KR20210037777A - Modified conjugated diene polymer and rubber composition comprising the same - Google Patents

Abstract

The present invention relates to a modified conjugated diene-based polymer and a rubber composition comprising the same. Provided is the modified conjugated diene-based polymer, satisfying following conditions: i) 1,2-vinyl bond content: 40 wt% or more; ii) Mooney viscosity measured under ASTM D1646 conditions: 40 to 100; iii) a phase difference index at 0.1 Hz measured at 160℃: 0.65 or more; iv) the content of Si atom and N atom: 50 ppm or more based on the total weight of the polymer; and v) Mooney relaxation rate measured at 100℃: 0.5 or more.

Description

Modified conjugated diene polymer and rubber composition containing the same TECHNICAL FIELD

The present invention relates to a modified conjugated diene-based polymer and a rubber composition comprising the same.

Recently, as interest in energy saving and environmental issues has increased, a low fuel economy is required for automobiles. Accordingly, as a rubber material for tires, a material that has low running resistance, excellent abrasion resistance, and excellent tensile properties, and has coordination stability represented by wet skid resistance. Is required.

In order to reduce the running resistance of the tire, there is a method of reducing the hysteresis loss of the vulcanized rubber. As an evaluation index of the vulcanized rubber, rebound elasticity of 50°C to 80°C, tan δ, Goodrich heat generation, and the like are used. That is, a rubber material having high repulsion elasticity at the above temperature or low tan δ and Goodrich heat generation is preferable.

As one of the methods for realizing this, a method of lowering the heat generation property of a tire by using an inorganic filler such as silica or carbon black in the rubber composition for forming a tire has been proposed, but it is not easy to disperse the inorganic filler in the rubber composition. Rather, there is a problem in that the physical properties of the rubber composition, including abrasion resistance, crack resistance, or processability, are deteriorated as a whole.

In order to solve such a problem, the polymerization active site of the conjugated diene-based polymer obtained by anionic polymerization using organic lithium is a method for increasing the dispersibility of inorganic fillers such as silica or carbon black in the rubber composition. A method of modifying with a functional group-containing modifier has been proposed, but there is still a problem in that low heat generation properties are improved, but tensile properties, abrasion resistance, and workability are deteriorated.

Therefore, in accordance with the recent increase in requirements for low fuel consumption, there is a need to develop a rubber composition in which the tensile properties are improved in a good balance along with improved fuel economy characteristics and damp road braking performance in tires.

JP, WO2013-077018, A1

The present invention was devised to solve the problems of the prior art, and when the rubber composition is applied by controlling the 1,2-vinyl bond content, Mooney viscosity, Mooney relaxation rate, and retardation index of the modified conjugated diene-based polymer It is an object of the present invention to provide a modified conjugated diene polymer capable of improving the rolling resistance and abrasion resistance of.

In addition, it is an object of the present invention to provide a rubber composition containing the modified conjugated diene-based polymer and a filler, with improved rolling resistance and abrasion resistance.

According to an embodiment of the present invention for solving the above problems, the present invention provides a modified conjugated diene-based polymer that satisfies the following conditions i) to v):

Ⅰ) 1,2-vinyl bond content: 40% by weight or more, ii) Mooney viscosity measured under ASTM D1646 conditions: 40 to 100, iii) retardation index at 0.1 Hz measured at 160°C: 0.65 or more, iv) Si atom And N atom content: 50 ppm or more with respect to the total weight of the polymer, and v) Mooney relaxation rate measured at 100° C.: 0.5 or more.

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

The modified conjugated diene-based polymer according to the present invention is applied to a rubber composition by having a 1,2-vinyl bond content, Mooney viscosity, Mooney relaxation rate, and retardation index that are complexly controlled in a specific range, and the rolling resistance properties of the rubber composition And abrasion resistance can be improved.

In addition, the rubber composition according to the present invention may have excellent rolling resistance properties and abrasion resistance by including the modified conjugated diene-based polymer and a filler.

Hereinafter, the present invention will be described in more detail to aid understanding of the present invention.

Terms and words used in the description and claims of the present invention should not be construed as being limited to their usual or dictionary meanings, and the inventors appropriately explain the concept of terms in order to explain their own invention in the best way. Based on the principle that it can be defined, it should be interpreted as a meaning and concept consistent with the technical idea of the present invention.

Justice

The term'polymer' as used herein, whether of the same or different types, refers to a polymer compound prepared by polymerizing monomers. In this way the generic term polymer encompasses the term homopolymer and the term copolymer, which are commonly used to refer to polymers made from only one monomer.

The term '1,2-vinyl bond content' as used herein is based on the conjugated diene monomer (butadiene, etc.) part (total amount of polymerized butadiene) in the polymer, the number 1 and 2 in the polymer chain. It refers to the mass (or weight) percent of butadiene contained in the position.

In the present invention, the term'monovalent hydrocarbon group' means 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. In addition, the minimum number of carbon atoms of the substituent represented by the monovalent hydrocarbon may be determined according to the type of each substituent.

In the present invention, the term'divalent hydrocarbon group' refers to 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, wherein carbon and hydrogen are bonded to each other. It may mean a valence group of atoms, and the minimum number of carbon atoms of a substituent represented by a divalent hydrocarbon may be determined according to the type of each substituent.

In the present invention, the term'alkyl group' may mean a monovalent saturated aliphatic hydrocarbon, and linear alkyl groups such as methyl, ethyl, propyl, and butyl, and isopropyl, sec-butyl, and tertiary It may mean including all branched alkyl groups such as tert-butyl and neo-pentyl.

In the present invention, the term'alkenyl group' may mean a monovalent aliphatic unsaturated hydrocarbon containing one or two or more double bonds.

In the present invention, the term'alkynyl group' may mean a monovalent aliphatic unsaturated hydrocarbon containing one or two or more triple bonds.

In the present invention, the term'alkylene group' may mean a divalent saturated aliphatic hydrocarbon such as methylene, ethylene, propylene, and butylene.

In the present invention, the term'aryl group' may mean a cyclic aromatic hydrocarbon, and also a monocyclic aromatic hydrocarbon having one ring formed, or a polycyclic aromatic hydrocarbon having two or more rings bonded thereto. hydrocarbon) may be included.

In the present invention, the term'heterocyclic group' refers to a cycloalkyl group or an aryl group in which a carbon atom is substituted with one or more heteroatoms, and may mean, for example, including both a heterocycloalkyl group or a heteroaryl group.

In the present invention, the terms'comprising','having' and their derivatives, whether they are specifically disclosed or not, are not intended to exclude the presence of any additional components, steps or procedures. . For the avoidance of any uncertainty, all compositions claimed through the use of the term'comprising', whether polymer or otherwise, may contain any additional additives, adjuvants, or compounds, unless stated to the contrary. Can include. In contrast, the term'consisting essentially of' excludes from the scope of any subsequent description any other component, step or procedure, except that it is not essential to operability. The term'consisting of' excludes any component, step or procedure not specifically described or listed.

Measurement method and conditions

In the present specification, '1,2-vinyl bond content' means that the vinyl content in each polymer is measured and analyzed using Varian VNMRS 500 MHz NMR, and the solvent is 1,1,2,2-tetra in NMR measurement. Chloroethane was used, and the solvent peak was calculated as 6.0 ppm, 7.2-6.9 ppm was random styrene, 6.9-6.2 ppm was block styrene, 5.8-5.1 ppm was 1,4-vinyl and 1,2-vinyl, and 5.1- 4.5 ppm was measured by calculating the 1,2-vinyl bond content in the entire polymer using the peak of 1,2-vinyl.

In the present specification,'weight average molecular weight (Mw)','number average molecular weight (Mn)' and'molecular weight distribution (MWD)' are measured through GPC (Gel permeation chromatohraph) analysis, and measured by checking the molecular weight distribution curve. will be. The molecular weight distribution (PDI, MWD, Mw/Mn) is calculated from the measured molecular weights. Specifically, the GPC is used by combining two columns of PLgel Olexis (Polymer Laboratories) and one column of PLgel mixed-C (Polymer Laboratories), and when calculating the molecular weight, the GPC standard material is PS (polystyrene). It is carried out using, and the GPC measurement solvent is prepared by mixing 2% by weight of an amine compound in tetrahydrofuran.

In the present specification,'Mooney viscosity (MV)' and'Mooney relaxation rate (-S/R)' are measured using a Rotor Speed 2±0.02 rpm at 100°C, Large Rotor using MV-2000 (ALPHA Technologies). At this time, the sample used is left at room temperature (23±3℃) for at least 30 minutes, and then 27±3 g is collected, filled inside the die cavity, and the platen is operated to measure for 4 minutes. After the Mooney viscosity measurement, the inclination value of the Mooney viscosity change that appears as the torque is released is measured, and its absolute value is taken as the Mooney relaxation rate.

In this specification, the'phase difference index' is a frequency (Hz) obtained by measuring at 160°C and 7% strain (0.5 degree) using SCARABAEUS's SCARABAEUS INSTRUMENTS SYSTEMS (SIS) V-50 Rubber Process Analyzer. ) To represent the Tan δ value at 0.1 Hz. Specifically, about 6 g of a polymer was prepared, placed on a disk, and measured using the analyzer under the above conditions to obtain a Tan δ graph for frequency (Hz). Obtained, and here, the Tan δ value at 0.1 Hz was read and expressed as a phase difference index.

In the present specification, the'Si content' is measured using an inductively coupled plasma emission analyzer (ICP-OES; Optima 7300DV) as an ICP analysis method. In the case of using the inductively coupled plasma emission analyzer, 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, heated at 300° C. for 3 hours, and the sample In an electric furnace (Thermo Scientific, Lindberg Blue M), after the conversation was conducted in the program of steps 1 to 3 below,

1) step 1: initial temp 0℃, rate (temp/hr) 180 ℃/hr, temp(holdtime) 180℃ (1hr)

2) step 2: initial temp 180℃, rate (temp/hr) 85 ℃/hr, temp(holdtime) 370℃ (2hr)

3) step 3: initial temp 370℃, rate (temp/hr) 47 ℃/hr, temp(holdtime) 510℃ (3hr)

Add 1 mL of concentrated nitric acid (48 wt%) and 20 µl of concentrated hydrofluoric acid (50 wt%) to the residue, seal the platinum crucible, shake it for 30 minutes or more, and add 1 mL of boric acid to the sample. Put it in, store it at 0°C for 2 hours or more, dilute in 30 mL of ultrapure water, and proceed to incinerate to measure.

In the present invention, the'N content' may be measured using an NSX analysis method, and the NSX analysis method may be measured using a trace nitrogen quantitative analyzer (NSX-2100H).

