Modified conjugated diene-based polymer, method for preparing the same, and rubber composition including the same.

Abstract

MODIFIED CONJUGATED DIENE-BASED POLYMER, METHOD FOR PREPARING THE SAME AND RUBBER COMPOSITION INCLUDING THE SAME. The present invention relates to a modified conjugated diene-based polymer having excellent rolling resistance and improved processability, a method for preparing the same and a rubber composition including the same, and provides a modified conjugated diene-based polymer that includes a repeating unit derived from a conjugated diene-based monomer, and a functional group derived from a modifier, and satisfies conditions (i) to (vii), a method for preparing the same and a rubber composition including the same.

Description

“MODIFIED CONJUGATED DIENE-BASED POLYMER, METHOD FOR PREPARING THE SAME AND RUBBER COMPOSITION INCLUDING THE SAME” TECHNICAL FIELD [Cross-reference to related requests]

[001] This application claims the benefit of priority based on Korean Patent Application No. 10-2020-0025512, filed on February 28, 2020, the entire content of which is incorporated herein by reference. [Technical Field]

[002] The present invention relates to a modified conjugated diene-based polymer having excellent rolling resistance and improved processability, a method for preparing the same and a rubber composition including the same. FUNDAMENTALS OF THE TECHNIQUE

[003] In accordance with the recent demand for cars having a low fuel consumption ratio, a diene-based conjugated polymer having modulation stability represented by wet slip resistance as well as low rolling resistance, and excellent abrasion resistance and traction properties is needed as a rubber material for tires.

[004] In order to reduce tire rolling resistance, there is a method of reducing the hysteresis loss of vulcanized rubber and the rebound resilience at 50 °C to 80 °C, tan δ, Goodrich heating or similar is used as an index for evaluating vulcanized rubber. That is, it is desirable to use a rubber material having high rebound resilience at the above temperature or a low tan δ or Goodrich heating value.

[005] Natural rubbers, polyisoprene rubbers, or polybutadiene rubbers are known as rubber materials having low hysteresis loss, but these rubbers have a limitation of low slip resistance. Petition 870260052105, dated 05 / 29 / 2026, page 9 / 86 2 / 65 wet. Thus, recently, diene-based conjugated polymers or copolymers, such as styrene-butadiene rubbers (hereinafter referred to as “SBR”) and butadiene rubbers (hereinafter referred to as “BR”), are prepared by emulsion polymerization or solution polymerization for use as tire rubbers. Among these polymerization methods, the greatest advantage of solution polymerization compared to emulsion polymerization is that the vinyl structure content and the styrene content, which specify the physical properties of the rubber, can be arbitrarily adjusted, and its molecular weight and physical properties can be controlled by coupling or modification.Thus, SBR prepared by solution polymerization is widely used as a rubber material for tires, since it is easy to alter the structure of the finally prepared SBR or BR, and the movement of terminal chains can be reduced and a coupling force with a filler, such as silica and carbon black, can be increased by coupling or modifying the terminal chains.

[006] Solution-polymerized SBR is prepared using an anionic polymerization initiator, and a method of introducing a functional group at a terminal by coupling or modifying the terminal chain of the polymer thus formed using various modifiers is being employed. For example, U.S. Patent No. 4,397,994 discloses a method of an active anion coupling of the terminal chain of a polymer obtained by polymerizing styrene-butadiene using alkyl-lithium, which is a monofunctional initiator, in a nonpolar solvent using a coupling agent, such as a tin compound.

[007] Furthermore, it is generally advantageous for solution-polymerized SBR to have a wide molecular weight distribution in relation to improving the processability of the composition, and a preparation method by high-temperature polymerization or introduction of a long-chain branch using a coupling agent has been attempted, but in the case of high-temperature polymerization, the Petition 870260052105, dated 05 / 29 / 2026, page 10 / 86 3 / 65 molecular weight distribution becomes wide, but a modification ratio is reduced, and in the case of using a coupling agent, there are problems in reducing rolling resistance due to steric hindrance between the coupling agent and a filler.

[008] Consequently, the development of a modified diene-based polymer having excellent rolling resistance and improved processability, having a wide molecular weight distribution and a high modification ratio is necessary. [State of the Art Document]

[009] (Patent Document 1) U.S. Patent No. 4,397,994 DISCLOSURE OF THE INVENTION TECHNICAL PROBLEM

[010] The present invention was conceived to solve the above-mentioned problems of the conventional art, and one objective is to provide a modified conjugated diene-based polymer including: a repeating unit derived from a conjugated diene-based monomer; and a functional group derived from a modifier, satisfying conditions (i) to (vii), and having excellent affinity with a filler and processability.

[011] Furthermore, another objective of the present invention is to provide a method for preparing a modified conjugated diene-based polymer whereby the modified conjugated diene-based polymer satisfying conditions (i) to (vii) can be easily prepared using an oligomer having an active anionic terminal as a polymerization initiator and which performs a polymerization reaction by injecting the polymerization initiator in at least two portions according to a polymerization conversion ratio during the preparation of an active polymer.

[012] In addition, another objective of the present invention is to provide a Petition 870260052105, dated 05 / 29 / 2026, page 11 / 86 4 / 65 rubber composition including modified diene-based polymer. TECHNICAL SOLUTION

[013] To solve the tasks described above, according to one embodiment of the present invention, the present invention provides a modified conjugated diene-based polymer including: a repeating unit derived from a conjugated diene-based monomer; and a functional group derived from a modifier, and satisfying the following conditions from (i) to (vii): (i) a molecular weight distribution curve obtained by gel permeation chromatography is unimodal; (ii) the molecular weight distribution is 2.0 or more; (iii) a weighted average molecular weight is from 100,000 g / mol to 2,000,000 g / mol; (vi) a modification rate is 70% or more; (v) a Mooney stress relaxation ratio measured at 100 °C is 0.7 or more; (vi) a large Mooney relaxation area (MLRA) measured at 100 °C and represented by the following Mathematical Formula 1 is 1500 MU-s or less; and (vii) nitrogen atom content is 100 ppm or more based on a weight of the polymer: [Mathematical Formula 1] jr i = ________I ; (o+l) _f(«r+lhA(a + 1)!°J

[014] In Mathematical Formula 1, A is a large Mooney relaxation area (MLRA), k is a Mooney intercept after 1 second of interruption of the operation of a Mooney viscometer rotor, a is a Mooney relaxation ratio, Petition 870260052105, dated 05 / 29 / 2026, page 12 / 86 5 / Q5 to is a Mooney relaxation initiation point, and tf is a Mooney relaxation termination point.

[015] In addition, the present invention provides a method for preparing a modified conjugated diene-based polymer, including: polymerizing a conjugated diene-based monomer, or a conjugated diene-based monomer and an aromatic vinyl-based monomer in a hydrocarbon solvent to prepare an active polymer (S1);and react or couple the active polymer prepared in step (S1) with a modifier (S2), wherein the polymerization of step (S1) is carried out by initiating the polymerization in the presence of a first polymerization initiator, and carry out the polymerization reaction by injecting a second polymerization initiator in at least one portion at a point where a polymerization conversion ratio is 50% to 95%, the first and second polymerization initiators are oligomers having an active anionic terminal, prepared by reacting an organometallic compound, a conjugated diene-based monomer and a compound represented by the following Formula 1, and step (S1) is continuously carried out in at least two polymerization reactors, where a polymerization conversion ratio in the first reactor between the polymerization reactors is 10% to 50%; [Formula 1] R2----N FU

[016] In Formula 1, Ri is a hydrogen atom or an alkyl group of 1 to 20 atoms of Petition 870260052105, dated 05 / 29 / 2026, p. 13 / 86 6 / 65 carbon, R2 is a single bond or an alkylene group substituted with a substituent or unsubstituted substituent of 1 to 20 carbon atoms, R3 and R4 are each independently an alkyl group substituted with a substituent or unsubstituted substituent of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms or an aryl group of 6 to 30 carbon atoms, and the substituent is one or more selected from the group consisting of an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms and an aryl group of 6 to 20 carbon atoms.

[017] In addition, the present invention provides a rubber composition including the modified diene-conjugated polymer and a filler. ADVANTAGEOUS EFFECTS

[018] The modified conjugated diene-based polymer according to the present invention is prepared by a preparation method suggested in the present invention, and may have a wide molecular weight distribution, a high modification ratio, a low branching structure of a 2-arm structure, and excellent processability as well as excellent affinity with a filler.

[019] In the method for preparing a modified diene-based conjugate polymer according to the present invention, the polymerization reaction is carried out by injecting a polymerization initiator in at least two parcels according to a polymerization conversion ratio during polymerization in step (S1) to prepare an active polymer using an oligomer having an active anionic terminal as a polymerization initiator and, consequently, an active polymer having a wide molecular weight distribution can be easily prepared even if not under high temperature conditions, and a diene-based conjugate polymer having a high modification ratio can be easily prepared.

[020] In addition, the rubber composition according to the present invention includes the modified diene-conjugated polymer and may have excellent Petition 870260052105, dated 05 / 29 / 2026, page 14 / 86 7 / 65 Wear resistance and processability in balance. BEST WAY TO CARRY OUT THE INVENTION

[021] The present invention will now be described in more detail in order to aid in understanding the present invention.

[022] It will be understood that the words or terms used in the description and claims of the present invention should not be interpreted as having the meaning defined in commonly used dictionaries. It will further be understood that the words or terms should be interpreted as having a meaning consistent with the meaning of the technical idea of ​​the invention, based on the principle that an inventor can adequately define the meaning of words or terms to better explain the invention. Definition of Terms

[023] The term “Mooney large relaxation area (MLRA)” in this disclosure is a measured value (measurement) of chain relaxation in a molten polymer, and indicates that the longer or more branched polymer chain can store more energy and requires more time to relax after the removal of the applied strain. For example, the Mooney large relaxation area of ​​an ultra-high molecular weight or long-chain branched polymer may be larger than that of a polymer having a wider or reduced molecular weight compared to a polymer having the same Mooney viscosity.

[024] The term “polymer” in this disclosure refers to a homopolymeric compound or a copolymeric compound prepared by polymerizing one type of monomer or two or more different types of monomers.

[025] The term “1,2-vinyl linkage content” in this disclosure refers to the mass (or weight) percentage of butadiene included in the 1,2 positions in a copolymer polymer chain, based on a portion derived from conjugated diene-based monomer (butadiene, etc.) (the total weight of butadiene Petition 870260052105, dated 05 / 29 / 2026, p. 15 / 86 8 / 65 polymerized) in the copolymer.

[026] The term “styrene linkage content” in this disclosure refers to the mass (or weight) percentage of styrene included in a copolymer chain derived from an aromatic vinyl-based monomer (styrene, etc.) in the copolymer.

[027] The term “modification ratio (%)” in this disclosure may mean the ratio of a modified copolymer chain to an unmodified copolymer chain in the case of modification of a copolymer where a polymerization active moiety is present with a modifier, and the ratio is represented as a percentage (%) based on the total copolymer including the modified copolymer chain and the unmodified copolymer chain.

[028] The term “substituted” in the present invention may mean the hydrogen of a functional group, an atomic group or a compound being replaced by a specific substituent. If the hydrogen of a functional group, an atomic group or a compound is replaced by the specific substituent, one or a plurality of substituents, including two or more substituents, may be present according to the number of hydrogens present in the functional group, atomic group or compound, and if a plurality of substituents is present, each substituent may be the same or different.

[029] The term “alkyl group” in this disclosure may mean a monovalent saturated aliphatic hydrocarbon, and may include a linear alkyl group, such as methyl, ethyl, propyl and butyl; a branched alkyl group, such as isopropyl, sec-butyl, tert-butyl and neo-pentyl; and a cyclic saturated hydrocarbon group or a cyclic unsaturated hydrocarbon group including one or two or more unsaturated bonds.

[030] The term “alkylene group” in this disclosure may mean a divalent aliphatic saturated hydrocarbon, such as methylene, ethylene, propylene and Petition 870260052105, dated 05 / 29 / 2026, p. 16 / 86 9 / 65 butylene.

[031] The term “cycloalkyl group” in this disclosure may mean cyclic saturated hydrocarbon.

[032] The term “aryl group” in this disclosure may mean cyclic aromatic hydrocarbon, and may include monocyclic aromatic hydrocarbon in which one ring is formed and polycyclic aromatic hydrocarbon in which two or more rings are attached.

[033] The term “aralkyl group” in this disclosure is also referred to as an aralkyl and may mean a combination group of an alkyl group that is formed by replacing a hydrogen atom bonded to the carbon that constitutes the alkyl group with an aryl group and an aryl group.

[034] The term “single bond” in this disclosure may mean a single covalent bond in itself, excluding a separate atomic or molecular group.

[035] The terms “derived unit”, “derived repeating unit” and “derived functional group” in this disclosure may represent a component or structure derived from a certain material or the material itself.

[036] The terms “comprising” and “having” and derivatives thereof in the present invention, whether particularly disclosed or not, are not intended to preclude the presence of optional additional components, steps, or processes. In order to avoid any uncertainty, all compositions claimed using the term “comprising” may include optional additional additives, auxiliaries, or compounds, including a polymer or any other materials, unless otherwise described. In contrast, the term “essentially consisting of ~” excludes those unnecessary for operation and excludes other optional components, steps, or processes from the scope of the optional continued description. The term “consisting of ~” excludes optional components, steps, or processes that are not particularly described or illustrated. Petition 870260052105, dated 05 / 29 / 2026, page 17 / 86 10 / 65 Measurement Methods and Conditions

[037] In the present disclosure, the “1,2-vinyl linkage content” is obtained by measuring and analyzing the vinyl content and styrene content in a copolymer and first and second copolymer units using Varian VNMRS 500 MHz NMR. 1,1,2,2-tetrachloroethane was used as a solvent during the NMR measurement, and a sample was prepared by dissolving a 0.02 M polymer in the solvent. The 1,2-vinyl linkage content and the styrene linkage content in a total polymer were measured by calculating 6.0 ppm as a solvent peak, 7.2 to 6.9 ppm as random styrene peaks, 6.9 to 6.2 ppm as block styrene peaks, 5.8 to 5.1 ppm as 1,4-vinyl and 1,2-vinyl peaks, and 5.1 to 4.5 ppm as 1,2-vinyl peaks.

