Modified conjugated diene-based polymer, method for preparing same, and rubber composition comprising same

Abstract

The present invention relates to a highly branched, high molecular weight modified conjugated diene-based polymer, a method for preparing same, and a rubber composition comprising same, and provides: a modified conjugated diene-based polymer comprising a unit derived from a conjugated diene-based monomer, a unit derived from a branching agent represented by chemical formula 1, and a modification moiety derived from a compound represented by chemical formula 2; a method for preparing same; and a rubber composition comprising same.

Description

Modified conjugated diene polymer, method for manufacturing the same, and rubber composition containing the same

[0001] [Cross-reference with related applications]

[0002] This application claims the benefit of priority based on Korean patent application 10-2024-0195785 filed December 24, 2024, and all contents disclosed in the literature of said Korean patent applications are incorporated herein as part of this specification.

[0003] [Technology Field]

[0004] The present invention relates to a highly branched and high molecular weight modified conjugated diene polymer, a method for manufacturing the same, and a rubber composition containing the same.

[0005]

[0006] Recently, in response to the demand for lower fuel consumption in automobiles, conjugated diene polymers are required as rubber materials for tires that possess low driving resistance, excellent wear resistance and tensile properties, and handling stability characterized by wet road resistance.

[0007] In order to reduce the driving resistance of a tire, there is a method to minimize the hysteresis loss of vulcanized rubber, and indicators for evaluating such vulcanized rubber include rebound elasticity at 50°C to 80°C, tan δ, and Goodrich heat generation. That is, a rubber material with high rebound elasticity at the above temperature or low tan δ and Goodrich heat generation is preferred.

[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. Accordingly, recently, conjugated diene polymers or copolymers such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) are manufactured by emulsion polymerization or solution polymerization and are used as rubber for tires. Among these, the greatest advantage of solution polymerization compared to emulsion polymerization is that the vinyl structure content and styrene content, which define rubber properties, can be arbitrarily controlled, and molecular weight and properties can be controlled through coupling or modification. Therefore, since structural changes in the final manufactured SBR or BR are easy, and chain end movement can be reduced through chain end bonding or modification, and bonding strength with fillers such as silica or carbon black can be increased, SBR produced by solution polymerization is widely used as rubber material for tires.

[0009] When such solution-polymerized SBR is used as a rubber material for tires, increasing the vinyl content within the SBR raises the glass transition temperature of the rubber, thereby allowing for the control of required tire properties such as driving resistance and braking force, as well as reducing fuel consumption 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 modifying agents. For example, U.S. Patent No. 4,397,994 discloses a technique in which active anions at the chain ends of a polymer obtained by polymerizing styrene-butadiene under a non-polar solvent using a monofunctional initiator, alkyl lithium, are bonded using a binder such as a tin compound.

[0010] Meanwhile, carbon black and silica are used as reinforcing fillers for tire treads. When silica is used as a reinforcing filler, it has the advantage of improving low hysteresis loss and wet road resistance. However, silica with a hydrophilic surface has the drawback of poor dispersibility due to its low affinity with rubber compared to carbon black with a hydrophobic surface. Therefore, it is necessary to use a separate silane coupling agent to improve dispersibility or to impart a bond between silica and rubber. Accordingly, methods are being attempted to introduce functional groups with affinity or reactivity with silica to the terminal ends of rubber molecules, but the effect is not sufficient.

[0011] [Prior Art Literature]

[0012] [Patent Literature]

[0013] (Patent Document 1) U.S. Patent No. 4,397,994

[0014]

[0015] The present invention was devised to solve the problems of the prior art described above, and aims to provide a modified conjugated diene polymer that can be applied to a rubber composition to improve compounding processability, tensile properties, and wear resistance by forming a branched structure by a branching agent represented by Formula 1 and modifying it by a compound represented by Formula 2 having a plurality of coupling sites to have a highly branched structure and high molecular weight.

[0016] In addition, the present invention aims to provide a method for manufacturing the modified conjugated diene-based polymer.

[0017] In addition, the present invention aims to provide a rubber composition having improved compounding processability, tensile properties, and wear resistance by including the above-mentioned modified conjugated diene polymer.

[0018]

[0019] According to one embodiment of the present invention for solving the above problems, the present invention provides a modified conjugated diene polymer, a method for manufacturing the same, and a rubber composition comprising the same.

[0020] (1) The present invention provides a modified conjugated diene polymer comprising a unit derived from a conjugated diene monomer; a unit derived from a branching agent represented by the following chemical formula 1; and a modified portion derived from a compound represented by the following chemical formula 2:

[0021] [Chemical Formula 1]

[0022]

[0023] In the above chemical formula 1,

[0024] R a1 It is a single bond or an alkylene group having 1 to 20 carbon atoms, and

[0025] R a2 and R a3 are independently alkylene groups having 1 to 20 carbon atoms, and

[0026] R a4 to R a9 is independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, wherein R a4 to R a6 One or more of and R a7 to R a9 One or more of them are alkoxy groups having 1 to 20 carbon atoms, and

[0027] R a10 It is a hydrogen atom or an alkenyl group having 2 to 10 carbon atoms, and

[0028] [Chemical Formula 2]

[0029]

[0030] In the above chemical formula 2,

[0031] R1 and R2 are independently alkylene groups having 1 to 20 carbon atoms, and

[0032] R3 is a single bond or an alkylene group having 1 to 20 carbon atoms, and

[0033] R4 to R8 are independently alkylene groups having 1 to 20 carbon atoms, and

[0034] A1 to A5 are independently -SiR9R 10 R 11 and, here R9 to R 11 The groups are independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, wherein R9 to R 11 At least one of them is an alkoxy group having 1 to 20 carbon atoms, and

[0035] n is an integer from 2 to 10.

[0036] (2) The present invention, in (1) above, wherein R in Chemical Formula 1 a1 is a single bond or an alkylene group having 1 to 10 carbon atoms, and R a2 and R a3 are independently alkylene groups having 1 to 10 carbon atoms, and R a4 to R a9 is independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, wherein R a4 to R a6 One or more of and R a7 to R a9 One or more of them are alkoxy groups having 1 to 10 carbon atoms, and R a10 It provides a modified conjugated diene polymer that is a hydrogen atom.

[0037] (3) The present invention provides a modified conjugated diene polymer in which, in (1) or (2), the branching agent represented by Formula 1 is one or more selected from compounds represented by Formulas 1-1 to 1-3 below:

[0038] [Chemical Formula 1-1]

[0039]

[0040] [Chemical Formula 1-2]

[0041]

[0042] [Chemical Formula 1-3]

[0043]

[0044] In the above chemical formulas 1-1 to 1-3, Me is a methyl group and Et is an ethyl group.

[0045] (4) In any one of (1) to (3) above, the present invention is such that in Formula 2, R1 and R2 are independently alkylene groups having 1 to 10 carbon atoms, R3 is a single bond or an alkylene group having 1 to 10 carbon atoms, R4 to R8 are independently alkylene groups having 1 to 10 carbon atoms, and A1 to A5 are independently -SiR9R 10 R 11 and, here R9 to R 11 The groups are independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, wherein R9 to R 11 At least one of the groups is an alkoxy group having 1 to 10 carbon atoms, and n is an integer from 2 to 8, providing a modified conjugated diene polymer.

[0046] (5) In any one of (1) to (4) above, the present invention is such that in Formula 2, R1 and R2 are independently alkylene groups having 1 to 6 carbon atoms, R3 is a single bond or an alkylene group having 1 to 6 carbon atoms, R4 to R8 are independently alkylene groups having 1 to 6 carbon atoms, and A1 to A5 are independently -SiR9R 10 R 11 and, here R9 to R 11 The groups are independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, wherein R9 to R 11 At least one of the groups is an alkoxy group having 1 to 6 carbon atoms, and n is an integer from 2 to 6, providing a modified conjugated diene-based polymer.

[0047] (6) The present invention provides a modified conjugated diene polymer in any one of (1) to (5), wherein the compound represented by Formula 2 is one or more selected from the compounds represented by Formulas 2-1 to 2-3 below:

[0048] [Chemical Formula 2-1]

[0049]

[0050] [Chemical Formula 2-2]

[0051]

[0052] [Chemical Formula 2-3]

[0053]

[0054] In the above chemical formulas 2-1 to 2-3, Me is a methyl group.

[0055] (7) The present invention provides a modified conjugated diene polymer, wherein, in any one of (1) to (6), a linear chain portion; and branched chain portions located at both ends of the linear chain portion, the linear chain portion comprises at least two polymer chains comprising units derived from conjugated diene monomers and a modified portion derived from a compound represented by Formula 2, each of the polymer chains is bonded to each other by the modified portion, and the branched chain portion comprises a branching point comprising a unit derived from a branching agent represented by Formula 1 and a branched polymer chain comprising a unit derived from a conjugated diene monomer that is bonded to the branching point.

