Modified conjugated diene polymer, preparation method thereof and rubber composition containing same

Abstract

The present invention relates to a modified conjugated diene polymer having excellent rolling resistance and improved processability, a method for preparing the same, and a rubber composition comprising the same, and provides a modified conjugated diene polymer comprising a repeating unit derived from a conjugated diene monomer and a functional group derived from a modifier and satisfying conditions (i) to (vii), a method for preparing the same, and a rubber composition comprising the same.

Description

Technical Field

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS

[0003] This application claims priority to Korean Patent Application No. 10-2020-0025512, filed on February 28, 2020, which is hereby incorporated by reference in its entirety. Technical Field

[0004] The present invention relates to a modified conjugated diene-based polymer having excellent rolling resistance and improved processability, a preparation method thereof, and a rubber composition containing the same. Background Art

[0005] According to recent demands for automobiles with low fuel consumption, conjugated diene-based polymers having modulation stability represented by wet skid resistance and low rolling resistance and excellent wear resistance and tensile properties are required as rubber materials for tires.

[0006] In order to reduce the rolling resistance of the tire, there is a method of reducing the hysteresis loss of the vulcanized rubber, and the rebound resilience at 50°C to 80°C, tan δ or Goodrich heating, etc. is used as an evaluation index of the vulcanized rubber. In other words, it is desirable to use a rubber material having high rebound resilience at the above temperature or low tan δ value or Goodrich heating.

[0007] Natural rubber, polyisoprene rubber or polybutadiene rubber are known as rubber materials with low hysteresis loss, but these rubbers have the limitation of low wet slip resistance. Therefore, recently, conjugated diene polymers or copolymers such as styrene-butadiene rubber (hereinafter referred to as "SBR") and butadiene rubber (hereinafter referred to as "BR") are prepared by emulsion polymerization or solution polymerization to be used as rubber for tires. Among these polymerization methods, the greatest advantage of solution polymerization compared with emulsion polymerization is that the vinyl structure content and styrene content of the physical properties of the specified rubber can be arbitrarily adjusted, and its molecular weight and physical properties can be controlled by coupling or modification. Therefore, SBR prepared by solution polymerization is widely used as a rubber material for tires, because it is easy to change the structure of the SBR or BR finally prepared, the movement of the chain end can be reduced, and the coupling force with fillers such as silica and carbon black can be increased by coupling or modification of the chain end.

[0008] Solution-polymerized SBR is prepared using an anionic polymerization initiator, and a method of introducing a functional group into the terminal by coupling or modifying the chain terminal of the polymer thus formed with various modifiers is used. For example, U.S. Pat. No. 4,397,994 discloses a method of coupling the active anion at the chain terminal of a polymer (obtained by polymerizing styrene-butadiene using an alkyl lithium as a monofunctional initiator) in a nonpolar solvent using a coupling agent such as a tin compound.

[0009] In addition, it is generally advantageous that solution-polymerized SBR has a broad molecular weight distribution in terms of improving compounding processability, and preparation methods have been attempted by conducting high-temperature polymerization or using a coupling agent to introduce long-chain branches, but in the case of high-temperature polymerization, the molecular weight distribution becomes broad but the modification ratio decreases, and in the case of using a coupling agent, there is a problem in reducing rolling resistance due to steric hindrance between the coupling agent and the filler.

[0010] Therefore, there is a need to develop a modified conjugated diene-based polymer having excellent rolling resistance and improved processability by having a wide molecular weight distribution and a high modification ratio.

[0011] [Prior art literature]

[0012] (Patent Document 1) U.S. Patent No. 4,397,994 Summary of the invention

[0013] [Technical issues]

[0014] The present invention has been devised to solve the problems of the above-mentioned conventional technologies, and one object is to provide a modified conjugated diene-based polymer comprising: a repeating unit derived from a conjugated diene-based monomer; and a functional group derived from a modifier, which satisfies conditions (i) to (vii) and has excellent filler affinity and processability.

[0015] In addition, another object of the present invention is to provide a method for preparing a modified conjugated diene polymer, whereby a modified conjugated diene polymer that satisfies conditions (i) to (vii) at the same time can be easily prepared by using an oligomer having an anionic active terminal as a polymerization initiator and injecting the polymerization initiator in at least two batches according to the polymerization conversion rate during the preparation of the active polymer to carry out a polymerization reaction.

[0016] In addition, another object of the present invention is to provide a rubber composition comprising the modified conjugated diene-based polymer.

[0017] [Technical solution]

[0018] In order to solve the above-mentioned tasks, according to an embodiment of the present invention, the present invention provides a modified conjugated diene-based polymer, which comprises: a repeating unit derived from a conjugated diene-based monomer; and a functional group derived from a modifier; and

[0019] Satisfy the following conditions (i) to (vii):

[0020] (i) the gel permeation chromatography molecular weight distribution curve is unimodal;

[0021] (ii) a molecular weight distribution of 2.0 or more;

[0022] (iii) a weight average molecular weight of 100,000 g / mol to 2,000,000 g / mol;

[0023] (vi) a modification ratio of 70% or more;

[0024] (v) a Mooney stress relaxation ratio measured at 100° C. of 0.7 to 3.0;

[0025] (vi) a Mooney Maximum Relaxation Area (MLRA) measured at 100° C. and represented by the following Mathematical Formula 1 is 1500 MU-s or less; and

[0026] (vii) a nitrogen atom content of 100 ppm or more based on the weight of the polymer,

[0027] [Mathematical formula 1]

[0028]

[0029] In mathematical formula 1

[0030] A is the Mooney maximum relaxation area (MLRA);

[0031] k is the Mooney intercept 1 second after stopping the rotor operation of the Mooney viscometer,

[0032] a is the Mooney relaxation ratio,

[0033] t o is the starting point of the Mooney relaxation, and

[0034] t f It is the end point of Mooney relaxation.

[0035] In addition, the present invention provides a method for preparing a modified conjugated diene polymer, the method comprising: polymerizing a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer in a hydrocarbon solvent to prepare a living polymer (S1); and reacting or coupling the living polymer prepared in step (S1) with a modifier (S2), wherein the polymerization in step (S1) is carried out in the following manner: initiating polymerization in the presence of a first polymerization initiator, and injecting a second polymerization initiator in at least one batch to carry out a polymerization reaction when the polymerization conversion rate is 50% to 95%, the first polymerization initiator and the second polymerization initiator are oligomers having anionic active ends, which are prepared by reacting an organic metal compound, a conjugated diene monomer and a compound represented by the following formula 1, and step (S1) is continuously carried out in at least two polymerization reactors, wherein the polymerization conversion rate in the first reactor of the polymerization reactors is 10% to 50%,

[0036] [Formula 1]

[0037]

[0038] In formula 1

[0039] R1 is a hydrogen atom or an alkyl group of 1 to 20 carbon atoms, R2 is a single bond or an alkylene group of 1 to 20 carbon atoms which may be substituted or unsubstituted by a substituent, R3 and R4 are each independently an alkyl group of 1 to 20 carbon atoms which may be substituted or unsubstituted by a substituent, 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.

[0040] In addition, the present invention provides a rubber composition comprising the modified conjugated diene-based polymer and a filler.

[0041] [Beneficial Effects]

[0042] The modified conjugated diene-based polymer of the present invention is prepared by the preparation method proposed in the present invention, and can have a wide molecular weight distribution, a high modification ratio, a low branching structure of a 2-arm structure, excellent processability, and excellent filler affinity.

[0043] In the method for preparing a modified conjugated diene polymer of the present invention, a polymerization reaction is carried out by injecting a polymerization initiator in at least two batches according to the polymerization conversion rate during the polymerization in step (S1) so that a living polymer is prepared using an oligomer having an anionic active terminal as a polymerization initiator, and therefore, a living polymer having a wide molecular weight distribution can be easily prepared even without high temperature conditions, and a conjugated diene polymer having a high modification ratio can be easily prepared.

[0044] In addition, the rubber composition of the present invention includes the modified conjugated diene-based polymer and can have both excellent running resistance and processability. DETAILED DESCRIPTION

[0045] Hereinafter, the present invention will be described in more detail to help understanding of the present invention.

[0046] It should be understood that the words or terms used in the specification and claims of the present invention should not be interpreted as the meanings defined in common dictionaries. It will also be understood that based on the principle that the inventor can appropriately define the meanings of words or terms to best explain the present invention, the words or terms should be interpreted as having a meaning consistent with the meaning of the technical concept of the present invention.

[0047] Definition of terms

[0048] The term "Mooney Large Relaxation Area (MLRA)" in the present invention is a measurement (measure) of chain relaxation in a molten polymer, and indicates that longer or more branched polymer chains can store more energy and require longer time for relaxation after the applied deformation is removed. For example, compared with a polymer with the same Mooney viscosity, the Mooney Large Relaxation Area of ​​an ultra-high molecular weight or long-chain branched polymer may be larger than that of a polymer with a wider or narrower molecular weight.

[0049] The term "polymer" in the present invention refers to a homopolymer compound or a copolymer compound prepared by polymerizing one type of monomer or two or more different types of monomers.

[0050] The term "1,2-vinyl bond content" in the present invention refers to the mass (or weight) percentage of butadiene contained in the 1,2-position in the polymer chain of the copolymer based on the conjugated diene monomer (butadiene, etc.) derived portion (total weight of polymerized butadiene) in the copolymer.

[0051] The term "styrene bond content" in the present invention refers to the mass (or weight) percentage of styrene contained in the copolymer chain derived from the aromatic vinyl-based monomer (styrene, etc.) in the copolymer.

[0052] The term "modification ratio (%)" in the present invention may mean a ratio of modified copolymer chains to unmodified copolymer chains in the case where a copolymer in which a polymerization active portion exists together with a modifier is modified, the ratio being represented by a percentage (%) based on the entire copolymer containing the modified copolymer chains and the unmodified copolymer chains.

[0053] The term "substituted" in the present invention may mean that the hydrogen of a functional group, an atomic group or a compound is replaced by a specific substituent. If the hydrogen of a functional group, an atomic group or a compound is replaced by a specific substituent, one or more including two or more substituents may be present depending on the number of hydrogens present in the functional group, the atomic group or the compound, and if multiple substituents are present, each substituent may be the same or different.

[0054] The term "alkyl" in the present invention may refer to a monovalent aliphatic saturated hydrocarbon, and may include straight-chain alkyl groups such as methyl, ethyl, propyl and butyl; branched-chain alkyl groups such as isopropyl, sec-butyl, tert-butyl and neopentyl; and cyclic saturated hydrocarbons, or cyclic unsaturated hydrocarbon groups containing one or more unsaturated bonds.

[0055] The "alkylene group" in the present invention may mean a divalent aliphatic saturated hydrocarbon such as methylene, ethylene, propylene and butylene.

[0056] The "cycloalkyl group" in the present invention may refer to a cyclic saturated hydrocarbon.

[0057] The term "aryl group" in the present invention may refer to a cyclic aromatic hydrocarbon, and may include a monocyclic aromatic hydrocarbon in which one ring is formed and a polycyclic aromatic hydrocarbon in which two or more rings are bonded.

[0058] The term "aralkyl group" in the present invention is also referred to as an aromatic alkyl group, and may mean a combination group of an alkyl group and an aryl group formed by substituting a hydrogen atom bonded to a carbon constituting the alkyl group with an aryl group.

[0059] The term "single bond" in the present invention may refer to a single covalent bond itself, not including separate atoms or molecular groups.

[0060] The terms "derived unit", "derived repeating unit" and "derived functional group" in the present invention may mean that a component or a structure is derived from a certain material, or the material itself.

[0061] Although the terms "comprising" and "having" and their derivatives are specifically disclosed or not specifically disclosed in the present invention, they are not intended to exclude the presence of optional additional components, steps or processes. In order to avoid any uncertainty, all compositions claimed by using the term "comprising" may include optional additional additives, adjuvants or compounds, including polymers or any other materials, unless otherwise stated. In contrast, the term "consisting essentially of excludes unnecessary operations and excludes optional other components, steps or processes within the scope of the optional continuous description. The term "consisting of excludes optional components, steps or processes that are not specifically described or shown.

