Alpha-omega-functionalized polymer

Abstract

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 end groups, side groups, and combinations thereof, the second functional group is an end group, the first functional group comprises at least one unit derived from a functionalized monomer represented by formula (1) (wherein R1, R2, and 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 selected from aliphatic residues or arylaliphatic residues having 3 to 30 carbon atoms, and R4 contains at least one tertiary amine group when n = 1, and at least one of the residues R4 contains at least one tertiary alkylamine group when n = 2 to 5); or (ii) the first functional group is obtained by using a polymerization initiator of 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 alkyls, R3 is a saturated, linear or branched alkyl carbanion, and M is an alkali cation), the second functional group is an end group, and comprises at least one group selected from -COOX; -OX; -SX (wherein X represents hydrogen or a cation), a plurality thereof, and combinations thereof. Also provided are a method for producing the polymer, an article obtained from the polymer, and a method for producing an article with the polymer, wherein the functionalized diene polymer is a homopolymer or copolymer of a conjugated diene, and 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.

Description

Technical Field

[0001] The present invention relates to a functionalized diene polymer having at least one first functional group and at least one second functional group.

Background Art

[0002] Diene rubbers are used in many different applications. They are typically combined with fillers and other additives to produce rubber compounds, which are then shaped into articles. The interaction between the rubber and the filler used to produce 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 having polar functional groups can lead to improved compounds, as described, for example, in (Patent Document 1) and (Patent Document 2) as well as in International Patent Application (Patent Document 3). Improved properties have also been reported for polymers prepared with amino-functionalized monomers, as described, for example, in (Patent Document 4) and (Patent Document 5). However, there is a continuing need for further diene polymers having improved properties.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Summary of the Invention

Means for Solving the Problem

[0004] Therefore, in one aspect, 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 end groups, side groups, and combinations thereof, and the second functional group is an end group, The first functional group is (i) Formula (1):

Chemical formula

[0005] In another aspect, a process for producing the above polymer, which includes polymerizing at least one conjugated diene by a polymerization reaction, (i) adding an active reaction product containing at least one functional monomer or at least two repeating units derived from the functional monomer to the conjugated diene before, at the start of, or during the polymerization reaction to produce a functionalized polymer having at least one first functional group containing at least one unit derived from the functional monomer, or (ii) starting the polymerization by using an initiator of the general formula: N(R1)(R2)(R3M) as described above, or a combination of (i) and (ii). The reaction further includes adding at least one functionalizing agent to the functionalized diene to generate a second functional group, and the functional monomer has the formula (1):

Chemical formula

[0006] 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. In a further aspect, there is provided a rubber compound comprising the polymer in a cured form.

[0007] In yet another aspect, there is provided a process for producing a rubber compound comprising combining the polymer with at least one curing agent capable of curing the polymer and optionally subjecting the polymer to curing.

[0008] In yet another aspect, there is provided a process for producing an article comprising subjecting a rubber compound comprising a polymer and at least one curing agent capable of curing the polymer to curing and shaping, wherein the shaping is carried out before, during or after the curing.

[0009] In another aspect, there is provided an article comprising a reaction product of a curing reaction of a composition comprising a polymer, wherein the article is selected from a tire, a tire tread, a shoe sole, a golf ball, a belt or a seal.

Mode for Carrying Out the Invention

[0010] In the following description, contrary to the term "consisting of", the terms "comprising", "containing", "including", and "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 be present in the composition.

[0011] The term "consisting of" is used when it is meant to exclude the presence of any additional components, steps, or procedures.

[0012] In the following description, norms may be used. Unless otherwise specified, the version of the norms that is effective as of March 1, 2020 is used. For example, if the norms are expired and the version is not valid on that date, the version that was valid on the date closest to March 1, 2020 is referred to.

[0013] In the following description, the amounts of the components of a composition or polymer may be expressed in the same sense 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 is 100% unless otherwise specified.

[0014] The term "phr" means parts per hundred parts of rubber.

[0015] The ranges specified in this disclosure include and disclose all values between the endpoints of the range and include the endpoints unless otherwise specified.

[0016] The term "substituted" is used to describe a hydrocarbon-containing organic compound in which at least one hydrogen atom is replaced by a chemical entity other than hydrogen. That chemical entity is referred to herein with the same meaning as "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 are replaced. For example, the term "unsubstituted methyl residue" refers to methyl, i.e., -CH3.

[0017] Diene polymer The 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, this first functional group is located at the beginning, i.e., the alpha position, of the polymer chain. However, in addition or as an alternative possibility, the first functional group can also be present as one or more side groups. The diene polymers according to the present disclosure further contain at least a second functional group. The second functional group is a terminal group and is preferably present on the opposite side of the polymer chain with respect to the position of the first functional group.

[0018] The diene polymers according to the present disclosure contain units derived from at least one conjugated diene. The diene polymers according to the present disclosure can be obtained by a polymerization reaction including the 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 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.

[0019] 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.

[0020] In another embodiment of the present disclosure, the diene polymer is a copolymer of conjugated dienes, preferably a copolymer comprising units derived from one or more conjugated dienes and / or one or more vinyl aromatic monomers as described above, and optionally one or more units derived from one or more other comonomers. Examples of vinyl aromatic monomers include, but are not limited to, styrene, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, para-tert-butylstyrene, vinylnaphthalene, and combinations thereof. Styrene is particularly preferred. Vinyl aromatic monomers also include substituted vinyl aromatic monomers in which one or more hydrogen atoms of the vinyl aromatic monomer are replaced by a group having one or more heteroatoms preferably selected from heteroatoms, or Si, N, O, H, Cl, F, Br, S, and combinations thereof. Substituted monomers also include vinyl aromatic monomers having a functional group having one or more heteroatoms, or a unit containing at least one functional group having one or more heteroatoms. Preferably, the heteroatom is selected from Si, N, O, H, Cl, F, Br, S, and combinations thereof. Examples of functional groups include, but are not limited to, hydroxy, thiol, thioether, ether, halogen carboxylic acid group or a salt thereof, and combinations thereof. Such functionalized conjugated monomers are preferably copolymerized with one or more of the above vinyl aromatic monomers. In a preferred embodiment, the diene polymer according to the present disclosure comprises repeating units derived from 1,3-butadiene and styrene.

[0021] Preferably, the polymer according to the present disclosure contains units derived from 1,3-butadiene of at least 50% by weight, preferably at least 60% by weight, based on the weight of the polymer. In one embodiment of the present disclosure, the diene polymer contains units derived from 1,3-butadiene of at least 60% by weight, or at least 75% by weight. In one embodiment, the polymer according to the present disclosure contains units derived from at least 75% by weight or at least 95% by weight of one or more conjugated monomers.

