阅读说明：本技术 改性共轭二烯类聚合物、其制备方法和包含其的橡胶组合物 (Modified conjugated diene polymer, method for producing same, and rubber composition containing same ) 是由 金贤俊 李鲁美 文珉植 金鲁马 于 2020-09-29 设计创作，主要内容包括：本发明涉及一种改性共轭二烯类聚合物和包含该改性共轭二烯类聚合物的橡胶组合物,并且涉及改性共轭二烯类聚合物、其制备方法和包括其的橡胶组合物,所述改性共轭二烯类聚合物可以具有1500MU-s以上的门尼大松弛面积,并且在混配到橡胶组合物中之后具有高分子量和低门尼粘度,因此在制造轮胎过程中具有优异的可加工性,具有良好的物理性能例如拉伸性能,以及优异的粘弹性性能。(The present invention relates to a modified conjugated diene-based polymer which can have a mooney large relaxation area of 1500MU-s or more and has a high molecular weight and a low mooney viscosity after being compounded into a rubber composition, and thus has excellent processability in manufacturing a tire, good physical properties such as tensile properties, and excellent viscoelastic properties, and a rubber composition comprising the same, a method for producing the same, and a rubber composition comprising the same.)

1. A modified conjugated diene-based polymer having a Mooney Large Relaxation Area (MLRA) of 1500MU-s or more, which is measured at 100 ℃ and represented by the following numerical formula 1:

[ mathematical formula 1]

In the case of the mathematical formula 1,

a is the Mooney Large Relaxed Area (MLRA),

k is a Mooney intercept after 1 second from the stop of the rotor of the Mooney viscometer,

a is a Mooney relaxation ratio of,

t_ois the starting point of the mooney relaxation,

t_fis the end point of mooney relaxation.

2. The modified conjugated diene-based polymer according to claim 1, wherein the mooney large relaxation area is 1500 to 4000 MU-s.

3. The modified conjugated diene polymer according to claim 1, which contains a functional group derived from an aminoalkoxysilane-based modifier and an epoxy-based modifier at least one terminal.

4. The modified conjugated diene-based polymer according to claim 3, wherein the aminoalkoxysilane-based modifier is one or more compounds selected from the group consisting of compounds represented by the following formulae 1 to 3:

[ formula 1]

In the formula 1, the first and second groups,

R_a1and R_a4Each independently a single bond or an alkylene group of 1 to 10 carbon atoms,

R_a2and R_a3Each independently an alkyl group of 1 to 10 carbon atoms,

R_a5is a hydrogen atom, an alkyl group of 1 to 10 carbon atoms, a mono-, di-or tri-substituted alkylsilyl group substituted with an alkyl group of 1 to 10 carbon atoms, or is-N [ R ]_a6Si(OR_a7)_n3(R_a8)_3-n3]₂Wherein R is_a6Is a single bond or alkylene of 1 to 10 carbon atoms, R_a7And R_a8Each independently an alkyl group of 1 to 10 carbon atoms, and n3 is an integer of 1 to 3,

n1 is an integer from 1 to 3, an

n2 is an integer from 0 to 2,

[ formula 2]

In the formula 2, the first and second groups,

R_b2to R_b4Each independently an alkylene group of 1 to 10 carbon atoms,

R_b5to R_b8Each independently an alkyl group of 1 to 10 carbon atoms,

R_b13and R_b14Each independently an alkylene group of 1 to 10 carbon atoms,

R_b15to R_b18Each independently an alkyl group of 1 to 10 carbon atoms, and

m1, m2, m3 and m4 are each independently an integer of 1 to 3,

[ formula 3]

In the formula 3, the first and second groups,

R_e1and R_e2Each independently an alkylene group of 1 to 10 carbon atoms,

R_e3to R_e6Each independently hydrogen, alkyl of 1 to 10 carbon atoms or-R_e7SiR_e8R_e9R_e10Wherein R is_e3To R_e6At least one of which is-R_e7SiR_e8R_e9R_e10And R is_e7Is a single bond or alkylene of 1 to 10 carbon atoms, and

R_e8to R_e10Each independently is an alkyl group of 1 to 10 carbon atoms or an alkoxy group of 1 to 10 carbon atoms, wherein R_e8To R_e10At least one of which is an alkoxy group of 1 to 10 carbon atoms.

5. The modified conjugated diene-based polymer according to claim 3, wherein the epoxy-based modifier is one or more compounds selected from the group consisting of compounds represented by the following formulae 4 to 7:

[ formula 4]

In the formula 4, the first and second organic solvents are,

R_d1to R_d3Each independently hydrogen, alkyl of 1 to 10 carbon atoms or-R_d4R_d5Wherein R is_d1To R_d3At least one of which is-R_d4R_d5；R_d4Is an alkylene group of 1 to 10 carbon atoms, which alkylene group may or may not contain heteroatoms; and R_d5Is an epoxy group, and is,

[ formula 5]

In the formula 5, the first and second groups,

R_e1and R_e2Each independently an alkylene group of 1 to 10 carbon atoms, and

R_e3to R_e6Each independently hydrogen, alkyl of 1 to 10 carbon atoms or-R_e7R_e8Wherein R is_e3To R_e6At least one of which is-R_e7R_e8；R_e7Is alkylene of 1 to 10 carbon atoms, which alkylene group contains or does not contain one or more heteroatoms selected from N, S and O; and R_e8Is an epoxy group, and is,

[ formula 6]

In the case of the formula 6, the,

x is O or S, and X is O or S,

R_f1and R_f2Each independently a single bond or an alkylene group of 1 to 10 carbon atoms, and

R_f3to R_f8Each independently is hydrogen, alkyl of 1 to 15 carbon atoms, alkoxy of 1 to 10 carbon atoms, aryl of 6 to 10 carbon atoms, cycloalkyl of 5 to 10 carbon atoms, aralkyl of 7 to 14 carbon atomsor-R_f9R_f10Wherein R is_f3To R_f8At least one of which is-R_f9R_f10，R_f9Is an alkylene group of 1 to 12 carbon atoms, which alkylene group may or may not contain heteroatoms; and R_f10Is an epoxy group, and is,

[ formula 7]

In the formula 7, the first and second groups,

R_g1to R_g4Each independently hydrogen, alkyl of 1 to 10 carbon atoms, alkoxy of 1 to 10 carbon atoms, aryl of 6 to 12 carbon atoms or-R_g5OR_g6Wherein R is_g1To R_g4At least one of which is-R_g5OR_g6，R_g5Is a single bond or alkylene of 1 to 10 carbon atoms, and R_g6Is an alkylene oxide group of 3 to 10 carbon atoms, and

y is C or N, wherein if Y is N, R_g4Is absent.

6. The modified conjugated diene-based polymer according to claim 1, wherein the modified conjugated diene-based polymer has a number average molecular weight (Mn) of 100,000 to 2,000,000g/mol, a weight average molecular weight (Mw) of 100,000 to 3,000,000g/mol, and a molecular weight distribution (PDI) of 1.5 or more.

7. The modified conjugated diene polymer according to claim 1, wherein the conjugated diene polymer is a homopolymer of a conjugated diene monomer or a copolymer of a conjugated diene monomer and an aromatic vinyl monomer.

8. A production method of the modified conjugated diene-based polymer according to claim 1, comprising:

s1: polymerizing a conjugated diene monomer or an aromatic vinyl monomer and a conjugated diene monomer in a hydrocarbon solvent in the presence of a polymerization initiator to prepare a living polymer; and

s2: reacting or coupling the living polymer prepared in step S1 with a first modifier and a second modifier,

wherein the first modifier is an aminoalkoxysilane-based modifier and the second modifier is an epoxy-based modifier.

9. The method for producing a modified conjugated diene-based polymer according to claim 8, wherein the polymerization initiator is used in an amount of 0.01mmol to 10mmol based on 100g of the monomer.

10. The method for producing a modified conjugated diene-based polymer according to claim 8, wherein the first modifier and the second modifier are injected sequentially or in batches to react or couple with the active polymer, and

the first modifier and the second modifier are used in a molar ratio of 10:1 to 5: 1.

11. The method for producing a modified conjugated diene-based polymer according to claim 8, wherein the total amount of the modifier used is 0.01mmol to 10mmol based on 100g of the total monomers, and

the total amount of the modifier is the total amount of the first modifier and the second modifier.

12. A rubber composition comprising the modified conjugated diene-based polymer according to claim 1 and a filler.

13. The rubber composition according to claim 12, wherein the rubber composition contains the filler in an amount of 0.1 to 200 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer.

Technical Field

[ Cross-reference to related applications ]

This application claims benefit based on the priority of korean patent application No.10-2019-0121197, filed on 30.9.9.2019, the entire contents of which are incorporated herein by reference.

[ technical field ]

The present invention relates to a modified conjugated diene-based polymer having excellent processability and good tensile strength and viscoelastic properties, and a rubber composition comprising the modified conjugated diene-based polymer.