[0062] Measurement methods and conditions

[0063] In the present invention, the "1,2-vinyl bond content" is obtained by measuring and analyzing the vinyl content and the styrene content in the copolymer and the first and second copolymer units using Varian VNMRS 500MHz NMR. 1,1,2,2-Tetrachloroethane is used as a solvent, and a sample is prepared by dissolving the polymer in the solvent to 0.02M. The 1,2-vinyl bond content and the styrene bond content are calculated by calculating 6.0ppm as a solvent peak, 7.2-6.9ppm as a random styrene peak, 6.9-6.2ppm as a block styrene peak, 5.8-5.1ppm as a 1,4-vinyl peak, and 5.1-4.5ppm as a 1,2-vinyl peak.

[0064] In the present invention, the molecular weight is measured by gel permeation chromatography (GPC) analysis and a molecular weight distribution curve is obtained to obtain "weight average molecular weight (Mw)", "molecular weight distribution (MWD)" and "unimodal properties". In addition, the molecular weight distribution (PDI, MWD, Mw / Mn) is calculated from each measured molecular weight. In particular, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured by gel permeation chromatography (GPC) (PL GPC220, Agilent Technologies) under the following conditions, a molecular weight distribution curve is obtained, and the molecular weight distribution (PDI, MWD, Mw / Mn) is obtained by calculation from each measured molecular weight.

[0065] - Column: A combination of two PLgel Olexis columns (Polymer Laboratories) and one PLgelmixed-C column (Polymer Laboratories) was used.

[0066] -Solvent: A mixture of tetrahydrofuran and 2 wt% of an amine compound was used.

[0067] -Flow rate: 1ml / min

[0068] -Sample concentration: 1-2 mg / ml (diluted in THF)

[0069] -Injection volume: 100μL

[0070] - Column temperature: 40℃

[0071] -Detector: Refractive index

[0072] -Standard: Polystyrene (cubic function calibration)

[0073] In the present invention, the "modification ratio (%)" is calculated according to the following mathematical formula 2 using the chromatogram obtained by the chromatographic measurement. The chromatographic measurement is performed as follows using, for example, gel permeation chromatography (GPC) (PL GPC220, Agilent Technologies). The copolymer is dissolved in cyclohexane and stored in the mobile phase reservoir (preparation, 1.0m / mL) of the sample, and tetrahydrofuran (THF) is stored in another mobile phase reservoir. The mobile phase reservoir is connected to a double-head pump, respectively, and first, the solution in the mobile phase reservoir in which the copolymer is dissolved is injected into a column filled with a silica absorbent by a pump and a syringe having a loop volume of 100 μl. In this case, the pressure of the pump is 450psi, and the injection flow rate is 0.7ml / min. Then, after confirming that the unmodified butadiene copolymer unit in the copolymer is no longer detected from the detector (ELSD, Waters Company), tetrahydrofuran is injected into the column by a pump based on 5 minutes from the start of injection. In this case, the pressure of the pump is 380psi, and the injection flow rate is 0.7ml / min. After confirming that the modified copolymer unit is no longer detected in the injected polymer according to tetrahydrofuran from the detector, the injection of the second solvent is completed. Then, the modification ratio (%) is calculated according to the following mathematical formula 2 from the detected chromatogram results.

[0074] [Mathematical formula 2]

[0075]

[0076] In Mathematical Formula 2, the peak area of ​​the unmodified polymer unit is the peak area of ​​the chromatogram on the first solution delivered to the detector, and the peak area of ​​the modified polymer unit is the peak area of ​​the chromatogram on the second solution delivered to the detector.

[0077] In the present invention, "N atomic content" is measured by the NSX analysis method. The measurement performed by the NSX analysis method uses a quantitative analyzer (NSX-2100H) for trace nitrogen. Specifically, the quantitative analyzer (autosampler, horizontal furnace, PMT and nitrogen detector) for trace nitrogen is turned on, the carrier flow rate is set to 250ml / min for Ar, 350mL / min for O2 and 300mL / min for the ozone generator, the heater is set to 800°C, and the analyzer is left to stand for about 3 hours for stabilization. After stabilizing the analyzer, a calibration curve of the calibration curve range of 5ppm, 10ppm, 50ppm, 100ppm and 500ppm is prepared using a nitrogen standard (AccuStandard S-22750-01-5ml), and the area corresponding to each concentration is obtained. Then, a straight line is made by using the ratio of concentration to area. Thereafter, a ceramic boat carrying 20mg of sample is placed in the autosampler of the analyzer and measured to obtain the area. By using the area of ​​the sample thus obtained and the calibration curve, the nitrogen atom content was calculated.

[0078] In this case, the sample used for the NSX analysis method is a modified conjugated diene-based polymer sample in which the sample is placed in hot water heated by steam and stirred to remove the solvent, and may be a sample from which the remaining monomer, remaining modifier, and oil have been removed. In addition, if oil is added to the sample, the sample may be a sample from which the oil has been extracted (removed).

[0079] In the present invention, the measurement is performed by using MV2000E of AlphaTechnologies using a large rotor at a rotor speed of 2±0.02 rpm at 100°C. Specifically, the polymer is left to stand at room temperature (23±5°C) for more than 30 minutes, 27±3 g is collected, and put into a mold cavity, and then the Platen is operated for 4 minutes while applying torque to measure, and the Mooney viscosity is obtained. Thereafter, the slope value of the change in the Mooney viscosity shown when the torque is released is measured, and its absolute value is displayed.

[0080] In the present invention, "Mooney Maximum Relaxation Area (MLRA)" is a value obtained by plotting a Mooney torque diagram according to time and calculating by Mathematical Formula 1, and can be obtained by measuring the slope value of the Mooney viscosity change shown while stopping the rotor to release the torque after measuring the Mooney viscosity, obtaining the Mooney relaxation ratio (a) as its absolute value, and obtaining it from the integral value of the Mooney relaxation curve during the period from 1 second to 120 seconds after stopping the rotor, which integral value can be calculated by Mathematical Formula 1.

[0081] Modified conjugated diene polymers

[0082] The modified conjugated diene-based polymer of the present invention can be produced by a production method to be described below, and can have a broad molecular weight distribution and a highly modified terminal.

[0083] Specifically, the modified conjugated diene polymer of the present invention is characterized by comprising a repeating unit derived from a conjugated diene monomer and a functional group derived from a modifier, and satisfies the following conditions (i) to (vii):

[0084] (i) the gel permeation chromatography molecular weight distribution curve is unimodal;

[0085] (ii) a molecular weight distribution of 2.0 or more;

[0086] (iii) a weight average molecular weight of 100,000 g / mol to 2,000,000 g / mol;

[0087] (vi) a modification ratio of 70% or more;

[0088] (v) a Mooney stress relaxation ratio measured at 100° C. of 0.7 to 3.0;

[0089] (vi) a Mooney Maximum Relaxation Area (MLRA) measured at 100° C. and represented by the following Mathematical Formula 1 is 1500 MU-s or less; and

[0090] (vii) a nitrogen atom content of 100 ppm or more based on the weight of the polymer,

[0091] [Mathematical formula 1]

[0092]

[0093] In mathematical formula 1

[0094] A is the Mooney maximum relaxation area (MLRA);

[0095] k is the Mooney intercept 1 second after stopping the rotor operation of the Mooney viscometer

[0096] a is the Mooney relaxation ratio,

[0097] to is the starting point of the Mooney relaxation, and

[0098] tf is the end point of the Mooney relaxation.

[0099] According to one embodiment of the present invention, the modified conjugated diene polymer is prepared by a preparation method including step (S1) to be described below, wherein during the polymerization in step (S1), an oligomer having an anionic active end is applied as a polymerization initiator, thereby controlling the polymerization conversion rate in the first reactor to be between 10% and 50%, and the polymerization reaction is carried out by injecting the polymerization initiator in at least two batches. By preparing by this preparation method, the above conditions (i) to (vii) can be met simultaneously.

[0100] In addition, an oligomer is prepared by reacting an organic metal compound, a conjugated diene-based monomer, and a compound represented by Formula 1, and the oligomer may include in the molecule a repeating unit derived from the compound represented by Formula 1. Therefore, by introducing the unit derived from the compound represented by Formula 1 separately from the modifier into the polymer, the above condition (vii) may be more advantageously satisfied.

[0101] According to these results, the modified conjugated diene-based polymer satisfies conditions (i) to (vii) at the same time and can simultaneously have excellent mechanical properties such as stretchability, viscoelasticity and processability, and thus can have an excellent balance of stretchability, wet slip resistance, rolling resistance and processability.

[0102] Main parameters of modified conjugated diene polymers

[0103] The modified conjugated diene polymer of one embodiment of the present invention has a unimodal molecular weight distribution curve by gel permeation chromatography (GPC), and can have a molecular weight distribution of more than 2.0, and here, the unimodal curve shape and molecular weight distribution can be satisfied simultaneously by the preparation method described below. In particular, the modified conjugated diene polymer can 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.

[0104] In addition, the modified conjugated diene-based polymer may have a weight 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 may be excellent in a balanced manner.

[0105] In addition, the modified conjugated diene 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 refer to a functional group derived from the modifier, which is present at one end of the active polymer through a reaction or coupling between the active polymer and the modifier.

[0106] In addition, the modification ratio may be affected by the modification or coupling degree of the modifier in the modification reaction, and can be controlled according to the amount of the modifier and the amount of the polar additive injected during the preparation process, the reaction time, the mixing time of the modifier and the active polymer, the mixing degree, etc.

[0107] In addition, the modification ratio may be affected by the polymerization initiator used during the preparation of the conjugated diene-based polymer, its reaction injection point, and its amount.

[0108] Meanwhile, the modified conjugated diene polymer can be prepared by the preparation method described below, which is continuously carried out in at least two polymerization reactors, the polymerization conversion rate in the first reactor is controlled to be 10% to 50%, and includes a preparation step of preparing a living polymer by injecting a polymerization initiator in at least two batches, and a modification step of reacting or coupling the living polymer with a modifier. By this preparation method, the molecular weight distribution curve can be unimodal, the molecular weight distribution can be wide and above 2.0, and the modification ratio of the above numerical value can be satisfied.

[0109] In particular, in a continuous polymerization method, the injection of raw materials and the discharge of products after the completion of the reaction are continuously carried out, and it can be considered that polymer chains of different molecular weights with different reactivity are mixed in the discharged products, including polymer chains injected and reacted from the starting point of the reaction, polymer chains formed by injecting and reacting from the middle of the reaction, and polymer chains formed by injecting and reacting at the end point of the polymerization. However, the raw materials injected into the reactor at the same point can undergo polymerization at a similar reaction rate to be discharged as a product, and therefore, the polymer chains in the product can have a similar degree of molecular weight and have a unimodal shape of molecular weight distribution narrower than expected. Then, in the case of a modification reaction by injecting a modifier, a polymer chain modified and / or coupled by a modifier can be prepared, or an unmodified and / or uncoupled polymer chain can be prepared, two or more groups with a large molecular weight difference can be formed, and a multimodal molecular weight distribution curve with two or more peaks of a molecular weight distribution curve can be formed. However, according to the preparation method of the present invention, a living polymer is prepared through a polymerization step in which the polymerization conversion rate in the first reactor is controlled to be 10% to 50% and the polymerization initiator is injected in at least two batches, and the raw materials (monomers) reacted and consumed at the starting point of the polymerization can be controlled, and it can be controlled to form new polymer chains with the polymerization initiator injected in batches, so that a polymer product containing polymer chains with different molecular weights can be obtained. Therefore, the polymer chains that are subsequently reacted with the modifier and / or coupled by the reaction can also have different molecular weights, there is no specific peak that is highlighted, the broad unimodal molecular weight distribution curve can be displayed as a single peak, and at the same time, the molecular weight distribution can be relatively wide.

