Alpha-omega-functionalized polymers

Abstract

Disclosed is a functionalized diene polymer having at least one first functional group and at least one second functional group, where the first functional group is selected from terminal groups, pendant groups, and combinations thereof, and where the second functional group is a terminal group, wherein the first functional group (i) comprises at least one unit derived from a functionalized monomer represented by formula (1) wherein R1, R2, R3 are selected from the group consisting of hydrogen and methyl, with the proviso that at least one of R1, R2 and R3 is hydrogen, preferably all of R1, R2 and R3 are hydrogen, n is 1, 2, 3, 4 or 5, each R4 is independently selected from the group consisting of aliphatic or aryl aliphatic residues having 3 to 30 carbon atoms, and wherein if n is 1, the first functional group (i) comprises at least one unit derived from a functionalized monomer represented by formula (1); if n is 2 to 5, R4 comprises at least one tertiary amine group, and if n is 2 to 5, at least one of these residues R4 comprises at least one tertiary alkylamine group; or (ii) wherein the first functional group is obtained by using a polymerization initiator having the general formula N (R1) (R2) (R3M) wherein R1 and R2, equal to or different from each other, are selected from a linear or branched saturated alkyl group, and R3 is a saturated, linear or branched alkyl negative carbon ion and M is a basic cation, and wherein the second functional group is a terminal group and comprises at least one group selected from-COOX,-OX,-SX, a variety thereof, and combinations thereof, where X represents hydrogen or a cation, and wherein the functionalized diene polymer is a homopolymer or copolymer of conjugated dienes, and wherein the conjugated diene is selected from the group consisting of butadiene, isoprene, isoprene, 1, 3-pentadiene, 2, 3-dimethylbutadiene, 1-phenyl-1, 3-butadiene, 1, 3-hexadiene, preferably butadiene, and a method for producing the same. Also provided are methods for producing these polymers, articles obtained from the polymer, and methods for making articles with the polymer. # imgabs0 #

Description

Background Art

[0001] Diene rubbers are used in many different applications. They are typically combined with fillers and other additives to produce rubber compounds and then formed into articles. The interaction between rubber and the filler used to make the rubber compound can be improved by introducing functional end groups into the polymer. Therefore, various diene rubbers functionalized with polar end groups have been developed. Diene rubbers with polar functional groups can lead to improved compounds, such as described in U.S. Patent Applications US2016 / 0075809 A1 and US2016 / 0083495A1 and International Patent Application WO 2021 / 009154. Improved properties have also been reported for polymers prepared with amino-functional monomers, such as described in US 2020 / 0277426A1 and EP2847264 A1. However, there is a continuing need for additional diene polymers with improved properties. Summary of the invention

[0002] Thus, in one aspect, there is provided a polymer composition comprising a functionalized diene polymer having at least one first functional group and at least one second functional group, wherein the first functional group is selected from a terminal group, a pendant group, and combinations thereof, and wherein the second functional group is a terminal group,

[0003] The first functional group

[0004] (i) comprising at least one unit derived from a functional monomer represented by formula (1)

[0005]

[0006]

[0007] wherein R1, R2, R3 are selected from hydrogen and methyl, provided that at least one of R1, R2 and R3 is hydrogen, preferably R1, R2 and R3 are all hydrogen,

[0008] n is 1, 2, 3, 4, or 5,

[0009] each R4 is independently chosen from aliphatic or arylaliphatic residues having from 3 to 30 carbon atoms and wherein, if n is 1, R4 comprises at least one tertiary amine group and, in the case where n is from 2 to 5, at least one of these residues R4 comprises at least one tertiary alkylamine group; or

[0010] (ii) wherein the first functional group is obtained by using a polymerization initiator having the general formula N(R1)(R2)(R3Li), wherein R1 and R2 are the same or different from each other and are selected from linear or branched saturated alkyl groups, R3 is a saturated, linear or branched alkyl carbonium ion and M is a basic cation,

[0011] and

[0012] wherein the second functional group is a terminal group and comprises at least one group selected from -COOX, -OX, -SX, a plurality thereof and combinations thereof, wherein X represents hydrogen or a cation, and

[0013] Wherein the functionalized diene polymer is a homopolymer or copolymer of a conjugated diene, and wherein the conjugated diene is selected from the group consisting of butadiene, isoprene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 1-phenyl-1,3-butadiene, 1,3-hexadiene, preferably butadiene.

[0014] In another aspect, a method for producing the above polymer is provided, the method comprising polymerizing at least one conjugated diene in a polymerization reaction to produce a diene polymer, wherein (i) at least one functionalized monomer, or an active reaction product comprising at least two repeating units derived from the functionalized monomer, is added to the conjugated diene before, at the beginning or during the polymerization reaction to produce a functionalized polymer having at least one first functional group, the at least one first functional group comprising at least one unit derived from the functionalized monomer, or (ii) the polymerization is initiated by using an initiator having the general formula N(R1)(R2)(R3M) as described above, or a combination of (i) and (ii),

[0015] Wherein the reaction further comprises adding at least one functionalizing agent to the functionalized diene polymer to produce a second functional group, wherein the functionalized monomer is represented by formula (1)

[0016]

[0017] wherein R1, R2, R3 are selected from hydrogen and methyl, provided that at least one of R1, R2 and R3 is hydrogen, preferably R1, R2 and R3 are all hydrogen,

[0018] n is 1, 2, 3, 4 or 5, each R4 is independently selected from aliphatic or arylaliphatic residues having 3 to 30 carbon atoms, and wherein if n is 1, R4 comprises at least one tertiary amine group, and in the case where n is 2 to 5, at least one of the residues R4 comprises at least one tertiary alkylamine group; and wherein the second functional group is a terminal group and comprises at least one group selected from -COOX, -OX, -SX, a plurality thereof or a combination thereof, wherein X represents hydrogen or a cation, and

[0019] The conjugated diene is selected from the group consisting of butadiene, isoprene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 1-phenyl-1,3-butadiene, 1,3-hexadiene, preferably butadiene.

[0020] In another aspect, there is provided a curable rubber compound comprising the above polymer and further comprising at least one curing agent capable of curing the polymer.

[0021] In another aspect, a rubber compound is provided comprising the above polymer in cured form.

[0022] In yet another aspect, there is provided a method of making a rubber compound, the method comprising combining the polymer with at least one curing agent capable of curing the polymer, and optionally subjecting the polymer to curing.

[0023] In yet another aspect, a method of making an article is provided, the method comprising subjecting a rubber compound comprising the polymer and at least one curing agent capable of curing the polymer to curing and shaping, wherein the shaping may occur before, during or after the curing.

[0024] In another aspect, an article is provided, comprising the reaction product of a curing reaction of a composition comprising the polymer, wherein the article is selected from a tire, a tire tread, a shoe sole, a golf ball, a belt, or a seal. DETAILED DESCRIPTION

[0025] In the following description, in contrast to the term "consisting of", the terms "comprising", "containing", "including", "having" are not intended to exclude the presence of any additional components, steps or procedures. For example, a composition referred to herein as "comprising components A and B" means that in addition to components A and B, other components may also be present in the composition.

[0026] The term "consisting of" is used if it is intended to exclude the presence of any additional components, steps or procedures.

[0027] In the following description, the specification may be used. If not otherwise indicated, the specification is used in the version valid on March 1, 2020. If there is no version valid on that date, for example because the specification has expired, reference is made to the version valid on the date closest to March 1, 2020.

[0028] In the following description, the amount of a component of a composition or polymer may be expressed interchangeably by "weight percent," "wt. %" or "% by weight." Unless otherwise indicated, the terms "weight percent," "wt. %" or "% by weight" are based on the total weight of the composition or polymer, respectively, which is 100%.

[0029] The term "phr" means parts per hundred parts of rubber.

[0030] Unless otherwise stated, ranges identified in this disclosure include and disclose all values ​​between and including the endpoints of the range.

[0031] The term "substituted" is used to describe a hydrocarbon-containing organic compound in which at least one hydrogen atom has been replaced by a chemical entity other than hydrogen. The chemical entity is referred to interchangeably herein as a "substituent," "residue," or "group." For example, the term "methyl substituted by fluorine" refers to a fluorinated methyl group and includes the groups -CF3, -CHF2, and -CH2F. The term "unsubstituted" is intended to describe a hydrocarbon-containing organic compound in which none of its hydrogen atoms have been replaced. For example, the term "unsubstituted methyl residue" refers to a methyl group, i.e., -CH3.