[0056] (8) The present invention provides a modified conjugated diene polymer having a weight-average molecular weight of 1,500,000 g / mol or more and 4,000,000 g / mol or less in any one of (1) to (7).

[0057] (9) The present invention provides a modified conjugated diene polymer having a molecular weight distribution of 1.0 or more and 5.0 or less in any one of (1) to (8).

[0058] (10) The present invention provides a modified conjugated diene polymer having a Mooney viscosity of 100 or more and 180 or less as measured at 140°C in any one of (1) to (9).

[0059] (11) The present invention provides a modified conjugated diene polymer that further comprises an aromatic vinyl monomer-derived unit in any one of (1) to (10).

[0060] (12) The present invention provides a method for preparing a modified conjugated diene polymer according to any one of (1) to (11), comprising: (S1) polymerizing a conjugated diene monomer, or an aromatic vinyl monomer and a conjugated diene monomer in a hydrocarbon solvent containing an organometallic compound to produce an active polymer bound to an organometallic compound; (S2) reacting the active polymer with a branching agent represented by the following chemical formula 1 to produce a branched active polymer; and (S3) reacting the branched active polymer with a compound represented by the following chemical formula 2.

[0061] [Chemical Formula 1]

[0062]

[0063] In the above chemical formula 1,

[0064] R a1 It is a single bond or an alkylene group having 1 to 20 carbon atoms, and

[0065] R a2 and R a3 are independently alkylene groups having 1 to 20 carbon atoms, and

[0066] R a4 to R a9is independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, wherein R a4 to R a6 One or more of and R a7 to R a9 One or more of them are alkoxy groups having 1 to 20 carbon atoms, and

[0067] R a10 It is a hydrogen atom or an alkenyl group having 2 to 10 carbon atoms, and

[0068] [Chemical Formula 2]

[0069]

[0070] In the above chemical formula 2,

[0071] R1 and R2 are independently alkylene groups having 1 to 20 carbon atoms, and

[0072] R3 is a single bond or an alkylene group having 1 to 20 carbon atoms, and

[0073] R4 to R8 are independently alkylene groups having 1 to 20 carbon atoms, and

[0074] A1 to A5 are independently -SiR9R 10 R 11 and, here R9 to R 11 The groups are independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, wherein R9 to R 11 At least one of them is an alkoxy group having 1 to 20 carbon atoms, and

[0075] n is an integer from 2 to 10.

[0076] (13) The present invention provides a method for producing a modified conjugated diene polymer according to (12), wherein the organometallic compound is used in an amount of 0.01 to 10 mmol per 100 g of total monomer.

[0077] (14) The present invention provides a method for manufacturing a modified conjugated diene polymer, wherein the branching agent represented by the formula 1 in (12) or (13) is used in an amount of 0.1 to 0.9 moles based on 1 mole of the organometallic compound.

[0078] (15) The present invention provides a method for preparing a modified conjugated diene polymer in any one of (12) to (14), wherein the compound represented by Chemical Formula 2 is used in an amount of 0.1 to 5.0 moles based on 1 mole of organometallic compound.

[0079] (16) The present invention provides a method for producing a modified conjugated diene polymer in which, in any one of (12) to (15), the branching agent represented by Formula 1 is one or more selected from compounds represented by Formulas 1-1 to 1-3 below:

[0080] [Chemical Formula 1-1]

[0081]

[0082] [Chemical Formula 1-2]

[0083]

[0084] [Chemical Formula 1-3]

[0085]

[0086] In the above chemical formulas 1-1 to 1-3, Me is a methyl group and Et is an ethyl group.

[0087] (17) The present invention provides a method for preparing a modified conjugated diene polymer, wherein in any one of (12) to (16), the compound represented by Formula 2 is one or more selected from the compounds represented by Formulas 2-1 to 2-3 below:

[0088] [Chemical Formula 2-1]

[0089]

[0090] [Chemical Formula 2-2]

[0091]

[0092] [Chemical Formula 2-3]

[0093]

[0094] In the above chemical formulas 2-1 to 2-3, Me is a methyl group.

[0095] (18) The present invention provides a rubber composition comprising a modified conjugated diene polymer and a filler according to any one of (1) to (11) above.

[0096]

[0097] The modified conjugated diene polymer according to the present invention can have a high molecular weight by introducing a highly branched structure, in which the active polymer end reacts with a branching agent represented by Formula 1 to form a branched structure and is modified into a compound represented by Formula 2 which has many modified functional group sites. Accordingly, it can be applied to a rubber composition to improve the compounding processability of the rubber composition while simultaneously improving tensile properties and wear resistance.

[0098] The rubber composition according to the present invention has excellent compounding processability, tensile properties, and wear resistance by including the modified conjugated diene polymer.

[0099]

[0100] Hereinafter, the present invention will be described in more detail to aid in understanding the invention.

[0101] Terms and words used in the description and claims of the present invention should not be interpreted as being limited to their ordinary or dictionary meanings, but should be interpreted in a meaning and concept consistent with the technical spirit of the present invention, based on the principle that the inventor can appropriately define the concept of the terms to best describe his invention.

[0102]

[0103] Definition of Terms

[0104] In this specification, the term "polymer" refers to a polymer compound produced by polymerizing monomers, whether of the same or different types. Thus, the general term polymer encompasses the term homopolymer, which is commonly used to refer to a polymer produced from a single type of monomer, and the term copolymer, as defined below.

[0105] In this specification, the term 'copolymer' refers to a polymer produced by the polymerization of at least two different monomers. Thus, the general term copolymer includes binary copolymers, which are commonly used to refer to polymers produced from two different monomers, and polymers produced from two or more different monomers.

[0106] In this specification, the term '1,2-vinyl bond content' refers to a mass (or weight) percentage of butadiene contained at the 1,2-position within the polymer chain of the polymer based on the portion derived from the conjugated diene monomer (butadiene, etc.) in the polymer (total amount of polymerized butadiene).

[0107] In this specification, the term 'styrene bond content' refers to the mass (or weight) percentage of styrene contained in the polymer chains of the polymer derived from an aromatic vinyl monomer (styrene, etc.) among the polymers.

[0108] In this specification, the term 'room temperature' means a temperature in its natural state without heating or cooling, and is a temperature of 20±5℃.

[0109] In this specification, the term 'substitution' may mean that a hydrogen of a functional group, atomic group, or compound is substituted with a specific substituent, and when a hydrogen of a functional group, atomic group, or compound is substituted with a specific substituent, one or more substituents may exist depending on the number of hydrogens present in the functional group, atomic group, or compound, and when multiple substituents exist, each substituent may be the same or different from one another.

[0110] In this specification, the term 'alkyl group' may mean a monovalent aliphatic saturated hydrocarbon and may include linear 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.

[0111] In this specification, the term 'alkylene group' may refer to divalent aliphatic saturated hydrocarbons such as methylene, ethylene, propylene, and butylene.

[0112] In this specification, the terms 'derived unit', 'derived repeating unit', and 'derived functional group' may refer to a component, structure, or the substance itself derived from a substance.

[0113] In this specification, the term 'single bond' may refer to a single covalent bond itself that does not include a separate atomic or molecular group.

[0114] In this specification, the terms “comprising,” “having,” and their derivatives are not intended to exclude the presence of any additional components, steps, or procedures, whether or not they are specifically disclosed. To avoid any uncertainty, any composition claimed by the use of the term “comprising” may include any additional additives, adjuvants, or compounds, whether polymers or otherwise, unless otherwise stated. In contrast, the term “essentially composed of” excludes any other components, steps, or procedures from the scope of any subsequent description, except those not essential to operability. The term “composed of” excludes any components, steps, or procedures that are not specifically described or enumerated.

[0115]

[0116] Measurement methods and conditions

[0117] In this specification, 'weight-average molecular weight (Mw)' and 'molecular weight distribution (MWD)' were obtained by measuring the weight-average molecular weight (Mw) and number-average molecular weight (Mn) under the following conditions using a Gel permeation chromatograph (GPC) (PL GPC220, Agilent Technologies), obtaining a molecular weight distribution curve, and calculating the molecular weight distribution (PDI, MWD, Mw / Mn) from each of the measured molecular weights.

[0118] - Columns: Use a combination of two PLgel Olexis columns (Polymer Laboratories) and one PLgel mixed-C column (Polymer Laboratories).

[0119] - Solvent: Use a mixture of 2 wt% amine compound with tetrahydrofuran

[0120] - Flow rate: 1 ml / min

[0121] - Sample concentration: 1–2 mg / ml (diluted in THF)

[0122] - Injection volume: 100 µl

[0123] - Column temperature: 40℃

[0124] - Detector: Refractive index

[0125] - Standard: Polystyrene (corrected by a cubic function)

[0126] In this specification, 'Moony viscosity' was measured using a Mooney viscometer, such as the MV2000E (ALPHA Technologies) Large Rotor, under conditions of 140°C and Rotor Speed ​​2±0.02 rpm. Specifically, after leaving the polymer at room temperature (23±5°C) for at least 30 minutes, 27±3g was taken and filled into the die cavity, and the measurement was taken while applying torque by operating the platen.

