Modified conjugated diene polymer, its production method, and rubber composition containing the same

Abstract

The present invention relates to a modified conjugated diene polymer and a rubber composition containing the same, which can have a Mooney large relaxation area of ​​1500 MU-s or more and have a high molecular weight but a low Mooney viscosity after compounding into the rubber composition, thereby providing excellent processability during tire production, excellent physical properties such as tensile properties, and excellent viscoelastic properties; a method for producing the same; and a rubber composition containing the same.

Description

[Technical field]

[0001] This application claims the benefit of priority based on Korean Patent Application No. 10-2019-0121197, filed on September 30, 2019, and all contents disclosed in the documents of that Korean patent application are incorporated herein by reference.

[0002] The present invention relates to a modified conjugated diene-based polymer which is excellent in processability, tensile strength and viscoelasticity, and a rubber composition containing the same. [Background technology]

[0003] In recent years, with the demand for lower fuel consumption for automobiles, there has been a demand for conjugated diene-based polymers as rubber materials for tires that have low rolling resistance, excellent abrasion resistance and tensile properties, as well as adjustment stability, as typified by wet skid resistance.

[0004] One method for reducing the rolling resistance of a tire is to reduce the hysteresis loss of vulcanized rubber, and the evaluation indexes for such vulcanized rubber are the rebound resilience, tan δ, Goodrich heat generation, etc. at 50° C. to 80° C. In other words, a rubber material that has high rebound resilience or low tan δ and Goodrich heat generation at the above temperatures is preferred.

[0005] Natural rubber, polyisoprene rubber, polybutadiene rubber, etc. are known as rubber materials with low hysteresis loss, but they have a problem of low wet skid resistance. In recent years, conjugated diene polymers or copolymers such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) have been produced by emulsion polymerization or solution polymerization and used as rubber for tires. Among them, the greatest advantage of solution polymerization over emulsion polymerization is that the content of vinyl structure and the content of styrene, which determine the physical properties of rubber, can be freely adjusted, and the molecular weight and physical properties can be adjusted by coupling, modification, etc. Therefore, the structure of the finally produced SBR or BR can be easily changed, and the movement of the chain ends can be reduced by bonding or modification of the chain ends, and the binding strength with fillers such as silica or carbon black can be increased, so SBR produced by solution polymerization is often used as a rubber material for tires.

[0006] When such SBR obtained by solution polymerization is used as a rubber material for tires, the glass transition temperature of the rubber can be increased by increasing the vinyl content in the SBR, thereby adjusting the physical properties required for tires, such as running resistance and braking force, and fuel consumption can be reduced by appropriately adjusting the glass transition temperature. The SBR obtained by solution polymerization is produced using an anionic polymerization initiator, and the formed polymer chain ends are bonded or modified using various modifiers before use. For example, U.S. Patent No. 4,397,994 proposes a technology in which active anions at the polymer chain ends obtained by polymerizing styrene-butadiene in a non-polar solvent using an alkyl lithium, which is a monofunctional initiator, are bonded using a binder such as a tin compound.

[0007] Meanwhile, the polymerization of SBR or BR can be carried out by batch or continuous polymerization, but the batch polymerization has the advantage of improving physical properties because the molecular weight distribution of the produced polymer is narrow, but has the problems of low productivity and poor processability, while the continuous polymerization has the advantage of being excellent in productivity and improving processability because the polymerization is carried out continuously, but has the problem of poor physical properties because the molecular weight distribution is wide. Therefore, there is a continuing need for research to simultaneously improve the productivity, processability, and physical properties during the production of SBR or BR. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] US4397994A Summary of the Invention [Problem to be solved by the invention]

[0009] The present invention has been made to solve the above-mentioned problems of the conventional art, and has an object to provide a modified conjugated diene-based polymer which has a high molecular weight but a controlled Mooney large relaxation area, and which, after compounding of the rubber composition, has a low Mooney viscosity and therefore excellent processability during tire production, while also having excellent physical properties such as tensile properties and excellent viscoelastic properties; a production method thereof; and a rubber composition containing the same. [Means for solving the problem]

[0010] According to one embodiment of the present invention for solving the above problems, the present invention provides a modified conjugated diene-based polymer having a Mooney Large Relaxation Area (MLRA) of 1500 MU-s or more measured at 100°C, as represented by the following mathematical formula 1:

[0011]

number

[0012] In the above mathematical formula 1, A is the Mooney Large Relaxation Area (MLRA), k is the Mooney intercept 1 second after the rotor of the Mooney viscometer is stopped, a is the Mooney relaxation factor, t o is the start point of Mooney relaxation, t f is the time when Mooney relaxation is completed.

[0013] The present invention also provides a method for producing a modified conjugated diene-based polymer, comprising: a step (S1) of polymerizing a conjugated diene-based monomer, or an aromatic vinyl-based monomer and a conjugated diene-based monomer, in a hydrocarbon solvent in the presence of a polymerization initiator to produce an activated polymer; and a step (S2) of reacting or coupling the activated polymer produced in the step (S1) with a first modifier and a second modifier, wherein the first modifier is an aminoalkoxysilane-based modifier and the second modifier is an epoxy-based modifier. The present invention also provides a rubber composition comprising the modified conjugated diene-based polymer and a filler. Effect of the Invention

[0014] The modified conjugated diene polymer according to the present invention has a Mooney large relaxation area of ​​1500 MU-s or more, and despite its high molecular weight, can have a low Mooney viscosity after compounding with a rubber composition, thereby providing excellent processability, tensile properties and viscoelastic properties. Furthermore, the modified conjugated diene polymer according to the present invention contains functional groups derived from two types of modifiers at at least one terminal, so that the tensile properties and viscoelastic properties can be further improved.

[0015] In addition, the method for producing a modified conjugated diene-based polymer according to the present invention includes a step of reacting or coupling an active polymer with both a first modifier and a second modifier, and thus it is possible to easily produce the above-mentioned modified conjugated diene-based polymer, which is adjusted to the above-mentioned large Mooney relaxation area, contains functional groups derived from the first and second modifiers in the molecule, and has excellent processability, tensile properties, and viscoelastic properties.

[0016] Furthermore, since the rubber composition according to the present invention contains the modified conjugated diene polymer having the large Mooney relaxation area, it is possible to produce a molded article having excellent processability, tensile properties, and viscoelastic properties. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] The present invention will now be described in more detail so that the present invention may be easily understood. The terms and words used in the description and claims of the present invention should not be interpreted in a limited manner to their ordinary or dictionary meanings, but should be interpreted in a manner that is consistent with the technical idea of ​​the present invention, based on the principle that the inventors can appropriately define the concepts of terms in order to best describe their invention.

[0018] [Terminology definition] In the present invention, the term "Mooney Large Relaxation Area (MLRA)" is a measure of chain relaxation in a molten polymer, suggesting that longer or branched polymer chains can store more energy and require longer time to relax after removal of applied strain. For example, the Mooney Large Relaxation Area of ​​an ultra-high molecular weight or long chain branched polymer may be larger than a polymer with a broad or narrow molecular weight when compared to a polymer with the same Mooney viscosity.

[0019] In the present invention, the term "substituted" means that hydrogen of a functional group, an atomic group, or a compound is replaced with a specific substituent. When hydrogen of a functional group, an atomic group, or a compound is replaced with a specific substituent, one or more substituents may be present depending on the number of hydrogen present in the functional group, the atomic group, or the compound, and when multiple substituents are present, each substituent may be the same or different from each other.

[0020] In the present invention, the term "alkyl group" means a monovalent aliphatic saturated hydrocarbon, and may mean all of straight-chain alkyl groups such as methyl, ethyl, propyl, and butyl; branched alkyl groups such as isopropyl, sec-butyl, tert-butyl, and neo-pentyl; and cyclic saturated hydrocarbons or cyclic unsaturated hydrocarbons containing one or more unsaturated bonds.

[0021] In the present invention, the term "alkylene group" may mean a divalent aliphatic saturated hydrocarbon such as methylene, ethylene, propylene, butylene, and the like. In the present invention, the term "cycloalkyl group" may mean a cyclic saturated hydrocarbon.

[0022] In the present invention, the term "aryl group" refers to an aromatic hydrocarbon and can be intended to include both monocyclic aromatic hydrocarbons, in which one ring is formed, or polycyclic aromatic hydrocarbons, in which two or more rings are linked together.

[0023] In the present invention, the term "heterocyclic group" refers to a cyclic saturated hydrocarbon or a cyclic unsaturated hydrocarbon containing one or more unsaturated bonds, in which carbon atoms may be replaced by one or more heteroatoms, where the heteroatoms may be selected from N, O, and S.

[0024] In the present invention, the term "monovalent hydrocarbon group" refers to a monovalent substituent derived from a hydrocarbon group, and refers to a monovalent atomic group in which carbon and hydrogen are bonded, such as, for example, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkyl group containing one or more unsaturated bonds, and an aryl group, and the monovalent atomic group may have a linear or branched structure depending on the bond structure.

