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

Abstract

The present invention relates to a modified conjugated diene polymer, a production method thereof, and a rubber composition containing the same. The modified conjugated diene polymer is produced by continuous polymerization and has excellent processability, a Mooney relaxation area of ​​300 to 1000 MU-s, a narrow molecular weight distribution of 1.7 or less, and when compounded into the rubber composition, the tensile properties and viscoelastic properties, particularly the tan δ value at high temperatures (60°C) among the viscoelastic properties, are improved, and the modified conjugated diene polymer and the rubber composition containing the same have excellent low hysteresis and fuel economy characteristics.

Description

[Technical field]

[0001] This application claims the benefit of priority based on Korean Patent Application No. 10-2019-0121198 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 viscoelastic properties, a production method thereof, 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 may have been made to solve the problems of the conventional techniques described above, and has an object to provide a modified conjugated diene-based polymer and a rubber composition containing the same, which have excellent processability, excellent physical properties due to a narrow molecular weight distribution, and excellent viscoelastic properties such as rotational resistance. [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 relaxation area (MLRA) of 300 MU-s to 1000 MU-s 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 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 a heterocyclic group-containing silane-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 relaxation area of ​​300 MU-s or more and 1000 MU-s or less, and therefore has excellent processability when compounded into a rubber composition, and also has improved tensile properties and viscoelastic properties, particularly the tan δ value at high temperatures (60°C) among the viscoelastic properties, thereby enabling low hysteresis and excellent fuel economy properties. Furthermore, the modified conjugated diene polymer according to the present invention can have further improved tensile properties and viscoelastic properties by containing functional groups derived from two types of modifiers at at least one terminal.

[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 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 above-mentioned 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 an applied strain. For example, the Mooney 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 is excellent in processability, tensile properties and viscoelastic properties. The modified conjugated diene-based polymer according to one embodiment of the present invention is characterized in that it has a Mooney relaxation area (MLRA) of 300 MU-s to 1000 MU-s measured at 100° C. and is represented by the following mathematical formula 1:

[0029]

number

[0030] In the above mathematical formula 1, A is the Mooney 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.

[0031] 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 .

[0032] According to one embodiment of the present invention, the t o may be 1 second, and t f In other words, the Mooney 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 to 150 seconds. f Specifically, the time may be 90 seconds to 130 seconds, or 100 seconds to 120 seconds.

[0033] On the other hand, generally, the molecular weight and Mooney viscosity of a polymer are proportional properties and show the same tendency, and in the case of a high molecular weight polymer, the Mooney viscosity is high, which causes a problem of poor processability, and in the case of a low molecular weight polymer, the Mooney viscosity is low, which causes a problem of relatively good processability but poor mechanical properties such as tensile properties. However, the modified conjugated diene-based polymer according to one embodiment of the present invention has a Mooney relaxation area of ​​300 MU-s or more and 1000 MU-s or less, which has the effect of providing a well-balanced excellent processability and tensile properties.

[0034] In the modified conjugated diene polymer of the present invention, the Mooney relaxation area of ​​300 MU-s to 1000 MU-s is one technical means for obtaining excellent processability while excellent tensile properties and viscoelastic properties, and when the Mooney relaxation area is within the above range, the effect of the present invention can be obtained. In addition, when the Mooney relaxation area has a very small value, mechanical properties such as tensile properties may be deteriorated, and in terms of obtaining better processability and exhibiting well-balanced and excellent properties in both tensile properties and viscoelastic properties, the Mooney relaxation area of ​​the modified conjugated diene polymer according to one embodiment of the present invention may be 300 MU-s to 1000 MU-s.

[0035] Specifically, the modified conjugated diene polymer may have a Mooney relaxation area of ​​300MU-s to 1000MU-s, preferably 400MU-s to 1000MU-s, 500MU-s to 1000MU-s, or 500MU-s to 900MU-s. The Mooney 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)MU) was measured 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 was taken and filled in the inside of the die cavity, and the platen was operated to measure the value for 4 minutes.

[0036] 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 relaxation area is the area measured 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 relaxation area satisfies the above range, an effect of improving viscoelastic properties, particularly rolling resistance (RR), can be obtained when compounding the rubber composition. In particular, when the Mooney relaxation area satisfies the above range under the condition of a Mooney viscosity of 80 or more, preferably 90 or more, an even greater effect of improving rolling resistance can be obtained.