[0022] In one embodiment of the present disclosure, the diene polymer contains units derived from one or more comonomers of 0 to 49% by weight, or 0% to 40% by weight, based on the total weight of the polymer.

[0023] In one embodiment, the diene polymer of the present disclosure contains units derived from one or more conjugated dienes other than 1,3-butadiene of 0 to 20% by weight.

[0024] In one embodiment, the diene polymer according to the present disclosure contains units derived from 1,3-butadiene of at least 50% by weight, preferably at least 60% by weight, based on the weight of the polymer, and units derived from one or more vinyl aromatic copolymers of at least 5% by weight, preferably 49% by weight or less, preferably 5% to 40% by weight, or 10% to 35% by weight, of one or more vinyl aromatic comonomers, preferably styrene. Optionally, such a polymer 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 units derived from one or more conjugated dienes of 55% to 92% by weight and units derived from a vinyl aromatic comonomer of 5.8% to 45% by weight.

[0025] Other suitable conjugated dienes as comonomers include, but are not limited to, myrcene, ocimene and / or farnesene. The conjugated dienes also include substituted conjugated dienes in which one or more hydrogen atoms of the diene are replaced by a group containing one or more heteroatoms selected from Si, N, O, H, Cl, F, Br, S and combinations thereof, or a functional group containing one or more heteroatoms, for example a functional group having one or more heteroatoms selected from Si, N, O, H, Cl, F, Br, S and combinations. Examples of functional groups include, but are not limited to, hydroxy, thiol, thioether, ether, halogen and one or more carboxylic acid groups or salts thereof and combinations thereof. Such functionalized conjugated dienes are preferably copolymerized with one or more of the above conjugated dienes. Suitable copolymerizable comonomers further include one or more alpha-olefins, such as ethene, propene, 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 units derived from 0 to 20% by weight of one or more alpha-olefins.

[0026] Suitable comonomers also include one or more other copolymerizable comonomers (other than the above functionalized comonomers) that introduce a functional group, including a crosslinking site, a branching site, a branch, or a functional group, but are not limited thereto. In one embodiment of the present disclosure, the diene polymer contains units derived from 0% to 10% by weight or 0% to 5% by weight of such other comonomers. Such comonomers include, for example, divinylbenzene, trivinylbenzene, divinylnaphthalene.

[0027] Combinations of one or more of the same chemical type of comonomers as those described above and 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 1% by weight or less.

[0028] The diene polymers according to the present disclosure preferably have an average molecular weight (number average, Mn) of from 10,000 to 2,000,000 g / mol, preferably from 100,000 to 1,000,000 g / mol.

[0029] Preferably, the diene polymers according to the present disclosure have a glass transition temperature (Tg) of from about -110 °C to about +20 °C, preferably from about -110 °C to about 0 °C.

[0030] Preferably, the diene polymers according to the present disclosure have a Mooney viscosity [ML 1+4(100 °C)] of from about 10 to about 200, preferably from about 30 to about 150 Mooney units.

[0031] Preferably, the polymer has a dispersity of from about 1.03 to about 3.5.

[0032] The diene polymers can be prepared by methods known in the art. Preferably, the polymers can be obtained by a process 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 non-metallic catalyst systems. Preferred coordination catalysts are those based on Ni, Co, Ti, Zr, Nd, V, Cr, Mo, W or Fe.

[0033] Preferably, the polymerization reaction includes anionic solution polymerization. The initiator for anionic solution polymerization preferably includes an organometal based on an alkali or alkaline earth metal. Examples include methyllithium, ethyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, pentyllithium, n-hexyllithium, cyclohexyllithium, octyllithium, decyllithium, 2-(6-lithio-n-hexoxy)tetrahydropyran, 3-(tert-butyldimethylsiloxy)-1-propyllithium, phenyllithium, 4-butylphenyllithium, 1-naphthyllithium, p-tolyllithium, and allyllithium compounds derived from tertiary N-allylamines such as [1-(dimethylamino)-2-propenyl]lithium, [1-[bis(phenylmethyl)amino]-2-propenyl]lithium, [1-(diphenylamino)-2-propenyl]lithium, [1-(1-pyrrolidinyl)-2-propenyl]lithium, lithium pyrrolide, lithium piperidide, lithium hexamethylene imide, lithium 1-methylimidazolid, lithium 1-methylpiperazide, lithium morpholide, lithium dicyclohexylamide, lithium dibenzylamide, lithium diphenylamide, etc., but are not limited thereto. Allyllithium compounds and lithium amides can also be prepared in situ by reacting an organolithium compound with each tertiary allylamine or each secondary amine. Difunctional and polyfunctional organolithium compounds, such as 1,4-dilithiobutane and dilithium piperazide, can also be used. Preferably, n-butyllithium, sec-butyllithium or a combination thereof is used.

[0034] To generate the first functional group, one or more amine-functionalized monomers are added before polymerization, at the start of polymerization, and / or during polymerization, but not at the end of polymerization. The amine-functionalized monomer can also be added as an active reaction product comprising at least two repeating units derived from the functionalized monomer. Such an active reaction product can be produced by reaction of one or more amine-functionalized monomers with an organometallic compound, such as an initiator for anionic polymerization as described above, preferably an organolithium compound, preferably an alkyllithium, more preferably butyllithium. The reaction can include oligomerization of the amine-functionalized monomer, or co-oligomerization of the amine-functionalized monomer with one or more other comonomers, such as a conjugated diene as described above. The oligomerization or co-oligomerization can lead to an oligomerized functionalized monomer having from 2 to 200 units derived from the amine-functionalized monomer. An active reaction product as referred to herein means having either or both an intact carbon-carbon double bond by which the monomer can participate in a polymerization reaction or a carbanion by which the monomer can participate in a polymerization reaction. The reaction product can be produced in a separate reaction and then added to the polymerization reactor, or it can be formed in situ, for example, by co-supplying one or more amine-functionalized monomers and a reaction initiator to the polymerization reaction, or by first reacting the initiator with the amine-functionalized monomer before adding a conjugated diene monomer.