[0032] Diene polymers

[0033] Diene polymers according to the present disclosure are functionalized polymers and they contain at least two functional groups. The first functional group is derived from one or more amine functionalized monomers. Preferably, the first functional group is located at the beginning of the polymer chain, that is, at the alpha position. However, additionally or as an alternative, the first functional group can also exist as one or more side groups. Diene polymers according to the present disclosure at least further contain a second functional group. The second functional group is a terminal group and is preferably present in the opposite position of the polymer chain compared to the position of the first functional group.

[0034] The diene polymer according to the present disclosure comprises units derived from at least one conjugated diene. The diene polymer according to the present disclosure can be obtained by polymerization, and the polymerization reaction includes polymerization of at least one conjugated diene as a monomer. Preferably, the diene polymer is a homopolymer or copolymer of at least one conjugated diene, and the at least one conjugated diene is preferably selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 1-phenyl-1,3-butadiene, 1,3-hexadiene. Butadiene and / or isoprene are particularly preferred.

[0035] In one embodiment of the present disclosure, the diene polymer is a polybutadiene homopolymer, more preferably a butadiene homopolymer. In another embodiment of the present disclosure, the diene polymer is a butadiene copolymer.

[0036] In another embodiment of the present disclosure, the diene polymer is a copolymer of a conjugated diene, preferably comprising a unit derived from one or more conjugated dienes as described above and / or one or more vinyl aromatic monomers and optionally a copolymer of one or more units derived from one or more other comonomers. Examples of vinyl aromatic monomers include, but are not limited to, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-tert-butylstyrene, vinylnaphthalene and combinations thereof. Styrene is particularly preferred. Vinyl aromatic monomers also include substituted vinyl aromatic monomers, wherein one or more hydrogen atoms of the vinyl aromatic monomer are replaced by heteroatoms or groups having one or more heteroatoms, and these heteroatoms are preferably selected from Si, N, O, H, Cl, F, Br, S and combinations thereof. Substituted monomers also include vinyl aromatic monomers, which monomers have one or more functional groups having one or more heteroatoms or contain at least one unit having a functional group having one or more heteroatoms. Preferably, heteroatoms are selected from Si, N, O, H, Cl, F, Br, S and combinations thereof. Examples of functional groups include, but are not limited to, hydroxyl, thiol, thioether, ether, halogen, carboxylic acid group or its salt, and combinations thereof. Such functionalized conjugated monomers are preferably copolymerized with one or more of the vinyl aromatic monomers described above. In preferred embodiments, the diene polymer according to the present disclosure comprises repeating units derived from 1,3-butadiene and styrene.

[0037] Preferably, the polymer according to the present disclosure contains at least 50% by weight, preferably at least 60% by weight, of units derived from 1,3-butadiene, based on the weight of the polymer. In one embodiment of the present disclosure, the diene polymer contains at least 60% by weight or at least 75% by weight of units derived from 1,3-butadiene. In one embodiment, the polymer according to the present disclosure comprises at least 75% or at least 95% by weight of units derived from one or more than one conjugated diene monomer.

[0038] In one embodiment of the present disclosure, the diene polymer contains 0% to 49% by weight, or 0% to 40% by weight, of units derived from one or more comonomers, based on the total weight of the polymer.

[0039] In one embodiment, the diene polymer of the present disclosure contains 0% to 20% by weight of units derived from one or more conjugated dienes other than 1,3-butadiene.

[0040] In one embodiment, the diene polymer according to the present disclosure contains at least 50% by weight, preferably at least 60% by weight, of units derived from 1,3-butadiene and at least 5% by weight, and preferably up to 49% by weight of units derived from one or more vinyl aromatic comonomers, preferably 5% to 40% by weight, or 10% to 35% by weight of units derived from one or more vinyl aromatic comonomers, preferably styrene, based on the weight of the polymer. Alternatively, such polymers may contain 0% to 25% by weight of one or more other comonomers, provided that the total amount of monomers is adjusted so that the polymer still has a total weight of 100%. In one embodiment, the polymer according to the present disclosure contains 55% to 92% by weight of units derived from one or more conjugated diene monomers and 5.8% to 45% by weight of units derived from vinyl aromatic comonomers.

[0041] Suitable other conjugated dienes as comonomers include but are not limited to myrcene, ocimene and / or farnesene.Conjugated dienes also include substituted conjugated dienes, wherein one or more hydrogen atoms of the diene are replaced by groups containing one or more heteroatoms selected from Si, N, O, H, Cl, F, Br, S and combinations thereof or containing one or more heteroatomic functional groups (for example, with one or more heteroatomic functional groups selected from Si, N, O, H, Cl, F, Br, S and combinations thereof). The example of functional group includes but is not limited to hydroxyl, thiol, thioether, ether, halogen and units with one or more carboxylic acid groups or their salts, and combinations thereof. Such functionalized conjugated dienes are preferably copolymerized with one or more of the conjugated dienes described above. Suitable copolymerizable comonomers further include one or more alpha-olefins, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and combinations thereof. In one embodiment, the diene polymer according to the present disclosure contains 0 to 20% by weight of units derived from one or more alpha-olefins.

[0042] Suitable comonomers also include, but are not limited to, one or more other copolymerizable comonomers other than the above functional comonomers, which introduce functional groups including crosslinking sites, branching sites, side chains or functionalized groups. In one embodiment of the present disclosure, the diene polymer contains 0% to 10% by weight or 0% to 5% by weight of units derived from one or more such other comonomers. Such comonomers include, for example, divinylbenzene, trivinylbenzene, divinylnaphthalene.

[0043] Combinations of one or more comonomers of the same chemical type as described above as well as combinations of one or more comonomers from different chemical types can be used. In one embodiment of the present disclosure, the other comonomers described above are absent, or account for less than 10% by weight, less than 5% by weight, or no more than 1% by weight.

[0044] The diene polymer according to the present disclosure preferably has an average molecular weight (number average, Mn) of 10,000 to 2,000,000 g / mol, preferably 100,000 to 1,000,000 g / mol.

[0045] Preferably, the diene polymer according to the present disclosure has a glass transition temperature (Tg) of about -110°C to about +20°C, preferably about -110°C to about 0°C.

[0046] Preferably, the diene polymer according to the present disclosure has a Mooney viscosity [ML 1+4 (100° C.)] of about 10 to about 200, preferably about 30 to about 150 Mooney units.

[0047] Preferably, the polymer has a dispersity of about 1.03 to about 3.5.

[0048] Diene polymers can be prepared by methods known in the art. Preferably, the polymer can be obtained by a method comprising anionic solution polymerization or polymerization using one or more coordination catalysts. The polymerization can be carried out in solution or in the gas phase. Coordination catalysts include Ziegler-Natta catalysts or monometallic catalyst systems. Preferred coordination catalysts are those based on Ni, Co, Ti, Zr, Nd, V, Cr, Mo, W or Fe.

[0049] Preferably, the polymerization reaction comprises anionic solution polymerization. The initiator for anionic solution polymerization comprises an organic metal, preferably based on an alkali metal or alkaline earth metal. Examples include, but are not limited to, methyl lithium, ethyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, amyl lithium, n-hexyl lithium, cyclohexyl lithium, octyl lithium, decyl lithium, 2-(6-lithium-n-hexyloxy) tetrahydropyran, 3-(tert-butyldimethylsilyloxy)-1-propyl lithium, phenyl lithium, 4-butylphenyl lithium, 1-naphthyl lithium, p-tolyl lithium and allyl lithium compounds derived from tertiary N-allyl amine, such as [1-(dimethyl [1-(1-diphenylamino)-2-propenyl] lithium, [1-(1-pyrrolidinyl)-2-propenyl] lithium; lithium amides of secondary amines, such as pyrrolidine lithium, piperidine lithium, hexamethyleneimide lithium, 1-methylimidazole lithium, 1-methylpiperazine lithium, morpholine lithium, dicyclohexylamide lithium, dibenzylamide lithium, diphenylamide lithium. Allyl lithium compounds and lithium amides can also be prepared in situ by reacting an organic lithium compound with a corresponding tertiary N-allylamine or with a corresponding secondary amine. Difunctional and polyfunctional organic lithium compounds can also be used, such as 1,4-dilithium butane, dilithium piperazine. Preferably, n-butyl lithium, sec-butyl lithium or a combination thereof is used.