[0127]

[0128] Modified conjugated diene polymer

[0129] The present invention provides a modified conjugated diene polymer having a highly branched structure and high molecular weight, which can be applied to a rubber composition to improve its compounding processability, tensile properties, and wear resistance.

[0130] The modified conjugated diene polymer according to one embodiment of the present invention is characterized by comprising: a unit derived from a conjugated diene monomer; a unit derived from a branching agent represented by the following chemical formula 1; and a modified portion derived from a compound represented by the following chemical formula 2.

[0131] [Chemical Formula 1]

[0132]

[0133] In the above chemical formula 1, R a1 is a single bond or an alkylene group having 1 to 20 carbon atoms, and R a2 and R a3 are independently alkylene groups having 1 to 20 carbon atoms, and R a4 to Ra9 is independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, wherein R a4 to R a6 One or more of and R a7 to R a9 One or more of them are alkoxy groups having 1 to 20 carbon atoms, and R a10 It is a hydrogen atom or an alkenyl group having 2 to 10 carbon atoms, and

[0134] [Chemical Formula 2]

[0135]

[0136] In the above Chemical Formula 2, R1 and R2 are independently alkylene groups having 1 to 20 carbon atoms, R3 is a single bond or an alkylene group having 1 to 20 carbon atoms, R4 to R8 are independently alkylene groups having 1 to 20 carbon atoms, and A1 to A5 are independently -SiR9R 10 R 11 and, here R9 to R 11 The groups are independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, wherein R9 to R 11 At least one of them is an alkoxy group having 1 to 20 carbon atoms, and n is an integer from 2 to 10.

[0137] Specifically, in the above Chemical Formula 1, R a1 is a single bond or an alkylene group having 1 to 10 carbon atoms, and R a2 and R a3 are independently alkylene groups having 1 to 10 carbon atoms, and R a4 to R a9 is independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, wherein R a4 to R a6 One or more of and R a7 to R a9 One or more of them are alkoxy groups having 1 to 10 carbon atoms, and R a10It can be a hydrogen atom.

[0138] More specifically, in the above Chemical Formula 1, R a1 is an alkylene group having 1 to 6 carbon atoms, and R a2 and R a3 are independently alkylene groups having 1 to 6 carbon atoms, and R a4 to R a9 is independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, wherein R a4 to R a6 One or more of and R a7 to R a9 One or more of them are alkoxy groups having 1 to 6 carbon atoms, and R a10 It can be a hydrogen atom.

[0139] More specifically, the branching agent represented by the above chemical formula 1 may be one or more selected from the compounds represented by the following chemical formulas 1-1 to 1-3.

[0140] [Chemical Formula 1-1]

[0141]

[0142] [Chemical Formula 1-2]

[0143]

[0144] [Chemical Formula 1-3]

[0145]

[0146] In the above chemical formulas 1-1 to 1-3, Me is a methyl group and Et is an ethyl group.

[0147]

[0148] Meanwhile, the branching agent represented by the above chemical formula 1 may be produced from a manufacturing method comprising the step of reacting a compound represented by the following chemical formula 3 with a compound represented by the chemical formula 4.

[0149] [Chemical Formula 3]

[0150]

[0151] [Chemical Formula 4]

[0152]

[0153] In the above chemical formulas 3 and 4, R b1 is a single bond or an alkylene group having 1 to 20 carbon atoms, and R b2 and R b3 ☐ are independently alkylene groups having 1 to 20 carbon atoms, and R b4 to R b9 is independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, wherein R b4 to R b6 One or more of and R b7 to R b9 One or more of them are alkoxy groups having 1 to 20 carbon atoms, and R b10 It can be a hydrogen atom or an alkenyl group having 2 to 10 carbon atoms.

[0154] In the above, the reaction of Chemical Formula 3 and Chemical Formula 4 can be carried out in a reaction solvent under basic conditions at a temperature of 80°C or higher, specifically at a temperature of 100°C to 200°C or 120°C to 180°C, and in this case, the reaction conversion rate may be superior, which may be advantageous for improving the yield.

[0155] The above basic conditions can be composed using a basic compound, and the basic compound can be any tertiary amine compound commonly used in the art without special limitation, but for example, triethylamine, diisopropylamine, or a mixture thereof can be used.

[0156] In addition, the compound represented by Chemical Formula 3 and the compound represented by Chemical Formula 4 may be reacted in an appropriate ratio according to the stoichiometric ratio, but specifically, they may be reacted in a molar ratio of 1:1 to 5. In this case, the reaction rate can be improved without excessive residual material.

[0157] In addition, in the above Chemical Formula 2, R1 and R2 are independently alkylene groups having 1 to 10 carbon atoms, R3 is a single bond or an alkylene group having 1 to 10 carbon atoms, R4 to R8 are independently alkylene groups having 1 to 10 carbon atoms, and A1 to A5 are independently -SiR9R 10 R 11 and, here R9 to R 11 The groups are independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, wherein R9 to R 11 At least one of them is an alkoxy group having 1 to 10 carbon atoms, and n can be an integer from 2 to 8.

[0158] More specifically, in the above Chemical Formula 2, R1 and R2 are independently alkylene groups having 1 to 6 carbon atoms, R3 is a single bond or an alkylene group having 1 to 6 carbon atoms, R4 to R8 are independently alkylene groups having 1 to 6 carbon atoms, and A1 to A5 are independently -SiR9R 10 R 11 and, here R9 to R 11 The groups are independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, wherein R9 to R 11 At least one of them is an alkoxy group having 1 to 6 carbon atoms, and n can be an integer from 2 to 6.

[0159] More specifically, the compound represented by the above chemical formula 2 may be one or more selected from the compounds represented by the following chemical formulas 2-1 to 2-3.

[0160] [Chemical Formula 2-1]

[0161]

[0162] [Chemical Formula 2-2]

[0163]

[0164] [Chemical Formula 2-3]

[0165]

[0166] In the above chemical formulas 2-1 to 2-3, Me is a methyl group.

[0167] Meanwhile, the compound represented by the above chemical formula 2 may be produced from a manufacturing method comprising the step of reacting a compound represented by the following chemical formula 5 with a compound represented by the chemical formula 6.

[0168] [Chemical Formula 5]

[0169]

[0170] In the above chemical formula 5, R 12 and R 13 ☐ are independently alkylene groups having 1 to 20 carbon atoms, and R 14 is a single bond or an alkylene group having 1 to 20 carbon atoms, and m is an integer from 2 to 10, and

[0171] [Chemical Formula 6]

[0172]

[0173] In the above chemical formula 6,

[0174] R 15 is an alkylene group having 1 to 20 carbon atoms, and R 16 to R 18 is independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, wherein R 16 to R 18 At least one of them is an alkoxy group having 1 to 20 carbon atoms, and X is a halogen element.

[0175] The above reaction can be carried out under basic conditions in a reaction solvent at a temperature of 120°C or higher, specifically at a temperature of 120°C to 200°C or 140°C to 180°C, in which case the reaction conversion rate may be superior, which may be advantageous for improving the yield.

[0176] The above basic conditions can be composed using a basic compound, and the basic compound can be any tertiary amine compound commonly used in the art without special limitation, but for example, triethylamine, diisopropylamine, or a mixture thereof can be used.

[0177] In addition, the above reaction may further utilize potassium iodide (KI), potassium bromide (KBr), or a mixture thereof acting as a catalyst as needed; in this case, it may be advantageous to achieve a smoother target reaction by increasing reaction activity and improving the reaction rate.

[0178] In addition, the compound represented by Chemical Formula 5 and the compound represented by Chemical Formula 6 may be reacted in an appropriate ratio according to the stoichiometric ratio, but specifically, they may be reacted in a molar ratio of 1:4 to 8. In this case, the reaction rate can be improved without excessive residual material.

[0179] In addition, in the above chemical formula 5, R 12 and R 13 ☐ are independently alkylene groups having 1 to 10 carbon atoms, and R 14 is a single bond or an alkylene group having 1 to 10 carbon atoms, and m may be an integer from 2 to 8. Specifically, R 12 and R 13 ☐ are independently alkylene groups having 1 to 6 carbon atoms, and R 14 is a single bond or an alkylene group having 1 to 6 carbon atoms, and m can be an integer from 2 to 6.

[0180] In addition, in the above chemical formula 6, R 15 is an alkylene group having 1 to 10 carbon atoms, and R 16 to R 18 ☐ are independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, wherein R 16 to R 18At least one of them is an alkoxy group having 1 to 10 carbon atoms, and X may be a halogen element. Here, the halogen element may be Br, Cl, I, or F.