[0035] An amine-functionalized monomer according to the present disclosure has the formula (1): [Chemical formula] (wherein R1, R2, and 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 selected from aliphatic residues or arylaliphatic residues having 3 to 30 carbon atoms. When n is 1, R4 contains at least one tertiary amine group. When n is 2 to 5, at least one of the residues R4 contains at least one tertiary alkylamine group.) corresponds to. In one embodiment of the present disclosure, R4 has the formula (2)

Chemical formula

Chemical formula

[0036] As specific examples, 4-(2-(N,N-bis(trimethylsilyl)amino)ethyl)styrene

Chemical formula

Chemical formula

Chemical formula

[0037] In another embodiment of the present disclosure, the first functional group is a general formula for initiating polymerization: N(R1)(R2)(R3M) (wherein R1 and R2 are the same or different from each other, preferably selected from linear or branched saturated alkyls having 2 to 18 carbon atoms, more preferably 3 to 12 or 3 to 8 carbon atoms, R3 is a saturated alkyl carbanion which may be linear or branched, preferably linear) It is obtained by using a polymerization initiator of

[0038] Preferably, R3 contains 2 to 12, preferably 3 to carbon atoms.

[0039] M is a metal cation, preferably an alkali metal cation, more preferably a lithium cation, Li + represents.

[0040] In one embodiment of the present disclosure, the polymerization initiator of 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 are linear, and more preferably all of R1, R2, and R3 are linear.

[0041] In another embodiment of the present disclosure, the polymerization initiator of the general formula: N(R1)(R2)(R3M) is branched, and at least one, preferably both, 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 the residue: (R4)(R5)(R6)C-CH2- (wherein R4, R5, and R6 are selected from hydrogen, linear or branched saturated alkyls having 1 to 14 carbon atoms, preferably 1 to 4 carbon atoms, provided that not all of R4, R5, and R6 are H, and provided that when both R4 and R5 are H, 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.

[0042] The initiator can be prepared, for example, by reacting a halogenated, preferably chlorinated, tertiary linear or branched amine, preferably a monohalogenated tertiary linear or branched amine, with an alkali metal, preferably lithium, as is known in the art. The halogenated tertiary amine corresponds to the above amine in a state where R1, R2 and R3 have the same meaning except that the residue R3 is not an alkyl carbanion and is preferably halogenated at the terminal position and is a halogenated alkyl.

[0043] A combination of at least one amine-containing initiator as described above and at least one amino-functionalized monomer as described above can be used.

[0044] Randomizing agents and controlling agents known in the art can be used in the polymerization to control the structure of the polymer. Such reagents include, for example, those described in

[0027] of US Patent Application Publication No. 2016 / 0075809 A1, which is incorporated herein by reference.

[0045] 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 and isomers thereof, but are not limited thereto. Further examples include alkenes 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. The solvent may also be mixed with a polar solvent if appropriate.

[0046] Coincidence can be carried out by first introducing the monomer and the solvent, and then initiating the polymerization by adding an initiator or a catalyst. The polymerization can also be carried out in a feeding process in which the polymerization reactor is filled by adding the monomer and the solvent. The initiator or the catalyst is introduced or added together with the monomer and the solvent. Modifications such as introducing the solvent into the reactor, adding the initiator or the catalyst, and subsequently adding the monomer can be applied. The polymerization can be carried out in a continuous mode or in a batch mode. Further monomers and solvents can be added during the polymerization or at the end of the polymerization. The polymerization can be carried out at standard pressure or at high pressure (e.g., 1 - 10 bar) or under reduced pressure. Typical reaction temperatures include temperatures from 35°C to 130°C.

[0047] In one embodiment of the present disclosure, there is provided a process for producing a functionalized polydiene polymer according to the present disclosure, the process comprising polymerizing at least one conjugated diene in a polymerization reaction to produce a diene polymer, and adding at least one functionalized monomer (or an active reaction product comprising at least two repeating units derived from the functionalized monomer, e.g., 2 - 200 units) derived from the functionalized monomer to the conjugated diene before, at the start of, or during the polymerization reaction to produce a functionalized polymer having at least one first functional group derived from the functionalized monomer, the reaction further comprising adding at least one functionalizing agent to the functionalized diene polymer to generate a second functional group at the polymer chain ends, wherein the second functional group comprises a carboxylic acid group or a salt thereof. Preferably, the active reaction product is a reaction product of the functionalized monomer and a reaction initiator, preferably an organolithium, more preferably butyllithium.

[0048] The formation of the second functional group involves at least one functionalization reaction to produce a functional group comprising a polar group selected from -COOX, -OX, and -SX groups (wherein X represents hydrogen or a cation), a plurality thereof, and combinations thereof. The functionalization reaction involves the addition of at least one functionalizing agent to the polymerization reaction, which may be followed by the addition of the same or at least one other functionalizing agent. For example, a first functionalizing agent may be added to the polymerization, and the same or a second functionalizing agent may be added simultaneously or subsequently to the reaction product of the first functionalizing reagent and the reactive polymer chain. The addition of the first or second functionalizing agent can be part of a continuous polymerization process or part of a batch process. Therefore, the diene polymer according to the present disclosure is functionalized with one or more suitable functionalizing agents to produce end groups on the opposite side of the polymer chain relative to the position of the second functional group, preferably the first functional group. The second functional group comprises at least one polar unit selected from the group -COOX group; -OX group; -SX group (wherein X represents hydrogen or a cation), a plurality thereof, and combinations thereof. The cation can be an organic or inorganic cation. 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, preferably Li, Na, K, Mg, and Ca. The polar groups introduced by the functionalized monomer are thought to interact positively with the polar groups of the second functional group introduced by the functionalizing agent.

[0049] Preferably, the second functional group further comprises at least one silyl, one silane, or siloxane unit. Preferably, the second functional group comprises 1 to 20 silicon atoms, and optionally oxygen atoms, in addition to carbon and hydrogen atoms. Preferably, the second functional group comprises 1 to 150 carbon atoms.

[0050] Preferably, the second functional group has the 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 are the same or different and each contains at least one group selected from H and a C1-C 12 alkyl group which may optionally contain a heteroatom selected from O, N, S and Si, such as an alkoxy group, a trialkylsilyl group, an alkylamino group, a dialkylamino group, a trialkylsilylamino group and combinations thereof). Preferably, these groups are bonded to the polymer chain via a silicon atom.

[0051] Preferably, 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, provided that not all of R1, R2 and R3 represent H), (iii) an ether group: -OR4 or -OR5- (wherein R4 is C1-C6 alkyl and R5 is C1-C6 alkylene), or a plurality or combination of such hetero groups.

[0052] In one embodiment, the second functional group is -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(Wherein X is halogen, x is the number of repeating units from 1 to 30, m is the number of linking groups which varies from 0 to 3, R1 and R2 are the same or different and in each case can be a linear or branched alkoxy or alkyl, cycloalkyl, aryl, alkylaryl, aralkyl or vinyl group having from 1 to 20 carbon atoms, and R3 is H or a linear or branched alkyl or monocyclic aryl group having from 1 to 20 carbon atoms in each case) and comprises at least one silyl, silanol or siloxane group selected therefrom.

