Modified conjugated diene polymer and rubber composition containing same

Abstract

The present invention relates to a modified conjugated diene polymer that is excellent in processability as well as in tensile strength and viscoelastic properties, and to a rubber composition containing the same. The modified conjugated diene polymer comprises: a unit derived from a modifier having three or more alkoxysilane groups; a non-functional chain that forms a silicon-carbon bond on one side of the unit derived from the modifier and contains a repeating unit derived from a conjugated diene monomer; and a functional chain that forms a silicon-carbon bond on the other side of the unit derived from the modifier and contains two or more units derived from an N-functional group-containing monomer, and the modified conjugated diene polymer has a Mooney viscosity change rate of 20% or less.

Description

[Technical field]

[0001] This application claims the benefit of priority based on Korean Patent Application No. 10-2019-0113004 filed on September 11, 2019, and Korean Patent Application No. 10-2020-0116403 filed on September 10, 2020, and all contents disclosed in the documents of the relevant Korean patent applications are incorporated herein by reference.

[0002] The present invention relates to a modified conjugated diene-based polymer having excellent processability, tensile strength and viscoelastic properties, and a rubber composition containing the same. [Background technology]

[0003] In recent years, with the demand for lower fuel consumption for automobiles, there has been a demand for conjugated diene-based polymers as rubber materials for tires that have low rolling resistance, excellent abrasion resistance and tensile properties, as well as adjustment stability, as typified by wet skid resistance.

[0004] One method for reducing the rolling resistance of a tire is to reduce the hysteresis loss of vulcanized rubber, and the evaluation indexes for such vulcanized rubber are the rebound resilience, tan δ, Goodrich heat generation, etc. at 50° C. to 80° C. In other words, a rubber material that has high rebound resilience or low tan δ and Goodrich heat generation at the above temperatures is preferred.

[0005] Natural rubber, polyisoprene rubber, polybutadiene rubber, etc. are known as rubber materials with low hysteresis loss, but they have a problem of low wet skid resistance. In recent years, conjugated diene polymers or copolymers such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) have been produced by emulsion polymerization or solution polymerization and used as rubber for tires. Among them, the greatest advantage of solution polymerization over emulsion polymerization is that the content of vinyl structure and the content of styrene, which determine the physical properties of rubber, can be freely adjusted, and the molecular weight and physical properties can be adjusted by coupling, modification, etc. Therefore, the structure of the finally produced SBR or BR can be easily changed, and the movement of the chain ends can be reduced by bonding or modification of the chain ends, and the binding strength with fillers such as silica or carbon black can be increased, so SBR produced by solution polymerization is often used as a rubber material for tires.

[0006] When such SBR obtained by solution polymerization is used as a rubber material for tires, the vinyl content in the SBR is increased to increase the glass transition temperature of the rubber, thereby making it possible to adjust the physical properties required for tires, such as running resistance and braking force, as well as to reduce fuel consumption by appropriately adjusting the glass transition temperature. The SBR obtained by solution polymerization is produced using an anionic polymerization initiator, and a technique is used in which the chain ends of the formed polymer are bonded or modified using various modifiers to introduce functional groups to the ends. For example, U.S. Patent No. 4,397,994 proposes a technique in which active anions at the chain ends of a polymer obtained by polymerizing styrene-butadiene in a non-polar solvent using an alkyl lithium, which is a monofunctional initiator, are bonded using a binder such as a tin compound.

[0007] On the other hand, as a modifier for introducing functional groups into the chain end of a polymer, a technique of applying an aminoalkoxysilane-based modifier that simultaneously contains an alkoxysilane group and an amine group in the molecule is widely known in order to maximize the dispersibility and reactivity of the filler.However, if the number of amine groups in the modifier increases, the solubility in the hydrocarbon solvent used in the production of the polymer decreases, which makes it difficult to carry out the modification reaction. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] U.S. Patent No. 4,397,994A Summary of the Invention [Problem to be solved by the invention]

[0009] The present invention has been made to solve the above-mentioned problems of the conventional techniques, and has an object to provide a modified conjugated diene polymer which, by arranging a non-functional chain, a unit derived from a modifier, and a functional chain rich in N-functional groups, suppresses change in Mooney viscosity over time, has excellent affinity with fillers, and is also excellent in processability and abrasion resistance.

[0010] It is another object of the present invention to provide a rubber composition containing the modified conjugated diene polymer. [Means for solving the problem]

[0011] According to one embodiment of the present invention for solving the above problems, there is provided a polymerizable composition comprising a modifier-derived unit having 3 or more alkoxy groups bonded to silicon, a non-functional chain including a repeating unit derived from a conjugated diene monomer and forming a silicon-carbon bond on one side of the modifier-derived unit, and a functional chain including 2 or more units derived from an N-functional group-containing monomer and forming a silicon-carbon bond on the other side of the modifier-derived unit, and the polymerizable composition has a Mooney viscosity change rate (MV RThe present invention provides a modified conjugated diene-based polymer in which the content of the copolymer (C) is 20% or less.

[0012]

number

[0013] In the above mathematical formula 1, MV R is the rate of change of Mooney viscosity, MV f is the Mooney viscosity at 100°C after the polymer is left at 25°C for 30 days, and MV i is the initial Mooney viscosity of the polymer at 100°C.

[0014] The present invention also provides a rubber composition comprising the modified conjugated diene polymer and a filler. Effect of the Invention

[0015] The modified conjugated diene-based polymer according to the present invention has excellent affinity with the filler and excellent mechanical properties, by introducing a functional chain to distribute abundantly functional groups that interact with the filler, and by appropriately arranging this functional chain, units derived from the modifier, and non-functional chains in the structure.

[0016] In addition, the rubber composition according to the present invention contains the modified conjugated diene polymer, and thus has the effects of not only excellent tensile properties and viscoelastic properties, but also excellent processability and improved abrasion resistance. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] The present invention will now be described in more detail so that the present invention may be easily understood.

[0018] The terms and words used in the description and claims of the present invention should not be interpreted in a limited manner to their ordinary or dictionary meanings, but should be interpreted in a manner that is consistent with the technical idea of ​​the present invention, based on the principle that the inventors can appropriately define the concepts of terms in order to best describe their invention.

[0019] Definition of Terms As used herein, the term "polymer" refers to a polymeric compound prepared by polymerizing monomers, whether the monomers are the same or different. The general term polymer thus encompasses the terms homopolymer and copolymer, both of which are commonly used to refer to polymers prepared from only one type of monomer.

[0020] As used herein, the term "functional" means having a property of containing a functional group and being capable of reacting with other functional groups or active sites, and may mean a property of containing and having a functional group that contains N, O, S, or Si in addition to carbon-carbon or carbon-hydrogen bonds.

[0021] In the present specification, the term "non-functional chain" refers to a molecular chain of a main skeleton forming a polymer, and may refer to a chain mainly including repeating units of a conjugated diene monomer, or a conjugated diene monomer and an aromatic vinyl monomer.

[0022] As used herein, the term "vinyl content" refers to the mass (or weight) percentage of butadiene incorporated in the 1- and 2-positions in the polymer chain based on the conjugated diene monomer (e.g., butadiene) moiety in the polymer (total amount of polymerized butadiene).

[0023] As used herein, the term "monovalent hydrocarbon group" may mean a monovalent atomic group in which carbon and hydrogen are bonded, such as a monovalent alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkyl group containing one or more unsaturated bonds, and an aryl group, and the minimum number of carbon atoms in a substituent represented by a monovalent hydrocarbon is determined depending on the type of each substituent.

[0024] As used herein, the term "divalent hydrocarbon group" may mean a divalent atomic group in which carbon and hydrogen are bonded, such as a divalent alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, a cycloalkylene group containing one or more unsaturated bonds, and an arylene group, and the minimum number of carbon atoms in a substituent represented by a divalent hydrocarbon is determined depending on the type of each substituent.

[0025] As used herein, the term "alkyl group" means a monovalent aliphatic saturated hydrocarbon group and may be meant to include both straight-chain alkyl groups, such as methyl, ethyl, propyl, and butyl, and branched alkyl groups, such as isopropyl, sec-butyl, tert-butyl, and neo-pentyl.

[0026] As used herein, the term "alkenyl group" may mean a monovalent aliphatic unsaturated hydrocarbon containing one or more double bonds.

[0027] As used herein, the term "alkynyl group" may mean a monovalent aliphatic unsaturated hydrocarbon containing one or more triple bonds.

[0028] As used herein, the term "alkylene group" may mean a divalent aliphatic saturated hydrocarbon such as methylene, ethylene, propylene, butylene, and the like.

[0029] As used herein, the term "aryl group" refers to an aromatic hydrocarbon and can be meant to include both monocyclic aromatic hydrocarbons, in which one ring is formed, or polycyclic aromatic hydrocarbons, in which two or more rings are linked together.

[0030] As used herein, the term "heterocyclic group" refers to a cycloalkyl or aryl group in which a carbon atom is replaced with one or more heteroatoms, and can include, for example, both a heterocycloalkyl group and a heteroaryl group.

[0031] In this specification, the term "substituted" means that hydrogen of a functional group, an atomic group, or a compound is replaced with a specific substituent, and when hydrogen of a functional group, an atomic group, or a compound is replaced with a specific substituent, there may be one or more multiple substituents depending on the number of hydrogens present in the functional group, atomic group, or compound. When there are multiple substituents, each of the substituents may be the same or different.

[0032] As used herein, the term "single bond" may refer to the single covalent bond itself, with no other atoms or molecular groups involved.

[0033] As used herein, the terms "derived unit," "derived repeating unit," and "derived functional group" can refer to a component or structure originating from a certain substance, or the substance itself.

[0034] In this specification, the terms "comprise", "have", and their derivatives are not intended to exclude the presence of any additional components, steps, or procedures, whether they are specifically disclosed or not. To avoid any uncertainty, all compositions claimed using the term "comprise" may include any additional additives, adjuvants, or compounds, whether polymeric or otherwise, unless stated to the contrary. In contrast, the term "consisting essentially of" excludes from the scope of any consecutive description any other components, steps, or procedures, except those that are not essential for operability. The term "consisting of" excludes any components, steps, or procedures not specifically stated or listed.

[0035] Measurement method and conditions In this specification, the "vinyl content" refers to the content of vinyl in each of the polymers measured and analyzed using a Varian VNMRS 500 MHz NMR. 1,1,2,2-tetrachloroethane was used as the solvent in the NMR measurement, the solvent peak was calculated to be 6.0 ppm, and the content of 1,2-vinyl bonds in the entire polymer was calculated based on the peaks of random styrene at 7.2 to 6.9 ppm, block styrene at 6.9 to 6.2 ppm, 1,4-vinyl and 1,2-vinyl at 5.8 to 5.1 ppm, and 1,2-vinyl at 5.1 to 4.5 ppm.

[0036] In this specification, "weight average molecular weight (Mw)", "number average molecular weight (Mn)" and "molecular weight distribution (MWD)" are measured by GPC (gel permeation chromatography) analysis and by checking the molecular weight distribution curve. The molecular weight distribution (PDI, MWD, Mw / Mn) is calculated from each of the measured molecular weights. Specifically, the GPC is performed using a combination of two PLgel Olexis (Polymer Laboratories) columns and one PLgel mixed-C (Polymer Laboratories) column, and PS (polystyrene) is used as a GPC standard material when calculating the molecular weight. The GPC measurement solvent is prepared by mixing 2 wt% of an amine compound with tetrahydrofuran.