[038] In this disclosure, “weighted average molecular weight (Mw)”, “molecular weight distribution (MWD)” and “unimodal properties” are obtained by measuring molecular weights using gel permeation chromatography (GPC) analysis and obtaining a molecular weight distribution curve. In addition, the molecular weight distribution (PDI, MWD, Mw / Mn) is calculated from each measured molecular weight. In particular, by gel permeation chromatography (GPC) (PL GPC220, Agilent Technologies) under the conditions below, a weighted average molecular weight (Mw) and a number-average molecular weight (Mn) were measured, a molecular weight distribution curve was obtained, and the molecular weight distribution (PDI, MWD, Mw / Mn) was obtained by calculating from the molecular weights thus measured. - Column: two Olexis PLgel columns (Polymer Laboratories Co.) and one mixed-C PLgel column (Polymer Laboratories Co.) were used in combination. - Solvent: a mixture of tetrahydrofuran and 2% by weight of an amine compound were used. - Flow rate: 1 ml / min Petition 870260052105, dated 05 / 29 / 2026, page 18 / 86 11 / 65 Sample concentration: 1 to 2 mg / ml (diluted in THF) Injection quantity: 100 μl - Column temperature: 40 °C Detector: Refractive index Standard: Polystyrene (calibration with cubic function)

[039] In this disclosure, the “change ratio (%)” is a value calculated according to Mathematical Formula 2 below using a chromatogram obtained from the chromatography measurement. The chromatography measurement was conducted as follows using, for example, gel permeation chromatography (GPC) (PL GPC220, Agilent Technologies). A copolymer was dissolved in cyclohexane and stored in a mobile phase reservoir of one sample (prepared at 1.0 m / ml), and tetrahydrofuran (THF) was stored in another mobile phase reservoir. The mobile phase reservoirs were connected with a double-head pump, respectively, and firstly, the solution in the mobile phase reservoir in which the polymer was dissolved was injected into a column packed with a silica absorbent through the pump and an injector with a cycle volume of 100 pl. In this case, the pump pressure was 450 psi, and the injection flow rate was 0.7 ml / min.Then, after confirming that an unmodified copolymer unit in the copolymer was not detected by a detector (ELSD, Waters Co.), based on 5 minutes from the start of the injection, tetrahydrofuran was injected into the column via the pump. In this case, the pump pressure was 380 psi, and the injection flow rate was 0.7 ml / min. After confirming that an unmodified copolymer unit in the polymer according to the tetrahydrofuran injection was no longer detected by the detector, the injection of a second solvent was completed. Then, from the detected results of the chromatogram, a modification ratio (%) was calculated according to Mathematical Formula 2 below. [Mathematical Formula 2] Petition 870260052105, dated 05 / 29 / 2026, page 19 / 86 12 / 65 Modification ratio (%) Peak area of ​​modified copolymer unit / Peak area of ​​unmodified copolymer unit + Peak area of ​​modified copolymer unit x 100

[040] In Mathematical Formula 2, the peak area of ​​the unmodified copolymer unit is the peak area of ​​the chromatogram in a first solution transported to the detector, and the peak area of ​​the unmodified copolymer unit is the peak area of ​​the chromatogram in a second solution transported to the detector.

[041] In the present disclosure, the “N atom content” can be measured using an NSX analysis method. The measurement by the NSX analysis method can use a quantitative trace nitrogen analyzer (NSX2100H). In particular, the quantitative trace nitrogen analyzer (Auto sampler, Horizontal furnace, PMT & Nitrogen detector) was switched on, the carrier gas flow rates were set to 250 ml / min for Ar, 350 ml / min for O2 and 300 ml / min for ozonizer, a heater was set to 800 °C, and the analyzer was left to stand for about 3 hours for stabilization. After the analyzer stabilized, a calibration curve with calibration curve ranges of 5 ppm, 10 ppm, 50 ppm, 100 ppm, and 500 ppm was fabricated using Nitrogen standard (AccuStandard S-22750-01-5 ml), and a corresponding area for each concentration was obtained. Then, using the concentration ratios for the areas, a straight line was drawn.Next, a ceramic boat containing 20 mg of a sample was placed in the analyzer's autosampler, and a measurement was taken to obtain an area. Using the area of ​​the sample thus obtained and the calibration curve, the nitrogen atom content was calculated.

[042] In this case, the sample used for the NSX analysis method is a modified conjugated diene-based polymer sample from which solvents are removed by placing the sample in hot water heated by steam and stirring, and may be a sample from which remaining monomers, remaining modifiers and oil are removed. In addition, if an oil is added to Petition 870260052105, dated 05 / 29 / 2026, page 20 / 86 13 / 65 sample, the sample can be one after the oil has been extracted (removed).

[043] In the present disclosure, the “Mooney stress relaxation ratio (-S / R)” was measured using an Alpha Technologies Co. MV2000E using a Large Rotor at 100 °C and a rotor speed of 2 ± 0.02 rpm. Specifically, a polymer is left at room temperature (23 ± 5 °C) for 30 minutes or more, and 27 ± 3 g are collected and placed in a mold cavity, and then the Platen is operated for 4 minutes while applying torque to measure and obtain the Mooney viscosity. Then, the slope value of the change in Mooney viscosity shown during torque release is measured, and the absolute value thereof is shown.

[044] In the present disclosure, the “Mooney large relaxation area (MLRA)” is a value obtained by plotting a Mooney torque versus time graph and computing Mathematical Formula 1, and can be obtained by measuring the slope value of the Mooney viscosity change shown during torque release by stopping a rotor after measuring a Mooney viscosity, obtaining a Mooney relaxation ratio (a) which is the absolute value of the same and obtaining, from the integration value of a Mooney relaxation curve during 1 second (to) to 120 seconds (tf) after stopping the rotor, and this integration value can be computed from Mathematical Formula 1. Modified Conjugated Diene Based Polymer

[045] The modified conjugated diene-based polymer according to the present invention can be prepared by a preparation method that will be described later and can have a wide molecular weight distribution and highly modified terminals.

[046] In particular, the modified conjugated diene-based polymer according to the present invention is characterized by including a repeating unit derived from a conjugated diene-based monomer, and a functional group derived from a modifier and satisfying the following conditions (i) to (vii): Petition 870260052105, dated 05 / 29 / 2026, page 21 / 86 14 / 65 (i) a molecular weight distribution curve by gel permeation chromatography is unimodal; (ii) the molecular weight distribution is 2.0 or more; (iii) urn weighted average molecular weight is from 100,000 g / mol to 2,000,000 g / mol; (vi) a modification rate is 70% or more; (v) a Mooney stress relaxation ratio measured at 100 °C is 0.7 or more; (vi) a large Mooney relaxation area (MLRA) measured at 100 °C and represented by the following Mathematical Formula 1 is 1500 Mll-s or less; and (vii) nitrogen atom content is 100 ppm or more based on a weight of the polymer: [Mathematical Formula 1] jrA(a + 1)!°J

[047] In Mathematical Formula 1, A is a large Mooney relaxation area (MLRA), k is a Mooney intercept after 1 second of interruption of the operation of a Mooney viscometer rotor, a is a Mooney relaxation ratio, to is a Mooney relaxation initiation point, and tf is a Mooney relaxation termination point.

[048] According to one embodiment of the present invention, the modified conjugated diene-based polymer is prepared by a preparation method in which step (S1) is carried out while controlling the polymerization conversion ratio in a first reactor at 10% to 50% by applying an oligomer having an active anionic terminal as a polymerization initiator. Petition 870260052105, dated 05 / 29 / 2026, page 22 / 86 15 / 65 during the polymerization of step (S1) which will be explained later, is included, and the polymerization reaction is carried out by injecting the polymerization initiator into at least two parcels, and preparing through a preparation method, conditions (i) to (vii) above can be satisfied at the same time.

[049] Furthermore, the oligomer is prepared by reacting an organometallic compound, a conjugated diene-based monomer and a compound represented by Formula 1 and may include the repeating unit derived from the compound represented by Formula 1 in one molecule. Consequently, by introducing the unit derived from the compound represented by Formula 1 into the polymer separately from a modifier, condition (vii) above may be satisfied more favorably.

[050] Based on these results, the modified conjugated diene-based polymer satisfies conditions (i) to (vii) simultaneously and can have excellent mechanical properties, such as tensile properties, viscoelasticity and processability of the composition simultaneously and, consequently, can have excellent tensile properties, wet slip resistance, rolling resistance and processability in equilibrium. Main Parameters of Modified Diene-Based Polymer

[051] The modified conjugated diene-based polymer according to an embodiment of the present invention has a unimodal molecular weight distribution curve by gel permeation chromatography (GPC) and may have a molecular weight distribution of 2.0 or more, and herein, the unimodal curve shape and the molecular weight distribution may be satisfied simultaneously by a preparation method described below. In particular, the modified conjugated diene-based polymer may have a unimodal molecular weight distribution curve and have a molecular weight distribution of 2.0 to 5.0, or 2.0 to 3.0.

[052] In addition, the modified diene-based conjugated polymer may have Petition 870260052105, dated 05 / 29 / 2026, page 23 / 86 16 / 65 a weighted average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 100,000 g / mol to 2,000,000 g / mol, 150,000 g / mol to 1,800,000 g / mol, or 200,000 g / mol to 1,600,000 g / mol and, within this range, rolling resistance and wet skid resistance can be excellent in a balanced way.

[053] In addition, the modified conjugated diene-based polymer may include a functional group derived from a modifier and may have a modification ratio of 70% or more or 90% or more. Here, the functional group derived from the modifier may mean a functional group derived from a modifier that is present at a terminal of an active polymer through the reaction or coupling between an active polymer and a modifier.

[054] Furthermore, the modification ratio can be influenced by the degree of modification or coupling by a modifier in the modification reaction, and can be controlled according to the amount of a modifier and the amount of a polar additive injected during preparation, the reaction time, the mixing time of a modifier and an active polymer, a degree of mixing, etc.

[055] Furthermore, the modification rate can be influenced by the polymerization initiator used, the reaction injection point of the same and the amount of the same used during the preparation of the modified diene-based polymer.

[056] Meanwhile, the modified conjugated diene-based polymer can be prepared by a preparation method described further below, which is carried out continuously in at least two polymerization reactors, controlling a polymerization conversion ratio in a first reactor from 10% to 50%, and including a polymerization step to prepare an active polymer by injecting a polymerization initiator in at least two portions and a reaction modification step or coupling of the active polymer with a modifier. Through this preparation method, a molecular weight distribution curve can be unimodal, the molecular weight distribution can be broad and 2.0 or more, and a ratio of Petition 870260052105, dated 05 / 29 / 2026, page 24 / 86 17 / 65 The modification of the numerical value described above can be satisfied.

[057] In particular, in a continuous polymerization method, the injection of a feedstock and the discharge of a product after the reaction is complete are carried out continuously, and it can be considered that polymer chains having different molecular weights with different degrees of reaction are mixed in the discharged product, including a polymer chain injected and reacted from the reaction initiation point, a polymer chain formed by injection and reaction from the middle of the reaction, and a polymer chain formed by injection and reaction at the polymerization endpoint. However, a feedstock injected into a reactor at the same point may undergo polymerization at similar reaction rates to be discharged as a product and, consequently, the polymer chains in the product may have similar molecular weight degrees and have a unimodal shape with a more restricted molecular weight distribution than expected.Therefore, in the case of carrying out the modification reaction by injecting a modifier, a polymer chain modified and / or coupled by a modifier, or an unmodified and / or uncoupled polymer chain can be produced, and two or more groups having a large difference in molecular weights can be formed, and a multimodal molecular weight distribution curve having two or more peaks of a molecular weight distribution curve can be formed.However, according to the preparation method of the present invention, an active polymer is prepared by a polymerization step in which a polymerization conversion ratio in a first reactor is controlled at 10% to 50%, and a polymerization initiator is injected in at least two portions, and a reacted and depleted raw material (monomer) at the polymerization initiation point can be controlled, and can be controlled to form a new polymer chain with the polymerization initiator injected in portions and, consequently, a polymeric product including polymer chains having various molecular weights can be obtained. Consequently, the chains... Petition 870260052105, dated 05 / 29 / 2026, page 25 / 86 18 / 65 Polymeric compounds reacted and / or coupled by reaction with a modifier subsequently may also have diverse molecular weights, and a specific peak is not predominantly shown; a broad unimodal molecular weight distribution curve may be shown as a single peak, and at the same time, the molecular weight distribution may be broad.

[058] Furthermore, by injecting the polymerization initiator in batches, the number of polymer chains having different molecular weight extensions having an active part with a modifier can be absolutely greater than the number of polymer chains in an active polymer prepared from common continuous type polymerization and, consequently, can show a higher modification ratio compared to a modified conjugated diene-based polymer prepared by common continuous type polymerization with the application of the same modifier.

[059] In another embodiment, the modified conjugated diene-based polymer may have a Mooney stress relaxation ratio measured at 100 °C of 0.7 to 3.0, 0.8 to 2.0, more particularly, 0.9 to 1.5.

[060] Here, the Mooney stress relaxation ratio can be used as an index of the branching structure (or linearity) of a corresponding polymer, for example, compared with a polymer with an equivalent Mooney viscosity, the Mooney stress relaxation ratio is reduced with increasing branching and can be used as an index of the degree of branching. The modified conjugated diene-based polymer according to the present invention satisfies conditions (i) to (iv), (vi) and (vii) and, at the same time, has a Mooney stress relaxation ratio in the range described above and, therefore, can have excellent processability and, at the same time, can have excellent tensile properties and viscoelastic properties.