For example, when using the trace nitrogen quantitative analyzer, turn on the trace nitrogen quantitative analyzer (Auto sampler, Horizontal furnace, PMT & Nitrogen detector), Ar 250 ml/min, O ₂ 350 ml/min, ozonizer 300 ml/ After setting the carrier gas flow rate in min, and setting the heater to 800°C, wait for about 3 hours to stabilize the analyzer. After the analyzer is stabilized, use the Nitrogen standard (AccuStandard S-22750-01-5 ml) to prepare calibration curves for the ranges of 5 ppm, 10 ppm, 50 ppm, 100 ppm and 500 ppm, and obtain the area corresponding to each concentration. After that, a straight line was created using the ratio of the density to the area. Thereafter, a ceramic boat containing 20 mg of a sample was placed on the auto sampler of the analyzer and measured to obtain an area. The N content was calculated using the obtained sample area and the calibration curve.

At this time, the sample used in the NSX analysis method is a modified conjugated diene-based polymer sample from which a solvent is removed by placing it in hot water heated by steam and stirring, and may be a sample from which residual monomers and residual denaturants have been removed. In addition, if oil is added to the above sample, it may be a sample after oil is extracted (removed).

The present invention provides a modified conjugated diene-based polymer capable of improving rolling resistance and abrasion resistance of the rubber composition by being applied to a rubber composition by complexly adjusting various physical properties to a specific range.

The modified conjugated diene-based polymer according to an embodiment of the present invention is characterized in that it satisfies all of the following conditions i) to v) at the same time.

I) 1,2-vinyl bond content: 40% by weight or more,

Ii) Mooney viscosity measured under ASTM D1646 conditions: 40 to 100,

Iii) Phase difference index at 0.1 Hz measured at 160°C: 0.65 or more,

Iv) Si atom and N atom content: 50 ppm or more based on the total weight of the polymer, and

V) Mooney relaxation rate measured at 100°C: 0.5 or more.

According to an embodiment of the present invention, the modified conjugated diene-based polymer may include a repeating unit derived from a conjugated diene-based monomer and a functional group derived from a denaturant, wherein the repeating unit derived from the conjugated diene-based monomer is polymerized by a conjugated diene-based monomer. It may mean a repeating unit formed during the time, and the functional group derived from the modifier refers to a functional group derived from a modifier present at one end of the active polymer through a reaction or coupling between an active polymer prepared by polymerization of a conjugated diene-based monomer and a modifier. can do.

According to an embodiment of the present invention, the conjugated diene-based monomer is 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.) It may be one or more selected from the group consisting of.

In another example, the modified conjugated diene-based polymer may include a repeating unit derived from a conjugated diene-based monomer, a functional group derived from a modification initiator, and a functional group derived from a denaturant. In this case, the modified conjugated diene-based polymer has a functional group derived from a modification initiator on one side, It may be a modified conjugated diene-based polymer at both ends containing a functional group derived from a denaturant on the other side.

As another example, the modified conjugated diene-based polymer may be a copolymer including a repeating unit derived from a conjugated diene-based monomer and a repeating unit derived from an aromatic vinyl monomer, and may include a functional group derived from a denaturant at one end, and at the other end It may be to further include a functional group derived from a denaturation initiator. In this case, the modified conjugated diene-based polymer may contain an aromatic vinyl monomer-derived repeating unit in an amount of less than 30% by weight, or 5% by weight or more and less than 30% by weight.

The aromatic vinyl monomer is, for example, styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene and 1 -It may be one or more selected from the group consisting of vinyl-5-hexylnaphthalene.

As another example, the modified conjugated diene-based polymer may be a copolymer further comprising a repeating unit derived from a diene-based monomer having 1 to 10 carbon atoms together with the repeating unit derived from the conjugated diene-based monomer. The diene-based monomer-derived repeating unit may be a repeating unit derived from a diene-based monomer different from the conjugated diene-based monomer, and the diene-based monomer different from the conjugated diene-based monomer may be, for example, 1,2-butadiene. . When the modified conjugated diene-based polymer is a copolymer further comprising a diene-based monomer, the modified conjugated diene-based polymer contains a diene-based monomer-derived repeating unit in excess of 0% to 1% by weight, more than 0% to 0.1% by weight, It may be included in an amount exceeding 0% by weight to 0.01% by weight, or exceeding 0% by weight to 0.001% by weight, and there is an effect of preventing gel formation within this range.

According to an embodiment of the present invention, the copolymer may be a random copolymer, and in this case, there is an effect of having an excellent balance between physical properties. The random copolymer may mean that the repeating units constituting the copolymer are randomly arranged.

The modified conjugated diene-based polymer according to an embodiment of the present invention may have a 1,2-vinyl bond content of 40% by weight or more based on the total weight of the polymer. The 1,2-vinyl bond content refers to the weight% of the 1,2-added conjugated diene-based monomer, not 1,4-added, with respect to the conjugated diene-based copolymer consisting of a monomer having a vinyl group and an aromatic vinyl-based monomer. In addition, during polymerization, it may be affected by the reaction environment at the time point at which the polymerization reaction is terminated and the time point at which the polymerization reaction is terminated.

Specifically, the 1,2-vinyl bond content may be 40% by weight or more and 60% by weight or less, and preferably 40% by weight or more and 55% by weight or less. Rolling resistance properties may be affected, and if the 1,2-vinyl bond content is less than 40% by weight, rolling resistance properties and abrasion resistance may be poor. Therefore, when preparing a modified conjugated diene-based polymer, 1,2-vinyl It is necessary to pay attention to the reaction conditions so that the binding content can satisfy the above range.

In addition, the modified conjugated diene-based polymer according to an embodiment of the present invention should satisfy the Mooney viscosity measured under ASTM D1646 conditions of 40 to 100, and specifically 50 to 90. There may be various measures for evaluating the workability, but when the Mooney viscosity satisfies the above range, the workability may be considerably excellent.

The modified conjugated diene-based polymer according to an embodiment of the present invention has a number average molecular weight (Mn) measured by gel permeation chromatography (GPC) 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, 10,000 g/mol to 2,000,000 g/mol, or 100,000 It may be from g/mol to 1,500,000 g/mol, and within this range, there is an excellent effect of rolling resistance properties and wet road surface resistance.

In another example, the modified conjugated diene-based polymer has a molecular weight distribution (PDI; MWD; Mw/Mn) of 1.5 to 3.5, preferably, 1.5 to 3.0, or 1.5 to 2.5, or 1.5 to 2.0, and this It has excellent tensile properties and viscoelastic properties within the range, and has an excellent balance between physical properties.

In addition, the modified conjugated diene-based polymer may have a unimodal molecular weight distribution curve obtained by gel permeation chromatography (GPC), and the unimodal form is a method aspect of continuous polymerization. And, it may be determined by the aspect of the denaturation reaction carried out by the denaturing agent or the coupling agent.

The Mooney relaxation rate measured at 100° C. of the modified conjugated diene-based polymer may be an index of the degree of branching of the modified conjugated diene-based polymer. The Mooney relaxation rate at 100° C. of the modified conjugated diene-based polymer is 0.5 or more, and may be 0.5 to 1.2 or 0.6 to 1.0. In addition, the higher the Mooney relaxation rate, the lower the degree of branching (higher linearity).

The Mooney relaxation rate measured at 100°C of the modified conjugated diene-based polymer may be an index of the degree of branching of the modified conjugated diene-based polymer as described above, and as the Mooney relaxation rate increases, the modified conjugated diene-based polymer The degree of branching of the polymer tends to decrease. For example, in the case of a modified conjugated diene-based polymer having an equivalent Mooney viscosity, the Mooney relaxation rate increases as the number of branches decreases, so it can be used as an index of linearity in the Mooney viscosity.

In order to make the Mooney relaxation rate more than 0.5, for example, it can be achieved by controlling the weight average molecular weight and the degree of branching of the prepared polymer in the range of 40 to 100 Mooney viscosity of the modified conjugated diene polymer. When this decreases, the degree of branching increases, and when the weight average molecular weight increases, the degree of branching may be controlled in the direction of lowering the degree of branching, and it can be controlled by the number of functional groups of the modifying agent, the amount of the modifying agent added, or the progress of metallization. In particular, when the number of functional groups of the denaturant is adjusted to 6 or less, or the number of functional groups to 2 or more and 6 or less, the Mooney relaxation rate can be more easily adjusted to 0.5 or more. For example, the modifier reacts with the active end of the polymer chain formed by polymerization of the monomer to introduce a functional group into the polymer chain, and at the same time acts like a coupling agent to couple the polymer chain, thereby branching the polymer. Therefore, when the number of functional groups of the modifier exceeds 6, the number of polymer chains to be coupled increases, resulting in a branched polymer structure, and a Mooney relaxation rate of 0.5 or more cannot be exhibited.

In addition, the modified conjugated diene-based polymer according to an embodiment of the present invention should have a retardation index of 0.65 or more at 0.1 Hz measured at 160°C, and may preferably be 0.65 to 5, or 0.7 to 3.5. Within this range, the degree of branching of the polymer may be controlled to exhibit a Mooney relaxation rate of 0.5 or more. Meanwhile, the retardation index may vary depending on the degree of branching of the polymer, but the degree of branching is not determined only by one, and may be fluid depending on the polymerization method and conditions.

The modified conjugated diene-based polymer according to an embodiment of the present invention may have an N and Si content of 50 ppm or more, 70 ppm to 10,000 ppm, or 100 ppm to 5,000 ppm, respectively, based on weight, and within this range The rubber composition containing the modified conjugated diene polymer has excellent mechanical properties such as tensile properties and viscoelastic properties. The N content and Si content may mean each content of Si atoms present in the modified conjugated diene-based polymer. Meanwhile, the N atom and the Si atom may be derived from a denaturing agent, or may be derived from any one or more of a denaturing initiator and a denaturing agent.

Meanwhile, the modified conjugated diene-based polymer according to an embodiment of the present invention may have a modification rate of 30% or more.

In addition, the modified conjugated diene-based polymer may have a modification rate of 50% or more, and when the content of the N atom and Si atom is 50 ppm (based on weight) or more, the modification rate may be 30% or more, and the modification rate is N It does not change independently of the content of atoms and Si atoms, but may change depending on some part.

However, in the denaturation reaction, the content of N atoms and Si atoms and the denaturation rate may exhibit some independence depending on how much coupling occurs by the modifier, and the denaturation rate is 50% or more, preferably 55% or more, Alternatively, in order to achieve a high modification rate of 60% or more, optimally 70% or more, it is necessary to reduce the amount of the polymer coupled during the modification reaction. It can be controlled according to the mixing time and mixing degree.