[0037] In addition, the modified conjugated diene-based polymer according to an embodiment of the present invention may be a homopolymer of a conjugated diene-based monomer; or a copolymer of a conjugated diene-based monomer and an aromatic vinyl-based monomer, and here, the homopolymer of a conjugated diene-based monomer means a polymer containing a repeating unit derived from a conjugated diene-based monomer formed by polymerization of a conjugated diene-based monomer, and the copolymer may mean a copolymer containing a repeating unit derived from a conjugated diene-based monomer and a repeating unit derived from an aromatic vinyl-based monomer formed by copolymerization of a conjugated diene-based monomer and an aromatic vinyl-based monomer.

[0038] 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.

[0042] As another example, the modified conjugated diene polymer according to the embodiment of the present invention may have a number average molecular weight (Mn) of 50,000g / mol to 2,000,000g / mol, 50,000g / mol to 1,000,000g / mol, or 100,000g / mol to 800,000g / mol, and a weight average molecular weight (Mw) of 100,000g / mol to 3,000,000g / mol, 200,000g / mol to 2,000,000g / mol, or 200,000g / mol to 1,500,000g / mol. Within this range, there is an effect of excellent rolling resistance and wet skid resistance. As another example, the modified conjugated diene polymer may have a molecular weight distribution (PDI; MWD; Mw / Mn) of 1.7 or less, 0.8 to 1.7, or 1.0 to 1.7. 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 1.7 or less.

[0043] As another example, the modified conjugated diene polymer may have a Mooney relaxation ratio (-S / R) measured at 100° C. of 0.5 or more, 0.5 or more and 3.0 or less, 0.5 or more and 2.5 or less, or 0.5 or more and 2.0 or less.

[0044] Here, the Mooney relaxation rate indicates the change in stress that occurs 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±3°C) for 30 minutes or more, taking 27±3g and filling the inside of a die cavity, operating a platen to apply torque and measuring the Mooney viscosity, and then measuring the slope of the change in Mooney viscosity that occurs as the torque is released.

[0045] 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.

[0046] The modified conjugated diene polymer may have a Mooney viscosity at 100° C. of 80 or more, 80 to 150, or 80 to 140. When it is within this range, it has the effect of providing excellent processability and productivity.

[0047] 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.

[0048] Meanwhile, the modified conjugated diene-based polymer according to an embodiment of the present invention may include a functional group derived from an aminoalkoxysilane-based modifier and a functional group derived from a heterocyclic group-containing silane-based modifier at at least one terminal.

[0049] In the past, modified conjugated diene polymers were 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, modified conjugated diene polymers modified with aminoalkoxysilane modifiers have problems in that the tensile properties and processability are reduced, although the viscoelastic properties are improved. As another example, modified conjugated diene polymers produced by modification with heterocyclic group-containing silane modifiers have problems in that the viscoelastic properties are reduced.

[0050] On the other hand, the modified conjugated diene polymer according to one embodiment of the present invention is produced using an aminoalkoxysilane-based modifier and a heterocyclic group-containing silane-based modifier, and therefore satisfies the above-mentioned Mooney relaxation area and can simultaneously contain functional groups derived from each of the modifiers in the molecule, thereby providing the effect of excellent processability, tensile properties, and viscoelastic properties.

[0051] As another example, the modified conjugated diene 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 a heterocyclic group-containing silane-based modifier at one end. 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 is capable of interaction between the silica-based filler and the functional group derived from the modifier.

[0052] Specifically, the aminoalkoxysilane-based modifier according to an embodiment of the present invention may be a compound represented by the following Chemical Formula 1:

[0053] [ka]

[0054] In the above Chemical Formula 1, R 1 is a single bond or an alkylene group having 1 to 10 carbon atoms, R 2 and R 3 are each independently an alkyl group having 1 to 10 carbon atoms,

[0055] R 4 represents a hydrogen atom, an epoxy group, an alkyl group having 1 to 10 carbon atoms, an allyl group having 2 to 10 carbon atoms, or a mono-, di-, or tri-substituted alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms,

[0056] R 21 is a single bond, an alkylene group having 1 to 10 carbon atoms, or -[R 42 O] j - where R 42 is an alkylene group having 1 to 10 carbon atoms, and j is an integer selected from 1 to 30; a and m are each independently an integer selected from 1 to 3; n is an integer from 0 to 2.