[061] In addition, the modified diene-based polymer modified according Petition 870260052105, dated 05 / 29 / 2026, p. 26 / 86 19 / 65 with an embodiment of the present invention needs to satisfy the Mooney viscosity measured under ASTM D1646 conditions of 50 to 100, particularly 70 to 100, preferably 70 to 90. There are several measurements to evaluate processability, but if the Mooney viscosity meets the range described above, the processability can be quite excellent.

[062] In another embodiment, the modified conjugated diene-based polymer may have a large Mooney relaxation area (MLRA) measured at 100 °C represented by Mathematical Formula 1 below 1500 Mll-s or less. [Mathematical Formula 1]

[063] In Mathematical Formula 1, A is a large Mooney relaxation area (MLRA), k is a Mooney intercept after 1 second of interruption of the operation of a Mooney viscometer rotor, a is a Mooney relaxation ratio, to is a Mooney relaxation initiation point, and tf is a Mooney relaxation termination point.

[064] Here, the Mooney relaxation initiation point can represent a point after 1 second of rotor operation stoppage, and can mean a point when Mooney torque has a value k. Furthermore, the Mooney relaxation termination point can represent a point where the Mooney relaxation measurement is finalized in the Mooney relaxation measurement test. That is, tf-to can represent a Mooney relaxation time.

[065] Furthermore, according to one embodiment of the present invention, to can be 1 second, and tf can be from 80 seconds to 150 seconds. In other words, the large Mooney relaxation area according to one embodiment Petition 870260052105, dated 05 / 29 / 2026, page 27 / 86 20 / 65 of the present invention can be an integrated area under a Mooney torque relaxation time curve from 1 second to 80 seconds to 150 seconds. Furthermore, tf can be particularly from 90 seconds to 130 seconds, or 100 seconds to 120 seconds.

[066] In the modified conjugated diene-based polymer of the present invention, a large Mooney relaxation area of ​​1500 MU-s or less is a technical means to provide excellent tensile and viscoelastic properties along with excellent processability. If the large Mooney relaxation area is in the above range, the target effects of the present invention can be shown. Furthermore, if the large Mooney relaxation area has a very small value, the mechanical properties, such as tensile properties, may be deteriorated, and in order to present excellent processability along with excellent tensile and viscoelastic properties in balance, the large Mooney relaxation area of ​​the modified conjugated diene-based polymer according to an embodiment of the present invention may be 300 MU-s or more.

[067] Meanwhile, generally, the molecular weight and Mooney viscosity physical properties of a polymer are proportionally related and tend to be similar, and a polymer with a high molecular weight has the disadvantages of high Mooney viscosity and inferior processability, and a polymer with a low molecular weight has low Mooney viscosity and relatively good processability, but has the disadvantages of inferior mechanical properties, such as tensile properties. However, the modified conjugated diene-based polymer according to an embodiment of the present invention has a large Mooney relaxation area of ​​1500 MU-s or less and achieves excellent processability and tensile properties in equilibrium.

[068] In addition, Mooney's large relaxation area tends to increase Petition 870260052105, dated 05 / 29 / 2026, page 28 / 86 21 / 65 with increasing branching compared to a polymer having the same Mooney viscosity and is used as an index of the degree of branching (or linearity), but it can be influenced by the molecular weight of a corresponding polymer as well as the degree of branching of the polymer and, consequently, the large Mooney relaxation area may be different, even though it has the same degree of branching (or linearity).

[069] However, the modified conjugated diene-based polymer according to the present invention can be prepared by the preparation method that will be explained later, and the molecular weight, modification ratio and degree of branching can be controlled simultaneously. Consequently, a molecular weight distribution curve can be unimodal, the molecular weight distribution can be broad, and a Mooney strain relaxation ratio and a large Mooney relaxation area can be controlled simultaneously, thus satisfying conditions (i) to (vii) at the same time.

[070] The large Mooney relaxation area can be a value obtained by plotting a graph of Mooney torque versus time and then computing from Mathematical Formula 1 and, in this case, the Mooney viscosity (MV, ML1 +4, @ 100 °C MU) can be measured using MV-2000 (ALPHA Technologies Co.) using Large Rotor at a rotor speed of 2 ± 0.02 rpm at 100 °C. In this case, a sample was left at room temperature (23 ± 5 °C) for 30 minutes or more, and 27 ± 3 g were collected and placed in a mold cavity and then the measurement was conducted for 4 minutes during the operation of the Platen.

[071] Furthermore, after measuring a Mooney viscosity, by measuring the slope value of the Mooney viscosity change shown while the torque is released by stopping the rotor, its absolute value can be obtained as a Mooney relaxation ratio (a). Additionally, the large Mooney relaxation area can be obtained from the integration value of the relaxation curve of Petition 870260052105, dated 05 / 29 / 2026, page 29 / 86 22 / 65 Mooney relaxation occurs from 1 second (t0) to 120 seconds (tf) after stopping the rotor, and this integration value can be computed from Mathematical Formula 1. If the Mooney relaxation area satisfies the range described above, the effects of improving viscoelastic properties, particularly rolling resistance (RR), during the compounding of a rubber compound can be obtained. In particular, if the large Mooney relaxation area satisfies the range described above under Mooney viscosity conditions of 80 or more, preferably 90 or more, even better rolling resistance improvement effects can be obtained.

[072] In another embodiment, the modified conjugated diene-based polymer may have a nitrogen atom content of 100 ppm or more, 100 ppm to 1,000 ppm, or 200 ppm to 500 ppm based on the weight of the polymer and, within this range, a rubber composition including the modified conjugated diene-based polymer may have excellent mechanical property effects, such as tensile properties and viscoelastic properties. However, the nitrogen atom may be derived from an oligomer which will be explained later, or from the oligomer and a modifier, and may be prepared by a preparation method which will be explained later as having a relatively high nitrogen atom content.

[073] In particular, the modified conjugated diene-based polymer according to the present invention is prepared by a method of preparation that will be explained later, controls a raw material (monomer) depleted by the reaction in the initial stage of polymerization, and has a nitrogen atom derived from a polymerization initiator through the formation of new polymer chains with a polymerization initiator that is injected in portions. Consequently, there can be a large number of active polymer chains having an active reactive part with a modifier and, therefore, the nitrogen atom content in a polymer. Petition 870260052105, dated 05 / 29 / 2026, page 30 / 86 23 / 65 may be larger than a common single terminal and / or both terminals. In the preparation of a modified conjugated diene-based polymer via a common continuous or batch-type polymerization method, a monomer is polymerized in the presence of a polymerization initiator to prepare an active polymer and then, through reaction or coupling with a modifier, a modified conjugated diene-based polymer is prepared. In this case, the active polymer is produced by initiating polymerization through the reaction of the polymerization initiator and the monomer and maintaining the reaction of terminal anions with the monomer to propagate a polymer chain.Finally, the number of polymer chains produced in the case of the common continuous polymerization method or the batch type, whereby a polymerization initiator is injected at one point before polymerization begins and polymerization is carried out, may be limited compared to that by the preparation method according to the present invention, whereby a polymerization initiator is injected in portions at specific points and new chains are consistently produced.

[074] Furthermore, although a polymerization initiator is injected in portions in a common continuous or batch-type polymerization method, if a monomer capable of reacting with the batch-injected polymerization initiator is not present or is present in a very small quantity, the newly formed polymer chains may be negligible or highly limited, and as a result, the number of polymer chains in the active polymer may not be virtually increased. However, in the preparation method according to the present invention, the polymerization initiator is injected in portions at specific points and, at the same time, a polymerization conversion ratio in a first polymerization reactor is controlled to 10% to 50%, that is, the initial degree of polymerization of a polymer is controlled to a specific range. Furthermore, by controlling the amount of monomer to produce sufficient new chains Petition 870260052105, dated 05 / 29 / 2026, page 31 / 86 24 / 65 polymeric chains, through reaction with the polymerization initiator injected in batches, can significantly increase the number of polymer chains in an active polymer thus prepared. Here, the polymer chain in the active polymer reacts or is coupled with a modifier subsequently, and the increase in the number of polymer chains signifies an increase in polymer chains modified by reaction or coupling with a modifier.

[075] Through preparation by the preparation method, the modified conjugated diene-based polymer according to an embodiment of the present invention can include a large number of polymer chains that include nitrogen atoms derived from an oligomer included in a polymerization initiator, and can have an absolutely increased nitrogen atom content compared with a polymer prepared by another polymerization method using the same polymerization initiator and / or a modifier. Modified Conjugated Diene Based Polymer Configuration

[076] According to one embodiment of the present invention, the modified conjugated diene-based polymer may include a polymer chain comprising a repeating unit derived from a conjugated diene-based monomer and a functional group derived from a modifier included at least at one terminal of the polymer chain. Herein, the repeating unit derived from the modified conjugated diene-based monomer may mean a repeating unit formed during the polymerization of the conjugated diene-based monomer, and the functional group derived from the modifier may mean a functional group derived from the modifier present at a terminal of the active polymer through the reaction or coupling between the active polymer prepared by polymerization of the conjugated diene-based monomer with the modifier.

[077] According to one embodiment of the present invention, the conjugated diene-based monomer may be one or more selected from the group consisting Petition 870260052105, dated 05 / 29 / 2026, p. 32 / 86 25 / 65 in 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, 2-phenyl-1,3-butadiene and 2-halo-1,3-butadiene (halo means a halogen atom).

[078] In another embodiment, the modified conjugated diene-based polymer may further include a repeating unit derived from a compound represented by Formula 1 below and, in this case, the modified conjugated diene-based polymer may include a repeating unit derived from a conjugated diene-based monomer, a repeating unit derived from the compound represented by Formula 1 and a functional group derived from a modifier. Furthermore, the repeating unit derived from the compound represented by Formula 1 may be included in a polymer chain including the repeating unit derived from the conjugated diene-based monomer and at least one terminal of the polymer chain. [Formula 1] R2----N R4

[079] In Formula 1, Ri is a hydrogen atom or an alkyl group of 1 to 20 carbon atoms. R2 is a single bond or an alkylene group substituted with a substituent or unsubstituted substituent of 1 to 20 carbon atoms; R3 and R4 are each independently a substituted alkyl group with a substituent or unsubstituted substituent of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms. Petition 870260052105, dated 05 / 29 / 2026, p. 33 / 86 26 / 65 carbon or an aryl group of 6 to 30 carbon atoms, and the substituent is one or more selected from the group consisting of an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, and an aryl group of 6 to 20 carbon atoms.

[080] Here, the repeating unit derived from the compound represented by Formula 1 can be derived from an oligomer that is the polymerization initiator used in a preparation method that will be explained later.

[081] In particular, in Formula 1, Ri can be a hydrogen atom or an alkyl group of 1 to 10 carbon atoms, R2 can be a single bond or an unsubstituted alkylene group of 1 to 10 carbon atoms, and R3 and R4 can each independently be an unsubstituted alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 3 to 10 carbon atoms, or an aryl group of 6 to 12 carbon atoms.

[082] In another embodiment, the modified conjugated diene-based polymer may further include a repeating unit derived from an aromatic vinyl-based monomer and, in this case, the modified conjugated diene-based polymer may include a repeating unit derived from a conjugated diene-based monomer, a repeating unit derived from an aromatic vinyl-based monomer, a repeating unit derived from a compound represented by Formula 1 and a functional group derived from a modifier.

[083] According to one embodiment of the present invention, the aromatic vinyl-based monomer may include one or more selected from the group consisting of styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, 1-vinyl-5-hexylnaphthalene, 3-(2-pyrrolidine ethyl)styrene, 4-(2-pyrrolidine ethyl)styrene and 3-(2-pyrrolidine-1-methyl ethyl)-α-methylstyrene.

[084] In another embodiment, the diene-based polymer Petition 870260052105, dated 05 / 29 / 2026, page 34 / 86 The modified 27 / 65 may be a copolymer that further includes a repeating unit derived from a diene-based monomer of 1 to 10 carbon atoms together with the repeating unit derived from the conjugated diene-based monomer. The repeating unit derived from the diene-based monomer may be a repeating unit derived from a diene-based monomer that is different from the conjugated diene-based monomer, and the diene-based monomer that is different from the conjugated diene-based monomer may be, for example, 1,2-butadiene.If the modified conjugated diene-based polymer is a copolymer also including a diene-based monomer, the modified conjugated diene-based polymer may include the repeating unit derived from the diene-based monomer in more than 0% by weight to 1% by weight, more than 0% by weight to 0.1% by weight, more than 0% by weight to 0.01% by weight, or more than 0% by weight to 0.001% by weight, and within this range, the gel-prevention effects may be obtained.

[085] In addition, the modified conjugated diene-based polymer may have a vinyl content of 5% by weight or more, 10% by weight or more, or 10% by weight to 60% by weight. Herein, vinyl content may mean the content of conjugated diene-based monomer not 1,4-added, but 1,2-added based on 100% by weight of a conjugated diene-based copolymer formed using a monomer having a vinyl group and an aromatic vinyl-based monomer. Modifier

[086] Furthermore, the modifier may be a modifier for modifying the terminal of a polymer, particularly a modifier having affinity for silica. The modifier having affinity for silica may mean a modifier containing a functional group having affinity for silica in a compound used as the modifier, and the functional group having affinity for silica may mean a functional group having excellent affinity for a filler, particularly a silica-based filler, and capable of interacting between the silica-based filler and the Petition 870260052105, dated 05 / 29 / 2026, page 35 / 86 28 / 65 functional group derived from the modifier.

[087] The modifier can be, for example, an alkoxysilane-based compound, particularly an alkoxysilane-based compound containing one or more heteroatoms, such as a nitrogen atom, an oxygen atom and a sulfur atom. In the case of using the alkoxysilane-based compound as the modifier, through the substitution reaction between an anionic active moiety positioned at a terminal of the active polymer and an alkoxy group of the alkoxysilane-based compound, the modification can be carried out in the coupled form of a terminal of the active polymer with a silyl group.Consequently, from the functional group derived from the modifier, present at one end of a first copolymer unit, the affinity of a modified conjugated diene-based polymer including the first copolymer unit with an inorganic filler can be improved, and thus, the effects of further improving the viscoelasticity of a rubber composition including a modified conjugated diene-based polymer can be obtained. Furthermore, if the alkoxysilane-based compound contains a nitrogen atom, improved effects of additional physical properties derived from the nitrogen atom can be expected, in addition to the effects derived from the silyl group.