[0181] Specifically, in the above chemical formula 6, R 15 is an alkylene group having 1 to 6 carbon atoms, and R 16 to R 18 is independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, wherein R 16 to R 18 At least one of them is an alkoxy group having 1 to 6 carbon atoms, and X may be Cl.

[0182] As another example, a modified conjugated diene polymer according to one embodiment of the present invention may comprise a linear chain portion; and branched chain portions located at both ends of the linear chain portion, wherein the linear chain portion comprises at least two polymer chains comprising units derived from a conjugated diene monomer and a modified portion derived from a compound represented by Formula 2, each of the polymer chains being bonded to each other by the modified portion, and the branched chain portion may comprise a branching point comprising a unit derived from a branching agent represented by Formula 1 and a branched polymer chain comprising a unit derived from a conjugated diene monomer that is bonded to the branching point.

[0183] For example, the modified conjugated diene polymer according to one embodiment of the present invention may have a bonding structure represented by the following chemical formula 7.

[0184] [Chemical Formula 7]

[0185]

[0186] In the above Chemical Formula 7, P represents a linear chain portion; A represents a branching point; and B represents a branched polymer chain. The linear chain portion includes a polymer chain containing a unit derived from a conjugated diene monomer and a modified portion derived from a compound represented by Chemical Formula 2. In this case, the polymer chain may be coupled and bonded to each other by the modified portion derived from a compound represented by Chemical Formula 2. Additionally, when the modified conjugated diene polymer according to one embodiment of the present invention includes a unit derived from an aromatic vinyl monomer, the unit derived from the aromatic vinyl monomer may constitute the polymer chain together with the unit derived from the conjugated diene monomer.

[0187] In addition, branching points may be located at both ends of the linear chain portion, and branched polymer chains may extend from the branching points to form a branched structure. Here, the branching points are units derived from a branching agent represented by Chemical Formula 1, and the branched polymer chains may be units derived from conjugated diene monomers or polymer chains comprising units derived from conjugated diene monomers and aromatic vinyl monomers that are bonded to the units derived from the branching agent to form chains that extend in a direction distinct from the linear chain portion.

[0188] In addition, the branched polymer chains can be formed in proportion to the number of alkoxy groups in the branching agent represented by Chemical Formula 1, and, for example, as the number of alkoxy groups in the branching agent represented by Chemical Formula 1 increases, the number of branched polymer chains can also increase.

[0189] In addition, depending on the case, the branching agent represented by the above chemical formula 1 may also serve as a denaturing agent.

[0190] The structure of the modified conjugated diene polymer according to one embodiment of the present invention as described above is formed by manufacturing a method described below, and may have such a structure through a reaction such as the reaction scheme 1 below, for example.

[0191] [Reaction Equation 1]

[0192]

[0193] In the above reaction scheme 1, M is a modified part derived from a compound represented by chemical formula 2, and It is a polymer chain.

[0194]

[0195] As described above, the modified conjugated diene polymer according to the present invention forms a branched structure by a branching agent represented by Formula 1 and is modified into a compound represented by Formula 2 that provides a plurality of coupling sites. In this way, the polymer is modified by introducing a modified portion, which is a filler-affinity functional group derived from the compound represented by Formula 2, into the polymer chain along with the branching of the polymer chain and increased coupling bonds between polymer chains, thereby greatly increasing the affinity with the filler. When applied to a rubber composition, it can improve compounding processability, tensile properties, and wear resistance.

[0196]

[0197] In addition, the modified conjugated diene polymer has units derived from conjugated diene monomers as its main units, and the conjugated diene monomer may include a hydrocarbon compound having a conjugated molecular structure in which single bonds and double bonds (or multiple bonds) are alternately connected and having two double bonds within the molecule. In addition, the conjugated diene monomer may be one or more selected from the group consisting of, for example, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, 2-phenyl-1,3-butadiene, 2-halo-1,3-butadiene (halo means halogen atom), 1,3-pentadiene, 1-methyl-1,3-pentadiene, 1,3-hexadiene, and 4,5-diethyl-1,3-octadiene.

[0198] In addition, the modified conjugated diene-based polymer may further include aromatic vinyl monomers in addition to conjugated diene monomers, and may further include units derived therefrom. Examples of the aromatic vinyl monomers include styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, ethylstyrene, t-butylstyrene, 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 It may be one or more selected from the group consisting of ethyl)-α-methylstyrene (3-(2-pyrrolidino-1-methyl ethyl)-α-methylstyrene).

[0199] As another example, the modified conjugated diene-based polymer may be a copolymer further comprising repeating units derived from a diene monomer having 1 to 10 carbon atoms together with repeating units derived from the conjugated diene monomer. The repeating units derived from the diene monomer may be repeating units 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 conjugated diene-based polymer is a copolymer further comprising a diene monomer, the conjugated diene-based polymer may contain repeating units derived from the diene monomer in an amount greater than 0 weight% to 1 weight%, greater than 0 weight% to 0.1 weight%, greater than 0 weight% to 0.01 weight%, or greater than 0 weight% to 0.001 weight%, and within this range, it has the effect of preventing gel formation.

[0200] According to one embodiment of the present invention, when two or more monomers are included in the chain of the conjugated diene-based polymer, the chain structure may have an intermediate form between a random copolymer and a block copolymer, and in this case, the control of the microstructure may be easy, and thus there is an effect of excellent balance between each physical property. The random copolymer may mean that the repeating units forming the copolymer are arranged in a disordered manner.

[0201]

[0202] According to one embodiment of the present invention, the modified conjugated diene polymer may have a weight-average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 1,500,000 g / mol to 4,000,000 g / mol, 1,600,000 g / mol to 3,500,000 g / mol, 1,700,000 g / mol to 3,000,000 g / mol, or 1,800,000 g / mol to 2,500,000 g / mol, and within this range, it is applied to a rubber composition to have excellent compounding processability and the effect of improving wear resistance.

[0203] In addition, the modified conjugated diene polymer may have a molecular weight distribution of 1.0 to 5.0, and specifically, 1.5 to 4.0, 1.7 to 3.0, or 2.0 to 2.8.

[0204] In addition, the modified conjugated diene polymer according to one embodiment of the present invention may have a Mooney viscosity at 140°C measured under ASTM D1646 conditions of 100 or more and 180 or less, specifically 105 to 175, 110 to 170, 115 to 165, 120 to 160, or 130 to 150. Although there may be various measures to evaluate processability, processability may be significantly excellent when the Mooney viscosity satisfies the above range.

[0205] In addition, the modified conjugated diene polymer may have a vinyl content of 5% or more by weight, 10% or more by weight, or 10% to 60% by weight, and within this range, the glass transition temperature can be controlled to an appropriate range, thereby having excellent rolling resistance, wet road resistance, and low fuel consumption. Here, the vinyl content may refer to the content of a 1,2-added conjugated diene monomer rather than a 1,4-added conjugated diene monomer with respect to 100% by weight of a conjugated diene copolymer composed of a monomer having a vinyl group and an aromatic vinyl monomer.

[0206]

[0207] Method for manufacturing a modified conjugated diene polymer

[0208] In addition, the present invention provides a method for manufacturing the modified conjugated diene-based polymer.

[0209] A method for preparing the modified conjugated diene polymer according to one embodiment of the present invention comprises: (S1) a step of preparing an active polymer to which an organometal 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) a step of preparing a branched active polymer by reacting the active polymer with a branching agent represented by the following chemical formula 1 (Step 2); and (S3) a step of reacting the branched active polymer with a compound represented by the following chemical formula 2 (Step 3).

[0210] [Chemical Formula 1]

[0211]

[0212] [Chemical Formula 2]

[0213]

[0214] The definitions for each substituent of Chemical Formula 1 and Chemical Formula 2 above are as previously defined.

[0215]

[0216] Step 1 above is a step for preparing an active polymer combined with an organometallic compound, which 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.

[0217] The above hydrocarbon solvent is not particularly limited, but may be one or more selected from the group consisting of, for example, n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene, and xylene.

[0218] The above conjugated diene monomers and aromatic vinyl monomers are as previously defined.

[0219]

[0220] According to one embodiment of the present invention, the organometallic compound may 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.

[0221] The above organometallic compound may be, for example, one or more 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-eicosillithium, 4-butylphenyl lithium, 4-tolylithium, 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 isopropylamide.

[0222] Meanwhile, the polymerization of step 1 above may be carried out including a polar additive, and the polar additive may be added in an amount of 0.001 to 50g, 0.001 to 10g, 0.005 to 0.2g, or 0.01 to 0.2g based on 100g of total monomer.

