Polydiene rubbers with functionalized end groups.

Abstract

General formula (I) TIFF2023519535000024.tif47155 (wherein R1 represents a saturated or unsaturated, linear or branched, preferably aliphatic hydrocarbon group having 1 to 20 carbon atoms, which may contain, in addition to C and H, one or more heteroatoms preferably selected from the group consisting of O, N, S, or Si; R2 and R3 are the same or different and represent saturated or unsaturated hydrocarbon groups having 1 to 20 carbon atoms, which may contain, in addition to C and H atoms, one or more heteroatoms preferably selected from the group consisting of O, N, S, and Si; A represents a residue selected from the group consisting of O-R4-OH, R5-OH, and R6-NH-R7, preferably O-R4-OH; R4, R5, and R6 are saturated or unsaturated hydrocarbon groups. and R7 represents H or a linear, branched, or cyclic, aliphatic or aromatic hydrocarbon group having 1 to 20 carbon atoms, which may contain, in addition to the C and H atoms, one or more heteroatoms independently selected from O, N, S, or Si, and which contains 1 to 20 carbon atoms, wherein the polymer is a homopolymer of a conjugated diene or a copolymer of at least one or more conjugated dienes with one or more vinyl aromatic monomers and, optionally, one or more other comonomers. Also provided are processes for making the polymers and articles made using the polymers.

Description

[Technical Field]

[0001] FIELD OF THE DISCLOSURE This disclosure relates to polydiene rubbers having functionalized end groups, their preparation and uses. [Background technology]

[0002] Polydiene rubbers are used in many different applications. Typically, they are combined with one or more fillers to make a rubber compound, which is then shaped into an article or combined with other ingredients to make an article. A primary use for polydiene rubbers is in tires or tire components such as tire treads.

[0003] By introducing functional end groups into the polymer chain, the polymer can better interact with the fillers used in preparing rubber compounds. The most commonly used fillers are carbon-based fillers such as silica and carbon black. By physically or chemically interacting with the filler surface, the mobility of the polymer chain in the compound matrix is ​​reduced, thereby reducing energy dissipation under dynamic stress. At the same time, these functional groups can improve the dispersion of the filler in the rubber composition, thereby weakening the filler network and improving the properties of the compound.

[0004] Various end-group modified rubbers have been developed. For example, Patent Document 1 discloses a rubber composition containing silica as a filler and a modified rubber containing amino end groups. It has been found that when a cyclic amine is used as a rubber modifier, tires with improved properties such as reduced rolling resistance can be produced. However, it has been found that polymers modified with cyclic amines have inferior processability compared to unmodified polymers, such as reduced Mooney scorch time. This reduces the time the rubber can be exposed to elevated temperatures. It has also been found that modifying polymers with cyclic amines is detrimental to the extrudability of the polymer and leads to the occurrence of (more) surface defects. These problems are particularly evident in rubber compositions containing carbon-based fillers. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] U.S. Patent No. 4,894,409 Summary of the Invention [Means for solving the problem]

[0006] It has now been discovered that the above-described problems can be reduced or overcome by using a second functionalizing agent in addition to a cyclic amine as the first functionalizing agent. Surprisingly, it has been found that any of the functionalized polymers thus produced have improved Mooney scorch time, improved extrudability, or both. Such polymers can be used to produce compounds for the production of articles with improved properties compared to compounds made with non-functionalized polymers.

[0007] Thus, in one embodiment, a compound of general formula (I) [ka] (In the formula, R1 represents a saturated or unsaturated, linear or branched, preferably aliphatic hydrocarbon group having 1 to 20 carbon atoms, which may contain, in addition to C and H, one or more heteroatoms, preferably selected independently from O, N, S or Si; R2 and R3 are the same or different and represent a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may contain, in addition to C and H atoms, one or more heteroatoms preferably selected from the group consisting of O, N, S, and Si; A represents a residue selected from the group consisting of O-R-OH, R-OH, and R-NH-R, preferably O-R-OH; R4, R5, and R6 each independently represent a saturated or unsaturated, linear or branched hydrocarbon group, which may contain, in addition to C and H atoms, one or more heteroatoms independently selected from O, N, S, or Si, and which contain 1 to 20 carbon atoms; R7 represents H or a linear, branched, or cyclic aliphatic or aromatic hydrocarbon group having 1 to 20 carbon atoms, which may contain one or more heteroatoms in addition to C and H atoms. An end-group functionalized polymer is provided having one or more end groups according to the formula: wherein the polymer is a homopolymer of a conjugated diene or a copolymer of a conjugated diene.

[0008] The polymer can be obtained by the method described below.

[0009] In another aspect, there is provided a method for preparing an end-group functionalized polymer, comprising the steps of: (a) polymerizing a conjugated diene to produce a polydiene homopolymer or polydiene copolymer; (b) General formula (II) [ka] to form a first functionalized polymer containing one or more end groups resulting from reaction of the polymer chain ends of the polydiene polymer with the functionalizing agent of formula (II); (c) adding a second functionalizing agent to react with the first functionalized polymer, wherein the second functionalizing agent is selected from the group consisting of Formulae (IIIa), (IIIb), and (IIIc): [ka] (wherein R1, R2, R3, R4, R5, R6, and R7 are as defined above). and wherein the carbonyl group is selected from the group consisting of: A method of preparation is provided, comprising:

[0010] In a further aspect, there is provided a compound comprising the polymer.

[0011] In yet a further aspect, there is provided a method of making a compound comprising mixing the polymer with at least one filler.

[0012] Also provided are articles comprising compositions obtained by vulcanizing the compounds. [Brief explanation of the drawings]

[0013] [Figure 1] 1 shows the extruded profiles obtained in the extrusion experiments described in the experimental section. DETAILED DESCRIPTION OF THE INVENTION

[0014] Preparation of polymer The end-group functionalized polydiene rubber according to the present disclosure can be obtained by a process comprising the polymerization of a conjugated diene. The polymerization can be homopolymerization or copolymerization. The process further comprises the addition of at least one first functionalizing agent to form a first functionalized polydiene polymer, and the addition of at least one second functionalizing agent to the first functionalized polydiene polymer.