[0110] In addition, by injecting the polymerization initiator batchwise, the number of polymer chains of different molecular weight sizes having the active portion having the modifier can be absolutely greater than the number of polymer chains in the active polymer prepared by the conventional continuous polymerization, and therefore, when compared with the modified conjugated diene polymer prepared by the conventional continuous polymerization applying the same modifier, it can show a higher modification ratio.

[0111] 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, and more specifically 0.9 to 1.5.

[0112] Here, the Mooney stress relaxation ratio can be used as an index (or linearity) of the branch structure of the corresponding polymer, for example, if the Mooney stress relaxation ratio decreases with increasing branching compared to a polymer with an equal Mooney viscosity, it can be used as an index of the degree of branching. The modified conjugated diene polymer of the present invention satisfies conditions (i) to (iv), (vi) and (vii) and has a Mooney stress relaxation ratio within the above range, and thus can have excellent processability, and can have excellent stretchability and viscoelasticity.

[0113] In addition, the modified conjugated diene-based polymer of one embodiment of the present invention needs to satisfy a Mooney viscosity measured under ASTM D1646 of 50 to 100, particularly 70 to 100, and preferably 70 to 90. There are various measurement values ​​of processability, but if the Mooney viscosity satisfies the above range, processability may be quite excellent.

[0114] In another embodiment, the modified conjugated diene-based polymer has a Mooney maximum relaxation area (MLRA) (represented by the following Mathematical Formula 1) measured at 100° C. of 1500 MU-s or less.

[0115] [Mathematical formula 1]

[0116]

[0117] In mathematical formula 1

[0118] A is the Mooney maximum relaxation area (MLRA);

[0119] k is the Mooney intercept 1 second after stopping the rotor operation of the Mooney viscometer

[0120] a is the Mooney relaxation ratio,

[0121] to is the starting point of the Mooney relaxation, and

[0122] tf is the end point of the Mooney relaxation.

[0123] Here, the start point of Mooney relaxation may indicate a point after 1 second from the stop of the rotor operation, and may indicate a point at which the Mooney torque has a k value. In addition, the end point of Mooney relaxation may indicate a point at which the measurement of Mooney relaxation is completed in a measurement experiment of Mooney relaxation. In other words, t f -t o It can represent the Mooney relaxation time.

[0124] In addition, according to one embodiment of the present invention, t o It can be 1 second, t f It can be 80 seconds to 150 seconds. In other words, the Mooney maximum relaxation area of ​​one embodiment of the present invention can be the integrated area under the Mooney torque-relaxation time curve from 1 second to 80 seconds to 150 seconds. In addition, t f It may in particular be 90 to 130 seconds or 100 to 120 seconds.

[0125] In the modified conjugated diene polymer of the present invention, the Mooney large relaxation area below 1500MU-s is a technical means having excellent stretchability and viscoelasticity and excellent processability. If the Mooney large relaxation area is within the above range, the target effect of the present invention can be shown. In addition, if the value of the Mooney large relaxation area is very small, mechanical properties such as stretchability may deteriorate. In view of excellent processability and excellent balance of stretchability and viscoelasticity, the Mooney large relaxation area of ​​the modified conjugated diene polymer of one embodiment of the present invention can be more than 300MU-s.

[0126] Meanwhile, generally, the molecular weight and physical properties of the Mooney viscosity of a polymer are properties in a proportional relationship and show an equal tendency, a high molecular weight polymer has the defects of high Mooney viscosity and poor processability, and a low molecular weight polymer has a low Mooney viscosity and relatively good processability, but has the defects of poor mechanical properties such as stretchability. However, the modified conjugated diene polymer of one embodiment of the present invention has a Mooney large relaxation area of ​​less than 1500 MU-s, and achieves excellent processability and stretchability in a balanced manner.

[0127] In addition, compared with polymers having the same Mooney viscosity, the Mooney large relaxation area tends to increase with increasing branches and is used as an index of the degree of branching (or linearity), but may be affected by the molecular weight of the corresponding polymer and the degree of branching of the polymer. Therefore, although the degree of branching (or linearity) is the same, the Mooney large relaxation area may be different.

[0128] Meanwhile, the modified conjugated diene polymer of the present invention can be prepared by the preparation method described below, and can control molecular weight, modification ratio and degree of branching simultaneously. Therefore, the molecular weight distribution curve can be unimodal, can have a wide molecular weight distribution, and can control Mooney stress relaxation ratio and Mooney maximum relaxation area simultaneously, thereby satisfying conditions (i) to (vii) simultaneously.

[0129] The Mooney maximum relaxation area may be a value obtained by plotting a Mooney torque diagram according to time and then calculating it by Mathematical Formula 1. In this case, the Mooney viscosity (MV, ML1+4, @100°C MU) may be measured at 100°C using a large rotor with a rotor speed of 2±0.02 rpm by using MV-2000 (ALPHA Technologies). In this case, the sample used is left to stand at room temperature (23±5°C) for more than 30 minutes, 27±3 g of the sample is collected and placed in a mold cavity, and then the measurement is performed for 4 minutes while the Platen is operated.

[0130] In addition, after measuring the Mooney viscosity, by measuring the slope value of the Mooney viscosity change shown when the torque is released by stopping the rotor, its absolute value can be obtained as the Mooney relaxation ratio (a). In addition, the absolute value can be obtained as the Mooney relaxation ratio (a) 1 second after stopping the rotor (t o ) to 120 seconds (t f ) during the Mooney relaxation curve to obtain the Mooney maximum relaxation area, and the integral value can be calculated by Mathematical Formula 1. If the Mooney relaxation area meets the above range, the viscoelasticity during the compounding of the rubber composition, especially the improvement effect of rolling resistance (RR) can be achieved. In particular, if the Mooney maximum relaxation area meets the above range under the Mooney viscosity conditions of more than 80, preferably more than 90, then the effect of even better improvement of rolling resistance can be obtained.

[0131] In another embodiment, the nitrogen atom content of the modified conjugated diene polymer may be 100 ppm or more, 100 ppm to 1,000 ppm, or 200 ppm to 500 ppm based on the weight of the polymer, within which range the rubber composition comprising the modified conjugated diene polymer may have excellent mechanical properties such as tensile properties and viscoelastic effects. Meanwhile, the nitrogen atom may be derived from the oligomer described below, or from the oligomer and the modifier, and may be prepared by the preparation method described below to have a relative nitrogen atom content.

[0132] In particular, the modified conjugated diene polymer of the present invention is prepared by the preparation method described below, by controlling the raw materials (monomers) consumed in the reaction in the early stage of polymerization, and by forming new polymer chains with the polymerization initiator injected in batches, and having nitrogen atoms derived from the polymerization initiator. Therefore, there may be a large number of active polymer chains with reactive parts with the modifier, and therefore the nitrogen atom content in the polymer may be higher than the common single end and / or two ends. When the modified conjugated diene polymer is prepared by a common continuous or intermittent polymerization method, the monomer is polymerized in the presence of a polymerization initiator to prepare an active polymer, and then the modified conjugated diene polymer is prepared by reaction or coupling with the modifier. In this case, polymerization is initiated by the reaction of the polymerization initiator and the monomer, and the reaction of the terminal anion with the monomer is maintained to propagate the polymer chain, thereby producing an active polymer. Finally, compared with the preparation method of the present invention in which the polymerization initiator is injected in batches at a specific point, the number of polymer chains produced in the case of the common continuous or intermittent polymerization method in which a polymerization initiator is injected at a point prior to initiating polymerization and polymerization is performed may be necessarily limited, and new chains are uniformly produced.

[0133] In addition, although the polymerization initiator is injected in batches in a common continuous or intermittent polymerization method, if there is no or a very small amount of monomers capable of reacting with the polymerization initiator injected in batches, there may be no newly formed polymer chains or their height is limited, so the number of polymer chains in the active polymer may not actually increase. However, in the preparation method of the present invention, the polymerization initiator is injected in batches at a specific point, and at the same time, the polymerization conversion rate in the first polymerization reactor is controlled to be 10% to 50%, that is, the initial polymerization degree of the polymer is controlled to be within a specific range. In addition, the amount of the monomer is controlled so that new polymer chains are fully generated by reacting with the polymerization initiator injected in batches, so that the number of polymer chains in the active polymer prepared thereby can be significantly increased. Here, the polymer chains in the active polymer react or couple with the modifier, and the increase in the number of polymer chains means that the polymer chains modified by reacting or coupling with the modifier increase.

[0134] The modified conjugated diene polymer of one embodiment of the present invention prepared by the preparation method may include a large number of polymer chains including nitrogen atoms derived from oligomers contained in the polymerization initiator, and may have an absolutely increased nitrogen atom content when compared to a polymer prepared by another polymerization method using the same polymerization initiator and / or modifier.

[0135] Structure of modified conjugated diene polymers

[0136] According to one embodiment of the present invention, the modified conjugated diene polymer may include a polymer chain including a repeating unit derived from a conjugated diene monomer and a functional group derived from a modifier contained in at least one end of the polymer chain. Here, the repeating unit derived from the modified conjugated diene monomer may represent a repeating unit formed during the polymerization of the conjugated diene monomer, and the functional group derived from the modifier may represent a functional group derived from a modifier present at one end of the living polymer by reaction or coupling between a living polymer prepared by polymerization of the conjugated diene monomer and the modifier.

[0137] According to one embodiment of the present invention, the conjugated diene-based monomer may be one or more selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, 2-phenyl-1,3-butadiene and 2-halogeno-1,3-butadiene (halogeno means a halogen atom).

[0138] In another embodiment, the modified conjugated diene polymer may further include a repeating unit derived from a compound represented by the following Formula 1, in which case the modified conjugated diene polymer may include a repeating unit derived from a conjugated diene monomer, a repeating unit derived from a compound represented by Formula 1, and a functional group derived from a modifier. In addition, the repeating unit derived from the compound represented by Formula 1 may be included in the polymer chain including the repeating unit derived from the conjugated diene monomer and in at least one end of the polymer chain.

[0139] [Formula 1]

[0140]

[0141] In formula 1

[0142] R1 is a hydrogen atom or an alkyl group of 1 to 20 carbon atoms,

[0143] R2 is a single bond, or an alkylene group of 1 to 20 carbon atoms which may be substituted or unsubstituted by a substituent, R3 and R4 are each independently an alkyl group of 1 to 20 carbon atoms which may be substituted or unsubstituted by a substituent, 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.

[0144] Here, the repeating unit derived from the compound represented by Formula 1 may be derived from an oligomer as a polymerization initiator used in a preparation method, which will be described later.

[0145] Preferably, in Formula 1, R1 may be a hydrogen atom or an alkyl group of 1 to 10 carbon atoms, R2 may be a single bond or an unsubstituted alkylene group of 1 to 10 carbon atoms, and 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.

[0146] In another embodiment, the modified conjugated diene polymer may also include repeating units derived from aromatic vinyl monomers. In this case, the modified conjugated diene polymer may include repeating units derived from conjugated diene monomers, repeating units derived from aromatic vinyl monomers, repeating units derived from compounds represented by Formula 1, and functional groups derived from modifiers.

[0147] According to one embodiment of the present invention, the aromatic vinyl 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-pyrrolidinylethyl)styrene, 4-(2-pyrrolidinylethyl)styrene and 3-(2-pyrrolidinyl-1-methylethyl)-α-methylstyrene.

[0148] In another embodiment, the modified conjugated diene polymer may be a copolymer further comprising repeating units of diene monomers of 1 to 10 carbon atoms and repeating units of conjugated diene monomers. The repeating units derived from diene monomers may be repeating units derived from diene monomers different from the conjugated diene monomers, and the diene monomers different from the conjugated diene monomers may be, for example, 1,2-butadiene. If the modified conjugated diene polymer is a copolymer further comprising a diene monomer, the repeating units derived from the diene monomers included in the modified conjugated diene polymer may be greater than 0 wt % to 1 wt %, greater than 0 wt % to 0.1 wt %, greater than 0 wt % to 0.01 wt %, or greater than 0 wt % to 0.001 wt %, within this range, the effect of preventing gel formation may be achieved.

