Modified conjugated diene-based polymer and method for preparing polymer

Abstract

The present invention relates to a modified conjugated diene-based polymer having a high modification ratio, excellent affinity with a filler, high strength without deteriorating processability, and enhanced abrasion resistance, and to a method for preparing the modified conjugated diene-based polymer.

Description

Modified conjugated diene polymer and method for producing the polymer

[0001] [Cross-reference with related applications]

[0002] This application claims the benefit of priority to Korean Patent Application No. 10-2024-0032726, filed March 7, 2024, the entire disclosure of which is incorporated herein by reference.

[0003]

[0004] [Technical Field]

[0005] The present invention relates to a modifier useful for modifying a conjugated diene polymer and having excellent affinity with a filler, thereby improving the compounding properties of the conjugated diene polymer, a modified conjugated diene polymer including a functional group derived from the modifier, and a method for producing the modified conjugated diene polymer.

[0006] In response to recent demands for fuel efficiency in automobiles, conjugated diene polymers with low rolling resistance, excellent wear resistance and tensile properties, and steering stability represented by wet road resistance are required as rubber materials for tires.

[0007] In order to reduce the rolling resistance of tires, there is a method to reduce the hysteresis loss of vulcanized rubber, and as evaluation indices of such vulcanized rubber, rebound elasticity, tan δ, Goodrich heat generation, etc. at 50℃ to 80℃ are used. In other words, a rubber material having a large rebound elasticity or a small tan δ Goodrich heat generation at the above temperature is desirable.

[0008] Natural rubber, polyisoprene rubber, or polybutadiene rubber are known as rubber materials with low hysteresis loss, but they have the problem of low wet road resistance. Recently, 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 manufactured through emulsion polymerization or solution polymerization and used as rubber for tires. Among these, the greatest advantage of solution polymerization over emulsion polymerization is that the vinyl structural content and styrene content, which determine the rubber properties, can be arbitrarily controlled, and the molecular weight and physical properties can be controlled through coupling or modification. Therefore, the structure of the final manufactured SBR or BR is easily changed, and the movement of the chain ends can be reduced through chain end bonding or modification, and the bonding strength with fillers such as silica or carbon black can be increased, so SBR manufactured through solution polymerization is widely used as a rubber material for tires.

[0009] When such solution-polymerized SBR is used as a rubber material for tires, not only can the required tire properties such as driving resistance and braking power be controlled by increasing the glass transition temperature of the rubber by increasing the vinyl content within the SBR, but fuel consumption can also be reduced by appropriately controlling the glass transition temperature. The solution-polymerized SBR is manufactured using an anionic polymerization initiator, and the chain ends of the formed polymer are bonded or modified using various modifiers and used. For example, U.S. Patent No. 4,397,994 proposes a technology in which the active anions at the chain ends of the polymer obtained by polymerizing styrene-butadiene in a nonpolar solvent using a monofunctional initiator, alkyl lithium, are bonded using a bonding agent such as a tin compound.

[0010] Meanwhile, carbon black and silica are used as reinforcing fillers in tire treads. Silica, when used as a reinforcing filler, offers the advantages of low hysteresis loss and improved wet road resistance. However, compared to carbon black with a hydrophobic surface, silica with a hydrophilic surface has a low affinity for rubber, resulting in poor dispersibility. Therefore, a separate silane coupling agent is needed to improve dispersibility or provide a silica-rubber bond. Therefore, methods of introducing functional groups with affinity or reactivity for silica to the ends of rubber molecules are being pursued, but the effects are not sufficient.

[0011] [Prior Art Literature]

[0012] [Patent Document]

[0013] (Patent Document 0001) KR 10-2020-0009181 A

[0014] The purpose of the present invention is to provide a modified conjugated diene polymer having a high modification rate, excellent affinity with fillers, high strength without deterioration in processability, and improved wear resistance, and a method for producing the same.

[0015] (1) The present invention provides a modified conjugated diene polymer comprising a repeating unit derived from a conjugated diene monomer, comprising a functional group derived from a modifier represented by the following chemical formula 1 at at least one terminal, and having a hydrogenation rate of 20% or more and 90% or less.

[0016] [Chemical Formula 1]

[0017]

[0018] In the above chemical formula 1,

[0019] A is an arylene group having 6 to 30 carbon atoms, or a heteroarylene group having 2 to 30 carbon atoms containing 1 to 3 N atoms,

[0020] L1 and L2 are each independently an alkylene group having 1 to 20 carbon atoms,

[0021] L3 and L4 are each independently an alkylene group having 1 to 20 carbon atoms,

[0022] R1 to R6 are each independently an alkyl group and / or alkoxy group having 1 to 20 carbon atoms, and at least 4 of R1 to R6 are alkoxy groups.

[0023] (2) The present invention provides a modified conjugated diene polymer having a hydrogenation rate of 50% or more and 80% or less in the above (1).

[0024] (3) The present invention provides a modified conjugated diene polymer in the above (1) or (2), wherein in the chemical formula 1, A is an arylene group having 6 to 20 carbon atoms, or a heteroarylene group having 3 to 20 carbon atoms and containing 1 or 2 N atoms.

[0025] (4) The present invention provides a modified conjugated diene polymer in any one of the above (1) to (3), wherein in the chemical formula 1, L1 and L2 are each independently an alkylene group having 1 to 10 carbon atoms, L1 and L2 are the same as each other, L3 and L4 are each independently an alkylene group having 1 to 10 carbon atoms, and L3 and L4 are the same as each other.

[0026] (5) The present invention provides a modified conjugated diene polymer in any one of the above (1) to (4), wherein the modifier represented by the chemical formula 1 is selected from compounds represented by the following chemical formulas 1A and 1B.

[0027] [Chemical Formula 1A]

[0028]

[0029] [Chemical Formula 1B]

[0030]

[0031] In the above chemical formulas 1A and 1B,

[0032] The definitions of L1 to L4 and R1 to R6 are as defined in the chemical formula 1 above.

[0033] (6) The present invention provides a modified conjugated diene polymer in any one of the above (1) to (5), wherein the modifier represented by the chemical formula 1 is selected from compounds represented by the following chemical formulas 1-1 to 1-3.

[0034] [Chemical Formula 1-1]

[0035]

[0036] [Chemical Formula 1-2]

[0037]

[0038] [Chemical Formula 1-3]

[0039]

[0040] (7) The present invention provides a modified conjugated diene polymer having a weight average molecular weight of 10,000 to 2,000,000 g / mol in any one of the above (1) to (6).

[0041] (8) The present invention provides a modified conjugated diene polymer having a molecular weight distribution of 1.0 to 8.0 in any one of the above (1) to (7).

[0042] (9) The present invention provides a method for producing a modified conjugated diene polymer, comprising the steps of (S1) producing an active polymer to which an organometallic compound is bonded by polymerizing a conjugated diene monomer, or an aromatic vinyl monomer and a conjugated diene monomer in a hydrocarbon solvent containing an organometallic compound; and (S2) reacting the active polymer with a modifier represented by the following chemical formula 1.