[0050] In order to produce the first functional group, one or more than one amine functionalized monomer is added before or at the beginning of polymerization and / or during polymerization but not at the end of polymerization. Amine functionalized monomers can also be added as an active reaction product comprising at least two repeating units derived from functionalized monomers. Such active reaction products can be produced by the reaction of one or more amine functionalized monomers with organometallic compounds (for example, initiators for anionic polymerization as described above), preferably organolithium compounds, preferably alkyl lithiums and more preferably butyl lithium. Reaction can include the oligomerization of amine functionalized monomers, or the co-oligomerization of amine functionalized monomers and one or more other comonomers (for example, conjugated dienes, as described above). Oligomerization or co-oligomerization can result in oligomeric functionalized monomers with 2 to 200 units derived from amine functionalized monomers. Active reaction products as mentioned herein mean that monomers have complete carbon-carbon double bonds that can participate in polymerization or negative carbon ions that can participate in polymerization or both. The reaction product can be produced in a separate reaction and then added to the polymerization reactor, or it can be formed in situ, such as by co-feeding the one or more amine-functional monomers and a reaction initiator into the polymerization reaction, or by first reacting the initiator and amine-functional monomer before adding the conjugated diene monomer.

[0051] The amine functional monomer according to the present disclosure corresponds to formula (1):

[0052]

[0053] wherein R1, R2, R3 are selected from hydrogen and methyl, provided that at least one of R1, R2 and R3 is hydrogen, preferably R1, R2 and R3 are all hydrogen,

[0054] n is 1, 2, 3, 4, or 5,

[0055] Each R4 is independently selected from aliphatic or arylaliphatic residues having 3 to 30 carbon atoms, and wherein if n is 1, R4 comprises at least one tertiary amine group, and in the case where n is 2 to 5, at least one of these residues R4 comprises at least one tertiary alkylamine group. In one embodiment of the present disclosure, R4 is selected from the formula (2)

[0056]

[0057] and a group represented by formula (3)

[0058]

[0059] Wherein in formula (2), R5 is selected from the group consisting of: a chemical bond, an unsubstituted or substituted straight or branched alkylene group having 1 to 20 carbon atoms, an unsubstituted or substituted cycloalkylene group having 5 to 20 carbon atoms; or an unsubstituted or substituted arylene group having 6 to 20 carbon atoms, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R6 and R7 are each independently a cycloalkyl group having 5 to 10 carbon atoms, or an unsubstituted or substituted cycloalkyl group having 6 to 2 R8 is hydrogen; an alkyl group having 1 to 30 carbon atoms; an alkenyl group having 2 to 30 carbon atoms; an alkynyl group having 2 to 30 carbon atoms; a heteroalkyl group having 1 to 30 carbon atoms; a heteroalkenyl group having 2 to 30 carbon atoms; a heteroalkynyl group having 2 to 30 carbon atoms; a cycloalkyl group having 5 to 30 carbon atoms; an aryl group having 6 to 30 carbon atoms; or a heterocyclyl group having 3 to 30 carbon atoms, and X is a chemical bond or a N, O or S atom, in which case X is O or S or a chemical bond, R8 is absent,

[0060] In formula (3), R9 is an unsubstituted or substituted alkylene group having 1 to 20 carbon atoms, an unsubstituted or substituted cycloalkylene group having 5 to 20 carbon atoms; or an unsubstituted or substituted arylene group having 6 to 20 carbon atoms, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R 11 and R 12Each is independently an alkyl group having 1 to 30 carbon atoms; an alkenyl group having 2 to 30 carbon atoms; an alkynyl group having 2 to 30 carbon atoms; a heteroalkyl group having 1 to 30 carbon atoms; a heteroalkenyl group having 2 to 30 carbon atoms; a heteroalkynyl group having 2 to 30 carbon atoms; a cycloalkyl group having 5 to 30 carbon atoms; an aryl group having 6 to 30 carbon atoms; or a heterocyclyl group having 3 to 30 carbon atoms.

[0061] Specific examples include, but are not limited to,

[0062] 4-(2-(N,N-bis(trimethylsilyl)amino)ethyl)styrene

[0063]

[0064] Vinylbenzylpyrrolidine,

[0065]

[0066] and N,N-dimethylaminomethylstyrene

[0067]

[0068] In another embodiment of the present disclosure, the first functional group is obtained by using a polymerization initiator having the general formula N(R1)(R2)(R3M) for starting polymerization, wherein R1 and R2 are the same or different from each other and are all selected from linear or branched saturated alkyl groups, which preferably have 2 to 18, more preferably 3 to 12 or 3 to 8 carbon atoms,

[0069] R3 is a saturated alkyl carbanion, which may be linear or branched and is preferably linear. Preferably, R3 contains 2 to 12, preferably 3 to 12 carbon atoms.

[0070] M represents a metal cation, preferably an alkali metal cation and more preferably a lithium cation Li + .

[0071] In one embodiment of the present disclosure, the polymerization initiator having the general formula N(R1)(R2)(R3M) has at least one of R1, R2 and R3 that is linear, preferably at least two of R1, R2 and R3 that are linear, and more preferably at least all of R1, R2 and R3 that are linear.

[0072] In another embodiment of the present disclosure, the polymerization initiator having the general formula N(R1)(R2)(R3M) is branched, and at least one, preferably two, of R1 and R2 are branched. In one embodiment of the present disclosure, R3 is branched. In one embodiment, R1 and R2 are the same or different and correspond to the residue (R4)(R5)(R6)C-CH2-, wherein R4, R5, R6 are selected from hydrogen, straight or branched saturated alkyl groups having 1 to 14 carbon atoms, preferably 1 to 4 carbon atoms, provided that not all R4, R5 and R6 are H and provided that if both R4 and R5 are H, then R6 is branched. Specific examples of R1 and R2 include, but are not limited to, n-butyl, sec-butyl, tert-butyl, n-propyl, isopropyl, 2-methylpentyl, 3-methylpentyl, n-pentyl. Specific examples of R3 include, but are not limited to, ethyl, methyl, n-propyl, isopropyl, n-butyl, 2-methyl-butyl, 3-methyl-butyl, 2-ethyl-butyl, 3-ethyl-butyl.

[0073] The initiator can be prepared, for example, by reacting a halogenated, preferably chlorinated, linear or branched tertiary amine, preferably a monohalogenated linear or branched tertiary amine, with an alkali metal, preferably lithium, as known in the art. The halogenated tertiary amine corresponds to the amine described above in which R1, R2 and R3 have the same meaning, except that the residue R3 is not an alkyl carbanion but an alkyl halide, which is preferably halogenated in the terminal position, and preferably R3 is monochlorinated.

[0074] Combinations of at least one amine-containing initiator as described above and at least one amino-functional monomer as described above may be used.

[0075] Randomizers and control agents known in the art can be used in polymerization to control the structure of the polymer. Such agents include, for example, those described in

[0027] of US2016 / 0075809 A1, which is incorporated herein by reference.

[0076] Preferred solvents for solution polymerization include inert aprotic solvents, such as aliphatic hydrocarbons. Specific examples include butane, pentane, hexane, heptane, octane, decane and cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, 1,4-dimethylcyclohexane and combinations thereof and including isomers thereof. Other examples include olefins (such as 1-butene) or aromatic hydrocarbons (such as benzene, toluene, ethylbenzene, xylene, diethylbenzene or propylbenzene) and combinations thereof. These solvents can be used alone or as a mixture. Preferred solvents are cyclohexane, methylcyclopentane and n-hexane. If appropriate, these solvents can also be mixed with polar solvents.

[0077] Polymerization can be carried out by first introducing monomers and solvents and then starting polymerization by adding initiators or catalysts. Polymerization can also be carried out in a feed process, where a polymerization reactor is loaded by adding monomers and solvents. Initiators or catalysts are introduced or added together with monomers and solvents. Modifications can be applied, such as introducing solvents, adding initiators or catalysts in the reactor, and then adding monomers. Polymerization can be carried out in a continuous manner or in an intermittent manner. Additional monomers and solvents can be added during polymerization or at the end of polymerization. Polymerization can be carried out at normal pressure or under pressure (e.g., 1 to 10 bars) or under reduced pressure. Typical reaction temperatures include temperatures between 35°C and 130°C.