[0053] In one embodiment, the second functional group has the formula: -[-Si(R1R2)-O-] n -Si(R1R2)-OH (Wherein R1 and R2 are the same or different and in each case can be a linear or branched alkoxy or alkyl, cycloalkyl, aryl, alkylaryl, aralkyl or vinyl group having from 1 to 20 carbon atoms, and n represents the number of units of the siloxane functional group before the silanol end group, which varies from 1 to 49, preferably from 1 to 29) and comprises or consists of a group represented by.

[0054] In one embodiment of the present disclosure, the second functional group has the formula (4):

Chemical formula

[0055] In formula (4), R 1 , R 2 are the same or different and are each selected from H or an organic residue selected from alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl groups having from 1 to 20 carbon atoms and optionally containing one or more oxygen atoms in the carbon chain, at the beginning of the chain bonded to the Si atom, or in the case of a cyclic residue in the carbon-carbon ring. An alkoxy residue in which an oxygen atom is bonded to the Si atom is represented by R 1 or R2 When represented by, preferably, R 1 or R 2 Either (but not both) represents an alkoxy residue. R 1 and R 2 may also optionally contain, independently of each other, one or more substituents selected from alkylamino, dialkylamino, alkylphosphino, alkylsilyl, alkylsilylamino groups and combinations thereof.

[0056] In formula (4), R 3 , R 4 are each selected from organic residues selected from alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl groups having 1 to 20 carbon atoms and optionally containing one or more oxygen atoms in the carbon chain or carbon ring. R 3 and R 4 may also optionally contain, independently of each other, one or more substituents selected from alkylamino, dialkylamino, alkylphosphino, alkylsilyl, alkylsilylamino groups and combinations thereof.

[0057] In formula (4), A is a divalent organic, aliphatic, aromatic or aliphatic and aromatic residue having 1 to 26 carbon atoms, and the residue represents a residue that may contain a heteroatom selected from O, N, S, and Si in addition to a hydrogen atom. Preferably, A is the group: -X’n-(CY1H)m-(CY2Y3)o-(CY1H)p- (wherein, n is 1 or 0, m is 1, 2, 3 or 4, o is 0, 1 or 2, p is 0, 1 or 2, X’ represents O, S, NR (where R is H or C1-C3 alkyl), or X’ is N(Si(alkyl)3) (where each “alkyl” independently represents C1-C6 alkyl, -oxyalkyl or alkoxy; 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) represents.

[0058] Specific, non-limiting examples of A include: -CH2-; -CH2CH2-; -CH2CH2CH2-; -C(CH3)-CH2-; -CH2-C(CH3)-CH2-; -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; -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-; -N(CH3)-CH2-C(CH3)H-CH2-; -N(CH3)-CH2CH2-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)-C(CH3)H-CH2-CH2- include the following.

[0059] In formula (4), F2 represents -COOX or -OX, and X represents hydrogen, an organic cation, or an inorganic cation.

[0060] In one embodiment of the present disclosure, the second functional group has the formula (5): [Chemical formula] is composed of or contains polar units represented by the following formula.

[0061] In formula (5), R4 represents a residue that links a carbonyl group and an F2 group. R4 represents a residue containing a C1-C3 alkylene group. Preferably, R4 may be saturated or unsaturated, and may be unsubstituted, saturated or unsaturated C1-C 18Alkyl (wherein the alkyl may be substituted by one or more groups selected from an alkoxy group and an oxyalkyl group having 1 to 6 carbon atoms) and -SiO(Rx)3 group (wherein each Rx independently represents an alkyl having 1 to 6 carbon atoms), preferably, is selected from C1-C3 alkylene groups which may be substituted by one or two or more substituents. Preferably, R4 is unsubstituted C1-C3 alkylene, such as -CH2- or -CH2CH2-. In formula (5), F2 has the same meaning as in formula 4.

[0062] The second functional group can be generated as known in the art, for example, as described in U.S. Patent No. 3,242,129 or U.S. Patent No. 4,020,036, U.S. Patent No. 4,465,809, U.S. Patent Application Publication No. 2016 / 0075809 A1 and U.S. Patent Application Publication No. 2016 / 0083495, International Publication No. 2021 / 009154 Pamphlet and U.S. Patent Application Publication No. 2013 / 0281605.

[0063] In one embodiment of the present disclosure, the second functional group is obtained by at least one functionalization reaction involving the use of 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 (wherein X represents H or a cation), or combinations thereof. Such suitable reagents may include polar reagents such as steam, water, alcohol, or acid. The silicon-containing compound, also referred to herein as a "compound containing silicon," preferably has from 1 to 12 silicon atoms. The silicon-containing compound is preferably a divalent compound having one Si atom per molecule or a divalent compound that is an open-chain siloxane having 2 to 12 Si atoms per molecule, or a cyclic siloxane having 3 to 12 silicon atoms per molecule, or a combination thereof. The remaining valences of the silicon atoms are preferably bonded to R groups, where each R group is independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, aralkyl, and alkaryl groups having 20 or fewer carbon atoms, where the groups may optionally be hetero groups bonded to a carbon chain or carbon ring selected from alkylamines and silylamines. The silicon-containing compounds include those of formula (6): [Chemical formula] (wherein R 5 and R 6 are the same or different and are each selected from residues having 1 to 20 carbon atoms, preferably selected from alkyl, cycloalkyl, aryl, alkaryl, or aralkyl groups, where the group may contain one or more heteroatoms, preferably O, N, S, or Si, and is preferably selected from methyl) and include cyclic siloxanes according to. Specific examples include, but are not limited to, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane, as well as mixtures of cyclic siloxanes of different ring sizes.

[0064] Other suitable silicon-containing compounds include those of formula (7):

Chem.

[0065] In formula (7), R 1 , R 2 , R 3 , R 4 and A are as described above with respect to formula (4).

[0066] Other suitable silicon-containing compounds include silalactones which may contain heteroatoms selected from Si, S, O and N in the ring structure in addition to carbon and hydrogen atoms. Suitable silalactones include general formula (8):

Chem.

[0067] In another embodiment of the present disclosure, the silicon-containing compound is a thiasiloxane, for example, of formula (9):

Chem.

[0068] Cyclic siloxanes, silalactones, and thiasiloxanes can be directly added to the reactive polymer chain ends or to the reaction products of the reactive polymer chain ends with the same or different silicon-containing compounds. Preferably, they are added to the reaction products of the reactive polymer chain ends with cyclic siloxanes, or their ring-opening equivalents, preferably according to formula (6).