[0025] In the present invention, the term "divalent hydrocarbon group" refers to a divalent substituent derived from a hydrocarbon group, and refers to a divalent atomic group in which carbon and hydrogen are bonded, such as, for example, an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, a cycloalkylene group containing one or more unsaturated bonds, and an arylene group, and the divalent atomic group may have a linear or branched structure depending on the bond structure.

[0026] In the present invention, the term "single bond" may refer to a single covalent bond itself, without any other atoms or molecular groups involved. In the present invention, the terms "derived unit" and "derived functional group" can mean a component or structure originating from a certain substance, or the substance itself.

[0027] [Measurement method and conditions] In the present invention, the "weight average molecular weight (Mw)", "number average molecular weight (Mn)" and "molecular weight distribution (MWD)" are measured by measuring the molecular weight by GPC (gel permeation chromatograph) analysis and obtaining a molecular weight distribution curve. The molecular weight distribution (PDI, MWD, Mw / Mn) is calculated from each of the measured molecular weights. Specifically, the GPC is performed using a combination of two PLgel Olexis (Polymer Laboratories) columns and one PLgel Mixed-C (Polymer Laboratories) column, and PS (polystyrene) is used as a GPC standard material when calculating the molecular weight. The GPC measurement solvent is prepared by mixing 2 wt% of an amine compound with tetrahydrofuran.

[0028] Modified conjugated diene polymer The present invention provides a modified conjugated diene-based polymer which, despite the formation of a high molecular weight polymer, has excellent processability due to its low Mooney viscosity after compounding with a rubber composition, and also has excellent tensile properties and viscoelastic properties.

[0029] The modified conjugated diene-based polymer according to one embodiment of the present invention is characterized in that it has a Mooney Large Relaxation Area (MLRA) of 1500 MU-s or more measured at 100° C. and is represented by the following mathematical formula 1:

[0030]

number

[0031] In the above mathematical formula 1, A is the Mooney Large Relaxation Area (MLRA), k is the Mooney intercept 1 second after the rotor of the Mooney viscometer is stopped, a is the Mooney relaxation factor, t o is the start point of Mooney relaxation, t f is the time when Mooney relaxation is completed.

[0032] Here, the Mooney relaxation start time is one second after the rotor operation is stopped. death, This means the point in time when the Mooney torque has a value of k. vinegar The Mooney relaxation completion time indicates the time when the Mooney relaxation measurement is completed in the Mooney relaxation measurement test. vinegar That is, t f -t o denotes the Mooney relaxation time vinegar .

[0033] According to one embodiment of the present invention, the t o may be 1 second, and t f In other words, the Mooney large relaxation area according to one embodiment of the present invention may be an integral area under the Mooney torque-relaxation time curve from 1 second to 80 seconds to 150 seconds. f Specifically, the time may be 90 seconds to 130 seconds, or 100 seconds to 120 seconds.

[0034] Generally, the molecular weight of a polymer and the Mooney viscosity are proportional to each other and tend to show the same tendency, and in the case of a high molecular weight polymer, the Mooney viscosity is high and the processability is poor. However, the modified conjugated diene polymer according to one embodiment of the present invention has a Mooney large relaxation area of ​​1500 MU-s or more, and thus has the effect of significantly improving the processability.

[0035] In the modified conjugated diene polymer of the present invention, a Mooney large relaxation area of ​​1500 MU-s or more is one technical means for obtaining excellent processability while also obtaining excellent tensile and viscoelastic properties, and when the Mooney large relaxation area is 1500 MU-s or more, the effect of the present invention can be obtained. However, when the Mooney large relaxation area has a very large value, the processability may be reduced, and in order to obtain better processability and to obtain excellent properties in a well-balanced manner in both tensile and viscoelastic properties, the Mooney large relaxation area of ​​the modified conjugated diene polymer according to one embodiment of the present invention may be 4000 MU-s or less.

[0036] Specifically, the modified conjugated diene-based polymer according to one embodiment of the present invention may have a Mooney large relaxation area of ​​1500 MU-s or more, preferably 1500 to 4000 MU-s, more preferably 1800 to 3000 MU-s, 2000 to 3000 MU-s, 2000 to 2800 MU-s, or 2400 to 2800 MU-s. The Mooney large relaxation area may be a value calculated from the above mathematical formula 1 by plotting a Mooney torque graph according to time. In this case, the Mooney viscosity (MV, ML1+4, @100°C) was measured by using a MV-2000 (manufactured by ALPHA Technologies) at 100°C, rotor speed 2±0.02 rpm, and large rotor. In this case, the sample used may be left at room temperature (23±3°C) for 30 minutes or more, and then 27±3g of the sample may be taken and filled into the die cavity, and the platen may be operated to measure the value for 4 minutes.

[0037] After measuring the Mooney viscosity, the rotor is stopped and the slope of the change in Mooney viscosity that occurs as the torque is released is measured, and the absolute value of the slope can be obtained as the Mooney relaxation rate (a). The Mooney large relaxation area is the area 1 second after the rotor stops (t o ) to 120 seconds (t f) and this integral value can be calculated from the above mathematical formula 1. When the Mooney large relaxation area satisfies the above range, an effect of improving processability can be obtained when compounding the rubber composition. In particular, when the Mooney large relaxation area satisfies the above range under the condition of a Mooney viscosity of 70 or more, preferably 80 or more, an even greater effect of improving processability can be obtained.

[0038] In addition, the modified conjugated diene polymer according to an embodiment of the present invention may be a homopolymer of a conjugated diene monomer; or a copolymer of a conjugated diene monomer and an aromatic vinyl monomer, where the homopolymer of a conjugated diene monomer means a polymer containing a repeating unit derived from a conjugated diene monomer formed by polymerization of a conjugated diene monomer, and the copolymer may mean a copolymer containing a repeating unit derived from a conjugated diene monomer and a repeating unit derived from an aromatic vinyl monomer formed by copolymerization of a conjugated diene monomer and a conjugated diene monomer. The conjugated diene monomer may be at least one selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, 2-phenyl-1,3-butadiene, and 2-halo-1,3-butadiene (halo means a halogen atom).

[0039] The aromatic vinyl monomer may be, for example, at least one selected from the group consisting of styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, 1-vinyl-5-hexylnaphthalene, 3-(2-pyrrolidino ethyl)styrene, 4-(2-pyrrolidino ethyl)styrene, and 3-(2-pyrrolidino-1-methyl ethyl)-α-methylstyrene.

[0040] As another example, the modified conjugated diene polymer may be a copolymer further including a repeating unit derived from a diene monomer having 1 to 10 carbon atoms in addition to the repeating unit derived from the conjugated diene monomer. The repeating unit derived from the diene monomer may be a repeating unit derived from a diene monomer different from the conjugated diene monomer, and the diene monomer different from the conjugated diene monomer may be, for example, 1,2-butadiene. When the modified conjugated diene polymer is a copolymer further including a diene monomer, the modified conjugated diene polymer may include the repeating unit derived from the diene monomer in an amount of more than 0% by weight to 1% by weight, more than 0% by weight to 0.1% by weight, more than 0% by weight to 0.01% by weight, or more than 0% by weight to 0.001% by weight. When the amount is within this range, it is effective in preventing the formation of gel.

[0041] In addition, when the modified conjugated diene-based polymer is the above-mentioned copolymer, the copolymer may be a random copolymer, in which case there is an effect of excellent balance between the various physical properties. The random copolymer may mean a copolymer in which the repeating units constituting the copolymer are randomly arranged. The modified conjugated diene polymer according to the present invention may contain a functional group derived from an aminoalkoxysilane-based modifier and a functional group derived from an epoxy-based modifier at at least one terminal.

[0042] Conventionally, modified conjugated diene polymers have been produced by modifying the ends of conjugated diene polymers with aminoalkoxysilane modifiers in order to improve the affinity for fillers and the viscoelastic properties. However, although the viscoelastic properties of modified conjugated diene polymers modified with aminoalkoxysilane modifiers are improved, there is a problem in that the tensile properties and processability are deteriorated.

[0043] On the other hand, the modified conjugated diene polymer according to one embodiment of the present invention simultaneously contains a functional group derived from an aminoalkoxysilane modifier and a functional group derived from an epoxy modifier, and thus has the effect of significantly improving the viscoelastic properties while also having excellent tensile properties and processability.

[0044] As another example, the modified conjugated diene-based polymer according to an embodiment of the present invention may include at least one first polymer chain having a functional group derived from an aminoalkoxysilane-based modifier at one end; and at least one second polymer chain having a functional group derived from an epoxy-based modifier at one end.