[0057] Specific examples of the compound represented by Chemical Formula 1 include N,N-dimethyl-3-(trimethoxysilyl)propan-1-amine, N,N-bis(3-(dimethoxy(methyl)silyl)propyl)-methyl-1-amine, and N,N-bis(3-(diethoxy(methyl)silyl)propyl)-methyl-1-amine. 1-amine (N,N-bis(3-(diethoxy(methyl)silyl)propyl)-methyl-1-amine), N-methyl-3,3´-bis(trimethoxysilyl)dipropylamine, N,N-bis(3-(triethoxysilyl)propyl)-methyl-1-amine, tri(trimethoxysilyl)propyl tri(trimethoxysilyl)amine, tri(3-(trimethoxysilyl)propyl)amine, N,N-bis(3-(diethoxy(methyl)silyl)propyl)-1,1,1-trimethylsilanamine, N-allyl-N-(3-(trimethoxysilyl)propyl)amine N-allyl-N-(3-(trimethoxysilyl)propyl)prop-2-en-1-amine, N,N-bis(oxiran-2-ylmethyl)-3-(trimethoxysilyl)propan-1-amine, 1,1,1-trimethyl-N-(3-(triethoxysilyl)propyl)-N-(trimethylsilyl)silanamineIt may be one selected from the group consisting of 1-trimethyl-N-(3-(triethoxysilyl)propyl)-N-(trimethylsilyl)silanamine, and N,N-bis(3-(triethoxysilyl)propyl)-2,5,8,11,14-pentaoxahexadecan-16-amine.

[0058] The imidazole-based denaturant may be a compound represented by the following chemical formula 2. [ka]

[0059] In the above Chemical Formula 2, R 5 and R 6 each independently represents an alkylene group having 1 to 10 carbon atoms, R 7 and R 8 are each independently an alkyl group having 1 to 10 carbon atoms, R 12 is hydrogen or an alkyl group having 1 to 10 carbon atoms, b is 1, 2, or 3; c is 1 or 2,

[0060] A is, [ka] where R 13 , R 14 , R 15 , and R 16 are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms, X is C or N, and when X is N, R 16 does not exist.

[0061] Specific examples of the compound represented by Chemical Formula 2 include N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine, N-(3-(1H-imidazol-1-yl)propyl)-3-(1H-imidazol-1-yl)-N-((triethoxysilyl)methyl)propan-1-amine, mine), N-(3-(1H-1,2,4-triazole-1-yl)propyl)-3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine, and 3-(4,5-dihydro-1H-imidazol-1-yl)-N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine.

[0062] 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.

[0063] 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.

[0064] More specifically, the N-functional group-containing compound may be a compound represented by the following formula 3:

[0065] [ka]

[0066] In the above Chemical Formula 3, R1 to R3 are each independently a hydrogen atom; 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;

[0067] R4 is 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;

[0068] R5 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 3a or 3b:

[0069] o is an integer of 1 to 5, and at least one of R5 is a functional group represented by the following chemical formula 3a or 3b, and when o is an integer of 2 to 5, multiple R5 may be the same or different from each other,

[0070] [ka]

[0071] In the above Chemical Formula 3a, R6 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;

[0072] R7 and R8 are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an alkylene group having 1 to 20 carbon atoms which is substituted or unsubstituted with an aryl group having 6 to 20 carbon atoms;

[0073] R9 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, and when Z is O or S, R9 is absent;

[0074] [ka]

[0075] In the chemical formula 3b, 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,

[0076] 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 R 11 and R 12 may be linked to each other to form, together with N, a heterocyclic group having 2 to 30 carbon atoms.

[0077] Specifically, in the above Chemical Formula 3, R1 to R3 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; R4 is a single bond; or an unsubstituted alkylene group having 1 to 10 carbon atoms; R5 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 3a or Chemical Formula 3b; in the above Chemical Formula 3a, R6 is an unsubstituted alkylene group having 1 to 10 carbon atoms; R7 and R8 are each independently an unsubstituted alkylene group having 1 to 10 carbon atoms; R9 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; in the above Chemical Formula 3b, R 10is an unsubstituted alkylene group having 1 to 10 carbon atoms, R 11 and R 12 may be, independently of each other, 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.

[0078] More specifically, the compound represented by Chemical Formula 3 may be one or more selected from the compounds represented by the following Chemical Formulas 3-1 to 3-3.