[0037] In the present specification, the "content of N atoms" can be measured, for example, by the NSX analysis method. In the NSX analysis method, the measurement is performed using an ultra-trace nitrogen quantitative analyzer (NSX-2100H). For example, when the ultra-trace nitrogen quantitative analyzer is used, the ultra-trace nitrogen quantitative analyzer (Auto sampler, Horizontal furnace, PMT & Nitrogen detector) is turned on, Ar is supplied at 250 ml / min, O is supplied at 250 ml / min, and the nitrogen detector is turned on at 250 ml / min. 2The carrier gas flow rate is set to 350 ml / min, the ozonizer to 300 ml / min, the heater to 800°C, and the analyzer is allowed to stabilize for about 3 hours. After the analyzer is stabilized, a calibration curve is created for the calibration range of 5 ppm, 10 ppm, 50 ppm, 100 ppm, and 500 ppm using a Nitrogen standard (AccuStandard S-22750-01-5 ml), and the area corresponding to each concentration is obtained, and a straight line is created using the concentration and area ratio. Then, a ceramic boat containing 20 mg of sample is placed in the auto sampler of the analyzer and measured to obtain the area. The N content is calculated using the area of ​​the obtained sample and the calibration curve. In this case, the sample is a modified conjugated diene-based polymer that has been placed in hot water heated with steam, stirred, and the solvent removed, and residual monomers, residual modifiers, and oil have been removed.

[0038] In this specification, the "Si atom content" is measured by ICP analysis using an inductively coupled plasma optical emission spectrometer (ICP-OES; Optima 7300DV). Specifically, about 0.7 g of a sample is placed in a platinum crucible, about 1 mL of concentrated sulfuric acid (98% by weight, electronic grade) is added, and the sample is heated at 300°C for 3 hours. The sample is then incinerated in an electric furnace (Thermo Scientific, Lindberg Blue M) according to the following program of steps 1 to 3, and then: 1) Step 1: initial temp 0℃, rate(temp / hr) 180℃ / hr, temp(hold time) 180℃(1hr) 2) Step 2: initial temp 180℃, rate(temp / hr) 85℃ / hr, temp(hold time) 370℃(2hr) 3) Step 3: initial temp 370℃, rate(temp / hr) 47℃ / hr, temp(hold time) 510℃(3hr). To the residue, add 1mL of concentrated nitric acid (48% by weight) and 20μl of concentrated hydrofluoric acid (50% by weight), seal the platinum crucible and shake for more than 30 minutes. Then, add 1mL of boric acid to the sample and store at 0℃ for more than 2 hours. Then, dilute with 30mL of ultrapure water and incinerate for measurement.

[0039] Modified conjugated diene polymer The present invention provides a modified conjugated diene-based polymer that has excellent affinity with a filler and, as a result, can provide a rubber composition that is excellent in processability, tensile properties, and viscoelastic properties.

[0040] The modified conjugated diene polymer according to one embodiment of the present invention includes a modifier-derived unit having 3 or more alkoxy groups bonded to silicon, a non-functional chain including a repeating unit derived from a conjugated diene monomer and forming a silicon-carbon bond on one side of the modifier-derived unit, and a functional chain including 2 or more units derived from an N-functional group-containing monomer and forming a silicon-carbon bond on the other side of the modifier-derived unit, and has a Mooney viscosity change rate (MV R ) is 20% or less.

[0041]

number

[0042] In the above mathematical formula 1, MV R is the rate of change of Mooney viscosity, MV f is the Mooney viscosity at 100°C after the polymer is left at 25°C for 30 days, and MV i is the initial Mooney viscosity of the polymer at 100°C.

[0043] The modified conjugated diene polymer may have a N atom content of 100 ppm or more, preferably 150 ppm or more, more preferably 170 ppm or more, based on weight, in the polymer, as determined by NSX analysis. The modified conjugated diene polymer may have a relatively high N atom content by introducing a functional chain that allows N-functional groups to be present repeatedly. In addition, the N-functional group has a structure in which it is bonded to the main chain of the polymer and to a unit derived from an alkoxysilane compound bonded to at least one end of the main chain, and thus the affinity and dispersibility with a filler, for example, silica, is significantly improved during the blending process, resulting in excellent viscoelastic properties and significantly improved processability. On the other hand, when an amine-containing alkoxysilane modifier is used, the N atom content may also include N atoms derived from the modifier.

[0044] According to one embodiment of the present invention, the modified conjugated diene-based polymer may have a Si atom content of 180 ppm or more, preferably 190 ppm or more, and more preferably 200 ppm or more, by weight, as determined by ICP analysis.

[0045] The content of the Si atoms is mainly derived from the modifier, which is an alkoxysilane compound, and may be derived from Si incidentally contained in the N-functional group-containing monomer in addition to the modifier. The content of the Si atoms is expected to improve the affinity with the functional group, i.e., the filler, present in the modified conjugated diene polymer, and can be a major factor in improving processability.

[0046] In addition, due to such a high content of N atoms, the modified conjugated diene-based polymer according to one embodiment of the present invention can satisfy the condition that the molar ratio of N atoms to Si atoms (N / Si) is 0.75 or more. Generally, a polymer modified with a modifying agent may contain Si atoms and N atoms due to a modified polymerization initiator, a modified monomer, etc., but as described above, the polymer according to one embodiment of the present invention contains an N-functional group-containing monomer as a repeating unit, so that the content of N atoms is relatively high. Therefore, symbolically, the molar ratio of N atoms to Si atoms may be 0.75 or more, preferably 0.77 or more, or 0.78 or more, more preferably 0.8 or more, and most preferably 0.9 or more. This improves the dispersibility during blending, thereby optimizing the effect of improving processability.

[0047] According to an embodiment of the present invention, the modified conjugated diene-based polymer has a Mooney viscosity change rate (MV R ) is 20% or less.

[0048]

number

[0049] In the above mathematical formula 1, MV R is the rate of change of Mooney viscosity, MV f is the Mooney viscosity at 100°C after the polymer is left at 25°C for 30 days, and MV i is the initial Mooney viscosity of the polymer at 100°C.

[0050] The rate of change in Mooney viscosity can be an index for confirming not only processability but also a small increase in Mooney viscosity occurring during storage after production. The polymer according to the present invention has a structural feature in which a functional chain containing an N-functional group-containing monomer and a unit derived from a modifier are bonded to a non-functional chain of the polymer in a specific arrangement, and therefore, in addition to improving processability, the rate of change in Mooney viscosity is low even when stored for a long period of time, and therefore the polymer has excellent storage stability.

[0051] The Mooney viscosity change rate is the rate of change between the initial Mooney viscosity of the polymer and the Mooney viscosity after storing the polymer at room temperature for 30 days, and the present invention provides a polymer having a Mooney viscosity change rate of 20% or less, preferably 15% or less. Here, the Mooney viscosity is the Mooney viscosity at 100° C., and can be measured by a conventional method applied in this technical field.

[0052] Structure of modified conjugated diene polymer According to one embodiment of the present invention, the modified conjugated diene-based polymer has a structure in which the non-functional chain and the functional chain are mutually bonded via a unit derived from a modifier. The non-functional chain and the functional chain are bonded (or coupled) with the unit derived from the modifier as a center, and the non-functional chain and the functional chain may each be independently bonded with one or more chains, and preferably, the functional chain may be bonded with two or more chains.

[0053] The functional and non-functional chains are bonded to each other via the unit derived from the modifying agent by the reaction between the living anion end of each chain and the Si-bonded alkoxy group of the modifying agent. That is, the above structure can be realized by the modification reaction after polymerization and the similar modification reaction.

[0054] In the case of the above structure, the functional groups are distributed at one end of the polymer, and when interacting with silica, only one end of the polymer is bonded to the silica, and the other end is free. This provides a remarkable effect on the dispersibility of the filler and prevention of aggregation, similar to the conventional one-end modified polymer, and provides excellent processability.

[0055] In addition, in conventional double-end modified polymers, functional group-containing monomers are generally bonded to the other end different from the unit derived from the modifier, and when such a structure is adopted, the affinity with the filler is improved due to the abundance of functional groups, and the viscoelastic properties can be improved, but the degree of freedom of the polymer structure is significantly reduced, resulting in very poor processability. However, the modified conjugated diene-based polymer according to the present invention has a structure in which the functional chain is adjacent to the unit derived from the modifier, and thus the effect of improving the viscoelastic properties due to the interaction with the filler can be achieved at the same level or higher, and the processability can be significantly improved.

[0056] Furthermore, the functional chain is present at the same end as the unit derived from the modifier, which brings about a synergistic interaction with the filler, and is also highly effective in improving the abrasion resistance.

[0057] That is, according to one embodiment of the present invention, a functional chain containing a repeating unit derived from an N-functional group-containing monomer and a unit derived from a modifier are arranged on one side of the entire polymer, thereby providing the advantages and solving the problems of conventional one-end-modified conjugated diene-based polymers and both-end-modified conjugated diene-based polymers.

[0058] Non-functional chains containing repeat units derived from conjugated diene monomers According to one embodiment of the present invention, the non-functional chain that is the main backbone of the modified conjugated diene polymer has a repeating unit derived from a conjugated diene monomer as a main unit, and the conjugated diene monomer may be, for example, 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-halo-1,3-butadiene (halo means a halogen atom).

[0059] In addition to the conjugated diene monomer, the non-functional chain may further include an aromatic vinyl monomer and may further include a repeating unit derived therefrom. The aromatic vinyl monomer may be, for example, 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-pyrrolidino ethyl)styrene, 4-(2-pyrrolidino ethyl)styrene, and 3-(2-pyrrolidino-1-methylethyl)-α-methylstyrene.

[0060] As yet another example, the non-functional chain of the modified conjugated diene polymer may be a copolymer further including a repeating unit derived from a diene monomer having 1 to 10 carbon atoms in addition to the repeating unit derived from the conjugated diene monomer. The repeating unit derived from the diene monomer may be a repeating unit derived from a diene monomer different from the conjugated diene monomer. The diene monomer different from the conjugated diene monomer may be, for example, 1,2-butadiene. When the modified conjugated diene polymer is a copolymer further including a diene monomer, the modified conjugated diene polymer may include the repeating unit derived from the diene monomer in an amount of more than 0% by weight to 1% by weight, more than 0% by weight to 0.1% by weight, more than 0% by weight to 0.01% by weight, or more than 0% by weight to 0.001% by weight, and when the amount is within this range, there is an effect of preventing gel formation.

[0061] According to one embodiment of the present invention, when the non-functional chain forming the backbone of the modified conjugated diene-based polymer contains two or more monomers, the non-functional chain may be a random copolymer chain, in which case there is an effect of excellent balance between each physical property. The random copolymer may mean a copolymer in which repeating units forming the copolymer are randomly arranged.

[0062] The non-functional chain of the modified conjugated diene-based polymer according to one embodiment of the present invention may be free of functional groups, and the functional groups may be N-containing, S-containing, O-containing, or Si-containing functional groups. In this way, by not distributing functional groups in one non-functional chain, the effect of arranging a functional chain at one end as described above can be achieved.

[0063] Functional chains containing repeat units derived from N-functional monomers According to one embodiment of the present invention, the functional chain of the modified conjugated diene-based polymer comprises repeat units derived from an N-functional group-containing monomer.

[0064] According to one embodiment of the present invention, the main unit constituting the functional chain is an N-functional group-containing monomer, and the N-functional group may be essentially an amino group, an aliphatic cyclic amino group, an aliphatic chain amino group, an aromatic amino group, etc.

[0065] The functional chain may be one in which one unit is coupled to a unit derived from a modifier, or two or more units in the functional chain may be coupled via two or more alkoxysilyl groups present in an alkoxysilane-based modifier.

[0066] The functional chain is in the form of N-functional group-containing monomers repeatedly bonded together, and the number of repeating units may be 2 to 80. When the number of repeating units is 2 to 80, it is possible to secure a desired level of functionality by arranging the functional chain on the structure, and it is possible to achieve both processability and compounding properties.