[0078] In one embodiment of the present disclosure, a method for producing a functionalized polydiene polymer according to the present disclosure is provided, wherein the method includes polymerizing at least one conjugated diene in a polymerization reaction to produce a diene polymer, wherein at least one functionalized monomer (or an active reaction product comprising at least two repeating units derived from the functionalized monomer, such as 2 to 200 units) is added to the conjugated diene before, at the beginning or during the polymerization reaction to produce a functionalized polymer having at least one first functional group derived from the functionalized monomer, wherein the reaction further includes adding at least one functionalizing agent to the functionalized diene polymer to produce a second functional group at the polymer chain end, wherein the second functional group comprises a carboxylic acid group or a salt thereof. Preferably, the active reaction product is a reaction product of a functionalized monomer and a reaction initiator, preferably an organic lithium, more preferably butyl lithium.

[0079] The formation of the second functional group involves at least one functionalization reaction to produce a functional group containing a polar group, which is selected from -COOX, -OX and -SX groups, multiple thereof and combinations thereof, wherein X represents hydrogen or a cation. The functionalization reaction includes adding at least one functionalizing agent to the polymerization reaction, and the same functionalizing agent or at least one other functionalizing agent may be added thereafter. For example, a first functionalizing agent may be added to the polymerization, and the same or second functionalizing agent may be added simultaneously or subsequently to the reaction product of the first functionalizing agent and the reactive polymer chain. The addition of the first or second functionalizing agent may be part of a continuous polymerization process or part of an intermittent process. Therefore, the diene polymer according to the present disclosure is functionalized by one or more appropriate functionalizing agents to produce a second functional group, preferably an end group at the opposite end of the polymer chain compared to the position of the first functional group. The second functional group comprises at least one polar unit selected from the following groups: -COOX group, -OX group, -SX group, multiple thereof and combinations thereof, wherein X represents hydrogen or a cation. The cation may be organic or inorganic. Examples of suitable cations include, but are not limited to, Li, Na, K, Mg, Ca, Zn, Fe, Co, Ni, Al, Nd, Gd, Ti, Sn, Si, Zr, V, Mo or W and preferably include Li, Na, K, Mg and Ca. It is believed that the polar group introduced by the functionalizing monomer interacts positively with the polar group of the second functional group introduced by the functionalizing agent.

[0080] Preferably, the second functional group further comprises at least one silyl group, a silane or siloxane unit. Preferably, the second functional group further comprises 1 to 20 silicon atoms and optional oxygen atoms in addition to carbon and hydrogen atoms. Preferably, the second functional group comprises 1 to 150 carbon atoms.

[0081] Preferably, the second functional group comprises at least one selected from the group consisting of: 1 )(R 2 )-C(R 3 )(R 4 )-、-Si(R 1 )(R 2 )-O-Si(R 3 )(R 4 )-or a combination thereof, wherein R 1 , R 2 , R 3 , R 4 the same or different and selected from H and optionally containing a heteroatom selected from O, N, S and Si C1-C 12 Alkyl groups, for example alkoxy, trialkylsilyl, alkylamino, dialkylamino, trialkylsilylamino and combinations thereof. Preferably, these groups are linked to the polymer chain via a silicon atom.

[0082] Preferably, the second functional group further comprises one or more hetero groups selected from the following: (i) a thioether group; (ii) an amino group -N(R1)-, -N(R1)(R2)- or -N(R1)(R2)(R3), wherein R1, R2 and R3 are independently selected from H, C1-C6 alkyl and -Si(C1-C6 alkyl)3, provided that not all R1, R2 and R3 represent H; (iii) an ether group -OR4 or -OR5-, wherein R4 is a C1-C6 alkyl and R5 is a C1-C6 alkylene; or a plurality or combination of such hetero groups.

[0083] In one embodiment, the second functional group comprises at least one silyl, silanol or siloxane group selected from: -SiH2(OH), -SiR2(OH), -SiH(OH)2, -SiR1(OH)2, -Si(OH)3, -Si(OR1)S, -(SiR1R2O) x -R3, -Si(R3) 3-m (X) m , in which X is a halogen, x is the number of repeating units between 1 and 30, m is the number of attached groups varying from 0 to 3, R1 and R2 are identical or different and can be linear or branched alkoxy or alkyl, cycloalkyl, aryl, alkaryl, aralkyl or vinyl having in each case 1 to 20 carbon atoms, and R3 is H or linear or branched alkyl, or mononuclear aryl having in each case 1 to 20 carbon atoms.

[0084] In one embodiment, the second functional group comprises or consists of a group represented by the formula

[0085] -[-Si(R1R2)-O-] n -Si(R1R2)-OH,

[0086] wherein R1 and R2 are identical or different and may be linear or branched alkoxy or alkyl, cycloalkyl, aryl, alkaryl, aralkyl or vinyl radicals having in each case 1 to 20 carbon atoms, and n represents the number of siloxane-functional units preceding the silanol end groups varying from 1 to 49, preferably from 1 to 29.

[0087] In one embodiment of the present disclosure, the second functional group consists of or comprises a polar unit represented by formula (4):

[0088]

[0089] In formula (4), R 1 , R 2are identical or different and are each selected from H or an organic residue selected from alkyl, cycloalkyl, aryl, alkaryl, aralkyl having 1 to 20 carbon atoms and which may optionally contain one or more oxygen atoms in the carbon chain or at the beginning of the chain connected to the Si atom or in the case of cyclic residues in the carbon-carbon ring. 1 or R 2 In the case of an alkoxy residue in which the oxygen atom is attached to the Si atom, preferably, R 1 or R 2 Rather than both, R represents an alkoxy residue. 1 and R 2 Optionally, the group may independently contain one or more substituents selected from the group consisting of alkylamino, dialkylamino, alkylphosphino, alkylsilyl, alkylsilylamino and combinations thereof.

[0090] In formula (4), R 3 , R 4 Each is selected from H or an organic residue selected from alkyl, cycloalkyl, aryl, alkaryl, aralkyl having 1 to 20 carbon atoms and which may optionally contain one or more oxygen atoms in the carbon chain or ring. 3 and R 4 Optionally, the group may independently contain one or more substituents selected from the group consisting of alkylamino, dialkylamino, alkylphosphino, alkylsilyl, alkylsilylamino and combinations thereof.

[0091] In formula (4), A represents a divalent organic, aliphatic, aromatic or aliphatic and aromatic residue having 1 to 26 carbon atoms, and wherein the residue may contain heteroatoms selected from O, N, S and Si in addition to hydrogen atoms. Preferably, A represents a group

[0092] -X'n-(CY1H)m-(CY2Y3)o-(CY1H)p-

[0093] in

[0094] n is 1 or 0, m is 1, 2, 3 or 4, o is 0, 1 or 2, p is 0, 1 or 2,

[0095] X' represents O, S, NR, wherein R is H or C1-C3 alkyl, or X' is N(Si(alkyl)3), wherein each "alkyl" independently represents C1-C6 alkyl, -oxyalkyl or alkoxy;

[0096] Y1 is H or C1-C3 alkyl, Y2 is H or C1-C3 alkyl, Y3 is H or C1-C3 alkyl, preferably at least one of Y2 and Y3 is H.