[0043] [Chemical Formula 1]

[0044]

[0045] In the above chemical formula 1,

[0046] A is an arylene group having 6 to 30 carbon atoms, or a heteroarylene group having 2 to 30 carbon atoms containing 1 to 3 N atoms,

[0047] L1 and L2 are each independently an alkylene group having 1 to 20 carbon atoms,

[0048] L3 and L4 are each independently an alkylene group having 1 to 20 carbon atoms,

[0049] R1 to R6 are each independently an alkoxy group having 1 to 20 carbon atoms.

[0050] (10) The present invention provides a method for producing a modified conjugated diene polymer, wherein the organometallic compound is used in an amount of 0.01 to 10 mmol based on 100 g of total monomers in (9).

[0051] (11) The present invention provides a method for producing a modified conjugated diene polymer, wherein the modifying agent and the organometallic compound represented by the chemical formula 1 are used in a molar ratio of 1:0.1 to 1:5.0 in the above (9) or (10).

[0052] (12) The present invention provides a rubber composition comprising a modified conjugated diene polymer according to any one of (1) to (8).

[0053] The modified conjugated diene polymer according to the present invention has a high modification rate, excellent affinity with fillers, high strength without deterioration in processability, and improved wear resistance.

[0054] Hereinafter, the present invention will be described in more detail to help understand the present invention.

[0055] The terms or words used in the description and claims of the present invention should not be interpreted as limited to their usual or dictionary meanings, and should be interpreted as meanings and concepts that conform to the technical idea of ​​the present invention, based on the principle that the inventor can appropriately define the concept of the term to explain his or her own invention in the best way.

[0056]

[0057] Definition of Terms

[0058] The term 'substitution' used in the present invention may mean that a hydrogen of a functional group, an atomic group, or a compound is substituted with a specific substituent, and when a hydrogen of a functional group, an atomic group, or a compound is substituted with a specific substituent, one or two or more substituents may be present depending on the number of hydrogens present in the functional group, an atomic group, or a compound, and when multiple substituents are present, each substituent may be the same or different from each other.

[0059] The term 'alkyl group' used in the present invention may mean a monovalent aliphatic saturated hydrocarbon, and may include both linear alkyl groups such as methyl, ethyl, propyl, and butyl, and branched alkyl groups such as isopropyl, sec-butyl, tert-butyl, and neo-pentyl.

[0060] The term 'alkylene group' used in the present invention may mean a divalent aliphatic saturated hydrocarbon such as methylene, ethylene, propylene, and butylene.

[0061] The term 'alkoxy group' used in the present invention may mean all functional groups, atomic groups, or compounds in which the hydrogen at the end of an alkyl group is replaced with an oxygen atom, such as methoxy, ethoxy, propoxy, and butoxy.

[0062] The term 'heteroalkyl group' used in the present invention may mean an alkyl group in which a carbon atom (excluding a terminal carbon atom) within the alkyl group is substituted with one or more heteroatoms.

[0063] The term 'cycloalkyl group' used in the present invention may be a cyclic saturated hydrocarbon.

[0064] The term 'aryl group' used in the present invention may mean an aromatic hydrocarbon, and may also mean a monocyclic aromatic hydrocarbon in which one ring is formed, or a polycyclic aromatic hydrocarbon in which two or more rings are combined.

[0065] The term 'heterocyclic group' used in the present invention may mean all aryl groups in which one or more carbon atoms in the aryl group are replaced with heteroatoms.

[0066] In the present invention, the terms 'derived unit' and 'derived functional group' may mean a component, structure, or the substance itself derived from a certain substance.

[0067] In this specification, the term 'hydrogenation rate' refers to the molar ratio of units derived from conjugated diene monomers in which unsaturated bonds are hydrogenated to form saturated bonds, relative to the total number of units derived from conjugated diene monomers in the copolymer. Specifically, the copolymer contains structural units (a), (b), (c), and (d) derived from conjugated diene monomers, and the hydrogenation rate refers to the molar ratio of the sum of structural units (b) and (d) relative to the total number of structural units, which are structural units (a) to (d).

[0068]

[0069]

[0070] Modified conjugated diene polymer

[0071] The present invention provides a modified conjugated diene polymer comprising a functional group derived from a modifier represented by Chemical Formula 1.

[0072] The modified conjugated diene polymer according to one embodiment of the present invention comprises a repeating unit derived from a conjugated diene monomer, comprises a functional group derived from a modifier represented by the following chemical formula 1 at at least one terminal, and is characterized in that the hydrogenation rate is 20% or more and 90% or less.

[0073] [Chemical Formula 1]

[0074]

[0075] In the above chemical formula 1,

[0076] A is an arylene group having 6 to 30 carbon atoms, or a heteroarylene group having 2 to 30 carbon atoms containing 1 to 3 N atoms,

[0077] L1 and L2 are each independently an alkylene group having 1 to 20 carbon atoms,

[0078] L3 and L4 are each independently an alkylene group having 1 to 20 carbon atoms,

[0079] R1 to R6 are each independently an alkyl group and / or an alkoxy group having 1 to 20 carbon atoms, and at least 4 of R1 to R6 are alkoxy groups.

[0080]

[0081] Specifically, in the above chemical formula 1, A may be an arylene group having 6 to 20 carbon atoms, or a heteroarylene group having 3 to 20 carbon atoms and containing 1 or 2 N atoms, or may be an arylene group having 6 to 10 carbon atoms, or a heteroarylene group having 3 to 20 carbon atoms and containing 1 or 2 N atoms. Specifically, A may be an arylene group such as a phenylene group, a naphthalene group, a biphenylene group, an anthracenylene group, a phenanthrenylene group, a fluorenylene group, or the like, and may be a pyrrolene group, a pyrazolene group, a pyridinylene group, a pyrimidinylene group, a triazinylene group, a carbazolylene group, or the like.

[0082] Specifically, in the above chemical formula 1, L1 and L2 are each independently an alkylene group having 1 to 10 carbon atoms, L1 and L2 are the same as each other, L3 and L4 are each independently an alkylene group having 1 to 10 carbon atoms, and L3 and L4 may be the same as each other. For example, L1 and L2 may be the same as each other and may be an alkylene group having 1 to 10 carbon atoms, an alkylene group having 1 to 6 carbon atoms, a methylene group, an ethylene group, a propylene group, a butylene group, etc., and L3 and L4 may be the same as each other and may be an alkylene group having 1 to 10 carbon atoms, an alkylene group having 1 to 6 carbon atoms, a methylene group, an ethylene group, a propylene group, a butylene group, etc., and L1 and L2 may be a methylene group, and L3 and L4 may be a propylene group.