Background

In accordance with recent demand for automobiles with low fuel consumption rates, conjugated diene-based polymers having modulation stability represented by wet skid resistance and low rolling resistance as well as excellent abrasion resistance and tensile properties are required as rubber materials for tires.

In order to reduce the rolling resistance of a tire, there is a method of reducing the hysteresis loss of a vulcanized rubber, and rebound resilience, tan δ, Goodrich heat generation (Goodrich heating) and the like at 50 ℃ to 80 ℃ are used as evaluation indexes of the vulcanized rubber. That is, it is desirable to use a rubber material having high resilience or low tan δ value or Goodrich heat generation at the above temperature.

Natural rubber, polyisoprene rubber or polybutadiene rubber is known as a rubber material having a low hysteresis loss, but these rubbers have a limitation of low wet skid resistance. Therefore, recently, conjugated diene-based polymers or copolymers such as styrene-butadiene rubber (hereinafter referred to as "SBR") and butadiene rubber (hereinafter referred to as "BR") are produced by emulsion polymerization or solution polymerization to be used as rubber for tires. Among these polymerization methods, the solution polymerization has the greatest advantage over the emulsion polymerization that the vinyl structure content and styrene content, which determine the physical properties of the rubber, can be arbitrarily adjusted, and the molecular weight and physical properties thereof can be controlled by coupling or modification. Therefore, SBR prepared by solution polymerization is widely used as a rubber material for tires, since the structure of SBR or BR finally prepared is easily changed, and the movement of chain ends can be reduced and the coupling force with fillers such as silica and carbon black can be improved by coupling or modification of the chain ends.

If solution-polymerized SBR is used as a rubber material for tires, since the glass transition temperature of rubber is increased by increasing the vinyl content in SBR, physical properties required for tires, such as running resistance and braking force, can be controlled, and fuel consumption can be reduced by appropriately adjusting the glass transition temperature. The solution-polymerized SBR is prepared by using an anionic polymerization initiator, and is used by coupling or modifying chain ends of the polymer thus formed using various modifiers. For example, U.S. patent No.4,397,994 discloses a method of coupling living anions at the ends of polymer chains using a coupling agent such as a tin compound, which is obtained by polymerizing styrene-butadiene using an alkyllithium that is a monofunctional initiator in a nonpolar solvent.

Meanwhile, the polymerization of SBR or BR may be carried out by batch polymerization or continuous polymerization. According to the batch polymerization, the molecular weight distribution of the polymer thus produced is narrow and advantageous in improvement of physical properties, but there are problems of low productivity and deteriorated processability. According to the continuous polymerization, the polymerization is continuously carried out and is advantageous in terms of excellent productivity and improvement of processability, but there are problems of wide molecular weight distribution and poor physical properties. Therefore, there is a continuous need for research on improving productivity, processability, and physical properties simultaneously in the process of preparing SBR or BR.

[ Prior art documents ]

(patent document 1) US 4397994A

Disclosure of Invention

Technical problem

The present invention is designed to solve the above-mentioned problems of the conventional art, and an object of the present invention is to provide a modified conjugated diene-based polymer having a high molecular weight and a controlled mooney large relaxation area, and having a low mooney viscosity and excellent processability in manufacturing a tire after compounding into a rubber composition, having good physical properties such as tensile properties, and excellent viscoelasticity, a method for producing the same, and a rubber composition comprising the same.

Technical scheme

In order to solve the above-mentioned task, according to an embodiment of the present invention, there is provided a modified conjugated diene-based polymer having a Mooney Large Relaxation Area (MLRA) as measured at 100 ℃ and represented by the following numerical formula 1 of 1500MU-s or more:

[ mathematical formula 1]

In the case of the mathematical formula 1,

a is the Mooney Large Relaxed Area (MLRA),

k is a Mooney intercept (Mooney intercept) after 1 second from the stop of the rotor of the Mooney viscometer,

a is a Mooney relaxation ratio of,

t_ois the starting point of the mooney relaxation,

t_fis the end point of mooney relaxation.

In addition, the present invention provides a method for producing a modified conjugated diene polymer, comprising: preparing a living polymer by polymerizing a conjugated diene monomer or an aromatic vinyl monomer and a conjugated diene monomer in a hydrocarbon solvent in the presence of a polymerization initiator (S1); and reacting or coupling the living polymer prepared in the step (S1) with a first modifier and a second modifier (S2), wherein the first modifier is an aminoalkoxysilane-based modifier and the second modifier is an epoxy-based modifier.

Further, the present invention provides a rubber composition comprising the above-mentioned modified conjugated diene-based polymer and a filler.

Advantageous effects

The modified conjugated diene-based polymer according to the present invention has a mooney large relaxation area of 1500MU-s or more and a high molecular weight, but may have a low mooney viscosity after compounded into a rubber composition, and therefore, the modified conjugated diene-based polymer has excellent processability, as well as good tensile properties and viscoelasticity.

In addition, the modified conjugated diene-based polymer according to the present invention contains functional groups derived from both modifiers at least one terminal thereof, thereby further improving tensile properties and viscoelastic properties.

Further, the method for producing a modified conjugated diene-based polymer according to the present invention includes a step of reacting or coupling a living polymer together with a first modifier and a second modifier, and can easily produce a modified conjugated diene-based polymer having a mooney large relaxation area controllable to the above range, containing functional groups in the molecule from the first modifier and the second modifier, and having excellent processability, tensile properties and viscoelastic properties.

Further, the rubber composition according to the present invention comprises the modified conjugated diene-based polymer having the above-mentioned Mooney large relaxation area, and a molded article having excellent processability, tensile properties and viscoelastic properties can be produced.

Detailed Description

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

It is to be understood that the words or terms used in the specification and claims of this invention should not be construed as meanings defined in commonly used dictionaries. It is further understood that the words or terms should be interpreted as having a meaning that is consistent with their meaning in the technical idea of the present invention, based on the principle that the inventor can appropriately define the meaning of the words or terms to best explain the present invention.

[ definition of terms ]

The term "Mooney Large Relaxation Area (MLRA)" as used in the present invention is a measure of chain relaxation in a molten polymer and may indicate that longer or more branched polymer chains may store more energy and take longer to relax after removing the applied deformation. For example, the mooney large relaxation area of an ultra-high molecular weight or long chain branched polymer may be greater than the mooney large relaxation area of a polymer having a broader or narrower molecular weight when compared to a polymer having the same mooney viscosity.

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

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

The term "alkylene" used in the present invention may refer to a divalent aliphatic saturated hydrocarbon group such as methylene, ethylene, propylene and butylene.

The term "cycloalkyl" used in the present invention may be a cyclic saturated hydrocarbon group.

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

The term "heterocyclyl" as used herein is a cyclic saturated hydrocarbon group or a cyclic unsaturated hydrocarbon group containing one or more unsaturated bonds, wherein the carbon atoms in the hydrocarbon group may be substituted with one or more heteroatoms, and the heteroatoms may be selected from N, O and S.

The term "monovalent hydrocarbon group" used in the present invention denotes a monovalent substituent group derived from a hydrocarbon group, and may refer to a carbon-and hydrogen-bonded monovalent radical group such as an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group having one or more unsaturated bonds, and an aryl group, and the monovalent radical group may have a linear or branched structure depending on the structure of its bond.

The term "divalent hydrocarbon group" used in the present invention denotes a divalent substituent derived from a hydrocarbon group, and may refer to a divalent radical bonded to carbon and hydrogen, such as alkylene, alkenylene, alkynylene, cycloalkylene having one or more unsaturated bonds, and arylene, and the divalent radical may have a linear or branched structure depending on the structure of the bond.

The term "single bond" as used in the present invention may refer to a single covalent bond per se that does not include a separate atomic or molecular group.

The terms "unit from … …" and "functional group from … …" as used herein may refer to a moiety or a structure from a particular substance, or the substance itself.

[ measurement method and conditions ]

In the present disclosure, "weight average molecular weight (Mw)", "number average molecular weight (Mn)" and "Molecular Weight Distribution (MWD)" are measured by Gel Permeation Chromatography (GPC) analysis and by checking a molecular weight distribution curve. The molecular weight distribution (PDI, MWD, Mw/Mn) was calculated from each measured molecular weight. Specifically, GPC uses two PLgel oxides columns (Polymer Laboratories Co.) and one PLgel mixed-C column (Polymer Laboratories Co.) in combination, and uses Polystyrene (PS) as a GPC standard substance for calculating molecular weight, and tetrahydrofuran mixed with 2 wt% of an amine compound as a GPC measurement solvent.

Modified conjugated diene polymer

The present invention provides a modified conjugated diene-based polymer which has a low mooney viscosity after compounded into a rubber composition, and realizes excellent processability as well as excellent tensile properties and viscoelastic properties, although it is a polymer having a high molecular weight.