[0069] In one embodiment of the present disclosure, the second functional group is obtained by at least one functionalization reaction involving the use of a cyclic anhydride, lactone, or a combination thereof as a functionalizing agent. Suitable anhydrides or lactones include the general formula (10)

Chemical formula

[0070] In formula (10), R4 represents a residue containing a C1-C3 alkylene group. Preferably, R4 may be saturated or unsaturated and may be unsubstituted, preferably a C1-C 18 C1-C3 alkylene group which may be substituted by one or more substituents selected from alkyl, which is a C1-C3 alkylene group which may be substituted by one or more groups selected from alkoxy groups and oxyalkyl groups having 1 to 6 carbon atoms and -SiO(Rx)3 groups (wherein each Rx independently represents an alkyl having 1 to 6 carbon atoms). Preferably, R4 represents an unsubstituted C1-C3 alkylene, such as -CH2- or -CH2CH2-.

[0071] Suitable lactones include formula (11):

Chemical formula

[0072] The lactone and the acid anhydride are preferably added simultaneously with or after the addition of at least one other functionalizing agent to the polymer chain. Preferably, the other functionalizing agent is a silicon-containing compound as described above, more preferably a cyclic siloxane as described above or a linear or branched equivalent thereof.

[0073] The functionalized polymer according to the present disclosure can be provided as such or as an oil-extended polymer. The diene polymer can be oil-extended and can contain up to 100 parts of extender oil per 100 parts of the polymer. In one embodiment of the present disclosure, a polymer composition is provided that includes at least 90% by weight, preferably at least 95% by weight, of a diene polymer and an extender oil, and preferably the weight ratio of the diene polymer to the extender oil is from 1:1 to 10:1. The extender oil includes oils such as those known and used for oil-extending diene rubbers, including their hydrogenated forms such as oils obtained from TDAE (treated distillate aromatic extract)-, MES (mild extract solvate)-, RAE (residual aromatic extract)-, TRAE (treated residual aromatic extract)-, naphthenic oil, paraffinic oil, and terpene and other plant-derived substances. 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.

[0074] Rubber compound The diene polymer according to the present disclosure can be used to produce a rubber compound by a process that includes combining at least one polymer composition with one or more fillers and / or one or more curing agents for at least crosslinking the diene polymer.

[0075] The rubber compound is typically suitable for manufacturing an article by a process that includes vulcanizing (curing) a composition that includes the rubber compound or a curable rubber compound. The resulting article typically contains the rubber compound in a vulcanized form.

[0076] Accordingly, in one aspect of the present disclosure, there is provided a process for manufacturing a rubber compound, which includes combining a polymer according to the present disclosure with at least one filler, at least one curing agent capable of curing at least one diene polymer or a combination of diene polymers, optional one or more rubber additives, and / or one or more additional rubbers other than the diene polymers according to the present disclosure.

[0077] The one or more fillers include both active and inactive fillers. Conventional fillers include silica and preferably one or two or more carbon-based fillers such as carbon black. Specific examples of suitable fillers are described in paragraphs

[0061] to

[0074] of US Patent Application Publication No. 2016 / 0075809 A1, which is incorporated herein by reference. Preferably, the rubber compound of the present disclosure contains one or more carbon blacks as fillers. The fillers can be used alone or as a mixture. In a particularly preferred form, the rubber composition contains a mixture of a silica filler, such as high-dispersion silica, and carbon black. The weight ratio of the silica filler to carbon black can be from 0.01:1 to 50:1, preferably from 0.05:1 to 20:1. The fillers can be used in an amount in the range of 10 to 500, preferably 20 to 200 parts by weight based on 100 parts by weight of the rubber.

[0078] The crosslinking agents include sulfur and sulfur donor compounds. Typical amounts of the crosslinking agents include 0.1 to 10 parts by weight per 100 parts by weight of the rubber.

[0079] The additional rubber includes, for example, natural rubber and synthetic rubber. If present, they can be used in an amount in the range of 0.5 to 95% by weight, preferably in the range of 10 to 80% by weight, based on the total amount of rubber in the composition. Examples of suitable synthetic rubbers include those described in paragraph

[0060] of US Patent Application Publication No. 2016 / 0075809 A1, which is 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.

[0080] The rubber additive is a component that can improve the processing characteristics of the rubber composition, and is useful for crosslinking the rubber composition, improving the physical properties of the crosslinked product produced from the rubber, improving the interaction between the rubber and the filler, or binding the rubber to the filler. Rubber auxiliaries include reaction accelerators, antioxidants, heat stabilizers, light stabilizers, ozone stabilizers, processing aids, plasticizers, tackifiers, foaming agents, dyes, pigments, waxes, extenders, organic acids, silanes, vulcanization retarders, metal oxides, and extender oils such as DAE (distillate aromatic extract)-, TDAE (treated distillate aromatic extract)-, MES (mild extract solvate)-, RAE (residual aromatic extract)-, TRAE (treated residual aromatic extract)-, naphthenic oil, and heavy naphthenic species. Typically, the vulcanization accelerator is used in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the rubber. The total amount of rubber additives can be in the range of 1 to 300 parts by weight, preferably 5 to 150 parts by weight, based on 100 parts by weight of the total rubber in the composition.

[0081] The rubber composition can be prepared using conventional processing equipment for the production and processing of (vulcanizable) rubber compounds, including rollers, kneaders, internal mixers, or mixing extruders. The rubber composition can be produced in a single-stage or multi-stage process, with 2 to 3 mixing stages being preferred. Crosslinking agents, such as sulfur, and vulcanization accelerators can be added in a separate mixing stage, for example, using rollers, and a temperature in the range of 30°C to 90°C is preferred. Crosslinking agents, such as sulfur, and vulcanization accelerators are preferably added in the final mixing stage.

[0082] Examples of rubber compound formulations include those shown in US Patent Application Publication No. 2016 / 0075809 A1 and US Patent Application Publication No. 2016 / 0083495 A1 (Steinhauser and Gross) and International Patent Application Publication No. 2021 / 009154 Pamphlet (Steinhauser).

[0083] Use The polymers according to the present disclosure can preferably be used for the production of rubber compounds and rubber vulcanizates, preferably for the production of tires or tire treads. Rubber compounds containing the polymers provided herein are also suitable for the production of molded articles, for example for the production of cable sheaths, hoses, drive belts, conveyor belts, roll linings, shoe soles, sealing rings and damping elements.

[0084] Therefore, in one aspect, there is provided an article obtained from the curing of a composition comprising a rubber compound according to the present disclosure. Another aspect of the present disclosure relates to a molded article, particularly a tire or tire tread, comprising a vulcanized rubber composition obtained by vulcanization of a vulcanizable rubber compound according to the present disclosure.