[0083] Specifically, in the above chemical formula 1, R1 to R6 may all be an alkyl group and / or an alkoxy group having 1 to 10 carbon atoms, for example, R1 to R6 may each independently be an alkyl group and / or an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 3 carbon atoms, a methyl group, an ethyl group and / or an alkoxy group having 1 to 3 carbon atoms, a methoxy group, an ethoxy group, etc.

[0084] In addition, in the above chemical formula 1, at least four of R1 to R6 may be alkoxy groups. As a specific example, at least five of R1 to R6 may be alkoxy groups, and all of R1 to R6 may be alkoxy groups.

[0085]

[0086] The modifier represented by the above chemical formula 1 can be selected from compounds represented by the following chemical formulas 1A and 1B.

[0087] [Chemical Formula 1A]

[0088]

[0089] [Chemical Formula 1B]

[0090]

[0091] In the above chemical formulas 1A and 1B,

[0092] The definitions of L1 to L4 and R1 to R6 are as defined in the chemical formula 1 above.

[0093]

[0094] Since the modifier represented by the above chemical formula 1 has an internal core ring structure of an arylene group having 6 to 20 carbon atoms or a heteroarylene group having 5 to 20 carbon atoms and containing 1 to 3 N atoms, the alkoxysilane functional groups at both terminals of the modifier have an electron density that can easily bond with the conjugated diene polymer. In addition, since the modifier represented by the chemical formula 1 forms a planar structure as a whole of the compound, it can easily form a bond with the conjugated diene polymer without steric hindrance, whereas if the internal core ring is a cycloalkyl structure, the modifier has a distorted structure, so the contact and reaction with the conjugated diene polymer may proceed more slowly.

[0095] In addition, when N atoms are included in the modifier, side reactions are likely to occur, and a strong basic substance tends to be required for smooth reaction progress. However, since aminosilane has a property of being weak to a strong basic substance, it is difficult to control the reaction environment and the problem of low synthetic yield of the modifier may occur, so in the present invention, in order to be efficiently manufactured and easily used in the modification reaction while not exhibiting the above-mentioned problems, when the inner core is a heteroarylene group, it is limited to containing 1 to 3 N atoms.

[0096] In addition, the modifier represented by the above chemical formula 1 has excellent solubility in a reaction solvent, and when a modified conjugated diene polymer is produced using the modifier, a modified conjugated diene polymer having a high modification rate can be produced.

[0097] In addition, the modifier represented by chemical formula 1 of the present invention can be easily manufactured without going through multiple steps.

[0098]

[0099] The modifier represented by the above chemical formula 1 can be selected from compounds represented by the following chemical formulas 1-1 to 1-3.

[0100] [Chemical Formula 1-1]

[0101]

[0102] [Chemical Formula 1-2]

[0103]

[0104] [Chemical Formula 1-3]

[0105]

[0106] In the present invention, the modifier represented by the chemical formula 1 may be manufactured through a step of reacting a compound represented by the chemical formula 2 below with a compound represented by the chemical formula 3 or 4 below.

[0107] [Chemical Formula 2]

[0108]

[0109] [Chemical Formula 3]

[0110]

[0111] [Chemical Formula 4]

[0112]

[0113] In the above chemical formula 2, A1 and A2 are each independently a halogen element, and may be specifically Cl.

[0114] In the above chemical formulas 2 to 4, the definition of each substituent is as defined above.

[0115]

[0116] In the above step, the compound represented by chemical formula 2 and the compound represented by chemical formula 3 or 4 can be reacted in a molar ratio of 1:1.5 to 1:5.0, a molar ratio of 1:1.5 to 1:3.0, or a molar ratio of 1:1.5 to 1:2.5.

[0117] In the above step, the compound represented by chemical formula 2 and the compound represented by chemical formula 3 or chemical formula 4 may be performed at a temperature of 20 to 200°C, 30 to 180°C, or 40 to 150°C for 1 to 72 hours.

[0118]

[0119] In the present invention, the repeating unit derived from the conjugated diene monomer may refer to a repeating unit formed when the conjugated diene monomer is polymerized, and the conjugated diene monomer may be, for example, 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 refers to a halogen atom).

[0120] Meanwhile, the above-described modified conjugated diene copolymer may be, for example, a copolymer further including an aromatic vinyl monomer-derived repeating unit together with the above-described conjugated diene monomer-derived repeating unit.

[0121] The above-mentioned aromatic vinyl monomer-derived repeating unit may refer to a repeating unit formed when an aromatic vinyl monomer is polymerized, and 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, and 1-vinyl-5-hexylnaphthalene.

[0122] When the above-mentioned modified conjugated diene polymer is a copolymer including a repeating unit derived from an aromatic vinyl monomer, the above-mentioned modified conjugated diene polymer may include at least 20 wt%, 30 wt%, 40 wt%, 50 wt%, 55 wt%, or 60 wt% of the repeating unit derived from the conjugated diene monomer, and may include at most 95 wt%, 90 wt%, or 80 wt% of the repeating unit derived from the aromatic vinyl monomer, and may include at least 5 wt%, 10 wt%, or 20 wt% of the repeating unit derived from the aromatic vinyl monomer, and may include at most 80 wt%, 70 wt%, 60 wt%, 55 wt%, 50 wt%, 45 wt%, or 40 wt% of the repeating unit, and within this range, excellent driving resistance and wear resistance are achieved.

[0123]

[0124] According to one embodiment of the present invention, the modified conjugated diene copolymer may have a hydrogenation rate of a conjugated diene monomer-derived unit of 20% or more and 90% or less. As a specific example, the modified conjugated diene copolymer may have a hydrogenation rate of a conjugated diene monomer-derived unit of 25% or more, 30% or more, 35% or more, 40% or more, 45% or more, 50% or more, 55% or more, or 60 wt% or more, and further may be 88 wt% or less, 86 wt% or less, 84 wt% or less, 82 wt% or less, 80 wt% or less, 78 wt% or less, 76 wt% or less, or 74 wt% or less. When the hydrogenation rate satisfies the above range, there is an effect of improving processability and wear resistance while having excellent running resistance.

[0125]

[0126] According to one embodiment of the present invention, the copolymer may be a random copolymer, in which case an excellent balance between each physical property is achieved. The random copolymer may mean that the repeating units forming the copolymer are arranged in a random manner.

[0127]

[0128] According to one embodiment of the present invention, the modified conjugated diene polymer may have a number average molecular weight (Mn) of 10,000 to 2,000,000 g / mol, 50,000 to 1,800,000 g / mol, or 120,000 to 1,500,000 g / mol, and a weight average molecular weight (Mw) of 10,000 to 5,000,000 g / mol, 100,000 to 3,500,000 g / mol, or 120,000 to 2,000,000 g / mol, and within this range, has excellent rolling resistance and wet road resistance. As another example, the modified conjugated diene polymer may have a molecular weight distribution (Mw / Mn) of 1.0 to 8.0, 1.0 to 4.0, or 1.0 to 3.5, and has an excellent balance of properties within this range.