The modified conjugated diene-based polymer according to one embodiment of the present invention is characterized in that the Mooney Large Relaxation Area (MLRA) of the modified conjugated diene-based polymer measured at 100 ℃ and represented by the following numerical formula 1 is 1500MU-s or more:

[ mathematical formula 1]

In the case of the mathematical formula 1,

a is the Mooney Large Relaxed Area (MLRA),

k is a Mooney intercept after 1 second from the stop of the rotor of the Mooney viscometer,

a is a Mooney relaxation ratio of,

t_ois the starting point of the mooney relaxation,

t_fis the end point of mooney relaxation.

Here, the starting point of the mooney relaxation may mean a point after 1 second from the stop of the rotor operation, and may refer to a point at which the mooney torque has a k value. In addition, the end point of the Mooney relaxation can be expressed in a Mooney relaxation measurement testPoint of completion of the measurement of mooney relaxation. I.e. t_f-t_oMay represent the mooney relaxation time.

Further, according to an embodiment of the present invention, t_oMay be 1 second, t_fAnd may be 80 seconds to 150 seconds. In other words, the mooney large relaxation area according to one embodiment of the present invention may be an integrated area under the mooney torque-relaxation time curve from 1 second to 80 seconds to 150 seconds. In addition, t_fAnd may specifically be 90 seconds to 130 seconds, or 100 seconds to 120 seconds.

Meanwhile, the molecular weight of the polymer and the physical properties of the mooney viscosity are properties in a proportional relationship and show an equal tendency, whereas the polymer having a high molecular weight has drawbacks of high mooney viscosity and poor processability. However, the modified conjugated diene-based polymer according to one embodiment of the present invention has a mooney large relaxation area of 1500MU-s or more, and realizes greatly improved processability.

In the modified conjugated diene-based polymer of the present invention, a Mooney large relaxation area of 1500MU-s or more is a technical means for providing excellent processability and excellent tensile properties and viscoelastic properties. The objective effect of the present invention can be exhibited if the Mooney large relaxation area is 1500MU-s or more. However, if the mooney large relaxation area has a very large value, the processability may be deteriorated, and the mooney large relaxation area of the modified conjugated diene-based polymer according to one embodiment of the present invention may be 4000MU-s or less in view of exhibiting excellent processability and excellent balance of tensile properties and viscoelastic properties.

Specifically, the modified conjugated diene-based polymer according to one embodiment of the present invention may have a mooney large relaxation area of 1500MU-s or more, preferably 1500 to 4000MU-s, more preferably 1800 to 3000MU-s, 2000 to 2800MU-s or 2400 to 2800 MU-s. The Mooney large relaxation area may be a value obtained by plotting a Mooney torque according to time and then calculating from mathematical formula 1, in which case the Mooney viscosity (MV, ML1+4, @100 ℃) may be measured at 100 ℃ using a large rotor at a rotor speed of 2 + -0.02 rpm by using MV-2000(ALPHA Technologies Co.). In this case, the sample was left at room temperature (23. + -. 3 ℃ C.) for 30 minutes or more, 27. + -.3 g of the polymer was collected and put into a cavity, and then measurement was performed for 4 minutes while operating a Platen (Platen).

Further, after the mooney viscosity is measured, by measuring a gradient value of a change in mooney viscosity exhibited when the torque is released by stopping the rotor, an absolute value thereof can be obtained as the mooney relaxation ratio (a). In addition, the Mooney large relaxation area can be controlled from 1 second (t) after stopping the rotor_o) To 120 seconds (t)_f) The integral value of the mooney relaxation curve of the period is obtained, and the integral value can be calculated by mathematical formula 1. If the Mooney relaxation area satisfies the above range, an effect of improving the processability in compounding the rubber composition can be achieved. In particular, if the mooney large relaxation area satisfies the above range under the condition that the mooney viscosity is 70 or more, preferably 80 or more, the effect of improving the processability even more can be achieved.

In addition, the modified conjugated diene-based polymer according to an embodiment of the present invention may be a homopolymer of a conjugated diene-based monomer, or a copolymer of a conjugated diene-based monomer and an aromatic vinyl-based monomer, where the homopolymer of a conjugated diene-based monomer may refer to a polymer including a repeating unit derived from a conjugated diene-based monomer, which is formed by polymerizing a conjugated diene-based monomer, and the copolymer may refer to a copolymer including a repeating unit derived from a conjugated diene-based monomer and a repeating unit derived from an aromatic vinyl-based monomer, which is formed by copolymerizing a conjugated diene-based monomer and an aromatic vinyl-based monomer. The conjugated diene monomer may be one or more selected from the group consisting of 1, 3-butadiene, 2, 3-dimethyl-1, 3-butadiene, piperylene, 3-butyl-1, 3-octadiene, isoprene, 2-phenyl-1, 3-butadiene and 2-halo-1, 3-butadiene (halo means a halogen atom).

The aromatic vinyl monomer may include, for example, one or more selected from the group consisting of styrene, α -methylstyrene, 3-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (p-methylphenyl) styrene, 1-vinyl-5-hexylnaphthalene, 3- (2-pyrrolidinylethyl) styrene, 4- (2-pyrrolidinylethyl) styrene and 3- (2-pyrrolidinyl-1-methylethyl) - α -methylstyrene.

In another embodiment, 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 a conjugated diene-based monomer. The repeating unit derived from a diene-based monomer 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. If the modified conjugated diene-based polymer is a copolymer further containing a diene-based monomer, the modified conjugated diene-based polymer may contain more than 0% by weight to 1% by weight, more than 0% by weight to 0.1% by weight, more than 0% by weight to 0.01% by weight, or more than 0% by weight to 0.001% by weight of a repeating unit derived from a diene-based monomer, within which range an effect of preventing formation of gel may be obtained.

In addition, if the modified conjugated diene-based polymer is a copolymer, the copolymer may be a random copolymer, in which case an excellent balance effect between physical properties can be achieved. Random copolymers may refer to the arrangement of repeat units forming the copolymer in a disorder.

In addition, the modified conjugated diene-based polymer according to the present invention may contain a functional group derived from an aminoalkoxysilane-based modifier and a functional group derived from an epoxy-based modifier at least one terminal.

In general, the modified conjugated diene-based polymer is prepared by modifying the terminal of the conjugated diene-based polymer with an aminoalkoxysilane-based modifier to improve the affinity with the filler and the viscoelastic properties. However, there are problems as follows: the modified conjugated diene-based polymer modified with the aminoalkoxysilane-based modifier exhibits improved viscoelastic properties, but exhibits reduced tensile properties and processability.

In contrast, the modified conjugated diene-based polymer according to an embodiment of the present invention, which contains both a functional group derived from an aminoalkoxysilane-based modifier and a functional group derived from an epoxy-based modifier, can realize excellent tensile properties and processability as well as greatly improved viscoelastic properties.

In another embodiment, the modified conjugated diene-based polymer according to one embodiment of the present invention may include at least one first polymer chain including a functional group derived from an aminoalkoxysilane-based modifier at one end and at least one second polymer chain including a functional group derived from an epoxy-based modifier at one end.

Meanwhile, specific examples of the modifier may include a modifier having affinity with silica. The modifier having affinity with silica may be a modifier containing a functional group having affinity with silica in a compound used as the modifier, and the functional group having affinity with silica may be a functional group having excellent affinity with a filler, particularly a silica-based filler, and being capable of causing interaction between the silica-based filler and the functional group derived from the modifier.

Specifically, according to an embodiment of the present invention, the aminoalkoxysilane-based modifier may be one or more selected from the group consisting of compounds represented by the following formulas 1 to 3.

[ formula 1]

In the formula 1, the first and second groups,

R_a1and R_a4Each independently a single bond or an alkylene group of 1 to 10 carbon atoms,

R_a2and R_a3Each independently an alkyl group of 1 to 10 carbon atoms,

R_a5is a hydrogen atom, an alkyl group of 1 to 10 carbon atoms, an alkylsilyl group which is mono-, di-or tri-substituted with an alkyl group of 1 to 10 carbon atoms, or is-N [ R ]_a6Si(OR_a7)_n3(R_a8)_3-n3]₂Wherein R is_a6Is a single bond or alkylene of 1 to 10 carbon atoms, R_a7And R_a8Each independently an alkyl group of 1 to 10 carbon atoms, and n3 is an integer of 1 to 3,

n1 is an integer from 1 to 3, an

n2 is an integer from 0 to 2,

[ formula 2]

In formula 2, R_b2To R_b4Each independently an alkylene group of 1 to 10 carbon atoms, R_b5To R_b8Each independently is an alkyl group of 1 to 10 carbon atoms, R_b13And R_b14Each independently an alkylene group of 1 to 10 carbon atoms, R_b15To R_b18Each independently an alkyl group of 1 to 10 carbon atoms, and m1, m2, m3 and m4 each independently an integer of 1 to 3,

[ formula 3]

In formula 3, R_e1And R_e2Each independently an alkylene group of 1 to 10 carbon atoms, R_e3To R_e6Each independently hydrogen, alkyl of 1 to 10 carbon atoms or-R_e7SiR_e8R_e9R_e10Wherein R is_e3To R_e6At least one of which is-R_e7SiR_e8R_e9R_e10，R_e7Is a single bond or alkylene of 1 to 10 carbon atoms, and R_e8To R_e10Each independently is an alkyl group of 1 to 10 carbon atoms or an alkoxy group of 1 to 10 carbon atoms, wherein R_e8To R_e10At least one of which is an alkoxy group of 1 to 10 carbon atoms.