As described above, when the modified conjugated diene-based polymer according to the present invention satisfies the above-described conditions, rolling resistance properties can be greatly improved when blended for reasons such as improved affinity with a filler such as silica or carbon black, and at the same time, wear resistance. It can be improved. Furthermore, in the case of a modified conjugated diene-based polymer that further satisfies the modification rate condition, it is possible to greatly improve tensile properties in addition to rolling resistance and abrasion resistance.

On the other hand, the modified conjugated diene-based polymer according to an embodiment of the present invention is prepared through batch or continuous polymerization, but the polymerization temperature, the amount of the reactant, the time of introduction of the reactant, the polymerization initiator, the denaturant so as to simultaneously meet the specific conditions. And the polymerization reaction rate, etc. may be prepared under conditions of controlling, and the above conditions may be appropriately controlled so that the desired physical properties may be expressed, thereby performing the manufacturing method.

For example, the modified conjugated diene-based polymer is prepared by polymerizing the conjugated diene-based monomer in a hydrocarbon solvent in the presence of a polymerization initiator (S1); And a step (S2) of reacting the active polymer prepared in step (S1) with a denaturant, the polymerization reaction (S1) and the denaturation reaction (S2) are carried out in a continuous manner, and the step (S1) is performed in two phases. It is carried out in the above polymerization reactor, the polymerization conversion rate in the first polymerization reactor of the polymerization reactor may be produced by a manufacturing method that is 50% or less.

The polymerization initiator may be an organometallic compound or a modified initiator prepared by reacting a modified functional group-containing compound, an organometallic compound, and a conjugated diene-based monomer, in terms of satisfying all the above-described physical properties of the modified conjugated diene-based polymer It may be preferable that the polymerization initiator is the above modified initiator.

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

According to an embodiment of the present invention, the polymerization initiator is 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 based on 100 g of monomers used for polymerization. To 0.8 mmol.

When the polymerization initiator is an organometallic compound, the organometallic compound is not particularly limited as long as it can easily initiate polymerization and does not affect polymer properties, and a conventional organometallic compound may be used. For example, methyllithium, ethyl Lithium, propyllithium, isopropyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octyllithium, phenyllithium, 1-naphthyllithium, n-ecosyl Lithium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naphthyl sodium, naphthyl potassium, lithium alkoxide, sodium alkoxide, It may be one or more selected from the group consisting of potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide and lithium isopropylamide.

In addition, when the polymerization initiator is a modification initiator, the modification initiator may be an oligomer type material prepared by reacting a modified functional group-containing compound, an organometallic compound, and a conjugated diene-based monomer as described above.

Specifically, the modification initiator is prepared by reacting a compound containing a modified functional group, an organometallic compound, and a conjugated diene-based monomer in a batch or continuous manner, wherein the modified functional group-containing compound is reacted in an excessive proportion to the organometallic compound, The conjugated diene-based monomer may be reacted in a ratio of 0.5 to 5 moles based on 1 mole of the modified functional group-containing compound, and in this case, the modified functional group-containing compound can be induced to bind in an oligomer form. By use, the modification initiator is bonded in the form of a copolymer, so that the ratio of the modification functional groups in the modification initiator is high and the solvent solubility may be excellent. Accordingly, when the modified conjugated diene-based polymer is prepared using the modified initiator, it is possible to more easily satisfy all of the above-described physical properties.

In addition, the modified functional group-containing compound is a compound capable of forming a modification initiator by introducing a modified functional group to one end of the polymerized polymer when polymerization is initiated, and being anionic through a reaction with an organometallic compound. It may be selected according to, for example, a hydrocarbon group-containing compound for improving solvent affinity, a hetero atom-containing compound for improving filler affinity, and the like, and a compound containing an unsaturated bond for smooth reaction with the organometallic compound Can be

As a specific example, the modified functional group-containing compound may be a compound represented by Formula 1 below.

The modification initiator according to the present invention is a compound capable of initiating polymerization and introducing a functional group to one end of a polymer chain formed by polymerization at the same time, such as a compound prepared by reacting an organometallic compound and an amine group-containing compound. , For example, it may be a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

R ₁ to R ₅ are each independently hydrogen; An alkyl group having 1 to 30 carbon atoms; An alkenyl group having 2 to 30 carbon atoms; An alkynyl group having 2 to 30 carbon atoms; A C1-C30 heteroalkyl group, a C2-C30 heteroalkenyl group; A heteroalkynyl group having 2 to 30 carbon atoms; A cycloalkyl group having 5 to 30 carbon atoms; Aryl group having 6 to 30 carbon atoms; Or a heterocyclic group having 3 to 30 carbon atoms, and R ₆ is an alkyl group having 1 to 30 carbon atoms; An alkenyl group having 2 to 30 carbon atoms; An alkynyl group having 2 to 30 carbon atoms; A C1-C30 heteroalkyl group, a C2-C30 heteroalkenyl group; A heteroalkynyl group having 2 to 30 carbon atoms; A cycloalkyl group having 5 to 30 carbon atoms; Aryl group having 6 to 30 carbon atoms; Or an alkylene group having 1 to 20 carbon atoms substituted or unsubstituted with a heterocyclic group having 3 to 30 carbon atoms, X is a functional group represented by the following Formula 1a or Formula 1b,

[Formula 1a]

In Formula 1a, R ₇ and R ₈ are each independently an alkylene group having 1 to 20 carbon atoms substituted or unsubstituted with 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 ₉ is hydrogen; An alkyl group having 1 to 30 carbon atoms; An alkenyl group having 2 to 30 carbon atoms; An alkynyl group having 2 to 30 carbon atoms; A heteroalkyl group having 1 to 30 carbon atoms; A heteroalkenyl group having 2 to 30 carbon atoms; A heteroalkynyl group having 2 to 30 carbon atoms; A cycloalkyl group having 5 to 30 carbon atoms; Aryl group having 6 to 30 carbon atoms; It is a heterocyclic group having 3 to 30 carbon atoms, Y is an N, O or S atom, and when Y is O or S, R ₉ does not exist,

[Formula 1b]

In Formula 1b, R ₁₁ and R ₁₂ are each independently an alkyl group having 1 to 30 carbon atoms; An alkenyl group having 2 to 30 carbon atoms; An alkynyl group having 2 to 30 carbon atoms; A heteroalkyl group having 1 to 30 carbon atoms; A heteroalkenyl group having 2 to 30 carbon atoms; A heteroalkynyl group having 2 to 30 carbon atoms; A cycloalkyl group having 5 to 30 carbon atoms; Aryl group having 6 to 30 carbon atoms; It is a C3-C30 heterocyclic group.

Specifically, in the compound represented by Formula 1, R ₁ to R ₅ in Formula 1 are independently hydrogen; An alkyl group having 1 to 10 carbon atoms; An alkenyl group having 2 to 10 carbon atoms; Or an alkynyl group having 2 to 10 carbon atoms, R ₆ is an unsubstituted alkylene group having 1 to 10 carbon atoms, X is a functional group represented by Formula 1a or Formula 1b, and in Formula 1a, R ₇ and R ₈ are each Independently an unsubstituted C1-C10 alkylene group, R ₉ is a C1-C10 alkyl group; A cycloalkyl group having 5 to 20 carbon atoms; Aryl group having 6 to 20 carbon atoms; Or a heterocyclic group having 3 to 20 carbon atoms, Y is N, and in Formula 1b, R ₁₁ and R ₁₂ are each independently an alkyl group having 1 to 10 carbon atoms; A cycloalkyl group having 5 to 20 carbon atoms; Aryl group having 6 to 20 carbon atoms; Or it may be a heterocyclic group having 3 to 20 carbon atoms.

More specifically, the compound represented by Formula 1 may be a compound represented by Formula 1-1 or Formula 1-2 below.

[Formula 1-1]

[Formula 1-2]

As another example, the modified functional group-containing compound may be a compound represented by Formula 2 below.

[Formula 2]

In Chemical Formula 2,

R ₈ to R ₁₀ are each independently a hydrogen atom; An alkyl group having 1 to 30 carbon atoms; An alkenyl group having 2 to 30 carbon atoms; An alkynyl group having 2 to 30 carbon atoms; A C1-C30 heteroalkyl group, a C2-C30 heteroalkenyl group; A heteroalkynyl group having 2 to 30 carbon atoms; A cycloalkyl group having 3 to 30 carbon atoms; Aryl group having 6 to 30 carbon atoms; Or a heterocyclic group having 3 to 30 carbon atoms, and R ₁₁ is a single bond; An alkylene group having 1 to 20 carbon atoms substituted or unsubstituted with a substituent; A cycloalkylene group having 3 to 20 carbon atoms substituted or unsubstituted with a substituent; Or an arylene group having 6 to 20 carbon atoms substituted or unsubstituted with a substituent, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R ₁₂ is An alkyl group having 1 to 30 carbon atoms; An alkenyl group having 2 to 30 carbon atoms; An alkynyl group having 2 to 30 carbon atoms; A heteroalkyl group having 1 to 30 carbon atoms; A heteroalkenyl group having 2 to 30 carbon atoms; A heteroalkynyl group having 2 to 30 carbon atoms; A cycloalkyl group having 3 to 30 carbon atoms; Aryl group having 6 to 30 carbon atoms; A heterocyclic group having 3 to 30 carbon atoms; Or a functional group represented by the following formula 2a or 2b, p is an integer of 1 to 5 _{, at least one of R 12} is a functional group represented by the following formula 1a or 1b, and p is an integer of 2 to 5 R ₁₂ may be the same or different from each other,

[Formula 2a]

In Formula 2a, R _2a1 is an alkylene group having 1 to 20 carbon atoms unsubstituted or substituted with a substituent; A cycloalkylene group having 3 to 20 carbon atoms substituted or unsubstituted with a substituent; Or an arylene group having 6 to 20 carbon atoms substituted or unsubstituted with a substituent, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms, R _2a2 and R _2a3 is each independently an alkylene group having 1 to 20 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R _2a4 is hydrogen; An alkyl group having 1 to 30 carbon atoms; An alkenyl group having 2 to 30 carbon atoms; An alkynyl group having 2 to 30 carbon atoms; A heteroalkyl group having 1 to 30 carbon atoms; A heteroalkenyl group having 2 to 30 carbon atoms; A heteroalkynyl group having 2 to 30 carbon atoms; A cycloalkyl group having 3 to 30 carbon atoms; Aryl group having 6 to 30 carbon atoms; It is a heterocyclic group having 3 to 30 carbon atoms, X is an N, O or S atom, and when X is O or S, R ₉ does not exist,

[Formula 2b]

In Formula 2b,

R _2b1 is an alkylene group having 1 to 20 carbon atoms unsubstituted or substituted with a substituent; A cycloalkylene group having 3 to 20 carbon atoms substituted or unsubstituted with a substituent; Or an arylene group having 6 to 20 carbon atoms substituted or unsubstituted with a substituent, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms, R _2b2 and R _2b3 are each independently an alkyl group having 1 to 30 carbon atoms; An alkenyl group having 2 to 30 carbon atoms; An alkynyl group having 2 to 30 carbon atoms; A heteroalkyl group having 1 to 30 carbon atoms; A heteroalkenyl group having 2 to 30 carbon atoms; A heteroalkynyl group having 2 to 30 carbon atoms; A cycloalkyl group having 3 to 30 carbon atoms; Aryl group having 6 to 30 carbon atoms; It is a C3-C30 heterocyclic group.