[0015] Preferred conjugated dienes include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 1-phenyl-1,3-butadiene, 1,3-hexadiene, myrcene, ocimene, and / or farnesene. 1,3-butadiene and / or isoprene are particularly preferred.

[0016] In a preferred embodiment, the functionalized polymer according to the present disclosure is a polybutadiene homopolymer, more preferably a 1,3-butadiene homopolymer.

[0017] In another preferred embodiment, the functionalized polymer according to the present disclosure is a copolymer of a conjugated diene.

[0018] In another preferred embodiment, the second functionalized polymer according to the present disclosure is a copolymer containing units derived from one or more conjugated dienes and one or more vinyl aromatic monomers 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, divinylbenzene, trivinylbenzene, divinylnaphthalene, and combinations thereof. Styrene is particularly preferred. In a preferred embodiment, the functionalized polymer according to the present disclosure contains repeating units derived from 1,3-butadiene and styrene. Such polymers are obtained by polymerization involving copolymerization of 1,3-butadiene and styrene.

[0019] The polydiene homopolymers or copolymers can be prepared by methods known in the art. Preferably, the polymers are obtained by a process involving anionic solution polymerization or polymerization using one or more coordination catalysts. The polymerization can be carried out in solution or in the gas phase. The coordination catalyst in this context is a Ziegler-Natta catalyst or a monometallic catalyst system. Preferred coordination catalysts are those based on Ni, Co, Ti, Zr, Nd, V, Cr, Mo, W, or Fe.

[0020] Preferably, the polymerization reaction involves anionic solution polymerization. Initiators for anionic solution polymerization include organometallics, preferably based on alkali metals or alkaline earth metals. Examples include, but are not limited to, 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-toluyllithium, and allyllithium compounds derived from tertiary N-allylamines, such as [1 Examples of suitable organolithium compounds include [1-(dimethylamino)-2-propenyl]lithium, [1-[bis(phenylmethyl)amino]-2-propenyl]lithium, [1-(diphenylamino)-2-propenyl]lithium, and [1-(1-pyrrolidinyl)-2-propenyl]lithium; and lithium amides of secondary amines, such as lithium pyrrolidide, lithium piperidide, lithium hexamethyleneimide, lithium 1-methylimidazolidide, lithium 1-methylpiperazide, lithium morpholide, lithium dicyclohexylamide, lithium dibenzylamide, and lithium diphenylamide. Allyllithium compounds and lithium amides can also be prepared in situ by reacting an organolithium compound with a tertiary N-allylamine or a secondary amine. Bifunctional 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.

[0021] Randomizers and control agents known in the art can be used in the polymerization to control the structure of the polymer, such as, for example, diethyl ether, di-n-propyl ether, diisopropyl ether, di-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol di-n-butyl ether, ethylene glycol di-tert-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-butyl ether, diethylene glycol di-tert-butyl ether, 2-(2-ethoxyethoxy)-2-methyl-propane, triethylene glycol, ... Examples of suitable amines include potassium and sodium salts of ethylene glycol dimethyl ether, tetrahydrofuran, ethyl tetrahydrofurfuryl ether, hexyl tetrahydrofurfuryl ether, 2,2-bis(2-tetrahydrofuryl)propane, dioxane, trimethylamine, triethylamine, N,N,N',N'-tetramethyl-ethylenediamine, N-methylmorpholine, N-ethylmorpholine, 1,2-dipiperidinoethane, 1,2-dipyrrolidinoethane, 1,2-dimorpholinoethane, alcohols, phenols, carboxylic acids, sulfonic acids, and combinations thereof.

[0022] Preferred solvents for solution polymerization include inert aprotic solvents such as aliphatic hydrocarbons. Specific examples include, but are not limited to, butane, pentane, hexane, heptane, octane, decane, and cyclopentane, including isomers, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, 1,4-dimethylcyclohexane, and combinations thereof. Further examples include alkenes such as 1-butene, or aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene, diethylbenzene, and propylbenzene, and combinations thereof. These solvents can be used individually or as a mixture. Preferred solvents are cyclohexane, methylcyclopentane, and n-hexane. The solvent may also be mixed with a polar solvent, if desired.

[0023] Polymerization can be carried out by first introducing the monomer and solvent, and then adding an initiator or catalyst to start the polymerization. Polymerization can also be carried out in a feed process, where the polymerization reactor is charged by adding the monomer and solvent. The initiator or catalyst is introduced or added along with the monomer and solvent. Modifications can also be made, such as introducing the solvent into the reactor, adding the initiator or catalyst, followed by the addition of the monomer. Polymerization can be carried out in continuous mode or batchwise. Additional monomer and solvent can be added during or at the end of the polymerization.

[0024] The polymerization time can vary from a few minutes to a few hours. The polymerization is usually carried out within a period of 10 minutes to 8 hours, preferably 20 minutes to 4 hours. The polymerization can be carried out at normal pressure, elevated pressure (for example, 1 to 10 bar), or reduced pressure.

[0025] Typical reaction temperatures include temperatures between 35°C and 130°C.

[0026] The preparation of end-group functionalized polymers according to the present disclosure further requires the addition of a second functionalizing agent following the addition of a first functionalizing agent. The addition of the second functionalizing agent can be part of a continuous process. However, it is also possible to perform the process batchwise, such as stopping the process after the addition of the first functionalizing agent and restarting the process before the addition of the second functionalizing agent. The first functionalized polymer can be isolated and then redissolved or suspended before, during, or after the addition of the second functionalizing agent. Preferably, the first functionalized polymer is not isolated. Preferably, the process is a continuous process.

[0027] The first functionalizing agent is a cyclic amine, or more specifically, a cyclic urea or urea derivative. The second functionalizing agent is a cyclic carbonyl. Both functionalizing agents are described in more detail below.