Specifically, in formula 1, R_a1And R_a4Each independently is a single bond or an alkylene group of 1 to 5 carbon atoms; r_a2And R_a3Each independently an alkyl group of 1 to 5 carbon atoms; r_a5Is a hydrogen atom, an alkyl group of 1 to 5 carbon atoms, a trialkylsilyl group substituted by an alkyl group of 1 to 5 carbon atoms, or is-N [ R ]_a6Si(OR_a7)_n3(R_a8)_3-n3]₂Wherein R is_a6Is a single bond or alkylene of 1 to 5 carbon atoms, R_a7And R_a8Each independently is an alkyl group of 1 to 5 carbon atoms, n3 is an integer from 2 to 3, n1 is an integer from 2 to 3, and n2 can be an integer from 0 to 2.

More specifically, the compound represented by formula 1 may be selected from the group consisting of N, N-bis (3- (dimethoxy (methyl) silyl) propyl) -methyl-1-amine, N-bis (3- (diethoxy (methyl) silyl) propyl) -methyl-1-amine, N-bis (3- (trimethoxysilyl) propyl) -methyl-1-amine, N-bis (3- (triethoxysilyl) propyl) -methyl-1-amine, N-diethyl-3- (trimethoxysilyl) -propan-1-amine, N-diethyl-3- (triethoxysilyl) -propan-1-amine, N-dimethyl-propyl-1-amine, N-dimethyl-methyl-1-amine, N-bis (3- (triethoxysilyl) propyl) -propan-1-amine, N-bis (triethoxy-propyl) -propan-1-amine, N-bis (3- (triethoxy silyl) propyl) -propan-1-amine, N-bis (3- (triethoxy) propyl) -propan-bis (3-1-amino) propan-yl) -propan-amide, N, tris (trimethoxysilyl) amine, tris (3- (trimethoxysilyl) propyl) amine, N-bis (3- (diethoxy (methyl) silyl) propyl) -1,1, 1-trimethylsilylamine and N¹,N¹,N³,N³-one or more of tetrakis (3- (trimethoxysilyl) propyl) propane-1, 3-diamine.

In another embodiment, in formula 2, R_b2To R_b4Each independently an alkylene group of 1 to 6 carbon atoms, R_b5To R_b8Each independently is an alkyl group of 1 to 6 carbon atoms, R_b13And R_b14Each independently an alkylene group of 1 to 6 carbon atoms, R_b15To R_b18Each independently is an alkyl group of 1 to 6 carbon atoms, and m1, m2, m3 and m4 each independently is an integer of 1 to 3.

More specifically, the compound represented by formula 2 may be 3,3' - (piperazine-1, 4-diyl) bis (N, N-bis (3- (triethoxysilyl) propyl) propan-1-amine).

In another embodimentIn formula 3, R_e1And R_e2Each independently an alkylene group of 1 to 6 carbon atoms, R_e3To R_e6Each independently is alkyl of 1 to 6 carbon atoms or-R_e7SiR_e8R_e9R_e10Wherein R is_e3To R_e6At least one of which is-R_e7SiR_e8R_e9R_e10，R_e7Is a single bond or alkylene of 1 to 6 carbon atoms, and R_e8To R_e10Each independently is an alkyl group of 1 to 6 carbon atoms or an alkoxy group of 1 to 6 carbon atoms, wherein R_e8To R_e10At least one of which is an alkoxy group of 1 to 6 carbon atoms.

More specifically, the compound represented by formula 3 may be N, N' - (cyclohexane-1, 3-diylbis (methylene)) bis (3- (triethoxysilyl) -N- (3- (triethoxysilyl) propyl) propan-1-amine).

According to an embodiment of the present invention, the epoxy-based modifier may be selected from compounds represented by the following formulae 4 to 7:

[ formula 4]

In the formula 4, the first and second organic solvents are,

R_d1to R_d3Each independently hydrogen, alkyl of 1 to 10 carbon atoms or-R_d4R_d5Wherein R is_d1To R_d3At least one of which is-R_d4R_d5；R_d4Is an alkylene group of 1 to 10 carbon atoms, which alkylene group may or may not contain heteroatoms; and R_d5Is an epoxy group, and is,

[ formula 5]

In the formula 5, the first and second groups,

R_e1and R_e2Each independently of the other being 1 to 10 carbon atomsAlkylene, and

R_e3to R_e6Each independently hydrogen, alkyl of 1 to 10 carbon atoms or-R_e7R_e8Wherein R is_e3To R_e6At least one of which is-R_e7R_e8；R_e7Is alkylene of 1 to 10 carbon atoms, which alkylene group contains or does not contain one or more heteroatoms selected from N, S and O; and R_e8Is an epoxy group, and is,

[ formula 6]

In the case of the formula 6, the,

x is O or S, and X is O or S,

R_f1and R_f2Each independently a single bond or an alkylene group of 1 to 10 carbon atoms, and

R_f3to R_f8Each independently is hydrogen, alkyl of 1 to 15 carbon atoms, alkoxy of 1 to 10 carbon atoms, aryl of 6 to 10 carbon atoms, cycloalkyl of 5 to 10 carbon atoms, aralkyl of 7 to 14 carbon atoms or-R_f9R_f10Wherein R is_f3To R_f8At least one of which is-R_f9R_f10，R_f9Is an alkylene group of 1 to 12 carbon atoms, which alkylene group may or may not contain heteroatoms; and R_f10Is an epoxy group, and is,

[ formula 7]

In the formula 7, the first and second groups,

R_g1to R_g4Each independently hydrogen, alkyl of 1 to 10 carbon atoms, alkoxy of 1 to 10 carbon atoms, aryl of 6 to 12 carbon atoms or-R_g5OR_g6Wherein R is_g1To R_g4At least one of which is-R_g5OR_g6，R_g5Is a single bond or alkylene of 1 to 10 carbon atomsAnd R is_g6Is an alkylene oxide group of 3 to 10 carbon atoms, and

y is C or N, wherein if Y is N, R_g4Is absent.

Specifically, in formula 4, R_d1To R_d3Each independently is alkyl of 1 to 6 carbon atoms or-R_d4R_d5Wherein R is_d1To R_d3At least one of which is-R_d4R_d5，R_d4Is alkylene of 1 to 6 carbon atoms, which alkylene optionally contains heteroatoms, R_d5Is an epoxy group, and the heteroatom may be O (oxygen atom).

More specifically, the compound represented by formula 2 may be a compound represented by the following formula 4-1:

[ formula 4-1]

In formula 5, R is_e1And R_e2Each independently an alkylene group of 1 to 6 carbon atoms, and R_e3To R_e6Each independently is alkyl of 1 to 6 carbon atoms or-R_e7R_e8Wherein R is_e3To R_e6At least one of which is-R_e7R_e8，R_e7Is alkylene of 1 to 6 carbon atoms, which alkylene optionally contains heteroatoms, R_e8Is an epoxy group and the heteroatom may be O.

More specifically, the compound represented by formula 5 may be a compound represented by the following formula 5-1:

[ formula 5-1]

Further, in formula 6, X is O or S, R_f1And R_f2Each independently a single bond or alkylene of 1 to 6 carbon atoms, and R_f3To R_f8Each independently is an alkyl group of 1 to 6 carbon atomsAlkoxy of 1 to 6 carbon atoms or-R_f9R_f10Wherein R is_f3To R_f8At least one of which is-R_f9R_f10，R_f9Is alkylene of 1 to 6 carbon atoms, which alkylene optionally contains heteroatoms, R_f10Is an epoxy group and the heteroatom may be O.

More specifically, the compound represented by formula 6 may be a compound represented by the following formula 6-1 or formula 6-2:

[ formula 6-1]

[ formula 6-2]

Further, in formula 7, R_g1To R_g4Each independently is an alkyl group of 1 to 6 carbon atoms, an alkoxy group of 1 to 6 carbon atoms or-R_g5OR_g6Wherein R is_g1To R_g4At least one of which is-R_g5OR_g6，R_g5Is a single bond or alkylene of 1 to 6 carbon atoms, R_g6Is an alkylene oxide of 3 to 6 carbon atoms, and Y is C or N, wherein if Y is N, then R is_g4Is absent.