[0223] In addition, the polar additive may be one or more selected from the group consisting of tetrahydrofuran, 2,2-di(tetrahydrofuryl)propane, diethyl ether, cyclopentyl ether, dipropyl ether, ethylenedimethyl ether, diethyl glycol, dimethyl ether, tertiary butoxyethoxyethane, bis(3-dimethylaminoethyl) ether, (dimethylaminoethyl)ethyl ether, trimethylamine, triethylamine, tripropylamine, and tetramethylethylenediamine, and specifically, it may be triethylamine or tetramethylethylenediamine. When the polar additive is included, it has the effect of inducing the easy formation of a random copolymer by compensating for the difference in reaction rates between conjugated diene monomers, or conjugated diene monomers and aromatic vinyl monomers when copolymerizing them.

[0224] 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 end by a growth polymerization reaction by anion. In addition, the polymerization of Step 1 above may be thermal polymerization, isothermal polymerization, or constant-temperature polymerization (adiabatic polymerization). The constant-temperature polymerization may refer to a polymerization method that includes a step of polymerizing using the heat of reaction itself without arbitrarily applying heat after adding the organometallic compound; the thermal polymerization may refer to a polymerization method that increases the temperature by arbitrarily applying heat after adding the organometallic compound; and the isothermal polymerization may refer to a polymerization method that maintains a constant temperature of the polymer by increasing the heat or removing heat after adding the organometallic compound.

[0225] In addition, the polymerization of step 1 above may be carried out in a temperature range of, for example, -20°C to 80°C, 0°C to 80°C, 10°C to 80°C, or 10°C to 70°C.

[0226] The active polymer prepared by Step 1 above may refer to a polymer in which a polymer anion and an organometallic cation are combined.

[0227]

[0228] Step 2 above is a step for preparing a branched active polymer by forming a branched structure in the active polymer, and may be performed by reacting the active polymer with a branching agent represented by Chemical Formula 1.

[0229] Here, the branching agent represented by the above chemical formula 1 may be used in an amount of 0.1 to 0.9 moles based on 1 mole of the organometallic compound, and specifically, may be used in an amount of 0.13 to 0.50 moles based on 1 mole of the organometallic compound.

[0230] In addition, the branching agent represented by Chemical Formula 1 can be added to the reaction in a controlled manner according to the polymerization conversion rate of Step 1, and in this case, the length of the polymer chains of the branched structure and the linear structure can be controlled. For example, the length of the polymer chains of the linear structure may be very short, or a star structure without polymer chains of the linear structure may be formed.

[0231] In addition, step 2 above may further include the step of adding a monomer and re-polymerizing after the reaction of the branching agent represented by Chemical Formula 1 and the active polymer.

[0232] Step 3 above is a step of reacting the branched active polymer with the compound represented by Formula 2 above in order to prepare a modified conjugated diene-based polymer.

[0233] According to one embodiment of the present invention, the compound represented by Chemical Formula 2 can 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.

[0234] In addition, according to one embodiment of the present invention, the compound represented by Formula 2 can be used in an amount of 0.1 to 5.0 moles, 0.1 to 4.0 moles, 0.1 to 3.0 moles, or 0.1 to 2.0 moles based on 1 mole of the organometallic compound, and a modification reaction with optimal performance can be performed within this range, thereby obtaining a high molecular weight conjugated diene polymer.

[0235]

[0236] The reaction of step 2 above is a modification reaction to introduce a functional group derived from the modification agent into the active polymer, and may be carried out at 0°C to 90°C for 1 minute to 5 hours.

[0237] In addition, according to one embodiment of the present invention, the method for producing the modified conjugated diene polymer may be carried out by a batch method or a continuous polymerization method comprising one or more reactors.

[0238] The above method for manufacturing a modified conjugated diene-based polymer may, for example, follow step 2 of the present invention and, if necessary, further include one or more steps among the solvent and unreacted monomer recovery and drying steps.

[0239]

[0240] Rubber composition

[0241] Furthermore, the present invention provides a rubber composition comprising the modified conjugated diene polymer.

[0242] The rubber composition according to one embodiment of the present invention may contain the modified conjugated diene polymer in an amount of 10% or more by weight, 10% to 100% by weight, or 20% to 90% by weight, and within this range, mechanical properties such as tensile strength and wear resistance are excellent, and there is an effect of excellent balance between each property.

[0243] In addition, the rubber composition may further include other rubber components as needed in addition to the modified conjugated diene polymer, wherein the rubber components may be included in an amount of 90% by weight or less relative to the total weight of the rubber composition. As a specific example, the other rubber components may be included in an amount of 1 to 900 parts by weight per 100 parts by weight of the modified conjugated diene polymer.

[0244] The above rubber component may be, for example, natural rubber or synthetic rubber, and specifically examples include natural rubber (NR) containing cis-1,4-polyisoprene; modified natural rubber such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber, which are obtained by modifying or purifying the above general natural rubber; It may be 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, butyl halogenated rubber, etc., and any one or more of these may be used.

[0245] The above rubber composition may, for example, comprise 0.1 to 200 parts by weight, or 10 to 120 parts by weight, of a filler per 100 parts by weight of the modified conjugated diene-based polymer of the present invention. The filler may, for example, be a silica-based filler, and specific examples may include wet silica (hydrated silica), dry silica (anhydrous silica), calcium silicate, aluminum silicate, or colloidal silica, and preferably, it may be wet silica, which has the best effect of improving fracture characteristics and achieving the same effect as wet grip. In addition, the above rubber composition may further comprise a carbon black-based filler as needed.

[0246] As another example, when silica is used as the above-mentioned filler, a silane coupling agent may be used together to improve reinforcement and low heat generation, and as specific examples, the above-mentioned silane coupling agent is 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. It may be 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 any one or a mixture of two or more of these may be used. Preferably, considering the effect of improving reinforcement, it may be bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide.

[0247] In addition, since the rubber composition according to one embodiment of the present invention uses a modified conjugated diene polymer in which a functional group with high affinity for silica is introduced to the active site as a rubber component, the amount of 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 per 100 parts by weight of silica, and within this range, the effect as a coupling agent is sufficiently exhibited while preventing gelation of the rubber component.

[0248] The rubber composition according to one embodiment of the present invention may be sulfur-crosslinkable and may further include a vulcanizing agent. Specifically, the vulcanizing agent may be sulfur powder and may be included in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the rubber component, and within this range, the necessary elastic modulus and strength of the vulcanized rubber composition are secured while having excellent low fuel consumption.

[0249] In addition to the above-mentioned components, the rubber composition according to one embodiment of the present invention may further include various additives commonly used in the rubber industry, specifically vulcanization accelerators, process oils, plasticizers, anti-aging agents, anti-scotch agents, zinc white, stearic acid, thermosetting resins, or thermoplastic resins.

[0250] The above vulcanization accelerator may be 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 (diphenylguanidine), and may be included in an amount of 0.1 to 5 parts by weight per 100 parts by weight of rubber component.

[0251] The above process oil acts as a softening agent within the rubber composition and may be, for example, a paraffinic, naphthenic, or aromatic compound; aromatic process oil may be used when considering tensile strength and wear resistance, while naphthenic or paraffinic process oil may be used when considering hysteresis loss and low-temperature characteristics. The above process oil may be included, for example, in an amount of 100 parts by weight or less per 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.

[0252] The above 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 condensation product 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 rubber component.

[0253] 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 formulation, and a rubber composition with low heat generation and excellent wear resistance can be obtained by a vulcanization process after molding.

[0254] Accordingly, the above rubber composition can be useful for manufacturing various components of a tire, such as tire treads, undertreads, sidewalls, carcass coating rubber, belt coating rubber, bead fillers, choppers, or bead coating rubber, or various industrial rubber products such as anti-vibration rubber, belt conveyors, and hoses.

[0255]

[0256] In addition, the present invention provides a tire manufactured using the above rubber composition.

[0257] The above tire may include a tire or a tire tread.

[0258]

[0259] Examples

[0260] Hereinafter, the present invention will be described in detail with reference to examples in order to specifically explain the invention. However, the embodiments according to the present invention may be modified in various different forms, and the scope of the present invention should not be interpreted as being limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the invention to those with average knowledge in the art.

[0261] Preparation Example 1

[0262] 10 g (65.5 mmol) of 1-chloromethyl-4-vinylbenzene, 23.5 g (68.5 mmol) of bis(3-(trimethoxysilyl)propyl)amine, and 13.7 ml of triethylamine were reacted at 120°C for 6 hours while stirring. After the reaction was complete, the solvent was removed by vacuum distillation, 50 ml of hexane was added, and the mixture was stirred for 15 minutes. Solid byproducts were removed using a Celite filler, and the solution and impurities were removed by vacuum distillation to produce a pale yellow oil, which is a branching agent represented by Chemical Formula 1-1. The prepared branching agent 1 It was confirmed to have been synthesized through H NMR analysis.

[0263] [Chemical Formula 1-1]

[0264]

[0265] In the above chemical formula 1-1, Me is a methyl group.