Specifically, the compound represented by Formula 2, in Formula 1, R ₈ to R ₁₀ are each independently hydrogen; An alkyl group having 1 to 10 carbon atoms; An alkenyl group having 2 to 10 carbon atoms; Or an alkynyl group having 2 to 10 carbon atoms, and R ₁₁ is a single bond; Or an unsubstituted C 1 to C 10 alkylene group, R ₁₂ is a C 1 to C 10 alkyl group; An alkenyl group having 2 to 10 carbon atoms; An alkynyl group having 2 to 10 carbon atoms; Or a functional group represented by the following formula 2a or formula 2b, in the formula 2a, R _2a1 is an unsubstituted alkylene group having 1 to 10 carbon atoms, and R _2a2 and R _2a3 are independently of each other unsubstituted 1 to 10 carbon atoms An alkylene group, R _2a4 is an alkyl group having 1 to 10 carbon atoms; A cycloalkyl group having 5 to 20 carbon atoms; Aryl group having 5 to 20 carbon atoms; Or a heterocyclic group having 3 to 20 carbon atoms, in Formula 2b, R _b1 is an unsubstituted alkylene group having 1 to 10 carbon atoms, and R _b2 and R _b3 are each independently an alkyl group having 1 to 10 carbon atoms; A cycloalkyl group having 5 to 20 carbon atoms; Aryl group having 5 to 20 carbon atoms; Alternatively, it may be a heterocyclic group having 3 to 20 carbon atoms.

More specifically, the compound represented by Formula 2 may be a compound represented by Formulas 2-1 to 2-3 below.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

In addition, the conjugated diene-based monomer used in the manufacture of the modification initiator may be the same material as the conjugated diene-based monomer used during polymerization, for example, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, It may be one or more selected from the group consisting of 3-butyl-1,3-octadiene, isoprene, and 2-phenyl-1,3-butadiene.

The polymerization in step (S1) may be an anionic polymerization as an example, and a specific example may be a living anionic polymerization having an anionic active site at the polymerization end by a growth polymerization reaction by an anion. In addition, the polymerization in the step (S1) may be elevated temperature polymerization, isothermal polymerization, or constant temperature polymerization (insulation polymerization), and the constant temperature polymerization includes polymerization of the organometallic compound by its own heat of reaction without optionally applying heat. It may mean a polymerization method, and the elevated temperature polymerization may refer to a polymerization method in which heat is arbitrarily applied after adding the organometallic compound to increase the temperature, and the isothermal polymerization is performed by adding heat after adding the organometallic compound. It may mean a polymerization method in which the temperature of the polymerized product is kept constant by increasing heat by adding or taking away heat.

In addition, according to an embodiment of the present invention, the polymerization in step (S1) may further include a diene-based compound having 1 to 10 carbon atoms in addition to the conjugated diene-based monomer. There is an effect of preventing this formation. The diene-based compound may be 1,2-butadiene, for example.

The polymerization of step (S1) may be carried out in a temperature range of 100°C or less, 80°C or less, -20°C to 80°C, 0°C to 70°C, or 10°C to 70°C, for example, and polymerization within this range. The conversion rate of the reaction can be increased, and the Mooney viscosity, the Mooney relaxation rate, and the retardation index in the above-described ranges can be satisfied while controlling the molecular weight distribution of the polymer, and thus there is an excellent effect of improving physical properties.

The active polymer prepared by the step (S1) may mean a polymer in which a polymer anion and an organometallic cation are bonded.

According to an embodiment of the present invention, the active polymer prepared by the polymerization in the step (S1) may be a random copolymer, and in this case, there is an excellent effect of balancing each physical property. The random copolymer may mean that the repeating units constituting the copolymer are arranged in a random order.

In addition, according to an embodiment of the present invention, the method for preparing the modified conjugated diene-based polymer may be carried out by a continuous polymerization method in a plurality of reactors including two or more polymerization reactors and a modification reactor. As a specific example, the step (S1) may be continuously performed in two or more polymerization reactors including the first reactor, and the number of polymerization reactors may be flexibly determined according to reaction conditions and environments. The continuous polymerization method may refer to a reaction process in which a reactant is continuously supplied to a reactor and the produced reaction product is continuously discharged. In the case of the above-described continuous polymerization method, there is an effect of excellent productivity and processability, and excellent uniformity of the polymer to be produced.

In addition, according to an embodiment of the present invention, when continuously preparing the active polymer in the polymerization reactor, the polymerization conversion rate in the first reactor may be 50% or less, 10% to 50%, or 20% to 50%, After starting the polymerization reactor within this range, it is possible to induce a polymer having a linear structure during polymerization by suppressing side reactions that occur while the polymer is formed, and accordingly, the Mooney viscosity, Mooney relaxation rate, and phase difference index in the above ranges Can be satisfied, there is an excellent effect of improving the physical properties.

At this time, the polymerization conversion rate may be adjusted according to the reaction temperature, the residence time of the reactor, and the like.

The polymerization conversion rate may be determined by measuring the solid concentration in the polymer solution containing the polymer, for example, during polymerization of the polymer.For example, in order to secure the polymer solution, a cylindrical container is mounted at the outlet of each polymerization reactor to A positive polymer solution was filled in a cylindrical container, the cylindrical container was separated from the reactor, and the weight (A) of the cylinder filled with the polymer solution was measured, and then the polymer solution filled in the cylindrical container was added to an aluminum container, For example, transfer to an aluminum dish and measure the weight (B) of a cylindrical container from which the polymer solution has been removed, and dry the aluminum container containing the polymer solution in an oven at 140° C. for 30 minutes, and determine the weight (C) of the dried polymer. After measurement, it may be calculated according to Equation 1 below.

[Equation 1]

On the other hand, the polymerized product polymerized in the first reactor is sequentially transferred to the polymerization reactor before the transformation reactor, so that the polymerization can be carried out until the polymerization conversion rate becomes 95% or more. After the polymerization in the first reactor, the second reactor Alternatively, the polymerization conversion rate for each reactor from the second reactor to the polymerization reactor before the modification reactor may be appropriately adjusted for each reactor in order to control the molecular weight distribution.

Meanwhile, in the step (S1), when preparing the active polymer, the residence time of the polymer in the first reactor may be 1 minute to 40 minutes, 1 minute to 30 minutes, or 5 minutes to 30 minutes, and within this range, polymerization It is easy to adjust the conversion rate, and accordingly, the Mooney viscosity, the Mooney relaxation rate, and the phase difference index in the above-described ranges can be satisfied, and thus there is an excellent effect of improving physical properties.

In the present invention, the term'polymer' refers to (S1) step or (S2) step is completed, prior to obtaining an active polymer or a modified conjugated diene-based polymer, during step (S1), polymerization is carried out in each reactor. It may refer to an intermediate in the form of a polymer being used, and may refer to a polymer having a polymerization conversion rate of less than 90% in which polymerization is carried out in a reactor.

Meanwhile, the polymerization of step (S1) may be carried out including a polar additive, and the polar additive may be added in a ratio of 0.001 g to 50 g, or 0.002 g to 0.1 g based on a total of 100 g of monomers. In another example, the polar additive is more than 0 g to 1 g, 0.01 g to 1 g, or at least one selected from the group consisting of ethylamine, tripropylamine, and tetramethylethylenediamine based on a total of 100 g of the organometallic compound. May be, preferably 2,2-(di-2(tetrahydrofuryl)propane) or tetramethylethylenediamine, and when the polar additive is included, a conjugated diene-based monomer, or a conjugated diene-based monomer and an aromatic vinyl In the case of copolymerization of the system monomers, there is an effect of inducing a random copolymer to be easily formed by compensating for a difference in reaction rate thereof.

According to an embodiment of the present invention, in the reaction of step (S2), the denaturant may be used in an amount of 0.01 mmol to 10 mmol based on a total of 100 g of monomers. As another example, the denaturant 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 organometallic compound in step (S1). Since the molar ratio of the modifier and the organometallic compound and the amount of modifier to the monomer added may have an effect on the Mooney viscosity and the Mooney relaxation rate of the polymer to be produced, it is preferable to select and apply an appropriate ratio within the above range. .

In addition, according to an embodiment of the present invention, the denaturant may be introduced into the denaturation reactor, and the (S2) step may be performed in the denaturation reactor. In another example, the denaturant may be added to a transport unit for transporting the active polymer prepared in step (S1) to a denaturing reactor for performing step (S2), and mixing the active polymer and the modifier in the transport unit In this case, the reaction may be a denaturation reaction in which the denaturant is simply bonded to the active polymer, or a coupling reaction in which the active polymer is connected based on the denaturant, and as described above, the denaturation reaction and the coupling reaction The ratio of is needed to be controlled, which can affect the Mooney viscosity, the Mooney relaxation rate, and the phase difference index.

In addition, the modifier may be a modifier for modifying the other end of the conjugated diene-based polymer, and a specific example may be a silica affinity modifier. The silica-affinity modifier may mean a modifier containing a silica-affinity functional group in a compound used as a modifier, and the silica-affinity functional group has excellent affinity with a filler, especially a silica-based filler, It may mean a functional group capable of interaction between the functional groups derived from the denaturant.

The modifier may be an alkoxy silane modifier as an example, and a specific example may be an alkoxy silane modifier containing at least one hetero atom such as a nitrogen atom, an oxygen atom, or a sulfur atom. In the case of using the alkoxysilane modifier, modification may be performed in a form in which one end of the active polymer is bonded to a silyl group through a substitution reaction between the anionic active site located at one end of the active polymer and the alkoxy group of the alkoxysilane modifier. Accordingly, there is an effect of improving the mechanical properties of the rubber composition including the modified conjugated diene polymer by improving affinity with the inorganic filler from the functional group derived from the modifier present at one end of the modified conjugated diene polymer. In addition, when the alkoxysilane modifier contains a nitrogen atom, in addition to the effect derived from the silyl group, an additional effect of increasing physical properties derived from the nitrogen atom can be expected.

According to an embodiment of the present invention, the denaturant may include a compound represented by the following formula (3).