[0129] Here, the weight average molecular weight (Mw) and number average molecular weight (Mn) are each a polystyrene-converted molecular weight analyzed by gel permeation chromatography (GPC), and the molecular weight distribution (Mw / Mn) is also called polydispersity and is calculated as the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn).

[0130] As another example, the above-described modified conjugated diene polymer may have a Mooney viscosity of 20 to 150 at 100°C and 20 to 150 at 140°C, and has excellent processability and productivity within this range.

[0131] Here, the Mooney viscosity was measured using a Mooney viscometer, for example, a Large Rotor from MV2000E (ALPHA Technologies Co., Ltd.) at 100°C and 140°C, and a Rotor Speed ​​of 2±0.02 rpm. Specifically, the polymer was left at room temperature (23±5°C) for more than 30 minutes, and then 27±3 g was collected and filled into the die cavity, and the measurement was performed while operating the platen to apply torque.

[0132]

[0133] In addition, the above-described modified conjugated diene polymer may have a vinyl content of 5 wt% or more, 10 wt% or more, or 10 wt% to 60 wt%, and within this range, the glass transition temperature may be adjusted to an appropriate range, thereby exhibiting excellent driving resistance. Here, the vinyl content may refer to the content of a 1,2-added, rather than a 1,4-added, conjugated diene monomer relative to 100 wt% of a conjugated diene copolymer composed of a monomer having a vinyl group and an aromatic vinyl monomer.

[0134] Meanwhile, the terms 'derived repeating unit', 'derived functional group' and 'derived group' used in the present invention may indicate a component, structure or the substance itself derived from a certain substance.

[0135]

[0136] Method for producing a modified conjugated diene polymer

[0137] In addition, the present invention provides a method for producing the modified conjugated diene polymer.

[0138] The method for producing the modified conjugated diene polymer according to one embodiment of the present invention is characterized by including the steps of (S1) producing an active polymer to which an organometallic compound is bonded by polymerizing a conjugated diene monomer, or an aromatic vinyl monomer and a conjugated diene monomer, in a hydrocarbon solvent containing an organometallic compound (step 1); (S2) reacting the active polymer with a modifier represented by the following chemical formula 1 (step 2); and (S3) adding a hydrogenation catalyst to the resultant product of step (S2) to react such that the hydrogenation rate becomes 20% or more and 90% or less (step 3).

[0139] [Chemical Formula 1]

[0140]

[0141] The definition of each substituent in the above chemical formula 1 is as defined above.

[0142]

[0143] The above step 1 is a step for producing an active polymer to which an organometallic compound is bound, and can be performed by polymerizing a conjugated diene monomer, or an aromatic vinyl monomer and a conjugated diene monomer in a hydrocarbon solvent containing an organometallic compound.

[0144] The hydrocarbon solvent is not particularly limited, but may be at least one selected from the group consisting of n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene, and xylene.

[0145] The above conjugated diene monomer and aromatic vinyl monomer are as defined above.

[0146]

[0147] According to one embodiment of the present invention, the organometallic compound can be used in an amount of 0.01 to 10 mmol, 0.05 to 5 mmol, 0.1 to 2 mmol, 0.1 to 1 mmol, or 0.15 to 0.8 mmol based on 100 g of total monomer.

[0148] The above organometallic compound may be, for example, at least one selected from the group consisting of methyllithium, ethyllithium, propyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octyllithium, phenyllithium, 1-naphthyllithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naphthylsodium, naphthylpotassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide, and lithium isopropylamide.

[0149] Meanwhile, the polymerization of step 1 can be carried out including a polar additive, and the polar additive can be added in an amount of 0.001 to 50 g, 0.001 to 10 g, 0.005 to 0.2 g, or 0.01 to 0.2 g based on 100 g of total monomer.

[0150] In addition, the polar additive may be at least one selected from the group consisting of tetrahydrofuran, 2,2-di(tetrahydrofuryl)propane, diethyl ether, cyclopentyl ether, dipropyl ether, ethylenedimethyl ether, diethyl glycol, dimethyl ether, tert-butoxyethoxyethane, bis(3-dimethylaminoethyl)ether, (dimethylaminoethyl)ethyl ether, trimethylamine, triethylamine, tripropylamine, and tetramethylethylenediamine, and specifically, may be triethylamine or tetramethylethylenediamine, and when the polar additive is included, when copolymerizing a conjugated diene monomer, or a conjugated diene monomer and an aromatic vinyl monomer, there is an effect of inducing easy formation of a random copolymer by compensating for the difference in reaction speeds thereof.

[0151] The polymerization of step 1 above may be, for example, anionic polymerization, and as a specific example, may be living anionic polymerization having an anionic active site at the polymerization terminal by a growth polymerization reaction by anion. In addition, the polymerization of step 1 above may be temperature-raising polymerization, isothermal polymerization, or isothermal polymerization (adiabatic polymerization), and the isothermal polymerization may refer to a polymerization method including a step of polymerizing by the heat of reaction itself without arbitrarily applying heat after introducing an organometallic compound, the temperature-raising polymerization may refer to a polymerization method of increasing the temperature by arbitrarily applying heat after introducing the organometallic compound, and the isothermal polymerization may refer to a polymerization method of maintaining the temperature of the polymer product constant by increasing the heat by applying heat or removing heat after introducing the organometallic compound.

[0152] Additionally, the polymerization of step 1 may be carried out at a temperature range of, for example, -20 to 80°C, 0 to 80°C, 10 to 80°C, or 10 to 70°C.

[0153] The active polymer manufactured by the above step 1 may mean a polymer in which a polymer anion and an organic metal cation are combined.

[0154]

[0155] The above step 2 is a step of reacting the active polymer with the modifier represented by the above chemical formula 1 to produce a modified conjugated diene polymer.

[0156] According to one embodiment of the present invention, the modifier represented by the chemical formula 1 may be used in an amount of 0.05 to 10 g, 0.05 to 5 g, specifically 0.05 to 1 g, based on 100 g of total monomer.

[0157] In addition, according to one embodiment of the present invention, the modifier and the organometallic compound represented by the chemical formula 1 can be used in a molar ratio of 1:0.1 to 1:5.0, or a molar ratio of 1:0.1 to 1:4.0, and a modification reaction with optimal performance can be performed within this range, thereby obtaining a high molecular weight conjugated diene polymer.

[0158] The reaction of step 2 above is a modification reaction for introducing a functional group derived from the denaturant into the active polymer, and may be performed at 0°C to 90°C for 1 minute to 5 hours.

[0159] In addition, according to one embodiment of the present invention, the method for producing the modified conjugated diene polymer may be performed by a batch method or a continuous polymerization method including one or more reactors.