[0028] The first functionalizing agent can be added neat or as a solution, spray, dispersion, or suspension. The first functionalizing agent reacts with the reactive polymer chain ends to produce a functionalized polymer, referred to herein as a "first functionalized polymer." Typically, the first functionalizing agent is added after the completion of monomer conversion or toward the end of the polymerization reaction before the completion of monomer conversion, for example, within the last 40%, last 20%, last 10%, last 5%, or last 1% of the polymerization time during which the monomer is converted. The addition of the first functionalizing agent is optionally carried out at the same temperature as the polymerization. However, the reaction temperature may be increased or decreased before, during, or after the addition of the first functionalizing agent.

[0029] The at least one first functionalizing agent can be added in an equal amount relative to the reactive polymer chain ends, in a molar excess, or in an amount less than the stoichiometric amount relative to the reactive polymer chain ends. Typical amounts include 0.3 to 2 molar equivalents relative to the molar amount of initiator or catalyst used in the polymerization. Preferably, the first functionalizing agent is used in an amount ranging from 0.6 to 1.5 molar equivalents based on the molar amount of initiator or catalyst used in the polymerization.

[0030] The second functionalizing agent is added after the addition of the first functionalizing agent has begun. Preferably, there is little or no overlap in the addition of the first and second functionalizing agents, and more preferably, the second functionalizing agent is added after the reaction of the first functionalizing agent with the polymer is complete. The second functionalizing agent can be added neat or as a solution, spray, dispersion, or suspension. Preferably, the second functionalizing agent is added to the first functionalized polymer. The reaction of the second functionalizing agent with the first functionalized polymer provides an end-group functionalized polymer according to the present disclosure.

[0031] The reaction of the second functionalizing agent is preferably carried out at the same temperature as used for the polymerization, or the temperature can be increased or decreased before, during, or after the addition of the second functionalizing agent. The time for which the second functionalization reaction is carried out can range from a few minutes to several hours.

[0032] The second functionalizing agent may be used in an amount of 0.3 to 2 molar equivalents relative to the molar amount of the first functionalizing agent, and more preferably 1 to 3 molar equivalents. In other words, the preferred molar ratio of the first functionalizing agent to the second functionalizing agent is 0.3 to 2, preferably 1:1 to 1:3 (inclusive).

[0033] To reduce chain end aggregation and increase the reactivity of the polymeric carbanion, one or more polar modifiers may be added before or during the addition of the first or second functionalizing agent. Examples include N,N,N',N'-tetramethylethylenediamine (TMEDA), tetrahydrofuran (THF), or ditetrahydrofurylpropane (DTHFP).

[0034] Alternatively, coupling reagents specific to anionic diene polymerization can be used to react with the reactive polymer chain ends. Examples of such coupling reagents include silicon tetrachloride, methyltrichlorosilane, dimethyldichlorosilane, tin tetrachloride, dibutyltin dichloride, tetraalkoxysilane, ethylene glycol diglycidyl ether, and 1,2,4-tris(chloromethyl)benzene. Such coupling reagents can be added before, simultaneously with, or after the addition of the first functionalizing agent.

[0035] After addition of the first and second functionalizing agents and optionally the coupling reagent, antioxidants known in the art, such as sterically hindered phenols, aromatic amines, phosphites, thioethers, etc., may be added to the reaction mixture, preferably before or during working up of the end-group functionalized polymers of the present disclosure.

[0036] The reaction may be completed with the addition of the second functionalizing agent, or the reaction may be completed after the addition of the second functionalizing agent. For example, the reaction may be quenched after the addition of the second functionalizing agent, e.g., within 1 to 60 minutes, or within 1 to 10 minutes, or within 10 to 30 minutes after the addition of the second functionalizing agent is complete. Quenching agents known in the art may be used, such as using an alcohol, e.g., octanol.

[0037] Before or during workup, extender oils used in diene rubbers, such as TDAE (treated distillate aromatic extract) oil, MES (light extract solvate) oil, RAE (residual aromatic extract) oil, TRAE (treated residual aromatic extract) oil, naphthenic oil, heavy naphthenic oil, etc. Fillers, for example, carbon-based fillers such as carbon black, silica, other rubbers, and rubber additives, can be added to the reaction mixture before, during, or even after workup on the isolated polymer, as described in more detail for the polymer compounds.

[0038] The solvent can be removed from the reaction mixture by conventional methods including distillation, steam stripping, or by applying vacuum or reduced pressure at elevated temperatures if necessary. The resulting polymer crumb can be further dried on a mill or processed into sheets or pressed into bales or the like.

[0039] The end-group functionalized polymers according to the present disclosure preferably have 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.

[0040] Preferably, the end-group functionalized 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.

[0041] Preferably, the end-group functionalized polymers according to the present disclosure have a Mooney viscosity [ML1+4] (100° C.) of from about 10 to about 200, preferably from about 30 to about 150 Mooney units.

[0042] The polymers typically have a dispersity of from about 1.03 to about 3.5.

[0043] First functionalizing agent: The first functionalizing agent according to the present disclosure is a cyclic urea or cyclic urea derivative, typically represented by the general formula (II): [ka] In formula (II), R1 represents a divalent saturated or unsaturated, linear or branched, preferably aliphatic hydrocarbon group having 1 to 20 carbon atoms, which may contain, in addition to C and H, one or more heteroatoms, preferably independently selected from O, N, S, or Si. Preferably, R1 corresponds to the general formula (IIa): -[CHX 1 ] o -[CHX 2 ] p -[O] z -[CHX 3 ] q - (IIa) wherein z is 1 or 0, and o, p, and q are independently selected from 0, 1, and 2, with the proviso that at least one of o, p, and q is not 0. X 1 , X 2 , and X 3 are independently selected from H, linear or branched alkyl, alkylaryl, and aryl groups having 1 to 12 carbon atoms, and aminoalkyl (NR) groups, where R is a linear, branched, or cyclic alkyl or alkylaryl residue having 1 to 12 carbon atoms, and X 1 and X 2 may represent a chemical bond between them to form a carbon-carbon bond, providing unsaturation in the carbon chain. 1 , X 2 , and X 3is selected so that the total number of carbon atoms is 20 or less.