[0045] Meanwhile, the modifier may be, as a specific example, a silica affinity modifier. The silica affinity modifier means a modifier containing a silica affinity functional group in a compound used as a modifier, and the silica affinity functional group may mean a functional group that has excellent affinity with a filler, particularly a silica-based filler, and can interact with the silica-based filler and the functional group derived from the modifier.

[0046] Specifically, according to one embodiment of the present invention, the aminoalkoxysilane-based modifier may be at least one selected from the group consisting of compounds represented by the following Formulas 1 to 3:

[0047] [ka]

[0048] In the above Chemical Formula 1, R a1 and R a4 are each independently a single bond or an alkylene group having 1 to 10 carbon atoms, R a2 and R a3 are each independently an alkyl group having 1 to 10 carbon atoms,

[0049] R a5is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a mono-, di-, or tri-substituted alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, or -N[R a6 Si(OR a7 ) n3 (R a8 ) 3-n3 ] 2 where R a6 is a single bond or an alkylene group having 1 to 10 carbon atoms, and R a7 and R a8 are each independently an alkyl group having 1 to 10 carbon atoms, and n3 is an integer of 1 to 3, n 1 is an integer from 1 to 3, n 2 is an integer between 0 and 2.

[0050] [ka]

[0051] In the above formula 2, R b2 ~R b4 are each independently an alkylene group having 1 to 10 carbon atoms; R b5 ~R b8 are each independently an alkyl group having 1 to 10 carbon atoms, and R b13 and R b14 are each independently an alkylene group having 1 to 10 carbon atoms; R b15 ~R b18 are each independently an alkyl group having 1 to 10 carbon atoms, m 1 , m 2 , m 3 , and m 4 are each independently an integer from 1 to 3.

[0052] [ka]

[0053] In the above Chemical Formula 3, R e1 and R e2are each independently an alkylene group having 1 to 10 carbon atoms; R e3 ~R e6 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or -R e7 SiR e8 R e9 R e10 and R e3 ~R e6 At least one of the following is -R e7 SiR e8 R e9 R e10 where R e7 is a single bond or an alkylene group having 1 to 10 carbon atoms, and R e8 ~R e10 are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and R e8 ~R e10 At least one of them is an alkoxy group having 1 to 10 carbon atoms.

[0054] Specifically, in the above formula 1, R a1 and R a4 are each independently a single bond or an alkylene group having 1 to 5 carbon atoms; R a2 and R a3 are each independently an alkyl group having 1 to 5 carbon atoms, and R a5 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a trialkylsilyl group substituted with an alkyl group having 1 to 5 carbon atoms, or -N[R a6 Si(OR a7 ) n3 (R a8 ) 3-n3 ] 2 where R a6 is a single bond or an alkylene group having 1 to 5 carbon atoms, and R a7 and R a8 are each independently an alkyl group having 1 to 5 carbon atoms, n3 is an integer of 2 or 3, and n 1 is an integer between 2 and 3, and n 2 may be an integer from 0 to 2.

[0055] More specifically, the compound represented by Chemical Formula 1 is N,N-bis(3-(dimethoxy(methyl)silyl)propyl)-methyl-1-amine, N,N-bis(3-(diethoxy(methyl)silyl)propyl)-methyl-1-amine, N,N-bis(3-(trimethoxysilyl)propyl)-methyl-1-amine, N,N-bis(3-(triethoxy ... e), N,N-diethyl-3-(trimethoxysilyl)propan-1-amine, N,N-diethyl-3-(triethoxysilyl)propan-1-amine, tri(trimethoxysilyl)amine, tri(3-(trimethoxysilyl)propyl)amine, N,N-bis(3-(diethoxy(methyl)silyl)propyl)-1,1,1-trimethlysilanamine, and N 1 ,N 1 ,N 3 ,N 3 -Tetrakis(3-(trimethoxysilyl)propyl)propane-1,3-diamine(N 1 ,N 1 ,N 3 ,N 3-tetrakis(3-(trimethoxysilyl)propyl)propane-1,3-diamine).

[0056] As another example, in the above-mentioned formula 2, R b2 ~R b4 are each independently an alkylene group having 1 to 6 carbon atoms; R b5 ~R b8 are each independently an alkyl group having 1 to 6 carbon atoms; R b13 and R b14 are each independently an alkylene group having 1 to 6 carbon atoms; R b15 ~R b18 are each independently an alkyl group having 1 to 6 carbon atoms, and m 1 , m 2 , m 3 , and m 4 are each independently an integer from 1 to 3.

[0057] More specifically, the compound represented by Chemical Formula 2 may be 3,3'-(piperazine-1,4-diyl)bis(N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine).

[0058] As another example, in Formula 3, R e1 and R e2 are each independently an alkylene group having 1 to 6 carbon atoms; R e3 ~R e6 are each independently an alkyl group having 1 to 6 carbon atoms or -R e7 SiR e8 R e9 R e10 and R e3 ~R e6 At least one of the following is -R e7 SiR e8 R e9 R e10 where Re7 is a single bond or an alkylene group having 1 to 6 carbon atoms, and R e8 ~R e10 are each independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and R e8 ~R e10 At least one of them is an alkoxy group having 1 to 6 carbon atoms.

[0059] More specifically, the compound represented by the formula 3 is N,N'-(cyclohexane-1,3-diylbis(methylene))bis(3-(trimethylsilyl)phenyl)-1,3-diphenyl-2,2-diphenyl ... M (3-(trimethoxysilyl)-N-( M N,N'-(cyclohexane-1,3-diylbis(methylene))bis(3-(trimethoxysilyl)propyl)propan-1-amine m ethoxysilyl)-N-(3-(tri m ethoxysilyl)propyl)propan-1-amine).

[0060] According to an embodiment of the present invention, the epoxy-based modifier may be selected from compounds represented by the following Formulas 4 to 7.

[0061] [ka]

[0062] In the above Chemical Formula 4, R d1 ~R d3 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or -R d4 R d5 and R d1 ~R d3 At least one of the following is -R d4 R d5 where R d4 is an alkylene group having 1 to 10 carbon atoms, which may or may not contain a heteroatom; R d5 is an epoxy group,

[0063] [ka]

[0064] In the above Chemical Formula 5, R e1 and R e2 are each independently an alkylene group having 1 to 10 carbon atoms, R e3 ~R e6 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or -R e7 R e8 and R e3 ~R e6 At least one of the following is -R e7 R e8 where R e7 is an alkylene group having 1 to 10 carbon atoms, which may or may not contain one or more heteroatoms selected from N, S, and O; R e8 is an epoxy group,

[0065] [ka]

[0066] In the above Chemical Formula 6, X is O or S; R f1 and R f2 are each independently a single bond or an alkylene group having 1 to 10 carbon atoms,

[0067] R f3 ~R f8 are each independently a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aralkyl group having 7 to 14 carbon atoms, or -R f9 R f10 and R f3 ~R f8 At least one of the following is -R f9 R f10 where R f9is an alkylene group having 1 to 12 carbon atoms, which may or may not contain a heteroatom; R f10 is an epoxy group,

[0068] [ka]

[0069] In the above Chemical Formula 7, R g1 ~R g4 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or -R g5 OR g6 and R g1 ~R g4 At least one of the following is -R g5 OR g6 where R g5 is a single bond or an alkylene group having 1 to 10 carbon atoms; R g6 is an epoxyalkyl group having 3 to 10 carbon atoms, Y is C or N, and when Y is N, R g4 does not exist.

[0070] Specifically, in the above Chemical Formula 4, R d1 ~R d3 are each independently an alkyl group having 1 to 6 carbon atoms, or -R d4 R d5 and R d1 ~R d3 At least one of the following is -R d4 R d5 where R d4 is an alkylene group having 1 to 6 carbon atoms, which may or may not contain a heteroatom; R d5 is an epoxy group, and the heteroatom may be O (oxygen atom).

[0071] More specifically, the compound represented by Chemical Formula 2 may be a compound represented by Chemical Formula 4-1 below.

[0072] [ka]

[0073] In addition, in the above-mentioned Chemical Formula 5, R e1 and R e2 are each independently an alkylene group having 1 to 6 carbon atoms; R e3 ~R e6 are each independently an alkyl group having 1 to 6 carbon atoms or -R e7 R e8 and R e3 ~R e6 At least one of the following is -R e7 R e8 where R e7 is an alkylene group having 1 to 6 carbon atoms, which may or may not contain a heteroatom; R e8 is an epoxy group, and the heteroatom may be O.

[0074] More specifically, the compound represented by Chemical Formula 5 may be a compound represented by Chemical Formula 5-1 below.

[0075] [ka]

[0076] In addition, in the above Chemical Formula 6, X is O or S, and R f1 and R f2 are each independently a single bond or an alkylene group having 1 to 6 carbon atoms; R f3 ~R f8 are each independently an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or -R f9 R f10 and R f3 ~R f8 At least one of the following is -R f9 R f10 where R f9 is an alkylene group having 1 to 6 carbon atoms, which may or may not contain a heteroatom; R f10 is an epoxy group, and the heteroatom may be O.