[0160] The above-described method for producing a modified conjugated diene polymer may further include, for example, one or more steps of solvent and unreacted monomer recovery and drying steps following step 2 of the present invention, as needed.

[0161]

[0162] The hydrogenation reaction of step 3 above can be carried out by contacting the modified conjugated diene polymer polymer manufactured after step (S2) with hydrogen, and specifically, can be carried out by contacting the polymer with hydrogen gas in an inert atmosphere in the presence of a hydrogenation catalyst.

[0163] The above hydrogenation catalyst is not particularly limited and can be applied as long as it is applied as a hydrogenation reaction catalyst of a conjugated diene polymer, but for example, it can be a supported heterogeneous catalyst in which a metal such as Ni, Pt, Pd or Ru is supported on carbon, silica, alumina or diatomaceous earth; a Ziegler-type catalyst in which an organic acid salt or a transition metal salt of an acetylacetone salt of Ni, Co, Fe or Cr is used together with a reducing agent such as an organic aluminum; or an organometallic complex homogeneous catalyst of Ti, Ru, Rh or Zr emnd.

[0164] As another example, the hydrogenation catalyst may be a titanocene compound or a mixture thereof with a reducing organometallic compound, and the titanocene compound may be a compound having a (substituted)cyclopentadienyl skeleton, an indenyl skeleton, or a fluorenyl skeleton, such as biscyclopentadienyl titanium chloride or monopentamethyl cyclopentadienyl titanium trichloride, and the reducing organometallic compound may be a free alkali metal compound such as organolithium, an organomagnesium compound, an organoaluminum compound, an organoboron compound, or an organozinc compound.

[0165] In addition, the hydrogenation reaction is not particularly limited, but may be performed, for example, at a temperature range of 0°C to 200°C or 30°C to 150°C and a pressure range of 0.1 MPa to 15 MPa, 0.2 MPa to 10 MPa, or 0.3 MPa to 5 MPa for 3 minutes to 10 hours, or 10 minutes to 5 hours.

[0166]

[0167] rubber composition

[0168] Furthermore, the present invention provides a rubber composition comprising the modified conjugated diene polymer.

[0169] The rubber composition according to one embodiment of the present invention may contain the modified conjugated diene polymer in an amount of 10 wt% or more, 10 wt% to 100 wt%, or 20 wt% to 90 wt%, and within this range, the rubber composition has excellent mechanical properties such as tensile strength and wear resistance, and has an excellent balance between each property.

[0170] In addition, the rubber composition may further include other rubber components as needed in addition to the modified conjugated diene polymer, and in this case, the rubber component may be included 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 component may be included in an amount of 1 to 900 parts by weight based on 100 parts by weight of the modified conjugated diene polymer.

[0171] The above rubber component may be, for example, natural rubber or synthetic rubber, and specific examples thereof include natural rubber (NR) including cis-1,4-polyisoprene; modified natural rubber such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber, which are modified or refined from the above general natural rubber; It may be a synthetic rubber such as styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, polyisobutylene-co-isoprene, 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 any one or a mixture of two or more of these may be used.

[0172] The above rubber composition may contain, for example, 0.1 to 200 parts by weight, or 10 to 120 parts by weight, of a filler based on 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 include wet silica (hydrated silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, or colloidal silica, and preferably wet silica, which has the best effect of improving fracture properties and achieving wet grip. In addition, the rubber composition may further contain a carbon black-based filler, if necessary.

[0173] As another example, when silica is used as the filler, a silane coupling agent may be used together to improve reinforcing properties and low heat generation properties, and 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-Triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 2-Triethoxysilylethyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-Trimethoxysilylpropylbenzothiazolyltetrasulfide, 3-Triethoxysilylpropylbenzolyltetrasulfide, 3-Triethoxysilylpropylmethacrylate monosulfide, 3-Trimethoxysilylpropylmethacrylate monosulfide, bis(3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, or dimethoxymethylsilylpropylbenzothiazolyltetrasulfide, and the like, and any one or a mixture of two or more of these may be used. Preferably, considering the effect of improving reinforcing properties, it may be bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide.

[0174] In addition, since the rubber composition according to one embodiment of the present invention uses a modified conjugated diene polymer having a functional group having high affinity for silica introduced into an active site as a rubber component, the amount of the silane coupling agent can be reduced compared to the usual case, and accordingly, the silane coupling agent can be used in an amount of 1 to 20 parts by weight, or 5 to 15 parts by weight, based on 100 parts by weight of silica, and within this range, the effect as a coupling agent is sufficiently exerted while also having the effect of preventing gelation of the rubber component.

[0175] The rubber composition according to one embodiment of the present invention may be sulfur crosslinkable and may further include a vulcanizing agent. The vulcanizing agent may be specifically sulfur powder and may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the rubber component. Within this range, the vulcanized rubber composition secures the required elastic modulus and strength while exhibiting excellent fuel efficiency.

[0176] The rubber composition according to one embodiment of the present invention may further include, in addition to the above-described components, various additives commonly used in the rubber industry, specifically, a vulcanization accelerator, a process oil, a plasticizer, an anti-aging agent, a scorch inhibitor, zinc white, stearic acid, a thermosetting resin, or a thermoplastic resin.

[0177] The above-mentioned vulcanization accelerator may be, for example, a thiazole-based compound such as M(2-mercaptobenzothiazole), DM(dibenzothiazyl disulfide), CZ(N-cyclohexyl-2-benzothiazylsulfenamide), or a guanidine-based compound such as DPG (diphenylguanidine), and may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the rubber component.

[0178] The above process oil acts as a softener in the rubber composition, and may be, for example, a paraffinic, naphthenic, or aromatic compound. When considering tensile strength and wear resistance, an aromatic process oil may be used, and when considering hysteresis loss and low-temperature characteristics, a naphthenic or paraffinic process oil may be used. The above process oil may be included in an amount of, for example, 100 parts by weight or less based on 100 parts by weight of the rubber component, and within this range, it has the effect of preventing a decrease in the tensile strength and low heat generation (low fuel consumption) of the vulcanized rubber.

[0179] The above-mentioned 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 based on 100 parts by weight of the rubber component.

[0180] The rubber composition according to one embodiment of the present invention can be obtained by mixing using a mixer such as a Banbury mixer, a roll mixer, or an internal mixer according to the above compounding prescription, and a rubber composition having low heat generation and excellent wear resistance can be obtained by a vulcanization process after molding processing.

[0181] Accordingly, the rubber composition can be useful in the manufacture of various industrial rubber products such as tire tread, undertread, side wall, carcass coating rubber, belt coating rubber, bead filler, squeegee, or bead coating rubber, as well as various parts of a tire, such as vibration-proof rubber, belt conveyor, and hose.

[0182]

[0183] In addition, the present invention provides a tire manufactured using the rubber composition.

[0184] The above tire may include a tire or tire tread.