[0149] In addition, the vinyl content of the modified conjugated diene polymer may be 5% by weight or more, 10% by weight or more, or 10% to 60% by weight. Here, the vinyl content may refer to the content of the 1,2-addition rather than 1,4-addition conjugated diene monomer based on 100% by weight of the conjugated diene copolymer formed using a monomer having a vinyl group and an aromatic vinyl monomer.

[0150] Modifier

[0151] In addition, the modifier may be a modifier for modifying the terminal of the polymer, in particular, a modifier having affinity for silica. A modifier having affinity for silica may refer to a modifier containing a functional group having affinity for silica in a compound used as a modifier, and a functional group having affinity for silica may refer to a functional group having excellent affinity for a filler (in particular, a silica-based filler) and capable of interacting between a silica-based filler and a functional group derived from the modifier.

[0152] The modifier can be, for example, an alkoxysilane compound, particularly an alkoxysilane compound containing one or more heteroatoms such as a nitrogen atom, an oxygen atom and a sulphur atom. In the case of using an alkoxysilane compound as a modifier, by a substitution reaction between an anion active part at one end of the active polymer and the alkoxy group of the alkoxysilane compound, modification can be carried out in the coupled form of a terminal of the active polymer and a silyl group. Therefore, by being derived from the functional group of the modifier present at one end of the first copolymer unit, the affinity of the modified conjugated diene polymer comprising the first copolymer unit and the inorganic filler can be improved, and therefore, the effect of further improving the viscoelasticity of the rubber composition comprising the modified conjugated diene polymer can be achieved. In addition, if the alkoxysilane compound contains a nitrogen atom, in addition to the effect derived from the silyl group, the effect of improving the additional physical properties derived from the nitrogen atom can also be expected.

[0153] According to one embodiment of the present invention, the modifier may include a compound represented by Formula 2 below.

[0154] [Formula 2]

[0155]

[0156] In formula 2, R 1 It can be a single bond or an alkylene group of 1 to 10 carbon atoms, R 2 and R 3 may be independently an alkyl group of 1 to 10 carbon atoms, R 4 can be hydrogen, an alkyl group having 1 to 10 carbon atoms, a mono-, di- or tri-substituted alkylsilyl group having an alkyl group having 1 to 10 carbon atoms, or a heterocyclic group having 2 to 10 carbon atoms, R 21 It may be a single bond, an alkylene group of 1 to 10 carbon atoms, or -[R 42 O] j -, R 42 The alkylene group may be an alkylene group of 1 to 10 carbon atoms, a and m may each independently be an integer of 1 to 3, n may be an integer of 0, 1 or 2, and j may be an integer selected from 1 to 30.

[0157] In one embodiment, in Formula 2, R1 It can be a single bond or an alkylene group of 1 to 5 carbon atoms, R 2 and R 3 can be independently hydrogen or an alkyl group of 1 to 5 carbon atoms, R 4 It can be hydrogen, an alkyl group of 1 to 5 carbon atoms, a trialkylsilyl group substituted by an alkyl group of 1 to 5 carbon atoms, or a heterocyclic group of 2 to 5 carbon atoms, R 21 It can be a single bond, an alkylene group of 1 to 5 carbon atoms, or -[R 42 O] j -, R 42 It may be an alkylene group of 1 to 5 carbon atoms, a may be an integer of 2 to 3, m may be an integer selected from 1 to 3, n may be an integer of 0, 1 or 2, wherein m+n=3 may be satisfied, and j may be an integer selected from 1 to 10.

[0158] In formula 2, if R 4 is a heterocyclic group, the heterocyclic group may be substituted by a trisubstituted alkoxysilyl group or may be unsubstituted, if the heterocyclic group is substituted by a trisubstituted alkoxysilyl group, the trisubstituted alkoxysilyl group may be substituted by an alkylene group of 1 to 10 carbon atoms via a connection to the heterocyclic group, and the trisubstituted alkoxysilyl group may mean an alkoxysilyl group substituted by an alkoxy group of 1 to 10 carbon atoms.

[0159] As a more specific example, the compound represented by Formula 2 can be selected from N,N-bis(3-(dimethoxy(methyl)silyl)propyl)-methyl-1-amine, N,N-bis(3-(diethoxy(methyl)silyl)propyl)-methyl-1-amine, N,N-bis(3-(trimethoxysilyl)propyl)-methyl-1-amine, N,N-bis(3-(triethoxysilyl)propyl)-methyl-1-amine, N,N-diethyl-3-(trimethoxysilyl)propyl- 1-amine, N,N-diethyl-3-(triethoxysilyl)propan-1-amine, tris(trimethoxysilyl)amine, tris(3-(trimethoxysilyl)propyl)amine, N,N-bis(3-(diethoxy(methyl)silyl)propyl)-1,1,1-trimethylsilylamine, N,N-bis(3-(1H-imidazol-1-yl)propyl)-(triethoxysilyl)methan-1-amine, N-(3-(1H-1,2,4-triazol-1-yl)propyl)-3-(triazol-1-yl)propyl)- 1-(3-(trimethoxysilyl)propyl)propan-1-amine, 3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)-N-(3-(1-(3-(trimethoxysilyl)propyl)-1H-1,2,4-triazol-3-yl)propyl)propan-1-amine, N,N-bis(2-(2-methoxyethoxy)ethyl)-3-(triethoxysilyl)propan-1-amine, N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine One of the group consisting of N-(2,5,8,11,14-pentaoxahexadecan-16-yl)-N-(3-(triethoxysilyl)propyl)-2,5,8,11,14-pentaoxahexadecan-16-amine and N-(3,6,9,12-tetraoxahexadecan-1-amine)-N-(3-(triethoxysilyl)propyl)-3,6,9,12-tetraoxahexadecan-1-amine.

[0160] In another embodiment, the modifier may include a compound represented by Formula 3 below.

[0161] [Formula 3]

[0162]

[0163] In formula 3, R 5 , R 6 and R 9 are each independently an alkylene group having 1 to 10 carbon atoms, R 7 , R 8 , R 10 and R 11 are each independently an alkyl group having 1 to 10 carbon atoms, R 12may be hydrogen or an alkyl group of 1 to 10 carbon atoms, b and c may each independently be 0, 1, 2 or 3, and may satisfy b+c≥1, and A may be Where R 13 , R 14 , R 15 and R 16 Each is independently hydrogen or an alkyl group of 1 to 10 carbon atoms.

[0164] In a specific embodiment, the compound represented by Formula 3 can 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-imidazol-1-yl)-N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine.

[0165] In another embodiment, the modifier may be a compound represented by Formula 4 below.

[0166] [Formula 4]

[0167]

[0168] In formula 4, A 1 and A 2 may be independently a divalent hydrocarbon group of 1 to 20 carbon atoms, which may contain oxygen atoms or not, R 17 To R 20 may be independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, L 1 To L 4 may be each independently a mono-substituted, di-substituted or tri-substituted alkylsilyl group of an alkyl group having 1 to 10 carbon atoms, or a monovalent hydrocarbon group having 1 to 20 carbon atoms, wherein L 1 and L 2 With L 3 and L 4 can be combined with each other to form a ring of 1 to 5 carbon atoms, and if L 1 and L 2 With L 3 and L 4 are combined with each other to form a ring, and the ring thus formed may include one to three hetero atoms of one or more types selected from the group consisting of N, O, and S.

[0169] In one embodiment, in Formula 4, A 1 and A 2 are each independently an alkylene group having 1 to 10 carbon atoms, R 17 To R 20 may be independently an alkyl group of 1 to 10 carbon atoms, L1 To L 4 may be each independently a trialkylsilyl group substituted by an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 10 carbon atoms, wherein L 1 and L 2 With L 3 and L 4 can be combined with each other to form a ring of 1 to 3 carbon atoms, and if L 1 and L 2 With L 3 and L 4 are combined with each other to form a ring, and the ring thus formed may include one to three hetero atoms of one or more types selected from the group consisting of N, O, and S.

[0170] In a more specific embodiment, the compound represented by Formula 4 can be selected from 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropane-1-amine, 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropane-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropane-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropane-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropane-1-amine. 1-propanamine), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1-amine), 3-Tetraethoxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethan-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethan-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethan-1-amine), (N,N-dipropylmethan-1-amine), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethan-1-amine), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethan-1-amine), N,N'-((1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silaneamine, N,N'-((1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silaneamine,N'-((1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silaneamine, N,N'-((1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilaneamine, N,N'-((1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilaneamine , one of the group consisting of N,N'-((1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(propyl-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilanamine, 1,3-bis(3-(1H-imidazol-1-yl)propyl)-1,1,3,3-tetramethoxydisiloxane, 1,3-bis(3-(1H-imidazol-1-yl)propyl)-1,1,3,3-tetraethoxydisiloxane and 1,3-bis(3-(1H-imidazol-1-yl)propyl)-1,1,3,3-tetrapropoxydisiloxane,

[0171] In another embodiment, the modifier may include a compound represented by Formula 5 below.

[0172] [Formula 5]

[0173]

[0174] In Formula 5, R 22 and R 23 may be independently an alkylene group having 1 to 20 carbon atoms or R 28 [OR 29 ] f -, R 24 To R 27 may be each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, R 28 and R 29 may be independently an alkylene group having 1 to 20 carbon atoms, R 47 and R 48 may each independently be a divalent hydrocarbon group of 1 to 6 carbon atoms, d and e may each independently be an integer selected from 0 or 1 to 3, wherein d+e is an integer greater than 1, and f may be an integer of 1 to 30.

[0175] Specifically, in Formula 5, R 22 and R 23 may be independently an alkylene group having 1 to 10 carbon atoms or R 28 [OR 29 ] f -, R 24 To R27 may be independently an alkyl group of 1 to 10 carbon atoms, R 28 and R 29 may each independently be an alkylene group of 1 to 10 carbon atoms, d and e may each independently be an integer selected from 0 or 1 to 3, wherein d+e is an integer greater than 1, and f may be an integer of 1 to 30.

[0176] More specifically, the compound represented by Formula 5 may be a compound represented by the following Formula 5a, Formula 5b or Formula 5c.

[0177] [Formula 5a]

[0178]

[0179] [Formula 5b]

[0180]

[0181] [Formula 5c]

[0182]

[0183] In Formula 5a, Formula 5b and Formula 5c, R 22 To R 27 , d and e are the same as above.

[0184] In a more specific embodiment, the compound represented by Formula 5 can be 1,4-bis(3-(3-(triethoxysilyl)propoxy)propyl)piperazine, 1,4-bis(3-(triethoxysilyl)propyl)piperazine, 1,4-bis(3-(trimethoxysilyl)propyl)piperazine, 1,4-bis(3-(dimethoxymethylsilyl)propyl)piperazine, 1-(3-(ethoxydimethylsilyl)propyl)-4-(3-(triethoxysilyl)propyl)piperazine, 1-(3-(ethoxydimethyl)propyl)-4-(3-(triethoxysilyl)propyl)piperazine, One of the group consisting of 1-(3-(ethoxydimethyl)methyl)piperazine, 1-(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-(triethoxysilyl)propyl)hexahydropyrimidine and 1,3-bis(3-(tributoxysilyl)propyl)-1,2,3,4-tetrahydropyrimidine.

[0185] In another embodiment, the modifier may include a compound represented by Formula 6 below.

[0186] [Formula 6]

[0187]

[0188] In formula 6, R 30 It can be a monovalent hydrocarbon group of 1 to 30 carbon atoms, R 31 To R 33 may be independently an alkylene group having 1 to 10 carbon atoms, R 34 To R 37 Each may independently be an alkyl group of 1 to 10 carbon atoms, and g and h may each independently be an integer selected from 0 or 1 to 3, wherein g+h may be an integer of 1 or more.

[0189] In another embodiment, the modifier may include a compound represented by Formula 7 below.

[0190] [Formula 7]

[0191]

[0192] In formula 7, A 3 and A 4 may be independently an alkylene group having 1 to 10 carbon atoms, R 38 To R 41 The groups may each independently be an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and i may be an integer selected from 1 to 30.