[0077] More specifically, the compound represented by Chemical Formula 6 may be a compound represented by the following Chemical Formula 6-1 or 6-2.

[0078] [ka]

[0079] [ka]

[0080] In addition, in the above-mentioned Chemical Formula 7, R g1 ~R g4 are each independently an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or -R g5 OR g6 and R g1 ~R g4 At least one of the following is -R g5 OR g6 where R g5 is a single bond or an alkylene group having 1 to 6 carbon atoms; R g6 is an epoxyalkyl group having 3 to 6 carbon atoms, Y is C or N, and when Y is N, R g4 does not exist.

[0081] More specifically, the compound represented by Chemical Formula 7 may be selected from the compounds represented by Chemical Formulas 7-1 to 7-4 below.

[0082] [ka]

[0083] [ka]

[0084] [ka]

[0085] [ka]

[0086] As another example, the modified conjugated diene-based polymer according to an embodiment of the present invention may contain a functional group derived from a modified initiator at the other end in addition to one end containing a functional group derived from a modifying agent, and the modified initiator may be a reaction product of an N-functional group-containing compound and an organometallic compound.

[0087] Specifically, the N-functional group-containing compound may be an aromatic hydrocarbon compound containing an N-functional group including an amino group, an amide group, an amino group, an imidazole group, a pyrimidyl group, or a cyclic amino group, which is substituted or unsubstituted with a substituent, and the substituent may be an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or an alkoxysilyl group having 1 to 10 carbon atoms.

[0088] More specifically, the N-functional group-containing compound may be a compound represented by the following formula 8:

[0089] [ka]

[0090] In the above Chemical Formula 8, R 1 ~R 3 are each independently hydrogen; an alkyl group having 1 to 30 carbon atoms; an alkenyl group having 2 to 30 carbon atoms; an alkynyl group having 2 to 30 carbon atoms; a heteroalkyl group having 1 to 30 carbon atoms, a heteroalkenyl group having 2 to 30 carbon atoms; a heteroalkynyl group having 2 to 30 carbon atoms; a cycloalkyl group having 5 to 30 carbon atoms; an aryl group having 6 to 30 carbon atoms; or a heterocyclic group having 3 to 30 carbon atoms,

[0091] R4 represents a single bond; a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; a substituted or unsubstituted cycloalkylene group having 5 to 20 carbon atoms; or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms,

[0092] R 5 is an alkyl group having 1 to 30 carbon atoms; an alkenyl group having 2 to 30 carbon atoms; an alkynyl group having 2 to 30 carbon atoms; a heteroalkyl group having 1 to 30 carbon atoms; a heteroalkenyl group having 2 to 30 carbon atoms; a heteroalkynyl group having 2 to 30 carbon atoms; a cycloalkyl group having 5 to 30 carbon atoms; an aryl group having 6 to 30 carbon atoms; a heterocyclic group having 3 to 30 carbon atoms; or a functional group represented by the following chemical formula 8a or chemical formula 8b,

[0093] n is an integer from 1 to 5; R 5 At least one of R is a functional group represented by the following chemical formula 8a or 8b, and when n is an integer of 2 to 5, 5 may be the same or different,

[0094] [ka]

[0095] In the above Chemical Formula 8a, R 6 is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; a substituted or unsubstituted cycloalkylene group having 5 to 20 carbon atoms; or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms,

[0096] R 7 and R 8each independently represents an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms,

[0097] R 9 is hydrogen; an alkyl group having 1 to 30 carbon atoms; an alkenyl group having 2 to 30 carbon atoms; an alkynyl group having 2 to 30 carbon atoms; a heteroalkyl group having 1 to 30 carbon atoms; a heteroalkenyl group having 2 to 30 carbon atoms; a heteroalkynyl group having 2 to 30 carbon atoms; a cycloalkyl group having 5 to 30 carbon atoms; an aryl group having 6 to 30 carbon atoms; or a heterocyclic group having 3 to 30 carbon atoms, Z is N, O, or S; when Z is O or S, R 9 does not exist,

[0098] [ka]

[0099] In the above Chemical Formula 8b, R 10 is a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms; a substituted or unsubstituted cycloalkylene group having 5 to 20 carbon atoms; or a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms,

[0100] R 11 and R 12 are each independently an alkyl group having 1 to 30 carbon atoms; an alkenyl group having 2 to 30 carbon atoms; an alkynyl group having 2 to 30 carbon atoms; a heteroalkyl group having 1 to 30 carbon atoms; a heteroalkenyl group having 2 to 30 carbon atoms; a heteroalkynyl group having 2 to 30 carbon atoms; a cycloalkyl group having 5 to 30 carbon atoms; an aryl group having 6 to 30 carbon atoms; or a heterocyclic group having 3 to 30 carbon atoms, or 11 and R 12 are linked to each other and form, together with N, a heterocyclic group having 2 to 20 carbon atoms.

[0101] More specifically, the compound represented by the formula 8 is 1 ~R 3 are each independently hydrogen; an alkyl group having 1 to 10 carbon atoms; an alkenyl group having 2 to 10 carbon atoms; or an alkynyl group having 2 to 10 carbon atoms; R 4 is a single bond; or an unsubstituted alkylene group having 1 to 10 carbon atoms; R 5 is an alkyl group having 1 to 10 carbon atoms; an alkenyl group having 2 to 10 carbon atoms; an alkynyl group having 2 to 10 carbon atoms; or a functional group represented by the following chemical formula 8a or 8b, in which R 6 is an unsubstituted alkylene group having 1 to 10 carbon atoms, R 7 and R 8 are each independently an unsubstituted alkylene group having 1 to 10 carbon atoms; R 9 is an alkyl group having 1 to 10 carbon atoms; a cycloalkyl group having 5 to 20 carbon atoms; an aryl group having 5 to 20 carbon atoms; or a heterocyclic group having 3 to 20 carbon atoms, and in the above Chemical Formula 8b, R 10 is an unsubstituted alkylene group having 1 to 10 carbon atoms, R 11 and R 12 are each independently an alkyl group having 1 to 10 carbon atoms; a cycloalkyl group having 5 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms; or a heterocyclic group having 3 to 20 carbon atoms; 11 and R 12 may be linked to each other to form, together with N, a heterocyclic group having 2 to 20 carbon atoms.

[0102] More specifically, the compound represented by Chemical Formula 8 may be the compounds represented by Chemical Formulas 8-1 to 8-3 below.

[0103] [ka]

[0104] [ka]

[0105] [ka]

[0106] The organometallic compound may be an organoalkali metal compound, for example, one or more selected from an organolithium compound, an organosodium compound, an organopotassium compound, an organorubidium compound, and an organocesium compound.

[0107] Specifically, the organometallic compound may be at least one selected from the group consisting of methyl lithium, ethyl lithium, propyl lithium, n-butyl lithium, s-butyl lithium, t-butyl lithium, hexyl lithium, n-decyl lithium, t-octyl lithium, phenyl lithium, 1-naphthyl lithium, n-eicosyl lithium, 4-butylphenyl lithium, 4-tolyl lithium, cyclohexyl lithium, 3,5-di-n-heptylcyclohexyl lithium, 4-cyclopentyl lithium, naphthyl sodium, naphthyl potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide, and lithium isopropyl amide.

[0108] In addition, the modified conjugated diene polymer according to an embodiment of the present invention may have a number average molecular weight (Mn) of 100,000g / mol to 2,000,000g / mol, 200,000g / mol to 1,000,000g / mol, or 400,000g / mol to 800,000g / mol, and a weight average molecular weight (Mw) of 100,000g / mol to 3,000,000g / mol, 400,000g / mol to 2,000,000g / mol, or 800,000g / mol to 1,500,000g / mol. When the weight average molecular weight is within this range, it has an effect of being excellent in rolling resistance and wet skid resistance. In another example, the modified conjugated diene polymer may have a molecular weight distribution (PDI; MWD; Mw / Mn) of 1.5 or more or 1.5 to 3.0. Within this range, the modified conjugated diene-based polymer has excellent tensile properties and viscoelastic properties, and has an excellent balance between the various physical properties. At the same time, the modified conjugated diene-based polymer has a unimodal molecular weight distribution curve measured by gel permeation chromatography (GPC), which is a molecular weight distribution that appears in a polymer polymerized by continuous polymerization, and may mean that the modified conjugated diene-based polymer has uniform properties. That is, the modified conjugated diene-based polymer according to one embodiment of the present invention may be produced by continuous polymerization and have a unimodal molecular weight distribution curve, but the molecular weight distribution may be 1.5 or more.

[0109] As another example, the modified conjugated diene polymer may have a Mooney relaxation ratio (-S / R value) measured at 100°C of 0.5 or less, 0.4 or less, or 0.3 or less, and the lower limit of the Mooney relaxation ratio is not particularly limited and may be, for example, 0.1 or more or 0.2 or more.