[0085] The following examples are provided to further illustrate the present disclosure, but are not intended to limit the present disclosure to the embodiments shown in these examples.

[0086] Method Polymer data: The number average molecular weight Mn, the weight average molecular weight (Mw), and the polydispersity D = Mw / Mn, also referred to as "PDI", were measured using gel permeation chromatography (GPC) at 35 °C (polystyrene calibration).

[0087] The Mooney viscosity was measured according to DIN ISO 289-1 (2018) under the measurement conditions ML(1+4) at 100 °C.

[0088] The comonomer content can be measured for the rubber film by FTIR spectroscopy. The content of vinyl, cis and trans units in the polymer can be measured by FT-IR spectroscopy using absorbance and absorbance ratios as described in standard ISO 12965-2000(E).

[0089] The glass transition temperature (Tg) can be determined from the second heating curve using DSC at a heating rate of 20 K / min.

[0090] Compound properties The temperature-dependent dynamic mechanical properties were determined by measuring the loss factor tan δ at 0 °C and 60 °C. An EPLEXOR device (Eplexor 500 N) from GABO was used for this purpose. The measurements were carried out in accordance with DIN 53513 at 10 Hz for an Ares strip in the temperature range from -100 °C to 100 °C. The rebound resilience at 60 °C was measured in accordance with DIN 53512.

[0091] The elastic properties were measured in accordance with DIN53513-1990. An elastomer test system (MTS Systems GmbH, 831 Elastomer Test System) was used. The measurements were carried out in double shear mode for cylindrical samples (two samples, each 20×6 mm, pre-compressed to 5 mm thickness) without static pre-strain in the shear direction and with an amplitude of approximately 0 and a strain range of 0.1 to 40% at a measurement frequency of 10 Hz. This method provides the following properties: G’(0.5%): Dynamic coefficient at 0.5% amplitude sweep, G’(15%): Dynamic coefficient at 15% amplitude sweep, G’(0.5%) - G’(15%): Difference in dynamic coefficient at 0.5% with respect to 15% amplitude sweep, tan δ(max): Maximum loss factor (G” / G’) over the entire measurement range at 60 °C were used. The difference G’(0.5%) - G’(15%) is an indicator of the Payne effect of the mixture. The lower this value, the better the filler distribution in the mixture and the better the rubber-filler interaction.

Examples

[0092] Comparative Example 1 (non-functionalized reference polymer); C1 An 8500 g of hexane, 1185 g of butadiene, 315 g of styrene and 5.43 mmol of DTHFP (ditetrahydrofurylpropane) were charged into a completely dry and nitrogen-flushed 20 L reactor. The reaction mixture was heated to 33 °C and the adiabatic polymerization was initiated by adding 9.8 mmol of butyllithium, and the reaction was carried out for 60 minutes (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 distillation and the polymer was dried at 60 °C under reduced pressure.

[0093] Comparative Example 2 (reference polymer functionalized with a terminal group containing a carboxylic acid group at the omega position); C2 The reaction of Example 1 was repeated except that 12 mmol of octamethylcyclotetrasiloxane was added after the polymerization was carried out for 60 minutes and reacted with the living polymer at 60 °C (Tmax was 60.8 °C) for 10 minutes. Then, 12 mmol of 2,2-dimethyl-1-oxa-4-thia-cyclohexan-5-one was added and reacted at 60 °C for 30 minutes. The reaction was terminated and worked up as described in Comparative Example 1.

[0094] Comparative Example 3 (reference polymer functionalized with an amine-monomer (VP) at the alpha position); C3 An 8500 g of hexane, 5.43 mmol of DTHFP and 25 mmol of 1-(4-vinylbenzyl)pyrrolidine (VP) were charged into a completely dry and nitrogen-flushed 20 L reactor. The reaction mixture was heated to 33 °C, 11.1 mmol of butyllithium was added and reacted for 10 minutes. A mixture of 1185 g of butadiene and 315 g of styrene was added and polymerized under adiabatic conditions for 60 minutes (Tmax was 60.8 °C). The reaction was terminated and worked up as described in Comparative Example 1.

[0095] Example Ex01 (functionalized at the alpha position with an amino - monomer (VP) and with an alcohol containing a terminal group); Ex01 The reaction mixture was worked - up as described in Comparative Example 1, repeating Comparative Example 3 except that 11.3 mmol of 2,2,4 - trimethyl -

[0142] - oxazasilane was added after 60 minutes of polymerization and the reaction was carried out at 60 °C for 30 minutes.

[0096] Comparative Example 4 (polymer alpha - functionalized with DMAMS); C4 Comparative Example 3 was repeated except that a different functionalized monomer (25 mmol of N,N - dimethylaminomethylstyrene, DMAMS) was used.

[0097] Example Ex02 (polymer alpha - functionalized with DMAMS and omega - functionalized with an alcohol containing a terminal group); Example 4 was repeated except that 11.3 mmol of 2,2,4 - trimethyl -

[0142] - oxazasilane was added after 60 minutes of polymerization and the reaction was carried out at 60 °C for 30 minutes. The reaction mixture was worked - up as described in Comparative Example 1.

[0098] Comparative Example 5; (polymer alpha - functionalized with TSAES); C5 An 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 which was completely dry and purged with nitrogen. The reaction mixture was heated to 33 °C, 12.1 mmol of butyllithium was added and the reaction was carried out for 60 minutes. A mixture of 1185 g of butadiene and 315 g of styrene was added and polymerized for 60 minutes under adiabatic conditions (Tmax was 59.0 °C). The reaction was terminated and worked - up as described in Comparative Example 1.

[0099] Example 1 (polymer functionalized with an amino monomer (VP) at the alpha position and with a functional group containing a carboxy group at the omega position); Ex1 After performing the overlap for 60 minutes, 12 mmol of octamethylcyclotetrasiloxane was added and reacted with the living polymer at 60 °C (Tmax was 60.8 °C) for 10 minutes, except for this, Comparative Example 3 was repeated. Then, 12 mmol of 2,2-dimethyl-1-oxa-4-thiasilacyclohexan-5-one was added and reacted at 60 °C for 30 minutes. The reaction was terminated and worked up as described in Comparative Example 1.

[0100] Example 2 (Polymer functionalized with an amino monomer (DMAMS) at the alpha position and a functional group containing a carboxy group at the omega position); Ex2 After performing the polymerization for 60 minutes, 12 mmol of octamethylcyclotetrasiloxane was added and reacted with the living polymer at 60 °C (Tmax was 60.8 °C) for 10 minutes, except for this, Comparative Example 4 was repeated. Then, 12 mmol of 2,2-dimethyl-1-oxa-4-thiasilacyclohexan-5-one was added and reacted at 60 °C for 30 minutes. The reaction was terminated and worked up as described in Comparative Example 1.