[0067] The functional chain may further include a unit derived from a conjugated diene monomer. That is, the functional chain may be polymerized (low polymerization) only with an N-functional group-containing monomer, but may also be prepared by polymerizing (low polymerization) both an N-functional group-containing monomer and a conjugated diene monomer for the purpose of increasing the molecular weight or length. In this case, the functional chain may be in the form of a random copolymer in which the conjugated diene monomer and the N-functional group-containing monomer are randomly arranged, or in the form of a block copolymer in which the same units are arranged, and the form is not limited.

[0068] The weight average molecular weight of the functional chain may be smaller than the weight average molecular weight of the non-functional chain, for example, 50% or less, 30% or less, preferably 10% or less, more preferably 5% or less of the weight average molecular weight of the non-functional chain. This is a level at which the non-functional chain can bind to the alkoxy residue present in the bound modifier, and it is sufficient that the difference is sufficient to overcome the steric hindrance of the non-functional chain modified or coupled by the modifier, and is not an absolute standard for the difference in molecular weight.

[0069] Meanwhile, in the past, as a method for additionally introducing functional groups into a polymer, a condensation reaction was applied in which an active polymer was modified with a modifying agent, and then a compound capable of condensing with the Si-O bond of the modifying agent was reacted. However, when using a condensation reaction in this manner, the bond between the substance having the additional functional group and the modified polymer is formed as -Si-O-Si-, and hydrolysis may occur during the subsequent steam stripping step, washing step, or storage, resulting in a problem that the bond is separated at the condensation bond site, resulting in a problem of loss of functional groups.

[0070] In contrast, in the modified conjugated diene polymer according to the present invention, the living end of the functional chain reacts with the Si-OR group of the modifier to form a Si-C bond, which is not subject to hydrolysis reaction like a condensation bond, and therefore is not likely to be separated. Therefore, there is an advantage that the storage stability is improved and there is no problem of loss of the functional group initially introduced.

[0071] According to an embodiment of the present invention, the N-functional group-containing monomer may be, for example, a compound represented by the following Chemical Formula 1:

[0072] [ka]

[0073] In the above formula 1, X is N or CH; R 8a ~R 8c are each independently a hydrogen atom; an alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 20 carbon atoms; an alkynyl group having 2 to 20 carbon atoms; a heteroalkyl group having 1 to 20 carbon atoms, a heteroalkenyl group having 2 to 20 carbon atoms; a heteroalkynyl group having 2 to 20 carbon atoms; a cycloalkyl group having 5 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms; or a heterocyclic group having 3 to 20 carbon atoms, R 8d represents a single bond, an alkylene group having 1 to 20 carbon atoms which may be substituted or unsubstituted; a cycloalkylene group having 5 to 20 carbon atoms which may be substituted or unsubstituted; or an arylene group having 6 to 20 carbon atoms which may be substituted or unsubstituted, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms, R 8eis an alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 20 carbon atoms; an alkynyl group having 2 to 20 carbon atoms; a heteroalkyl group having 1 to 20 carbon atoms; a heteroalkenyl group having 2 to 20 carbon atoms; a heteroalkynyl group having 2 to 20 carbon atoms; a cycloalkyl group having 5 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms; a heterocyclic group having 3 to 20 carbon atoms; or a functional group represented by the following chemical formula 1a, O is an integer from 0 to 5, and R 8e At least one of R is a functional group represented by the following chemical formula 1a, and when O is an integer of 2 to 5, multiple R 8e may be the same or different,

[0074] [ka]

[0075] In the above formula 1a, R 8f represents a single bond, an alkylene group having 1 to 20 carbon atoms which may be substituted or unsubstituted; a cycloalkylene group having 5 to 20 carbon atoms which may be substituted or unsubstituted; or an arylene group having 6 to 20 carbon atoms which may be substituted or unsubstituted, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms, R 8g and R 8h are each independently an alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 20 carbon atoms; an alkynyl group having 2 to 20 carbon atoms; a heteroalkyl group having 1 to 20 carbon atoms; a heteroalkenyl group having 2 to 20 carbon atoms; a heteroalkynyl group having 2 to 20 carbon atoms; a cycloalkyl group having 5 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms; a heterocyclic group having 3 to 20 carbon atoms, or a mono-, di-, or tri-substituted alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, or R 8g and R 8h are linked to each other to form, together with N, a heterocyclic group having 2 to 10 carbon atoms.

[0076] The N-functional group-containing monomer may be a compound represented by the following formula 2:

[0077] [ka]

[0078] In the above Chemical Formula 2, X 1 -X 2 is CH 2 -CH 2 or CH=CH and X 3 -X 4 is CH 2 -CH 2 , CH=N, or N=N.

[0079] The N-functional group-containing monomer may be a compound represented by the following formula 3:

[0080] [ka]

[0081] In the above Chemical Formula 3, R 11a and R 11b are each independently an alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 20 carbon atoms; an alkynyl group having 2 to 20 carbon atoms; a heteroalkyl group having 1 to 20 carbon atoms; a heteroalkenyl group having 2 to 20 carbon atoms; a heteroalkynyl group having 2 to 20 carbon atoms; a cycloalkyl group having 5 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms; a heterocyclic group having 3 to 20 carbon atoms; or a functional group represented by the following chemical formula 3a, R 11c is an alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 20 carbon atoms; an alkynyl group having 2 to 20 carbon atoms; a heteroalkyl group having 1 to 20 carbon atoms; a heteroalkenyl group having 2 to 20 carbon atoms; a heteroalkynyl group having 2 to 20 carbon atoms; a cycloalkyl group having 5 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms; a heterocyclic group having 3 to 20 carbon atoms; a vinyl group; or a functional group represented by the following chemical formula 4a: R 11a , R 11b, and R 11c At least one of the functional groups represented by formula 3a is

[0082] [ka]

[0083] In the above formula 3a, R 11d represents a single bond, or an alkylene group having 1 to 20 carbon atoms which may be substituted or unsubstituted; a cycloalkylene group having 5 to 20 carbon atoms which may be substituted or unsubstituted; or an arylene group having 6 to 20 carbon atoms which may be substituted or unsubstituted, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms, R 11e and R 11f are each independently an alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 20 carbon atoms; an alkynyl group having 2 to 20 carbon atoms; a heteroalkyl group having 1 to 20 carbon atoms; a heteroalkenyl group having 2 to 20 carbon atoms; a heteroalkynyl group having 2 to 20 carbon atoms; a cycloalkyl group having 5 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms; a heterocyclic group having 3 to 20 carbon atoms; or a mono-, di-, or tri-substituted alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms.

[0084] The N-functional group-containing monomer may be a compound represented by the following formula 4:

[0085] [ka]

[0086] In the above Chemical Formula 4, R 12arepresents a single bond, or an alkylene group having 1 to 20 carbon atoms which may be substituted or unsubstituted; a cycloalkylene group having 5 to 20 carbon atoms which may be substituted or unsubstituted; or an arylene group having 6 to 20 carbon atoms which may be substituted or unsubstituted, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms, R 12b and R 12c are each independently an alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 20 carbon atoms; an alkynyl group having 2 to 20 carbon atoms; a heteroalkyl group having 1 to 20 carbon atoms; a heteroalkenyl group having 2 to 20 carbon atoms; a heteroalkynyl group having 2 to 20 carbon atoms; a cycloalkyl group having 5 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms; a heterocyclic group having 3 to 20 carbon atoms; or a mono-, di-, or tri-substituted alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms.

[0087] Modifier: Alkoxysilane compound In addition, the modified conjugated diene polymer is in a form in which a non-functional chain and a functional chain are coupled by an alkoxysilane-based modifier, and the non-functional chain and the functional chain can be bonded with the alkoxysilane-based modifier as a hub. Therefore, the alkoxysilane-based modifier may contain at least three alkoxy groups bonded to Si.

[0088] According to an embodiment of the present invention, the alkoxysilane-based modifier contained in the modified conjugated diene-based polymer may be an amine-containing alkoxysilane-based compound or an amine-free alkoxysilane-based compound.

[0089] In addition, the amine-containing alkoxysilane compound among the alkoxysilane-based modifiers may be, for example, a compound represented by the following chemical formula 5.

[0090] [ka]

[0091] In the above Chemical Formula 5, R 1 may be a single bond or an alkylene group having 1 to 10 carbon atoms; R 2 and R 3 may each independently be an alkyl group having 1 to 10 carbon atoms; R 4 may be hydrogen, an epoxy group, an alkyl group having 1 to 10 carbon atoms, an allyl group having 2 to 10 carbon atoms, a mono-, di- or tri-substituted alkylsilyl group substituted with an alkyl 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 having 1 to 10 carbon atoms, or -[R 42 O] j - may be R 42 may be an alkylene group having 1 to 10 carbon atoms, a and m may each independently be an integer selected from 1 to 3, n may be an integer selected from 0 to 2, and j may be an integer selected from 1 to 30.

[0092] Specific examples of the compound represented by Chemical Formula 5 include N,N-bis(3-(dimethoxy(methyl)silyl)propyl)-methyl-1-amine, N,N-bis(3-(diethoxy(methyl)silyl)propyl)-methyl-1-amine, and N,N-bis(3-(trimethoxysilyl)propyl)- N,N-bis(3-(trimethoxysilyl)propyl)-methyl-1-amine, N,N-bis(3-(triethoxysilyl)propyl)-methyl-1-amine, tri(trimethoxysilyl)amine, tri(3-(trimethoxysilyl)propyl)amine amine), N,N-bis(3-(diethoxy(methyl)silyl)propyl)-1,1,1-trimethylsilanamine, N-(3-(1H-1,2,4-triazole-1-yl)propyl)-3-(trimethoxysilyl)-N-(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-amine4-triazol-3-yl)propyl)propan-1-amine, N-allyl-N-(3-(trimethoxysilyl)propyl)prop-2-en-1-amine, N,N-bis(oxiran-2-ylmethyl)-3-(trimethoxysilyl)propan-1-amine, 1,1,1-trimethyl-N-(3-(trimethoxysilyl)propyl)propan-1-amine It may be one selected from the group consisting of 1,1,1-trimethyl-N-(3-(triethoxysilyl)propyl)-N-(trimethylsilyl)silanamine, and N,N-bis(3-(triethoxysilyl)propyl)-2,5,8,11,14-pentaoxahexadecan-16-amine.

[0093] As yet another example, the amine-containing alkoxysilane compound among the alkoxysilane-based modifiers may include a compound represented by the following Chemical Formula 6.

[0094] [ka]

[0095] In the above formula 6, R 5 , R 6 , and R 9 may each independently be an alkylene group having 1 to 10 carbon atoms; R 7 , R 8 , R 10 , and R 11 may each independently be an alkyl group having 1 to 10 carbon atoms; R 12may be hydrogen or an alkyl group having 1 to 10 carbon atoms; b and c are each independently 1, 2, or 3, and may satisfy b+c≧4; A is

[0096] [ka]

[0097] In this case, R 13 , R 14 , R 15 , and R 16 may each independently be hydrogen or an alkyl group having 1 to 10 carbon atoms.

[0098] As a specific example, the compound represented by Chemical Formula 6 may be one selected from the group consisting of N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine and 3-(4,5-dihydro-1H-imidazol-1-yl)-N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine.

[0099] As yet another example, the amine-containing alkoxysilane compound among the alkoxysilane-based modifiers may include a compound represented by the following Chemical Formula 7.