[0097] Specific, non-limiting examples of A include:

[0098] -CH2-;-CH2CH2-;-CH2CH2CH2-;-C(CH3)-CH2-;-CH2-C(CH3)-CH-;-CH(CH3)-C(CH3)H-;-CH(CH3)-CH2-C(CH3)H-;-CH2-C(CH3)H-C(CH3)H-;-CH(CH3)-C(CH3)H-CH2-;-O-CH2-;-O-CH2CH2-;-O-CH2CH2-CH2-;-O-C(CH3)H-;-O-CH2CH2-;-O-C(CH3)H-CH2-;-O-CH2-C(CH3)H-;-O-CH2-C(CH3)H-CH2-;-O-CH2CH2-C(CH3)H-;-O-C(CH3)H-CH2-CH2-;-S-CH2-;-S-CH2CH2-;-S-CH2CH2-CH2-;-S-C(CH3)H-;-S-CH2CH2-;-S-C(CH3)H-CH2-;-S-CH2-C(CH3)H-;-S-CH2-C(CH3)H-CH2-;-S-CH2CH2-C(CH3)H-;-S-C(CH3)H-CH2-CH2-;

[0099] -NH-CH2-; -NH-CH2CH2-; -NH-CH2CH2-CH2-; -NH-C(CH3)H-CH2-; -NH-CH2-C(CH3)H-; -NH-CH2-C(CH3)H-CH2-; -NH-CH2CH2-C(CH3)H-; -NH-C(CH3)H-CH2-CH2-; -N( CH3)-CH2-;-N(CH3)-CH2-;-N(CH3)-CH2CH2-;-N(CH3)-CH2CH2-CH2-;-N(CH3)-C(CH3)H-CH2-; -N(CH3)-CH2-C(CH3)H-; CH2-C(CH3)H-; -N(CH3)-C(CH3)H-CH2-CH2-; N(Si(alkyl)3)-CH2-; -N(Si(alkyl)3)-CH2CH2-; N(Si(alkyl)3)-CH2CH2CH2-; -N(Si(alkyl)3)-C(CH3)H-; -N(Si(alkyl)3)-CH2CH2-; -N(Si(alkyl)3)-C(CH3)H-CH2-; -N(Si(alkyl)3)-CH2-C(CH3)H-; -N(Si(alkyl)3)-CH2-C(CH3)H-CH2-; -N(Si(alkyl)3)-CH2CH2-C(CH3)H-; -N(Si(alkyl)3)-CH2-CH2-.

[0100] In formula (4), F2 represents -COOX or -OX and X represents hydrogen, an organic cation or an inorganic cation.

[0101] In one embodiment of the present disclosure, the second functional group consists of or comprises a polar unit represented by formula (5):

[0102]

[0103] In formula (5), R4 represents a residue connecting the carbonyl group and the F2 group. R4 represents a residue comprising a C1-C3-alkylene group. Preferably, R4 is selected from C1-C3-alkylene groups which may be saturated or unsaturated and may be unsubstituted or substituted by one or more substituents, preferably selected from saturated or unsaturated C1-C 18-alkyl, wherein the alkyl group may be substituted by one or more groups selected from the group consisting of alkoxy and oxyalkyl groups having 1 to 6 carbon atoms and -SiO(Rx)3 groups, wherein each Rx independently represents an alkyl group having 1 to 6 carbon atoms. Preferably, R4 is an unsubstituted C1-C3-alkylene group, such as -CH2- or -CH2CH2-. In formula (5), F2 has the same meaning as in formula 4.

[0104] The second functional group can be generated as known in the art, for example as described in US 3,242,129 or US 4,020,036, US 4,465,809, US patent applications US2016 / 0075809 A1 and US 2016 / 0083495, WO 2021 / 009154 and US2013 / 0281605.

[0105] In one embodiment of the present disclosure, the second functional group is obtained by at least one functionalization reaction, and the at least one functionalization reaction includes using at least one silicon-containing compound as a functionalizing agent. If necessary, the reaction product is treated with a suitable reagent to obtain at least one terminal unit selected from -OX, -COOX, -SX or a combination thereof, wherein X represents H or a cation. Such suitable reagents may include steam, water, polar agents (including alcohols or acids). Silicon-containing compounds (also referred to herein as "silicon compounds") preferably have 1 to 12 silicon atoms. Silicon-containing compounds are preferably selected from divalent compounds having one Si atom per molecule, or divalent compounds of cyclic siloxanes having 3 to 12 silicon atoms per molecule as open-chain siloxanes having 2 to 12 silicon atoms per molecule, or combinations thereof. The remaining valence of the silicon atom is preferably attached to an R group, wherein each R group is independently selected from the group consisting of: hydrogen, alkylcycloalkyl, aryl aralkyl, alkaryl with up to 20 carbon atoms, wherein these groups may be optionally heterogeneous groups selected from alkylamines and silylamines connected to a carbon chain or a carbocyclic ring. Silicon-containing compounds include cyclosiloxanes according to formula (6):

[0106]

[0107] Where R 5 and R 6 Identical or different and each selected from H, residues having 1 to 20 carbon atoms, preferably selected from alkyl, cycloalkyl, aryl, alkaryl or aralkyl, wherein the group may contain one or more heteroatoms, preferably O, N, S or Si, and preferably selected from methyl. Specific examples include, but are not limited to, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane, and mixtures of cyclosiloxanes of different ring sizes.

[0108] Other suitable silicon compounds include cyclic siloxanes represented by formula (7):

[0109]

[0110] In formula (7), R 1 , R 2 , R 3 , R 4 and A are as described above with respect to formula (4).

[0111] Other suitable silicon-containing compounds include silalactones, which in addition to carbon and hydrogen atoms may contain heteroatoms selected from Si, S, O and N, preferably in a ring structure. Suitable silalactones include those corresponding to the general formula (8):

[0112]

[0113] In formula (8), R 1 , R 2 , R 3 , R 4 and A are as described above with respect to formula (4).

[0114] In another embodiment of the present disclosure, the silicon compound is selected from sulfur siloxanes, such as sulfur siloxanes according to the formula

[0115]

[0116] Wherein in formula (9), R3 and R4 are the same as R described above for formula (4) 1 and R 2 The same, and x and y are selected independently of each other and each represent 0 or 1, and preferably, the sum of x+y is 1 or 2. In formula (9), R5 is the same as A in formula (4) described above.

[0117] Cyclosiloxanes, silacolatones and thiosiloxanes can be added directly to the reactive polymer chain ends or to the reaction product of the reactive polymer chain ends with the same or different silicon compounds. Preferably, they are added to the reaction product of the reactive polymer chain ends with a cyclic siloxane, preferably a cyclic siloxane according to formula (6), or its open chain equivalent.

[0118] In one embodiment of the present disclosure, the second functional group is obtained by at least one functionalization reaction, the at least one functionalization reaction comprising using a cyclic anhydride, a lactone or a combination thereof as a functionalizing agent. Suitable anhydrides or lactones include but are not limited to those represented by the general formula (10):

[0119]

[0120] In formula (10), R4 represents a residue comprising C1-C3-alkylene. Preferably, R4 is selected from C1-C3-alkylene which may be saturated or unsaturated and may be unsubstituted or substituted by one or more substituents, preferably selected from saturated or unsaturated C1-C 18 -alkyl, wherein the alkyl group may be substituted by one or more groups selected from: alkoxy and oxyalkyl groups having 1 to 6 carbon atoms and -SiO(Rx)3 groups, wherein each Rx independently represents an alkyl group having 1 to 6 carbon atoms. Preferably, R4 is an unsubstituted C1-C3-alkylene group, such as -CH2- or -CH2CH2-.

[0121] Suitable lactones include those corresponding to formula (11):

[0122]

[0123] wherein R5 is the same as R4 described in formula (10).

[0124] The lactone and anhydride are preferably added to the polymer chain simultaneously with or subsequent to the addition of at least one other functionalizing agent. Preferably, the other functionalizing agent is a silicon compound as described above and more preferably a cyclic siloxane as described above or a linear or branched equivalent thereof.

[0125] Functionalized polymers according to the present disclosure can be provided as is or as an oil-extended polymer. Diene polymers can be oil-extended and can contain up to 100 parts of extender oil per 100 parts of polymer. In one embodiment of the present disclosure, a polymer composition is provided, which comprises at least 90% by weight, preferably at least 95% by weight of diene polymer and extender oil, and preferably the weight ratio of diene polymer to extender oil is 1:1 to 10:1. Extender oils include oils known and used for diene rubber oil extension and include oils such as TDAE (treated distillate aromatic extract)-, MES (mild extraction solvate)-, RAE (residual aromatic extract)-, TRAE (treated residual aromatic extract)-, cycloparaffin oil, paraffin oil and hydrogenated forms thereof, including oils obtained from plant-based materials (including terpenes). They are preferably added to the reaction mixture before or during solvent removal. In one embodiment of the present disclosure, the polymer is not oil-extended.

[0126] Rubber compounds

[0127] The diene polymers according to the present disclosure may be used to make rubber compounds by a process comprising combining at least one polymer composition with one or more fillers and / or one or more curing agents for crosslinking at least the diene polymer.