[0266] 1 H NMR (500 MHz, CDCl3) δ 7.35-7.26 (m, 4H), 6.70 (dd, J=17.6, 10.9 Hz, 1H), 5.71 (d, J=17.6 Hz, 1H), 5.0 (d, J=10.9 Hz, 1H), 3.57 (s, 2H), 3.54 (s, 18H), 2.46-2.36 (m, 4H), 1.60-1.48 (m, 4H), 0.63-0.56 (m, 4H).

[0267]

[0268] Preparation Example 2

[0269] 10 g (65.5 mmol) of 1-chloromethyl-4-vinylbenzene, 29.3 g (68.8 mmol) of bis(3-(triethoxysilyl)propyl)amine, and 13.7 ml of triethylamine were reacted at 120°C for 6 hours while stirring. After the reaction was complete, the solvent was removed by vacuum distillation, 50 ml of hexane was added, and the mixture was stirred for 15 minutes. Solid byproducts were removed using a Celite filler, and the solution and impurities were removed by vacuum distillation to produce a pale yellow oil, which is a branching agent represented by Chemical Formula 1-2. The prepared branching agent 1 It was confirmed to have been synthesized through H NMR analysis.

[0270] [Chemical Formula 1-2]

[0271]

[0272] In the above chemical formula 1-2, Et is a methyl group.

[0273] 1 H NMR (500 MHz, CDCl3) δ 7.35-7.26 (m, 4H), 6.70 (dd, J=17.6, 10.9 Hz, 1H), 5.71 (d, J=17.6 Hz, 1H), 5.28-5.14 (m, 1H), 3.84-3.75 (m, 12H), 3.54 (s, 2H), 2.46-2.36 (m, 4H), 1.56 (dt, J=15.9, 8.1 Hz, 4H), 1.22 (q, J=7.2 Hz, 18H), 0.64-0.52 (m, 4H).

[0274]

[0275] Preparation Example 3

[0276] 10 g (65.5 mmol) of 1-chloromethyl-4-vinylbenzene, 25.2 g (70.6 mmol) of bis(3-(diethoxy(methyl)silyl)propyl)amine), and 13.7 ml of triethylamine were reacted at 120°C for 6 hours while stirring. After the reaction was complete, the solvent was removed by vacuum distillation, 50 ml of hexane was added, and the mixture was stirred for 15 minutes. Solid byproducts were removed using a Celite filler, and the solution and impurities were removed by vacuum distillation to produce a pale yellow oil, which is a branching agent represented by Chemical Formula 1-3. The prepared branching agent 1 It was confirmed to have been synthesized through H NMR analysis.

[0277] [Chemical Formula 1-3]

[0278]

[0279] In the above chemical formula 1-3, Me is a methyl group and Et is an ethyl group.

[0280] 1 H NMR (500 MHz, CDCl3) δ 7.25 (d, J=8.1 Hz, 2H), 7.19 (d, J=8.2 Hz, 2H). 6.62 (dd, J=17.6, 10.9 Hz, 1H), 5.63 (dd, J=17.6, 0.6 Hz, 1H), 5.15-5.06 (m, 1H), 3.67-3.62 (m, 8H), 3.45 (s, 2H), 2.36-2.27 (m, 4H), 1.46-1.37 (m, 4H), 1.11 (t, J=7.0 Hz, 12H), 0.50-0.40 (m, 4H), -0.00 (s. 6H).

[0281]

[0282] Preparation Example 4

[0283] N 1 -(2-aminoethyl)-N 21.89 g (10 mmol) of -(2-((2-aminoethyl)amino)ethyl)ethane-1,2-diamine, 17.8 g (90 mmol) of (3-chloropropyl)trimethoxysilane, 166 mg (1 mmol) of potassium iodide, and 10.1 g (100 mmol) of triethylamine were reacted at 60°C for 3 days while stirring. After the reaction was complete, the temperature was lowered to room temperature, 50 ml of a mixture of diethyl ether and hexane (1:1 volume ratio) was added, and the mixture was stirred for 15 minutes. Solid byproducts were removed using a Celite filter, and the solution and impurities were removed by vacuum distillation to prepare a light brown oil, represented by Chemical Formula 2-2. The prepared compound is 1 It was confirmed to have been synthesized through H NMR analysis.

[0284] [Chemical Formula 2-2]

[0285]

[0286] In the above chemical formula 2-2, Me is a methyl group.

[0287] 1 H NMR (500 MHz, CDCl3) δ 3.58 (s, 63H), 2.54-2.44 (m, 30H), 1.60-1.50 (m, 14H), 0.64-0.59 (m, 14H).

[0288]

[0289] Preparation Example 5

[0290] N 1 ,N 1' -(ethane-1,2-diyl)bis(N 2232.4 g (10 mmol) of (2-aminoethyl)ethane-1,2-diamine), 19.8 g (80 mmol) of (3-chloropropyl)trimethoxysilane, 166 mg (1 mmol) of potassium iodide, and 11.1 g (110 mmol) of triethylamine were reacted at 60°C for 3 days while stirring. After the reaction was complete, the temperature was lowered to room temperature, 50 ml of a mixture of diethyl ether and hexane (1:1 volume ratio) was added, and the mixture was stirred for 15 minutes. Solid byproducts were removed using a Celite filter, and the solution and impurities were removed by vacuum distillation to prepare a light brown oil compound represented by Chemical Formula 2-3. The prepared compound 1 It was confirmed to have been synthesized through H NMR analysis.

[0291] [Chemical Formula 2-3]

[0292]

[0293] In the above chemical formula 2-3, Me is a methyl group.

[0294] 1 H NMR (500 MHz, CDCl3) δ 3.49 (s, 72H), 2.45-2.33 (m, 36H), 1.50-1.46 (m, 16H), 0.55-0.50 (m, 16H).

[0295]

[0296] Example 1

[0297] 4,812.0 g of n-hexane, 260.0 g of styrene, 710.0 g of 1,3-butadiene, and 0.3 g of 2,2-di(tetrahydrofuran)propane (DTP) as a polar additive were added to a 20 L autoclave reactor, followed by the addition of 4.0 g of n-butyllithium (10 wt% in n-hexane), the internal temperature of the reactor was adjusted to 40°C, and an adiabatic heating reaction was carried out. After 10 minutes, 0.3 g of the branching agent represented by Chemical Formula 1-1 prepared in Preparation Example 1 was added and the reaction was carried out for 10 minutes. Subsequently, 37.0 g of 1,3-butadiene was added to cap the polymer ends with butadiene. Subsequently, 0.9 g of the compound represented by Formula 2-2 prepared in Preparation Example 4 was added as a modifying agent and reacted for 40 minutes ([DTP]:[act. Li]=0.51:1 molar ratio, [branching agent]:[act. Li]=0.30:1 molar ratio, [modifying agent]:[act. Li]=0.20:1 molar ratio). Afterward, the reaction was stopped using ethanol, and 17 g of a solution in which the antioxidant Wingstay K was dissolved in hexane at 30 wt% was added. The resulting polymer was placed in hot water heated with steam and stirred to remove the solvent, and then roll-dried to remove the remaining solvent and water to produce a modified styrene-butadiene copolymer.

[0298]

[0299] Example 2

[0300] A modified styrene-butadiene copolymer was prepared in the same manner as in Example 1, except that the branching agent represented by Formula 1-2 prepared in Preparation Example 2 was used instead of the branching agent represented by Formula 1-1 in Example 1, and the compound represented by Formula 2-3 prepared in Preparation Example 5 was used instead of the compound represented by Formula 2-2 as the modifying agent ([DTP]:[act. Li]=0.51:1 molar ratio, [branching agent]:[act. Li]=0.30:1 molar ratio, [modifying agent]:[act. Li]=0.20:1 molar ratio).

[0301]

[0302] Example 3

[0303] A modified styrene-butadiene copolymer was prepared in the same manner as in Example 1, except that the branching agent represented by Formula 1-3 prepared in Preparation Example 3 was used instead of the branching agent represented by Formula 1-1 in Example 1 ([DTP]:[act. Li]=0.52:1 molar ratio, [branching agent]:[act. Li]=0.20:1 molar ratio, [modifying agent]:[act. Li]=0.20:1 molar ratio).

[0304]

[0305] Example 4

[0306] A modified styrene-butadiene copolymer was prepared in the same manner as in Example 1, except that the branching agent represented by Formula 1-3 prepared in Preparation Example 3 was used instead of the branching agent represented by Formula 1-1 in Example 1, and the compound represented by Formula 2-3 prepared in Preparation Example 5 was used instead of the compound represented by Formula 2-2 as the modifying agent ([DTP]:[act. Li]=0.51:1 molar ratio, [branching agent]:[act. Li]=0.30:1 molar ratio, [modifying agent]:[act. Li]=0.20:1 molar ratio).