[Formula 3]

In Formula 3, R _a1 is a single bond or an alkylene group having 1 to 10 carbon atoms, R _a2 and R _a3 are each independently an alkyl group _{having 1 to 10 carbon atoms, and R a5} is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms , A divalent, trivalent or tetravalent alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, or a heterocyclic group having 2 to 10 carbon atoms, and R _a4 is It may be a single bond, an alkylene group having 1 to 10 carbon atoms, or -[R ⁴² O] _j -, R ⁴² may be an alkylene group having 1 to 10 carbon atoms, n ₁ is an integer of 1 to 3, n ₂ Is an integer of 0 to 2 _{, but when n 2} is 0, n ₁ is 1 or 2, and j may be an integer of 1 to 30.

As a specific example, in Formula 3, R _a1 may be a single bond or an alkylene group having 1 to 5 carbon atoms, R _a2 and R _a3 may each independently be a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and R _a5 May be a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a tetravalent alkylsilyl group substituted with an alkyl group having 1 to 5 carbon atoms, or a heterocyclic group having 2 to 5 carbon atoms, and R _a4 is a single bond, or It may be an alkylene group, or -[R ⁴² O] _j -, and R ⁴² may be an alkylene group having 1 to 5 carbon atoms.

In Formula 3, when R _a5 is a heterocyclic group, the heterocyclic group may be substituted or unsubstituted with a trisubstituted alkoxysilyl group, and when the heterocyclic group is substituted with a trisubstituted alkoxysilyl group, the trisubstituted alkoxysilyl group It may be connected to and substituted with the heterocyclic group by an alkylene group having 1 to 10 carbon atoms, and the trisubstituted alkoxy silyl group may mean an alkoxy silyl group substituted with an alkoxy group having 1 to 10 carbon atoms. If R _{a5 is a heterocyclic group substituted with an alkoxysilyl group, n 1} and n ₂ may be adjusted so that the total number of alkoxy groups in the compound represented by Formula 3 is 6 or less.

In a more specific example, the compound represented by Formula 3 is N,N-bis(3-(dimethoxy(methyl)silyl)propyl)-methyl-1-amine (N,N-bis(3-(dimethoxy(methyl)) silyl)propyl)-methyl-1-amine), N,N-bis(3-(diethoxy(methyl)silyl)propyl)-methyl-1-amine(N,N-bis(3-(diethoxy(methyl)) silyl)propyl)-methyl-1-amine), N,N-bis(3-(trimethoxysilyl)propyl)-methyl-1-amine (N,N-bis(3-(trimethoxysilyl)propyl)-methyl -1-amine), N,N-bis(3-(triethoxysilyl)propyl)-methyl-1-amine (N,N-bis(3-(triethoxysilyl)propyl)-methyl-1-amine), N,N-diethyl-3-(trimethoxysilyl)propan-1-amine (N,N-diethyl-3-(trimethoxysilyl)propan-1-amine), N,N-diethyl-3-(tri Ethoxysilyl)propan-1-amine (N,N-diethyl-3-(triethoxysilyl)propan-1-amine), N,N-bis(3-(diethoxy(methyl)silyl)propyl)-1,1 ,1-trimethylsilaneamine (N,N-bis(3-(diethoxy(methyl)silyl)propyl)-1,1,1-trimethlysilanamine), N,N-bis(3-(1H-imidazole-1- Yl)propyl)-(triethoxysilyl)methan-1-amine (N,N-bis(3-(1H-imidazol-1-yl)propyl)-(triethoxysilyl)methan-1-amine), N-( 3-(1H-1,2,4-triazol-1-yl)propyl)-3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine (N -(3-(1H-1,2,4-triazole-1-yl)propyl)-3-(trimethoxysilyl)-N-(trimethoxysilyl)propyl)propan-1-amine), N,N-bis(2- (2-methoxyethoxy)ethyl)-3-(triethoxysilyl)propan-1-amine (N,N-bis(2-(2-methoxyethoxy)eth yl)-3-(triethoxysilyl)propan-1-amine), N,N-bis(3-(triethoxysilyl)propyl)-2,5,8,11,14-pentaoxahexadecane-16-amine (N,N-bis(3-(triethoxysilyl)propyl)-2,5,8,11,14-pentaoxahexadecan-16-amine), N-(2,5,8,11,14-pentaoxahexadecane- 16-yl)-N-(3-(triethoxysilyl)propyl)-2,5,8,11,14-pentaoxahexadecane-16-amine (N-(2,5,8,11,14 -pentaoxahexadecan-16-yl)-N-(3-(triethoxysilyl)propyl)-2,5,8,11,14-pentaoxahexadecan-16-amine) and N-(3,6,9,12-tetraoxahexa Decyl)-N-(3-(triethoxysilyl)propyl)-3,6,9,12-tetraoxahexadecane-1-amine (N-(3,6,9,12-tetraoxahexadecyl)-N- (3-(triethoxysilyl)propyl)-3,6,9,12-tetraoxahexadecan-1-amine).

As another example, the denaturant may include a compound represented by the following formula (4).

[Formula 4]

In Chemical Formula 4,

R _c1 is hydrogen or an alkyl group having 1 to 10 carbon atoms,

R _c2 to R _c4 are each independently an alkylene group having 1 to 10 carbon atoms,

R _c5 to R _c8 are each independently an alkyl group having 1 to 10 carbon atoms,

또는

이고, 여기에서 R_c9 내지 R_c12는 서로 독립적으로 수소, 또는 탄소수 1 내지 10의 알킬기이며, A ₅ is

or

And, wherein R _c9 to R _c12 are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms,

m ₁ and m ₂ are each independently an integer of 0 to 3, but m ₁ +m ₂ ≥1.

또는

이고, 여기에서 R_c9 내지 R_c12는 서로 독립적으로 수소, 또는 탄소수 1 내지 5의 알킬기인 것일 수 있다. Specifically, in Formula 4, R _c1 is hydrogen or an alkyl group having 1 to 5 carbon atoms, R _c2 to R _c4 are each independently an alkylene group having 1 to 5 carbon atoms, and R _c5 to R _c8 are independently of each other 5 is an alkyl group, and A ₅ is

or

And, wherein R _c9 to R _c12 may be each independently hydrogen or an alkyl group having 1 to 5 carbon atoms.

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

As another example, the denaturant may include a compound represented by the following formula (5).

[Formula 5]

In Formula 5, A ¹ and A ² may each independently be a divalent hydrocarbon group having 1 to 20 carbon atoms containing or not including an oxygen atom, and R _b1 to R _b4 are each independently monovalent having 1 to 20 carbon atoms It may be a hydrocarbon group, and L ¹ to L ⁴ are each independently a divalent, trivalent or tetravalent alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or L ¹ and L ² and L ³ and L ⁴ may be connected to each other to form a ring having 1 to 3 carbon atoms, and when L ¹ and L ² and L ³ and L ⁴ are connected to each other to form a ring, the formed ring is It may contain 1 to 3 heteroatoms selected from the group consisting of N, O and S.

As a specific example, in Formula 5, A ¹ and A ² may each independently be an alkylene group of 1 to 10, R _b1 to R _b4 may each independently be an alkyl group having 1 to 10 carbon atoms, and L ¹ to L ⁴ is a tetravalent alkylsilyl group or an alkyl group having 1 to 10 carbon atoms, each independently substituted with an alkyl group having 1 to 5 carbon atoms, or L ¹ and L ² and L ³ and L ⁴ are connected to each other to form a ring having 1 to 3 carbon atoms In the case where L ¹ and L ² and L ³ and L ⁴ are connected to each other to form a ring, the formed ring contains one or more heteroatoms selected from the group consisting of N, O, and S. It can contain three.

In a more specific example, the compound represented by Formula 5 is 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine) (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)(3,3'-(1,1,3,3-tetraethoxydisiloxane-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-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-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimpropylpropan-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-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine) (3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine), 3,3'-(1,1,3,3- Tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine)(3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis (N,N-dipropylpropan-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1-amine) )(3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1-amine), 3,3'-(1,1,3,3 -Tetraethoxydisiloxane-1,3-diyl)bis(N,N-diethylmethane-1-amine)(3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl) bis(N,N-diethylmethan-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1 -Amine) (3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1-amine), 3,3'-(1,1,3 ,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethane-1-amine)(3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl) bis(N,N-dimethylmethan-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethane-1- Amine) (3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethan-1-amine), 3,3'-(1,1,3, 3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethane-1-amine)(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-dipropylmethane-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-dimethyl Methane-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-dipropylmethane-1-amine)(3,3'-(1,1,3,3-tetraethoxydisiloxane-1 ,3-diyl)bis(N,N-dipropylmethan-1-amine), N,N'-((1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(propane-3, 1-diyl)) bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine (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(propane-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-phenylsilaneamine (N,N'-((1,1,3,3-tetramethoxydisiloxane-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(propane-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilaneamine (N,N'-((1,1,3,3-tetraethoxydisiloxane-1 ,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilanamine), N,N'-((1,1,3,3-tetrapropoxydi Siloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilaneamine (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-imidazole-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)1,1,3,3-tetrapropoxydisiloxane (1, It may be one selected from the group consisting of 3-bis(3-(1H-imidazol-1-yl)propyl)-1,1,3,3-tetrapropoxydisiloxane).

As another example, the denaturant may include a compound represented by the following formula (6).

[Formula 6]

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

Specifically, in Formula 6, R ²² and R ²³ may each independently be an alkylene group having 1 to 10 carbon atoms, or -R ²⁸ [OR ²⁹ ] _f -, and R ²⁴ to R ²⁷ may each independently have 1 carbon number It may be an alkyl group of to 10, R ²⁸ and R ²⁹ may each independently be an alkylene group having 1 to 10 carbon atoms, d and e are each independently 0, or an integer selected from 1 to 3, d+e is It may be an integer greater than or equal to 1, and f may be an integer selected from 1 to 30.

More specifically, the compound represented by Formula 6 may be a compound represented by Formula 6a, Formula 6b, or Formula 6c.

[Formula 6a]

[Formula 6b]

[Formula 6c]

In Formula 6a, Formula 6b, and Formula 6c, R ²² to R ²⁷ , d and e are as described above.