[0100] [ka]

[0101] In the above Chemical Formula 7, A 1 and A 2are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms, which may or may not contain an oxygen atom; R 17 ~R 20 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms; L 1 ~L 4 are each independently a mono-, di-, or tri-substituted alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, or a monovalent hydrocarbon group having 1 to 20 carbon atoms; 1 and L 2 And, L 3 and L 4 may be linked together to form a ring having 1 to 5 carbon atoms, L 1 and L 2 And, L 3 and L 4 When are linked to each other to form a ring, the formed ring may contain 1 to 3 heteroatoms of one or more types selected from the group consisting of N, O, and S.

[0102] As a specific example, the compound represented by Chemical Formula 7 is 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine), siloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine) (3, 3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl )bis(N,N-diethylpropan-1-amine) (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-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine), 3,3'-(1,1,3,3,3'-(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-diprop 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1-amine), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1-amine) -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-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,3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethan-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(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-dimethylmethan-1-amine), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethan-1-amine) methan-1-amine), N,N'-((1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine), N,N'-((1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine) N,N'-((1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine), N,N'-((1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine (N,N'-((1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine), N,N'-((1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilanamine) ethoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilanamine), N,N'-((1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilanamine) imethyl-N-phenylsilanamine), N,N'-((1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(propan-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-tetramethoxydisiloxane), 1,3-bis(3-(1H-imidazol-1-yl)propyl)-1,1,3,3-tetraethoxydisiloxane (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,It may be one selected from the group consisting of 3-tetrapropoxydisiloxane (1,3-bis(3-(1H-imidazol-1-yl)propyl)-1,1,3,3-tetrapropoxydisiloxane).

[0103] As yet another example, the amine-containing alkoxysilane compound among the alkoxysilane compounds may include a compound represented by the following Chemical Formula 8.

[0104] [ka]

[0105] In the above Chemical Formula 8, R b2 ~R b4 are each independently an alkylene group having 1 to 10 carbon atoms; R b5 ~R b8 are each independently an alkyl group having 1 to 10 carbon atoms, and R b13 and R b14 are each independently an alkylene group having 1 to 10 carbon atoms; R b15 ~R b18 are each independently an alkyl group having 1 to 10 carbon atoms, m 1 , m 2 , m 3 , and m 4 are each independently an integer from 1 to 3.

[0106] As yet another example, the amine-containing alkoxysilane compound among the alkoxysilane compounds may include a compound represented by the following Chemical Formula 9.

[0107] [ka]

[0108] In the above Chemical Formula 9, R e1 and R e2 are each independently an alkylene group having 1 to 10 carbon atoms; R e3 ~Re6 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or -R e7 SiR e8 R e9 R e10 Where R e3 ~R e6 At least one of them is -R e7 SiR e8 R e9 R e10 where R e7 is a single bond or an alkylene group having 1 to 10 carbon atoms, and R e8 ~R e10 are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and R e8 ~R e10 At least one of them is an alkoxy group having 1 to 10 carbon atoms.

[0109] As yet another example, the amine-free alkoxysilane compound among the alkoxysilane compounds may include a compound represented by the following Chemical Formula 10.

[0110] [ka]

[0111] In the above formula 10, X is O or S, and R f1 and R f2 are each independently a single bond or an alkylene group having 1 to 10 carbon atoms, R f3 ~R f8 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aralkyl group having 7 to 14 carbon atoms; p is an integer of 0 or 1, and when p is 0, R f1 is an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

[0112] As yet another example, the amine-free alkoxysilane compound among the alkoxysilane compounds may include a compound represented by the following Chemical Formula 11.

[0113] [ka]

[0114] In the above formula 11, R g1 ~R g4 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or -R g5 SiOR g6 Where R g1 ~R g4 At least one of them is -R g5 SiOR g6 where R g5 is a single bond or an alkylene group having 1 to 10 carbon atoms, and R g6 is an alkyl group having 1 to 10 carbon atoms, Y is C or N, and when Y is N, R g4 does not exist.

[0115] As yet another example, the amine-containing alkoxysilane compound among the alkoxysilane compounds may include a compound represented by the following Chemical Formula 12.

[0116] [ka]

[0117] In the above formula 12, R h1 and R h2 are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and R h3 is a single bond or an alkylene group having 1 to 10 carbon atoms; A 3 is -Si(R h4 R h5 R h6 ) or -N[Si(R h7 Rh8 R h9 )] 2 where R h4 ~R h9 are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

[0118] As yet another example, the amine-free alkoxysilane compound among the alkoxysilane compounds may include a compound represented by the following Chemical Formula 13.

[0119] [ka]

[0120] In the above formula 13, R g1 ~R g3 are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and R g4 is an alkoxy group having 1 to 10 carbon atoms, and q is an integer of 2 to 100.

[0121] General The modified conjugated diene polymer according to one embodiment of the present invention may have a number average molecular weight (Mn) of 1,000 g / mol to 2,000,000 g / mol, 10,000 g / mol to 1,000,000 g / mol, or 100,000 g / mol to 800,000 g / mol, and a weight average molecular weight (Mw) of 1,000 g / mol to 3,000,000 g / mol, 10 The peak average molecular weight (Mp) may be 1,000g / mol to 3,000,000g / mol, 10,000g / mol to 2,000,000g / mol, or 100,000g / mol to 2,000,000g / mol. When it is within this range, it has an effect of excellent rolling resistance and wet skid resistance. As another example, the modified conjugated diene polymer may have a molecular weight distribution (PDI; MWD; Mw / Mn) of 1.0 to 3.0, or 1.1 to 2.5, or 1.1 to 2.0, and when it is within this range, it has an effect of excellent tensile properties and viscoelastic properties as well as excellent balance between each physical property.

[0122] The modified conjugated diene polymer may have a Mooney viscosity at 100° C. of 30 or more, 40 to 150, or 40 to 140. When the viscosity is within this range, the polymer has excellent processability and productivity.

[0123] Here, the Mooney viscosity can be measured using a Mooney viscometer. Specifically, using a Monsanto MV2000E Large Rotor, the polymer is left at room temperature (23±5°C) for 30 minutes or more under the conditions of 100°C and rotor speed 2±0.02 rpm, and then 27±3 g is taken and filled into the die cavity, and the platen is operated to apply torque to measure.

[0124] The modified conjugated diene polymer may have a vinyl content of 5% by weight or more, 10% by weight or more, or 10% by weight to 60% by weight. Here, the vinyl content may refer to the content of 1,2-added conjugated diene monomers, not 1,4-added, relative to 100% by weight of a conjugated diene copolymer composed of a vinyl group-containing monomer and an aromatic vinyl monomer.

[0125] Method for producing modified conjugated diene polymer The present invention also provides a method for producing the modified conjugated diene polymer.

[0126] The method for producing the modified conjugated diene polymer according to one embodiment of the present invention includes the steps of: (S1) producing an active non-functional chain by polymerizing 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; (S2) reacting the active non-functional chain with an alkoxysilane modifier to produce a modified active non-functional chain; and (S3) reacting the modified active non-functional chain with a functional chain containing a repeating unit derived from an N-functional group-containing monomer.

[0127] The hydrocarbon solvent is not particularly limited, and may be, for example, one or more selected from the group consisting of n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene, and xylene.

[0128] The polymerization initiator is not particularly limited, and may be, for example, one or more selected from the group consisting of methyl lithium, ethyl lithium, propyl lithium, isopropyl lithium, n-butyl lithium, s-butyl lithium, t-butyl lithium, hexyl lithium, n-decyl lithium, t-octyl lithium, phenyl lithium, 1-naphthyl lithium, n-eicosyl lithium, 4-butylphenyl lithium, 4-tolyl lithium, cyclohexyl lithium, 3,5-di-n-heptylcyclohexyl lithium, 4-cyclopentyl lithium, naphthyl sodium, naphthyl potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide, and lithium isopropyl amide.

[0129] According to one embodiment of the present invention, the polymerization initiator may be used in an amount of 0.01 mmol to 10 mmol, 0.05 mmol to 5 mmol, 0.1 mmol to 2 mmol, 0.1 mmol to 1 mmol, or 0.15 mmol to 0.8 mmol based on 100 g of the total monomers, where the total 100 g of the monomers may represent the total amount of the conjugated diene monomer, or the conjugated diene monomer and the aromatic vinyl monomer.

[0130] S1 Step The polymerization in the step (S1) may be, for example, an anionic polymerization, and may be, for example, a living anionic polymerization having an anionic active site at the polymerization end by a growth polymerization reaction by an anion. The polymerization in the step (S1) may be a temperature-increasing polymerization, an isothermal polymerization, or a constant temperature polymerization (adiabatic polymerization). The constant temperature polymerization refers to a polymerization method including a step of polymerizing by its own reaction heat without adding any heat after adding a polymerization initiator, the temperature-increasing polymerization refers to a polymerization method in which the temperature is increased by adding any heat after adding the polymerization initiator, and the isothermal polymerization refers to a polymerization method in which the temperature of the polymer is maintained constant by adding heat to increase the heat or removing heat after adding the polymerization initiator.

[0131] According to one embodiment of the present invention, the polymerization in step (S1) may further include a diene compound having 1 to 10 carbon atoms in addition to the conjugated diene monomer, and in this case, there is an effect of preventing gel formation on the wall of the reactor during long-term operation. The diene compound may be 1,2-butadiene, for example.

[0132] The polymerization in the step (S1) may be carried out at a temperature range of, for example, 80° C. or less, −20° C. to 80° C., 0° C. to 80° C., 0° C. to 70° C., or 10° C. to 70° C. Within this range, the molecular weight distribution of the polymer can be narrowly adjusted, and there is an excellent effect in improving physical properties.

[0133] The activated polymer chain prepared in step (S1) may refer to a polymer in which a polymer anion and an organometallic cation are bonded.

[0134] On the other hand, the polymerization in the step (S1) may be carried out by including a polar additive, and the polar additive may be added at a ratio of 0.001 g to 50 g, 0.001 g to 10 g, or 0.005 g to 0.1 g based on a total of 100 g of the monomers. As yet another example, the polar additive may be added at a ratio of 0.001 g to 10 g, 0.005 g to 5 g, or 0.005 g to 4 g based on a total of 1 mmol of the polymerization initiator.

[0135] The polar additive may be, for example, one or more selected from the group consisting of tetrahydrofuran, 2,2-di(2-tetrahydrofuryl)propane, diethyl ether, cyclopentyl ether, dipropyl ether, ethylene methyl ether, ethylene dimethyl ether, diethyl glycol, dimethyl ether, tertiary butoxyethoxyethane, bis(3-dimethylaminoethyl)ether, (dimethylaminoethyl)ethyl ether, trimethylamine, triethylamine, tripropylamine, N,N,N',N'-tetramethylethylenediamine, sodium mentholate, and 2-ethyl tetrahydrofurfuryl ether, and may be preferably 2,2-di(2-tetrahydrofuryl)propane, triethylamine, tetramethylethylenediamine, sodium mentholate, or 2-ethyl tetrahydrofurfuryl ether. When the polar additive is contained, it has an effect of inducing the easy formation of a random copolymer by complementing the difference in reaction rate between a conjugated diene monomer and an aromatic vinyl monomer when they are copolymerized.

[0136] S2 Step The (S2) step is a step for preparing a modified active non-functional chain by reacting the active non-functional chain with an alkoxysilane compound, where the reaction may be a modification or coupling reaction, in which case the modifying agent may be used in an amount of 0.01 mmol to 10 mmol based on a total of 100 g of monomers. As yet another example, the modifying agent may be used in a molar ratio of 1:0.1 to 10, 1:0.1 to 5, or 1:0.1 to 1:3 based on 1 mole of the polymerization initiator in the (S1) step.