More specifically, the compound represented by formula 7 may be selected from compounds represented by the following formulae 7-1 to 7-4:

[ formula 7-1]

[ formula 7-2]

[ formula 7-3]

[ formulae 7-4]

In another embodiment, the modified conjugated diene-based polymer according to one embodiment of the present invention may contain a functional group derived from a modification initiator at the other end than the end containing the functional group derived from the modifier, and in this case, the modification initiator may be a reaction product of an N-functional group-containing compound and an organometallic compound.

Specifically, the N-functional group-containing compound may be an N-functional group-containing aromatic hydrocarbon compound including an amino group, an amide group, an amino group, an imidazole group, a pyrimidine group, or a cyclic amino group, which may be substituted or unsubstituted with a substituent, which may be an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkylaryl group of 7 to 20 carbon atoms, an arylalkyl group of 7 to 20 carbon atoms, or an alkoxysilyl group of 1 to 10 carbon atoms.

More specifically, the N-functional group-containing compound may be a compound represented by the following formula 8:

[ formula 8]

In the case of the formula 8,

R₁to R₃Each independently is hydrogen; alkyl of 1 to 30 carbon atoms; alkenyl of 2 to 30 carbon atoms; alkynyl of 2 to 30 carbon atoms; heteroalkyl of 1 to 30 carbon atoms; heteroalkenyl of 2 to 30 carbon atoms; heteroalkynyl of 2 to 30 carbon atoms; cycloalkyl of 5 to 30 carbon atoms; aryl of 6 to 30 carbon atoms; or a heterocyclic group of 3 to 30 carbon atoms,

R₄is a single bond, an alkylene group of 1 to 20 carbon atoms which may be substituted or unsubstituted with a substituent; cycloalkylene of 5 to 20 carbon atoms substituted or unsubstituted with a substituent; or an arylene group of 6 to 20 carbon atoms substituted or unsubstituted with a substituent, wherein the substituent is an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms, or an aryl group of 6 to 20 carbon atoms,

R₅is an alkyl group of 1 to 30 carbon atoms; alkenyl of 2 to 30 carbon atoms; alkynyl of 2 to 30 carbon atoms; heteroalkyl of 1 to 30 carbon atoms; heteroalkenyl of 2 to 30 carbon atoms; heteroalkynyl of 2 to 30 carbon atoms; cycloalkyl of 5 to 30 carbon atoms; aryl of 6 to 30 carbon atoms; a heterocyclic group of 3 to 30 carbon atoms; or a functional group represented by the following formula 8a or formula 8b, and

n is an integer of 1 to 5, at least one R₅The group is a functional group represented by the following formula 8a or formula 8b, and if n is an integer of 2 to 5, a plurality of R₅The groups may be the same or different,

[ formula 8a ]

In the case of the formula 8a,

R₆is an alkylene group of 1 to 20 carbon atoms which may be substituted or unsubstituted with a substituent; cycloalkylene of 5 to 20 carbon atoms substituted or unsubstituted with a substituent; or an arylene group of 6 to 20 carbon atoms substituted or unsubstituted with a substituent, wherein the substituent is an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms, or an aryl group of 6 to 20 carbon atoms,

R₇and R₈Each independently an alkylene group of 1 to 20 carbon atoms which is substituted or unsubstituted with an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms or an aryl group of 6 to 20 carbon atoms,

R₉is hydrogen; alkyl of 1 to 30 carbon atoms; alkenyl of 2 to 30 carbon atoms; alkynyl of 2 to 30 carbon atoms;heteroalkyl of 1 to 30 carbon atoms; heteroalkenyl of 2 to 30 carbon atoms; heteroalkynyl of 2 to 30 carbon atoms; cycloalkyl of 5 to 30 carbon atoms; aryl of 6 to 30 carbon atoms; or a heterocyclic group of 3 to 30 carbon atoms, and

z is N, O or S atom, wherein if Z is O or S, then R₉Is absent.

[ formula 8b ]

In the case of the formula 8b,

R₁₀is an alkylene group of 1 to 20 carbon atoms which may be substituted or unsubstituted with a substituent; cycloalkylene of 5 to 20 carbon atoms substituted or unsubstituted with a substituent; or an arylene group of 6 to 20 carbon atoms substituted or unsubstituted with a substituent, wherein the substituent is an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms, or an aryl group of 6 to 20 carbon atoms, and

R₁₁and R₁₂Each independently an alkyl group of 1 to 30 carbon atoms; alkenyl of 2 to 30 carbon atoms; alkynyl of 2 to 30 carbon atoms; heteroalkyl of 1 to 30 carbon atoms; heteroalkenyl of 2 to 30 carbon atoms; heteroalkynyl of 2 to 30 carbon atoms; cycloalkyl of 5 to 30 carbon atoms; aryl of 6 to 30 carbon atoms; or a heterocyclic group of 3 to 30 carbon atoms, wherein R₁₁And R₁₂Together with N, to form a heterocyclic group of 2 to 20 carbon atoms.

More specifically, the compound represented by formula 8 may be, in formula 8, R₁To R₃Each independently is hydrogen, alkyl of 1 to 10 carbon atoms, alkenyl of 2 to 10 carbon atoms, or alkynyl of 2 to 10 carbon atoms; r₄Is a single bond, or an unsubstituted alkylene group of 1 to 10 carbon atoms; r₅Is an alkyl group of 1 to 10 carbon atoms, an alkenyl group of 2 to 10 carbon atoms, an alkynyl group of 2 to 10 carbon atoms, or a functional group represented by formula 8a or formula 8b, in formula 8a, R₆Is unsubstituted alkylene of 1 to 10 carbon atoms, R₇And R₈Each independently being an unsubstituted alkylene group of 1 to 10 carbon atoms, R₉Is an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 20 carbon atoms, an aryl group of 5 to 20 carbon atoms or a heterocyclic group of 3 to 20 carbon atoms, in formula 8b, R₁₀Is unsubstituted alkylene of 1 to 10 carbon atoms, R₁₁And R₁₂Each independently is an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms or a heterocyclic group of 3 to 20 carbon atoms, wherein R is₁₁And R₁₂Together with N, to form a heterocyclic group of 2 to 20 carbon atoms.

Further specifically, the compound represented by formula 8 may be a compound represented by the following formula 8-1 to formula 8-3:

[ formula 8-1]

[ formula 8-2]

[ formula 8-3]

In addition, the organometallic compound may be an organic alkali metal compound, for example, one or more selected from the group consisting of an organolithium compound, an organosodium compound, an organopotassium compound, an organorubidium compound and an organocesium compound.

Specifically, the organometallic compound may be one or more selected from methyllithium, ethyllithium, propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, hexyllithium, n-decyllithium, tert-octyllithium, phenyllithium, 1-naphthyllithium, n-eicosyllithium, 4-butylphenyl lithium, 4-tolyllithium, cyclohexyllithium, 3, 5-di-n-heptylcyclohexylithium, 4-cyclopentyllithium, naphthylsodium, potassium naphthylate, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide, and lithium isopropylamide.

In addition, the modified conjugated diene-based polymer according to one embodiment of the present invention may have a number average molecular weight (Mn) of 100,000 to 2,000,000g/mol, 200,000 to 1,000,000g/mol, or 400,000 to 800,000g/mol, and a weight average molecular weight (Mw) of 100,000 to 3,000,000g/mol, 400,000 to 2,000,000g/mol, or 800,000 to 1,500,000 g/mol. Within these ranges, the effects of excellent rolling resistance and wet skid resistance can be achieved. In another embodiment, the molecular weight distribution (PDI; MWD; Mw/Mn) of the modified conjugated diene-based polymer may be 1.5 or more or 1.5 to 3.0, and within this range, the effect of excellent balance between tensile properties, viscoelastic properties, and physical properties may be achieved. Meanwhile, the modified conjugated diene-based polymer has a monomodal-shaped molecular weight distribution curve corresponding to the molecular weight distribution exhibited by a polymer prepared by continuous type polymerization by Gel Permeation Chromatography (GPC), and it can be shown that the modified conjugated diene-based polymer has uniform properties. That is, the modified conjugated diene-based polymer according to one embodiment of the present invention is prepared by continuous type polymerization, and thus has a molecular weight distribution curve of a monomodal shape and a molecular weight distribution of 1.5 or more.

In another embodiment, the modified conjugated diene-based polymer may have a mooney relaxation ratio (-S/R value) measured at 100 ℃ of 0.5 or less, 0.4 or less, or 0.3 or less, the lower limit of the mooney relaxation ratio is not particularly limited, and may be, for example, 0.1 or more or 0.2 or more.

Herein, the mooney relaxation ratio represents a change in stress exhibited as a reaction to the same amount of strain, and may be measured using a mooney viscometer. Specifically, the Mooney relaxation ratio was measured by using a large rotor of MV2000E from Monsanto Co. at 100 ℃ and a rotor speed of 2. + -. 0.02 rpm. The polymer was left at room temperature (23. + -. 5 ℃ C.) for 30 minutes or more, 27. + -.3 g of the polymer was collected and placed in a cavity, and then the platens were operated to measure the Mooney viscosity while applying a torque and to measure the gradient value of the change in Mooney torque exhibited when releasing the torque.