In a more specific example, the compound represented by Formula 6 is 1,4-bis(3-(3-(triethoxysilyl)propoxy)propyl)piperazine (1,4-bis(3-(3-(triethoxysilyl) )propoxy)propyl)piperazine, 1,4-bis(3-(triethoxysilyl)propyl)piperazine (1,4-bis(3-(triethoxysilyl)propyl)piperazine), 1,4-bis(3- (Trimethoxysilyl)propyl) piperazine (1,4-bis(3-(trimethoxysilyl)propyl)piperazine), 1,4-bis(3-(dimethoxymethylsilyl)propyl) piperazine (1,4- bis(3-(dimethoxymethylsilyl)propyl)piperazine), 1-(3-(ethoxydimethylsilyl)propyl)-4-(3-(triethoxysilyl)propyl)piperazine (1-(3-(ethoxydimethlylsilyl) propyl)-4-(3-(triethoxysilyl)propyl)piperazine), 1-(3-(ethoxydimethyl)propyl)-4-(3-(triethoxysilyl)methyl)piperazine (1-(3- (ethoxydimethyl)propyl)-4-(3-(triethoxysilyl)methyl)piperazine), 1-(3-(ethoxydimethyl)methyl)-4-(3-(triethoxysilyl)propyl)piperazine (1- (3-(ethoxydimethyl)methyl)-4-(3-(triethoxysilyl)propyl)piperazine), 1,3-bis(3-(triethoxysilyl)propyl)imidazolidine (1,3-bis(3 -(triethoxysilyl)propyl)imidazolidine), 1,3-bis(3-(dimethoxyethylsilyl)propyl)imidazolidine (1,3-bis (3-(dimethoxyethylsilyl)propyl)imidazolidine), 1,3- Bis(3-(trimethoxysilyl)propyl)hexahydropyrimidine (1,3-bis(3-(trimethoxysilyl)propyl)hexahydropyrimidine), 1,3-bis(3-(triethoxysilyl)propyl)hexa Hydropyrimidine (1,3-bis(3-(triethoxysilyl)p) ropyl)hexahydropyrimidine) and 1,3-bis(3-(tributoxysilyl)propyl)-1,2,3,4-tetrahydropyrimidine (1,3-bis(3-(tributoxysilyl)propyl)-1 ,2,3,4-tetrahydropyrimidine) may be one selected from the group consisting of.

As another example, the denaturant may include a compound represented by the following formula (7).

[Formula 7]

In Formula 7, R ³⁰ may be a monovalent hydrocarbon group having 1 to 30 carbon atoms, R ³¹ to R ³³ may each independently be an alkylene group having 1 to 10 carbon atoms, and R ³⁴ to R ³⁷ may each independently have a carbon number It may be an alkyl group of 1 to 10, g and h are each independently 0, or an integer selected from 1 to 3, g+h may be an integer of 1 or more.

As another example, the denaturant may include a compound represented by the following formula (8).

[Formula 8]

In Formula 8, A ³ and A ⁴ may each independently be an alkylene group ^{having 1 to 10, and R 38} to R ⁴¹ may each independently be an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and , i may be an integer selected from 1 to 30.

As another example, the denaturant may include a compound represented by the following formula (9).

[Formula 9]

In Formula 9, R ⁴³ , R ⁴⁵ and R ⁴⁶ may each independently be an alkyl group ^{having 1 to 10 carbon atoms, R 44} may be an alkylene group having 1 to 10 carbon atoms, and k may be an integer selected from 1 to 4 have.

In a more specific example, the compound represented by Formula 9 is 8,8-dibutyl-3,13-dimethoxy-3,13-dimethyl-2,14-dioxa-7,9-dithia-3,13- Disila-8-stanpentadecane (8,8-dibutyl-3,13-dimethoxy-3,13-dimethyl-2,14-dioxa-7,9-dithia-3,13-disila-8-stannapentadecane), 8,8-dimethyl-3,13-dimethoxy-3,13-dimethyl-2,14-dioxa-7,9-dithia-3,13-disila-8-stanpentadecane (8,8- dimetyl-3,13-dimethoxy-3,13-dimethyl-2,14-dioxa-7,9-dithia-3,13-disila-8-stannapentadecane), and 8,8-dibutyl-3,3,13 ,13-tetramethoxy-2,14-dioxa-7,9-dithia-3,13-disila-8-stanpentadecane (8,8-dibutyl-3,3,13,13-tetramethoxy- 2,14-dioxa-7,9-dithia-3,13-disila-8-stannapentadecane).

According to the present invention, a rubber composition comprising the modified conjugated diene polymer is provided.

The rubber composition may contain the modified conjugated diene-based polymer in an amount of 10% by weight or more, 10% by weight to 100% by weight, or 20% by weight to 90% by weight, and within this range, tensile strength, abrasion resistance, etc. It has excellent mechanical properties and excellent balance between properties.

In addition, the rubber composition may further include other rubber components as necessary in addition to the modified conjugated diene-based polymer, and in this case, the rubber component may be included in an amount of 90% by weight or less based on the total weight of the rubber composition. As a specific example, the other rubber component may be included in an amount of 1 to 900 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer.

The rubber component may be, for example, natural rubber or synthetic rubber, and specific examples include natural rubber (NR) including cis-1,4-polyisoprene; Modified natural rubber such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), hydrogenated natural rubber, etc. obtained by modifying or purifying the general natural rubber; Styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, polyisobutylene-co-isoprene, neoprene, poly(ethylene-co- Propylene), poly(styrene-co-butadiene), poly(styrene-co-isoprene), poly(styrene-co-isoprene-co-butadiene), poly(isoprene-co-butadiene), poly(ethylene-co-propylene -Co-diene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, halogenated butyl rubber, and the like, and any one or a mixture of two or more of them may be used.

The rubber composition may include, for example, 0.1 parts by weight to 200 parts by weight, or 10 parts by weight to 120 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene-based polymer of the present invention. The filler may be a silica-based filler as an example, and a specific example may be wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, or colloidal silica, and preferably, the effect of improving fracture properties and wet It may be wet-type silica that has the most excellent wet grip effect. In addition, the rubber composition may further include a carbon-based filler if necessary.

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, and as a specific example, the silane coupling agent is bis(3-triethoxysilylpropyl)tetrasulfide , Bis(3-triethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilyl) Propyl) tetrasulfide, bis(2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide Feed, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilylpropylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzolyltetrasulfide, 3-triethoxysilylpropylmethacrylate monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, bis(3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethyl Silane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, dimethoxymethylsilylpropylbenzothiazolyltetrasulfide, and the like, and any one or a mixture of two or more of them may be used. Preferably, when considering the effect of improving reinforcing properties, it may be bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide.

In addition, in the rubber composition according to an embodiment of the present invention, since a modified conjugated diene-based polymer in which a functional group having high affinity with silica is introduced as a rubber component is used, the amount of the silane coupling agent is usually It may be less than the case, and accordingly, the silane coupling agent may be used in an amount of 1 to 20 parts by weight, or 5 to 15 parts by weight based on 100 parts by weight of silica, and the effect as a coupling agent within this range is While sufficiently exerted, there is an effect of preventing the gelation of the rubber component.

The rubber composition according to an embodiment of the present invention may be sulfur crosslinkable, and may further include a vulcanizing agent. The vulcanizing agent may specifically be a sulfur powder, and may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the rubber component, within this range, while securing the required elastic modulus and strength of the vulcanized rubber composition, and at the same time having low fuel economy. It has an excellent effect.

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

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

The process oil acts as a softener in the rubber composition, and may be, for example, a paraffinic, naphthenic, or aromatic compound, and when considering tensile strength and abrasion resistance, when considering aromatic process oil price, hysteresis loss, and low-temperature characteristics Naphthenic or paraffinic process oil may be used. For example, the process oil may be included in an amount of 100 parts by weight or less based on 100 parts by weight of the rubber component, and within this range, there is an effect of preventing a decrease in tensile strength and low heat generation (low fuel economy) of the vulcanized rubber.

The anti-aging agent is, for example, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 6-ethoxy-2 ,2,4-trimethyl-1,2-dihydroquinoline, or a high-temperature condensation product of diphenylamine and acetone, and the like, 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.

The rubber composition according to an embodiment of the present invention can be obtained by kneading using a kneader such as a Banbury mixer, a roll, or an internal mixer according to the formulation, and has low heat generation and abrasion resistance by a vulcanization process after molding processing. This excellent rubber composition can be obtained.

Accordingly, the rubber composition is a tire tread, under tread, side wall, carcass coated rubber, belt coated rubber, bead filler, pancreas, or bead coated rubber, and other tire members, anti-vibration rubber, belt conveyor, hose, etc. It may be useful in the manufacture of various industrial rubber products.

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

The tire may include a tire or a tire tread.

Hereinafter, examples will be described in detail in order to describe the present invention in detail. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to more completely describe the present invention to those of ordinary skill in the art.

Manufacturing Example 1

Three vacuum-dried 4L stainless steel pressure vessels were prepared. Cyclohexane, a compound represented by the following formula 1-1, and tetramethylethylenediamine were added to the first pressure vessel to prepare a first reaction solution. At the same time, liquid 2.0 M n-butyllithium and cyclohexane were added to a second pressure vessel to prepare a second reaction solution. In addition, 1,3-butadiene and cyclohexane were added to a third pressure vessel to prepare a third reaction solution. With the pressure of each pressure vessel maintained at 7 bar, the first reaction solution, the second reaction solution and the third reaction solution were respectively injected into the continuous reactor using a mass flow meter, and the temperature of the reactor was set to -10°C. , The reaction was carried out by adjusting the residence time in the reactor to be within 10 minutes while maintaining the internal pressure of 3 bar. At this time, the molar ratio of the compound represented by Formula 1-1, n-butyllithium, and 1,3-butadiene was 1.5:1:1. Thereafter, the reaction was terminated to obtain a denaturing initiator.

[Formula 1-1]

Manufacturing Example 2

Three vacuum-dried 4L stainless steel pressure vessels were prepared. Cyclohexane, a compound represented by the following Formula 2-3, and tetramethylethylenediamine were added to the first pressure vessel to prepare a first reaction solution. At the same time, liquid 2.0 M n-butyllithium and cyclohexane were added to a second pressure vessel to prepare a second reaction solution. In addition, 1,3-butadiene and cyclohexane were added to a third pressure vessel to prepare a third reaction solution. With the pressure of each pressure vessel maintained at 7 bar, the first reaction solution, the second reaction solution and the third reaction solution were respectively injected into the continuous reactor using a mass flow meter, and the temperature of the reactor was set to -10°C. , The reaction was carried out by adjusting the residence time in the reactor to be within 10 minutes while maintaining the internal pressure of 3 bar. At this time, the molar ratio of the compound represented by Chemical Formula 2-3, n-butyllithium, and 1,3-butadiene was 1.5:1:1. Thereafter, the reaction was terminated to obtain a denaturing initiator.

[Formula 2-3]

Example 1

In one of the three continuous stirring liquid phase reactors (CSTR), a styrene solution in which 60% by weight of styrene is dissolved in n-hexane is 5.38 kg/h, and 1,3-butadiene is dissolved in 60% by weight in n-hexane. The prepared 1,3-butadiene solution was 16.1 kg/h, n-hexane 71.3 kg/h, and a 1,2-butadiene solution in which 2.0 wt% of 1,2-butadiene was dissolved in n-hexane was 40 g/h, polar A polar additive solution in which 10% by weight of 2,2-(di-2(tetrahydrofuryl)propane) was dissolved in n-hexane as an additive was dissolved in 270 g/h, and prepared in Preparation Example 2 in n-hexane as a denaturing initiator. A denaturation initiator solution in which the denaturation initiator was dissolved in 20% by weight was injected at a rate of 112.0 g/h. At this time, the temperature inside the reactor was maintained at 50° C., and when the polymerization conversion rate reached 45%, the polymer was transferred from the first reactor to the second reactor through a transfer pipe.