[0193] 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-silantridec-7-yl)propan-1-amine, 2,4-bis(2-methoxyethoxy)-6-((trimethylsilyl)methyl)-1,3,5-triazine, and 3,14-dimethoxy-3,8,8,13-tetramethyl-2,14-dioxa-7,9-dithia-3,8,13-trisilopentadecane.

[0194] In another embodiment, the modifier may include a compound represented by Formula 8 below.

[0195] [Formula 8]

[0196]

[0197] In formula 8, R 43 , R 45 and R 46 may be independently an alkyl group of 1 to 10 carbon atoms, R 44 The alkylene group may be an alkylene group of 1 to 10 carbon atoms, and k may be an integer selected from 1 to 4.

[0198] In a more specific embodiment, the compound represented by Formula 8 can be selected from 8,8-dibutyl-3,13-dimethoxy-3,13-dimethyl-2,14-dioxa-7,9-dithia-3,13-disila-8-stannopentadecane, 8,8-dimethyl-3,13-dimethoxy-3,13-dimethyl-2,14-dioxa-7,9-dithia-3,13-disila-8-stannopentadecane, One of the group consisting of pentadecane, 8,8-dibutyl-3,3,13,13-tetramethoxy-2,14-dioxa-7,9-dithia-3,13-disila-8-stannopentadecane and 8-butyl-3,3,13,13-tetramethoxy-8-((3-(trimethoxysilyl)propyl)thio)-2,14-dioxa-7,9-dithia-3,13-disila-8-stannopentadecane.

[0199] Preparation method of modified conjugated diene polymer

[0200] The present invention provides a method for preparing a modified conjugated diene polymer, whereby the modified conjugated diene polymer satisfies the above conditions (i) to (vii) at the same time.

[0201] In the preparation method of 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 in at least two batches during the polymerization of the active polymer, and an active polymer having a wide molecular weight distribution can be prepared under non-high temperature conditions. Therefore, the defect of deactivating the active part of the active polymer due to high temperature can be avoided, and the modification reaction between the active polymer and the modifier can be advantageously achieved, thereby easily preparing a modified conjugated diene polymer having a wide molecular weight distribution and a high modification ratio.

[0202] The preparation method of the modified conjugated diene polymer is characterized in that it includes: polymerizing a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer in a hydrocarbon solvent to prepare a living polymer (S1); and reacting or coupling the living polymer prepared in step (S1) with a modifier (S2), wherein the polymerization in step (S1) is carried out in the following manner: initiating polymerization in the presence of a first polymerization initiator, and injecting a second polymerization initiator in at least one batch when the polymerization conversion rate is 50% to 95%, the first and second polymerization initiators are oligomers, which are prepared by reacting an organic metal compound, a conjugated diene monomer and a compound represented by the following formula 1, and have an anionic active terminal, step (S1) is continuously carried out in at least two polymerization reactors, and the polymerization conversion rate in the first reactor of the polymerization reactors is 10% to 50%.

[0203] The conjugated diene-based monomer, the aromatic vinyl-based monomer, and the compound represented by Formula 1 used in the preparation method are the same as those described above, and a detailed description thereof will be omitted.

[0204] The hydrocarbon solvent is not particularly 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.

[0205] Step S1

[0206] The polymerization in step (S1) can be, for example, anionic polymerization, particularly living anionic polymerization, in which an anionic active portion is formed at the polymerization end by an anionic growth reaction. In addition, the polymerization in step (S1) can be heating polymerization, isothermal polymerization or polymerization at a constant temperature (adiabatic polymerization). Here, polymerization at a constant temperature can mean a polymerization method, which includes a step of utilizing self-generated reaction heat without optionally applying heat after injecting a polymerization initiator; and heating polymerization can refer to a polymerization method including injecting a polymerization initiator and then raising the temperature by optionally applying heat. Isothermal polymerization can refer to a polymerization method in which heat is increased by applying heat or absorbing heat after adding a polymerization initiator so that the temperature of the polymer remains constant.

[0207] In addition, the polymerization in step (S1) is carried out by reacting a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer in a hydrocarbon solvent in the presence of a polymerization initiator, and in particular can be carried out in the following manner: the polymerization is initiated in the presence of a first polymerization initiator, and the second polymerization initiator is injected in at least one batch at a polymerization conversion rate of 50% to 95% to carry out the polymerization reaction. In the polymerization of step (S1), the second polymerization initiator is injected in at least one batch at the above-mentioned polymerization conversion rate to facilitate the reaction of the monomers, thereby easily forming new polymer chains separated from the initially generated polymer chains, and therefore, in the active polymer prepared thereby, a large number of polymer chains with different molecular weights can be present in the active polymer, and the active polymer can have a wide molecular weight distribution.

[0208] Here, the first polymerization initiator and the second polymerization initiator may be the same or different, and if the same, "first" and "second" may indicate the order of injection into the reaction.

[0209] In addition, the first and second polymerization initiators are oligomers having anionic active terminals, which are prepared by reacting an organic metal compound, a conjugated diene monomer and a compound represented by Formula 1, and may have a weight average molecular weight of 100 g / mol to 30,000 g / mol or 150 g / mol to 15,000 g / mol.

[0210] In another embodiment, the oligomer includes repeating units derived from conjugated diene monomers and repeating units derived from the compound represented by Formula 1 in the molecule, in which case the number of repetitions of the repeating units derived from the conjugated diene monomers and the repeating units derived from the compound represented by Formula 1 can be controlled within the range of the oligomer satisfying the above-mentioned weight average molecular weight range.

[0211] In addition, the oligomer with anionic active terminal can be prepared by anionic polymerization of conjugated diene monomers and compounds represented by Formula 1 in the presence of an organic metal compound, in which case the amount of the conjugated diene monomers and the compound represented by Formula 1 can be controlled to meet the above weight average molecular weight range. For example, the organic metal compound can be used in an amount of 0.001mol to 1.0mol or 0.01mol to 1.0mol based on 1mol of the conjugated diene monomer, and the compound represented by Formula 1 can be used in an amount of 0.001mol to 100mol or 0.01mol to 10mol based on 1mol of the conjugated diene monomer.

[0212] According to one embodiment of the present invention, based on a total of 100g of monomer, step (S1) can use 0.01mmol to 10mmol of a polymerization initiator, and here, the polymerization initiator can include a first and a second polymerization initiator. In particular, based on a total of 100g of monomer, the polymerization initiator can be used in an amount of 0.05mmol to 5mmol, 0.1mmol to 2mmol, 0.1mmol to 1mmol, or 0.15mmol to 0.8mmol.

[0213] In addition, the second polymerization initiator may be used in an amount of 0.001 mol to 100 mol or 0.1 mol to 10 mol based on 1 mol of the first polymerization initiator.

[0214] In the present invention, for example, the organometallic compound can be one or more selected from the group consisting of methyllithium, ethyllithium, propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, hexyllithium, n-decyllithium, tert-octyllithium, 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.

[0215] In addition, the batch injection of the second polymerization initiator may be batch injection or batch continuous injection, in particular, the batch injection may include: a first continuous batch injection of a portion of the total amount of the second polymerization initiator when the polymerization conversion rate is greater than 50% and less than 80%, and a second continuous batch injection of the remainder of the total amount when the polymerization conversion rate is 80% to 95%, and the batch continuous injection may be the injection of the total amount at a constant rate and a constant amount from the start of the injection to the end of the injection.

[0216] In addition, according to one embodiment of the present invention, the polymerization in step (S1) is carried out in two or more polymerization reactors, and the polymerization conversion in the first polymerization reactor in the polymerization reactor can be 10% to 50% or 20% to 50%. That is, the polymerization in step (S1) can be carried out only until the polymerization conversion in the first polymerization reactor becomes 10% to 50% or 20% to 50%. Within this range, the side reactions generated while forming a polymer after initiating the polymerization reaction can be suppressed, a polymer with a linear structure can be induced during polymerization, and the monomer discharged in the initial stage of the reaction can be controlled to easily control the amount of the monomer that can react with the second polymerization initiator injected in batches. Therefore, the above-mentioned unimodal molecular weight distribution curve can be obtained, and the above-mentioned molecular weight distribution can be satisfied. In this case, the polymerization conversion can be controlled according to the reaction temperature, the retention time in the reactor, etc.

[0217] More specifically, the polymerization in step (S1) can be carried out in two or more polymerization reactors, and the conjugated diene monomer or the conjugated diene monomer and the aromatic vinyl monomer can be polymerized in the first polymerization reactor in a hydrocarbon solvent in the presence of a first polymerization initiator until the polymerization conversion rate becomes 10% to 50% to prepare a living polymer having the polymerization conversion rate, and the polymerization can be continued in a second polymerization reactor and a subsequent polymerization reactor to prepare a living polymer. The second polymerization initiator can be injected in at least one batch during the polymerization when the polymerization conversion rate is 50% to 95%. In this case, the batch injection of the second polymerization initiator can be performed by injecting the first reactor, the second reactor, and the subsequent polymerization reactor according to the point of the polymerization conversion rate.

[0218] Meanwhile, the polymerization in step (S1) can be further carried out by including a polar additive as required, in which case the total amount of the polar additive can be in a ratio of 0.001 g to 50 g or 0.002 g to 1.0 g based on a total of 100 g of monomer. In another embodiment, the total amount of the polar additive can be in a ratio of greater than 0 g to 1 g, 0.01 g to 1 g, or 0.1 g to 0.9 g based on a total of 100 g of monomer.

[0219] For example, the polar additive may be one or more selected from the group consisting of tetrahydrofuran, di(tetrahydrofuranyl)propane, ethyl ether, cyclopentyl ether, dipropyl ether, vinyl methyl ether, vinyl dimethyl ether, diethylene glycol, dimethyl ether, tert-butoxyethoxyethane, bis(3-dimethylaminoethyl)ether, (dimethylaminoethyl)ethyl ether, trimethylamine, triethylamine, tripropylamine and tetramethylethylenediamine, and may particularly be triethylamine or tetramethylethylenediamine.

[0220] At the same time, the polymerization conversion rate can be determined by, for example, measuring the solid concentration in the copolymer solution phase containing the copolymer during polymerization, and in a specific embodiment, in order to fix the copolymer solution, a cylindrical container is installed at the outlet of each polymerization reactor to fill a certain amount of copolymer solution in the cylindrical container, and then, the cylindrical 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 cylindrical container is transferred to an aluminum container (e.g., an aluminum pan), the weight (B) of the cylindrical 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 the dried polymer is measured, and calculation is performed according to the following mathematical formula 3.

[0221] [Mathematical formula 3]

[0222]

[0223] In Mathematical Formula 3, the total solid content is the total solid content in the 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, it can be calculated by substituting 20 / 100 (i.e., 0.2 in Mathematical Formula 3).

[0224] Meanwhile, the polymerized reactants polymerized in the first reactor can be transported to the polymerization reactor before the modification reactor, and can be polymerized until the final polymerization conversion becomes greater than 95%. After polymerization in the first reactor, the polymerization conversion of each reactor of 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.

[0225] In addition, the living polymer prepared in step (S1) may refer to a polymer in which a polymer anion and an organic metal cation of a polymerization initiator are combined.

[0226] In addition, the polymerization in step (S1) may be performed, 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 conversion rate of the polymerization reaction may be increased.

[0227] The term "polymer reactant" in the present invention may refer to an intermediate of a polymer type under polymerization in each reactor during the step (S1), or may refer to a polymer having a polymerization conversion rate of 95% or less under polymerization in a reactor after completing step (S1) or step (S2) and before obtaining a living polymer or a modified conjugated diene polymer.

[0228] Step S2

[0229] According to one embodiment of the present invention, in the reaction of step (S2), based on 100g of monomer, the amount of the modifier can be 0.01mmol to 10mmol. In another embodiment, based on 1mol of the polymerization initiator in step (S1), 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.

[0230] In addition, according to one embodiment of the present invention, the modifier can be injected into the modification reactor, and step (S2) can be carried out in the modification reactor. In another embodiment, the modifier can be injected into the transporting part for transporting the active polymer prepared in step (S1) to the modification reactor for carrying out step (S2), and the reaction can be carried out by mixing the active polymer and the modifier in the transporting part. In this case, the reaction can be a modification reaction for simply coupling the modifier with the active polymer, or a coupling reaction for connecting the active polymer based on the modifier.