[0307]

[0308] Comparative Example 1

[0309] 4,729.0 g of n-hexane, 160.0 g of styrene, 798.0 g of 1,3-butadiene, and 0.40 g of 2,2-di(tetrahydrofuran)propane (DTP) as a polar additive were added to a 20 L autoclave. Subsequently, 4.5 g of n-butyllithium (10 wt% in n-hexane) was added, the internal temperature of the reactor was adjusted to 40°C, and an adiabatic heating reaction was carried out. After 10 minutes, 42.0 g of 1,3-butadiene was added to cap the polymer ends with butadiene. Afterward, SiCl4 was added as a modifying agent and the reaction was carried out for 40 minutes ([DTP]:[act. Li]=0.43:1 molar ratio, [modifying agent]:[act. Li]=0.48:1 molar ratio). Subsequently, the reaction was stopped using ethanol, and 17 g of a solution in which the antioxidant Wingstay K was dissolved in hexane at 30 wt% was added. The resulting polymer was placed in hot water heated with steam and stirred to remove the solvent, and then roll-dried to remove the remaining solvent and water to produce a modified styrene-butadiene copolymer.

[0310]

[0311] Comparative Example 2

[0312] A modified styrene-butadiene copolymer was prepared by carrying out the same procedure as in Example 1, except that N-methyl-3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propane-1-amine was used instead of SiCl4 in Comparative Example 1 above ([DTP]:[act. Li]=0.43:1 molar ratio, [modifier]:[act. Li]=0.35:1 molar ratio).

[0313]

[0314] Experimental Example 1. Evaluation of Polymer Characteristics

[0315] For each modified styrene-butadiene copolymer prepared in the above examples and comparative examples, the styrene unit content and vinyl content within the polymer, and the weight-average molecular weight (Mw, ×10⁻¹⁰) were respectively 3 g / mol), number average molecular weight (Mn, ×10⁻⁶) 3g / mol), molecular weight distribution (MWD), and Mooney viscosity (MV) were measured, respectively.

[0316] 1) Styrene bond content and 1,2-vinyl bond content

[0317] The styrene bond content (SM) and 1,2-vinyl bond content (Vi) in each polymer were measured and analyzed using Varian VNMRS 500 MHz NMR. For NMR measurements, 1,1,2,2-tetrachloroethane was used as the solvent, and the solvent peak was calculated as 6.00 ppm. The styrene unit bond content and 1,2-vinyl bond content were calculated by using peaks of 7.2–6.9 ppm as random styrene, 6.9–6.2 ppm as blocked styrene, 5.8–5.1 ppm as 1,4-vinyl and 1,2-vinyl, and 5.1–4.5 ppm as 1,2-vinyl.

[0318]

[0319] 2) Weight-average molecular weight (Mw, ×10⁻¹⁰) 3 g / mol), number average molecular weight (Mn, ×10⁻⁶) 3 g / mol) and molecular weight distribution (MWD)

[0320] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) were measured under the following conditions using gel permeation chromatography (GPC) (PL GPC220, Agilent Technologies), respectively, and the molecular weight distribution (MWD, Mw / Mn) was obtained by calculating from each of the measured molecular weights.

[0321] - Columns: Use a combination of two PLgel Olexis columns (Polymer Laboratories) and one PLgel mixed-C column (Polymer Laboratories).

[0322] - Solvent: Use a mixture of 2 wt% amine compound with tetrahydrofuran

[0323] - Flow rate: 1 mL / min

[0324] - Sample concentration: 1–2 mg / mL (diluted in THF)

[0325] - Infusion volume: 100 uL

[0326] - Column temperature: 40℃

[0327] - Detector: Refractive index

[0328] - Standard: Polystyrene (corrected by a cubic function)

[0329]

[0330] 3) Mooney dots

[0331] The above Mooney viscosity (MV, (ML1+4, @140℃)) was measured using the MV-2000 (ALPHA Technologies) at 140℃ with a Rotor Speed ​​of 2±0.02 rpm and a Large Rotor. The sample used was left at room temperature (23±5℃) for at least 30 minutes, then 27±3 g was collected, filled into the die cavity, and the Platen was operated to measure for 4 minutes.

[0332] Classification Preliminary Comparative Example 1 2 3 4 1 2 SM (wt%) 2 2 5 2 5 2 5 2 5 Vi (wt%) 2 1 2 0 2 2 1 2 2 1 Mooney Viscosity 1 4 4 1 4 0 1 4 2 1 3 9 1 0 5 1 1 0 GP CM w (×10 3 g / mol)203319492000192710221100Mn(×10 3 g / mol)813789797793543587MWD(Mw / Mn)2.52.472.512.431.881.87

[0333] As shown in Table 1 above, it was confirmed that Examples 1 to 4 showed a significant increase in weight-average molecular weight and a significant increase in Mooney viscosity compared to Comparative Examples 1 and 2. Through this, it was confirmed that the modified conjugated diene polymer according to the present invention is modified by a branching agent to form a branched structure and, together with, a compound represented by Formula 2 that provides a plurality of coupling sites, thereby increasing the inter-chain coupling bonds constituting the polymer and simultaneously introducing a modified part derived from the compound into the polymer chain, resulting in a highly modified structure and high molecular weight.

[0334]

[0335] Experimental Example 2

[0336] In order to compare and analyze the physical properties of the rubber composition containing the modified styrene-butadiene copolymer prepared in the above examples and comparative examples and the molded article prepared therefrom, tensile properties, wear resistance, processability, and viscoelastic properties were measured. The results are shown in Table 3 below.

[0337] 1) Preparation of rubber specimens

[0338] The modified conjugated diene polymers of the examples and comparative examples were used as raw rubber and blended under the blending 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.

[0339]

[0340] Specifically, the rubber specimen is mixed through a first stage of mixing and a second stage of mixing. In the first stage of mixing, raw rubber, silica (filler), organosilane coupling agent (X50S, Evonik), process oil (TDAE oil), zinc oxide (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 a primary mixture was obtained at an discharge temperature of 150°C. In the second stage of mixing, after cooling the primary mixture to room temperature, the primary mixture, sulfur powder, rubber accelerator (DPG (diphenylguanidine)), and vulcanization accelerator (CZ (N-cyclohexyl-2-benzothiazylsulfenamide)) were added to the mixer, and A secondary mixture was obtained by mixing at a temperature of 100℃ or lower. Subsequently, a rubber specimen was prepared by undergoing a curing process at 160℃ for 20 minutes.

[0341]

[0342] 2) Tensile properties

[0343] Tensile properties were measured by preparing each specimen according to the tensile testing method of ASTM 412, and measuring the tensile stress (300% modulus) at 300% elongation of the specimen, the fracture strength (tensile strength) and tensile modulus of the specimen, and toughness.

[0344] Specifically, tensile properties were measured at room temperature at a speed of 50 cm / min using a Universal Test Machine 4204 (Instron) tensile testing machine. The results in Table 3 are expressed as an Index (%) based on the results of Comparative Example 1, where a higher value indicates superior performance.

[0345]

[0346] 3) Viscoelastic properties

[0347] Viscoelastic properties were measured by varying the deformation in torsional mode at a frequency of 10 Hz and at each measurement temperature (-60℃ to 70℃) using a dynamic mechanical analyzer (TA Company) to measure tan δ. A higher tan δ at low temperature (0℃) indicates superior wet road resistance, while a lower tan δ at high temperature (70℃) indicates less hysteresis loss and superior rolling resistance (fuel efficiency). However, the results in Table 3 are expressed as an index based on the measurement value of Comparative Example 1 as the reference value, so a higher value indicates superior performance.

[0348]

[0349] 4) Processability characteristics

[0350] The Mooney viscosity (MV, (ML1+4, at 125℃)) of the secondary compound obtained when manufacturing the rubber specimen in step 1) above was measured to compare and analyze the processability characteristics of each polymer. At this time, a lower Mooney viscosity measurement value indicates superior processability characteristics. However, the results in Table 3 are expressed as an index based on the measurement value of Comparative Example 1 as the reference value, so a higher value indicates superiority.

[0351] Specifically, using the MV-2000 (ALPHA Technologies) at 125℃ with a Rotor Speed ​​of 2±0.02 rpm and a Large Rotor, each secondary mixture was left at room temperature (23±5℃) for at least 30 minutes, then 27±3 g was collected, filled into the die cavity, and the Platen was operated to measure for 4 minutes.

[0352]

[0353] 5) Wear resistance (DIN wear test)

[0354] For each rubber specimen, a DIN abrasion test was conducted in accordance with ASTM D5963, and the results were expressed as the DIN loss index (loss volume index): ARIA (Abration Resistance Index, Method A). A higher value indicates superior performance.