[0101] Example 3 (Polymer functionalized with an amino monomer (TSAES) at the alpha position and a functional group containing a carboxy group at the omega position); Ex3 After a 60-minute reaction, it was repeated for Comparative Example C4 except that it was functionalized to have a carboxylic acid terminal group as described in Example 1, and worked up as described in Comparative Example 1.

[0102] The compound was essentially prepared as described in U.S. Patent Application Publication No. 2016 / 0083495 A1, which is incorporated herein by reference. The properties of the compound are shown in Table 1.

[0103]

Table 1

[0104] The comparison of Ex01 with C3 and the comparison of Ex02 with C4 show improved tan δ values for polymers that are alpha - amino functionalized and omega - functionalized with hydroxy - containing functional groups, as compared to counterparts that are only alpha - functionalized.

[0105] The comparison of Ex1 with Ex01 and the comparison of Ex2 with Ex02 show that the performance of the alpha - omega - functionalized polymers is further enhanced by replacing the omega - hydroxy functional group with an omega - carboxy functional group.

[0106] Examples 1 - 7. The preparation of the α - ω - functionalized styrene - butadiene polymers as described in Examples 1 - 3 was carried out by varying the preparation with different amino - containing initiators to produce α - ω - polymers having different α - groups (Examples 4 - 6), or by preparing only ω - polymers (Comparative Example 7) without an amino - group - containing initiator. In Example 4, a Li - tertiary amine initiator (di - n - butylaminopropyl lithium) was used. In Example 5 (Comparative Example), a Li - secondary amine initiator (a mixture of lithium hexamethyleneimine and lithium pyrrolidine) was used. In Example 6, the amino - functionalized monomer DMAMS was used. In Example 7 (Comparative), the same polymer was produced using butyl lithium as the initiator instead of an amino - containing initiator, and the polymer was not α - functionalized. These polymers were compounded and cured. The compound recipe is shown in Table 2, and the compound properties are shown in Table 3. As can be understood from Table 3, the compound Mooney value of the polymer having an α - amino group according to the present disclosure was lower than that obtained with the secondary amine initiator (Comparative Example 5). This means that it is easier to process the compound. The Payne effect was greater (lower value) for the polymers having the groups according to the present disclosure as compared to Comparative Examples 5 and 7, showing better filler dispersion. All compounds had similar rebound values (43% at 23 °C and 63% - 64% at 60 °C) and Shore A hardness values (60 - 63). The Mooney scorch results were improved over Comparative Examples 5 and 7.

[0107] [Table 2]

[0108] [Table 3]

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 terminal groups, side groups and combinations thereof, and the second functional group is a terminal group. The first functional group is (i) Equation (1): 【Chemistry 1】 (wherein, R １ , R ２ , R ３ is selected from hydrogen and methyl, provided that at least one of R １ , R ２ and R ３ is hydrogen, preferably, R １ , R ２ , and R ３ are all hydrogen, n is 1, 2, 3, 4, or 5. Each R ４ R is independently selected from aliphatic residues or aryl aliphatic residues having 3 to 30 carbon atoms. ４ When n is 1, it contains at least one tertiary amine group, and when n is 2 to 5, it contains residue R ４ (At least one of them contains at least one tertiary alkylamine group.) It contains at least one unit derived from a functionalized monomer represented by; or (ii) General formula: N(R １ ) (Caution ２ ) (Caution ３ M) (wherein, R １ and R ２ They are either identical or distinct from each other, selected from linear or branched saturated alkyl groups, R ３ This is obtained by using a polymerization initiator (where M is a saturated, linear or branched alkylcarbanion, and M is an alkali cation), The second functional group is a terminal group and comprises at least one group selected from -COOX; -OX; -SX (wherein X represents hydrogen or a cation), a plurality thereof, and combinations thereof. The functionalized diene polymer is a homopolymer or copolymer of a conjugated diene, and the conjugated diene is selected from the group consisting of butadiene, isoprene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 1-phenyl-1,3-butadiene, and 1,3-hexadiene, and is preferably butadiene. polymer.

2. In formula (1), R ４ However, equation (2): 【Chemistry 2】 and equation (3): 【Transformation 3】 A polymer according to claim 1, selected from groups represented by, In formula (2), R ５ However, selected from the group consisting of a linear or branched alkylene group of 1 to 20 carbon atoms that is chemically bonded, unsubstituted or substituted; a cycloalkylene group of 5 to 20 carbon atoms that is unsubstituted or substituted; or an arylene group of 6 to 20 carbon atoms that is unsubstituted or substituted, wherein the substituent is an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms, or an aryl group of 6 to 20 carbon atoms, R ６ and R ７ However, each is independently a cycloalkylene group of 5 to 10 carbon atoms, or an alkylene group of 1 to 20 carbon atoms that is unsubstituted or substituted with an aryl group of 6 to 20 carbon atoms, R ８ However, if X is hydrogen; an alkyl group with 1 to 30 carbon atoms; an alkenyl group with 2 to 30 carbon atoms; an alkynyl group with 2 to 30 carbon atoms; a heteroalkyl group with 1 to 30 carbon atoms; a heteroalkenyl group with 2 to 30 carbon atoms; a heteroalkynyl group with 2 to 30 carbon atoms; a cycloalkyl group with 5 to 30 carbon atoms; an aryl group with 6 to 30 carbon atoms; or a heterocyclic group with 3 to 30 carbon atoms, and X is a chemical bond or an N, O, or S atom, and X is O, S, or a chemical bond, then R ８ It does not exist, In formula (3), R ９ However, the alkylene group is unsubstituted or substituted with a substituent and comprises 1 to 20 carbon atoms; the cycloalkylene group is unsubstituted or substituted with a substituent and comprises 5 to 20 carbon atoms; or the arylene group is unsubstituted or substituted with a substituent and comprises 6 to 20 carbon atoms, where the substituent is an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms, or an aryl group of 6 to 20 carbon atoms, R １０ and R １１ However, each is independently an alkyl group with 1 to 30 carbon atoms; an alkenyl group with 2 to 30 carbon atoms; an alkynyl group with 2 to 30 carbon atoms; a heteroalkyl group with 1 to 30 carbon atoms; a heteroalkenyl group with 2 to 30 carbon atoms; a heteroalkynyl group with 2 to 30 carbon atoms; a cycloalkyl group with 5 to 30 carbon atoms; an aryl group with 6 to 30 carbon atoms; or a heterocyclic group with 3 to 30 carbon atoms. polymer.