[0044] In one embodiment, R1 is selected from substituted alkylene, for example, X 1 , X 2 , and X 3 is selected from substituted alkylenes corresponding to formula (IIa) in which at least one of: is not H.

[0045] In one embodiment, R1 is selected from unsubstituted alkylene, for example, X 1 , X 2 , and X 3 and n is an integer from 1 to 5, preferably from 1 to 3, more preferably 1 or 2. n -corresponds to

[0046] In one embodiment, R1 is selected from unsaturated substituted or unsubstituted alkylene, for example, X 1 and X 2 together form a carbon-carbon bond. Specific examples of unsaturated alkylene include, but are not limited to, -CH=CH- or -CH-CH=CH-.

[0047] In formula (II), R2 and R3 may be the same or different and represent a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may contain, in addition to C and H atoms, one or more heteroatoms preferably selected from the group consisting of O, N, S, and Si. For example, R2 and R3 may be the same or different and may be -(C1 to C 20 )-Alkyl group, -(C3-C 20 )-cycloalkyl group, -(C6-C 20 )-aryl group, -(C6-C 20 )-alkaryl group, or -(C6-C 20)-aralkyl groups, which may contain one or more heteroatoms, preferably independently selected from O, N, S, or Si. Preferably, R2, R3 are independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, trialkylsilyl having alkyl groups of 1 to 4 carbon atoms per alkyl group, phenyl, and phenyl independently substituted with 1, 2, or 3 methyl, ethyl, propyl, and / or butyl residues.

[0048] Preferred specific examples of the first functionalizing agent include, but are not limited to, 1,3-dimethyl-2-imidazolidinone (1), 1,3-diethyl-2-imidazolidinone (2), 1-methyl-3-phenyl-2-imidazolidinone (3), 1,3-diphenyl-2-imidazolidinone (4), 1,3-dimethyl-2-imidazolidinone (3), 1,3-dimethyl -2-Imidazolidinone (3), 1,3-dimethyl-2-imidazolidinone (3), 1,3-dimethyl-2-imidazolidinone (3), 1,3-dimethyl-2-imidazolidinone (3), 1,3-dimethyl-2-imidazolidinone (4), 1,3-dimethyl-2-imidazolidinone (4), 1,3-dimethyl-2-imidazolidinone (3), 1,3,4 -Trimethyl-2-imidazolidinone (6), 1,3-bis(trimethylsilyl)-2-imidazolidinone (7), 1,3-dihydro-1,3-dimethyl-2H-imidazol-2-one (8), tetrahydro-1,3-dimethyl-2(1H)-pyrimidinone (9), tetrahydro-1-methyl-3-phenyl-2(1H)-pyrimidinone (10), tetrahydro-1,3,5-trimethyl-2(1H)-pyrimidinone (11), tetrahydro-3,5-dimethyl-4H-1,3,5-oxadiazin-4-one (12), tetrahydro-1,3,5-trimethyl-1,3,5-triazin-2(1H)-one (13), hexahydro-1,3-dimethyl-2H-1,3-diazepin-2-one (14): [ka] Examples include:

[0049] A particularly preferred example is 1,3-dimethyl-2-imidazolidinone (1), also known as DMI. [ka] That is, R1 is -CH2-CH2- and / or R2 and R3 are both -CH3.

[0050] Second functionalizing agent: The second functionalizing agent according to the present disclosure is typically a cyclic carbonyl selected from the group consisting of a cyclic carbonate, a cyclic lactone, and a cyclic lactam. In one embodiment of the present disclosure, the cyclic carbonate is represented by formula (IIIa), and in one embodiment of the present disclosure, the cyclic lactone is represented by formula (IIIb), and in a further embodiment of the present disclosure, the cyclic lactam is represented by formula (IIIc). [ka] In the formula, R4, R5, and R6 represent a saturated or unsaturated, linear or branched hydrocarbon group having 1 to 20 carbon atoms, which may contain one or more heteroatoms independently selected from O, N, S, or Si in addition to C and H. R4, R5, and R6 are represented by the general formula (IIId): -[CHX 1 ] o -[CHX 2 ] p -[O] z -[CHX 3 ] q - (IIId) wherein z is 1 or 0, and o, p, and q are independently selected from 0, 1, and 2, with the proviso that at least one of o, p, and q is not 0. X 1 , X 2 , and X 3are independently selected from H, linear or branched alkyl, alkylaryl, and aryl groups having 1 to 12 carbon atoms, and aminoalkyl (NR) groups, where R is a linear, branched, or cyclic alkyl or alkylaryl residue having 1 to 12 carbon atoms, and X 1 and X 2 may represent a chemical bond between them to form a carbon-carbon bond, providing unsaturation in the carbon chain. 1 , X 2 , and X 3 is selected so that the total number of carbon atoms is 20 or less.

[0051] Preferably, R4, R5, and R6 are unsubstituted alkylene groups, i.e., —[CH2] where n is an integer from 1 to 5. n - group, or -[CH2] n - is a substituted alkylene group in which at least one hydrogen atom of the unit is replaced by an alkyl group, an aryl group, or an alkaryl group. Preferred substituents are selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, phenyl, benzyl, and cyclohexyl.

[0052] R7 represents H or a linear, branched, or cyclic aliphatic or aromatic hydrocarbon group having 1 to 20 carbon atoms, which may contain, in addition to C and H atoms, one or more heteroatoms preferably selected from O, N, S, or Si. Typical examples include, but are not limited to, H, methyl, ethyl, propyl, butyl, phenyl, cyclohexyl, 2-phenylethyl, phenylmethyl, and trialkylsilyl.