[0355] Classification Preliminary Comparative Example 1 2 3 4 12 Tensile Properties (Index, %) 300% Modulus 108 109 110 109 100 10 3 Tensile Strength 108 107 106 108 100 10 5 Tensile Modulus 104 105 105 104 100 9 8 Toughness 110 11 11 13 117 100 11 2 Viscoelastic Properties (Index, %) tan δ @ 0℃ 103 106 102 106 100 11 5 tan δ @ 70℃ 103 108 102 107 100 10 7 Machinability Properties (Index, %) 104 107 106 108 100 9 4 Wear Resistance (Index, %) 115 118 114 115 100 10 3

[0356] As shown in Table 3 above, it was confirmed that the modified styrene-butadiene copolymer of the examples has the effect of improving tensile properties, viscoelastic properties, wear resistance, and processability properties in a balanced manner. Specifically, Examples 1 to 4 exhibited superior viscoelastic properties and processability properties compared to Comparative Example 1, while showing tensile properties that were significantly improved by more than 10% overall and wear resistance that was significantly improved by more than 15%.

[0357] In addition, Comparative Example 2, prepared using a conventionally known aminoalkoxysilane-based modifier, showed slightly improved wet road resistance compared to the example, but the tensile properties were reduced and the processability and wear resistance were significantly poor, so it did not exhibit excellent properties in balance of tensile properties, processability properties, wear resistance, and viscoelastic properties.

[0358] Through the above results, it can be seen that the modified conjugated diene polymer of the present invention forms a branched structure by a branching agent and is modified into a compound represented by Formula 2, which has many polymer modification functional group sites, and includes a modified portion derived from the compound represented by Formula 2, thereby having excellent filler affinity and being able to have a high molecular weight through the introduction of a highly branched structure, and thus, when applied to a rubber composition, it has the effect of improving the compounding processability of the rubber composition while simultaneously improving tensile properties, viscoelastic properties, and wear resistance.

Claims

1. Unit derived from conjugated diene monomers; A branching agent-derived unit represented by the following chemical formula 1; and Modified conjugated diene polymer comprising a modified portion derived from a compound represented by the following chemical formula 2: [Chemical Formula 1] In the above chemical formula 1, R a1 It is a single bond or an alkylene group having 1 to 20 carbon atoms, and R a2 and R a3 are independently alkylene groups having 1 to 20 carbon atoms, and R a4 to R a9 is independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, wherein R a4 to R a6 One or more of and R a7 to R a9 One or more of them are alkoxy groups having 1 to 20 carbon atoms, and R a10 It is a hydrogen atom or an alkenyl group having 2 to 10 carbon atoms, and [Chemical Formula 2] In the above chemical formula 2, R1 and R2 are independently alkylene groups having 1 to 20 carbon atoms, and R3 is a single bond or an alkylene group having 1 to 20 carbon atoms, and R4 to R8 are independently alkylene groups having 1 to 20 carbon atoms, and A1 to A5 are independently -SiR9R 10 R 11 and, here R9 to R 11 The groups are independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, wherein R9 to R 11 At least one of them is an alkoxy group having 1 to 20 carbon atoms, and n is an integer from 2 to 10.

2. In Paragraph 1, In the above chemical formula 1, R a1 is a single bond or an alkylene group having 1 to 10 carbon atoms, and R a2 and R a3 are independently alkylene groups having 1 to 10 carbon atoms, and R a4 to R a9 is independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, wherein R a4 to R a6 One or more of and R a7 to R a9 One or more of them are alkoxy groups having 1 to 10 carbon atoms, and R a10 A modified conjugated diene polymer in which the atom is hydrogen.

3. In Paragraph 1, A modified conjugated diene polymer in which the branching agent represented by the above chemical formula 1 is one or more selected from the compounds represented by the following chemical formulas 1-1 to 1-3: [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3] In the above chemical formulas 1-1 to 1-3, Me is a methyl group and Et is an ethyl group.

4. In Paragraph 1, In the above Chemical Formula 2, R1 and R2 are independently alkylene groups having 1 to 10 carbon atoms, R3 is a single bond or an alkylene group having 1 to 10 carbon atoms, R4 to R8 are independently alkylene groups having 1 to 10 carbon atoms, and A1 to A5 are independently -SiR9R 10 R 11 and, here R9 to R 11 The groups are independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, wherein R9 to R 11 A modified conjugated diene polymer in which at least one of the groups is an alkoxy group having 1 to 10 carbon atoms, and n is an integer from 2 to 8.

5. In Paragraph 1, In the above Chemical Formula 2, R1 and R2 are independently alkylene groups having 1 to 6 carbon atoms, R3 is a single bond or an alkylene group having 1 to 6 carbon atoms, R4 to R8 are independently alkylene groups having 1 to 6 carbon atoms, and A1 to A5 are independently -SiR9R 10 R 11 and, here R9 to R 11 The groups are independently an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, wherein R9 to R 11 A modified conjugated diene polymer in which at least one of the groups is an alkoxy group having 1 to 6 carbon atoms, and n is an integer from 2 to 6.

6. In Paragraph 1, A modified conjugated diene polymer in which the compound represented by Chemical Formula 2 above is one or more selected from the compounds represented by Chemical Formulas 2-1 to 2-3 below: [Chemical Formula 2-1] [Chemical Formula 2-2] [Chemical Formula 2-3] In the above chemical formulas 2-1 to 2-3, Me is a methyl group.

7. In Paragraph 1, It includes a linear chain portion; and branched chain portions located at both ends of the linear chain portion, The linear chain portion comprises at least two polymer chains containing units derived from conjugated diene monomers and a modified portion derived from a compound represented by Formula 2, and each of the polymer chains is bonded to one another by the modified portion, and A modified conjugated diene polymer in which the branched chain portion comprises a branching point containing a branching agent-derived unit represented by Chemical Formula 1 and a branched polymer chain containing a conjugated diene monomer-derived unit bonded to the branching point.

8. In Paragraph 1, Modified conjugated diene polymer having a weight-average molecular weight of 1,500,000 g / mol or more and 4,000,000 g / mol or less.

9. In Paragraph 1, Modified conjugated diene polymer with a molecular weight distribution of 1.0 or more and 5.0 or less.

10. In Paragraph 1, A modified conjugated diene polymer having a Mooney viscosity of 100 or more and 180 or less as measured at 140℃.

11. In Paragraph 1, A modified conjugated diene polymer that further comprises units derived from aromatic vinyl monomers.

12. (S1) A step of preparing an active polymer bound to an organometallic compound 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 preparing a branched active polymer by reacting the above active polymer with a branching agent represented by the following chemical formula 1; and (S3) A method for preparing a modified conjugated diene polymer comprising the step of reacting the above branched active polymer with a compound represented by the following chemical formula 2: [Chemical Formula 1] In the above chemical formula 1, R a1 It is a single bond or an alkylene group having 1 to 20 carbon atoms, and R a2 and R a3 are independently alkylene groups having 1 to 20 carbon atoms, and R a4 to R a9 is independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, wherein R a4 to R a6 One or more of and R a7 to R a9 One or more of them are alkoxy groups having 1 to 20 carbon atoms, and R a10 It is a hydrogen atom or an alkenyl group having 2 to 10 carbon atoms, and [Chemical Formula 2] In the above chemical formula 2, R1 and R2 are independently alkylene groups having 1 to 20 carbon atoms, and R3 is a single bond or an alkylene group having 1 to 20 carbon atoms, and R4 to R8 are independently alkylene groups having 1 to 20 carbon atoms, and A1 to A5 are independently -SiR9R 10 R 11 and, here R9 to R 11 The groups are independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, wherein R9 to R 11 At least one of them is an alkoxy group having 1 to 20 carbon atoms, and n is an integer from 2 to 10.

13. In Paragraph 12, A method for preparing a modified conjugated diene polymer using the above organometallic compound in an amount of 0.01 to 10 mmol per 100 g of total monomer.

14. In Paragraph 12, A method for preparing a modified conjugated diene polymer, wherein the branching agent represented by the above chemical formula 1 is used in an amount of 0.1 to 0.9 moles based on 1 mole of the organometallic compound.

15. In Paragraph 12, A method for preparing a modified conjugated diene polymer using the compound represented by Chemical Formula 2 above in an amount of 0.1 to 5.0 moles based on 1 mole of organometallic compound.

16. In Paragraph 12, A method for preparing a modified conjugated diene polymer in which the branching agent represented by the above chemical formula 1 is one or more selected from the compounds represented by the following chemical formulas 1-1 to 1-3: [Chemical Formula 1-1] [Chemical Formula 1-2] [Chemical Formula 1-3] In the above chemical formulas 1-1 to 1-3, Me is a methyl group and Et is an ethyl group.

17. In Paragraph 12, A method for preparing a modified conjugated diene polymer, wherein the compound represented by Chemical Formula 2 above is one or more selected from the compounds represented by Chemical Formulas 2-1 to 2-3 below: [Chemical Formula 2-1] [Chemical Formula 2-2] [Chemical Formula 2-3] In the above chemical formulas 2-1 to 2-3, Me is a methyl group.

18. A rubber composition comprising a modified conjugated diene polymer and a filler according to claim 1.

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