[088] According to one embodiment of the present invention, the modifier may include a compound represented by Formula 2 below. [Formula 2]

[089] In Formula 2, R1 can be a single bond or an alkylene group of 1 to 10 carbon atoms, R2 and R3 can each independently be an alkyl group of 1 to 10 carbon atoms, R4 can be hydrogen, an alkyl group of 1 to 10 carbon atoms, a monosubstituted alkylsilyl group, a disubstituted alkylsilyl group Petition 870260052105, dated 05 / 29 / 2026, p. 36 / 86 29 / 65 or trisubstituted with alkyl groups of 1 to 10 carbon atoms, or a heterocyclic group of 2 to 10 carbon atoms, R21 can be a single bond, an alkylene group of 1 to 10 carbon atoms, or -[R42O]j-, R42 can be an alkylene group of 1 to 10 carbon atoms, aem can each be independently an integer selected from 1 to 3, n can be an integer of 0, 1 or 2, and j can be an integer selected from 1 to 30.

[090] In a particular embodiment, in Formula 2, R1 can be a single bond or an alkylene group of 1 to 5 carbon atoms, R2 and R3 can each independently be hydrogen or an alkyl group of 1 to 5 carbon atoms, R4 can be hydrogen, an alkyl group of 1 to 5 carbon atoms, a trialkylsyl group substituted with an alkyl group of 1 to 5 carbon atoms, or a heterocyclic group of 2 to 5 carbon atoms, R21 can be a single bond, an alkylene group of 1 to 5 carbon atoms, or -[R42O]j-, R42 can be an alkylene group of 1 to 5 carbon atoms, a can be an integer from 2 to 3, m can be an integer selected from 1 to 3, n can be an integer from 0, 1 or 2, where m + n = 3 can be satisfied, ej can be an integer selected from 1 to 10.

[091] In Formula 2, if R4 is the heterocyclic group, the heterocyclic group may be substituted or unsubstituted with a trisubstituted alkoxysyl group, and if the heterocyclic group is substituted with the trisubstituted alkoxysyl group, the trisubstituted alkoxysyl group may be substituted through the connection with the heterocyclic group by an alkylene group of 1 to 10 carbon atoms, and the trisubstituted alkoxysyl group may mean an alkoxysyl group substituted with an alkoxy group of 1 to 10 carbon atoms.

[092] As more particular examples, the compound represented by Formula 2 may be selected from the group consisting of N,N-bis(3-(dimethoxy(methyl)silyl)propyl)-methyl-1-amine, N,N-bis(3-(diethoxy(methyl)silyl)propyl)-methyl-1-Petition 870260052105, dated 29 / 05 / 2026, page 37 / 86 30 / 65 amina, N,N-bis(3-(trimethoxysilyl)propil)-metil-1-amina, N,N-bis(3-(triethoxysilyl)propil)metil-1 -amina, N,N-diethyl-3-(trimethoxysilyl)propan-1 -amina, N,N-dieti I-3(triethoxysilyl)propan-1 -amina, tri(triethoxysilyl)propan-1 -amine, tri-(3(trimethoxysilyl)propyl)amina, N,N-bis(3-(dietóxi(metil)silyl)propyl)-1,1,1trimetilsilanamina, N,N-bis(3-(1 H-imidazol-1 -yl)propyl)-(triethoxysilyl)methan-1 -amina, N(3-(1 H-1,2,4-triazol-1 -yl)propil)-3-(trimethoxysilyl)propil)-1,1,1trimethylsilanamina li l)propi l)propan-1 amine, 3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)-N-(3-(1-(3-(trimethoxysilyl)propyl)1 H-1,2,4-triazol-3-yl)propyl)propan-1 -amina, N,N-bis(2-(2-methoxyethoxy)ethyl)-3(triethoxysilyl)propan-l-amina, N,N-bis(3-(triethoxysilyl)propyl)-2,5,8,11,14-pentaoxahexadecan-16-amina, N -(2,5,8,11,14-pentaoxa-hexadecan-16-yl)-N-(3(triethoxysilyl)propyl)-2,5,8,11,14-pentaoxa-hexadecan-16-amina e N-(3,6,9,12tetraoxa-hexadecyl)-N-(3-(triethoxysilyl)propyl)-3,6,9,12-tetraoxa-hexadecan-1-amine.

[093] In another embodiment, the modifier may include a compound represented by Formula 3 below. [Formula 3] R12 IR—Si(0R7)b(R8L K N^N — R — N V— Si(0R1°)c(R11)3_c

[094] In Formula 3, R5, R6 and R9 can each independently be an alkylene group of 1 to 10 carbon atoms, R7, R8, R10 and R11 can each independently be an alkyl group of 1 to 10 carbon atoms, R12 can be hydrogen or an alkyl group of 1 to 10 carbon atoms, b and c can each independently be 0, 1, 2 or 3, b + c > 1 can be satisfied, and A can be orR'5 R16, where R13, R14, R15 and R16 can each be, Petition 870260052105, dated 05 / 29 / 2026, p. 38 / 86 31 / 65 independently, hydrogen or an alkyl group of 1 to 10 carbon atoms.

[095] In a particular embodiment, the compound represented by Formula 3 may be one selected from the group consisting of N-(3-(1H-imidazol-1-yl)propyl)-3(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine) and 3-(4,5-dihydro-1H-imidazol1-yl)-N, N-bis(3-(triethoxysi I i I) propyl)prop n-1 -amine.

[096] In another embodiment, the modifier may include a compound represented by Formula 4 below. [Formula 4] R17R L1° 0L \l __ a1— S i— 0 — S i — A2— / II 4 L 0 0 R1SR20

[097] In Formula 4, A1 and A2 can each independently be a divalent hydrocarbon group of 1 to 20 carbon atoms, containing an oxygen atom or not, R17 to R20 can each independently be a monovalent hydrocarbon group of 1 to 20 carbon atoms, L1 to L4 can each independently be a monosubstituted, disubstituted or trisubstituted alkylsilyl group with alkyl groups of 1 to 10 carbon atoms or a monovalent hydrocarbon group of 1 to 20 carbon atoms, wherein L1 and L2, and L3 and L4 can be combined to form rings of 1 to 5 carbon atoms, and if L1 and L2, and L3 and L4 are combined to form rings, the rings thus formed may include one to three heteroatoms of one or more types selected from the group consisting of N, O and S.

[098] In a particular embodiment, in Formula 4, A1 and A2 can each independently be an alkylene group of 1 to 10 carbon atoms, R17 and R20 can each independently be an alkyl group of 1 to 10 carbon atoms Petition 870260052105, dated 05 / 29 / 2026, p. 39 / 86 32 / 65 carbon, L1a L4 can each independently be a trialkylsilyl group substituted with an alkyl group of 1 to 5 carbon atoms or an alkyl group of 1 to 10 carbon atoms, wherein L1 and L2, and L3 and L4 can be combined with each other to form rings of 1 to 3 carbon atoms, and if L1 and L2, and L3 and L4 are combined with each other to form rings, the rings thus formed can include from one to three heteroatoms of one or more types selected from the group consisting of N, O and S.

[099] In a more particular embodiment, the compound depicted by Formula 4 can be a selected from the group consisting of 3,3'-(1,1,3,3tetramethoxysiloxane-1,3-di-yl)bis(N,N-dimethylpropane-1-amine, 3,3'-(1,1,3,3tetraethoxysiloxano-1,3-di-yl)bis(N,N-dimethylpropane-1-amine), 3,3'-(1,1,3,3tetrapropoxysiloxano-1,3-di-yl)bis(N,N-dimethylpropane-1-amine), 3,3'-(1,1,3,3tetramethoxysiloxano-1,3-di-yl)bis(N,N-diethylpropane-1-amine), 3,3'-(1,1,3,3tetramethoxysiloxano-1,3-di-yl)bis(N,N-dimpropylpropane-1 -amine), 3,3'-(1,1,3,3tetraethoxysiloxano-1,3-di-yl)bis(N,N-diethylpropane-1-amine), 3,3'-(1,1,3,3tetrapropoxysiloxano-1,3-di-yl)bis(N,N-diethylpropane-1-amine), 3,3'-(1,1,3,3tetraethoxysiloxano-1,3-di-yl)bis(N,N-dipropylpropane-1-amine), 3,3'-(1,1,3,3tetrapropoxysiloxano-1,3-di-yl)bis(N,N-dipropylpropane-1-amine), 3,3'-(1,1,3,3tetramethoxysiloxano-1,3-di-yl)bis(N,N-diethylmethane-1-amine), 3,3'-(1,1,3,3tetraethoxysiloxano-1,3-di-yl)bis(N,N-diethylmethane-1-amine),3tetrapropoxide siloxano-1,3-di-yl)bis(N,N-diethylmethane-1-amine), 3,3'-(1,1,3,3tetramethoxysiloxano-1,3-di-yl)bis(N,N-dimethylmethane-1-amine), 3,3'-(1,1,3,3tetramethoxysiloxano-1,3-di-yl)bis(N,N-dipropylmethane-1-amine), 3,3'-(1,1,3,3tetrapropoxysiloxano-1,3-di-yl)bis(N,N-dimethylmethane-1-amine), 3,3'-(1,1,3,3tetrapropoxidysiloxano-1,3-di-yl)bis(N,N-dipropylmethane-1-amine), 3,3'-(1,1,3,3tetraethoxysiloxano-1,3-di-yl)bis(N,N-dimethylmethane-1-amine), 3,3'-(1,1,3,3tetraethoxysiloxano-1,3-di-yl)bis(N,N-dipropylmethane-1-amine), N,N'-((1,1,3,3tetramethoxysiloxano-1,3-di-yl)bis(propan-3,1 -di-yl))bis(1,1,1,1-trimethyl-NP 870260052105, of 29 / 05 / 2026, page 40 / 86, 33 / 65 (trimethylsilyl)silanamine, N,N'-((1,1,3,3-tetraethoxydisiloxano-1,3-di-yl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine, N,N'-((1,1,3,3-tetrapropoxydisiloxano1,3-di-yl)bis(propan-3,1 -di-yl))bis( 1,1,1 -trimethyl-N-(trimethyIsiIyl)silanamine, N,N'-((1,1,3,3-tetradinoxydis-1 l)bis(propan-3,1 -di-i l))bis( 1,1,1 -trimethyl-Nphenylsilanamine, N, N' -((1,1,3,3-tetraethoxydissiloxano-1,3-d ii l)bis(propan-3,1 -diyl))bis(1,methyl-triaminate N,N'-((1,1,3,3-tetrapropoxydisiloxano-1,3-diyl)bis(propan-3,1 -di-yl))bis(1,1,1-trimethyl-N-phenylsilanamine, 1,3-bis(3-(1 H-imidazol-1yl)propyl,3,3-1,te 1,3-bis(3-(1 H-im idazol-1 -yl)propyl)-1,1,3,3tetraethoxydisiloxane and 1,3-bis(3-( 1 H-im idazol-1 -yl)propi 1)-1,1,3,3tetrapropoxydisiloxane.

[0100] In another embodiment, the modifier can include a compound depicted in Formula 5 below. [Formula 5] (0R24)d(R25)3_dIf X R—NZ XN— R23'si(0R26)e(R27)3.e

[0101] In Formula 5, R22 and R23 can each independently be an alkylene group of 1 to 20 carbon atoms, or -R28[OR29]f-, R24 and R27 can each independently be an alkyl group of 1 to 20 carbon atoms or an aryl group of 6 to 20 carbon atoms, R28 and R29 can each independently be an alkylene group of 1 to 20 carbon atoms, R47 and R48 can each independently be a divalent hydrocarbon group of 1 to 6 carbon atoms, d and e can each independently be an integer selected from 0, or 1 to 3, where d + e is an integer of 1 or more, and f can be an integer from 1 to 30.

[0102] In particular, in Formula 5, R22 and R23 can each be, Petition 870260052105, dated 05 / 29 / 2026, p. 41 / 86 34 / 65 independently, an alkylene group of 1 to 10 carbon atoms, or -R28[OR29]f, R24a R27 can each independently be an alkyl group of 1 to 10 carbon atoms, R28e R29 can each independently be an alkylene group of 1 to 10 carbon atoms, d and e can each independently be an integer selected from 0, or 1 to 3, where d + e is an integer of 1 or more, and f can be an integer from 1 to 30.

[0103] More specifically, the compound represented by Formula 5 may be a compound represented by Formula 5a, Formula 5b, or Formula 5c below. [Formula 5a] (0R24)d(R25)3_dSi / ---\ R—NN— R23\--- / \i (OR26)e(R27)3_e [Formula 5b] (0R24)d(R25)3_dSi / X R— NN— R23\---- / 'si (OR26) ( R27)3_e [Formula 5c]

[0104] In Formula 5a, Formula 5b and Formula 5c, R22a, R27, and dee are the same as described above.

[0105] In a more particular embodiment, the compound represented by Formula 5 can be selected from the group consisting of 1,4-bis(3-(3(triethoxysilyl)propoxy)propyl)piperazine, 1,4-bis(3-(triethoxysilyl)propyl)piperazine, 1,4bis(3-(trimethoxysilyl)propyl)piperazine, 1,4-bis(3-(dimethoximethylsilyl)piperazine) l)propyl)piperazine, 1 Petition 870260052105, de 29 / 05 / 2026, pág. 42 / 86 35 / 65 (3-(ethoxydimethylsilyl)propyl)-4-(3-(triethoxysilyl)propyl)piperazine, 1-(3-(ethoxydimethyl)propyl)4-(3-(triethoxysilyl)methyl)piperazine, -(3-(ethoxydimethyl)methyl)-4-(3(triethoxysilyl)propyl)piperazine, 1,3-bis(3-(triethoxysilyl)propyl)imidazolidine, 1,3-bis(3(dimethoxyethylsilyl)propyl)imidazolidine, 1,3-bis(3-(trimethoxysilyl)propyl)hexahydropyrimidine, 1,3-bis(3-(trimethoxysilyl)propyl)hexahydropyrimidine and 1,3-bis(3-(triethoxysilyl)propyl)hexa-hydropyrimidine.