[0053] Specific examples of cyclic carbonates represented by formula (IIIa) include, but are not limited to, ethylene carbonate (R4 is -H2C-H2C-), propylene carbonate (4-methyl-1,3-dioxolan-2-one, R4 is -(HC)CH-CH2-), butylene carbonate (4-ethyl-1,3-dioxolan-2-one, R4 is -(H5C2)CH-CH2), and styrene carbonate (4-phenyl-1,3-dioxolan-2-one, R4 is -(Ph-)CH-CH2-).

[0054] Specific examples of lactones having formula (IIIb) include, but are not limited to, alpha-acetolactone (R = methylene -CH-), beta-propiolactone (R = ethylene -CHCH-), gamma-butyrolactone (R = n-propylene -CHCHCH-), delta-valerolactone (gamma methyl-gamma butyrolactone (R = -(CH)CHCHCH- = methyl substituted propylene), delta valerolactone (R = n-butylene -CHCHCHCHCH-), and epsilon-caprolactone (R = pentylene -CHCHCHCHCHCH-).

[0055] Specific examples of lactams represented by formula (IIIc) include, but are not limited to, N-methyl-2-pyrrolidone (R6 = propylene-CH2CH2CH2-, R7 = methyl), N-ethyl-2-pyrrolidone (R6 = propylene-CH2CH2CH2-, R7 = ethyl), N-phenyl-2-pyrrolidone (R6 = propylene-CH2CH2CH2-, R7 = phenyl), N-cyclohexyl-2-pyrrolidone (R6 = propylene-CH2CH2CH2-, R7 = cyclohexyl), N-methyl-ε-caprolactam (R6 = pentylene-CH2CH2CH2CH2-, R7 = H), and N-isobutyl-2-piperidone (R6 = butylene-CH2CH2CH2CH2-, R7 = isobutyl).

[0056] Preferably, the second functionalizing agent is selected from formula (IIIa):

[0057] Also, a combination of two or more functionalizing agents may be used in place of a single first functionalizing agent, and a combination of two or more second functionalizing agents may be used in place of a single second functionalizing agent.

[0058] The polymers of the present disclosure are the reaction products of the reactions described above, i.e., the reaction of a polymer functionalized by reaction with a first functionalizing agent with a second functionalizing agent.

[0059] The resulting polymer has the formula (I): [ka] wherein A represents a residue selected from the group consisting of O-R-OH, R-OH, and R-NH-R, preferably O-R-OH, and R, R, R, R, R, and R have the same meanings as described above.

[0060] In a preferred embodiment of the present disclosure, the polymer is the reaction product of a polymer functionalized with the first functionalizing agent described above and a second functionalizing agent of formula (IIa). In one embodiment, such a polymer has the general formula (Ia): [ka] wherein "polymer" refers to a diene homopolymer or copolymer as described herein and contains at least one of the end groups shown in formula (Ia), and R1, R2, R3, and R4 have the same meanings as previously described.

[0061] In another embodiment of the present disclosure, the polymer is the reaction product of a polymer functionalized with the first functionalizing agent described above and a second functionalizing agent having the formula (IIb). In one embodiment, such a polymer has the general formula (Ib): [ka] wherein "polymer" refers to a diene homopolymer or copolymer as described herein and contains at least one end group shown in formula (Ib), and R1, R2, R3, and R5 have the same meanings as previously described.

[0062] In another embodiment of the present disclosure, the polymer is the reaction product of a polymer functionalized with the first functionalizing agent described above and a second functionalizing agent represented by formula (IIc). In one embodiment, such a polymer has the general formula (Ic): [ka] wherein "polymer" refers to a diene homopolymer or copolymer as described herein and contains at least one end group shown in formula (Ic), and R1, R2, R3, R6, and R7 have the same meanings as previously described.

[0063] rubber compound The end-group functionalized polymers of the present disclosure can be used to make rubber compounds by a process comprising blending the end-group functionalized polymer with one or more fillers. The end-group functionalized polymers of the present disclosure can be used to make vulcanizable rubber compounds by a process comprising blending the end-group functionalized polymer with one or more fillers and one or more crosslinking agents for crosslinking at least the end-group functionalized polymer. The rubber compounds are suitable for making tires or tire components such as sidewalls and tire treads. The vulcanizable rubber compounds of the present disclosure contain one or more curatives or cure systems for crosslinking the end-group functionalized polymers of the present disclosure, and optionally other crosslinkable fillers or ingredients. The resulting tire or tire component will typically contain the rubber compound in its vulcanized form.

[0064] The rubber compounds and vulcanizable rubber compounds contain one or more fillers, including both active and inactive fillers. Conventional fillers can be used. Conventional fillers include silica, silicates, and preferably one or more carbon-based fillers, such as carbon black.

[0065] Examples of suitable silicas include, but are not limited to: - 5 to 1000, preferably 20 to 400 m 2 Highly dispersible silica with a specific surface area of ​​0.15g / g (BET surface) and a primary particle size of 10-400nm, for example, produced by precipitation from silicate solutions or by flame hydrolysis of silicon halides. Silica can also exist as mixed oxides with other metal oxides, such as Al, Mg, Ca, Ba, Zn, Zr, Ti oxides. - 20~400m 2 / g BET surface and a primary particle diameter of 10 to 400 nm. Synthetic silicates, such as aluminum silicate, alkaline earth silicates, such as magnesium silicate or calcium silicate. - Natural silicates, such as kaolin, montmorillonite, and other naturally occurring silicas.

[0066] Examples of suitable non-silica and non-carbon-based fillers include, but are not limited to: - glass fibres and glass fibre products (mats, strands) or microspheres (which may contain silica or silicates); metal oxides, such as zinc oxide, calcium oxide, magnesium oxide, aluminum oxide, Metal carbonates, such as magnesium carbonate, calcium carbonate, zinc carbonate, metal hydroxides, such as aluminum hydroxide, magnesium hydroxide, Metal sulfates, such as calcium sulfate, barium sulfate, Rubber gels, in particular those based on BR, E-SBR and / or polychloroprene, preferably with a particle size of 5 to 1000 nm.