[0231] Rubber composition

[0232] According to the present invention, there is provided a rubber composition comprising a modified conjugated diene-based polymer.

[0233] The rubber composition may include the modified conjugated diene polymer in an amount of 10 wt % or more, 10 wt % to 100 wt % or 20 wt % to 90 wt %, within which mechanical properties such as tensile strength and wear resistance are excellent and an excellent balance between physical properties can be achieved.

[0234] In addition, in addition to the modified conjugated diene polymer, the rubber composition may also include other rubber components as required, in which case the content of the rubber component may be 90% by weight or less based on the total weight of the rubber composition. In a specific embodiment, based on 100 parts by weight of the modified conjugated diene polymer, 1 to 900 parts by weight of other rubber components may be included.

[0235] 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 obtained by modifying or purifying a common natural rubber, such as epoxidized natural rubber (ENR), deprotected natural rubber (DPNR) and hydrogenated natural rubber; and a synthetic rubber, such as a styrene-butadiene copolymer (SBR), a polybutadiene (BR), a polyisoprene (IR), a butyl rubber (IIR), an ethylene-propylene copolymer, a copolymerized isobutylene-isoprene, a chloroprene rubber, a copolymerized (ethylene-propylene), a copolymerized (styrene-butadiene), a copolymerized (styrene-isoprene), a copolymerized (styrene-isoprene-butadiene), a copolymerized (isoprene-butadiene), a copolymerized (ethylene-propylene-diene), a polysulfide rubber, an acryl rubber, a polyurethane rubber, a silicone rubber, an epichlorohydrin rubber and a halogenated butyl rubber, and any one of these or a mixture of two or more thereof may be used.

[0236] Based on 100 parts by weight of the modified conjugated diene polymer of the present invention, the rubber composition may include 0.1 to 200 parts by weight or 10 to 120 parts by weight of filler. The filler may be, for example, a filler based on silica, particularly wet silica (hydrated silicate), dry silica (anhydrous silicate), calcium silicate, aluminum silicate, colloidal silica, etc. Preferably, the filler may be wet silica, which has the most significant effect on improving the compatibility of the damage characteristics and wet grip. In addition, the rubber composition may further include a carbon-based filler as required.

[0237] In another embodiment, if silica is used as a filler, a silane coupling agent may be used together to improve the strengthening properties and low exothermic properties. Specific 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(2-trimethoxysilylethyl)tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilane The present invention can be used in combination with bis(3-triethoxysilylpropyl)tetrasulfide, bis(3-diethoxymethylsilylpropyl)tetrasulfide, 3-trimethoxysilylpropyl benzothiazolyl tetrasulfide, bis(3-triethoxysilylpropyl)polysulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis(3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, bis(dimethoxymethylsilylpropyl)-N,N-dimethylthiocarbamoyl tetrasulfide, or bis(dimethoxymethylsilylpropyl)benzothiazolyl tetrasulfide, and any one thereof or a mixture of two or more thereof can be used. Preferably, in consideration of the improvement effect of strengthening properties, bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropyl benzothiazolyl tetrasulfide can be used.

[0238] In addition, in the rubber composition of one embodiment of the present invention, since the modified conjugated diene polymer having a functional group having a high affinity with silica is introduced in the active part is used as the rubber component, the compounding amount of the silane coupling agent can be smaller than in the conventional case. Therefore, the silane coupling agent can be used in an amount of 1 to 20 parts by weight or 5 to 15 parts by weight based on 100 parts by weight of silica, and within the above range, the effect as a coupling agent can be fully shown, and the effect of preventing the rubber component from gelling can be achieved.

[0239] The rubber composition of one embodiment of the present invention may also be sulfur crosslinkable and may further include a vulcanizing agent. The vulcanizing agent may be particularly sulfur powder, and the content may be 0.1 to 10 parts by weight based on 100 parts by weight of the rubber component, within which the elasticity and strength required for the vulcanized rubber composition may be ensured, and at the same time, an excellent low fuel consumption ratio may be achieved.

[0240] In addition to the above components, the rubber composition of one embodiment of the present invention may also contain various additives used in the general rubber industry, especially vulcanization accelerators, process oils, plasticizers, anti-aging agents, scorch retardants, zinc white, stearic acid, thermosetting resins or thermoplastic resins.

[0241] The vulcanization accelerator may include, for example, thiazole compounds such as 2-mercaptobenzothiazole (M), dibenzoyl disulfide (DM) and N-cyclohexyl-2-benzothiazolylsulfenamide (CZ), or guanidine compounds such as diphenylguanidine (DPG), and the content may be 0.1 parts by weight to 5 parts by weight based on 100 parts by weight of the rubber component.

[0242] Process oil is used as the softener in rubber composition, and can include for example paraffin, cycloalkane or aromatic compound.In view of tensile strength and wear resistance, aromatic process oil can be used, and can consider hysteresis loss and performance at low temperature, can use cycloalkane or paraffin process oil.Based on the rubber component of 100 weight parts, the content of process oil can be below 100 weight parts.Within the above range, the tensile strength of vulcanized rubber and the deterioration of low heat release property (low fuel consumption ratio) can be prevented.

[0243] 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, and the content may be 0.1 to 6 parts by weight based on 100 parts by weight of the rubber component.

[0244] The rubber composition according to one embodiment of the present invention can be obtained by kneading using kneading equipment such as a Banbury mixer, a roll and an internal mixer according to a compounding recipe, and a rubber composition having low exothermic properties and good wear resistance can be obtained through a vulcanization process after a molding process.

[0245] Therefore, the rubber composition can be used to manufacture various components of a tire, such as a tire tread, an undertread, a sidewall, a carcass coating rubber, a belt coating rubber, a bead filler, a chafer, and a bead coating rubber, or to manufacture rubber products in various industries, such as anti-vibration rubber, a belt conveyor, and a hose.

[0246] In addition, the present invention provides a tire manufactured using the rubber composition.

[0247] The tire may be a tire or include a tire tread.

[0248] Example

[0249] Hereinafter, the embodiment will be explained in detail to specifically explain the present invention. However, embodiments according to the present invention can be modified into various other types, and the scope of the present invention should not be limited to the embodiments described below. Embodiments of the present invention are provided for fully explaining the present invention to those of ordinary skill in the art.

[0250] Preparation Example 1

[0251] Under a nitrogen atmosphere, 100 g of n-butyllithium (10 wt% n-hexane solution) was placed in a 5 L pressure reactor, and 2,000 g of n-hexane, 337 g of 1,3-butadiene and 23.0 g of 4-(dimethylamino)styrene were added thereto, followed by reaction at 40° C. for 20 minutes to prepare an oligomer solution containing 14.9 wt% of an oligomer having an anionic active terminal and a weight average molecular weight of 3,100 g / mol.

[0252] Preparation Example 2

[0253] An oligomer solution containing 15.1 wt % of an oligomer having an anionic active terminal and a weight average molecular weight of 3,200 g / mol was prepared by conducting the same reaction as in Preparation Example 1, except that 25 g of N,N-dimethylvinylbenzylamine was used instead of 4-(dimethylamino)styrene in Preparation Example 1.

[0254] Example 1

[0255] Into the first reactor of three continuously stirred liquid phase reactors (CSTR), n-hexane was continuously injected at a flow rate of 4 kg / hr, a monomer solution in which 60 wt% of a monomer mixture (80 wt% of 1,3-butadiene and 20 wt% of styrene) was dissolved in n-hexane was injected at a flow rate of 1.6 kg / h, the oligomer solution prepared in Preparation Example 1 in n-hexane as a polymerization initiator was injected at a flow rate of 139 g / hr, a polar additive solution in which 10 wt% of ditetrahydrofurylpropane was dissolved in n-hexane as a polar additive was injected at a flow rate of 0.5 g / hr, and a solution in which 15 wt% of 1,2-butadiene was dissolved in n-hexane was injected at a flow rate of 1 g / hr. In this case, the internal temperature of the reactor was maintained at 50° C., and when the polymerization conversion rate reached 45%, the polymer product was transported from the first reactor to the second reactor through a transport pipe.

[0256] Then, the temperature of the second reactor was maintained at 65°C, and when the polymerization conversion rate reached 85%, while the polymerization product was transported from the second reactor to the third reactor through the transfer pipe, the oligomer solution prepared in Preparation Example 1 was injected into the pipeline at a rate of 146 g / h.

[0257] Then, the temperature of the third reactor is maintained at 65°C, and when the polymerization conversion rate reaches more than 98%, the polymerization product is continuously supplied from the third reactor to the fourth reactor through a transfer pipe, and a solution of 20 wt% of N,N-bis(3-(dimethoxy(methyl)silyl)propyl)-methyl-1-amine dissolved in n-hexane is continuously supplied as a modifier to carry out a modification reaction (act.Li:modifier=1:0.5 molar ratio).

[0258] Thereafter, IR1520 (BASF) solution was injected into the polymer solution discharged from the third reactor at a rate of 100 g / h and stirred, and 30 wt % thereof was dissolved as an antioxidant. The polymer thus obtained was injected into hot water heated with steam, stirred to remove the solvent and roll dried to remove the remaining solvent and water to prepare a conjugated diene polymer with both ends modified.

[0259] Example 2

[0260] A modified conjugated diene polymer was prepared by carrying out the same method as in Example 1, except that in Example 1, the oligomer solution prepared in Preparation Example 1 was injected into the pipeline at a rate of 147 g / h, and when the polymerization conversion rate reached 95%, the polymerization product was transported from the second reactor to the third reactor through a transport pipe (act. Li: modifier = 1:0.5 molar ratio).

[0261] Example 3

[0262] A modified conjugated diene polymer was prepared by carrying out the same method as in Example 1, except that in Example 1, the oligomer solution prepared in Preparation Example 1 was injected into the pipeline at a rate of 147 g / h, and when the polymerization conversion rate reached 75%, the polymerization product was transported from the second reactor to the third reactor through a transport pipe (act. Li: modifier = 1:0.5 molar ratio).

[0263] Example 4

[0264] A modified conjugated diene polymer is prepared by carrying out the same method as in Example 1, except that in Example 1, the oligomer solution prepared in Preparation Example 1 is injected into the pipeline at a rate of 147 g / h, and the polymerization product is transported from the second reactor to the third reactor through a transport pipe when the polymerization conversion rate reaches 80%, and a solution in which 20 weight % of N-(4-methylpiperazinyl)-N,N-bis(3-(triethoxysilyl)propyl)amine is dissolved as a modifier is continuously injected into the fourth reactor (act.Li:modifier=1:0.5 molar ratio).

[0265] Example 5

[0266] Into the first reactor of three continuously stirred liquid phase reactors (CSTR), n-hexane was continuously injected at a flow rate of 4 kg / hr, a monomer solution in which 60 wt% of a monomer mixture (80 wt% of 1,3-butadiene and 20 wt% of styrene) was dissolved in n-hexane was injected at a flow rate of 1.6 kg / h, the oligomer solution prepared in Preparation Example 2 in n-hexane as a polymerization initiator was injected at a flow rate of 156 g / hr, a polar additive solution in which 10 wt% of ditetrahydrofurylpropane was dissolved in n-hexane as a polar additive was injected at a flow rate of 0.5 g / hr, and a solution in which 15 wt% of 1,2-butadiene was dissolved in n-hexane was injected at a flow rate of 1 g / hr. In this case, the internal temperature of the reactor was maintained at 50° C., and when the polymerization conversion rate reached 45%, the polymer product was transported from the first reactor to the second reactor through a transport pipe.

[0267] Then, the temperature of the second reactor was maintained at 65°C, and when the polymerization conversion rate reached 85%, while the polymerization product was transported from the second reactor to the third reactor through the transfer pipe, the oligomer solution prepared in Preparation Example 2 was injected into the pipeline at a rate of 147 g / h.