[0106] In another embodiment, the modifier may include a compound represented by Formula 6 below. [Formula 6]

[0107] In Formula 6, R30 can be a monovalent hydrocarbon group of 1 to 30 carbon atoms, R31 to R33 can each independently be an alkylene group of 1 to 10 carbon atoms, R34 to R37 can each independently be an alkyl group of 1 to 10 carbon atoms, and g and h can each independently be an integer selected from 0, or 1 to 3, where g + h can be an integer of 1 or more.

[0108] In another embodiment, the modifier may include a compound represented by Formula 7 below. [Formula 7]

[0109] In Formula 7, A3 and A4 can each independently be an alkylene group of 1 to 10 carbon atoms, R38 and R41 can each be, Petition 870260052105, dated 05 / 29 / 2026, p. 43 / 86 36 / 65 independently, an alkyl group of 1 to 10 carbon atoms or an alkoxy group of 1 to 10 carbon atoms, ei can be an integer selected from 1 to 30.

[0110] In another embodiment, the modifier may include one or more selected from the group consisting of 3,4-bis(2-methoxyethoxy)-N-(4(trimethylsilyl)butyl)aniline, N,N-diethyl-3-(7-methyl-3,6,8,11-tetraoxa-7-silatridecan-7yl)propan-1-amine, 2,4-bis(2-methoxyethoxy)-6-((trimethylsilyl)methyl)-1,3,5-triazine and 3,14dimtheoxy-3,8,8,13-tetramethyl-2,14-dioxa-7,9-dithio-3,8,13-trisylpentadecane.

[0111] In another embodiment, the modifier may include a compound represented by Formula 8 below. [Formula 8] (R^-)—Sn—4s — R — S i (OR45), (R46k_ \ / 4-k \ / k

[0112] In Formula 8, R43, R45 and R46 can each independently be an alkyl group of 1 to 10 carbon atoms, R44 can be an alkylene group of 1 to 10 carbon atoms, and ek can be an integer selected from 1 to 4.

[0113] In a more particular embodiment, the compound represented by Formula 8 may be one selected from the group consisting of 8,8-dibutyl-3,13dimethoxy-3,13-dimethyl-2,14-dioxa-7,9-dithio-3,13-dissil-8-stanapentadecane, 8,8dimethyl-3,13-dimethoxy-3,13-dimethyl I-2,14-dioxa-7,9-dithio-3,13-d issi I-8stanapentadecane, 8,8-dibutyl-3,3,13,13-tetramethoxy-2,14-dioxa-7,9-dithio-3,13-dissil8-stanapentadecane and 8-butyl-3,3,13,13-tetram ethoxy-8-((3-(trim ethoxyssi I yl)propy l)thio)2,14-dioxa-7,9-dithio-3,13-disyl-8-stanapentadecane. Method for Preparing Modified Conjugated Diene-Based Polymer

[0114] The present invention provides a method for preparing a modified conjugated diene-based polymer, whereby a modified conjugated diene-based polymer satisfying conditions (i) to (vii) above simultaneously. Petition 870260052105, dated 05 / 29 / 2026, page 44 / 86 37 / 65

[0115] In the preparation method according to the present invention, the polymerization reaction is carried out by applying an oligomer having an anionic active terminal as a polymerization initiator and injecting it at least twice during the polymerization of an active polymer, and an active polymer having a wide molecular weight distribution can be prepared under conditions other than high temperature. Consequently, defects in the deactivation of the active part of the active polymer due to high temperature may not be generated, and the modification reaction between the active polymer and a modifier can be favorably achieved, thus easily preparing a modified diene-based polymer having a wide molecular weight distribution and a high modification ratio.

[0116] The modified conjugated diene-based polymer preparation method is characterized by including: polymerizing a conjugated diene-based monomer, or a conjugated diene-based monomer and an aromatic vinyl-based monomer in a hydrocarbon solvent to prepare an active polymer (S1);and react or couple the active polymer prepared in step (S1) and a modifier (S2), wherein the polymerization in step (S1) is carried out by initiating the polymerization in the presence of a first polymerization initiator and injecting a second polymerization initiator at least once at a point where a polymerization conversion ratio is 50% to 95%, the first and second polymerization initiators are oligomers prepared by reacting an organometallic compound, a conjugated diene-based monomer and a compound represented by Formula 1 and having an anionic active terminal, step (S1) is continuously carried out in at least two polymerization reactors, and a polymerization conversion ratio in the first reactor between the polymerization reactors is 10% to 50%.

[0117] The conjugated diene-based monomer, the aromatic vinyl-based monomer and the compound represented by Formula 1 used in the preparation method Petition 870260052105, dated 05 / 29 / 2026, page 45 / 86 38 / 65 are the same as described above, and the specific description will be omitted.

[0118] The hydrocarbon solvent is not specifically limited, but may be, for example, one or more selected from the group consisting of n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene and xylene. Stage S1

[0119] Polymerization in step (S1) can be, for example, anionic polymerization and, particularly, living anionic polymerization whereby an anionic active moiety is formed at the polymerization terminal via anion propagation reaction. Furthermore, polymerization in step (S1) can be a heating polymerization, an isothermal polymerization, or a constant temperature polymerization (adiabatic polymerization). Here, constant temperature polymerization can mean a polymerization method including a polymerization step using high-generated reaction heat without optionally applying heat after injecting a polymerization initiator, and heating polymerization can mean a polymerization method including injecting the polymerization initiator and then raising the temperature by optionally applying heat.Isothermal polymerization can refer to a polymerization method in which the temperature of a polymer is kept constant by increasing the heat through the application of heat or by receiving heat after adding the polymerization initiator.

[0120] Furthermore, step (S1) polymerization is carried out by reacting a conjugated diene-based monomer, or a conjugated diene-based monomer and an aromatic vinyl-based monomer in the presence of a polymerization initiator in a hydrocarbon solvent, and particularly it can be carried out by initiating polymerization in the presence of a first polymerization initiator and carrying out the polymerization reaction by injecting a second polymerization initiator at least once at a point where a polymerization conversion ratio is 50% to 95%. In step (S1) polymerization, the second Petition 870260052105, dated 05 / 29 / 2026, page 46 / 86 39 / 65 polymerization initiator is injected at least once at a point in the polymerization conversion ratio described above for the reaction of a monomer to readily form a new polymer chain separate from the polymer chain initially produced and, consequently, in the active polymer thus prepared, a large number of polymer chains having different molecular weights may be present in the active polymer, and the active polymer may have a wide molecular weight distribution.

[0121] Here, the first and second polymerization initiators may be the same or different and, if they are the same, “the first” and “the second” may mean the injection order for the reaction.

[0122] Furthermore, the first and second polymerization initiators are oligomers having an anionic active terminal, prepared by reacting an organometallic compound, a conjugated diene-based monomer and a compound represented by Formula 1, and may have a weighted average molecular weight of 100 g / mol to 30,000 g / mol or 150 g / mol to 15,000 g / mol.

[0123] In another embodiment, the oligomer includes a repeating unit derived from a conjugated diene-based monomer and a repeating unit derived from a compound represented by Formula 1 in one molecule and, in this case, the repeating numbers of the repeating unit derived from the conjugated diene-based monomer and the repeating unit derived from the compound represented by Formula 1 can be controlled within the ranges for the oligomer satisfying the weighted average molecular weight ranges described above.

[0124] Furthermore, the oligomer having an anionic active terminal can be prepared by anionic polymerization of a conjugated diene-based monomer and a compound represented by Formula 1 in the presence of an organometallic compound and, in this case, the amounts used of the conjugated diene-based monomer and the compound represented by Formula 1 can be controlled by Petition 870260052105, dated 05 / 29 / 2026, page 47 / 86 40 / 65 in order to satisfy the weighted average molecular weight range described above. For example, the organometallic compound can be used in 0.001 mol to 1.0 mol or 0.01 mol to 1.0 mol based on 1 mol of the conjugated diene-based monomer, and the compound represented by Formula 1 can be used in 0.001 mol to 100 mol or 0.01 mol to 10 mol based on 1 mol of the conjugated diene-based monomer.

[0125] According to one embodiment of the present invention, step (S1) may use the polymerization initiator at 0.01 mmol to 10 mmol based on a total of 100 g of monomer and, herein, the polymerization initiator may include the first and second polymerization initiators. In particular, the polymerization initiator may be used at 0.05 mmol to 5 mmol, 0.1 mmol to 2 mmol, 0.1 mmol to 1 mmol or 0.15 to 0.8 mmol based on a total of 100 g of monomer.

[0126] Furthermore, the second polymerization initiator can be used at 0.001 mol to 100 mol or 0.1 mol to 10 mol based on 1 mol of the first polymerization initiator.

[0127] In the present invention, the organometallic compound may be, for example, one or more selected from the group consisting of methyllithium, ethyllithium, propyllithium, isopropyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, toctyllithium, phenyllithium, 1-naphthyllithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, sodium naphthyl, potassium naphthyl, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide and lithium isopropylamide.

[0128] Furthermore, the injection of the second polymerization initiator in batches may be batch injection in batches or continuous injection in batches and, in particular, batch injection may include first continuous injection in batches of a portion of the total quantity of the second polymerization initiator at a point where a polymerization conversion ratio is 50% less than Petition 870260052105, dated 05 / 29 / 2026, page 48 / 86 41 / 65% and the second continuous injection in installments of the remainder between the total quantity at a point where a polymerization conversion ratio is 80% to 95%, the continuous injection in installments can be injection of the total quantity injected from the initiation of the injection until the end of the injection at a constant rate with a constant quantity.

[0129] Furthermore, according to one embodiment of the present invention, polymerization in step (S1) is carried out in two or more polymerization reactors, and a polymerization conversion ratio in the first polymerization reactor among the polymerization reactors can be 10% to 50% or 20% to 50%. That is, polymerization in step (S1) can be carried out only until the polymerization conversion ratio in the first polymerization reactor becomes 10% to 50% or 20% to 50%. Within this range, secondary reactions generated during the formation of a polymer after initiating the polymerization reaction can be restricted, and a polymer with a linear structure can be induced during polymerization, and the monomer depleted in the initial stage of the reaction can be controlled to easily control the amount of monomer capable of reacting with the second polymerization initiator injected in batches.Consequently, the previously mentioned unimodal molecular weight distribution curve can be obtained, and the previously mentioned molecular weight distribution can be satisfied. In this case, the polymerization conversion ratio can be controlled according to the reaction temperature, the retention time in the reactor, etc.

[0130] More particularly, the polymerization in step (S1) can be carried out in two or more polymerization reactors, a conjugated diene-based monomer, or a conjugated diene-based monomer and an aromatic vinyl-based monomer can be polymerized in the presence of a first polymerization initiator in a hydrocarbon solvent in the first polymerization reactor until a polymerization conversion ratio becomes 10% to 50% to prepare Petition 870260052105, dated 05 / 29 / 2026, page 49 / 86 42 / 65 an active polymer having the polymerization conversion ratio, and the polymerization can be continued in a second polymerization reactor and subsequent polymerization reactors to prepare the active polymer. The second polymerization initiator can be injected at least once during polymerization at a point where a polymerization conversion ratio is 50% to 95%. In this case, the injection of the second polymerization initiator in batches can be carried out by injecting into a first reactor, a second reactor, and a subsequent polymerization reactor according to the polymerization conversion ratio point.

[0131] Meanwhile, polymerization in step (S1) can be carried out by including a polar additive as needed and, in this case, the total amount of polar additive used can be in a ratio of 0.001 g to 50 g or 0.002 g to 1.0 g based on the total 100 g of monomer. In another embodiment, the total amount of polar additive used can be in a ratio greater than 0 g to 1 g, 0.01 g to 1 g or 0.1 g to 0.9 g based on the total 100 g of polymerization initiator.

[0132] The polar additive may be, for example, one or more selected from the group consisting of tetrahydrofuran, ditetrahydrofurylpropane, diethyl ether, cyclopentyl ether, dipropyl ether, ethylene methyl ether, ethylene dimethyl ether, diethyl glycol, dimethyl ether, tert-butoxyethoxyethane, bis(3-dimethylaminoethyl)ether, (dimethylaminoethyl)ethyl ether, trimethylamine, triethylamine, tripropilamine and tetramethylethylenediamine, and may be particularly triethylamine or tetramethylethylenediamine.

[0133] Meanwhile, the polymerization conversion ratio can be determined, for example, by measuring the solid concentration in a copolymer solution phase including the copolymer during polymerization and, in a particular embodiment, in order to protect the copolymer solution, a cylinder-type container is installed at the outlet of each polymerization reactor to fill a certain amount Petition 870260052105, dated 05 / 29 / 2026, page 50 / 86 43 / 65 of the copolymer solution is placed in the cylinder-type container, and then the cylinder-type container is separated from the reactor, the weight (A) of the cylinder filled with the copolymer solution is measured, the copolymer solution filled in the cylinder-type container is transferred to an aluminum container, for example, an aluminum plate, the weight (B) of the cylinder-type container from which the copolymer solution is removed is measured, the aluminum container containing the copolymer solution is dried in an oven at 140 °C for 30 minutes, the weight (C) of a dried polymer is measured, and the calculation is performed according to Mathematical Formula 3 below. [Mathematical Formula 3] Weight (C) Polymer conversion rate (%) =---------------------------------------------x 100 [(Weight (A) - Weight (B)) x Total Solids Content (TSC)]

[0134] In Mathematical Formula 3, the total solid content is the total solid content in a copolymer solution separated from each reactor and is the weight percentage of the solid content relative to 100% of the copolymer solution. For example, if the total solid content is 20% by weight, the calculation can be performed by substituting 20 / 100, i.e., 0.2, into Mathematical Formula 3.