[0067] Examples of suitable carbon-based fillers include, but are not limited to, carbon blacks produced by the flame soot process, channel process, furnace process, gas soot process, thermal process, acetylene soot process, or arc process. The carbon-based fillers may have a BET surface area of ​​9 to 200 m / g. Specific examples of carbon blacks include, but are not limited to, SAF-, ISAF-LS-, ISAF-HM-, ISAF-LM-, ISAF-HS-, CF-, SCF-, HAF-LS-, HAF-, HAF-HS-, FF-HS-, SPF-, XCF-, FEF-LS-, FEF-, FEF-HS-, GPF-HS-, GPF-, APF-, SRF-LS-, SRF-LM-, SRF-HS-, SRF-HM-, and and MT-soot, or ASTM conforming N110-, N219-, N220-, N231-, N234-, N242-, N294-, N326-, N327-, N330-, N332-, N339-, N347-, N351-, N356, N358, N375, N472, N539, N550, N568, N650, N660, N754, N762, N765, N774, N787, and N990 carbon blacks.

[0068] Preferably, the rubber compounds of the present disclosure contain one or more carbon blacks as fillers.

[0069] The fillers can be used alone or in mixtures. In a particularly preferred embodiment, the rubber composition contains a mixture of a silica filler, such as highly dispersed silica, and carbon black. The weight ratio of silica filler to carbon black can be from 0.01:1 to 50:1, preferably from 0.05:1 to 20:1.

[0070] Fillers may be used in amounts ranging from 10 to 500, preferably 20 to 200 parts by weight based on 100 parts by weight of rubber.

[0071] The rubber compounds and vulcanizable rubber compounds may further contain one or more additional rubbers other than the functionalized rubbers according to the present disclosure, and one or more rubber additives.

[0072] Examples of additional rubbers include natural rubber and synthetic rubber. When present, they can be used in an amount ranging from 0.5 to 95% by weight, preferably from 10 to 80% by weight, based on the total amount of rubber in the composition. Examples of suitable synthetic rubbers include BR (polybutadiene), acrylic acid alkyl ester copolymer, IR (polyisoprene), E-SBR (styrene-butadiene copolymer produced by emulsion polymerization), S-SBR (styrene-butadiene copolymer produced by solution polymerization), IIR (isobutylene-isoprene copolymer), NBR (butadiene-acrylonitrile copolymer), HNBR (partially or fully hydrogenated NBR rubber), EPDM (ethylene-propylene-diene terpolymer), and mixtures thereof. Natural rubber, E-SBR and S-SBR with glass temperatures above -60°C, polybutadiene rubber with a high cis content (>90%) produced using catalysts based on Ni, Co, Ti, or Nd, polybutadiene rubber with a vinyl content of up to 80%, and mixtures thereof are of particular interest for the production of automobile tires.

[0073] Rubber additives are components that can improve the processability of rubber compositions, crosslink the rubber composition, improve the physical properties of vulcanizates made from the rubber, improve the interaction between the rubber and fillers, or bond the rubber to the fillers. Examples of rubber adjuvants include crosslinking agents such as sulfur or sulfur-donating compounds, accelerators, antioxidants, heat stabilizers, light stabilizers, ozone stabilizers, processing aids, plasticizers, tackifiers, blowing agents, dyes, pigments, waxes, extenders, organic acids, silanes, retarders, metal oxides, extender oils such as DAE (distillate aromatic extract) oil, TDAE (treated distillate aromatic extract) oil, MES (light extract solvate) oil, RAE (residual aromatic extract) oil, TRAE (treated residual aromatic extract) oil, naphthenic oil, and heavy naphthenic oil, as well as activators.

[0074] The total amount of rubber additives can 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.

[0075] The rubber composition can be prepared by conventional processing equipment for making and processing (vulcanizable) rubber compounds, including rollers, kneaders, internal mixers, or mixing extruders. The rubber composition can be made in a single-stage or multi-stage process, preferably with 2 to 3 mixing stages. Crosslinking agents such as sulfur and accelerators can be added in separate mixing stages, such as by rollers, at temperatures preferably in the range of 30°C to 90°C. Crosslinking agents such as sulfur and accelerators are preferably added in the final mixing stage.

[0076] Purpose The rubber compositions according to the present disclosure can be used to make rubber vulcanizates, particularly tires, especially tire treads.

[0077] The (vulcanizable) rubber compositions provided herein are also suitable for the production of molded articles, such as cable sheaths, hoses, drive belts, conveyor belts, roll linings, shoe soles, sealing rings, and damping elements.

[0078] Another aspect of the present disclosure relates to molded articles, particularly tires, containing vulcanized rubber compositions obtained by vulcanizing the vulcanizable rubber compositions provided in accordance with the present disclosure.

[0079] The following examples are provided to further illustrate the present disclosure, but are not intended to limit the disclosure to the embodiments set forth in these examples. [Example]

[0080] method Polymer Data: Number average molecular weight Mn and dispersity of styrene-butadiene rubber

number

[0081] The Mooney viscosity of the polymer was determined according to DIN ISO 289-1 (2018) at 100°C under the measurement conditions ML(1+4).

[0082] The vinyl and styrene content can be determined on rubber films by FTIR spectroscopy.

[0083] Compound properties: The Mooney scorch time was measured at 125 °C according to DIN ISO 289-2 (2018). The values ​​MS-t3, MS-t5, and MS-t10 correspond to the time (starting from the insertion of the sample material) when the viscosity increased by 3 MU, 5 MU, and 10 MU, respectively, compared to the viscosity minimum.

[0084] The compounds were extruded in a Brabender Plastograph EC Plus extruder (L / D=19 / 10) using a Garvey Die (ASTM D-2230) with half the die size. Extrusion experiments were carried out at 100°C.