[0079] [ka]

[0080] [ka]

[0081] [ka]

[0082] 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.

[0083] 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.

[0084] As described above, the modified conjugated diene-based polymer according to one embodiment of the present invention may have a specific structure and a specific molecular weight distribution and morphology. The structure of the polymer may be expressed by the physical properties of molecular weight, Mooney viscosity, and molecular weight distribution (PDI), and in the present invention, modification with a specific modifier may affect the structure of the polymer, the molecular weight distribution, and the shape of the molecular weight distribution curve. The parameters representing the structure of the polymer and the characteristics related to the molecular weight distribution may be satisfied by the preparation method and the structure of the modifier described below. Furthermore, it is preferable to manufacture the semiconductor device by such a manufacturing method since it satisfies the above-mentioned characteristics, and if all of the above-mentioned characteristics are satisfied, the effect that the present invention aims to realize can be achieved.

[0085] Method for producing modified conjugated diene polymer The present invention also provides a method for producing the modified conjugated diene polymer. A 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 a heterocyclic group-containing silane-based modifier. The aminoalkoxysilane-based modifier and the heterocyclic group-containing silane-based modifier are as described above.

[0086] 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.

[0087] 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.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] 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.

[0092] 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.

[0093] 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.

[0094] 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.

[0095] 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 further improving processability, it may be preferably carried out by a continuous polymerization method.

[0096] 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%.

[0097] According to one embodiment of the present invention, the molecular weight distribution (Mw / Mn) of the activated polymer prepared in step (S1) may be 1.7 or less, 0.8 to 1.7, or 1.0 to 1.7. When the molecular weight distribution is within this range, the processability can be improved.

[0098] Meanwhile, the polymerization in the step (S1) 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.

[0099] 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.

[0100] 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.

[0101] The total amount of the modifying agent used may be 0.01 mmol to 10 mmol per 100 g of the total monomers, and the total amount of the modifying agent used is the combined amount of the first modifying agent and the second modifying agent.

[0102] As another example, the total amount of the modifying agent used may be in a molar ratio of 1:0.1 to 10, 1:0.1 to 5, or 1:0.1 to 1:3 relative to 1 mole of the polymerization initiator in the (S1) step.

[0103] 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.

[0104] 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.

[0105] 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.

[0106] 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.

[0107] 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.

[0108] 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.

[0109] 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.

[0110] 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.

[0111] 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.

[0112] 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.

[0113] 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.

[0114] 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.

[0115] 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.

[0116] 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.

[0117] 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.

[0118] 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.

[0119] [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.

[0120] [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 21.0 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.

[0121] The polymer was transferred from the first reactor to the second reactor, and a solution of 4% by weight of N,N-dimethyl-3-(trimethoxysilyl)propan-1-amine dissolved in n-hexane as a modifier was added to the second reactor at a rate of 16.5 g / h and a solution of 4% by weight of N-(3-(1H-imidazole-1-yl)propyl)-N,N-bis(3-(triethoxysilyl)propyl)amine dissolved in n-hexane was added to the second reactor at a rate of 21.0 g / h. The temperature of the second reactor was maintained at 70°C.

[0122] 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 both-end modified conjugated diene-based polymer.

[0123] [Example 2] A modified conjugated diene polymer was prepared in the same manner as in Example 1, except that a solution of 4 wt% N,N-dimethyl-3-(trimethoxysilyl)propan-1-amine dissolved in n-hexane was added at a rate of 23.3 g / h and a solution of 4 wt% N-(3-(1H-imidazol-1-yl)propyl)-N,N-bis(3-(triethoxysilyl)propyl)amine dissolved in n-hexane was added at a rate of 12.5 g / h as the modifier.

[0124] [Example 3] A modified conjugated diene polymer was prepared in the same manner as in Example 1, except that a solution of 4 wt% N,N-dimethyl-3-(trimethoxysilyl)propan-1-amine dissolved in n-hexane was added at a rate of 30.0 g / h and a solution of 4 wt% N-(3-(1H-imidazol-1-yl)propyl)-N,N-bis(3-(triethoxysilyl)propyl)amine dissolved in n-hexane was added at a rate of 3.8 g / h as the modifier.