[0135] Meanwhile, the polymerization reagent polymerized in the first reactor can be transported to polymerization reactors before a modification reactor in order, and polymerization can be carried out until the final polymerization conversion ratio becomes greater than 95%. After carrying out polymerization in the first reactor, the polymerization conversion ratio for each reactor from the second reactor or from the second reactor to the polymerization reactor before the modification reactor can be appropriately controlled to control the molecular weight distribution.

[0136] Furthermore, the active polymer prepared by step (S1) may mean a polymer in which a polymer anion and the organometallic cation of the polymerization initiator are combined.

[0137] In addition, polymerization in step (S1) can be carried out, by Petition 870260052105, dated 05 / 29 / 2026, page 51 / 86 44 / 65 For example, in a temperature range of 100 °C or less, 50 °C to 100 °C, or 50 °C to 80 °C, and within this range, the rate of the conversion polymerization reaction can be increased.

[0138] The term “polymerization reagent” in the present invention may mean an intermediate of a type of polymer, which is under polymerization in each reactor during the performance of step (S1) or may mean a polymer with a polymerization conversion ratio of 95% or less under polymerization in a reactor, after the completion of step (S1) or step (S2) and before obtaining the active polymer or the modified diene-based polymer. Stage S2

[0139] According to one embodiment of the present invention, in the reaction of step (S2), the modifier can be used in an amount of 0.01 mmol to 10 mmol based on a total of 100 g of monomer. In another embodiment, the modifier can be used in a molar ratio of 1:0.1 to 10, 1:0.1 to 5 or 1:0.1 to 1:3, based on 1 mol of the polymerization initiator in step (S1).

[0140] Furthermore, according to one embodiment of the present invention, the modifier can be injected into a modification reactor, and step (S2) can be conducted in the modification reactor. In another embodiment, the modifier can be injected into a transport part to transport the active polymer prepared in step (S1) to a modification reactor to conduct step (S2), and the reaction can be carried out by mixing the active polymer and the modifier in the transport part. In this case, the reaction can be a modification reaction to simply couple the modifier with the active polymer or a coupling reaction to connect the active polymer based on the modifier. Rubber Composition

[0141] According to the present invention, a rubber composition including the modified diene-based conjugated polymer is provided. Petition 870260052105, dated 05 / 29 / 2026, page 52 / 86 45 / 65

[0142] The rubber composition may include the modified diene-based polymer in an amount of 10% by weight or more, 10% by weight to 100% by weight or 20% by weight to 90% by weight and, within this range, the mechanical properties, such as tensile strength and abrasion resistance, are excellent, and the effects of excellent balance between the physical properties can be obtained.

[0143] In addition, the rubber composition may also include other rubber components, if necessary, in addition to the modified diene-conjugated polymer, and in this case, the rubber components may be included in an amount of 90% by weight or less based on the total weight of the rubber composition. In a particular embodiment, the other rubber components may be included in 1 part by weight to 900 parts by weight based on 100 parts by weight of the modified diene-conjugated polymer.

[0144] The rubber component may be, for example, a natural rubber or a synthetic rubber, and may be particularly a natural rubber (NR) including cis-1,4-polyisoprene; a modified natural rubber that is obtained by modifying or purifying a common natural rubber, such as an epoxidized natural rubber (ENR), a deproteinized natural rubber (DPNR) and a hydrogenated natural rubber;and a synthetic rubber, such as a styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), an ethylene-propylene copolymer, polyisobutylene-co-isoprene, neoprene, poly(ethylene-co-propylene), poly(styrene-co-butadiene), poly(styrene-coisoprene), poly(styrene-co-isoprene-co-butadiene), poly(isoprene-co-butadiene), poly(ethylene-co-propylene-co-diene), a polysulfide rubber, an acrylic rubber, a urethane rubber, a silicone rubber, an epichlorohydrin rubber, and a halogenated butyl rubber, and any one or mixtures of two or more of the same may be used. Petition 870260052105, dated 05 / 29 / 2026, page 53 / 86 46 / 65

[0145] The rubber composition may include a filler in 0.1 parts by weight to 200 parts by weight or 10 parts by weight to 120 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer of the present invention. The filler may be, for example, a silica-based filler, particularly wet silica (hydrated silicate), dry silica (anhydrous silicate), calcium silicate, aluminum silicate, colloidal silica, etc., and preferably the filler may be wet silica which has the most significant effect of improving the destruction characteristics and compatible floor adhesion effect. In addition, the rubber composition may also include a carbon-based filler, as required.

[0146] In another embodiment, if silica is used as the filler, a silane coupling agent may be used in conjunction to improve the reinforcing and low exothermic properties. Particular examples of the silane coupling agent may include bis(3-triethoxysilylpropyl)tetrasulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2trimethoxysilylethyl)tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 2-triethoxysilylethyl-N,Ndimethylthiocarbamoyltetrasulfide, 3-trimethoxysilylpropylbenzothiazolyltetrasulfide, 3triethoxysilylpropylbenzolyltetrasulfide, 3-triethoxysilylpropylmethacrylatemonosulfide,3-trimethoxysilylpropylmethacrylate monosulfide, bis(3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide or dimethoxymethylsilylpropylbenzothiazolyltetrasulfide, and any one of them or mixtures of two or more of them may be used. Preferably, bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazolyltetrasulfide may be used taking into account the, Petition 870260052105, dated 05 / 29 / 2026, page 54 / 86 47 / 65 effects of improving reinforcing properties.

[0147] Furthermore, in the rubber composition according to one embodiment of the present invention, since a modified conjugated diene-based polymer in which a functional group having high affinity for silica is introduced into an active part is used as a rubber component, the amount of the silane coupling agent in the composition can be less than in a common case. Thus, the silane coupling agent can be used in 1 part by weight to 20 parts by weight or 5 parts by weight to 15 parts by weight based on 100 parts by weight of silica, and within the above range, the effects as a coupling agent can be sufficiently demonstrated, and the gelation prevention effects of a rubber component can be obtained.

[0148] 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 particularly a sulfur powder and may be included in 0.1 parts by weight to 10 parts by weight based on 100 parts by weight of a rubber component and, within the range, the elasticity and strength required for a vulcanized rubber composition may be confirmed and, at the same time, an excellent low fuel consumption ratio may be obtained.

[0149] The rubber composition according to one embodiment of the present invention may also include various additives used in a common rubber industry in addition to the components described above, particularly a vulcanization accelerator, a process oil, a plasticizer, an anti-aging agent, a burn prevention agent, a zinc white, stearic acid, a thermosetting resin or a thermoplastic resin.

[0150] The vulcanization accelerator may include, for example, thiazole-based compounds such as 2-mercaptobenzothiazole (M), dibenzothiazyl disulfide (DM) and N Petition 870260052105, dated 05 / 29 / 2026, page 55 / 86 48 / 65 cyclohexyl-2-benzothiazylsulfenamide (CZ), or guanidine-based compounds, such as diphenylguanidine (DPG), in 0.1 parts by weight to 5 parts by weight based on 100 parts by weight of the rubber component.

[0151] Process oil acts as a softener in a rubber compound and may include, for example, paraffin-based compounds, naphthene-based compounds, or aromatic compounds. Aromatic process oil may be used in consideration of tensile strength and abrasion resistance, and naphthene-based or paraffin-based process oil may be used in consideration of hysteresis loss and low-temperature properties. Process oil may be included in an amount of 100 parts by weight or less based on 100 parts by weight of the rubber component. Within the range described above, deterioration of tensile strength and low exothermic properties (low fuel consumption rate) of the vulcanized rubber can be avoided.

[0152] The anti-aging agent may include, 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 condensate of diphenylamine and acetone at high temperature, in 0.1 parts by weight to 6 parts by weight based on 100 parts by weight of the rubber component.

[0153] The rubber composition according to one embodiment of the present invention can be obtained by grinding using a grinding apparatus, such as a banbury mixer, a roller and an internal mixer according to a composition prescription and a rubber composition with low exothermic properties and good abrasion properties can be obtained by a vulcanization process after a molding process.

[0154] Therefore, the rubber compound can be useful for the manufacture of each element of a tire, such as a tread, a sidewall, a carcass lining rubber, a belt lining rubber, a Petition 870260052105, dated 05 / 29 / 2026, p. 56 / 86 49 / 65 bead filler, a bead lining and coating rubber, or for the manufacture of rubber products in various industries, such as vibration-proof rubber, a conveyor belt and a hose.

[0155] In addition, the present invention provides a tire manufactured using a rubber compound.

[0156] The tire may be a tire or include a tire tread. Examples

[0157] Next, the embodiments will be explained in detail to particularly explain the present invention. However, the embodiments according to the present invention may be modified into various other types, and the scope of the present invention should not be limited to the embodiments described below. The embodiments of the present invention are provided to fully explain the present invention to a person with an average knowledge of the art. Example of Preparation 1

[0158] Under a nitrogen atmosphere, in a 5 L pressurized reactor, 100 g (10 wt% n-hexane) of n-butyllithium were placed and 2,000 g of n-hexane, 337 g of 1,3-butadiene and 23.0 g of 4-(dimethylamino)styrene were added, followed by reaction at 40 °C for 20 minutes to prepare an oligomer solution including 14.9 wt% of an oligomer with an anionic active terminal and a weighted average molecular weight of 3,100 g / mol. Example of Preparation 2

[0159] An oligomer solution including 15.1 wt% of an oligomer having an anionic active terminal and a weighted average molecular weight of 3,200 g / mol was prepared by carrying out the same reaction as in Preparation Example 1 except for the use of 25 g of N,N-dimethylvinylbenzylamine instead of 4(dimethylamino)styrene in Preparation Example 1. Example 1 Petition 870260052105, dated 05 / 29 / 2026, page 57 / 86 50 / 65

[0160] For a first reactor among three continuously stirred liquid phase reactors (CSTRs), continuously injected were n-hexane at a flow rate of 4 kg / h, a monomer solution in which 60 wt% of a monomer mixture (80 wt% 1,3-butadiene and 20 wt% styrene) was dissolved in n-hexane at a flow rate of 1.6 kg / h, an oligomer solution prepared in Preparation Example 1 in n-hexane as a polymerization initiator at a flow rate of 139 g / h, a polar additive solution in which 10 wt% ditetrahydrofurylpropane was dissolved in n-hexane as a polar additive at a flow rate of 0.5 g / h, and a solution in which 15 wt% 1,2-butadiene was dissolved in n-hexane at a flow rate of 1 g / h.In this case, the internal temperature of the reactor was maintained at 50 °C, and when the polymerization conversion rate reached 45%, a polymerization product was transported from the first reactor to a second reactor via a transport tube.

[0161] Next, the temperature of the second reactor was maintained at 65 °C, and when a polymerization conversion rate reached 85%, while transporting a polymerization product from the second reactor to a third reactor via a transport tube, the oligomer solution prepared in Preparation Example 1 was injected into the tube at a rate of 146 g / h.

[0162] Next, the temperature of the third reactor was maintained at 65 °C and, when a polymerization conversion rate reached 98% or more, a polymerization product was continuously supplied from the third reactor to a fourth reactor via a transport tube and a solution in which 20% by weight of N,N-bis(3(dimethoxy(methyl)silyl)propyl)-methyl-1-amine was dissolved in n-hexane was continuously supplied as a modifier to carry out the modification reaction (molar ratio of act.Li:modifier = 1:0.5).

[0163] Next, for a polymerization solution discharged from the third reactor, a solution of IR1520 (BASF Co.) in which 30% by weight was Petition 870260052105, dated 05 / 29 / 2026, page 58 / 86 51 / 65 dissolved as an antioxidant was injected at a rate of 100 g / h and stirred. The polymer thus obtained was injected into hot water heated with steam and stirred to remove solvents and rolled dried to remove remaining solvents and water to prepare a modified diene-conjugated polymer at both ends. Example 2

[0164] A modified conjugated diene-based polymer was prepared by performing the same method as in Example 1, except for injecting the oligomer solution prepared in Preparation Example 1 into the tube at a rate of 147 g / h, while transporting a polymerization product from the second reactor to the third reactor through the transport tube at a point where the polymerization conversion ratio reached 95%, in Example 1 (molar ratio of act.Li:modifier = 1:0.5). Example 3

[0165] A modified conjugated diene-based polymer was prepared by performing the same method as in Example 1, except for injecting the oligomer solution prepared in Preparation Example 1 into the tube at a rate of 147 g / h, while transporting a polymerization product from the second reactor to the third reactor through the transport tube at a point where the polymerization conversion ratio reached 75%, in Example 1 (molar ratio of act.Li:modifier = 1:0.5). Example 4

[0166] A modified conjugated diene-based polymer was prepared by performing the same method as in Example 1, except for injecting the oligomer solution prepared in Preparation Example 1 into the tube at a rate of 147 g / h, while transporting a polymerization product from the second reactor to the third reactor through the transport tube at a point where the polymerization conversion rate reached 80%, and continuously injecting a solution in which 20 wt% of N-(4-methylpiperazinyl)-N,N-bis(3-(triethoxysilyl)propyl)amine was dissolved as a modifier into the fourth reactor, in Example 1 (molar ratio of act.Li:modifier). Petition 870260052105, dated 05 / 29 / 2026, page 59 / 86 52 / 65 = 1:0.5). Example 5

[0167] For a first reactor among three continuously stirred liquid phase reactors (CSTRs), continuously injected were n-hexane at a flow rate of 4 kg / h, a monomer solution in which 60 wt% of a monomer mixture (80 wt% 1,3-butadiene and 20 wt% styrene) was dissolved in n-hexane at a flow rate of 1.6 kg / h, an oligomer solution prepared in Preparation Example 2 in n-hexane as a polymerization initiator at a flow rate of 156 g / h, a polar additive solution in which 10 wt% ditetrahydrofurylpropane was dissolved in n-hexane as a polar additive at a flow rate of 0.5 g / h, and a solution in which 15 wt% 1,2-butadiene was dissolved in n-hexane at a flow rate of 1 g / h.In this case, the internal temperature of the reactor was maintained at 50 °C, and when the polymerization conversion rate reached 45%, a polymerization product was transported from the first reactor to a second reactor via a transport tube.