[0085] Properties of vulcanized compounds: To determine the temperature-dependent dynamic mechanical properties, the loss factor tan δ (also referred to herein as "tan delta") was measured at 0°C and 60°C. For this purpose, an Eplexor device (Eplexor 500N) manufactured by Gabo was used. Measurements were performed on Ares strips at temperatures ranging from -100°C to 100°C at 10 Hz in accordance with DIN 53513. The Eplexor 500N was used for this purpose. To determine the strain-dependent dynamic mechanical properties, ΔG' was determined as the difference between the shear modulus at 0.5% strain and the shear modulus at 15% strain, as well as the maximum loss factor tan δmax. These measurements were performed on cylindrical specimens (20 x 6 mm) at a temperature of 60°C, with a compression of 2 mm, and at a measurement frequency of 10 Hz in the strain range of 0.1% to 40% in accordance with DIN 53513-1990 on an MTS Elastomer Testing System.

[0086] The rebound resilience was determined at 60° C. according to DIN 53512.

[0087] Example 1. Polymer Synthesis Comparative Example 1 (C1): Synthesis of Unmodified Polybutadiene 8500 g hexane, 4.18 ml n-butyllithium (23 wt. % in hexane), and 1500 g 1,3-butadiene were charged into a 20 L reactor and polymerized at 70 °C for 1 h. The polymerization was subsequently quenched with octanol, which terminates the polymerization of the anionic polymer chain ends. 4.5 g IRGANOX1520 was added to stabilize the polymer. The solution was precipitated in ethanol and dried under reduced pressure at 70 °C. The resulting polymer had a yield of 369700 g mol -1 Molecular weight (M n ), 1.10

number

[0088] Comparative Example 2 (C2): Synthesis of DMI-functionalized polybutadiene 8500 g hexane, 3.98 ml n-butyllithium (23 wt. % in hexane), and 1500 g butadiene were charged into a 20 L reactor and polymerized at 70 °C for 1 h. 1.84 ml ditetrahydrofurylpropane (DTHFP) was added and stirred for 5 min, and 1.09 ml 1,3-dimethyl-2-imidazolidinone (DMI) was added and stirred for 20 min. The polymerization was then quenched with octanol. 4.5 g IRGANOX1520 was added. The solution was precipitated in ethanol and dried under reduced pressure at 70 °C. The resulting polymer had a yield of 340,700 g mol -1 Molecular weight (M n ), 1.10

number

[0089] Example 1 (E1): Synthesis of DMI / EC functionalized polybutadiene 8500 g hexane, 4.48 ml n-butyllithium (23 wt. % in hexane), and 1500 g butadiene were charged into a 20 L reactor and polymerized at 70 °C for 1 h. 2.09 ml DTHFP was added and stirred for 5 min, and 1.23 ml 1,3-dimethyl-2-imidazolidinone was added and stirred for 20 min. 0.99 g ethylene carbonate dissolved in tetrahydrofuran was added and stirred for an additional 20 min. Subsequently, the polymerization was quenched with octanol. 4.5 g IRGANOX1520 was added. The solution was precipitated in ethanol and dried under reduced pressure at 70 °C. The resulting polymer had a yield of 361,800 g mol -1 Molecular weight (M n ), 1.23

number

[0090] Example 2 (E2): Synthesis of DMI / BL functionalized polybutadiene 8500 g hexane, 3.98 ml n-butyllithium (23 wt. % in hexane), and 1500 g butadiene were charged into a 20 L reactor and polymerized at 70 °C for 1 h. 1.84 ml DTHFP was added and stirred for 5 min, and 1.09 ml 1,3-dimethyl-2-imidazolidinone was added and stirred for 20 min. 0.77 ml gamma-butyrolactone (BL) was added and stirred for an additional 20 min. Subsequently, the polymerization was quenched with octanol. 4.5 g IRGANOX1520 was added. The solution was precipitated in ethanol and dried under reduced pressure at 70 °C. The resulting polymer had a yield of 361000 g mol -1 Molecular weight (M n ), 1.09

number

[0091] 2. Preparation of Compound The polymers obtained in Examples C1, C2, E1, and E2 were mixed in an internal mixer with the ingredients and amounts summarized in Table 1 to prepare compounds C3 and C4 (comparative) and E3 and E4 (according to the present disclosure). Sulfur and accelerators were added separately to the compound compositions prepared in the internal mixer, and the mixture was subjected to a rolling mill at 40°C.

[0092] [Table 1]

[0093] 3. Vulcanization Compounds C3, C4, E3, and E4 were vulcanized in a heated mold at 160° C. for 11 minutes and tested for their properties shown in Table 3.

[0094] [Table 2]

[0095] As can be seen from Table 2, all modified polymers improved the performance of the vulcanizates.

[0096] Compound properties Mooney Coach Time: Compounds C3, C4, E3, and E4 were tested for their Mooney scorch times at 125° C. as described in the experimental section, and the results are shown in Table 3.

[0097] [Table 3]

[0098] The results shown in Table 3 suggest that Compound C4, made with the DMI-modified polymer, had a shorter Mooney scorch time than Compound C3, made with the unmodified polymer. Compound E3, made with the DMI- and EC-modified polymer, had a Mooney scorch time superior to Compound C4 and a scorch time similar to Compound C3, made with the unmodified polymer. Compound E4, made with the DMI- and BL-modified polymer, also had a Mooney scorch time superior to the compound made with the DMI-modified polymer.

[0099] Extrusion Experiments: The compounds were extruded in a Brabender Plastograph EC Plus extruder (L / D=19 / 10) using a Garvey Die (ASTM D-2230) with a reduced die size by half. Extrusion experiments were carried out at 100°C. The results are shown in Figure 1.

[0100] The DMI modification degrades extrudability, as can be seen from a comparison of the profile obtained with the compound made with the unmodified polymer (C3, profile a in Figure 1) with the profile obtained with the compound made with the DMI-modified polymer of Comparative Example 2 (C4, profile b in Figure 1). The extrusion of the compound containing the DMI / EC-modified polymer (E3, profile c in Figure 1) is superior to that of the compound containing the DMI-modified polymer. The compound made with the DMI / BL-modified polymer (E4, profile d) had extrusion profiles similar to those of the DMI-modified polymer C4.