[0110] Here, the Mooney relaxation rate indicates the change in stress that appears as a reaction to the same amount of strain, and may be measured using a Mooney viscometer. Specifically, the Mooney relaxation rate was obtained by using a Monsanto MV2000E Large Rotor under the conditions of 100°C and a rotor speed of 2±0.02 rpm, leaving the polymer at room temperature (23±5°C) for 30 minutes or more, taking 27±3g and filling the inside of the die cavity, operating the platen to apply torque and measuring the Mooney viscosity, and then measuring the slope of the Mooney torque change that appears as the torque is released.

[0111] On the other hand, the Mooney relaxation rate can be used as an index of the branched structure of the polymer. For example, when comparing polymers with the same Mooney viscosity, the more branches there are, the smaller the Mooney relaxation rate becomes, and therefore the Mooney relaxation rate can be used as an index of the branching degree.

[0112] The modified conjugated diene polymer may have a Mooney viscosity at 100° C. of 70 or more, 80 to 150, or 80 to 120. When it is within this range, it has the effect of providing excellent processability and productivity.

[0113] The modified conjugated diene polymer may have a vinyl content of 5% by weight or more, 10% by weight or more, or 10% by weight to 60% by weight. Here, the vinyl content may refer to the content of 1,2-added conjugated diene monomer, not 1,4-added, relative to 100% by weight of a conjugated diene copolymer composed of a monomer having a vinyl group and an aromatic vinyl monomer.

[0114] As described above, the modified conjugated diene polymer according to one embodiment of the present invention may have a large Mooney relaxation area of ​​1500 MU-s or more, and may further include first and second polymer chains having functional groups derived from the first and second modifiers at one end. Meanwhile, the modified conjugated diene polymer is preferably produced by the production method described below in order to satisfy the above characteristics, but when all of the above characteristics are satisfied, the effects to be realized by the present invention can be achieved.

[0115] Method for producing modified conjugated diene polymer The present invention also provides a method for producing the modified conjugated diene polymer. The method for producing the modified conjugated diene-based polymer according to one embodiment of the present invention includes a step (S1) of polymerizing a conjugated diene-based monomer or an aromatic vinyl-based monomer and a conjugated diene-based monomer in a hydrocarbon solvent in the presence of a polymerization initiator to produce an activated polymer, and a step (S2) of reacting or coupling the activated polymer produced in the step (S1) with a first modifier and a second modifier, wherein the first modifier is an aminoalkoxysilane-based modifier and the second modifier is an epoxy-based modifier. The aminoalkoxysilane-based modifier and the epoxy-based modifier are as described above.

[0116] The hydrocarbon solvent is not particularly limited, and may be, for example, one or more selected from the group consisting of n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene, and xylene.

[0117] The polymerization initiator may be used in an amount of 0.1 to 3.0 equivalents, preferably 0.1 to 2.0 equivalents, and more preferably 0.5 to 1.5 equivalents, relative to 1.0 equivalent of the monomer.

[0118] As another example, the polymerization initiator may be used in an amount of 0.01 mmol to 10 mmol, 0.05 mmol to 5 mmol, 0.1 mmol to 2 mmol, 0.1 mmol to 1 mmol, or 0.15 to 0.8 mmol, based on 100 g of the total monomers, where the total 100 g of the monomers may be the conjugated diene monomer or the total amount of the conjugated diene monomer and the aromatic vinyl monomer.

[0119] On the other hand, the polymerization initiator may be an organometallic compound, for example, one or more selected from an organolithium compound, an organosodium compound, an organopotassium compound, an organorubidium compound, and an organocesium compound.

[0120] Specifically, the organometallic compound may be at least one selected from the group consisting of methyl lithium, ethyl lithium, propyl lithium, n-butyl lithium, s-butyl lithium, t-butyl lithium, hexyl lithium, n-decyl lithium, t-octyl lithium, phenyl lithium, 1-naphthyl lithium, n-eicosyl lithium, 4-butylphenyl lithium, 4-tolyl lithium, cyclohexyl lithium, 3,5-di-n-heptylcyclohexyl lithium, 4-cyclopentyl lithium, naphthyl sodium, naphthyl potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide, and lithium isopropyl amide. As another example, the polymerization initiator may be a modified initiator, which may be a reaction product of an N-functional compound and the organometallic compound.

[0121] The polymerization in the step (S1) may be, for example, an anionic polymerization, and may be, for example, a living anionic polymerization having an anionic active site at the polymerization end by a growth polymerization reaction by an anion. The polymerization in the step (S1) may be a temperature-increasing polymerization, an isothermal polymerization, or a constant temperature polymerization (adiabatic polymerization). The constant temperature polymerization refers to a polymerization method including a step of polymerizing by its own reaction heat without adding heat after adding a polymerization initiator, the temperature-increasing polymerization refers to a polymerization method of increasing the temperature by adding heat after adding the polymerization initiator, and the isothermal polymerization refers to a polymerization method of increasing the temperature by adding heat or removing heat after adding the polymerization initiator to maintain the temperature of the polymer constant.

[0122] According to one embodiment of the present invention, the polymerization in step (S1) may be carried out by further including a diene compound having 1 to 10 carbon atoms in addition to the conjugated diene monomer. In this case, there is an effect of preventing gel formation on the wall of the reactor during long-term operation. The diene compound may be, for example, 1,2-butadiene.

[0123] The polymerization in step (S1) may be carried out at a temperature range of, for example, 80° C. or less, −20° C. to 80° C., 0° C. to 80° C., 0° C. to 70° C., or 10° C. to 70° C. Within this range, the molecular weight distribution of the polymer can be narrowly adjusted, resulting in excellent improvement of physical properties.

[0124] The activated polymer prepared in step (S1) may refer to a polymer in which a polymer anion and an organometallic cation are bonded. The (S1) step may be carried out by appropriately selecting a continuous polymerization method or a batch polymerization method, and from the viewpoint of improving productivity and processability, it may be preferably carried out by a continuous polymerization method.

[0125] In the present invention, the term "polymer" refers to an intermediate in the form of a polymer undergoing polymerization in each reactor during the implementation of step (S1) prior to the completion of step (S1) or step (S2) to obtain an activated polymer or a modified conjugated diene-based polymer, and may refer to a polymer undergoing polymerization in a reactor with a polymerization conversion rate of less than 95%.

[0126] According to an embodiment of the present invention, the molecular weight distribution (Mw / Mn) of the activated polymer prepared in step (S1) may be 1.5 or more, or 1.3 to 3.0. When it is within this range, it has an effect of excellent improvement in processability.

[0127] Meanwhile, the polymerization in the (S1) step may be carried out by including a polar additive, and the polar additive may be added in an amount of 0.001 g to 50 g, 0.001 g to 10 g, or 0.005 g to 0.1 g relative to a total of 100 g of monomers. As another example, the polar additive may be added in an amount of 0.001 g to 10 g, 0.005 g to 5 g, or 0.005 g to 4 g relative to a total of 1 mmol of polymerization initiator.

[0128] The polar additive may be, for example, one or more selected from the group consisting of tetrahydrofuran, 2,2-di(2-tetrahydrofuryl)propane, diethyl ether, cyclopentyl ether, dipropyl ether, ethylene methyl ether, ethylene dimethyl ether, diethyl glycol, dimethyl ether, tertiary-butoxyethoxyethane, bis(3-dimethylaminoethyl)ether, (dimethylaminoethyl)ethyl ether, trimethylamine, triethylamine, tripropylamine, N,N,N',N'-tetramethylethylenediamine, sodium mentholate, and 2-ethyl tetrahydrofurfuryl ether, and may be preferably 2,2-di(2-tetrahydrofuryl)propane, triethylamine, tetramethylethylenediamine, sodium mentholate, or 2-ethyl tetrahydrofurfuryl ether. When the polar additive is included, when a conjugated diene monomer and an aromatic vinyl monomer are copolymerized, the polar additive has the effect of compensating for the difference in reaction rate between them, thereby inducing the easy formation of a random copolymer.

[0129] According to one embodiment of the present invention, the reaction or coupling in step (S2) may be carried out in a modification reactor, specifically, by reacting or coupling the activated polymer with a first modifier and a second modifier. Here, the first modifier and the second modifier may be added sequentially or all at once to react or couple with the activated polymer, and the first modifier and the second modifier may be used in a molar ratio of 10:1 to 5:1 or 2:1 to 1:1.

[0130] In this case, the modifying agent may be used in an amount of 0.01 mmol to 10 mmol per 100 g of the total monomers. As another example, the modifying agent may be used in a molar ratio of 1:0.1 to 10, 1:0.1 to 5, or 1:0.1 to 1:3 per 1 mole of the polymerization initiator in the (S1) step.