[0168] Next, the temperature of the second reactor was maintained at 65 °C, and when a polymerization conversion rate reached 85%, while transporting a polymerization product from the second reactor to a third reactor via a transport tube, the oligomer solution prepared in Preparation Example 2 was injected into the tube at a rate of 147 g / h.

[0169] Next, the temperature of the third reactor was maintained at 65 °C and, when a polymerization conversion rate reached 98% or more, a polymerization product was continuously supplied from the third reactor to a fourth reactor via a transport tube and a solution in which 20% by weight of N-(3-(1-Himidazol-1-yl)propyl-N,N-bis(3-(triethoxysilyl)propyl)amine was dissolved in n-hexane was continuously supplied as a modifier to carry out the modification reaction (molar ratio of act.Li:modifier = 1:0.5). Petition 870260052105, dated 05 / 29 / 2026, pp. 60 / 86 53 / 65

[0170] Next, for a polymerization solution discharged from the third reactor, a solution of IR1520 (BASF Co.) in which 30% by weight was dissolved as an antioxidant, was injected at a rate of 100 g / h and stirred. The polymer thus obtained was injected into hot water heated with steam and stirred to remove solvents and roller dried to remove remaining solvents and water to prepare a modified diene-based polymer at both ends. Example 6

[0171] A modified conjugated diene-based polymer was prepared by performing the same method as in Example 1, except for injecting the oligomer solution prepared in Preparation Example 2 into the tube at a rate of 147 g / h, while transporting a polymer from the second reactor to the third reactor through the transport tube at a point where the polymerization conversion rate reached 70% and continuously injecting a solution in which 20 wt% of N,N-bis(3(dimethoxy(methyl)silyl)propyl)-methyl-1-amine was dissolved in n-hexane as a modifier into the fourth reactor, in Example 5 (molar ratio of act.Li:modifier = 1:0.5). Example 7

[0172] A modified conjugated diene-based polymer was prepared by carrying out the same method as in Example 2, except for continuously injecting a solution in which 20 wt% of N-(4-methylpiperazinyl)-N,N-bis(3-(triethoxysilyl)propyl)amine was dissolved in n-hexane as a modifier into the fourth reactor, in Example 2 (molar ratio of act.Li:modifier = 1:0.5). Comparative Example 1

[0173] A modified conjugated diene-based polymer was prepared using the same method as in Example 1, except that the oligomer solution was not injected while transporting the polymerization product from the second reactor to the third reactor through the transport tube, as in Example 1 (molar ratio of Petition 870260052105, dated 05 / 29 / 2026, pp. 61 / 86 54 / 65 act.Li:modifier = 1:0.5). Comparative Example 2

[0174] A modified conjugated diene-based polymer was prepared by performing the same method as in Example 6, except for injecting an n-butyl-lithium solution in which 10 wt% n-butyl-lithium was dissolved in n-hexane into the first reactor at a rate of 6.0 g / h instead of the oligomer solution as the polymerization initiator and not injecting the polymerization initiator while transporting the polymerization product from the second reactor to the third reactor through the transport tube, in Example 6 (molar ratio of act.Li:modifier = 1:0.5). Comparative Example 3

[0175] A modified conjugated diene-based polymer was prepared by performing the same method as in Example 1, except for injecting an n-butyl-lithium solution in which 10 wt% n-butyl-lithium was dissolved in n-hexane into the first reactor at a rate of 6.0 g / h instead of the oligomer solution as the polymerization initiator and injecting the n-butyl-lithium solution at a rate of 3.0 g / h at a point at which a polymerization conversion ratio reached 43%, in Example 1 (molar ratio of act.Li:modifier = 1:0.5). Comparative Example 4

[0176] A modified conjugated diene-based polymer was prepared by performing the same method as in Example 1, except for injecting an n-butyl-lithium solution in which 10 wt% n-butyl-lithium was dissolved in n-hexane into the first reactor at a rate of 6.0 g / h instead of the oligomer solution as the polymerization initiator and injecting the n-butyl-lithium solution at a rate of 2.4 g / h at a point at which a polymerization conversion ratio reached 80%, in Example 1 (molar ratio of act.Li:modifier = 1:0.5). Comparative Example 5 Petition 870260052105, dated 05 / 29 / 2026, pp. 62 / 86 55 / 65

[0177] A modified conjugated diene-based polymer was prepared by carrying out the same method as in Example 5, except for continuously injecting a solution in which 20 wt% of tin tetrachloride (SnCl4) was dissolved in nhexane into the fourth reactor as the modifier, in Example 5 (molar ratio of act.Li:modifier = 1:0.5). Comparative Example 6

[0178] A modified conjugated diene-based polymer was prepared by performing the same method as in Example 5, except that the polymerization initiator was not injected while transporting the polymerization product from the second reactor to the third reactor through the transport tube, and a solution in which 20 wt% of tris(3-(triethoxysilyl)propyl)amine was dissolved in nhexane was continuously injected into the fourth reactor as the modifier, in Example 5 (molar ratio of act.Li:modifier = 1:0.5). Experimental Examples Experimental Example 1

[0179] With respect to each of the copolymers prepared in the Examples and Comparative Examples, the styrene linkage content and the 1,2-vinyl linkage content, a weighted average molecular weight (Mw, x103g / mol), molecular weight distribution (MWD), a molecular weight distribution curve, a shrinkage factor, the nitrogen atom content and a modification ratio were measured, respectively, and the results are shown in Table 1 below. 1) Microstructure analysis (styrene bond content (SM)) and 1,2-vinyl bond content (1,2-vinyl)

[0180] The styrene and 1,2-vinyl linkage contents in each modified conjugated diene-based polymer were measured and analyzed using Varian VNMRS 500 MHz NMR.

[0181] During the NMR measurement, 1,1,2,2-tetrachloroethane was used as Petition 870260052105, dated 05 / 29 / 2026, pp. 63 / 86 56 / 65 a solvent, and a sample was prepared by dissolving the polymer in the solvent at 0.02 M. The styrene linkage content (wt%) and the 1,2-vinyl linkage content (wt%) were calculated by calculating a solvent peak at 5.97 ppm, and relating 7.2 to 6.9 ppm as random styrene peaks, 6.9 to 6.2 ppm as block styrene peaks, 5.8 to 5.1 ppm as 1,4-vinyl peaks, and 5.1 to 4.5 ppm as 1,2-vinyl peaks. 2) Weighted average molecular weight (Mw), molecular weight distribution (MWD), and molecular weight distribution curve.

[0182] By gel permeation chromatography (GPC) (PL GPC220, Agilent Technologies), a weighted average molecular weight (Mw) and a number average molecular weight (Mn) were measured under the conditions below, a molecular weight distribution curve was obtained and the molecular weight distribution (PDI, MWD, Mw / Mn) was obtained by calculating from each of the measured molecular weights. - Column: two Olexis PLgel columns (Polymer Laboratories Co.) and one mixed-C PLgel column (Polymer Laboratories Co.) were used in combination. - Solvent: a mixture of tetrahydrofuran and 2% by weight of an amine compound were used. - Flow rate: 1 ml / min Sample concentration: 1 to 2 mg / ml (diluted in THF) Injection quantity: 100 μl - Column temperature: 40 °C Detector: Refractive index 3) Mooney stress relaxation ratio (-S / R) and large Mooney relaxation area (MLRA)

[0183] The measurement was performed using an Alpha Technologies Co. MV2000E using a Large Rotor at a rotor speed of 2 ± 0.02 rpm at 100 °C. Specifically, a polymer was left at room temperature (23 ± 5 °C) for 30 Petition 870260052105, dated 05 / 29 / 2026, pp. 64 / 86 For 57 / 65 minutes or more, 27 ± 3 g of material were collected and placed in a mold cavity. Then, the platen was operated and measurements were taken for 4 minutes to obtain the Mooney viscosity. Afterward, the slope of the Mooney viscosity change during torque release was measured, and the Mooney stress relaxation ratio was obtained as its absolute value. Furthermore, the large Mooney relaxation area is an integration value of a Mooney relaxation curve from 1 second to 120 seconds after rotor stop, calculated using Mathematical Formula 1 below. [Mathematical Formula 1]

[0184] In Mathematical Formula 1, A is a large Mooney relaxation area (MLRA), k is a Mooney intercept after 1 second of interruption of the operation of a Mooney viscometer rotor, a is a Mooney relaxation ratio, to is a Mooney relaxation initiation point, and tf is a Mooney relaxation termination point. 4) Nitrogen atom content (N content)

[0185] The measurement was performed using an NSX analysis method, and the measurement by the NSX analysis method used a quantitative analyzer for a trace amount of nitrogen (NSX-2100H).

[0186] Specifically, the quantitative analyzer for a trace amount of nitrogen (Auto sampler, horizontal oven, PMT & nitrogen detector) was switched on, the carrier gas flow rates were set to 250 ml / min for Ar, 350 ml / min for O2, and 300 ml / min for the ozonizer, a heater was set to 800 °C and the analyzer was left to stand for about 3 hours to Petition 870260052105, dated 05 / 29 / 2026, pages 65 / 86 58 / 65 Stabilization. After stabilizing the analyzer, a calibration curve was created using calibration curve ranges of 5 ppm, 10 ppm, 50 ppm, 100 ppm, and 500 ppm using a nitrogen standard (AccuStandard S-22750-01-5 ml), and an area corresponding to each concentration was obtained. Then, using the ratios of the concentrations to the areas, a straight line was drawn. Next, a ceramic boat containing 20 mg of a sample was placed in the analyzer's autosampler, and the area was measured. Using the area of ​​the sample thus obtained and the calibration curve, the nitrogen atom content was calculated. 5) Rate of change (%)

[0187] The modification ratio (%) was calculated according to Mathematical Formula 2 below using a chromatogram obtained from the chromatography measurement, and the chromatography measurement was conducted using a gel permeation chromatograph (GPC) (PL GPC220, Agilent Technologies) as follows. Each copolymer was dissolved in cyclohexane and stored in a mobile phase reservoir of one sample (prepared at 1.0 m / ml) and tetrahydrofuran (THF) was stored in another mobile phase reservoir. The mobile phase reservoirs were connected with a double-head pump, respectively, and firstly, the solution in the mobile phase reservoir in which the copolymer was dissolved was injected into a column filled with a silica absorbent through the pump and an injector with a cycle volume of 100 pl. In this case, the pump pressure was 450 psi and the injection flow rate was 0.7 ml / min.So, after confirming that an unmodified butadiene copolymer unit in the copolymer was no longer detected by a detector (ELSD, Waters Co.), based on 5 minutes from the start of the injection, tetrahydrofuran was injected into the column via the pump. In this case, the pump pressure was 380 psi and the injection flow rate was 0.7 ml / min. After confirming that a modified copolymer unit was no longer detected in the polymer according to the tetrahydrofuran injection detector, the injection of... Petition 870260052105, dated 05 / 29 / 2026, pages 66 / 86 59 / 65 a second solvent was completed. Then, from the chromatogram results detected, a modification ratio (%) was calculated according to Mathematical Formula 2 below. [Mathematical Formula 2] Modification ratio (%) / peak area of ​​modified copolymer unit = (peak area of ​​unmodified copolymer unit + peak area of ​​modified copolymer unit) x 100

[0188] In Mathematical Formula 2, the peak area of ​​the unmodified polymer unit is the peak area of ​​the chromatogram in a first solution transported to the detector and the peak area of ​​the modified polymer unit is the peak area of ​​the chromatogram in a second solution transported to the detector. [Table 1] Microstructure Division (% by weight) GPC -S / R MLRA (MU-s) Modification Ratio (%) N Content (ppm) SM 1,2-inyl Molecular Weight Distribution Curve Mw (x103 g / mol) MWD Example 1 19.9 50.2 Unimodal 511 2.42 1.15 651 98 240 Example 2 20.5 50.2 Unimodal 478 2.38 1.21 672 98 264 Example 3 20.4 50.1 Unimodal 507 2.28 1.14 641 99 258 Example 4 20.5 49.8 Unimodal 473 2.31 1.18 701 97 246 Example 5 20.1 49.9 Unimodal 572 Example 6: 20.1 50.0 Unimodal 559 2.12 1.16 699 98 295 Example 7: 20.5 50.2 Unimodal 487 2.30 1.12 685 98 285 Example Comparative 1: 20.4 49.5 Unimodal 464 1.60 0.87 820 95 156 Example Comparative 2: 20.2 50.5 Unimodal 527 1.70 0.79 840 85 86 Example Comparative 3: 20.8 50.1 Unimodal 570 1.90 0.80 950 85 91 Example Comparative 4: 20.5 50.2 Unimodal 490 2.40 0.85 680 98 75 Comparative Example 5 20.4 49.8 Unimodal 466 2.34 1.20 695 65 204 Comparative Example 6 20.8 49.9 Unimodal 980 1.90 0.40 1900 98 240

[0189] As shown in Table 1, Examples 1 to 7 satisfied all conditions (i) to (vii) suggested in this disclosure at the same time. Petition 870260052105, dated 05 / 29 / 2026, pp. 67 / 86 60 / 65

[0190] However, Comparative Examples 1 to 6 showed a molecular weight distribution of 2.0 or less, a nitrogen atom content of 100 ppm or less, or a Mooney strain relaxation ratio of less than 0.7, and did not satisfy conditions (i) to (vii) suggested in this disclosure at the same time.

[0191] Here, when compared with Example 1, Comparative Example 1 was prepared by a preparation method whereby the step of injecting a polymerization initiator in batches was not performed, and Comparative Example 3 was prepared by a preparation method whereby a polymerization initiator was injected at a point where a polymerization conversion ratio was 43%, which was less than 50%, and the broad molecular weight distribution properties were not shown. In particular, although Comparative Example 1 used the same polymerization initiator and modifier as those of Example 1, the nitrogen atom content in a polymer was markedly reduced to a degree of 65%, and in the case of Comparative Example 3, the modification ratio was markedly reduced to a degree of 87%.