Subsequently, a 1,3-butadiene solution in which 60% by weight of 1,3-butadiene was dissolved in n-hexane was injected into the second reactor at a rate of 3.5 kg/h. At this time, the temperature of the second reactor was maintained to be 65°C, and when the polymerization conversion rate became 95% or more, the polymer was transferred from the second reactor to the third reactor through a transfer pipe.

Transfer the polymer from the second reactor to the third reactor, and 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropane) as a denaturing agent. A solution in which 20% by weight of -1-amine) (3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine) was dissolved was added to 154. It was introduced into the third reactor at a rate of g/h, and the temperature of the third reactor was maintained at 65°C.

Thereafter, a solution of IR1520 (BASF) dissolved in 30% by weight as an antioxidant was injected into the polymerization solution discharged from the third reactor at a rate of 200 g/h, followed by stirring. The resulting polymer was put in hot water heated with steam and stirred to remove the solvent, and then roll-dried to remove the remaining amount of solvent and water, thereby preparing a modified conjugated diene-based polymer at both ends. The analysis results for the modified conjugated diene-based polymer at both ends are shown in Table 1 below.

Example 2

In Example 1, in the same manner as in Example 1, except that the modified initiator prepared in Preparation Example 1 was used instead of the modified initiator prepared in Preparation Example 2 as the modified initiator, the modified conjugated diene polymer at both ends was Was prepared.

Example 3

In one of three continuous stirring liquid phase reactors (CSTR), a styrene solution in which 60% by weight of styrene is dissolved in n-hexane is dissolved at 7.20 kg/h, and 1,3-butadiene is dissolved in 60% by weight in n-hexane. The prepared 1,3-butadiene solution was 12.5 kg/h, n-hexane 72.1 kg/h, and a 1,2-butadiene solution in which 2.0 wt% of 1,2-butadiene was dissolved in n-hexane was 40 g/h, polar A polar additive solution in which 10% by weight of 2,2-(di-2(tetrahydrofuryl)propane) was dissolved in n-hexane as an additive was 180 g/h, and prepared in Preparation Example 2 in n-hexane as a denaturing initiator. A denaturation initiator solution in which the denaturation initiator was dissolved in 20% by weight was injected at a rate of 111.8 g/h. At this time, the temperature inside the reactor was maintained at 50° C., and when the polymerization conversion rate reached 45%, the polymer was transferred from the first reactor to the second reactor through a transfer pipe.

Subsequently, a 1,3-butadiene solution in which 60% by weight of 1,3-butadiene was dissolved in n-hexane was injected into the second reactor at a rate of 5.3 kg/h. At this time, the temperature of the second reactor was maintained to be 65°C, and when the polymerization conversion rate became 95% or more, the polymer was transferred from the second reactor to the third reactor through a transfer pipe.

Transfer the polymer from the second reactor to the third reactor, and 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropane) as a denaturing agent. A solution in which 20% by weight of -1-amine) (3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine) was dissolved was added to 154. It was introduced into the third reactor at a rate of g/h, and the temperature of the third reactor was maintained at 65°C.

Thereafter, a solution of IR1520 (BASF) dissolved in 30% by weight as an antioxidant was injected into the polymerization solution discharged from the third reactor at a rate of 200 g/h, followed by stirring. The resulting polymer was put in hot water heated with steam and stirred to remove the solvent, and then roll-dried to remove the remaining amount of solvent and water, thereby preparing a modified conjugated diene-based polymer at both ends. The analysis results for the modified conjugated diene-based polymer at both ends are shown in Table 1 below.

Comparative Example 1

In one of three continuous stirring liquid phase reactors (CSTR), a styrene solution in which 60% by weight of styrene is dissolved in n-hexane is dissolved at 5.38 kg/h, and 1,3-butadiene is dissolved in 60% by weight in n-hexane. The prepared 1,3-butadiene solution was 16.1 kg/h, n-hexane 72.1 kg/h, and a 1,2-butadiene solution in which 2.0 wt% of 1,2-butadiene was dissolved in n-hexane was 40 g/h, polar As an additive, a polar additive solution in which 2,2-(di-2(tetrahydrofuryl)propane) was dissolved in 10% by weight in n-hexane was 270 g/h, and n-butyllithium was in 20% by weight in n-hexane. The dissolved n-butyllithium solution was injected at a rate of 38.3 g/h. At this time, the temperature inside the reactor was maintained at 55°C, and when the polymerization conversion rate reached 48%, the polymer was transferred from the first reactor to the second reactor through a transfer pipe.

Subsequently, a 1,3-butadiene solution in which 60% by weight of 1,3-butadiene was dissolved in n-hexane was injected into the second reactor at a rate of 3.5 kg/h. At this time, the temperature of the second reactor was maintained to be 65°C, and when the polymerization conversion rate became 95% or more, the polymer was transferred from the second reactor to the third reactor through a transfer pipe.

The polymer is transferred from the second reactor to the third reactor, and a solution in which dimethyl dichlorosilane is dissolved in 20% by weight as a coupling agent is introduced into the third reactor at a rate of 45 g/h, and at this time, the third The temperature of the reactor was maintained at 65°C.

Thereafter, a solution of IR1520 (BASF) dissolved in 30% by weight as an antioxidant was injected into the polymerization solution discharged from the third reactor at a rate of 200 g/h, followed by stirring. The resulting polymer was put in hot water heated with steam and stirred to remove the solvent, and then roll-dried to remove the remaining amount of solvent and water, thereby preparing an unmodified styrene-butadiene copolymer. The analysis results for the thus prepared unmodified styrene-butadiene copolymer are shown in Table 1 below.

Comparative Example 2

In one of three continuous stirring liquid phase reactors (CSTR), a styrene solution in which 60% by weight of styrene is dissolved in n-hexane is dissolved at 5.38 kg/h, and 1,3-butadiene is dissolved in 60% by weight in n-hexane. The prepared 1,3-butadiene solution was 16.09 kg/h, n-hexane 72.1 kg/h, and a 1,2-butadiene solution in which 2.0 wt% of 1,2-butadiene was dissolved in n-hexane was 40 g/h, polar A polar additive solution in which 10% by weight of 2,2-(di-2(tetrahydrofuryl)propane) was dissolved in n-hexane as an additive was dissolved in 270 g/h, and prepared in Preparation Example 2 in n-hexane as a denaturing initiator. A denaturation initiator solution in which the denaturation initiator was dissolved in 20% by weight was injected at a rate of 111.8 g/h. At this time, the temperature inside the reactor was maintained at 50° C., and when the polymerization conversion rate reached 45%, the polymer was transferred from the first reactor to the second reactor through a transfer pipe.

Subsequently, a 1,3-butadiene solution in which 60% by weight of 1,3-butadiene was dissolved in n-hexane was injected into the second reactor at a rate of 3.5 kg/h. At this time, the temperature of the second reactor was maintained to be 65°C, and when the polymerization conversion rate became 95% or more, the polymer was transferred from the second reactor to the third reactor through a transfer pipe.

Transfer the polymer from the second reactor to the third reactor, and 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropane) as a denaturing agent. -1-amine) (3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine) was dissolved in 20% by weight of 41.3 It was introduced into the third reactor at a rate of g/h, and the temperature of the third reactor was maintained at 65°C.

Thereafter, a solution of IR1520 (BASF) dissolved in 30% by weight as an antioxidant was injected into the polymerization solution discharged from the third reactor at a rate of 200 g/h, followed by stirring. The resulting polymer was put in hot water heated with steam and stirred to remove the solvent, and then roll-dried to remove the remaining amount of solvent and water, thereby preparing a modified conjugated diene-based polymer at both ends. The analysis results for the modified conjugated diene-based polymer at both ends are shown in Table 1 below.

Comparative Example 3

In Example 1, in place of 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine) as a denaturing agent, n -A solution in which 20% by weight of tris(3-(trimethoxysilyl)propyl)amine) was dissolved in hexane was added to the third reactor at a rate of 75 g/h. In the same manner as in Example 1, except that the denaturation reaction was performed, a modified conjugated diene-based polymer at both ends was prepared.

Comparative Example 4

In Example 1, in place of 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine) as a denaturing agent, n -3.3-(piperazin-1,4-diyl)bis(N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine)((3,3-(piperazine-1, A solution in which 20% by weight of 4-diyl)bis(N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine)) is dissolved is added to the third reactor at a rate of 135 g/h for a denaturation reaction. Except for performing, it was carried out in the same manner as in Example 1, to prepare a modified conjugated diene-based polymer at both ends.

Experimental Example 1

^{1,2-vinyl bond content, weight average molecular weight (Mw, X10 3} g/mol), number average molecular weight (Mn, X10 ³ g) for each modified or unmodified conjugated diene polymer prepared in the above Examples and Comparative Examples /mol), molecular weight distribution (PDI, MWD), Mooney viscosity (MV), Mooney relaxation rate (-S/R), contents of Si atoms and N atoms, and retardation index were measured, respectively, and are shown in Table 1 below. .

1) 1,2-vinyl bond content

The vinyl content in each of the polymers was measured and analyzed using Varian VNMRS 500 MHz NMR.

In the NMR measurement, 1,1,2,2-tetrachloroethane was used as the solvent, and the solvent peak was calculated as 5.97 ppm, 7.2 to 6.9 ppm was random styrene, 6.9 to 6.2 ppm was block styrene, and 5.8 to 5.1 ppm was 1,4-vinyl, 5.1 to 4.5 ppm was calculated as the peak of 1,2-vinyl, and the 1,2-vinyl bond content (% by weight) was calculated.

2) Weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (MWD)

The weight average molecular weight (Mw) and number average molecular weight (Mn) were measured through GPC (Gel permeation chromatohraph) analysis, and the molecular weight distribution (PDI, MWD, Mw/Mn) was calculated from the measured molecular weights. Specifically, the GPC is used by combining two columns of PLgel Olexis (Polymer Laboratories) and one column of PLgel mixed-C (Polymer Laboratories), and when calculating the molecular weight, the GPC standard material is PS (polystyrene). It was carried out using. The GPC measurement solvent was prepared by mixing 2% by weight of an amine compound in tetrahydrofuran.