[0128] The rubber compound is suitable for making an article typically by a process comprising vulcanizing (curing) the rubber compound or a composition comprising a curable rubber compound.The resulting article typically contains the rubber compound in vulcanized form.

[0129] Thus, in one aspect of the present disclosure, there is provided a method of making a rubber compound, the method comprising combining a polymer according to the present disclosure with at least one filler, at least one curing agent capable of curing at least a diene polymer, or a combination thereof, and optionally one or more rubber additives, and / or one or more additional rubbers other than the diene polymer according to the present disclosure.

[0130] The one or more fillers include both active and inactive fillers. Conventional fillers include silica and preferably one or more than one carbon-based fillers, such as carbon black.

[0131] Specific examples of suitable fillers are described in

[0061] to

[0074] of US2016 / 0075809 A1, which are incorporated herein by reference. Preferably, the rubber compound of the present disclosure contains one or more carbon blacks as fillers. The filler can be used alone or in a mixture. In a particularly preferred form, the rubber composition contains a mixture of a silica filler (such as highly dispersed silica) and carbon black. The weight ratio of the silica filler to the carbon black can be 0.01: 1 to 50: 1, preferably 0.05: 1 to 20: 1. Based on 100 parts by weight of the rubber, the filler can be used in an amount ranging from 10 to 500 parts by weight, preferably 20 to 200 parts by weight.

[0132] Crosslinking agents include sulfur and sulfur donating compounds. Typical amounts of crosslinking agents include 0.1 to 10 parts by weight per 100 parts by weight of rubber.

[0133] Other rubbers include, for example, natural rubber and synthetic rubber. If present, they can be used in an amount ranging from 0.5% to 95% by weight, preferably ranging from 10% to 80% by weight, based on the total amount of rubber in the composition. Examples of suitable synthetic rubbers include those described in

[0060] of US 2016 / 0075809A1, which are incorporated herein by reference. Specific examples include high cis-polybutadiene and linear or branched low cis-polybutadiene, such as those available from ARLANXEO Deutschland GmbH.

[0134] Rubber additives are components that can improve the processing characteristics of rubber compositions, be used to crosslink rubber compositions, improve the physical properties of vulcanized products produced by rubber, improve the interaction between rubber and fillers, or be used to combine rubber with fillers. Rubber additives include reaction accelerators, antioxidants, heat stabilizers, light stabilizers, ozone stabilizers, processing aids, plasticizers, tackifiers, foaming agents, dyes, pigments, waxes, fillers, organic acids, silanes, retarders, metal oxides, and filler oils (such as DAE (distillate aromatic extracts)-, TDAE (treated distillate aromatic extracts)-, MES (mild extract solvates)-, RAE (residual aromatic extracts)-, TRAE (treated residual aromatic extracts)-, cycloparaffin oils, and heavy cycloparaffin oils). Typically, based on 100 parts by weight of rubber, vulcanization accelerators are used in an amount of 0.1 to 5 parts by weight. The total amount of rubber additives may range from 1 to 300 parts by weight, preferably 5 to 150 parts by weight, based on 100 parts by weight of total rubber in the composition.

[0135] The rubber composition can be prepared with conventional processing equipment for making and processing (vulcanizable) rubber compounds, and includes rollers, kneaders, internal mixers or mixing extruders. The rubber composition can be produced in a single stage or multi-stage process, wherein 2 to 3 mixing stages are preferred. Crosslinking agents (e.g., sulfur) and accelerators can be added in separate mixing stages, such as on rollers, wherein temperatures in the range of 30° C. to 90° C. are preferred. Crosslinking agents (e.g., sulfur) and accelerators are preferably added in the final mixing stage.

[0136] Examples of typical formulations for rubber compounds include those shown in US 2016 / 0075809 A1 and US 2016 / 0083495 A1 (Steinhauser and Gross) and International Patent Application WO 2021 / 009154 (Steinhauser).

[0137] application

[0138] Polymers according to the present disclosure can be used to produce rubber compounds and rubber vulcanized products, preferably for the production of tires or tire treads. Rubber compounds containing polymers provided herein are also suitable for the manufacture of molded articles, such as cable sheaths, hoses, transmission belts, conveyor belts, roller linings, shoe soles, sealing rings and damping elements.

[0139] Therefore, in one aspect, an article is provided, which is obtained by curing a composition comprising a rubber compound according to the present disclosure. Another aspect of the present disclosure relates to a molded article, in particular a tire or tire tread, comprising a vulcanized rubber composition obtained by vulcanizing a vulcanizable rubber compound according to the present disclosure.

[0140] The following examples are provided to further illustrate the present disclosure but are not intended to limit the present disclosure to the embodiments set forth in these examples.

[0141] method

[0142] Polymer data :

[0143] Number average molecular weight (Mn), weight average molecular weight (Mw), dispersity (also referred to as "PDI") is determined using gel permeation chromatography (GPC) (polystyrene calibration) at 35°C.

[0144] The Mooney viscosity is measured according to DIN ISO 289-1 (2018) under measuring conditions ML (1+4) at 100°C.

[0145] The comonomer content can be determined by FTIR spectroscopy on rubber films.The content of vinyl units, cis units and trans units in the polymer can be determined by FT-IR spectroscopy using absorbance and absorbance ratios as described in standard ISO 12965:2000(E).

[0146] The glass transition temperature (Tg) can be determined using DSC from the 2nd heating curve at a heating rate of 20 K / min.

[0147] Compound properties

[0148] The loss factor tan δ was measured at 0° C. and at 60° C. to determine the temperature-dependent dynamic mechanical properties. An EPLEXOR device from GABO (Eplexor 500N) was used for this purpose. The measurements were carried out at 10 Hz on Ares tapes in the temperature range of -100° C. to 100° C. in accordance with DIN 53513. The rebound resilience at 60° C. was determined in accordance with DIN 53512.

[0149] Determine the elastic properties according to DIN53513-1990. Use an elastomer testing system (MTS Systems GmbH, 831 elastomer testing system). These measurements are carried out in double shear mode, without static prestrain in the shear direction, and oscillate around 0 on cylindrical samples (two samples each 20×6 mm, pre-compressed to 5 mm thickness), and at a measuring frequency of 10 Hz in the strain range of 0.1% to 40%. This method is used to obtain the following properties:

[0150] G'(0.5%): dynamic modulus at 0.5% amplitude sweep, G'(15%): dynamic modulus at 15% amplitude sweep, G'(0.5%)-G'(15%): difference in dynamic modulus at 0.5% versus 15% amplitude sweep, tan δ(max): maximum loss factor (G" / G') over the entire measurement range at 60°C. The difference between G'(0.5%)-G'(15%) is an indication of the Payne effect of the mixture. The lower the value, the better the distribution of the filler in the mixture and the better the rubber-filler interaction.

[0151] Examples

[0152] Comparative Example 1 (Non-functionalized reference polymer); C1

[0153] A 20 L reactor free of moisture and purged with nitrogen was charged with 8500 g of hexane, 1185 g of butadiene, 315 g of styrene and 5.43 mmol of DTHFP (ditetrahydrofurylpropane). The reaction mixture was heated to 33° C. and adiabatic polymerization was initiated by adding 9.8 mmol of butyl lithium and the reaction was run for 60 min (Tmax was 60.8° C.). The reaction was terminated by adding 10 mmol of 1-octanol and stabilized with 4.5 g of IRGANOX 1520. The solvent was removed by steam stripping and the polymer was dried at 60° C. under reduced pressure.

[0154] Comparative Example 2 (reference polymer functionalized at the ω position with an end group comprising a carboxylic acid group); C2

[0155] The reaction of Example 1 was repeated, except that after the polymerization was allowed to run for 60 min, 12 mmol of octamethylcyclotetrasiloxane was added and reacted with the living polymer at 60° C. for 10 min (Tmax was 60.8° C.). Subsequently, 12 mmol of 2,2-dimethyl-1-oxa-4-thia-silacyclohexan-5-one was added and reacted at 60° C. for 30 min. The reaction was terminated and post-processed as described in Comparative Example 1.