[0192] Furthermore, in the case of Comparative Example 6, the same polymerization initiator as in Example 5 was used, and a modifier containing nitrogen atoms was used and the nitrogen atom content in the polymer was high to the degree of the Examples, but the molecular weight distribution was narrow and less than 2.0, and the Mooney strain relaxation ratio was less than 0.7, showing high branching. In this case, Comparative Example 6 was prepared by a preparation method whereby a polymerization initiator was not injected in parcels.

[0193] Through the above results, it can be confirmed that the modified diene-based polymer that satisfies conditions (i) to (vii) according to the present invention can be obtained by controlling the conditions simultaneously through preparation by a preparation method including the Petition 870260052105, dated 05 / 29 / 2026, pp. 68 / 86 61 / 65 control of a polymerization conversion ratio in a first polymerization reactor to a specific point suggested in the present invention and including a polymerization step of injecting a polymerization initiator in portions at specific points. Experimental Example 2

[0194] In order to compare and analyze the physical properties of rubber compositions, including modified diene-based copolymers prepared in Examples and Comparative Examples and molded products manufactured from them, tensile properties, viscoelasticity properties and processability properties were measured, respectively, and the results are presented in Table 3 below. 1) Preparation of the rubber sample

[0195] The composition was carried out using each of the modified diene-based polymers from the Examples and Comparative Examples as a rubber feedstock under the composition conditions shown in Table 3 below. The feedstocks in Table 3 are represented by parts by weight based on 100 parts by weight of the rubber feedstock. [Table 2] Raw Material Breakdown Quantity (parts by weight) First-stage grinding Rubber 100 Silica 70 Coupling agent (X50S) 11.2 Process oil 37.5 Zinc white 3 Stearic acid 2 Antioxidant 2 Anti-aging agent 2 Petition 870260052105, dated 05 / 29 / 2026, pp. 69 / 86 62 / 65 Wax 1 Second-stage grinding Sulfur 1.5g Rubber accelerator 1.75g ​​Vulcanization accelerator 2g

[0196] Specifically, the rubber sample was ground using first-stage and second-stage grinding. In the first-stage grinding, a rubber raw material, silica (filler), a silane organic coupling agent (X50S, Evonik), a process oil (TDAE oil), zinc oxide (ZnO), stearic acid, an antioxidant (TMQ (RD)) (2,2,4-trimethyl-1,2-dihydroquinoline polymer), an anti-aging agent (6PPD ((dimethylbutyl)-N-phenyl-phenylenediamine)) and wax (Microcrystalline Wax) were ground using a Banbury mixer equipped with a temperature control device. In this case, the initial temperature of the grinding apparatus was controlled at 70 °C and, after the composition was complete, a first mixture of compounds was obtained at a discharge temperature of 145 °C to 155 °C.In the second-stage grinding, the first compound mixture was cooled to room temperature, and the first compound mixture, sulfur, a rubber accelerator (DPD (diphenylguanine)), and a vulcanization accelerator (CZ (N-cyclohexyl-2-benzothiazylsulfenamide)) were added to the grinding apparatus and mixed at a temperature of 100 °C or less to obtain a second compound mixture. Then, through a curing process at 160 °C for 20 minutes, a rubber sample was formed. 2) Tensile properties

[0197] Tensile properties were measured by fabricating each sample and measuring tensile strength when broken and tensile stress when stretched at 300% (300% modulus) of each sample according to an ASTM 412 tensile test method. Specifically, tensile properties were measured using a Universal Test Machin 4204 tensile tester (Instron Co.) at a rate of 50 cm / min at room temperature. Petition 870260052105, dated 05 / 29 / 2026, pp. 70 / 86 63 / 65 3) Viscoelastic properties

[0198] Viscoelastic properties were ensured by measuring the viscoelastic behavior in thermodynamic deformation at each measurement temperature (-60 °C to 60 °C) with a frequency of 10 Hz using a dynamic mechanical analyzer (GABO Co.) in a film stress mode and ensuring a tan δ value. In this case, if the tan δ value at a low temperature of 0 °C increases, the wet skid resistance improves, and if the tan δ value at a high temperature of 60 °C decreases, the hysteresis loss decreases and the rolling resistance (fuel consumption ratio) improves. The resulting values ​​in Table 3 were indexed based on the resulting values ​​from Comparative Example 1, and therefore, the higher the value, the better the results. 4) Processability properties

[0199] By measuring the Mooney viscosity (MV, ML 1+4, @ 100 °C MU) of the second compound mixture obtained during 1) preparation of the rubber specimen, the processability properties of each polymer were compared and analyzed and, in this case, the lower the measured Mooney viscosity value, the better the processability properties.

[0200] Specifically, using MV-2000 (ALPHA Technologies Co.) using Large Rotor at a rotor speed of 2 ± 0.02 rpm at 100 °C, each second mixture of compounds was kept at room temperature (23 ± 5 °C) for 30 minutes or more, and 27 ± 3 g were collected and placed in a mold cavity, and then the Platen was operated for 4 minutes for measurement. [Table 3] Division Tensile properties (index, %) Viscoelastic properties (index, %) Processability properties (index, %) Tensile strength Modulus at 300 % tan δ at 0 °C tan δ at 60 °C Petition 870260052105, dated 05 / 29 / 2026, pp. 71 / 86 64 / 65 Example 1 103 115 99 134 110 Example 2 101 115 100 136 120 Example 3 99 112 100 130 109 Example 4 102 111 101 129 111 Example 5 100 114 102 132 113 Example 6 100 110 99 125 107 Example 7 101 110 99 130 110 Comparative Example 1 100 110 101 125 66 Comparative Example 2 100 100 100 100 100 Comparative Example 3 100 99 98 95 110 Comparative Example 4 100 101 98 102 101 Comparative Example 5 100 105 97 102 110 Comparative Example 6 100 105 95 125 65

[0201] In Table 3, the tensile properties and the tan δ value at 0 °C of Examples 1 to 7, Comparative Example 1 and Comparative Example 3 to 6 were calculated based on the measurement values ​​of Comparative Example 2 using Mathematical Formula 4 below, and the tan δ value at 60 °C was calculated based on the measurement value of Comparative Example 2 using Mathematical Formula 5 below. [Mathematical Formula 4] Petition 870260052105, dated 05 / 29 / 2026, pp. 72 / 86 65 / 65 Percentage (%) = (measured value / reference value) x 100 [Mathematical Formula 5] Percentage (%) = (reference value / measured value) x 100

[0202] As shown in Table 3, Examples 1 to 7 according to embodiments of the present invention showed markedly excellent tensile properties, wet slip resistance, rolling resistance and processability in equilibrium when compared with Comparative Examples 1 to 6.

[0203] In this case, Examples 1 to 7 satisfied all conditions (i) to (vii) suggested in the present invention, and Comparative Examples 1 to 6 did not satisfy any or more of the conditions.

[0204] The results in Table 1 and Table 3 mean that the modified diene-based polymer of the present invention is prepared by a preparation method suggested in the present invention and can satisfy specific conditions defined by (i) to (vii) at the same time and, consequently, improve the effects of tensile properties, wet slip resistance, rolling resistance and processability in equilibrium can be achieved.

Claims

1. Modified conjugated diene-based polymer CHARACTERIZED in that it comprises: a repeating unit derived from a conjugated diene-based monomer; and a functional group derived from a modifier, and satisfying the following conditions from (i) to (vii): (i) a molecular weight distribution curve by gel permeation chromatography is unimodal; (ii) the molecular weight distribution is 2.0 or more; (iii) a weighted average molecular weight is from 100,000 g / mol to 2,000.000 g / mol; (vi) a modification ratio is 70% or more; (v) a Mooney stress relaxation ratio measured at 100 °C is 0.7 to 3.0; (vii) a large Mooney relaxation area (MLRA) measured at 100 °C and represented by the following Mathematical Formula 1 is 1500 Mll-s or less; and (v ii) nitrogen atom content is 100 ppm or more based on a weight of the polymer: [Mathematical Formula 1] In Mathematical Formula 1, A is a large Mooney relaxation area (MLRA), k is a Mooney intercept after 1 second of interruption of the operation of a Mooney viscometer rotor, a is a Mooney relaxation ratio, to is a Mooney relaxation initiation point, and tf is a Mooney relaxation termination point, Petition 870260052105, 2026-05-29, p.75 / 86 2 / 6 wherein the weighted average molecular weight and molecular weight distribution are measured by gel permeation chromatography, wherein the Mooney strain relaxation ratio and the large Mooney relaxation area are measured by Mooney viscometer.

2. Modified conjugated diene-based polymer according to claim 1, CHARACTERIZED in that it further comprises a repeating unit derived from a compound represented by the following Formula 1: [Formula 1] R2----N FU in Formula 1, R1 is a hydrogen atom or an alkyl group of 1 to 20 carbon atoms, R2 is a single bond or an alkylene group substituted or unsubstituted of 1 to 20 carbon atoms, R3 and R4 are each independently an alkyl group substituted or unsubstituted of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms or an aryl group of 6 to 30 carbon atoms, and the substituent is one or more selected from the group consisting of an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms and an aryl group of 6 to 20 carbon atoms.

3. Modified conjugated diene-based polymer according to claim 2, CHARACTERIZED in that, in Formula 1, Petition 870260052105, dated 05 / 29 / 2026, p. 76 / 86 3 / 6 R1 is a hydrogen atom or an alkyl group of 1 to 10 carbon atoms, R2 is a single bond or an unsubstituted alkylene group of 1 to 10 carbon atoms, R3 and R4 are each independently an unsubstituted alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 3 to 10 carbon atoms or an aryl group of 6 to 12 carbon atoms.

4. Modified conjugated diene-based polymer, according to claim 1, CHARACTERIZED in that the modifier is an alkoxysilane-based compound.

5. Modified conjugated diene-based polymer according to claim 1, CHARACTERIZED in that a repeating unit derived from an aromatic vinyl-based monomer is further comprised, and the aromatic vinyl-based monomer is one or more selected from the group consisting of styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, 1-vinyl-5-hexylnaphthalene, 3-(2-pyrrolidine ethyl)styrene, 4-(2-pyrrolidine ethyl)styrene and 3-(2-pyrrolidine-1-methyl ethyl)-α-methylstyrene.

6. Method for preparing the modified conjugated diene-based polymer, as defined in claim 1, the method CHARACTERIZED in that it comprises: polymerizing a conjugated diene-based monomer, or a conjugated diene-based monomer and an aromatic vinyl-based monomer in a hydrocarbon solvent to prepare an active polymer (S1); and reacting or coupling the active polymer prepared in step (S1) with a modifier (S2), Petition 870260052105, dated 05 / 29 / 2026, p. 77 / 86 4 / 6 wherein the polymerization of step (S1) is carried out by initiating polymerization in the presence of a first polymerization initiator, and carrying out the polymerization reaction by injecting a second polymerization initiator into at least one portion at a point where a polymerization conversion ratio is 50% to 95%, the first and second polymerization initiators are oligomers having an anionic active terminal, prepared by reacting an organometallic compound,a conjugated diene-based monomer and a compound represented by the following Formula 1, and step (S1) is continuously carried out in at least two polymerization reactors, wherein a polymerization conversion ratio in the first reactor between the polymerization reactors is 10% to 50%: [Formula 1] R2----N R4 in Formula 1, R1 is a hydrogen atom or an alkyl group of 1 to 20 carbon atoms, R2 is a single bond or a substituted or unsubstituted alkylene group of 1 to 20 carbon atoms, R3 and R4 are each independently a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms or an aryl group of 6 to 30 carbon atoms, and Petition 870260052105, of 29 / 05 / 2026, p. 78 / 86 5 / 6 the substituent is one or more selected from the group consisting of an alkyl group of 1 to 20 carbon atoms,a cycloalkyl group of 3 to 20 carbon atoms and an aryl group of 6 to 20 carbon atoms.

7. Method for preparing the modified conjugated diene-based polymer according to claim 6, CHARACTERIZED in that the oligomer has a weighted average molecular weight of 100 g / mol to 30,000 g / mol, measured by gel permeation chromatography.

8. Method for preparing the modified conjugated diene-based polymer according to claim 6, CHARACTERIZED in that step (S1) uses the polymerization initiator at 0.01 mmol to 10 mmol based on a total of 100 g of monomer, and the polymerization initiator comprises the first and second polymerization initiators.

9. Method for preparing the modified conjugated diene-based polymer according to claim 6, CHARACTERIZED in that the second polymerization initiator is used at 0.01 mol to 10 mol based on 1 mol of the first polymerization initiator.

10. Method for preparing the modified conjugated diene-based polymer according to claim 6, CHARACTERIZED in that the batch injection comprises the first continuous batch injection of a portion of the total amount of the second polymerization initiator at a point where a polymerization conversion ratio is 50% to less than 80%, and the second continuous batch injection of the remaining amount of the total amount at a point where a polymerization conversion ratio is 80% to 95%, and the first continuous batch injection and the second continuous batch injection are injections of the second polymerization initiator at a constant rate from initiation to the end of the injection.

11. Method for preparing the modified conjugated diene-based polymer, Petition 870260052105, dated 05 / 29 / 2026, page 79 / 86 6 / 6 according to claim 6, CHARACTERIZED in that the polymerization in step (S1) is carried out also comprising a polar additive.

12. Method for preparing the modified conjugated diene-based polymer according to claim 6, CHARACTERIZED in that the modifier is an alkoxysilane-based compound.

13. Rubber composition, CHARACTERIZED in that it comprises the modified diene-based polymer, as defined in claim 1, and a filler.

14. Rubber composition, according to claim 13, CHARACTERIZED in that the rubber composition comprises 0.1 parts by weight to 200 parts by weight of the filler based on 100 parts by weight of the modified diene-based polymer.

15. Rubber composition according to claim 13, CHARACTERIZED in that it further comprises a vulcanizing agent.