[0125] [Comparative Example 1] A modified conjugated diene polymer was prepared in the same manner as in Example 1, except that a solution of 4 wt% N-(3-(1H-imidazol-1-yl)propyl)-N,N-bis(3-(triethoxysilyl)propyl)amine dissolved in n-hexane as a modifier was added at a rate of 42.0 g / h.

[0126] [Comparative Example 2] A modified conjugated diene-based polymer was prepared in the same manner as in Example 1, except that a solution of 4 wt% N,N-dimethyl-3-(trimethoxysilyl)propan-1-amine dissolved in n-hexane as a modifier was added at a rate of 33.3 g / h.

[0127] [Comparative Example 3] A modified conjugated diene polymer was prepared in the same manner as in Example 1, except that a solution of 4 wt% N-methyl-3,3'-bis(trimethoxysilyl)dipropylamine dissolved in n-hexane was added at a rate of 14.8 g / h and a solution of 4 wt% N,N-dimethyl-3-(trimethoxysilyl)propan-1-amine dissolved at a rate of 16.5 g / h as a modifying agent.

[0128] <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 3 g / mol), number average molecular weight (Mn, 3 The molecular weight distribution (PDI, MWD), coupling number, Mooney viscosity (MV), and Mooney relaxation area were measured, and the results are shown in Table 1 below.

[0129] 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.

[0130] 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.

[0131] 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). The molecular weight distribution (PDI, MWD, Mw / Mn) was calculated from each of the measured molecular weights. Specifically, the GPC was performed using two PLgel Olexis (Polymer Laboratories) columns and one PLgel Mixed-C (Polymer Laboratories) column in combination, and PS (polystyrene) was used as a GPC standard material when calculating the molecular weight. The GPC measurement solvent was prepared by mixing 2% by weight of an amine compound in tetrahydrofuran. In addition, the coupling number was calculated by taking a part of the polymer before adding the modifier or coupling agent in each example and comparative example to obtain the peak molecular weight (Mp1) of the polymer, and then obtaining the peak molecular weight (Mp2) of each modified conjugated diene polymer, according to the following mathematical formula 2.

[0132] [Mathematical formula 2] Coupling number (CN) = Mp2 / Mp1

[0133] 3) Mooney Viscosity (MV) and Mooney 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.

[0134] After measuring the Mooney viscosity, the slope of the change in the Mooney viscosity that occurs as the torque is released was measured, and the absolute value of the slope was obtained as the Mooney relaxation rate. The Mooney 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.

[0135]

number

[0136] In the above mathematical formula 1, A is the Mooney 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.

[0137] [Table 1]

[0138] *Modifier A: N,N-dimethyl-3-(trimethoxysilyl)propan-1-amine *Modifier B: N-(3-(1H-imidazol-1-yl)propyl)-N,N-bis(3-(triethoxysilyl)propyl)amine *Modifier C: N-methyl-3,3'-bis(trimethoxysilyl)dipropylamine

[0139] As shown in Table 1, the modified conjugated diene-based polymers of Examples 1 to 3 according to one embodiment of the present invention were confirmed to have Mooney relaxation areas (MLRA) of 300 MU-s to 1000 MU-s measured at 100° C. In addition, it was confirmed that the modified conjugated diene-based polymers of Examples 1 to 3 had similar levels of molecular weight, Mooney relaxation rate, and Mooney viscosity compared to Comparative Examples 1 to 3, but only the Mooney relaxation area was adjusted to a specific range proposed in the present invention.

[0140] <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 tensile properties and viscoelastic properties were measured, and the results are shown in Table 3 below.

[0141] 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.

[0142] [Table 2]

[0143] 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.

[0144] 2) 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 measurements, the higher the tan δ value at a low temperature of 0°C, the better the wet skid resistance, and the lower the tna δ value at a high temperature of 60°C, the lower the hysteresis loss and the better the rolling resistance (fuel economy). Meanwhile, 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 results.

[0145] 3) 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).

[0146] 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.

[0147] 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.

[0148] [Table 3]

[0149] 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 tensile properties, viscoelastic properties, and processability properties compared to Comparative Examples 1 to 3. Specifically, Examples 1 to 3 are generally excellent in tensile properties, viscoelastic properties, and processability properties compared to Comparative Examples 1 to 3, and also show similarly excellent processability properties compared to Comparative Example 1, and the tensile properties and rolling resistance are significantly improved, and show similarly excellent viscoelastic properties compared to Comparative Example 2, and show a significantly improved effect on the tensile properties and processability properties. In addition, Examples 1 to 3 show a similar level of excellent wet skid resistance compared to Comparative Example 3, and show a significantly improved effect on the tensile properties, rolling resistance, and processability properties.