Claims

1. General formula (I) 【Chemistry 1】 (In the formula, R1 represents a saturated or unsaturated, linear or branched hydrocarbon group having 1 to 20 carbon atoms, which may contain one or more heteroatoms in addition to C and H, R2 and R3 are the same or different and represent a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, which may contain one or more heteroatoms in addition to C and H atoms; A represents a residue selected from the group consisting of O-R4-OH, R5-OH, and R6-NH-R7; R4, R5, and R6 each independently represent a saturated or unsaturated, linear or branched hydrocarbon group, which may contain, in addition to C and H atoms, one or more heteroatoms independently selected from O, N, S, or Si, and which contain 1 to 20 carbon atoms; R7 represents H or a linear, branched or cyclic aliphatic or aromatic hydrocarbon group having 1 to 20 carbon atoms, which may contain one or more heteroatoms in addition to C and H atoms. an end-group functionalized polymer having one or more end groups according to * indicates that the bond is attached to the polymer chain; An end-group functionalized polymer, wherein the polymer is a homopolymer of a conjugated diene or a copolymer of a conjugated diene.

2. 2. The polymer of claim 1, wherein the conjugated diene is selected from 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 1-phenyl-1,3-butadiene, and combinations thereof.

3. 3. The polymer of claim 1 or 2, wherein the polymer is selected from homopolymers of 1,3-butadiene and copolymers of 1,3-butadiene with one or more vinyl aromatic monomers and one or more optional comonomers, wherein the vinyl aromatic monomers are selected from the group consisting of styrene, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, para-tert-butylstyrene, vinylnaphthalene, divinylbenzene, trivinylbenzene, divinylnaphthalene, and combinations thereof.

4. 4. The polymer of any one of claims 1 to 3, wherein the polymer is selected from homopolymers of 1,3-butadiene and copolymers of 1,3-butadiene with styrene and one or more optional comonomers.

5. R1 is a group represented by the general formula (IIa): -[CHX １ ] ｏ -[CHX ２ ] ｐ -[O] ｚ -[CHX ３ ] ｑ - (IIa) wherein z is 1 or 0, and o, p, and q are independently selected from 0, 1, and 2, provided that at least one of o, p, and q is not 0 and X １ , X ２ , and X ３ from H, from linear or branched alkyl, alkylaryl, and aryl groups having 1 to 12 carbon atoms, and from aminoalkyl groups N—R, where R is a linear, branched, or cyclic alkyl or alkylaryl residue having 1 to 12 carbon atoms, and from X, which together form a carbon-carbon bond to provide unsaturation in the carbon chain. １ and X ２ and o, p, q, X are independently selected from １ , X ２ , and X ３ are selected so that the total number of carbon atoms is 20 or less. The polymer according to any one of claims 1 to 4, which corresponds to

6. R ２ , R ３ are the same or different and are selected from methyl, ethyl, propyl, phenyl, benzyl, and trialkylsilyl, wherein each alkyl group of said trialkylsilyl can contain 1 to 4 carbon atoms, and wherein said phenyl and benzyl can contain one or more substituents.

7. R4, R5, and R6 are groups represented by the general formula -[CH ２ ] ｎ -, and the unsubstituted alkylene group corresponding to -[CH ２ ] ｎ 7. A polymer according to any one of claims 1 to 6, corresponding to the general formula wherein at least one hydrogen atom of the - unit is selected from the group consisting of substituted alkylene groups in which an alkyl, aryl, alkaryl, or aralkyl group has been replaced, provided that the total number of carbon atoms is 20 or less.

8. The polymer of any one of claims 1 to 7, wherein R7 is selected from H, methyl, ethyl, propyl, butyl, phenyl, cyclohexyl, 2-phenylethyl, phenylmethyl, and trialkylsilyl.

9. R1 is —CH ２ CH ２ - and R2 and R3 are selected from the group consisting of methyl and ethyl.

10. 1. A method for preparing an end-group functionalized polymer, comprising: (a) polymerizing a conjugated diene to produce a polydiene homopolymer or polydiene copolymer; (b) General formula (II) 【Chemistry 2】 to form a first functionalized polymer containing one or more end groups resulting from reaction of the polymer chain ends of said polydiene polymer with the functionalizing agent of formula (II); (c) adding a second functionalizing agent to react with the first functionalized polymer, wherein the second functionalizing agent is selected from the group consisting of formulas (IIIa), (IIIb), and (IIIc): 【Transformation 3】 (In the formula, R1 represents a saturated or unsaturated, linear or branched hydrocarbon group having 1 to 20 carbon atoms, which may contain one or more heteroatoms in addition to C and H, R2 and R3 are the same or different and represent a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, which may contain one or more heteroatoms in addition to C and H atoms; R4, R5, and R6 each independently represent a saturated or unsaturated, linear or branched hydrocarbon group, which may contain, in addition to C and H atoms, one or more heteroatoms independently selected from O, N, S, or Si, and which contain 1 to 20 carbon atoms; R7 represents H or a linear, branched or cyclic aliphatic or aromatic hydrocarbon group having 1 to 20 carbon atoms, which may contain one or more heteroatoms in addition to C and H atoms. and wherein the cyclic carbonyl is selected from the group of cyclic carbonyls represented by the formula: A preparation method comprising:

11. The method of claim 10, wherein the polymerization comprises anionic solution polymerization.

12. 12. The method of claim 10 or 11, wherein the polymerization comprises anionic solution polymerization and the solvent comprises cyclohexane, methylcyclopentane, n-hexane, and mixtures thereof, and the polymerization further comprises the presence of at least one initiator.

13. A compound, which is a vulcanizable compound, comprising a polymer according to any one of claims 1 to 9 and at least one filler.

14. A method for making a compound according to claim 13, comprising mixing a polymer according to any one of claims 1 to 9 with at least one filler.

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