[0185]

[0186] Example

[0187] Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to illustrate the present invention and are not intended to limit the scope of the present invention solely to these examples.

[0188]

[0189] Manufacturing Example 1

[0190] 3.5 g (20 mmol) of 1,4-bis(chloromethyl)benzene, 15.4 g of bis(3-(trimethoxysilyl)propyl)amine, and 8.4 mL of triethylamine were stirred at 150°C for 6 hours. After completion of the reaction, the temperature was lowered to room temperature, 50 mL of hexane was added, and the mixture was stirred for 15 minutes. Solid byproducts were removed through a celite filter, and the solution and impurities were distilled under reduced pressure to obtain a light brown oil. The H nuclear magnetic resonance spectroscopy spectrum was observed to confirm that it was a compound represented by the following chemical formula.

[0191] [Chemical Formula 1-1]

[0192]

[0193] 1 H NMR (CDCl3, 500 MHz): δ 7.24 (s, 4H), 3.56 (d, J=9.2Hz, 40H), 2.48-2.37 (m, 8H), 1.63-1.53 ​​(m, 8H), 0.65-0.56 (m, 8H)

[0194]

[0195] Manufacturing Example 2

[0196] 3.5 g (20 mmol) of 1,3-bis(chloromethyl)benzene, 15.4 g of bis(3-(trimethoxysilyl)propyl)amine, and 8.4 mL of triethylamine were stirred at 150°C for 6 hours. After completion of the reaction, the temperature was lowered to room temperature, 50 mL of hexane was added, and the mixture was stirred for 15 minutes. Solid byproducts were removed through a celite filter, and the solution and impurities were distilled under reduced pressure to obtain a light brown oil. The H nuclear magnetic resonance spectroscopy spectrum was observed to confirm that it was a compound represented by the following chemical formula.

[0197] [Chemical Formula 1-2]

[0198]

[0199] 1 H NMR (CDCl3, 500 MHz): δ 7.24 (s, 4H), 3.56 (d, J=9.2Hz, 40H), 2.48-2.37 (m, 8H), 1.63-1.53 ​​(m, 8H), 0.65-0.56 (m, 8H)

[0200]

[0201] Manufacturing Example 3

[0202] 3.5 g (20 mmol) of 2,6-bis(chloromethyl)pyridine, 15.4 g of bis(3-(trimethoxysilyl)propyl)amine, and 8.4 mL of triethylamine were stirred at 150°C for 6 hours. After completion of the reaction, the temperature was lowered to room temperature, 50 mL of hexane was added, and the mixture was stirred for 15 minutes. Solid byproducts were removed through a celite filter, and the solution and impurities were distilled under reduced pressure to obtain a light brown oil. The H nuclear magnetic resonance spectroscopy spectrum was observed to confirm that it was a compound represented by the following chemical formula.

[0203] [Chemical Formula 1-3]

[0204]

[0205] 1H NMR (CDCl3, 500 MHz): δ 7.60 (t, 1H), 7.35 (d, 2H), 3.56 (d, J = 9.2 Hz, 40H), 2.48-2.37 (m, 8H), 1.63-1.53 ​​(m, 8H), 0.65-0.56 (m, 8H)

[0206]

[0207] Manufacturing Example 4

[0208] 1 L of purified cyclohexane was added to a dried reaction vessel that had been replaced with nitrogen, 100 mmol of bis(η5-cyclopentadienyl)titanium dichloride was added, and an n-hexane solution containing 200 mmol of trimethylaluminum was added while sufficiently stirring, and the mixture was reacted at room temperature for about 3 days to obtain a hydrogenation catalyst.

[0209]

[0210] Example 1

[0211] In a 20 L autoclave reactor, 4.733 g of n-hexane, 375.0 g of styrene, 593.8 g of 1,3-butadiene, and 1.4 g of N,N,N',N-tetramethylethylenediamine (TMEDA) as a polar additive were charged, then 5.0 g of n-butyllithium (10 wt% in hexane) was added, the internal temperature of the reactor was adjusted to 40°C, and an adiabatic temperature-raising reaction was performed. After approximately 30 minutes, 31.3 g of 1,3-butadiene was added to cap the ends of the polymer with butadiene. Afterwards, the compound represented by the chemical formula 1-1 manufactured in Manufacturing Example 1 as a modifier was added (1.84 g, 2.3 mmol) and reacted for 30 minutes to manufacture a dielectric styrene-butadiene copolymer ([TMEDA]:[act.Li]=3.1:1 molar ratio, [modifier]:[act.Li]=0.3:1 molar ratio). Next, the hydrogenation catalyst manufactured in Manufacturing Example 4 and hydrogen were added, and the hydrogenation reaction was performed at a temperature of 80°C and a hydrogen pressure of 0.7 Mpa. At this time, the hydrogenation catalyst was added in the form of 150 ppm titanium per 100 parts by weight of the polymer. Thereafter, 17 g of a solution containing 30 wt% of Wingstay K as an antioxidant dissolved in hexane was added. The resulting polymer was placed in hot water heated with steam, stirred to remove the solvent, and then roll-dried to remove the remaining solvent and water, thereby producing a modified styrene-butadiene copolymer.

[0212]

[0213] Example 2

[0214] A modified styrene-butadiene copolymer was prepared in the same manner as in Example 1, except that the compound represented by Chemical Formula 1-2 prepared in Manufacturing Example 2 was added as a modifier ([TMEDA]:[act.Li]=3.1:1 molar ratio, [modifier]:[act.Li]=0.3:1 molar ratio).

[0215]

[0216] Example 3

[0217] A modified styrene-butadiene copolymer was prepared in the same manner as in Example 1, except that the compound represented by Chemical Formula 1-3 prepared in Manufacturing Example 3 was added as a modifier ([TMEDA]:[act.Li]=3.1:1 molar ratio, [modifier]:[act.Li]=0.3:1 molar ratio).

[0218]

[0219] Example 4

[0220] A modified styrene-butadiene copolymer was prepared in the same manner as in Example 1, except that the hydrogenation catalyst was added at 130 ppm as titanium per 100 parts by weight of the polymer.

[0221]

[0222] Comparative Example 1

[0223] A dielectric styrene-butadiene copolymer was prepared in the same manner as in Example 1, except that SiCl4 was added as a modifier ([TMEDA]:[act.Li] = 3.1:1 molar ratio, [modifier]:[act.Li] = 0.48:1 molar ratio). Then, 17 g of a solution containing 30 wt% Wingstay K as an antioxidant in hexane was added without a hydrogenation process. The resulting polymer was placed in hot water heated with steam, stirred to remove the solvent, and then roll-dried to remove the remaining solvent and water, thereby preparing a modified styrene-butadiene copolymer.

[0224]

[0225] Comparative Example 2

[0226] A modified styrene-butadiene copolymer was prepared in the same manner as in Example 1, except that SiCl4 was used as a modifier ([TMEDA]:[act.Li]=3.1:1 molar ratio, [modifier]:[act.Li]=0.48:1 molar ratio).