Meanwhile, the mooney relaxation ratio may be used as an index of a branched structure of a corresponding polymer. For example, when comparing polymers having the same mooney viscosity, the mooney relaxation ratio decreases as the branching increases, and the mooney relaxation ratio can be used as an index of the branching degree.

In addition, the modified conjugated diene-based polymer may have a mooney viscosity at 100 ℃ of 70 or more, 80 to 150, or 80 to 120, and in this range, excellent effects of processability and productivity may be achieved.

In addition, the vinyl content of the modified conjugated diene-based polymer may be 5% by weight or more, 10% by weight or more, or 10% by weight to 60% by weight. Here, the vinyl content may mean the amount of the 1, 2-added conjugated diene monomer other than the 1, 4-addition based on 100% by weight of the conjugated diene copolymer formed using the vinyl group-having monomer and the aromatic vinyl monomer.

As described above, the modified conjugated diene-based polymer according to one embodiment of the present invention may have a high mooney large relaxation area of 1500MU-s or more, and may include a first polymer chain and a second polymer chain including a functional group derived from the first modifier and the second modifier at one end, respectively. Meanwhile, the modified conjugated diene-based polymer may be preferably produced by the production method described below to satisfy the above-mentioned characteristics, but if all of the above-mentioned characteristics are satisfied, the effects to be achieved in the present invention can be achieved.

Method for preparing modified conjugated diene polymer

In addition, the invention provides a preparation method of the modified conjugated diene polymer.

The method for producing the modified conjugated diene-based polymer according to one embodiment of the present invention comprises: preparing a living polymer by polymerizing a conjugated diene monomer or an aromatic vinyl monomer and a conjugated diene monomer in a hydrocarbon solvent in the presence of a polymerization initiator (S1); and reacting or coupling the living polymer prepared in the step (S1) with a first modifier and a second modifier (S2), wherein the first modifier is an aminoalkoxysilane-based modifier and the second modifier is an epoxy-based modifier.

The aminoalkoxysilane-based modifier and the epoxy-based modifier are the same as described above.

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

The polymerization initiator may be used in an amount of 0.1 to 3.0 equivalents, preferably 0.1 to 2.0 equivalents, more preferably 0.5 to 1.5 equivalents, based on 1.0 equivalent of the monomer.

In another embodiment, the polymerization initiator may be used in an amount of 0.01mmol to 10mmol, 0.05mmol to 5mmol, 0.1mmol to 2mmol, 0.1mmol to 1mmol, or 0.15mmol to 0.8mmol, based on a total of 100g of the monomers. Herein, the total of 100g of the monomers may represent the conjugated diene monomer or the sum of the conjugated diene monomer and the aromatic vinyl monomer.

Meanwhile, the polymerization initiator may be an organometallic compound, for example, one or more selected from the group consisting of an organolithium compound, an organosodium compound, an organopotassium compound, an organorubidium compound and an organocesium compound.

Specifically, the organometallic compound may be one or more selected from methyllithium, ethyllithium, propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, hexyllithium, n-decyllithium, tert-octyllithium, phenyllithium, 1-naphthyllithium, n-eicosyllithium, 4-butylphenyl lithium, 4-tolyllithium, cyclohexyllithium, 3, 5-di-n-heptylcyclohexylithium, 4-cyclopentyllithium, naphthylsodium, potassium naphthylate, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide, and lithium isopropylamide.

In another embodiment, the polymerization initiator may be a modified initiator, and the modified initiator may be a reaction product of a compound containing an N functional group and an organometallic compound.

The polymerization of step (S1) may be, for example, anionic polymerization, and specifically may be living anionic polymerization in which an anionic living moiety is formed at the end of the polymerization by a propagation reaction caused by an anion. Further, the polymerization of step (S1) may be heating polymerization, isothermal polymerization, or constant temperature polymerization (adiabatic polymerization). Here, the isothermal polymerization refers to a polymerization method comprising a step of performing polymerization using heat generated by the reaction itself without optionally supplying heat after adding a polymerization initiator, and the heating polymerization refers to a polymerization method comprising injecting a polymerization initiator and then increasing the temperature by optionally supplying heat. Isothermal polymerization refers to a polymerization method in which the temperature of a polymer is kept constant by adding heat or removing heat by supplying heat after a polymerization initiator is added.

Further, according to an embodiment of the present invention, the polymerization of step (S1) may be carried out by a diene-based compound including 1 to 10 carbon atoms in addition to the conjugated diene-based monomer, in which case an effect of preventing gel formation on the wall side of the reactor during long-time operation can be achieved. The diene-based compound may include, for example, 1, 2-butadiene.

The polymerization of step (S1) may be performed at a temperature ranging from-20 ℃ to 80 ℃,0 ℃ to 70 ℃, or 10 ℃ to 70 ℃ below 80 ℃. Within the range, the molecular weight distribution of the polymer can be controlled to be narrow, and the effect of improving physical properties is excellent.

The living polymer prepared by the step (S1) may refer to a polymer in which a polymer anion is coupled with an organometallic cation.

The step (S1) may be carried out by appropriately selecting a continuous polymerization method or a batch polymerization method, and the step (S1) may preferably be carried out by using a continuous polymerization method in view of improvement of productivity and processability.

The term "polymerization reactant" in the present invention may refer to an intermediate of a polymer type in polymerization in each reactor during the step (S1) is carried out, or may refer to a polymer in which a polymerization conversion rate in polymerization in the reactor is less than 95% after the step (S1) or the step (S2) is completed and before a living polymer or a modified conjugated diene-based polymer is obtained.

According to an embodiment of the present invention, the molecular weight distribution (PDI, polydispersity index; MWD, Mw/Mn) of the living polymer prepared in the step (S1) may be 1.5 or more or 1.3 to 3.0, and within this range, an excellent effect of improving processability may be achieved.

Meanwhile, the polymerization of step (S1) may be performed by including a polar additive, which may be added in a ratio of 0.001g to 50g, 0.001g to 10g, or 0.005g to 0.1g, based on a total of 100g of monomers. In another embodiment, the polar additive may be added in a ratio of 0.001g to 10g, 0.005g to 5g, or 0.005g to 4g, based on 1mmol of the polymerization initiator in total.

The polar additive may be, for example, one or more selected from tetrahydrofuran, 2-bis (2-tetrahydrofuryl) propane, diethyl ether, cyclopentyl ether, dipropyl ether, ethylene glycol methyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, t-butoxyethoxyethane, bis (3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine, N' -tetramethylethylenediamine, sodium menthol and 2-ethyltetrahydrofuryl ether, and may preferably be 2, 2-bis (2-tetrahydrofuryl) propane, triethylamine, tetramethylethylenediamine, sodium menthol or 2-ethyltetrahydrofuryl ether. If the polar additive is contained, and if the conjugated diene-based monomer is copolymerized with the aromatic vinyl-based monomer, the difference in their reaction rates can be compensated for, and the effect of inducing easy formation of the random copolymer can be achieved.

According to an embodiment of the present invention, the reaction or coupling of step (S2) may be performed in a modification reactor, and specifically, may be performed by reacting or coupling the living polymer with the first modifier and the second modifier. Herein, the first modifier and the second modifier may be injected sequentially or in batches and then reacted or coupled with the living polymer, and the first modifier and the second modifier may be used in a molar ratio of 10:1 to 5:1 or 2:1 to 1: 1.

In this case, the modifier may be used in an amount of 0.01mmol to 10mmol, based on a total of 100g of the monomers. In another embodiment, the modifier 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 1mol of the polymerization initiator of step (S1).

In addition, according to an embodiment of the present invention, a modifier may be injected into the modification reactor, and the step (S2) may be performed in the modification reactor. In another embodiment, the modifier may be injected into a transfer part for transferring the living polymer prepared in the step (S1) to the modification reactor for performing the step (S2), and the reaction or coupling may be performed by mixing the living polymer with the modifier in the transfer part.

The method for producing a modified conjugated diene-based polymer according to an embodiment of the present invention is a method for satisfying the properties of the above-described modified conjugated diene-based polymer. If the above properties are satisfied as described above, the effects intended to be achieved in the present invention can be achieved, but the physical properties of the modified conjugated diene-based polymer according to the present invention can be achieved by variously controlling other polymerization conditions.

Rubber composition

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

The rubber composition may contain 10% by weight or more, 10% by weight to 100% by weight, or 20% by weight to 90% by weight of the modified conjugated diene-based polymer, within which the mechanical properties such as tensile strength and abrasion resistance are excellent, and the effect of excellent balance between physical properties can be achieved.