[0150] In this case, Comparative Example 1 is a polymer produced without using an aminoalkoxysilane-based modifier, does not contain a functional group derived from an aminoalkoxysilane-based modifier in the molecule, and has a Mooney relaxation area of ​​more than 1000 MU-s; Comparative Example 2 is a polymer produced without using a heterocyclic group-containing silane-based modifier, does not contain a functional group derived from a heterocyclic group-containing silane-based modifier in the molecule, and has a Mooney relaxation area of ​​less than 300 MU-s; and Comparative Example 3 is a polymer produced using two types of modifiers, but not the combination of an aminoalkoxysilane-based modifier and a heterocyclic group-containing silane-based modifier proposed in the present invention, but using two other types of modifiers, and has a Mooney relaxation area of ​​more than 1000 MU-s.

[0151] From the results of Tables 1 and 3, it was confirmed that the modified conjugated diene polymer according to the present invention has an effect of significantly improving the tensile properties and viscoelastic properties (especially the rotational resistance) while having excellent processability when applied to a rubber composition by adjusting the Mooney relaxation area to a specific range of 300 MU-s or more and 1000 or less.

Claims

1. The Mooney relaxation area (MLRA) measured at 100° C., as represented by the following mathematical formula 1, is 300 to 1000 MU-s; containing a functional group derived from an aminoalkoxysilane-based modifier and a functional group derived from a heterocyclic group-containing silane-based modifier at at least one end, The heterocyclic group-containing silane-based modifier is a compound represented by the following chemical formula 2, which is a modified conjugated diene-based polymer. [0045] In the above mathematical formula 1, A is the Mooney Relaxation Area (MLRA), k is the Mooney intercept 1 second after the rotor of the Mooney viscometer is stopped, a is 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), 【number】 In the above Chemical Formula 2, R 5 and R 6 each independently represent an alkylene group having 1 to 10 carbon atoms; R 7 and R 8 are each independently an alkyl group having 1 to 10 carbon atoms; R 12 is hydrogen or an alkyl group having 1 to 10 carbon atoms; b is 1, 2, or 3; c is 1 or 2; A is, 【number】 where R 13 , R 14 , R 15 , and R 16 are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms; X is C or N; and when X is N, R 16 does not exist.

2. The modified conjugated diene polymer according to claim 1, which has a Mooney viscosity measured at 100° C. of 80 or more.

3. The modified conjugated diene polymer according to claim 1 , wherein the aminoalkoxysilane-based modifier is a compound represented by the following chemical formula 1: 【Chemistry 10】 In the above Chemical Formula 1, R 1 is a single bond or an alkylene group having 1 to 10 carbon atoms, R 2 and R 3 are each independently an alkyl group having 1 to 10 carbon atoms, R 4 represents a hydrogen atom, an epoxy group, an alkyl group having 1 to 10 carbon atoms, an allyl group having 2 to 10 carbon atoms, or a mono-, di- or tri-substituted alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, R 21 is a single bond, an alkylene group having 1 to 10 carbon atoms, or -[R 42 O] j -, where R 42 is an alkylene group having 1 to 10 carbon atoms, j is an integer selected from 1 to 30, a and m are each independently an integer selected from 1 to 3; n is an integer from 0 to 2.

4. The modified conjugated diene polymer according to any one of claims 1 to 3, 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 1.7 or less.

5. 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 4, which is a copolymer of a conjugated diene monomer and an aromatic vinyl monomer.

6. 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 active 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 5, wherein the second modifier is a heterocyclic group-containing silane modifier.

7. The method for producing a modified conjugated diene-based polymer according to claim 6, wherein the polymerization initiator is used in an amount of 0.01 mmol to 10 mmol per 100 g of the monomer.

8. The total amount of the modifier used is 0.01 mmol to 10 mmol per 100 g of the total of the monomers, The method for producing a modified conjugated diene-based polymer according to claim 6 or 7, wherein the total amount of the modifiers used is a total amount of the first modifier and the second modifier.

9. A rubber composition comprising the modified conjugated diene polymer according to any one of claims 1 to 5 and a filler.

10. The rubber composition according to claim 9, 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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