[0227]

[0228] Comparative Example 3

[0229] A modified styrene-butadiene copolymer was prepared in the same manner as in Example 1, except that N-methyl-3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine was added as a modifier ([TMEDA]:[act.Li] = 3.1:1 molar ratio, [modifier]:[act.Li] = 0.35:1 molar ratio).

[0230] *N-methyl-3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine

[0231]

[0232] Comparative Example 4

[0233] A modified conjugated diene polymer was prepared in the same manner as in Comparative Example 3, except that the hydrogenation catalyst was added at 200 ppm as titanium per 100 parts by weight of the polymer.

[0234]

[0235] Experimental Example 1

[0236] For the modified conjugated diene polymers manufactured in the above examples and comparative examples, the styrene unit content and vinyl content, hydrogenation rate, Mooney viscosity (MV), and weight average molecular weight (Mw, X10) in the polymer were measured. 3 g / mol), number-average molecular weight (Mn, X10 3 g / mol), and molecular weight distribution (MWD) were measured using the following methods, respectively.

[0237]

[0238] 1) Styrene bond content and 1,2-vinyl bond content

[0239] The styrene bond content (SM) and 1,2-vinyl bond content (Vi) in each polymer were measured and analyzed using a Varian VNMRS 500 MHz NMR. 1,1,2,2-tetrachloroethane was used as the solvent for NMR measurements, and the solvent peak was calculated as 6.00 ppm, 7.2–6.9 ppm as random styrene, 6.9–6.2 ppm as block styrene, 5.8–5.1 ppm as 1,4-vinyl and 1,2-vinyl, and 5.1–4.5 ppm as 1,2-vinyl.

[0240]

[0241] 2) Hydrogenation rate

[0242] The hydrogenation rate was obtained by obtaining the spectra of the structural units (a) to (d) by 1H NMR analysis, and calculating the relative molar ratio of the sum of the structural units (b) and (d) to the entire structural unit by integrating the area of ​​each peak.

[0243] Specifically, NMR spectra were obtained using a Varian VNMRS 500 MHz NMR, and 4.0 to 6.0 ppm were assigned to structural units (a) and (c), and 0.5 to 2.5 ppm were assigned to structural units (b) and (d), and the relative molar ratio of the sum of structural units (b) and (d) to the total structural units was calculated. Meanwhile, 1,1,2,2-tetrachloroethane was used as the solvent during NMR measurement, and the solvent peak was calculated as 6.00 ppm.

[0244]

[0245]

[0246] 3) Mooney point

[0247] The Mooney viscosity (MV, (ML1+4, @140℃ MU) above was measured using MV-2000 (ALPHA Technologies) at 140℃, Rotor Speed ​​2±0.02 rpm, Large Rotor. The sample used was left at room temperature (23±5℃) for more than 30 minutes, and then 27±3 g was collected and filled into the die cavity, and the Platen was operated for measurement for 4 minutes.

[0248]

[0249] 4) Weight average molecular weight, number average molecular weight, molecular weight distribution

[0250] The above weight average molecular weight (Mw) and number average molecular weight (Mn) were measured through GPC (Gel permeation chromatography) analysis, and the molecular weight distribution (MWD, Mw / Mn) was calculated from the measured molecular weights.

[0251] Specifically, the above GPC was performed using a combination of two PLgel Olexis (Polymer Laboratories) columns and one PLgel mixed-C (Polymer Laboratories) column, and all newly replaced columns were mixed bed type columns. When calculating molecular weight, the GPC standard material was PS (polystyrene).

[0252]

[0253] Example Comparative Example 1 2 3 4 1 2 3 4 SM (wt%) 3 6 3 7 3 6 3 6 3 7 3 6 3 7 3 6 Vi (wt%) 2 5 2 6 2 5 2 6 2 7 2 5 2 6 Hydrogenation Rate 7 7 7 7 5 6 6 7 0 7 7 7 7 9 MV (@ 140°C) 1 0 5 1 0 4 8 7 9 4 7 5 9 0 1 1 0 1 4 1 Mn 6 0 5 7 5 9 0 3 6 3 6 4 6 5 2 Mw 1 1 5 1 0 8 1 1 1 1 2 7 5 7 9 8 3 9 3 PDI (Mw / Mn) 1.9 2 1.8 9 1.8 7 1.8 7 2.1 2.2 0 1.8 0 1.7 8

[0254] As shown in the above results, the modified conjugated diene polymer of the example using the modifier represented by Chemical Formula 1 according to the present invention showed a much higher molecular weight than the comparative example, but it was confirmed that the increase in Mooney viscosity was relatively small. This is a result showing that the modified conjugated diene polymer prepared in the example has a star-shaped polymer morphology. In addition, it can be seen that the modified conjugated diene polymer of the example having such a structure will have improved processability and excellent wear performance due to its high molecular weight characteristics.

[0255] Experimental Example 2

[0256] In order to compare and analyze the properties of the rubber compositions containing the modified conjugated diene polymers manufactured in the above examples and comparative examples and the molded products manufactured therefrom, the processability, tensile strength, running resistance, and wear resistance were each measured.

[0257]

[0258] 1) Manufacturing of rubber specimens

[0259] The modified conjugated diene polymers of the examples and comparative examples were mixed as raw rubber under the mixing conditions shown in Table 2 below. The raw materials in Table 2 are each part by weight based on 100 parts by weight of rubber.

[0260]

[0261] Classification Raw material content (weight parts) 1st stage mixed rubber 100 Silica 70 Coupling agent 11.2 Process oil 25 Zinc agent 3 Stearic acid 2 Antioxidant 2 Anti-aging agent 2 Wax 1 2nd stage mixed sulfur 1.5 Rubber accelerator 1.75 Vulcanization accelerator 2

[0262] Specifically, the above rubber specimen is kneaded through first-stage kneading and second-stage kneading. In the first stage mixing, raw rubber, silica (filler), organosilane coupling agent (X50S, Evonik), process oil (TDAE oil), zincating agent (ZnO), stearic acid, antioxidant (TMQ(RD) (2,2,4-trimethyl-1,2-dihydroquinoline polymer), anti-aging agent (6PPD ((dimethylbutyl)-N-phenyl-phenylenediamine)) and wax (Microcrystaline Wax)) were mixed using a Banbury mixer equipped with a temperature control device. At this time, the temperature of the mixer was controlled, and the first mixture was obtained at a discharge temperature of 150℃. In the second stage mixing, the first mixture was cooled to room temperature, and then the first mixture, sulfur powder, rubber accelerator (DPG (diphenylguanidine)) and vulcanization accelerator (CZ (N-cyclohexyl-2-benzothiazylsulfenamide)) were added to the mixer. and mixed at a temperature below 100℃ to obtain a secondary compound. Afterwards, a curing process was performed at 160℃ for 20 minutes to manufacture a rubber specimen.