[0268] Then, the temperature of the third reactor is maintained at 65°C, and when the polymerization conversion rate reaches more than 98%, the polymerization product is continuously supplied from the third reactor to the fourth reactor through a transfer pipe, and a solution in which 20 wt% of N-(3-(1H-imidazole-1-yl)propyl-N,N-bis(3-(triethoxysilyl)propyl)amine is dissolved in n-hexane is continuously supplied as a modifier to carry out a modification reaction (act.Li:modifier=1:0.5 molar ratio).

[0269] Thereafter, IR1520 (BASF) solution was injected into the polymer solution discharged from the third reactor at a rate of 100 g / h and stirred, and 30 wt % thereof was dissolved as an antioxidant. The polymer thus obtained was injected into hot water heated with steam, stirred to remove the solvent and roll dried to remove the remaining solvent and water to prepare a conjugated diene polymer with both ends modified.

[0270] Example 6

[0271] A modified conjugated diene polymer is prepared by carrying out the same method as in Example 1, except that in Example 5, the oligomer solution prepared in Preparation Example 2 is injected into the pipeline at a rate of 147 g / h, and when the polymerization conversion rate reaches 70%, the polymer is transported from the second reactor to the third reactor through a transport pipe, and a solution of 20 wt% of N,N-bis(3-(dimethoxy(methyl)silyl)propyl)-methyl-1-amine dissolved in n-hexane is continuously injected into the fourth reactor as a modifier (act.Li:modifier=1:0.5 molar ratio).

[0272] Example 7

[0273] A modified conjugated diene polymer was prepared by carrying out the same method as in Example 2, except that in Example 2, a solution of 20 wt % of N-(4-methylpiperazinyl)-N,N-bis(3-(triethoxysilyl)propyl)amine dissolved in n-hexane was continuously injected into the fourth reactor as a modifier (act.Li:modifier = 1:0.5 molar ratio).

[0274] Comparative Example 1

[0275] A modified conjugated diene-based polymer was prepared by performing the same method as in Example 1, except that in Example 1, the oligomer solution was not injected while the polymerization product was transferred from the second reactor to the third reactor through the transfer pipe (act. Li:modifier=1:0.5 molar ratio).

[0276] Comparative Example 2

[0277] A modified conjugated diene polymer was prepared by carrying out the same method as in Example 6, except that in Example 6, an n-butyl lithium solution in which 10 wt % of n-butyl lithium was dissolved in n-hexane was injected into the first reactor at a rate of 6.0 g / h instead of the oligomer solution as a polymerization initiator, and the polymerization initiator was not injected while the polymerization product was transported from the second reactor to the third reactor through a transport pipe (act. Li:modifier=1:0.5 molar ratio).

[0278] Comparative Example 3

[0279] A modified conjugated diene polymer was prepared by carrying out the same method as in Example 1, except that in Example 1, an n-butyllithium solution in which 10 wt % of n-butyllithium was dissolved in n-hexane was injected into the first reactor at a rate of 6.0 g / h as a polymerization initiator instead of the oligomer solution, and the n-butyllithium solution was injected at a rate of 3.0 g / h when the polymerization conversion rate reached 43% (act.Li:modifier=1:0.5 molar ratio).

[0280] Comparative Example 4

[0281] A modified conjugated diene polymer was prepared by carrying out the same method as in Example 1, except that in Example 1, an n-butyllithium solution in which 10 wt % of n-butyllithium was dissolved in n-hexane was injected into the first reactor at a rate of 6.0 g / h as a polymerization initiator instead of the oligomer solution, and the n-butyllithium solution was injected at a rate of 2.4 g / h when the polymerization conversion rate reached 80% (act.Li:modifier=1:0.5 molar ratio).

[0282] Comparative Example 5

[0283] A modified conjugated diene polymer was prepared by the same method as in Example 5, except that in Example 5, a solution of 20 wt % tin tetrachloride (SnCl4) dissolved in n-hexane was continuously injected into the fourth reactor as a modifier (act.Li:modifier=1:0.5 molar ratio).

[0284] Comparative Example 6

[0285] A modified conjugated diene polymer was prepared by carrying out the same method as in Example 5, except that, in Example 5, the polymerization initiator was not injected while the polymerization product was transported from the second reactor to the third reactor through the transport pipe, and a solution of 20 wt % of tris(3-(triethoxysilyl)propyl)amine dissolved in n-hexane was continuously injected into the fourth reactor as a modifier (act. Li: modifier = 1:0.5 molar ratio).

[0286] Experimental example

[0287] Experimental Example 1

[0288] For each copolymer prepared in the examples and comparative examples, the styrene bond content and 1,2-vinyl bond content, weight average molecular weight (Mw, ×10 3 g / mol), molecular weight distribution (PDI, MWD), molecular weight distribution curve, shrinkage factor, nitrogen atom content and modification ratio. The results are shown in Table 1 below.

[0289] 1) Microstructure analysis (styrene bond content (SM)) and 1,2-vinyl bond content (1,2-vinyl)

[0290] The styrene and 1,2-vinyl bond contents in each modified conjugated diene-based polymer were measured and analyzed using Varian VNMRS 500 MHz NMR.

[0291] During the measurement of NMR, 1,1,2,2-tetrachloroethane was used as a solvent, and a sample was prepared by dissolving a polymer in the solvent to 0.02 M. The styrene bond content (weight %) and the 1,2-vinyl bond content (weight %) were calculated by calculating the solvent peak as 5.97 ppm and targeting 7.2-6.9 ppm as a random styrene peak, 6.9-6.2 ppm as a block styrene peak, 5.8-5.1 ppm as a 1,4-vinyl peak, and 5.1-4.5 ppm as a 1,2-vinyl peak.

[0292] 2) Weight average molecular weight (Mw), molecular weight distribution (MWD) and molecular weight distribution curve

[0293] The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by gel permeation chromatography (GPC) (PL GPC220, Agilent Technologies) under the following conditions to obtain a molecular weight distribution curve, and the molecular weight distribution (PDI, MWD, Mw / Mn) was obtained by calculation from each measured molecular weight.

[0294] - Column: A combination of two PLgel Olexis columns (Polymer Laboratories) and one PLgelmixed-C column (Polymer Laboratories) was used.

[0295] -Solvent: A mixture of tetrahydrofuran and 2 wt% of an amine compound was used.

[0296] -Flow rate: 1ml / min

[0297] -Sample concentration: 1-2 mg / ml (diluted in THF)

[0298] -Injection volume: 100μL

[0299] - Column temperature: 40℃

[0300] -Detector: Refractive index

[0301] 3) Mooney stress relaxation ratio (-S / R) and Mooney maximum relaxation area (MLRA)

[0302] The measurement is performed by using the MV2000E of AlphaTechnologies using a large rotor at a rotor speed of 2±0.02 rpm at 100°C. Specifically, the polymer is allowed to stand at room temperature (23±5°C) for more than 30 minutes, 27±3 g is collected, and placed in a mold cavity, and then the Platen is operated and measured for 4 minutes to obtain the Mooney viscosity. Thereafter, the slope value of the change in the Mooney viscosity displayed when the torque is released is measured, and the Mooney stress relaxation ratio as its absolute value is obtained. In addition, the Mooney maximum relaxation area is the integral value of the Mooney relaxation curve from 1 second to 120 seconds after stopping the rotor, and is calculated by the following mathematical formula 1.

[0303] [Mathematical formula 1]

[0304]

[0305] In mathematical formula 1

[0306] A is the Mooney maximum relaxation area (MLRA);

[0307] k is the Mooney intercept 1 second after stopping the rotor operation of the Mooney viscometer

[0308] a is the Mooney relaxation ratio,

[0309] t o is the starting point of the Mooney relaxation, and

[0310] t f It is the end point of Mooney relaxation.

[0311] 4) Nitrogen atom content (N content)

[0312] The measurement was performed by the NSX analysis method, and the measurement by the NSX analysis method used a quantitative analyzer of trace nitrogen (NSX-2100H).

[0313] Specifically, open the quantitative analyzer (automatic sampler, horizontal furnace, PMT and nitrogen detector) of trace nitrogen, set the carrier flow rate to 250ml / min for Ar, 350mL / min for O2 and 300mL / min for ozone generator, set the heater to 800 ℃, and leave the analyzer for about 3 hours to stabilize.After stabilizing the analyzer, use nitrogen standard (AccuStandard S-22750-01-5ml) to prepare the calibration curve of the calibration curve range of 5ppm, 10ppm, 50ppm, 100ppm and 500ppm, and obtain the area corresponding to each concentration.Then, by using the ratio of concentration to area, make a straight line.After this, the ceramic boat carrying 20mg sample is put into the automatic sampler of analyzer, and is measured to obtain area.By using the area and the calibration curve of the sample thus obtained, calculate the nitrogen atomic content.

[0314] 5) Modification ratio (%)

[0315] The chromatogram obtained by chromatographic measurement is used to calculate the modification ratio (%) according to the following mathematical formula 2, and gel permeation chromatography (GPC) (PL GPC220, Agilent Technologies) is used to perform chromatographic measurement as follows. Each copolymer is dissolved in cyclohexane and stored in the mobile phase tank (preparation, 1.0m / mL) of the sample, and tetrahydrofuran (THF) is stored in another mobile phase tank. The mobile phase tank is connected to a double-head pump respectively, and first, the solution in the mobile phase tank in which the copolymer is dissolved is injected into the column filled with a silica absorbent by a syringe that is 100 μl by pump and loop volume. In this case, the pressure of the pump is 450psi, and the injection flow rate is 0.7ml / min. Then, after confirming that the unmodified butadiene copolymer unit in the copolymer is no longer detected from the detector (ELSD, Waters company), based on 5 minutes from the injection, tetrahydrofuran is injected into the column by a pump. In this case, the pressure of the pump is 380psi, and the injection flow rate is 0.7ml / min. After confirming that the modified copolymer unit is no longer detected in the injected polymer according to tetrahydrofuran from the detector, the injection of the second solvent is completed. Then, based on the detected chromatogram results, the modification ratio (%) is calculated according to the following mathematical formula 2.

[0316] [Mathematical formula 2]

[0317]

[0318] In Mathematical Formula 2, the peak area of ​​the unmodified polymer unit is the peak area of ​​the chromatogram on the first solution delivered to the detector, and the peak area of ​​the modified polymer unit is the peak area of ​​the chromatogram on the second solution delivered to the detector.

[0319] [Table 1]

[0320]

[0321] As shown in Table 1, Examples 1 to 7 simultaneously satisfy all conditions (i) to (vii) proposed in the present invention.

[0322] 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 stress relaxation ratio of less than 0.7, and did not simultaneously satisfy all of the conditions (i) to (vii) set forth in the present invention.

[0323] Here, compared with Example 1, Comparative Example 1 was prepared by a preparation method without performing a step of injecting a polymerization initiator in batches, and Comparative Example 3 was prepared by a preparation method of injecting a polymerization initiator when the polymerization conversion rate was 43% (less than 50%), and did not show a wide molecular weight distribution property. In particular, although Comparative Example 1 used the same polymerization initiator and modifier as Example 1, the nitrogen atom content in the polymer was significantly reduced to a level of 65%, and in the case of Comparative Example 3, the modification ratio was significantly reduced to a level of 87%.

[0324] In addition, in the case of Comparative Example 6, the same polymerization initiator as in Example 5 was used, a nitrogen atom-containing modifier was used, and the nitrogen atom content in the polymer was as high as that of the example, but the molecular weight distribution was narrow and less than 2.0, and the Mooney stress relaxation ratio was less than 0.7, showing a high degree of branching. In this case, Comparative Example 6 was prepared by a preparation method without batch injection of a polymerization initiator.

[0325] From the above results, it can be confirmed that by preparing by a preparation method including controlling the polymerization conversion rate in the first polymerization reactor at the specific point proposed in the present invention and including a polymerization step of introducing a polymerization initiator in batches at a specific point, by simultaneously controlling the conditions, a modified conjugated diene polymer that simultaneously satisfies conditions (i) to (vii) of the present invention can be obtained.

