carbon atoms, said organic residue optionally further comprising one or more heteroatoms selected from O, S, N, Si and combinations thereof.

2. In formula (I), R １ and R ２ independently from each other and from each unit n, represent hydrogen, a C1-C10 alkyl group, a C2-C10 alkenyl group, or a C6-C20 aryl group, wherein the alkyl, aryl, and alkenyl groups are unsubstituted or substituted, where at least one hydrogen atom of the group is replaced by a substituent selected from a halogen, preferably Cl or F, an alkylamino group, an alkylphosphino group, an alkylsilyl group, an (alkylamino)alkyl group, an (alkylphosphino)alkyl group, an (alkylsilyl)alkyl group, and combinations thereof, wherein each alkyl group of the substituents has from 1 to 19 carbon atoms and is either unsubstituted or substituted with a halogen, preferably Cl or F.

3. In formula (II), R ３ represents a linear or branched C1-C12 alkyl group that is either unsubstituted or at least one hydrogen atom of said alkyl group is substituted with a substituent selected from halogen, alkoxy group, alkoxysilyl group, (alkoxysilyl)alkyl group, alkylsilyl group, (alkylsilyl)alkyl group, (alkylamino)alkyl group, alkylamino group, and combinations thereof, wherein each substituent other than halogen may include another substituent selected from halogen, phenyl, benzyl, alkylphenyl, alkylbenzyl, and 3. The process according to claim 1 or 2, wherein A represents ethylene, propylene, butylene, unsubstituted or substituted, in which at least one hydrogen atom is replaced by Cl or a halogen selected from F, C1-C7 alkyl groups, aryl groups (preferably phenyl groups), alkylaryl groups (preferably alkylphenyl groups), (alkylaryl)alkyl groups, arylalkyl groups (preferably benzyl groups), each of the alkyl or aryl residues of said substituents may carry one or more further substituents selected from Cl and F.

4. In formula (II), R' １ and R' ２ are each independently a linear or branched C1-C12 alkyl, preferably a C1-C4 alkyl, and R ３ represents a C1-C6 alkyl group or a trialkoxysilyl alkyl group preferably selected from trialkoxybutyl, trialkoxypropyl, trialkoxyethyl and trialkoxymethyl, the alkyl groups of the trialkoxy units being independently selected from C1-C6 alkyl.

5. 5. The process of claim 1, wherein in formula (I), R1 and R2, independently of each other and of each unit n, are selected from a C1 to C6 alkyl group, a C2 to C6 alkenyl group, or a C6 to C12 aryl group, and the alkyl, aryl, and alkenyl groups are unsubstituted or substituted, wherein at least one hydrogen atom of the group is replaced by a substituent selected from Cl, F, alkylamino groups, alkylphosphino groups, alkylsilyl groups, (alkylamino)alkyl groups, (alkylphosphino)alkyl groups, (alkylsilyl)alkyl groups, and combinations thereof, and each alkyl group of the substituents has 1 to 19 carbon atoms and is either unsubstituted or substituted with a halogen, preferably Cl or F.

6. The first functionalizing reagent is selected from the group consisting of 2,2,4,4,6,6-hexamethylcyclotrisiloxane, 2,2,4,4,6,6,8,8-octamethylcyclotetrasiloxane, 2,2,4,4,6,6,8,8,10,10-decamethylcyclopentasiloxane, 2,2,4,4,6,6,8,8,10,10,12,12-dodecamethylcyclohexasiloxane, 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane, 2,4,6-trimethyl-2,4,6-triphenylcyclotrisiloxane, 2,4,6-trimethylcyclotrisiloxane, cyclotrisiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, 2,4,6,8- 6. The process of any one of claims 1 to 5, wherein the hydroxyl group is selected from tetramethyl-2,4,6,8-tetraphenylcyclotetrasiloxane, 2,4,6,8-tetramethylcyclotetrasiloxane, 2,2,4,4,6,6-hexaphenylcyclotrisiloxane, 2,2,4,4,6,6,8,8-octaphenylcyclotetrasiloxane, 2,4,6,8,10-pentamethylcyclopentasiloxane, 2,4,6,8,10-pentamethyl-2,4,6,8,10-pentavinylcyclopentasiloxane, 2,4,6,8-tetraethylcyclotetrasiloxane, and 2,4,6,8-tetramethyl-2,4,6,8-tetrakis(2-diphenylphosphinoethyl)cyclotetrasiloxane.

7. 7. The process of any one of claims 1 to 6, wherein the functionalized diene polymer comprises up to 49 wt%, based on the total weight of the polymer, of units derived from one or more conjugated dienes other than 1,3-butadiene having from 5 to 20 carbon atoms, one or more vinyl aromatic comonomers having from 8 to 30 carbon atoms, preferably styrene, and combinations thereof.

8. 8. The process of any one of claims 1 to 7, wherein the functionalized diene polymer has at least one of the following properties: a number average molecular weight of 100,000 to 1,000,000, determined by gel permeation chromatography using a polystyrene calibration, a Mooney viscosity ML1+4 at 100°C of 30 to 150 units, determined according to DIN 53523, and a glass transition temperature of -110°C to 0°C, determined by differential scanning calorimetry (DSC) from a second heating curve at a heating rate of 20 K / min.

9. The functionalized diene polymer has the general formula (III): 【Chemistry 3】 (In the formula, R １ , R ２ , R' １ , R' ２ , A, R ３ and n have the same meaning as in claim 1) The process of any one of claims 1 to 8, wherein the hydroxyl group has at least one group according to

10. A functionalized diene polymer obtainable by the process according to any one of claims 1 to 9.

11. 11. A curable compound comprising the functionalized diene polymer of claim 10 and at least one curative for curing said functionalized diene polymer, optionally further comprising at least one rubber other than said functionalized polymer, at least one filler, or a combination thereof.

12. 11. A method for making a curable rubber compound, comprising combining at least one functionalized diene polymer according to claim 10 with at least one rubber component selected from at least one curative for curing said functionalized diene polymer, at least one filler, at least one rubber other than said functionalized diene polymer, or combinations thereof.

13. 11. An article comprising the reaction product of a curing reaction, the curing reaction comprising curing a composition comprising the functionalized diene polymer of claim 10 and at least one curing agent.

14. 14. The article of claim 13, which is a tire or tire component.

15. 11. A method of making an article, comprising subjecting a composition comprising the functionalized diene polymer of claim 10 to curing and shaping, said shaping can occur before, after, or during said curing.

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