[0263] 2) Processability characteristics

[0264] The Mooney viscosity (MV, (ML1+4, at 100℃ MU) of the secondary compound obtained during the manufacture of the above 1) rubber specimen was measured to compare and analyze the processability characteristics of each polymer. At this time, the lower the Mooney viscosity measurement value, the better the processability characteristics are. However, since the result values ​​in Table 3 are expressed by indexing the measurement value of Comparative Example 1 as the reference value, the higher the value, the better the processability characteristics are.

[0265] Specifically, using MV-2000 (ALPHA Technologies), a large rotor at 100°C with a rotor speed of 2±0.02 rpm, each secondary compound was left at room temperature (23±5°C) for more than 30 minutes, and then 27±3 g was collected and filled into the die cavity, and the platen was operated for measurement for 4 minutes.

[0266]

[0267] 3) Tensile strength

[0268] Each test specimen was manufactured according to the tensile test method of ASTM 412, and the tensile strength of the test specimen was measured at room temperature at a speed of 50 cm / min using a Universal Test Machin 4204 (Instron) tensile tester. The results in Table 3 are expressed as Index (%) based on the results of Comparative Example 1, and a higher value indicates better results.

[0269]

[0270] 4) Driving resistance

[0271] Viscoelastic properties were measured using a dynamic mechanical analyzer (GABO) in Film Tension mode at a frequency of 10 Hz and at each measurement temperature (-60℃ to 64℃) to determine the tan δ value for dynamic deformation. The lower the tan δ value at high temperature 60℃, the less hysteresis loss and the better the driving resistance (fuel efficiency). However, since the results in Table 3 are expressed as an Index (%) based on the results of Comparative Example 1, a higher value indicates better results.

[0272]

[0273] 5) Wear resistance (DIN wear test)

[0274] For each rubber specimen, a DIN abrasion test was performed in accordance with ASTM D5963, and the results were expressed as a DIN loss index (loss volume index: ARIA (Abration resistance index, Method A). The results in Table 3 are expressed as an index using the measured values ​​of Comparative Example 1 as the reference values, so a higher value indicates better results.

[0275]

[0276] Example Comparative Example 12341234 Processability 105104103104100807570 Tensile strength 124126110120100124123131 Running resistance 10310311111410010310478 Wear resistance 120117119122100119120125

[0277] As shown in Table 3 above, it was confirmed that the modified conjugated diene polymer of the example has the effect of improving processability, tensile strength, running resistance, and wear resistance in a balanced manner. Through the above results, the modified conjugated diene polymer of the present invention has excellent filler affinity by including a functional group derived from the modifier represented by Chemical Formula 1, and due to the structural characteristics of the polymer chain bonded to the functional group derived from the modifier, the processability, tensile strength, etc. of the rubber composition including the same are all improved. Through this, it can be seen that the modified conjugated diene polymer of the present invention has a remarkable effect that cannot be realized by polymers modified with other modifiers of a similar structure by being modified with the modifier represented by Chemical Formula 1.

[0278] In addition, it can be confirmed that the wear performance of the conjugated diene polymer of the present invention is improved compared to Comparative Example 1 in which hydrogenation did not occur because the unsaturated bonds are hydrogenated into saturated bonds.

Claims

1. Contains repeating units derived from conjugated diene monomers, At least one terminal thereof comprises a functional group derived from a modifier represented by the following chemical formula 1, Modified conjugated diene polymer having a hydrogenation rate of 20% or more and 90% or less: [Chemical Formula 1] In the above chemical formula 1, A is an arylene group having 6 to 30 carbon atoms, or a heteroarylene group having 2 to 30 carbon atoms containing 1 to 3 N atoms, L1 and L2 are each independently an alkylene group having 1 to 20 carbon atoms, L3 and L4 are each independently an alkylene group having 1 to 20 carbon atoms, R1 to R6 are each independently an alkyl group and / or alkoxy group having 1 to 20 carbon atoms, and at least 4 of R1 to R6 are alkoxy groups.

2. In claim 1, A modified conjugated diene polymer having a hydrogenation rate of 50% or more and 80% or less.

3. In claim 1, In the above chemical formula 1, A modified conjugated diene polymer in which A is an arylene group having 6 to 20 carbon atoms or a heteroarylene group having 3 to 20 carbon atoms containing 1 or 2 N atoms.

4. In claim 1, In the above chemical formula 1, L1 and L2 are each independently an alkylene group having 1 to 10 carbon atoms, and L1 and L2 are the same as each other. L3 and L4 are each independently an alkylene group having 1 to 10 carbon atoms, and L3 and L4 are the same modified conjugated diene polymer.

5. In claim 1, The modifier represented by the above chemical formula 1 is a modified conjugated diene polymer selected from compounds represented by the following chemical formulas 1A and 1B: [Chemical Formula 1A] [Chemical Formula 1B] In the above chemical formulas 1A and 1B, The definitions of L1 to L4 and R1 to R6 are as defined in the chemical formula 1 above.

6. In claim 1, A modified conjugated diene polymer in which the modifier represented by the above chemical formula 1 is selected from compounds represented by the following chemical formulas 1-1 to 1-3. [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3] 7. In claim 1, A modified conjugated diene polymer having a weight average molecular weight of 10,000 to 2,000,000 g / mol.

8. In claim 1, A modified conjugated diene polymer having a molecular weight distribution of 1.0 to 8.

0. 9.(S1) A step of producing an active polymer to which an organometallic compound is bonded by polymerizing a conjugated diene monomer, or an aromatic vinyl monomer and a conjugated diene monomer in a hydrocarbon solvent containing an organometallic compound; (S2) a step of reacting the active polymer and a modifier represented by the following chemical formula 1; and (S3) A method for producing a modified conjugated diene polymer, comprising a step of adding a hydrogenation catalyst to the resultant product of the step (S2) to cause a reaction so that the hydrogenation rate becomes 20% or more and 90% or less: [Chemical Formula 1] In the above chemical formula 1, A is an arylene group having 6 to 30 carbon atoms, or a heteroarylene group having 2 to 30 carbon atoms containing 1 to 3 N atoms, L1 and L2 are each independently an alkylene group having 1 to 20 carbon atoms, L3 and L4 are each independently an alkylene group having 1 to 20 carbon atoms, R1 to R6 are each independently an alkoxy group having 1 to 20 carbon atoms.

10. In claim 9, A method for producing a modified conjugated diene polymer using 0.01 to 10 mmol of the above organometallic compound based on 100 g of total monomers.

11. In claim 9, A method for producing a modified conjugated diene polymer, wherein the modifying agent and the organometallic compound represented by the above chemical formula 1 are used in a molar ratio of 1:0.1 to 1:5.

0.

12. A rubber composition comprising a modified conjugated diene polymer according to claim 1.