[0137] S3 Step The (S3) step is a step for producing a modified conjugated diene-based polymer by reacting the modified active non-functional chain with a functional chain containing a repeating unit derived from an N-functional group-containing monomer.

[0138] Meanwhile, the preparation method according to one embodiment of the present invention may further include a step of preparing a functional chain before the step (S3), and the step of preparing the functional chain may be carried out by polymerizing an N-functional group-containing monomer, or an N-functional group-containing monomer and a conjugated diene monomer in a hydrocarbon solvent in the presence of an organolithium compound. In this case, the polymerization reaction may be a living anionic polymerization having an anionic active site at the polymerization end due to a growth polymerization reaction by anion, and thus, one end of the functional chain may be a living anionic end that can act as a monomer.

[0139] Here, the organolithium compound may be an alkyllithium compound, specifically methyllithium, ethyllithium, propyllithium, isopropyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octyllithium, phenyllithium, 1-naphthyllithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, or 4-cyclopentyllithium, more specifically n-butyllithium.

[0140] For example, the functional chain may be prepared according to the following reaction scheme 1, and may be a compound having a structure represented by the following chemical formula M1.

[0141] [ka]

[0142] As another example, the functional chain may be prepared according to the following reaction scheme 2, and may be a compound having a structure represented by the following chemical formula M2.

[0143] [ka]

[0144] As another example, the functional chain may be prepared according to the following reaction formula 3, and may be a compound having a structure represented by the following chemical formula M3.

[0145] [ka]

[0146] As another example, the functional chain may be prepared according to the following reaction formula 4, and may be a compound having a structure represented by the following chemical formula M4.

[0147] [ka]

[0148] In the above reaction formulas 1 to 4, R 8d , R 8 , X, X 1 -X 2 , X 3 -X 4 , R 11a ~R 11c , R 12a ~R 12c and o are as defined in Chemical Formulae 1 to 4, R-Li is an alkyllithium compound, and R is an alkyl group derived from the alkyllithium.

[0149] In addition, the functional chain includes 1 to 80, 1 to 60, or 1 to 50 repeating units derived from an N-functional group-containing monomer selected from the compounds represented by Chemical Formulas 1 to 4. For example, in Chemical Formulas M1 to M4, 1 ~r 4 may be 1 to 80, 1 to 60, or 1 to 50. In this case, the modified conjugated diene-based polymer including the second chain derived from the functional chain may have the above-mentioned Si and N contents, and may have excellent processability, tensile properties, and viscoelastic properties in a well-balanced manner.

[0150] Meanwhile, in the step (S3), the modified activated polymer and the functional chain are reacted with the functional group derived from the modifying agent in the modified activated polymer and the living anion end of the functional chain to produce a modified conjugated diene-based polymer.

[0151] Specifically, the modified activated polymer chain produced in step (S2) contains a functional group derived from a modifying agent, and the functional group derived from the modifying agent contains an alkoxy group that remains without reacting with the polymer chain, and thus the living anion end of the functional chain reacts with the alkoxy group to produce the modified conjugated diene-based polymer.

[0152] The functional chain may be used in an amount of 0.1 to 4.0 mol, 0.1 mol to 2.0 mol, or 0.5 mol to 1.5 mol, per mol of the polymerization initiator.

[0153] When applying the manufacturing method according to one embodiment of the present invention, there is an advantage that more functional groups can be introduced than when only a modifying agent having many functional groups is used. Specifically, the alkoxy groups of the active polymer and the modifying agent are difficult to bind two or more polymer chains to one molecule of the modifying agent due to the steric hindrance of the polymer, and although three or more chains may be bound, the amount of modified polymers in which three or more chains are coupled is only small. However, as in the present invention, the functional chain, which has a weight average molecular weight of about 10% compared to the non-functional chain, can overcome the steric hindrance effect, and can be bound to the alkoxy residue of the modifying agent to which one or two non-functional chains are bound, and more functional groups can be introduced into the polymer chain.

[0154] That is, there is indeed a limit to the introduction of functional groups into one molecule of a modifying agent, and no matter how many are introduced, there will only be a difference in absolute amount compared to the present invention, in which a functional chain at a level that is not affected by steric hindrance effects is bonded to an alkoxy residue.

[0155] Therefore, the modified conjugated diene polymer produced by the method for producing the modified conjugated diene polymer according to the present invention can have superior tensile properties and viscoelastic properties compared to conventional one-end modified polymers. In addition, since it is a method utilizing alkoxy residues, the initiation end can be maintained as non-functional due to the additional introduction of functional groups, so that the processability can be significantly improved compared to conventional both-end modified polymers, and since the amount of alkoxy residues remaining in the units derived from the modifier is reduced compared to conventional production methods, side effects such as condensation reaction or hydrolysis reaction caused by the presence of -OR group or -OH group in the polymer can be significantly reduced, thereby improving processability, significantly reducing changes over time, and improving storage stability.

[0156] Rubber composition The present invention also provides a rubber composition containing the above modified conjugated diene-based polymer.

[0157] The rubber composition may contain the modified conjugated diene polymer in an amount of 10% by weight or more, 10% by weight to 100% by weight, or 20% by weight to 90% by weight. When the amount is within this range, the rubber composition has excellent mechanical properties such as tensile strength and abrasion resistance, and has an excellent balance between the various physical properties.

[0158] The rubber composition may further contain other rubber components, if necessary, in addition to the modified conjugated diene polymer, and in this case, the rubber components may be contained in an amount of 90% by weight or less based on the total weight of the rubber composition. As a specific example, the other rubber components may be contained in an amount of 1 part by weight to 900 parts by weight based on 100 parts by weight of the modified conjugated diene polymer.

[0159] The rubber component may be, for example, natural rubber or synthetic rubber, and specific examples thereof include natural rubber (NR) containing cis-1,4-polyisoprene; modified natural rubbers such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber, which are obtained by modifying or refining the general natural rubber; styrene-butadiene copolymers (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymers, polyisobutylene-co-isoprene, ne The rubber may be synthetic rubber such as polyolefin, poly(ethylene-co-propylene), poly(styrene-co-butadiene), poly(styrene-co-isoprene), poly(styrene-co-isoprene-co-butadiene), poly(isoprene-co-butadiene), poly(ethylene-co-propylene-codiene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, halogenated butyl rubber, etc., and any one or a mixture of two or more of these may be used.

[0160] The rubber composition may contain, for example, 0.1 to 200 parts by weight, or 10 to 120 parts by weight of a filler relative to 100 parts by weight of the modified conjugated diene polymer of the present invention. The filler may be, for example, a silica-based filler, and specific examples thereof may be wet silica (hydrated silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, colloidal silica, or the like, and preferably wet silica, which has the highest effect of improving fracture properties and wet grip properties. The rubber composition may further contain a carbon black-based filler as necessary.

[0161] As another example, when silica is used as the filler, a silane coupling agent for improving reinforcing properties and low heat generation properties may be used together.Specific examples of the silane coupling agent include bis(3-triethoxysilylpropyl)tetrasulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-triethoxy ... silyl tetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropyl benzothiazolyl tetrasulfide, 3-triethoxysilylpropyl benzolyl tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis(3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyl dimethoxymethyl silane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, or dimethoxymethylsilylpropyl benzothiazolyl tetrasulfide, and any one or a mixture of two or more of these can be used. Preferably, in consideration of the effect of improving reinforcing properties, bis(3-triethoxysilylpropyl) polysulfide or 3-trimethoxysilylpropyl benzothiazyl tetrasulfide may be used.

[0162] In addition, the rubber composition according to one embodiment of the present invention uses a modified conjugated diene polymer in which a functional group having high affinity with silica is introduced into an active site as a rubber component, so that the amount of the silane coupling agent can be reduced more than usual. Therefore, the silane coupling agent may be used in an amount of 1 to 20 parts by weight, or 5 to 15 parts by weight, per 100 parts by weight of silica. Within this range, the effect of the coupling agent is sufficiently exhibited, while the gelation of the rubber component is prevented.

[0163] The rubber composition according to one embodiment of the present invention may be sulfur crosslinkable and may further contain a vulcanizing agent. Specifically, the vulcanizing agent may be sulfur powder, and may be contained in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the rubber component. When the amount is within this range, the vulcanized rubber composition has the required elastic modulus and strength, and is excellent in fuel economy.

[0164] In addition to the above-mentioned components, the rubber composition according to an embodiment of the present invention may further include various additives commonly used in the rubber industry, specifically, a vulcanization accelerator, a process oil, an antioxidant, a plasticizer, an anti-aging agent, a scorch inhibitor, zinc white, stearic acid, a thermosetting resin, or a thermoplastic resin.

[0165] As the vulcanization accelerator, for example, a thiazole-based compound such as M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazylsulfenamide), or a guanidine-based compound such as DPG (diphenylguanidine) can be used, and may be contained in an amount of 0.1 to 5 parts by weight per 100 parts by weight of the rubber component.

[0166] The process oil acts as a softener in the rubber composition and may be, for example, a paraffinic, naphthenic, or aromatic compound, and aromatic process oils can be used in consideration of tensile strength and abrasion resistance, and naphthenic or paraffinic process oils can be used in consideration of hysteresis loss and low temperature properties. The process oil may be contained in an amount of 100 parts by weight or less per 100 parts by weight of the rubber component, and within this range, it is effective in preventing a decrease in the tensile strength and low heat generation property (fuel economy) of the vulcanized rubber.

[0167] The antioxidant may be, for example, 2,6-di-t-butyl-paracresol, dibutylhydroxytoluene, 2,6-bis((dodecylthio)methyl)-4-nonylphenol, or 2-methyl-4,6-bis((octylthio)methyl)phenol, and may be used in an amount of 0.1 to 6 parts by weight based on 100 parts by weight of the rubber component.

[0168] The anti-aging agent may be, for example, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, or a high-temperature condensate of diphenylamine and acetone, and may be used in an amount of 0.1 to 6 parts by weight per 100 parts by weight of the rubber component.

[0169] The rubber composition according to one embodiment of the present invention is obtained by kneading the rubber composition according to the compounding recipe using a kneading machine such as a Banbury mixer, a roll, or an internal mixer. After molding, a vulcanization process is performed to obtain a rubber composition having low heat build-up and excellent abrasion resistance.

[0170] As a result, the rubber composition is useful in the production of tire components such as tire treads, undertreads, sidewalls, carcass coating rubber, belt coating rubber, bead fillers, chafers, and bead coating rubber, as well as various industrial rubber products such as dustproof rubber, belt conveyors, and hoses.

[0171] The present invention also provides a tire produced using the rubber composition.

[0172] The tire may include a tire or a tire tread.

[0173] [Example] Hereinafter, the present invention will be described in detail with reference to examples in order to specifically explain the present invention. However, the examples according to the present invention can be modified in various forms, and the scope of the present invention should not be construed as being limited to the examples described below. The examples of the present invention are provided to more completely explain the present invention to those having average knowledge in the art.

[0174] Test #1 [Production Example 1] In a 500 ml round-bottom flask, 100 ml of tetrahydrofuran and 1 g of n-butyl lithium (10 wt% in n-hexane) were placed, and N,N,N',N',1-pentamethyl-1-vinylsilanediamine was added (3 moles per mole of [act.Li]), and the mixture was reacted at 10°C for 30 minutes to produce a solution (15.6 mmol / l) containing functional chains. GC analysis confirmed that the reaction had taken place, as no N,N,N',N',1-pentamethyl-1-vinylsilanediamine was detected after the reaction.