[0131] According to an embodiment of the present invention, the modifying agent may be added to a modification reactor, and the step (S2) may be carried out in the modification reactor. As another example, the modifying agent may be added to a transfer section for transferring the activated polymer produced in the step (S1) to a modification reactor for carrying out the step (S2), and a reaction or coupling may proceed in the transfer section by mixing the activated polymer and the modifying agent.

[0132] The method for producing the modified conjugated diene polymer according to one embodiment of the present invention is a method that satisfies the above-mentioned characteristics of the modified conjugated diene polymer. As described above, the effects to be achieved by the present invention can be achieved when the above-mentioned characteristics are satisfied. In the case of other polymerization conditions, the physical properties of the modified conjugated diene polymer according to the present invention can be realized by controlling them in various ways.

[0133] Rubber composition Furthermore, the present invention provides a rubber composition containing the above modified conjugated diene-based polymer. The rubber composition may contain the modified conjugated diene polymer in an amount of 10% by weight or more, 10% by weight to 100% by weight, or 20% by weight to 90% by weight. When the amount is within this range, the rubber composition has excellent mechanical properties such as tensile strength and abrasion resistance, and has an excellent balance between the various physical properties.

[0134] The rubber composition may further contain other rubber components, if necessary, in addition to the modified conjugated diene polymer, and in this case, the rubber components may be contained in an amount of 90% by weight or less based on the total weight of the rubber composition. As a specific example, the other rubber components may be contained in an amount of 1 part by weight to 900 parts by weight based on 100 parts by weight of the modified conjugated diene polymer.

[0135] The rubber component may be, for example, natural rubber or synthetic rubber, and specific examples thereof include natural rubber (NR) containing cis-1,4-polyisoprene; modified natural rubbers obtained by modifying or refining the general natural rubber, such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber; styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, polyisobutylene-co-isoprene, and neoprene. , poly(ethylene-co-propylene), poly(styrene-co-butadiene), poly(styrene-co-isoprene), poly(styrene-co-isoprene-co-butadiene), poly(isoprene-co-butadiene), poly(ethylene-co-propylene-co-diene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, halogenated butyl rubber, and other synthetic rubbers, and any one or a mixture of two or more of these may be used.

[0136] The rubber composition may contain, for example, 0.1 to 200 parts by weight, or 10 to 120 parts by weight of a filler relative to 100 parts by weight of the modified conjugated diene polymer of the present invention. The filler may be, for example, a silica-based filler, and specific examples thereof may be wet silica (hydrated silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, colloidal silica, or the like, and preferably wet silica, which has the best effect of improving fracture properties and wet grip properties. The rubber composition may further contain a carbon black-based filler as necessary.

[0137] As another example, when silica is used as the filler, a silane coupling agent for improving reinforcing properties and low heat generation properties may be used together.Specific examples of the silane coupling agent include bis(3-triethoxysilylpropyl)tetrasulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-triethoxy ... silyl tetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropyl benzothiazolyl tetrasulfide, 3-triethoxysilylpropyl benzolyl tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis(3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyl dimethoxymethyl silane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, or dimethoxymethylsilylpropyl benzothiazolyl tetrasulfide, or any one or a mixture of two or more of these may be used. Preferably, in consideration of the effect of improving reinforcing properties, bis(3-triethoxysilylpropyl) polysulfide or 3-trimethoxysilylpropyl benzothiazyl tetrasulfide may be used.

[0138] In addition, the rubber composition according to one embodiment of the present invention uses a modified conjugated diene polymer having a functional group having high affinity with silica introduced into an active site as a rubber component, so the amount of the silane coupling agent may be reduced compared to normal cases. As a result, the silane coupling agent may be used in an amount of 1 to 20 parts by weight, or 5 to 15 parts by weight, per 100 parts by weight of silica. Within this range, the effect of the coupling agent is sufficiently exhibited, while the effect of preventing the rubber component from gelling is also achieved.

[0139] The rubber composition according to one embodiment of the present invention may be sulfur crosslinkable and may further contain a vulcanizing agent. Specifically, the vulcanizing agent may be sulfur powder, and may be contained in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the rubber component. When the amount is within this range, the necessary elastic modulus and strength of the vulcanized rubber composition are ensured, and the effect of excellent fuel economy is obtained.

[0140] In addition to the above components, the rubber composition according to an embodiment of the present invention may further include various additives commonly used in the rubber industry, specifically, a vulcanization accelerator, a process oil, an antioxidant, a plasticizer, an anti-aging agent, a scorch inhibitor, zinc white, stearic acid, a thermosetting resin, or a thermoplastic resin.

[0141] As the vulcanization accelerator, for example, a thiazole-based compound such as M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), or CZ (N-cyclohexyl-2-benzothiazylsulfenamide), or a guanidine-based compound such as DPG (diphenyl guanidine) may be used, and may be contained in an amount of 0.1 to 5 parts by weight per 100 parts by weight of the rubber component.

[0142] The process oil acts as a softener in the rubber composition, and may be, for example, a paraffinic, naphthenic, or aromatic compound. In consideration of tensile strength and abrasion resistance, aromatic process oils may be used, and in consideration of hysteresis loss and low temperature properties, naphthenic or paraffinic process oils may be used. The process oil may be contained in an amount of 100 parts by weight or less per 100 parts by weight of the rubber component. When the amount is within this range, it has the effect of preventing a decrease in the tensile strength and low heat generation property (fuel economy) of the vulcanized rubber.

[0143] The antioxidant may be, for example, 2,6-di-t-butyl-paracresol, dibutylhydroxytoluene, 2,6-bis((dodecylthio)methyl)-4-nonylphenol, or 2-methyl-4,6-bis((octylthio)methyl)phenol, and may be used in an amount of 0.1 to 6 parts by weight based on 100 parts by weight of the rubber component.

[0144] The anti-aging agent may be, for example, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, or a high-temperature condensate of diphenylamine and acetone, and may be used in an amount of 0.1 to 6 parts by weight per 100 parts by weight of the rubber component.

[0145] The rubber composition according to one embodiment of the present invention is obtained by kneading the rubber composition according to the compounding recipe using a kneading machine such as a Banbury mixer, a roll, or an internal mixer. After molding, a vulcanization process is performed to obtain a rubber composition having low heat build-up and excellent abrasion resistance.

[0146] As a result, the rubber composition is useful in the production of tire components such as tire treads, undertreads, sidewalls, carcass coating rubber, belt coating rubber, bead fillers, chafers, and bead coating rubber, as well as various industrial rubber products such as dustproof rubber, belt conveyors, and hoses. The present invention further provides a tire manufactured using the rubber composition. The tire may include a tire or a tire tread.

[0147] Working Example Hereinafter, the present invention will be described in detail with reference to examples in order to specifically explain the present invention. However, the examples according to the present invention can be modified in various forms, and the scope of the present invention should not be construed as being limited to the examples described below. The examples of the present invention are provided to more completely explain the present invention to those having average knowledge in the art.

[0148] [Example 1] In the first reactor of the continuous reactor in which two reactors are connected in series, styrene solution in which styrene is dissolved at 60 wt% in n-hexane was 258.3 g / h, 1,3-butadiene solution in which 1,3-butadiene is dissolved at 60 wt% in n-hexane was 1.41 kg / h, n-hexane was 4.68 kg / h, 2,2-(di-2(tetrahydrofuryl)propane as a polar additive was dissolved at 2 wt% in n-hexane was 11.5 g / h, and n-butyllithium solution in which n-butyllithium was dissolved at 2 wt% in n-hexane was 29.5 g / h. At this time, the temperature of the first reactor was maintained at 65°C, and when the polymerization conversion rate reached 95%, the polymer was transferred from the first reactor to the second reactor through the transfer pipe.

[0149] The polymer was transferred from the first reactor to the second reactor, and a solution containing 2% by weight of N,N'-(cyclohexane-1,3-diylbis(methylene))bis(3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine) as a modifier was added to the second reactor at a rate of 92.5g / h and a solution containing 1% by weight of tris((oxiran-2-ylmethoxy)methyl)amine was added at a rate of 64.5g / h. The temperature of the second reactor was maintained at 70°C.

[0150] Thereafter, a solution of IR1520 (BASF) dissolved at 30 wt% as an antioxidant was added to the polymerization solution discharged from the second reactor at a rate of 97.6 g / h and stirred. The resulting polymer was placed in hot water heated with steam and stirred to remove the solvent, producing a modified conjugated diene polymer.

[0151] [Example 2] A modified conjugated diene polymer was prepared in the same manner as in Example 1, except that a solution containing 2 wt % N,N'-(cyclohexane-1,3-diylbis(methylene))bis(3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine) and a solution containing 1 wt % tris((oxiran-2-ylmethoxy)methyl)amine were added at a rate of 61.7 g / h and 43.0 g / h, respectively, as the modifier.