[0326] Experimental Example 2

[0327] In order to compare and analyze the physical properties of the rubber compositions including the modified conjugated diene-based copolymers prepared in Examples and Comparative Examples and the molded products made therefrom, stretchability, viscoelasticity and processability were measured, respectively, and the results are shown in Table 3 below.

[0328] 1) Preparation of rubber samples

[0329] The modified conjugated diene-based polymers of Examples and Comparative Examples were compounded as raw materials under the compounding conditions shown in Table 3. The raw materials in Table 3 are expressed by parts by weight based on 100 parts by weight of the raw material rubber.

[0330] [Table 2]

[0331]

[0332] Specifically, the rubber sample was kneaded by first-stage kneading and second-stage kneading. In the first-stage kneading, raw rubber, silica (filler), organic silane coupling agent (X50S, Evonik), process oil (TDAE oil), zinc oxide (ZnO), stearic acid, antioxidant (TMQ (RD)) (2,4-trimethyl-1,2-dihydroquinoline polymer), anti-aging agent (6PPD ((dimethylbutyl)-N-phenyl-phenylenediamine) and wax (microcrystalline wax) were kneaded using a Banbury mixer equipped with a temperature control device. In this case, the initial temperature of the kneading device was controlled to At 70°C, after the compounding was completed, the first compounded mixture was obtained at a discharge temperature of 145°C to 155°C. In the second stage kneading, the first compounded mixture was cooled to room temperature, and the first compounded mixture, sulfur, rubber accelerator (DPD (diphenylguanidine)) and vulcanization accelerator (CZ (N-cyclohexyl-2-benzothiazolylsulfenamide)) were added to the kneading device and bonded at a temperature below 100°C to obtain a second compounded mixture. Then, through a curing process at 160°C for 20 minutes, a rubber sample was formed.

[0333] 2) Stretchability

[0334] Each sample was prepared and the tensile strength at break and the tensile stress at 300% stretch (300% modulus) of each sample were measured according to the ASTM 412 tensile test method. Specifically, the tensile property was measured at a rate of 50 cm / min using a Universal Test Machin 4204 tensile tester (Instron) at room temperature.

[0335] 3) Viscoelasticity

[0336] The viscoelastic behavior of thermodynamic deformation was measured at a frequency of 10 Hz at each measurement temperature (-60°C to 60°C) using a dynamic mechanical analyzer (Gabo) in the film tension mode, and the tan δ value was fixed, thereby fixing the viscoelasticity. In this case, if the tan δ value at a low temperature of 0°C increases, the wet skid resistance becomes better, 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) becomes better. The obtained values ​​in Table 3 are indexed based on the obtained values ​​of Comparative Example 1, so the higher the value, the better the result.

[0337] 4) Processability

[0338] The processability of each polymer was compared and analyzed by measuring 1) the Mooney viscosity (MV, ML 1+4, @100°C MU) of the second compounded mixture obtained during the preparation of the rubber sample, in which case the lower the measured value of the Mooney viscosity, the better the processability.

[0339] Specifically, using a large rotor with a rotor speed of 2±0.02 rpm at 100°C, by using MV-2000 (Alpha Technologies), each second compounded mixture was allowed to stand at room temperature (23±5°C) for more than 30 minutes, 27±3 g was collected and placed in a mold cavity, and then Platen was operated for 4 minutes for measurement.

[0340] [Table 3]

[0341]

[0342] In Table 3, the stretchability and tan δ values ​​at 0°C of Examples 1 to 7, Comparative Example 1, and Comparative Examples 3 to 6 were calculated based on the measured values ​​of Comparative Example 2 by the following Mathematical Formula 4, and the tan δ values ​​at 60°C were calculated based on the values ​​of Comparative Example 2 by the following Mathematical Formula 5.

[0343] [Formula 4]

[0344] Index (%) = (measured value / reference value) x 100

[0345] [Formula 5]

[0346] Index (%) = (measured value / reference value) x 100

[0347] As shown in Table 3, Examples 1 to 7 according to the embodiment of the present invention showed remarkably excellent stretchability, wet slip resistance, rolling resistance, and processability compared to Comparative Examples 1 to 6.

[0348] In this case, Examples 1 to 7 satisfy all of the conditions (i) to (vii) set forth in the present invention, whereas Comparative Examples 1 to 6 do not satisfy any one or more of the conditions.

[0349] The results in Table 1 and Table 3 mean that the modified conjugated diene polymer of the present invention is prepared by the preparation method proposed in the present invention and can simultaneously meet the specific conditions defined in (i) to (vii), and therefore, the improvement effects of stretchability, wet slip resistance, rolling resistance and processability can be achieved in a balanced manner.

Claims

1. A modified conjugated diene polymer, comprising: a repeating unit derived from a conjugated diene monomer; a repeating unit derived from an aromatic vinyl monomer; a repeating unit derived from a compound represented by the following formula 1; and a functional group derived from a modifier; and Satisfying the following conditions (i) to (vii) and Mooney viscosity: (i) the gel permeation chromatography molecular weight distribution curve is unimodal; (ii) a molecular weight distribution of 2.0 or more; (iii) a weight average molecular weight of 100,000 g / mol to 2,000,000 g / mol; (vi) a modification ratio of 70% or more; (v) a Mooney stress relaxation ratio measured at 100° C. of 0.7 to 3.0; (vi) a Mooney Maximum Relaxation Area (MLRA) measured at 100° C. and represented by the following Mathematical Formula 1 is 1500 MU-s or less; and (vii) a nitrogen atom content of 100 ppm or more based on the weight of the polymer, Mooney viscosity is 50 to 100, [Mathematical formula 1] In mathematical formula 1, A is the Mooney Maximum Relaxation Area (MLRA), k is the Mooney intercept 1 second after stopping the rotor operation of the Mooney viscometer, a is the slope of the logarithmic plot of Mooney torque versus time, t o is the starting point of the Mooney relaxation, and t f is the end point of Mooney relaxation, [Formula 1] 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 of 1 to 20 carbon atoms which may be substituted or unsubstituted, R3 and R4 are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 30 carbon atoms, which may be substituted or unsubstituted, and The substituent is one or more selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, in, The modifier is a compound represented by the following formula 2, formula 3 or formula 6: [Formula 2] In formula 2, R 1 is a single bond or an alkylene group of 1 to 10 carbon atoms, R 2 and R 3 are each independently an alkyl group having 1 to 10 carbon atoms, R 4 is hydrogen, an alkyl group having 1 to 10 carbon atoms, a mono-, di- or tri-substituted alkylsilyl group having 1 to 10 carbon atoms, or a heterocyclic group having 2 to 10 carbon atoms, R 21 is a single bond, an alkylene group of 1 to 10 carbon atoms, or -[R 42 O] j -, R 42 is an alkylene group of 1 to 10 carbon atoms, a and m are each independently an integer from 1 to 3, n is an integer of 0, 1 or 2, and j is an integer selected from 1 to 30, [Formula 3] In formula 3, R 5 , R 6 and R 9 are each independently an alkylene group having 1 to 10 carbon atoms, R 7 , R 8 , R 10 and R 11 are each independently an alkyl group having 1 to 10 carbon atoms, R 12 is hydrogen or an alkyl group of 1 to 10 carbon atoms, b and c are each independently 0, 1, 2 or 3, satisfying b+c≥1, and A is Where R 13 , R 14 , R 15 and R 16 are each independently hydrogen or an alkyl group of 1 to 10 carbon atoms, [Formula 6] In formula 6, R 30 is a monovalent hydrocarbon group of 1 to 30 carbon atoms, R 31 To R 33 are each independently an alkylene group having 1 to 10 carbon atoms, R 34 To R 37 are each independently an alkyl group of 1 to 10 carbon atoms, and g and h are each independently an integer selected from 0 or 1 to 3, wherein g+h is an integer of 1 or greater.

2. The modified conjugated diene polymer according to claim 1, wherein In formula 1, 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.

3. The modified conjugated diene polymer according to claim 1, wherein The aromatic vinyl 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-pyrrolidinylethyl)styrene, 4-(2-pyrrolidinylethyl)styrene and 3-(2-pyrrolidine-1-methylethyl)-α-methylstyrene.

4. The method for preparing the modified conjugated diene polymer according to claim 1, comprising: polymerizing a conjugated diene monomer and an aromatic vinyl monomer in a hydrocarbon solvent to prepare a living polymer (S1); and reacting or coupling the active polymer prepared in step (S1) with a modifier (S2), The polymerization in step (S1) is carried out by initiating polymerization in the presence of a first polymerization initiator, and injecting a second polymerization initiator in at least one batch to carry out a polymerization reaction when the polymerization conversion rate is 50% to 95%, The first polymerization initiator and the second polymerization initiator are oligomers having an anion active terminal, which are prepared by reacting an organic metal 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 the polymerization conversion rate in the first reactor of the polymerization reactors is 10% to 50%, [Formula 1] 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 of 1 to 20 carbon atoms which may be substituted or unsubstituted, R3 and R4 are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 30 carbon atoms, which may be substituted or unsubstituted, and The substituent is one or more selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, The modifier is a compound represented by the following formula 2, formula 3 or formula 6: [Formula 2] In formula 2, R 1 is a single bond or an alkylene group of 1 to 10 carbon atoms, R 2 and R 3 are each independently an alkyl group having 1 to 10 carbon atoms, R 4 is hydrogen, an alkyl group having 1 to 10 carbon atoms, a mono-, di- or tri-substituted alkylsilyl group having 1 to 10 carbon atoms, or a heterocyclic group having 2 to 10 carbon atoms, R 21 is a single bond, an alkylene group of 1 to 10 carbon atoms, or -[R 42 O] j -, R 42 is an alkylene group of 1 to 10 carbon atoms, a and m are each independently an integer from 1 to 3, n is an integer of 0, 1 or 2, and j is an integer selected from 1 to 30, [Formula 3] In formula 3, R 5 , R 6 and R 9 are each independently an alkylene group having 1 to 10 carbon atoms, R 7 , R 8 , R 10 and R 11 are each independently an alkyl group having 1 to 10 carbon atoms, R 12 is hydrogen or an alkyl group of 1 to 10 carbon atoms, b and c are each independently 0, 1, 2 or 3, satisfying b+c≥1, and A is Where R 13 , R 14 , R 15 and R 16 are each independently hydrogen or an alkyl group of 1 to 10 carbon atoms, [Formula 6] In formula 6, R 30 is a monovalent hydrocarbon group of 1 to 30 carbon atoms, R 31 To R 33 are each independently an alkylene group having 1 to 10 carbon atoms, R 34 To R 37 are each independently an alkyl group of 1 to 10 carbon atoms, and g and h are each independently an integer selected from 0 or 1 to 3, wherein g+h is an integer of 1 or greater.

5. The method for preparing the modified conjugated diene polymer according to claim 4, wherein: The weight average molecular weight of the oligomer is 100 g / mol to 30000 g / mol.

6. The method for preparing a modified conjugated diene polymer according to claim 4, wherein: The step (S1) uses 0.01 mmol to 10 mmol of the polymerization initiator based on 100 g in total of the monomer, and the polymerization initiator includes a first polymerization initiator and a second polymerization initiator.

7. The method for preparing a modified conjugated diene polymer according to claim 4, wherein: 0.01 mol to 10 mol of the second polymerization initiator is used based on 1 mol of the first polymerization initiator.

8. The method for preparing a modified conjugated diene polymer according to claim 4, wherein: The batch injection includes: a first continuous batch injection of a part of the total amount of the second polymerization initiator when the polymerization conversion rate is greater than 50% and less than 80%, and a second continuous batch injection of the remaining amount of the total amount when the polymerization conversion rate 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 the start to the end of the injection.

9. The method for preparing a modified conjugated diene polymer according to claim 4, wherein the polymerization in step (S1) is carried out by further comprising a polar additive. 10 . A rubber composition comprising the modified conjugated diene polymer according to claim 1 and a filler.

11. The rubber composition according to claim 10, wherein The rubber composition includes 0.1 parts by weight to 200 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene-based polymer.

12. The rubber composition according to claim 10, further comprising a vulcanizing agent.

Images