[0156] Comparative Example 3 (reference polymer functionalized with an amine monomer (VP) at the α position); C3

[0157] 8500 g of hexane, 5.43 mmol of DTHFP and 25 mmol of 1-(4-vinylbenzyl)pyrrolidine (VP) were loaded into a 20 L reactor free of moisture and purged with nitrogen. The reaction mixture was heated to 33° C., and 11.1 mmol of butyl lithium was added and reacted for 10 min. A mixture of 1185 g of butadiene and 315 g of styrene was added and polymerized for 60 min under adiabatic conditions (Tmax was 60.8° C.). The reaction was terminated and post-processed as described in Comparative Example 1.

[0158] Example Ex01 (functionalized polymer having an amino monomer (VP) at the α position and having an alcohol-containing end group); Ex01

[0159] Comparative Example 3 was repeated, except that after the polymerization was allowed to proceed for 60 minutes, 11.3 mmol of 2,2,4-trimethyl-

[142] -oxazasilane was added and reacted at 60° C. for 30 min. The reaction mixture was worked up as described in Comparative Example 1.

[0160] Comparative Example 4 (polymer α-functionalized with DMAMS); C4

[0161] Comparative Example 3 was repeated except that a different functionalized monomer (25 mmol N,N-dimethylaminomethylstyrene, DMAMS) was used.

[0162] Example Ex02 (polymer α-functionalized with DMAMS and ω-functionalized with end groups containing alcohols); Ex02

[0163] Comparative Example 4 was repeated, except that after 60 min of polymerization, 11.3 mmol of 2,2,4-trimethyl-

[142] -oxazasilane was added and reacted at 60° C. for 30 min. The reaction mixture was worked up as described in Comparative Example 1.

[0164] Comparative Example 5; (Polymer α-functionalized with TSAES); C5

[0165] 8500 g of hexane, 5.43 mmol of DTHFP and 24 mmol of 4-(2-[N,N-bis(trimethylsilyl]ethyl)styrene (TSAES) were charged into a 20 L reactor free of moisture and purged with nitrogen. The reaction mixture was heated to 33° C., and 12.1 mmol of butyl lithium was added and reacted for 60 min. A mixture of 1185 g of butadiene and 315 g of styrene was added, and polymerized under adiabatic conditions for 60 min (Tmax was 59.0° C.). The reaction was terminated and post-processed as described in Comparative Example 1.

[0166] Example 1 (functionalized polymer having an amino monomer (VP) at the α position and a functional group containing a carboxyl group at the ω position); Ex1

[0167] Comparative Example 3 was repeated, except that after the polymerization was allowed to proceed for 60 minutes, 12 mmol of octamethylcyclotetrasiloxane was added and reacted with the living polymer at 60° C. for 10 min (Tmax was 60.8° C.). Subsequently, 12 mmol of 2,2-dimethyl-1-oxa-4-thia-silacyclohexan-5-one was added and reacted at 60° C. for 30 min. The reaction was terminated and post-processed as described in Comparative Example 1.

[0168] Example 2 (functionalized polymer having an amino monomer (DMAMS) at the α position and a functional group containing a carboxyl group at the ω position); Ex2

[0169] Comparative Example 4 was repeated, except that after the polymerization was allowed to proceed for 60 minutes, 12 mmol of octamethylcyclotetrasiloxane was added and reacted with the living polymer at 60° C. for 10 min (Tmax was 60.8° C.). Subsequently, 12 mmol of 2,2-dimethyl-1-oxa-4-thia-silacyclohexan-5-one was added and reacted at 60° C. for 30 min. The reaction was terminated and post-processed as described in Comparative Example 1.

[0170] Example 3 (functionalized polymer having an amino monomer (TSAES) at the α position and a functional group containing a carboxyl group at the ω position); Ex3

[0171] Comparative Example C4 was repeated except that after 60 minutes of reaction it was functionalized as described in Example 1 to have carboxylic acid end groups and worked up as described in Comparative Example 1.

[0172] The compounds were prepared essentially as described in US 2016 / 0083495 A1, which is incorporated herein by reference. The properties of the compounds are shown in Table 1.

[0173] Table 1

[0174]

[0175]

[0176] Δtanδ=tanδ(0℃) / tanδ(60℃);

[0177] ΔResilience = Resilience (60°C) / Resilience (23°C)

[0178] MV(polymer) = Mooney viscosity of polymer at 100°C ML 1+4 [Mooney units]

[0179] MV(compound) = Mooney viscosity of the compound at 100°C ML 1+4 [Mooney units]

[0180] ΔMV = MV(polymer) / MV(compound)

[0181] The values ​​of tan δ and rebound resilience in Table 1 are referenced to the values ​​obtained with the reference polymer of C1 and indicate the variation relative to the values ​​obtained with C1. The corresponding values ​​of C1 were set to 100.

[0182] Comparison of Ex01 to C3 and Ex02 to C4 shows the improved tan delta values ​​for polymers that are α-amino functionalized and ω-functionalized with hydroxyl-containing functional groups compared to their α-functionalized counterparts only.

[0183] Comparison of Ex1 with Ex01 and Ex2 with Ex02 shows that the properties of the α-ω-functionalized polymers can be further improved by replacing the ω-hydroxyl functional groups with ω-carboxyl functional groups.

[0184] Example 4-7.

[0185] Prepare α-ω-functionalized styrene-butadiene polymers as described in Examples 1-3, but with different amino-containing initiators to produce α-ω-polymers with different α-groups (Examples 4-6) or without amino-containing initiators to produce only ω-polymers (Comparative Example 7). In Example 4, Li-tertiary amine initiator (di-n-butylaminopropyl lithium) was used. In Example 5 (Comparative Example), Li-secondary amine initiator (mixture of lithium hexamethyleneimine and lithium pyrrolidine) was used. In Example 6, amino-functionalized monomer DMAMS was used. In Example 7 (Comparative Example), butyl lithium was used instead of amino-containing initiator as initiator to produce the same polymer, and the polymer was not α-functionalized. The polymers were compounded and cured. The compound formula is shown in Table 2, and the compound properties are shown in Table 3. As can be seen from Table 3, the compound Mooney value of the polymer with α-amino group according to the present disclosure is lower than the polymer obtained with secondary amine initiator (Comparative Example 5). This means that these compounds are easier to process. The Payne effect of the polymers with a-groups according to the present disclosure is larger (lower values) than that of Comparative Examples 5 and 7, indicating better filler dispersion. All compounds have similar rebound values ​​(43% at 23°C and between 63% and 64% at 60°C) and Shore A hardness values ​​(between 60 and 63). The Mooney scorch results are improved compared to Comparative Examples 5 and 7.

[0186] Table 2 Compound formula:

[0187]

[0188]

[0189] Table 3: Properties of the compounds:

[0190]

Claims

1. A functionalized diene polymer having at least one first functional group and at least one second functional group, wherein the first functional group is selected from a terminal group, a pendant group, and combinations thereof, and wherein the second functional group is a terminal group, The first functional group (i) comprising at least one unit derived from a functional monomer represented by formula (1) wherein R1, R2, R3 are selected from hydrogen and methyl, provided that at least one of R1, R2 and R3 is hydrogen, preferably R1, R2 and R3 are all hydrogen, n is 1, 2, 3, 4, or 5, each R4 is independently chosen from aliphatic or arylaliphatic residues having from 3 to 30 carbon atoms and wherein, if n is 1, R4 comprises at least one tertiary amine group and, in the case where n is from 2 to 5, at least one of these residues R4 comprises at least one tertiary alkylamine group; or (ii) wherein the first functional group is obtained by using a polymerization initiator having the general formula N(R1)(R2)(R3M), wherein R1 and R2 are the same or different from each other and are selected from linear or branched saturated alkyl groups, and R3 is a saturated, linear or branched alkyl carbanion and M is a basic cation, and wherein the second functional group is a terminal group and comprises at least one group selected from -COOX, -OX, -SX, a plurality thereof and combinations thereof, wherein X represents hydrogen or a cation, and wherein the functionalized diene polymer is a homopolymer or copolymer of a conjugated diene, and wherein the conjugated diene is selected from the group consisting of butadiene, isoprene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 1-phenyl-1,3-butadiene, 1,3-hexadiene, preferably butadiene.