[0152] [Example 3] A modified conjugated diene polymer was prepared in the same manner as in Example 1, except that a solution containing 2 wt % N,N'-(cyclohexane-1,3-diylbis(methylene))bis(3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine) and a solution containing 1 wt % tris((oxiran-2-ylmethoxy)methyl)amine were added at a rate of 30.8 g / h and 21.5 g / h, respectively, as the modifier.

[0153] [Comparative Example 1] A modified conjugated diene-based polymer was prepared in the same manner as in Example 1, except that a 2 wt% n-butyllithium solution in n-hexane was added at a rate of 29.5 g / h, and a 2 wt% solution of N,N'-(cyclohexane-1,3-diylbis(methylene))bis(3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine) was added as a modifier at a rate of 92.5 g / h.

[0154] [Comparative Example 2] A modified conjugated diene-based polymer was prepared in the same manner as in Example 1, except that a 2 wt% n-butyllithium solution in n-hexane was added at a rate of 29.5 g / h, and a 1 wt% solution of tris((oxiran-2-ylmethoxy)methyl)amine was added as a modifier at a rate of 64.5 g / h.

[0155] [Comparative Example 3] A modified conjugated diene-based polymer was prepared in the same manner as in Example 1, except that a 2 wt% n-butyllithium solution in n-hexane was added at a rate of 21.0 g / h, and a 1 wt% solution of 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine) was added as a modifier at a rate of 98.0 g / h.

[0156] [Comparative Example 4] A modified conjugated diene polymer was prepared in the same manner as in Example 1, except that a solution of 2 wt% N,N'-(cyclohexane-1,3-diylbis(methylene))bis(3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine) was added at a rate of 92.5 g / h and a solution of 1 wt% 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine) was added at a rate of 98.0 g / h as the modifier.

[0157] [Comparative Example 5] A modified conjugated diene polymer was prepared in the same manner as in Example 1, except that a solution of 1 wt% tris((oxiran-2-ylmethoxy)methyl)amine was added at a rate of 64.5 g / h and a solution of 1 wt% 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine) was added at a rate of 98.0 g / h as a modifier.

[0158] <Experimental Example 1> For each modified conjugated diene polymer prepared in the examples and comparative examples, the styrene unit content and vinyl content in the polymer, and the weight average molecular weight (Mw, x10 3g / mol), number average molecular weight (Mn, 3 The molecular weight distribution (PDI, MWD), coupling number, Mooney viscosity (MV), Mooney relaxation rate (-S / R), and Mooney large relaxation area were measured. The results are shown in Table 1 below.

[0159] 1) Styrene unit and vinyl content (wt%) The styrene unit (SM) and vinyl content in each of the polymers were measured and analyzed using a Varian VNMRS 500 MHz NMR.

[0160] In the NMR measurement, 1,1,2,2-tetrachloroethane was used as the solvent, and the solvent peak was calculated at 5.97 ppm. The styrene unit and vinyl contents were calculated by assuming that 7.2 to 6.9 ppm was the random styrene peak, 6.9 to 6.2 ppm was the block styrene peak, 5.8 to 5.1 ppm was the 1,4-vinyl peak, and 5.1 to 4.5 ppm was the 1,2-vinyl peak.

[0161] 2) Weight average molecular weight (Mw, X10 3 g / mol), number average molecular weight (Mn, 3 g / mol), molecular weight distribution (PDI, MWD), and coupling number (CN) The weight average molecular weight (Mw) and number average molecular weight (Mn) were measured by GPC (Gel permeation chromatography) analysis. The molecular weight distribution (PDI, MWD, Mw / Mn) was calculated from each of the measured molecular weights. Specifically, the GPC was performed using a combination of two PLgel Olexis (Polymer Laboratories) columns and one PLgel Mixed-C (Polymer Laboratories) column, and PS (polystyrene) was used as a GPC standard material when calculating the molecular weight. The GPC measurement solvent was prepared by mixing 2 wt% of an amine compound in tetrahydrofuran.

[0162] In each of the Examples and Comparative Examples, the coupling number was determined by taking a part of the polymer before adding the modifier or coupling agent and measuring the peak molecular weight (Mp 1 ) was obtained, and then the peak molecular weight (Mp 2 ) was obtained and calculated according to the following mathematical formula 2.

[0163]

number

[0164] 3) Mooney viscosity (MV), Mooney relaxation ratio (-S / R), and Mooney large Relaxation area (MLRA) The Mooney viscosity (MV, (ML1+4, @100°C)MU) was measured using a MV-2000 (manufactured by ALPHA Technologies) at 100°C, rotor speed 2±0.02 rpm, large rotor. The sample used was left at room temperature (23±3°C) for 30 minutes or more, and then 27±3 g was taken and filled into the die cavity, and the platen was operated to measure for 4 minutes.

[0165] After measuring the Mooney viscosity, the slope of the change in the Mooney viscosity that occurs as the torque is released is measured, and the absolute value of the slope is obtained as the Mooney relaxation rate. The Mooney large relaxation area is the integral value of the Mooney relaxation curve from 1 second after the rotor stops to 120 seconds, and is calculated using the following mathematical formula 1.

[0166]

number

[0167] In the above mathematical formula 1, A is the Mooney Large Relaxation Area (MLRA), k is the Mooney intercept 1 second after the rotor of the Mooney viscometer is stopped, a is the Mooney relaxation factor, t o is the start point of Mooney relaxation, tf is the time when Mooney relaxation is completed.

[0168] [Table 1]

[0169] *Modifier A: N,N'-(cyclohexane-1,3-diylbis(methylene))bis(3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine) *Modifier B: Tris((oxiran-2-ylmethoxy)methyl)amine *Modifier C: 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine)

[0170] As shown in Table 1, the modified conjugated diene polymers of Examples 1 to 3 according to one embodiment of the present invention were confirmed to have a Mooney large relaxation area (MLRA) of 1500 MU-s or more measured at 100° C. In this regard, the modified conjugated diene polymers of Examples 1 to 3 had molecular weights equal to or greater than those of Comparative Examples 1 to 5, and showed reduced Mooney relaxation ratios (-S / R).

[0171] <Experimental Example 2> In order to compare and analyze the physical properties of the rubber compositions containing each modified conjugated diene copolymer prepared in the above examples and comparative examples and the molded products prepared therefrom, the processability characteristics, tensile characteristics, and viscoelastic characteristics were measured, and the results are shown in Table 3 below.

[0172] 1) Preparation of rubber test specimens The modified or unmodified conjugated diene polymers of the Examples and Comparative Examples were used as raw rubber and were compounded under the compounding conditions shown in Table 2. The raw material contents in Table 2 are in parts by weight based on 100 parts by weight of the raw rubber.

[0173] [Table 2]

[0174] Specifically, the rubber test pieces are kneaded through a first stage kneading and a second stage kneading. In the first stage kneading, raw rubber, silica (filler), an organic silane coupling agent (X50S, Evonik), process oil (TDAE oil), zinc oxide (ZnO), stearic acid, an antioxidant (TMQ(RD) (2,2,4-trimethyl-1,2-dihydroquinoline polymer), an anti-aging agent (6PPD ((dimethylbutyl)-N-phenyl-phenylenediamine), and a wax (Microcrystaline Wax) was mixed into the mixer. At this time, the initial temperature of the mixer was controlled at 70°C, and after the mixer was completed, the first mix was obtained at a discharge temperature of 145°C to 155°C. In the second mixer, the first mixer was cooled to room temperature, and then the first mixer, sulfur, rubber accelerator (DPG (diphenyl guanidine)), and vulcanization accelerator (CZ (N-cyclohexyl-2-benzothiazylsulfenamide)) were added to the mixer and mixed at a temperature of 100°C or less to obtain a second mixer. Then, the mixture was cured at 160°C for 20 minutes to produce rubber test pieces.

[0175] 2) Tensile properties The tensile properties were measured by preparing test pieces according to the tensile test method of ASTM 412, and measuring the tensile strength at break and the tensile stress at 300% elongation (300% modulus) of the test pieces. Specifically, the tensile properties were measured at room temperature at a speed of 50 cm / min using a Universal Test Machine 4204 (manufactured by Instron).

[0176] 3) Viscoelastic properties The viscoelastic properties were measured using a dynamic mechanical analyzer (manufactured by GABO) in Film Tension mode at a frequency of 10 Hz and at each measurement temperature (-60°C to 60°C) to determine the tan δ value. In the measured values, the higher the tan δ value at a low temperature of 0°C, the better the wet skid resistance, and the lower the tan δ value at a high temperature of 60°C, the lower the hysteresis loss and the better the rolling resistance (fuel economy). In Table 3 below, the results are shown as an index based on the results of Comparative Example 1, so the higher the value, the better the performance.

[0177] 4) Processability characteristics The Mooney viscosity (MV, (ML1+4, @100℃)MU) of the secondary compound obtained during the preparation of the rubber test specimens was measured, and the processability characteristics of each polymer were compared and analyzed. At this time, the lower the measured Mooney viscosity, the better the processability characteristics.