3) Mooney viscosity (MV) and Mooney relaxation rate (-S/R)

The Mooney viscosity (MV, (ML1+4, @100°C MU) was measured using a Rotor Speed 2±0.02 rpm, Large Rotor at 100°C using MV-2000 (ALPHA Technologies), and the sample used at this time Was left at room temperature (23±3℃) for at least 30 minutes, then 27±3 g was collected, filled inside the die cavity, and then measured for 4 minutes by operating the platen. The slope value of the change was measured to obtain a Mooney relaxation rate.

4) Content of Si atom

The Si content was measured using an inductively coupled plasma emission analyzer (ICP-OES; Optima 7300DV) as an ICP analysis method. In the case of using the inductively coupled plasma emission analyzer, 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, heated at 300° C. for 3 hours, and the sample In an electric furnace (Thermo Scientific, Lindberg Blue M), after the conversation was conducted in the program of steps 1 to 3 below,

1) step 1: initial temp 0℃, rate (temp/hr) 180 ℃/hr, temp(holdtime) 180℃ (1hr)

2) step 2: initial temp 180℃, rate (temp/hr) 85 ℃/hr, temp(holdtime) 370℃ (2hr)

3) step 3: initial temp 370℃, rate (temp/hr) 47 ℃/hr, temp(holdtime) 510℃ (3hr)

Add 1 mL of concentrated nitric acid (48 wt%) and 20 µl of concentrated hydrofluoric acid (50 wt%) to the residue, seal the platinum crucible, shake it for 30 minutes or more, and add 1 mL of boric acid to the sample. Then, the mixture was stored at 0° C. for 2 hours or more, and then diluted in 30 mL of ultrapure water, followed by inhalation and measured.

5) N atom content

The N content may be measured using an NSX analysis method as an example, and the NSX analysis method may be measured using a trace nitrogen quantitative analyzer (NSX-2100H).

For example, when using the trace nitrogen quantitative analyzer, turn on the trace nitrogen quantitative analyzer (Auto sampler, Horizontal furnace, PMT & Nitrogen detector), Ar 250 ml/min, O ₂ 350 ml/min, ozonizer 300 ml/ After setting the carrier gas flow rate in min, and setting the heater to 800°C, wait for about 3 hours to stabilize the analyzer. After the analyzer is stabilized, use the Nitrogen standard (AccuStandard S-22750-01-5 ml) to prepare calibration curves for the ranges of 5 ppm, 10 ppm, 50 ppm, 100 ppm and 500 ppm, and obtain the area corresponding to each concentration. After that, a straight line was created using the ratio of the density to the area. Thereafter, a ceramic boat containing 20 mg of a sample was placed on the auto sampler of the analyzer and measured to obtain an area. The N content was calculated using the obtained sample area and the calibration curve.

6) phase difference index

From the Tan δ graph for the frequency (Hz) obtained by measuring at 160℃ and 7% strain (0.5 degree) using SCARABAEUS INSTRUMENTS SYSTEMS (SIS) V-50 Rubber Process Analyzer of SCARABAEUS It represents the Tan δ value at 0.1 Hz. Specifically, about 6 g of a polymer is prepared, placed on a disk, and measured using the analyzer under the above conditions to obtain a Tan δ graph for frequency (Hz), where at 0.1 Hz The Tan δ value of was read and expressed as a phase difference index.

division 1,2-vinyl bond
(weight%) GPC MV -S/R Si
(ppm) N
(ppm) Phase difference index Mw(X10 ³ g/mol) Mn(X10 ³ g/mol) MWD Example 1 50 430 280 1.5 56 0.88 200 185 1.89 Example 2 50 440 282 1.6 55 0.82 210 175 1.93 Example 3 43 420 280 1.5 58 0.85 185 182 2.24 Comparative Example 1 50 428 285 1.5 54 0.78 36 15 1.95 Comparative Example 2 50 520 286 1.8 62 0.46 64 115 0.54 Comparative Example 3 50 485 282 1.7 59 0.48 85 112 0.56 Comparative Example 4 50 510 284 1.8 61 0.52 96 134 0.46

Example 4

85 parts by weight of the both-end modified conjugated diene polymer prepared in Example 1, based on 100 parts by weight of the rubber component, 15 parts by weight of natural rubber, and 90 parts by weight of silica (filler) using a Banbari mixer attached with a temperature control device And 6.4 parts by weight of a silane coupling agent (Si-69, Evonik) were kneaded to prepare a rubber composition.

Example 5

In Example 4, the rubber composition was carried out in the same manner as in Example 4, except that the modified conjugated diene-based polymer at both ends prepared in Example 2 was included instead of the modified conjugated diene-based polymer at both ends prepared in Example 1. Was prepared.

Example 6

In Example 4, the rubber composition was carried out in the same manner as in Example 4, except that the both ends modified conjugated diene-based polymer prepared in Example 3 was included instead of the both-end modified conjugated diene-based polymer prepared in Example 1. Was prepared.

Comparative Example 5

In Example 4, a rubber composition was prepared in the same manner as in Example 4, except that the unmodified conjugated diene-based polymer prepared in Comparative Example 1 was included instead of the both-end modified conjugated diene-based polymer prepared in Example 1. Was prepared.

Comparative Example 6

In Example 4, a rubber composition was prepared in the same manner as in Example 4, except that the modified conjugated diene-based polymer prepared in Comparative Example 2 was included instead of the modified conjugated diene-based polymer at both ends prepared in Example 1. I did.

Comparative Example 7

In Example 4, the rubber composition was carried out in the same manner as in Example 4, except that the modified conjugated diene-based polymer at both ends prepared in Comparative Example 3 was included instead of the modified conjugated diene-based polymer at both ends prepared in Example 1. Was prepared.

Comparative Example 8

In Example 4, the rubber composition was carried out in the same manner as in Example 4, except that the both ends modified conjugated diene-based polymer prepared in Comparative Example 4 was included instead of the both-end modified conjugated diene-based polymer prepared in Example 1. Was prepared.

Experimental Example 2

After preparing a rubber specimen using each rubber composition, which is a single-stage kneading composition prepared in the above Examples and Comparative Examples, tensile strength, 300% modulus, rolling resistance and abrasion resistance were measured in the following manner. The results are shown in Table 2 below.

To each of the above rubber compositions, 1.5 parts by weight of sulfur, 2.0 parts by weight of a rubber accelerator (DPD (diphenylguanine)), and 1.75 parts by weight of a vulcanization accelerator (CZ (N-cyclohexyl-2-benzothiazylsulfenamide)) were added and not more than 100°C. Mixing at a temperature of to obtain a blend. Thereafter, a rubber specimen was prepared through a curing process at 160° C. for 20 minutes. In this case, the parts by weight are expressed based on 100 parts by weight of the rubber component when the rubber composition is prepared.

1) tensile properties

For tensile properties, each test piece was prepared according to the tensile test method of ASTM 412, and the tensile strength at the time of cutting and the tensile stress at the time of 300% elongation (300% modulus) were measured. Specifically, tensile properties were measured at a rate of 50 cm/min at room temperature using a Universal Test Machin 4204 (Instron) tensile tester.

2) Rolling resistance characteristics

Rolling resistance characteristics were confirmed through viscoelastic characteristics analysis. For viscoelastic properties, the tan δ value was confirmed by measuring the viscoelastic behavior against dynamic deformation at a frequency of 10 Hz and each measurement temperature (-60℃~60℃) in Film Tension mode using a dynamic mechanical analyzer (GABO). At this time, the lower the high-temperature 60°C tan δ value, the less hysteresis loss and excellent rolling resistance characteristics (fuel economy). Since it is expressed by indexing (Index, %) through Equation 2, the higher the value, the better.

[Equation 2]

Index(%)=(reference value/measured value)X100

3) Wear resistance (DIN wear test)

For each rubber specimen, a DIN wear test was conducted in accordance with ASTM D5963, and DIN wt loss index (loss volume index): ARIA (Abration resistance index, Method A) based on the measured value of Comparative Example 1. The higher the value, the better it is.

As shown in Table 2, Examples 4 to 6 according to an embodiment of the present invention have excellent tensile properties compared to Comparative Examples 5 to 8, and at the same time, Tan δ and abrasion resistance at 60° C. are significantly improved.

At this time, Examples 4 to 6 are modified in Examples 1 to 3 in which 1,2-vinyl bond content, Mooney viscosity, Mooney relaxation rate, Si atom and N atom content, and retardation index are adjusted to a specific range suggested by the present invention. Conjugated diene polymer is included, and Comparative Examples 5 to 8 are in a specific range suggested by at least one of the above 1,2-vinyl bond content, Mooney viscosity, Mooney relaxation rate, Si atom and N atom content, and retardation index. It contains the modified conjugated diene polymer of Comparative Examples 1 to 4 which is not controlled.

The above result is that the modified conjugated diene-based polymer of the present invention has a 1,2-vinyl bond content, Mooney viscosity, Mooney relaxation rate, Si atom and N atom content, and retardation index adjusted to a specific range, thereby being applied to a rubber composition. This means that there is an effect of improving the rolling resistance and abrasion resistance without deteriorating the tensile properties of the rubber composition.

Claims (11)

Modified conjugated diene polymer satisfying the conditions of the following i) to v):
I) 1,2-vinyl bond content: 40% by weight or more,
Ii) Mooney viscosity measured under ASTM D1646 conditions: 40 to 100,
Iii) Phase difference index at 0.1 Hz measured at 160°C: 0.65 or more,
Iv) Si atom and N atom content: 50 ppm or more based on the total weight of the polymer, and
V) Mooney relaxation rate measured at 100°C: 0.5 or more.
The method of claim 1,
The modified conjugated diene polymer having a Mooney relaxation rate measured at 100°C of 0.5 to 1.2.
The method of claim 1,
The modified conjugated diene polymer having a retardation index of 0.65 to 5 at 0.1 Hz measured at 160°C.
The method of claim 1,
A modified conjugated diene-based polymer having a number average molecular weight (Mn) of 1,000 g/mol to 2,000,000 g/mol and a weight average molecular weight (Mw) of 1,000 g/mol to 3,000,000 g/mol.
The method of claim 1,
The modified conjugated diene-based polymer in which the 1,2-vinyl bond content in the polymer is 40% by weight or more and 55% by weight or more.
The method of claim 1,
Modified conjugated diene polymer having a molecular weight distribution of 1.5 to 3.5.
The method of claim 1,
A modified conjugated diene-based polymer comprising a functional group derived from a modification initiator at one end and a functional group derived from a modifying agent at the other end.
A rubber composition comprising the modified conjugated diene polymer according to claim 1 and a filler.
The method of claim 8,
The filler is a silica-based filler or a carbon black-based filler.
The method of claim 8,
A rubber composition comprising 0.1 to 200 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene-based polymer.
The method of claim 7,
A rubber composition comprising a vulcanizing agent.