2. The polymer according to claim 1, wherein In formula (1), R4 is selected from formula (2) and a group represented by formula (3) Wherein in formula (2), R5 is selected from the group consisting of: a chemical bond, an unsubstituted or substituted straight or branched alkylene group having 1 to 20 carbon atoms, an unsubstituted or substituted cycloalkylene group having 5 to 20 carbon atoms; or an unsubstituted or substituted arylene group having 6 to 20 carbon atoms, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R6 and R7 are each independently a cycloalkyl group having 5 to 10 carbon atoms, or an unsubstituted or substituted cycloalkyl group having 6 to 2 R8 is hydrogen; an alkyl group having 1 to 30 carbon atoms; an alkenyl group having 2 to 30 carbon atoms; an alkynyl group having 2 to 30 carbon atoms; a heteroalkyl group having 1 to 30 carbon atoms; a heteroalkenyl group having 2 to 30 carbon atoms; a heteroalkynyl group having 2 to 30 carbon atoms; a cycloalkyl group having 5 to 30 carbon atoms; an aryl group having 6 to 30 carbon atoms; or a heterocyclyl group having 3 to 30 carbon atoms, and X is a chemical bond or a N, O or S atom, in which case X is O or S or a chemical bond, R8 is absent, In formula (3), R9 is an unsubstituted or substituted alkylene group having 1 to 20 carbon atoms, an unsubstituted or substituted cycloalkylene group having 5 to 20 carbon atoms; or an unsubstituted or substituted arylene group having 6 to 20 carbon atoms, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R 10 and R 11 Each is independently an alkyl group having 1 to 30 carbon atoms; an alkenyl group having 2 to 30 carbon atoms; an alkynyl group having 2 to 30 carbon atoms; a heteroalkyl group having 1 to 30 carbon atoms; a heteroalkenyl group having 2 to 30 carbon atoms; a heteroalkynyl group having 2 to 30 carbon atoms; a cycloalkyl group having 5 to 30 carbon atoms; an aryl group having 6 to 30 carbon atoms; or a heterocyclyl group having 3 to 30 carbon atoms.

3. A polymer according to any one of the preceding claims, wherein In formula (1), R4 is selected from the group according to formula (2) or (3), and wherein In formula (2): R5 is selected from the group consisting of a chemical bond or a linear or branched alkylene group having 1 to 20 carbon atoms, R6 is an alkylene group -(CH2) n -, wherein n is 2, 3 or 4 and one or more than one but not all H atoms can be substituted by an alkyl group selected from C1 to C6 alkyl, preferably C1 to C3 alkyl; R7 is alkylene -(CH2) n -, wherein n is 2, 3 or 4 and one or more than one but not all H atoms can be substituted by an alkyl group selected from C1 to C6 alkyl, preferably C1 to C3 alkyl; X is a chemical bond connecting R6 and R7 to form a ring structure, R8 does not exist; and where In formula (3): R9 represents a chemical bond, alkylene -(CH2) n -, wherein n is 1, 2, 3 or 4 and one or more than one but not all H atoms can be substituted by an alkyl group selected from C1 to C6 alkyl, preferably C1 to C3 alkyl; R 10 Represents C1 to C3 alkyl, tri(C1-C3-)alkylsilyl R 11 Independently represent a C1 to C3 alkyl group, a tri(C1-C3-)alkylsilyl group.

4. The polymer according to any one of the preceding claims, comprising at least 50% by weight of units derived from the at least one conjugated diene.

5. The polymer according to any one of the preceding claims, further comprising units derived from a conjugated diene and further comprising units derived from at least one other conjugated diene, or at least one vinyl aromatic comonomer or a combination thereof, and preferably the vinyl aromatic comonomer is selected from styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-tert-butylstyrene, vinylnaphthalene and combinations thereof, and preferably selected from styrene.

6. A polymer according to any one of the preceding claims, wherein The second functional group comprises hydrogen atoms, 1 to 150 carbon atoms and 1 to 20 Si atoms in addition to the group selected from -COOX, -OX and -SX groups, and comprises at least one group selected from the following formula -Si(R 1 )(R 2 )-C(R 3 )(R 4 )-、-Si(R 1 )(R 2 )-O-Si(R 3 )(R 4 )- or a combination thereof, wherein R 1 , R 2 , R 3 , R 4 the same or different and selected from H and optionally containing a heteroatom selected from O, N, S and Si C1-C 12 Alkyl groups are exemplified by alkoxy, trialkylsilyl, alkylamino, dialkylamino, trialkylsilylamino, and combinations thereof.

7. A polymer according to any one of the preceding claims, wherein The second functional group has 1 to 150 carbon atoms and 1 to 20 Si atoms in addition to the group selected from -COOX, -OX and -SX, and further comprises at least one group selected from the following formula *-Si(R 1 )(R 2 )-C(R 3 )(R 4 )- and *-Si(R 1 )(R 2 )-O-Si(R 3 )(R 4 )-, Where R 1 , R 2 , R 3 , R 4 the same or different and selected from H and optionally containing a heteroatom selected from O, N, S and Si C1-C 12 Alkyl groups, for example, alkoxy, trialkylsilyl, alkylamino, dialkylamino, trialkylsilylamino, and combinations thereof, wherein "*-" indicates a bond to the polymer chain.

8. The polymer according to any one of claims 6 or 7, wherein The second functional group further comprises one or more hetero groups selected from: (i) a thioether group; (ii) an amino group -N(R1)-, -N(R1)(R2)- or -N(R1)(R2)(R3), wherein R1, R2 and R3 are independently selected from H, C1-C6 alkyl and -Si(C1-C6 alkyl)3, with the proviso that not all R1, R2 and R3 represent H; (iii) an ether group -OR4 or -OR5-, wherein R4 is a C1-C6 alkyl and R5 is a C1-C6 alkylene; or a plurality or combination of such hetero groups.

9. A polymer according to any one of the preceding claims, wherein The polymers are suitable for the production of mouldings, preferably for the production of tyres or tyre treads.

10. A method for producing a polymer according to any one of claims 1 to 9, the method comprising polymerizing at least one conjugated diene in a polymerization reaction to produce a diene polymer, wherein (i) before, at the beginning or during the polymerization reaction, at least one functionalized monomer, or an active reaction product comprising at least two repeating units derived from the functionalized monomer, is added to the conjugated diene to produce a functionalized polymer having at least one first functional group, the at least one first functional group comprising at least one unit derived from the functionalized monomer, or (ii) the polymerization is initiated by using an initiator having the general formula N(R1)(R2)(R3M) as defined in claim 1, or a combination of (i) and (ii), Wherein the reaction further comprises adding at least one functionalizing agent to the functionalized diene polymer to produce a second functional group, wherein the functionalized monomer is represented by formula (1) wherein R1, R2, R3 are selected from hydrogen and methyl, provided that at least one of R1, R2 and R3 is hydrogen, preferably R1, R2 and R3 are all hydrogen, n is 1, 2, 3, 4, or 5, each R4 is independently chosen from aliphatic or arylaliphatic residues having from 3 to 30 carbon atoms and wherein, if n is 1, R4 comprises at least one tertiary amine group and, in the case where n is from 2 to 5, at least one of these residues R4 comprises at least one tertiary alkylamine group; and Wherein the second functional group is a terminal group and comprises at least one group selected from -COOX, -OX, -SX, a plurality thereof or a combination thereof, wherein X represents hydrogen or a cation, and wherein the conjugated diene is selected from the group consisting of butadiene, isoprene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 1-phenyl-1,3-butadiene, 1,3-hexadiene, preferably butadiene.

11. A vulcanizable rubber compound comprising a polymer according to any one of claims 1 to 9 and further comprising at least one curing agent capable of curing the polymer.

12. A rubber compound comprising a polymer according to any one of claims 1 to 9 in cured form.

13. A method of making a rubber compound, the method comprising combining a polymer according to any one of claims 1 to 9 with at least one curing agent capable of curing the polymer, and optionally subjecting the polymer to curing.

14. A method of manufacturing an article, the method comprising subjecting a rubber compound comprising a polymer according to any one of claims 1 to 9 and at least one curing agent capable of curing the polymer to curing and shaping, wherein The shaping may take place before, during or after the curing.

15. An article comprising the reaction product of a curing reaction of a composition comprising a polymer according to any one of claims 1 to 9, wherein The article is selected from a tire, a tire tread, a shoe sole, a golf ball, a belt or a seal.

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