In addition, the rubber composition may contain other rubber components as needed in addition to the modified conjugated diene-based polymer, and in this case, the content of the rubber component may be 90% by weight or less based on the total weight of the rubber composition. In a specific embodiment, the other rubber component may be contained in an amount of 1 part by weight to 900 parts by weight, based on 100 parts by weight of the modified conjugated diene-based copolymer.

The rubber component may be, for example, natural rubber or synthetic rubber, and may be specifically Natural Rubber (NR) including cis-1, 4-polyisoprene; modified natural rubber obtained by modifying or purifying conventional natural rubber, such as Epoxidized Natural Rubber (ENR), deproteinized natural rubber (DPNR) and hydrogenated natural rubber; and synthetic rubbers such as styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, polyisobutylene-isoprene copolymer, chloroprene rubber, poly (ethylene-propylene) copolymer, poly (styrene-butadiene) copolymer, poly (styrene-isoprene-butadiene) copolymer, poly (ethylene-propylene-diene) copolymer, polysulfide rubber, acrylic rubber, polyurethane rubber, silicone rubber, epichlorohydrin rubber and halogenated butyl rubber, and any one or a mixture of two or more thereof may be used.

The rubber composition may contain 0.1 to 200 parts by weight or 10 to 120 parts by weight of the filler, based on 100 parts by weight of the modified conjugated diene-based polymer of the present invention. The filler may be, for example, a silica-based filler, specifically, wet silica (hydrated silicate), dry silica (anhydrous silicate), calcium silicate, aluminum silicate, or colloidal silica. Preferably, the filler may be wet silica having the most remarkable improvement effect of the deterioration property and the compatible effect of the wet-road adhesion. Further, the rubber composition may further contain a carbon-based filler, as necessary.

In another embodiment, if silica is used as the filler, a silane coupling agent may be used together to improve the reinforcement and low heat release properties. Specific examples of the silane coupling agent may include: bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, and mixtures thereof, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzoyl tetrasulfide, 3-triethoxysilylpropylmethacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide or dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide, and any one or a mixture of two or more thereof may be used. Preferably, in view of the property-enhancing improvement effect, bis (3-triethoxysilylpropyl) polysulfide or 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide may be used.

In addition, in the rubber composition according to one embodiment of the invention, since the modified conjugated diene-based polymer in which a functional group having high affinity with silica is introduced into an active site is used as a rubber component, the compounding amount of the silane coupling agent can be smaller than that in the conventional case. Therefore, the silane coupling agent may be used in an amount of 1 to 20 parts by weight or 5 to 15 parts by weight, based on 100 parts by weight of the silica. Within the above amount range, the effect as a coupling agent can be sufficiently exhibited, and the effect of preventing gelation of the rubber component can be obtained.

The rubber composition according to one embodiment of the present invention may be sulfur-crosslinkable and, therefore, may further contain a vulcanizing agent. The vulcanizing agent may specifically be sulfur powder, and may be contained in an amount of 0.1 to 10 parts by weight, based on 100 parts by weight of the rubber component. Within the above range, the elasticity and strength required for the vulcanized rubber composition can be secured, and at the same time, an excellent low fuel consumption rate can be obtained.

The rubber composition according to one embodiment of the present invention may further contain various additives used in the conventional rubber industry, in particular, a vulcanization accelerator, a processing oil, an antioxidant, a plasticizer, an age resistor, an anti-scorching agent, zinc white, stearic acid, a thermosetting resin or a thermoplastic resin, in addition to the above components.

The vulcanization accelerator may include, for example, thiazole compounds such as 2-mercaptobenzothiazole (M), dibenzothiazyl Disulfide (DM) and N-cyclohexyl-2-benzothiazylsulfenamide (CZ); or a guanidine compound such as diphenyl guanidine (DPG) may be contained in an amount of 0.1 parts by weight to 5 parts by weight based on 100 parts by weight of the rubber component.

The processing oil acts as a softener in the rubber composition and may include, for example, paraffins, naphthenes, or aromatics. In view of tensile strength and abrasion resistance, aromatic processing oils may be used; naphthenic or paraffinic process oils may be used in view of hysteresis loss and low temperature performance. The content of the processing oil may be 100 parts by weight or less based on 100 parts by weight of the rubber component. Within the above range, the tensile strength and low heat release performance (low fuel consumption rate) of the vulcanized rubber can be prevented from deteriorating.

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

The age resistor may include, for example, N-isopropyl-N '-phenyl-p-phenylenediamine, N- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine, 6-ethoxy-2, 2, 4-trimethyl-1, 2-dihydroquinoline, or a condensate of diphenylamine and acetone at a high temperature, and may be contained 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 one embodiment of the present invention can be obtained by mixing according to the mixing formulation using a mixing device such as a banbury mixer, a roll and an internal mixer. By the vulcanization process after the molding process, a rubber composition having low heat release properties and good abrasion resistance can be obtained.

Thus, the rubber composition can be used for manufacturing various members of a tire, such as a tire tread, a tread base, a sidewall, a carcass coating rubber, a belt coating rubber, a bead filler, a chafer and a bead coating rubber, or for manufacturing rubber products in various industries, such as a vibration damping rubber, a conveyor belt and a hose.

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

The tire may be a tire or include a tire tread.

Examples

Hereinafter, the present invention will be described in more detail with reference to embodiments. Embodiments according to the present invention may be changed to various other types, and the scope of the present invention should not be limited to the embodiments described below. The embodiments of the present invention are provided to fully explain the present invention to those skilled in the art.

Example 1

To the first reactor among the continuous reactors of the two reactors connected in series, a styrene solution in which 60% by weight of styrene was dissolved in n-hexane was injected at a rate of 258.3g/h, a 1, 3-butadiene solution in which 60% by weight of 1, 3-butadiene was dissolved in n-hexane at a rate of 1.41kg/h, and n-hexane at a rate of 4.68kg/h, a solution in which 2% by weight of 2, 2-bis (2-tetrahydrofuryl) propane was dissolved as a polar additive in n-hexane at a rate of 11.5g/h, and an n-butyllithium solution in which 2% by weight of n-butyllithium was dissolved in n-hexane at a rate of 29.5 g/h. In this case, the temperature of the first reactor was maintained to 65 ℃, and at the time when the polymerization conversion rate reached 95%, the polymerization reactant was transferred from the first reactor to the second reactor through the transfer pipe.

The above polymerization reactant was transferred from the first reactor to the second reactor, and as a modifier, into the second reactor, a solution in which 2% by weight of N, N' - (cyclohexane-1, 3-diylbis (methylene)) bis (3- (trimethoxysilyl) -N- (3- (trimethoxysilyl) propyl) propan-1-amine) was dissolved was injected at a rate of 92.5g/h, and a solution in which 1% by weight of tris ((oxiran-2-ylmethoxy) methyl) amine) was dissolved was injected at a rate of 64.5 g/h. The temperature of the second reactor was maintained at 70 deg.C

Thereafter, to the polymerization solution discharged from the second reactor, a solution in which 30% by weight of IR1520(BASF Co.) as an antioxidant was dissolved was injected at a rate of 97.6g/h and stirred. The thus-obtained polymerization reaction product was poured into hot water heated with steam and stirred to remove the solvent, thereby producing a modified conjugated diene-based polymer.

Example 2

A modified conjugated diene-based polymer was produced by carrying out the same method as in example 1 except that in example 1, a solution in which 2% by weight of N, N' - (cyclohexane-1, 3-diylbis (methylene)) bis (3- (trimethoxysilyl) -N- (3- (trimethoxysilyl) propyl) propan-1-amine) was dissolved was injected as a modifier at a rate of 61.7g/h and a solution in which 1% by weight of tris ((oxiran-2-ylmethoxy) methyl) amine) was dissolved at a rate of 43.0 g/h.

Example 3

A modified conjugated diene-based polymer was produced by carrying out the same method as in example 1 except that in example 1, a solution in which 2% by weight of N, N' - (cyclohexane-1, 3-diylbis (methylene)) bis (3- (trimethoxysilyl) -N- (3- (trimethoxysilyl) propyl) propan-1-amine) was dissolved was injected as a modifier at a rate of 30.8g/h and a solution in which 1% by weight of tris ((oxiran-2-ylmethoxy) methyl) amine) was dissolved at a rate of 21.5 g/h.

Comparative example 1

A modified conjugated diene polymer was produced by carrying out the same process as in example 1 except that in example 1, an N-butyllithium solution in which 2% by weight of N-butyllithium was dissolved in N-hexane was injected at a rate of 29.5g/h as a modifier, and a solution in which 2% by weight of N, N' - (cyclohexane-1, 3-diylbis (methylene)) bis (3- (trimethoxysilyl) -N- (3- (trimethoxysilyl) propyl) propan-1-amine) was dissolved at a rate of 92.5g/h as a modifier.

Comparative example 2

A modified conjugated diene-based polymer was prepared by carrying out the same process as in example 1, except that in example 1, an n-butyllithium solution in which 2% by weight of n-butyllithium was dissolved in n-hexane was injected as a modifier at a rate of 29.5g/h and a solution in which 1% by weight of tris ((oxiran-2-ylmethoxy) methyl) amine was dissolved at a rate of 64.5 g/h.