[0178] Specifically, using MV-2000 (manufactured by ALPHA Technologies) at 100°C, rotor speed 2±0.02 rpm, large rotor, each secondary compound was left at room temperature (23±3°C) for 30 minutes or more, and then 27±3 g was taken and filled into the die cavity, and the platen was operated to measure for 4 minutes.

[0179] [Table 3]

[0180] As shown in Table 3, it was confirmed that Examples 1 to 3 according to one embodiment of the present invention have well-balanced and excellent viscoelastic properties, tensile properties, and processability properties compared to Comparative Examples 1 to 5. Specifically, Examples 1 to 3 are generally excellent in tensile properties, viscoelastic properties, and processability properties compared to Comparative Examples 1 to 3, and have significantly improved tensile properties and processability properties compared to Comparative Examples 1 and 3, and rotation resistance compared to Comparative Example 2.

[0181] Moreover, in Examples 1 to 3, the tensile properties, viscoelastic properties, and processability properties are generally superior to those of Comparative Examples 4 and 5, while the tensile properties and processability properties are significantly improved to those of Comparative Example 4, and the tensile properties and rotational resistance are significantly improved to those of Comparative Example 5. In this case, Comparative Example 1 and Comparative Example 3 are polymers produced without using an epoxy-based modifier, do not contain functional groups derived from the epoxy-based modifier in the molecule, and have a Mooney large relaxation area of ​​less than 1500 MU-s, and Comparative Example 2 is a polymer produced without using an aminoalkoxysilane-based modifier, do not contain functional groups derived from the aminoalkoxysilane-based modifier in the molecule, and have a Mooney large relaxation area of ​​less than 1500 MU-s. On the other hand, Comparative Example 4 and Comparative Example 5 use two types of modifiers, but are not the combination of the aminoalkoxysilane-based modifier and the epoxy-based modifier proposed in the present invention, but are polymers produced using two other types of modifiers and have a Mooney large relaxation area of ​​less than 1500 MU-s. From the results of Tables 1 and 3, it was confirmed that the modified conjugated diene polymer according to the present invention has a high molecular weight and high branching characteristics, and also has a Mooney large relaxation area of ​​1500 MU-s or more, and therefore, when applied to a rubber composition, it has the effect of significantly improving processability characteristics while having excellent tensile properties and viscoelastic properties.

Claims

1. The Mooney Large Relaxation Area (MLRA) measured at 100°C, as represented by the following mathematical formula 1, is 1500MU-s or more; A modified conjugated diene polymer containing, at least at one end thereof, a functional group derived from an aminoalkoxysilane-based modifier and an epoxy-based modifier. [0050] In the above mathematical formula 1, A is the Mooney Large Relaxation Area (MLRA), k is the Mooney intercept 1 second after the rotor of the Mooney viscometer is stopped, a is the absolute value of the slope of the change in Mooney viscosity, t o is the start time of Mooney relaxation (1 second), t f is the time when Mooney relaxation is completed (120 seconds).

2. The modified conjugated diene-based polymer according to claim 1, wherein the Mooney large relaxation area is 1500 to 4000 MU-s.

3. The modified conjugated diene polymer according to claim 1, wherein the aminoalkoxysilane-based modifier is one or more compounds selected from the group consisting of compounds represented by the following chemical formulas 1 to 3: 【Chemistry 22】 In the above Chemical Formula 1, R a1 and R a4 are each independently a single bond or an alkylene group having 1 to 10 carbon atoms, R a2 and R a3 are each independently an alkyl group having 1 to 10 carbon atoms, R a5 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a mono-, di-, or tri-substituted alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, or -N[R a6 Si(OR a7 ) n3 (R a8 ) 3-n3 ] 2 where R a6 is a single bond or an alkylene group having 1 to 10 carbon atoms, R a7 and R a8 are each independently an alkyl group having 1 to 10 carbon atoms, and n3 is an integer of 1 to 3, n 1 is an integer from 1 to 3, n 2 is an integer from 0 to 2, 【Chemistry 23】 In the above Chemical Formula 2, R b2 ~R b4 are each independently an alkylene group having 1 to 10 carbon atoms, R b5 ~R b8 are each independently an alkyl group having 1 to 10 carbon atoms, R b12 ~R b14 are each independently an alkylene group having 1 to 10 carbon atoms, R b15 ~R b18 are each independently an alkyl group having 1 to 10 carbon atoms, m 1 , m 2 , m 3 , and m 4 are each independently an integer from 1 to 3, 【Chemistry 24】 In the above Chemical Formula 3, R e1 and R e2 are each independently an alkylene group having 1 to 10 carbon atoms, R e3 ~R e6 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or -R e7 SiR e8 R e9 R e10 and R e3 ~R e6 At least one of the groups is -R e7 SiR e8 R e9 R e10 where R e7 is a single bond or an alkylene group having 1 to 10 carbon atoms, R e8 ~R e10 are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms; R e8 ~R e10 At least one of the groups is an alkoxy group having 1 to 10 carbon atoms.

4. The modified conjugated diene polymer according to claim 1 or 3, wherein the epoxy-based modifier is one or more compounds selected from the group consisting of compounds represented by the following Chemical Formulas 4 to 7. 【Chemistry 25】 In the above Chemical Formula 4, R d1 ~R d3 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or -R d4 R d5 and R d1 ~R d3 At least one of the groups is -R d4 R d5 where R d4 is an alkylene group having 1 to 10 carbon atoms, which may or may not contain a heteroatom; R d5 is an epoxy group, 【Chemistry 26】 In the above Chemical Formula 5, R e1 and R e2 are each independently an alkylene group having 1 to 10 carbon atoms, R e3 ~R e6 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or -R e7 R e8 and R e3 ~R e6 At least one of the groups is -R e7 R e8 where R e7 is an alkylene group having 1 to 10 carbon atoms, which may or may not contain one or more heteroatoms selected from N, S, and O; R e8 is an epoxy group, 【Chemistry 27】 In the above Chemical Formula 6, X is O or S; R f1 and R f2 are each independently a single bond or an alkylene group having 1 to 10 carbon atoms, R f3 ~R f8 are each independently a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, an aralkyl group having 7 to 14 carbon atoms, or -R f9 R f10 and R f3 ~R f8 At least one of the groups is -R f9 R f10 where R f9 is an alkylene group having 1 to 12 carbon atoms, which may or may not contain a heteroatom; R f10 is an epoxy group, 【Chemistry 28】 In the above Chemical Formula 7, R g1 ~R g4 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or -R g5 OR g6 and R g1 ~R g4 At least one of the groups is -R g5 OR g6 where R g5 is a single bond or an alkylene group having 1 to 10 carbon atoms; R g6 is an epoxyalkyl group having 3 to 10 carbon atoms, Y is C or N, and when Y is N, R g4 does not exist.

5. The modified conjugated diene polymer according to any one of claims 1 to 4, wherein the modified conjugated diene polymer has a number average molecular weight (Mn) of 100,000 g / mol to 2,000,000 g / mol, a weight average molecular weight (Mw) of 100,000 g / mol to 3,000,000 g / mol, and a molecular weight distribution (PDI) of 1.5 or more.

6. The conjugated diene polymer is a homopolymer of a conjugated diene monomer, or The modified conjugated diene polymer according to any one of claims 1 to 5, which is a copolymer of a conjugated diene monomer and an aromatic vinyl monomer.

7. A step (S1) of polymerizing a conjugated diene monomer, or an aromatic vinyl monomer and a conjugated diene monomer in a hydrocarbon solvent in the presence of a polymerization initiator to produce an activated polymer; and (S2) reacting or coupling the activated polymer prepared in the (S1) step with a first modifier and a second modifier, the first modifier is an aminoalkoxysilane-based modifier, The method for producing a modified conjugated diene polymer according to any one of claims 1 to 6, wherein the second modifier is an epoxy-based modifier.

8. The method for producing a modified conjugated diene-based polymer according to claim 7, wherein the polymerization initiator is used in an amount of 0.01 mmol to 10 mmol per 100 g of the monomer.

9. The first and second modifiers are added sequentially or all at once to react or couple with the activated polymer, The method for producing a modified conjugated diene-based polymer according to claim 7 or 8, wherein the first modifier and the second modifier are used in a molar ratio of 10:1 to 5:

1.

10. The total amount of the modifier used is 0.01 mmol to 10 mmol per 100 g of the total monomers, The method for producing a modified conjugated diene-based polymer according to any one of claims 7 to 9, wherein the total amount of the modifiers used is a total amount of the first modifier and the second modifier.

11. A rubber composition comprising the modified conjugated diene polymer according to any one of claims 1 to 6 and a filler.

12. The rubber composition according to claim 11, wherein the rubber composition contains 0.1 to 200 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene polymer.

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