[0175] [Example 1-1] In a 20L autoclave reactor, 3kg of n-hexane, 215g of styrene, 745g of 1,3-butadiene, and 1.29g of 2,2-bis(2-oxolanyl)propane as a polar additive were added, and then 3.2g of n-butyllithium (10wt% in n-hexane) was added, and the internal temperature of the reactor was adjusted to 60°C to carry out an adiabatic heating reaction. After about 30 minutes, 39g of 1,3-butadiene was added to cap the ends of the polymer with butadiene. After about 10 minutes, N,N-diethyl-3-(trimethoxysilyl)propan-1-amine was added as a modifier and reacted for 15 minutes ([DTP]:[act.Li]=1.5:1 molar ratio, [modifier]:[act.Li]=0.7:1 molar ratio). Then, the solution containing the functional chain prepared in Preparation Example 1 was added and reacted for 15 minutes ([act.Li]:[macromonomer] = 1:1 molar ratio), the reaction was stopped with ethanol, and 33 g of a solution in which the antioxidant Wingstay K was dissolved in hexane at 30 wt % was added. The resulting polymer was placed in hot water heated with steam and stirred to remove the solvent, and then roll-dried to remove the remaining solvent and water, producing a modified styrene-butadiene copolymer.

[0176] [Example 1-2] A modified styrene-butadiene copolymer was produced in the same manner as in Example 1-1, except that N,N-bis(3-(triethoxysilyl)propyl)-3,6,9,12,15-pentaoxanonadecan-1-amine was used instead of N,N-diethyl-3-(trimethoxysilyl)propan-1-amine as a modifier ([modifier]:[act.Li]=0.7:1 molar ratio).

[0177] [Examples 1-3] In Example 1-1, 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine) was used as a modifying agent instead of N,N-diethyl-3-(trimethoxysilyl)propan-1-amine, but the procedure was the same as in Example 1-1 to produce a modified styrene-butadiene copolymer ([modifying agent]:[act.Li]=0.7:1 molar ratio).

[0178] [Comparative Example 1-1] A modified styrene-butadiene copolymer was produced in the same manner as in Example 1-1, except that the solution containing the functional chain produced in Preparation Example 1 was added instead of n-butyllithium in Example 1-1 so that the molar ratio of n-butyllithium in Example 1-1 and the macromonomer was equimolar, and an adiabatic heating reaction was carried out, and then, the step of adding a modifier and a functional chain to react was not carried out, and the reaction was terminated after butadiene capping.

[0179] [Comparative Example 1-2] In a 20L autoclave reactor, 3kg of n-hexane, 215g of styrene, 745g of 1,3-butadiene, and 1.29g of 2,2-bis(2-oxolanyl)propane as a polar additive were added, and then 3.2g of n-butyllithium (10wt% in n-hexane) was added, and the internal temperature of the reactor was adjusted to 60℃ to carry out an adiabatic heating reaction. After about 30 minutes, 39g of 1,3-butadiene was added to cap the ends of the polymer with butadiene. After about 10 minutes, N,N-diethyl-3-(trimethoxysilyl)propan-1-amine was added as a modifier and reacted for 15 minutes ([DTP]:[act.Li]=1.5:1 molar ratio, [modifier]:[act.Li]=0.7:1 molar ratio). Then, the reaction was stopped using ethanol, and 33 g of a solution in which the antioxidant Wingstay K was dissolved in hexane at 30 wt % was added. The resulting polymer was placed in hot water heated with steam and stirred to remove the solvent, and then roll-dried to remove the remaining solvent and water, producing a modified styrene-butadiene copolymer.

[0180] [Comparative Example 1-3] In Comparative Example 1-2, the above-mentioned procedure was repeated except that 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine) was used as the modifier instead of N,N-diethyl-3-(trimethoxysilyl)propan-1-amine. Comparative Example 1-2 A modified styrene-butadiene copolymer was produced in the same manner as described above ([modifier]:[act.Li]=0.7:1 molar ratio).

[0181] [Comparative Example 1-4] In Comparative Example 1-2, N,N-bis(3-(triethoxysilyl)propyl)-3,6,9,12,15-pentaoxanonadecane-1-amine was used instead of N,N-diethyl-3-(trimethoxysilyl)propane-1-amine as a modifier, and the same procedure as in Comparative Example 1-2 was carried out to produce a modified styrene-butadiene copolymer ([modifier]:[act.Li]=0.7:1 molar ratio).

[0182] [Comparative Example 1-5] A modified styrene-butadiene copolymer was prepared in the same manner as in Comparative Example 1-2, except that the solution containing the macromonomer prepared in Preparation Example 1 was added instead of n-butyllithium in Comparative Example 1-2 in an amount such that the functional chain was equimolar to n-butyllithium in Comparative Example 1-2, and the adiabatic heating reaction was carried out. Manufactured.

[0183] Polymer characterization For each modified or unmodified conjugated diene polymer prepared in the above examples and comparative examples, the styrene unit content, vinyl content, weight average molecular weight (Mw, x10 3 g / mol), number average molecular weight (Mn, 3 The molecular weight distribution (PDI, MWD), Mooney viscosity (MV), Mooney viscosity change rate, and Si and N contents were measured. The results are shown in Table 1 below.

[0184] 1) Styrene unit and vinyl content (wt%) The styrene unit (SM) and vinyl content in each of the polymers were measured and analyzed using a Varian VNMRS 500 MHz NMR.

[0185] In the NMR measurement, 1,1,2,2-tetrachloroethane was used as the solvent, and the solvent peak was calculated at 5.97 ppm. The styrene unit and vinyl contents were calculated by assuming that 7.2 to 6.9 ppm was the peak for random styrene, 6.9 to 6.2 ppm was the peak for block styrene, 5.8 to 5.1 ppm was the peak for 1,4-vinyl, and 5.1 to 4.5 ppm was the peak for 1,2-vinyl.

[0186] 2) Weight average molecular weight (Mw, X10 3 g / mol), number average molecular weight (Mn, 3 g / mol), molecular weight distribution (PDI, MWD) The weight average molecular weight (Mw) and number average molecular weight (Mn) were measured by GPC (Gel permeation chromatography) analysis to obtain a molecular weight distribution curve. The molecular weight distribution (PDI, MWD, Mw / Mn) was calculated from the measured molecular weights. Specifically, the GPC was performed using a combination of two PLgel Olexis (Polymer Laboratories) columns and one PLgel mixed-C (Polymer Laboratories) column, and PS (polystyrene) was used as a GPC standard material when calculating the molecular weight. The GPC measurement solvent was prepared by mixing 2 wt% of an amine compound with tetrahydrofuran.

[0187] 3) Mooney viscosity and rate of change of Mooney viscosity The Mooney viscosity (MV, (ML1+4, @100°C)MU) was measured using a MV-2000 (ALPHA Technologies) at 100°C, rotor speed 2±0.02 rpm, large rotor. The sample used was left at room temperature (23±3°C) for 30 minutes or more, and then 27±3g was taken and filled into the die cavity, and the platen was operated to measure for 4 minutes.

[0188] In addition, the rate of change in Mooney viscosity was calculated by measuring the Mooney viscosity of each sample by the above-mentioned method after leaving the same sample at room temperature for 30 days and calculating it by the following mathematical formula 1.

[0189]

number

[0190] In the above mathematical formula 1, MV R is the rate of change of Mooney viscosity, MV f is the Mooney viscosity at 100°C after the polymer is left at 25°C for 30 days, and MV i is the initial Mooney viscosity of the polymer at 100°C.

[0191] 4) Silicon content The content of Si was measured by ICP analysis using an inductively coupled plasma optical emission spectrometer (ICP-OES; Optima 7300DV). Specifically, about 0.7 g of the sample was placed in a platinum crucible, and about 1 mL of concentrated sulfuric acid (98 wt%, electronic grade) was added and heated at 300° C. for 3 hours. The sample was then incinerated in an electric furnace (Thermo Scientific, Lindberg Blue M) according to the following program of steps 1 to 3, and then: 1) Step 1: initial temp 0℃, rate(temp / hr) 180℃ / hr, temp(hold time) 180℃(1hr) 2) Step 2: initial temp 180℃, rate(temp / hr) 85℃ / hr, temp(hold time) 370℃(2hr) 3) Step 3: initial temp 370℃, rate(temp / hr) 47℃ / hr, temp(hold time) 510℃(3hr). The residue was added with 1 mL of concentrated nitric acid (48 wt%) and 20 μL of concentrated hydrofluoric acid (50 wt%), and the platinum crucible was sealed and shaken for more than 30 minutes. Then, 1 mL of boric acid was added to the sample and stored at 0°C for more than 2 hours. The sample was then diluted with 30 mL of ultrapure water and incinerated for measurement.

[0192] 5) Nitrogen content The N content was measured using an ultratrace nitrogen quantitative analyzer (NSX-2100H) according to the NSX analysis method. Specifically, the ultratrace nitrogen quantitative analyzer (Auto sampler, Horizontal furnace, PMT & Nitrogen detector) was turned on, Ar was supplied at 250 ml / min, O 2The carrier gas flow rate was set to 350 ml / min, the ozonizer to 300 ml / min, the heater to 800 °C, and the analyzer was left to stabilize for about 3 hours. After the analyzer was stabilized, a calibration curve was created using a Nitrogen standard (AccuStandard S-22750-01-5ml) with a calibration range of 5 ppm, 10 ppm, 50 ppm, 100 ppm, and 500 ppm, and the area corresponding to each concentration was obtained, and a straight line was created using the concentration and area ratio. Then, a ceramic boat containing 20 mg of sample was placed in the auto sampler of the analyzer and measured to obtain the area. The N content was calculated using the obtained sample area and the calibration curve.

[0193] [Table 1]

[0194] As shown in Table 1, in Examples 1-1 and 1-2, Si and N atoms exist in the polymer molecule, and the N atom content is significantly increased compared to Comparative Examples 1-2 to 1-4. This shows that the N content was measured to be significantly lower due to the absence of functional chains.

[0195] Characterization of rubber molded products In order to compare and analyze the physical properties of the rubber compositions containing the modified styrene-butadiene copolymers prepared in the examples and comparative examples, and the molded products prepared therefrom, the tensile properties and viscoelastic properties were measured, and the results are shown in Table 3 below.

[0196] 1) Preparation of rubber test specimens The modified or unmodified conjugated diene polymers of the Examples, Comparative Examples, and Reference Examples were used as raw rubber and were compounded under the compounding conditions shown in Table 2. The raw material contents in Table 2 are in parts by weight based on 100 parts by weight of the raw rubber.

[0197] [Table 2]

[0198] Specifically, the rubber test pieces are kneaded through a first stage kneading and a second stage kneading. In the first stage kneading, raw rubber, silica (filler), an organic silane coupling agent (X50S, Evonik), process oil (TDAE oil), zinc oxide (ZnO), stearic acid, an antioxidant (TMQ(RD) (2,2,4-trimethyl-1,2-dihydroquinoline polymer), an anti-aging agent (6PPD ((dimethylbutyl)-N-phenyl-phenylenediamine), and a wax (Microcrystaline Wax) was mixed into the kneader. At this time, the initial temperature of the kneader was controlled at 70°C, and after the completion of the mixing, the first compound was obtained at a discharge temperature of 145°C to 155°C. In the second mixing stage, the first compound was cooled to room temperature, and then the first compound, sulfur, rubber accelerator (DPD (diphenyl guanidine)), and vulcanization accelerator (CZ (N-cyclohexyl-2-benzothiazylsulfenamide)) were added to the kneader and mixed at a temperature of 100°C or less to obtain a second compound. Then, a curing process was performed at 160°C for 20 minutes to produce a rubber test piece.

[0199] 2) Tensile properties The tensile properties were measured by preparing test pieces according to the tensile test method of ASTM 412 and measuring the tensile stress (300% modulus) of the test pieces at 300% elongation. Specifically, the tensile properties were measured at room temperature at a speed of 50 cm / min using a Universal Test Machine 4204 (Instron).