3. In formula (1), R ４ However, the polymer according to claim 1 or 2, wherein the group is selected from a group according to formula (2) or (3), In formula (2): R ５ However, R is selected from the group consisting of a chemical bond or a linear or branched alkylene group of 1 to 20 carbon atoms. ６ However, the alkylene group - (CH ２ ) ｎ - (wherein n is 2, 3, or 4, and in the formula one or more, but not all, H atoms are C １ ~C ６ Alkyl, preferably C １ ~C ３ (May be substituted with an alkyl group selected from alkyl groups); R ７ However, the alkylene group - (CH ２ ) ｎ - (wherein n is 2, 3, or 4, and in the formula one or more, but not all, H atoms are C １ ~C ６ Alkyl, preferably C １ ~C ３ (May be substituted with an alkyl group selected from alkyl groups) X is R ６ and R ７ It is a chemical bond that connects and forms a ring structure. R ８ It does not exist; In formula (3): R ９ However, chemical bonds, alkylene groups - (CH ２ ) ｎ - (wherein n is 1, 2, 3 or 4, and in the formula one or more, but not all, H atoms are C １ ~C ６ Alkyl, preferably C １ ~C ３ (May be substituted with an alkyl group selected from alkyl groups.) It represents; R １０ However, C １ ~C ３ Alkyl, tri(C) １ ~C ３ ) Represents alkylsilyl, R １１ However, R １０ Independent from C １ ~C ３ Alkyl, tri(C) １ ~C ３ ) Represents alkylsilyl, polymer.

4. The polymer according to claim 1, comprising at least 50% by weight of units derived from at least one of the conjugated dienes.

5. The polymer according to claim 1, 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, wherein the vinyl aromatic comonomer is selected from styrene, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, para-tert-butylstyrene, vinylnaphthalene, vinylnaphthalene, and combinations thereof, and preferably selected from styrene.

6. The second functional group comprises a hydrogen atom, 1 to 150 carbon atoms, and 1 to 20 Si atoms, in addition to a group selected from -COOX, -OX, and -SX groups, and the formula is: Si(R １ )(R ２ )-C(R ３ )(R ４ )-、-Si(R １ )(R ２ )-O-Si(R ３ )(R ４ )- (In the formula, R １ , R ２ , R ３ , R ４ These may be identical or different, and may contain H and a heteroatom optionally selected from O, N, S, and Si. １ ~C １２ Alkyl groups (selected from, for example, alkoxy groups, trialkylsilyl groups, alkylamino groups, dialkylamino groups, trialkylsilylamino groups, and combinations thereof) The polymer according to claim 1, comprising at least one group selected from or a combination thereof.

7. The second functional group comprises a group selected from -COOX, -OX, and -SX, in addition to 1 to 150 carbon atoms and 1 to 20 Si atoms, and the formula is: *-Si(R １ )(R ２ )-C(R ３ )(R ４ )--*--Si(R １ )(R ２ )-O-Si(R ３ )(R ４ )- (wherein R １ , R ２ , R ３ , R ４ are the same or different and are C １ to C １２ alkyl groups which may optionally contain heteroatoms selected from H and optionally O, N, S and Si, for example selected from alkoxy groups, trialkylsilyl groups, alkylamino groups, dialkylamino groups, trialkylsilylamino groups and combinations thereof) The polymer according to claim 1, further comprising at least one group selected from, where "*" indicates bonding to the polymer chain.

8. The second functional group is (i) a thioether group, (ii) an amino group: -N(R １ ) -, -N(R １ )(R ２ ) - or -N(R １ )(R ２ )(R ３ )(where R １ , R ２ and R ３ are independently selected from H, C １ ~C ６ alkyl and -Si(C １ ~C ６ alkyl) ３ , provided that it is not the case that all of R １ , R ２ and R ３ represent H), (iii) an ether group: -OR ４ or -OR ５ -(where R ４ is C １ ~C ６ alkyl and R ５ is C １ ~C ６ alkylene), and further includes one or more hetero groups selected therefrom, or a plurality or combination of such hetero groups. The polymer according to claim 6.

9. The polymer according to claim 1, wherein the polymer is suitable for manufacturing molded articles, preferably tires or tire treads.

10. A method for producing a polymer according to claim 1, comprising polymerizing at least one conjugated diene by a polymerization reaction to produce a diene polymer, (i) Adding an active reaction product comprising at least one functionalized monomer, or at least two repeating units derived from the functionalized monomer, to the conjugated diene before the polymerization reaction, at the start of the polymerization reaction, or during the polymerization reaction to produce a functionalized polymer having at least one first functional group comprising at least one unit derived from the functionalized monomer, or (ii) carrying out the polymerization according to the general formula: N(R) defined in claim 1. １ ) (Caution ２ ) (Caution ３ Either by using an initiator (M), or by a combination of (i) and (ii), The above reaction involves adding at least one functionalizing agent to the functionalized diene to generate a second functional group, and the functionalized monomer is of formula (1) 【Chemistry 4】 (In the formula, R １ , R ２ , R ３ R is selected from hydrogen and methyl, however, １ , R ２ and R ３ The condition is that at least one of them is hydrogen, preferably R １ , R ２ , and R ３ It is all hydrogen, n is 1, 2, 3, 4, or 5. Each R ４ R is independently selected from aliphatic residues or aryl aliphatic residues having 3 to 30 carbon atoms. ４ When n is 1, it contains at least one tertiary amine group, and when n is 2 to 5, the residue R ４ (At least one of them contains at least one tertiary alkylamine group.) It is represented by; The second functional group is a terminal group and comprises at least one group selected from -COOX; -OX; -SX (wherein X represents hydrogen or a cation), a plurality of such groups, or a combination thereof. The conjugated diene is selected from the group consisting of butadiene, isoprene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 1-phenyl-1,3-butadiene, and 1,3-hexadiene, and is preferably butadiene. method.

11. A curable rubber compound comprising the polymer described in claim 1, and further comprising at least one curing agent capable of curing the polymer.

12. A rubber compound comprising the polymer described in claim 1 for the cured form.

13. A method for producing a rubber compound, comprising combining the polymer described in claim 1 with at least one curing agent capable of curing the polymer, and optionally subjecting the polymer to curing.

14. A method for producing an article, comprising subjecting a rubber compound containing the polymer described in claim 1 and at least one curing agent capable of curing the polymer to curing and molding, wherein the molding is performed before curing, during curing, or after curing.

15. An article comprising a reaction product of a curing reaction of a composition containing the polymer described in claim 1, wherein the article is selected from a tire, tire tread, shoe sole, golf ball, belt, or seal.

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