[0200] 3) Viscoelastic properties The viscoelastic properties were measured using a dynamic mechanical analyzer (GABO) in Film Tension mode at a frequency of 10 Hz and at each measurement temperature (-60°C to 60°C) to determine the tan δ value. In the measurement results, a higher tan δ value at a low temperature of 0°C means better wet skid resistance, and a lower tan δ value at a high temperature of 60°C means less hysteresis loss and better low running resistance (fuel economy). The results in Table 3 below are shown as an Index (%) based on the results of Comparative Example 1-1, so the higher the value, the better the performance.

[0201] 4) Processability characteristics The Mooney viscosity (MV, (ML1+4, @100°C)MU) of the secondary compound obtained during the preparation of the rubber test specimens was measured, and the processability characteristics of each polymer were compared and analyzed. In this case, the lower the measured Mooney viscosity value, the better the processability characteristics. In Table 3 below, the results of Comparative Example 1-2 are used as the standard and are expressed as an Index (%), with the higher value indicating better performance.

[0202] Specifically, using MV-2000 (ALPHA Technologies) at 100°C, rotor speed 2±0.02 rpm, large rotor, each secondary compound was left at room temperature (23±3°C) for 30 minutes or more, and then 27±3 g was taken and filled into the die cavity, and the platen was operated to measure for 4 minutes.

[0203] [Table 3]

[0204] As shown in Table 3, it was confirmed that Examples 1-1 and 1-2 using the modified conjugated diene polymer according to one embodiment of the present invention exhibited superior processability characteristics as well as superior tensile properties and viscoelastic properties compared to Comparative Examples 1-1 to 1-5.

[0205] Comparing Examples 1-1 and 1-2 with Comparative Examples 1-1 to 1-4, it was confirmed that there was a very significant difference in rotation resistance and that the tensile properties were also improved, and while showing tensile properties equal to or better than Comparative Example 1-5, there was also improved viscoelastic properties and significantly improved processability. This is because the functional chains in the Examples were used together with the modified initiator, and the structure was not one in which the functional chains were bonded to the modifier, resulting in a very significant difference in processability.

[0206] From this, it can be confirmed that the modified conjugated diene-based polymer of the present invention can exhibit remarkable effects not observed in Comparative Examples 1-3 by being produced by a production method including a step of reacting with a functional chain after the modification reaction. Due to such a difference in effect, it can be predicted that the modified conjugated diene-based polymer of the present invention is a copolymer having a structure different from that of Comparative Examples 1-5, for example, a functional chain containing a repeating unit derived from an N-functional group-containing monomer derived from the functional chain is coupled to a non-functional chain of the modified polymer via a functional group derived from the modifier, and is bonded in a structure similar to that of a graft copolymer.

[0207] Experiment #2 [Production Example 2] In a 500 ml round-bottom flask, 100 ml of tetrahydrofuran and 1 g of n-butyl lithium (10 wt% in n-hexane) were placed, and N,N'-diethyl-N,N'-diisopropyl-1,1-divinylsilanediamine was added (3 moles per mole of [act.Li]), and the mixture was reacted at 10°C for 30 minutes to produce a solution (15.6 mmol / l) containing functional chains. GC analysis confirmed that the reaction had taken place, as no N,N'-diethyl-N,N'-diisopropyl-1,1-divinylsilanediamine was detected after the reaction.

[0208] [Example 2-1] 3 kg of n-hexane, 215 g of styrene, 745 g of 1,3-butadiene, and 1.29 g of 2,2-bis(2-oxolanyl)propane as a polar additive were added to a 20 L autoclave reactor, and then 3.2 g of n-butyllithium (10 wt% in n-hexane) was added and the internal temperature of the reactor was adjusted to 60° C. to carry out an adiabatic heating reaction. After about 30 minutes, 39 g of 1,3-butadiene was added to cap the ends of the polymer with butadiene. After about 10 minutes, N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine was added as a modifier and reacted for 15 minutes ([DTP]:[act.Li]=1.5:1 molar ratio, [modifier]:[act.Li]=0.7:1 molar ratio). Then, the solution containing the functional chain produced in Preparation Example 2 was added and reacted for 15 minutes ([functional chain]:[act.Li]=1:1 molar ratio), the reaction was stopped with ethanol, and 33 g of a solution in which the antioxidant Wingstay K was dissolved in hexane at 30% by weight was added. The resulting polymer was placed in steam-heated hot water and stirred to remove the solvent, and then roll-dried to remove the remaining solvent and water, producing a modified styrene-butadiene copolymer.

[0209] [Example 2-2] In Example 2-1, 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine) was used instead of N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine as a modifier, but the same procedure as in Example 2-1 was carried out to produce a modified styrene-butadiene copolymer ([modifier]:[act.Li]=0.7:1 molar ratio).

[0210] [Comparative Example 2-1] In Example 2-1, instead of n-butyllithium, the solution containing the functional chain prepared in Preparation Example was added in an amount that would result in the same molar amount of n-butyllithium and the functional chain in Example 2-1, and an adiabatic heating reaction was carried out. Thereafter, the step of adding a modifier and a functional chain to react was not carried out, and the reaction was terminated after butadiene capping. A modified styrene-butadiene copolymer was produced in the same manner as in Example 2-1.

[0211] [Comparative Example 2-2] In a 20L autoclave reactor, 3kg of n-hexane, 215g of styrene, 745g of 1,3-butadiene, and 1.29g of 2,2-bis(2-oxolanyl)propane as a polar additive were added, and then 3.2g of n-butyllithium (10wt% in n-hexane) was added, and the internal temperature of the reactor was adjusted to 60℃ to carry out an adiabatic heating reaction. After about 30 minutes, 39g of 1,3-butadiene was added to cap the ends of the polymer with butadiene. After about 10 minutes, N,N-diethyl-3-(trimethoxysilyl)propan-1-amine was added as a modifier and reacted for 15 minutes ([DTP]:[act.Li]=1.5:1 molar ratio, [modifier]:[act.Li]=0.7:1 molar ratio). Then, the reaction was stopped using ethanol, and 33 g of a solution in which the antioxidant Wingstay K was dissolved in hexane at 30 wt % was added. The resulting polymer was placed in hot water heated with steam and stirred to remove the solvent, and then roll-dried to remove the remaining solvent and water, producing a modified styrene-butadiene copolymer.

[0212] [Comparative Example 2-3] A modified styrene-butadiene copolymer was produced in the same manner as in Comparative Example 2-2, except that 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine) was used instead of N,N-diethyl-3-(trimethoxysilyl)propan-1-amine as a modifier ([modifier]:[act.Li]=0.7:1 molar ratio).

[0213] [Comparative Example 2-4] In Comparative Example 2-2, instead of n-butyllithium, the solution containing the functional chain prepared in Preparation Example 2 was added in an amount equivalent to the molar amount of n-butyllithium and the functional chain in Comparative Example 2-2, and the adiabatic heating reaction was carried out in the same manner as in Comparative Example 2-2 to prepare a modified styrene-butadiene copolymer.

[0214] [Comparative Example 2-5] A modified styrene-butadiene copolymer was produced in the same manner as in Comparative Example 2-4, except that 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine) was used instead of N,N-diethyl-3-(trimethoxysilyl)propan-1-amine as a modifier ([modifier]:[act.Li]=0.7:1 molar ratio).

[0215] Polymer characterization For each modified or unmodified conjugated diene polymer prepared in the above examples and comparative examples, the styrene unit content, vinyl content, weight average molecular weight (Mw, x10 3 g / mol), number average molecular weight (Mn, 3 The molecular weight distribution (PDI, MWD), Mooney viscosity (MV), Mooney viscosity change rate, and Si and N contents were measured in the same manner as in Experiment #1. The results are shown in Table 4 below.

[0216] [Table 4]

[0217] As shown in Table 4, in Examples 2-1 and 2-2, Si and N atoms exist in the polymer molecule, and the content of N atoms is significantly increased compared to Comparative Examples 2-1 to 2-3.

[0218] Characterization of rubber molded products In order to compare and analyze the physical properties of the rubber compositions containing each modified styrene-butadiene copolymer prepared in the Examples and Comparative Examples and the molded articles prepared therefrom, the tensile properties and viscoelastic properties were measured in the same manner as in Experiment #1, and the results are shown in Table 5. Molded test pieces were also prepared in the same manner as in Experiment #1.

[0219] [Table 5]

[0220] As shown in Table 5, it was confirmed that Examples 2-1 and 2-2 using the modified conjugated diene polymer according to one embodiment of the present invention exhibited superior processability properties as well as superior tensile properties and viscoelastic properties compared to Comparative Examples 2-1 to 2-5.

[0221] Comparing Examples 2-1 and 2-2 with Comparative Examples 2-1 to 2-3, it can be seen that there is a very significant difference in rotation resistance, and the tensile properties are also improved, and while showing tensile properties equal to or better than those of Comparative Examples 2-4 and 2-5, there are also improved viscoelastic properties and significantly improved processability properties. This is because the functional chains in the Examples are used together with the modified initiator, and the structure is not one in which the functional chains are bonded to the modifier, which shows a very significant difference in processability.

[0222] From this, it can be confirmed that the modified conjugated diene-based polymer of the present invention can exhibit remarkable effects not observed in Comparative Examples 2-4 and 2-5 by being produced by a production method including a step of reacting with a functional chain after the modification reaction. Due to such a difference in effect, it can be predicted that the modified conjugated diene-based polymer of the present invention is a copolymer having a different structure from that of the comparative examples, for example, a functional chain containing a repeating unit derived from an N-functional group-containing monomer derived from the functional chain is coupled to a non-functional chain of the modified polymer via a functional group derived from the modifier, and is bonded in a structure similar to that of a graft copolymer.

[0223] Experiment #3 [Production Example 3] In a 500 ml round-bottom flask, 100 ml of tetrahydrofuran and 1 g of n-butyllithium (10 wt% in n-hexane) were placed, and N,N-dimethyl-4-methylenehex-5-en-1-amine was added (3 moles per mole of [act.Li]), and the mixture was reacted at 10°C for 30 minutes to produce a solution (15.6 mmol / l) containing a functional chain. GC analysis confirmed that the reaction had taken place, since no N,N-dimethyl-4-methylenehex-5-en-1-amine was detected after the reaction.

[0224] [Example 3-1] 3 kg of n-hexane, 215 g of styrene, 745 g of 1,3-butadiene, and 1.29 g of 2,2-bis(2-oxolanyl)propane as a polar additive were added to a 20 L autoclave reactor, and then 3.2 g of n-butyllithium (10 wt% in n-hexane) was added and the internal temperature of the reactor was adjusted to 60° C. to carry out an adiabatic heating reaction. After about 30 minutes, 39 g of 1,3-butadiene was added to cap the ends of the polymer with butadiene. After about 10 minutes, 1,1,1-trimethyl-N-(3-(triethoxysilyl)propyl)-N-(trimethylsilyl)silanamine was added as a modifier and reacted for 15 minutes ([DTP]:[act.Li] = 1.5:1 molar ratio, [modifier]:[act.Li] = 0.7:1 molar ratio). Then, the solution containing the functional chain produced in Preparation Example 3 was added and reacted for 15 minutes ([act.Li]:[functional chain] = 1:2 molar ratio), the reaction was stopped using ethanol, and 33 g of a solution in which the antioxidant Wingstay K was dissolved in hexane at 30 wt% was added. The resulting polymer was placed in hot water heated with steam, stirred to remove the solvent, and roll-dried to remove the remaining solvent and water, producing a modified styrene-butadiene copolymer.

[0225] [Example 3-2] A modified styrene-butadiene copolymer was produced in the same manner as in Example 3-1, except that 3-(2,2-dimethoxy-1,2-azasilodidin-1-yl)-N,N-bis(3-(trimethoxysilyl)propyl)propan-1-amine was used instead of 1,1,1-trimethyl-N-(3-(triethoxysilyl)propyl)-N-(trimethylsilyl)silaneamine as a modifier ([modifier]:[act.Li]=0.7:1 molar ratio).

[0226] [Comparative Example 3-1] In Example 3-1, instead of n-butyllithium, the solution containing the functional chain prepared in Preparation 3 was added in an amount that would result in equimolar amounts of n-butyllithium and the functional chain in Example 3-1 to carry out an adiabatic heating reaction, and then, the step of adding a modifier and a functional chain to react was not carried out, and the reaction was terminated after butadiene capping. A modified styrene-butadiene copolymer was produced in the same manner as in Example 3-1.

[0227] [Comparative Example 3-2] 3 kg of n-hexane, 215 g of styrene, 745 g of 1,3-butadiene, and 1.29 g of 2,2-bis(2-oxolanyl)propane as a polar additive were added to a 20 L autoclave reactor, and then 3.2 g of n-butyllithium (10 wt% in n-hexane) was added and the internal temperature of the reactor was adjusted to 60° C. to carry out an adiabatic heating reaction. After about 30 minutes, 39 g of 1,3-butadiene was added to cap the ends of the polymer with butadiene. After about 10 minutes, 3,3'-(piperazine-1,4-diyl)bis(N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine) was added as a modifier and reacted for 15 minutes ([DTP]:[act.Li] = 1.5:1 molar ratio, [modifier]:[act.Li] = 0.7:1 molar ratio). The reaction was then stopped using ethanol, and 33 g of a solution in which the antioxidant Wingstay K was dissolved in hexane at 30% by weight was added. The resulting polymer was placed in hot water heated with steam, stirred to remove the solvent, and roll-dried to remove the remaining solvent and water, producing a modified styrene-butadiene copolymer.

[0228] [Comparative Example 3-3] A modified styrene-butadiene copolymer was prepared in the same manner as in Comparative Example 3-2, except that the solution containing the functional chain prepared in Preparation Example 3 was added instead of n-butyllithium in Comparative Example 3-2 in an amount such that the n-butyllithium and the functional chain were equimolar to each other to carry out an adiabatic heating reaction.

[0229] Polymer characterization For each modified or unmodified conjugated diene polymer prepared in the above examples and comparative examples, the styrene unit content, vinyl content, weight average molecular weight (Mw, x10 3 g / mol), number average molecular weight (Mn, 3 The molecular weight distribution (PDI, MWD), Mooney viscosity (MV), Mooney viscosity change rate, and Si and N contents were measured in the same manner as in Experiment #1. The results are shown in Table 6 below.

[0230] [Table 6]

[0231] As shown in Table 6, in Examples 3-1 and 3-2, Si and N atoms exist in the polymer molecule, and the content of N atoms is significantly increased compared to Comparative Examples 3-1 and 3-2.

[0232] Characterization of rubber molded products In order to compare and analyze the physical properties of the rubber compositions containing each modified styrene-butadiene copolymer prepared in the Examples and Comparative Examples and the molded articles prepared therefrom, the tensile properties and viscoelastic properties were measured in the same manner as in Experiment #1, and the results are shown in Table 7. Molded test pieces were also prepared in the same manner as in Experiment #1.

[0233] [Table 7]

[0234] As shown in Table 7, it was confirmed that Examples 3-1 and 3-2 using the modified conjugated diene polymer according to one embodiment of the present invention exhibited superior processability properties as well as superior tensile properties and viscoelastic properties compared to Comparative Examples 3-1 to 3-3.

[0235] Comparing Examples 3-1 and 3-2 with Comparative Examples 3-1 and 3-2, it was confirmed that there was a very significant difference in rotation resistance and that the tensile properties were also improved, and while showing tensile properties equal to or better than Comparative Example 3-3, there was also improved viscoelastic properties and significantly improved processability. This is because the functional chain in the Examples was used together with the modified initiator, and the structure was not one in which the functional chain was bonded to the modifier, resulting in a very significant difference in processability.

[0236] From this, it can be confirmed that the modified conjugated diene-based polymer of the present invention can exhibit remarkable effects not observed in Comparative Example 3-3 by being produced by a production method including a step of reacting with a functional chain after the modification reaction. Due to such a difference in effect, it can be predicted that the modified conjugated diene-based polymer of the present invention is a copolymer having a different structure from that of Comparative Example 3-3, for example, a functional chain containing a repeating unit derived from an N-functional group-containing monomer derived from the functional chain is coupled to a non-functional chain of the modified polymer via a functional group derived from the modifier, and is bonded in a structure similar to that of a graft copolymer.

Claims

1. a unit derived from a modifier containing three or more alkoxy groups bonded to silicon; a non-functional chain including a repeating unit derived from a conjugated diene monomer, wherein a bond exists between a silicon of the modifier and a carbon of the conjugated diene monomer at an end of the chain on one side of the unit derived from the modifier, and the non-functional chain including a repeating unit derived from a conjugated diene monomer; a functional chain containing two or more units derived from an N-functional group-containing monomer, wherein a bond exists between a silicon atom of the modifier and a carbon atom of the N-functional group-containing monomer at an end of the chain on the other side of the unit derived from the modifier, the functional chain containing two or more units derived from an N-functional group-containing monomer; the non-functional chain is a chain composed of repeating units of a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer; The functional chain is bonded to one or more units derived from a modifying agent, The N-functional group-containing monomer is any one of compounds represented by the following formulas 3 and 4: The denaturant is any one of compounds represented by the following formulas 5 and 7: The Mooney viscosity change rate (MV) according to the following mathematical formula 1 R ) is 20% or less. [Mathematical formula 1] MV R =[(MV f -MV i ) / MV i ]x100 (In the above mathematical formula 1, Music Video R is the rate of change of Mooney viscosity, Music Video f is the Mooney viscosity at 100° C. after the polymer is left at 25° C. for 30 days, Music Video i is the initial Mooney viscosity of the polymer at 100°C. 【Chemistry 4】 [In the above Chemical Formula 3, R 11a and R 11b are each independently an alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 20 carbon atoms; an alkynyl group having 2 to 20 carbon atoms; a heteroalkyl group having 1 to 20 carbon atoms; a heteroalkenyl group having 2 to 20 carbon atoms; a heteroalkynyl group having 2 to 20 carbon atoms; a cycloalkyl group having 5 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms; a heterocyclic group having 3 to 20 carbon atoms; or a functional group represented by the following chemical formula 3a: R 11c is an alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 20 carbon atoms; an alkynyl group having 2 to 20 carbon atoms; a heteroalkyl group having 1 to 20 carbon atoms; a heteroalkenyl group having 2 to 20 carbon atoms; a heteroalkynyl group having 2 to 20 carbon atoms; a cycloalkyl group having 5 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms; a heterocyclic group having 3 to 20 carbon atoms; a vinyl group; or a functional group represented by the following chemical formula 3a: The R 11a , R 11b , and R 11c At least one of the functional groups represented by formula 3a is 【Chemistry 5】 In the above formula 3a, R 11d represents a single bond, or an alkylene group having 1 to 20 carbon atoms which may be substituted or unsubstituted; a cycloalkylene group having 5 to 20 carbon atoms which may be substituted or unsubstituted; or an arylene group having 6 to 20 carbon atoms which may be substituted or unsubstituted, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms, R 11e and R 11f are each independently an alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 20 carbon atoms; an alkynyl group having 2 to 20 carbon atoms; a heteroalkyl group having 1 to 20 carbon atoms; a heteroalkenyl group having 2 to 20 carbon atoms; a heteroalkynyl group having 2 to 20 carbon atoms; a cycloalkyl group having 5 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms; a heterocyclic group having 3 to 20 carbon atoms; or a mono-, di-, or tri-substituted alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms.] 【Chemistry 6】 [In the above Chemical Formula 4, R 12a represents a single bond, or an alkylene group having 1 to 20 carbon atoms which may be substituted or unsubstituted; a cycloalkylene group having 5 to 20 carbon atoms which may be substituted or unsubstituted; or an arylene group having 6 to 20 carbon atoms which may be substituted or unsubstituted, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms, R 12b and R 12c are each independently an alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 20 carbon atoms; an alkynyl group having 2 to 20 carbon atoms; a heteroalkyl group having 1 to 20 carbon atoms; a heteroalkenyl group having 2 to 20 carbon atoms; a heteroalkynyl group having 2 to 20 carbon atoms; a cycloalkyl group having 5 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms; a heterocyclic group having 3 to 20 carbon atoms; or a mono-, di-, or tri-substituted alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms.] 【Chemistry 7】 [In the above Chemical Formula 5, R 1 is a single bond or an alkylene group having 1 to 10 carbon atoms; R 2 and R 3 are each independently an alkyl group having 1 to 10 carbon atoms, R 4 is a hydrogen atom, an epoxy group, an alkyl group having 1 to 10 carbon atoms, an allyl group having 2 to 10 carbon atoms, an alkylsilyl group which is mono-, di- or tri-substituted with an alkyl 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 having 1 to 10 carbon atoms, or -[R 42 O] j - and R 42 is an alkylene group having 1 to 10 carbon atoms, a and m are each independently an integer selected from 1 to 3, n is an integer from 0 to 2, and j is an integer selected from 1 to 30. 【Chemistry 8】 [In the above Chemical Formula 7, A 1 and A 2 are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms, which may or may not contain an oxygen atom; R 17 ~R 20 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms; L 1 ~L 4 are each independently a mono-, di-, or tri-substituted alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, or a monovalent hydrocarbon group having 1 to 20 carbon atoms; 1 and L 2 And, L 3 and L 4 may be linked together to form a ring having 1 to 5 carbon atoms; L 1 and L 2 And, L 3 and L 4 are linked together to form a ring, the ring formed may contain 1 to 3 heteroatoms of one or more types selected from the group consisting of N, O, and S.

2. The modified conjugated diene polymer according to claim 1, wherein the N atom content is 150 ppm or more by weight.

3. Mooney viscosity change rate (MV) according to mathematical formula 1 R 3. The modified conjugated diene polymer according to claim 1, wherein the ratio of the tungsten sulphate to the total tungsten sulphate is 15% or less.

4. The modified conjugated diene polymer according to any one of claims 1 to 3, wherein the functional chain further comprises a unit derived from a conjugated diene monomer.

5. The modified conjugated diene-based polymer according to any one of claims 1 to 4, wherein the functional chain contains 2 to 80 units derived from an N-functional group-containing monomer.

6. The modified conjugated diene polymer according to any one of claims 1 to 5, wherein the modifying agent is an amine-containing alkoxysilane compound or an amine-free alkoxysilane compound.

7. The modified conjugated diene polymer according to any one of claims 1 to 6, wherein the non-functional chain further comprises a repeating unit derived from an aromatic vinyl monomer.

8. The modified conjugated diene polymer according to any one of claims 1 to 7, having a number average molecular weight (Mn) of 1,000 g / mol to 2,000,000 g / mol, a weight average molecular weight (Mw) of 1,000 g / mol to 3,000,000 g / mol, and a peak average molecular weight (Mp) of 1,000 g / mol to 3,000,000 g / mol.

9. A rubber composition comprising the modified conjugated diene-based polymer according to any one of claims 1 to 8 and a filler.

10. The rubber composition according to claim 9, comprising 0.1 to 200 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene polymer.

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