Comparative example 3

A modified conjugated diene-based polymer was produced by carrying out the same process as in example 1 except that in example 1, an N-butyllithium solution in which 2% by weight of N-butyllithium was dissolved in N-hexane was injected at a rate of 21.0g/h as a modifier and a solution in which 1% by weight of 3,3' - (1,1,3, 3-tetramethoxydisiloxane-1, 3-diyl) bis (N, N-diethylpropane-1-amine) was dissolved at a rate of 98.0g/h as a modifier.

Comparative example 4

A modified conjugated diene polymer was produced by carrying out the same process as in example 1 except that in example 1, a solution in which 2% by weight of N, N '- (cyclohexane-1, 3-diylbis (methylene)) bis (3- (trimethoxysilyl) -N- (3- (trimethoxysilyl) propyl) propan-1-amine) was dissolved was injected at a rate of 92.5g/h as a modifier, and a solution in which 1% by weight of 3,3' - (1,1,3, 3-tetramethoxydisiloxane-1, 3-diyl) bis (N, N-diethylpropane-1-amine) was dissolved at a rate of 98.0g/h as a modifier.

Comparative example 5

A modified conjugated diene polymer was produced by carrying out the same process as in example 1 except that in example 1, a solution in which 1% by weight of tris ((oxyethylene-2-ylmethoxy) methyl) amine was dissolved was injected at a rate of 64.5g/h as a modifier and a solution in which 1% by weight of 3,3' - (1,1,3, 3-tetramethoxydisiloxane-1, 3-diyl) bis (N, N-diethylpropane-1-amine) was dissolved at a rate of 98.0g/h as a modifier.

Test example 1

For each of the modified conjugated diene-based polymers prepared in examples and comparative examples, the styrene unit content and vinyl group content, weight average molecular weight (Mw,. times.10) in each polymer were measured, respectively³g/mol), number average molecular weight (Mn,. times.10)³g/mol), molecular weight distribution (PDI, MWD), number of couplings, Mooney Viscosity (MV), Mooney relaxation ratio (-S/R), and Mooney large relaxation area. The results are shown in table 1 below.

1) Styrene Unit content and vinyl content (% by weight)

The styrene unit (SM) content and vinyl content in each polymer were measured and analyzed using a Varian VNMRS 500MHz NMR.

In the course of measuring NMR, 1,1,2, 2-tetrachloroethane was used as a solvent, and the styrene unit content and vinyl group content were calculated by calculating that the peak of the solvent was 5.97ppm, and 7.2 to 6.9ppm was considered as a random styrene peak, 6.9 to 6.2ppm was a block styrene peak, 5.8 to 5.1ppm was a 1, 4-vinyl peak, and 5.1 to 4.5ppm was a 1, 2-vinyl peak.

^{3 3}2) Weight average molecular weight (Mw,. times.10 g/mol), number average molecular weight (Mn,. times.10 g/mol), molecular weight distribution (PDI, MWD) and number of couplings (C.N)

The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by Gel Permeation Chromatography (GPC) analysis. Further, the molecular weight distribution (PDI, MWD, Mw/Mn) was calculated from the respective molecular weights thus measured. Specifically, GPC was performed using two PLgel oxides columns (Polymer Laboratories Co.) and one PLgel mixed-C column (Polymer Laboratories Co.) in combination, and using Polystyrene (PS) as a GPC standard for calculating molecular weight. The solvent for GPC measurement was prepared by mixing tetrahydrofuran with 2 wt% of an amine compound.

In addition, the coupling numbers were obtained as follows: in each of examples and comparative examples, a part of the polymer was collected before the injection of the modifier or the coupling agent to obtain a peak molecular weight (Mp) of the polymer₁) To obtain a peak molecular weight (Mp) per modified conjugated diene-based polymer₂) And is calculated by the following mathematical formula 2:

[ mathematical formula 2]

Coupling number (C.N) ═ Mp₂/Mp₁

3) Mooney viscosity, Mooney relaxation ratio (-S/R) and Mooney Large Relaxation Area (MLRA)

Mooney viscosity (MV, (ML1+4, @100 ℃) MU) was measured at 100 ℃ using a large rotor at a rotor speed of 2. + -. 0.02rpm using MV-2000(Alpha Technologies Co.). In this case, the used sample was left at room temperature (23. + -. 3 ℃ C.) for 30 minutes or more, and 27. + -.3 g of the sample was collected and put into the cavity, and then, the platen was operated for 4 minutes to measure.

After the mooney viscosity was measured, the value of the slope of the change in mooney viscosity exhibited when the torque was released was measured, and the mooney relaxation ratio was obtained as the absolute value thereof. In addition, the mooney large relaxation area is an integrated value of a mooney relaxation curve from 1 second to 120 seconds after stopping the rotor, and the calculation formula can be represented by the following mathematical formula 1:

[ mathematical formula 1]

In the case of the mathematical formula 1,

a is the Mooney Large Relaxed Area (MLRA),

k is a Mooney intercept after 1 second from the stop of the rotor of the Mooney viscometer,

a is a Mooney relaxation ratio of,

t_ois the starting point of the mooney relaxation,

t_fis the end point of mooney relaxation.

[ Table 1]

Modifier a: n, N' - (cyclohexane-1, 3-diylbis (methylene)) bis (3- (trimethoxysilyl) -N- (3- (trimethoxysilyl) propyl) propan-1-amine)

Modifier B: tris ((oxiran-2-ylmethoxy) methyl) amine

Modifier C: 3,3' - (1,1,3, 3-tetramethoxydisiloxane-1, 3-diyl) bis (N, N-diethylpropane-1-amine)

As shown in table 1, it was confirmed that the Mooney Large Relaxation Area (MLRA) of the modified conjugated diene-based polymers of examples 1 to 3 according to the embodiment of the invention was 1500MU-s or more as measured at 100 ℃. In this case, the modified conjugated diene-based polymers of examples 1 to 3 exhibited the same level or more of molecular weight and a reduced Mooney relaxation ratio (-S/R) value when compared with comparative examples 1 to 5.

Test example 2

In order to compare and analyze physical properties of the rubber compositions comprising the modified conjugated diene-based polymers prepared in examples and comparative examples and molded articles manufactured from the rubber compositions, processability, tensile properties, and viscoelastic properties were measured, respectively, and the results thereof are shown in table 3 below.

1) Preparation of rubber test specimens

Using each of the modified or unmodified conjugated diene polymers of examples and comparative examples as a raw material rubber, mixing was performed under the compounding conditions shown in table 2 below. The amounts of the raw materials in table 2 are represented by parts by weight based on 100 parts by weight of the raw rubber.

[ Table 2]

Specifically, the rubber sample was obtained by kneading in the first stage and the second stage. In the first-stage mixing, a raw material rubber, silica (filler), an organosilane coupling agent (X50S, Evonik), a processing oil (TADE oil), zinc white (ZnO), stearic acid, an antioxidant (tmq (rd)) (2,2, 4-trimethyl-1, 2-dihydroquinoline polymer), an antiaging agent (6PPD ((dimethylbutyl) -N-phenyl-phenylenediamine), and a wax (microcrystalline wax) were mixed using a banbury mixer equipped with a temperature control device, in which case the initial temperature of the mixing device was controlled to 70 ℃, and after completion of mixing, a first mixed mixture was obtained at a discharge temperature of 145 ℃ to 155 ℃ Amide)) was added to the mixing apparatus and mixed at a temperature of 100 ℃ or less to give a second compounded mixture. Then, a rubber sample was formed by performing a curing process at 160 ℃ for 20 minutes.

2) Tensile Properties

Tensile properties were measured as follows: each specimen was prepared and the tensile strength at break and the tensile stress at 300% elongation (300% modulus) of each specimen were measured according to ASTM 412 tensile test method. Specifically, tensile properties were measured at 50cm/min at room temperature using a Universal Test machine 4204 tensile tester (Instron co.).

3) Viscoelastic Properties

Viscoelastic properties were determined as follows: the viscoelastic behavior of the thermodynamic deformation was measured at each measurement temperature (-60 ℃ to 60 ℃) at a frequency of 10Hz in the film stretching mode using a dynamic mechanical analyzer (GABO Co.) and the tan δ value was obtained. From the obtained values, if the tan δ value increases at a low temperature of 0 ℃, the wet skid resistance becomes better, and if the tan δ value decreases at a high temperature of 60 ℃, the hysteresis loss decreases, and the rolling resistance (fuel consumption rate) becomes better. The values obtained in table 3 are indexed based on the values obtained in comparative example 1, so higher values indicate better results.

4) Processability (M-Y-Y

The processability of the individual polymers was compared and analyzed by measuring the Mooney viscosity (MV, (ML1+4 @100 ℃ C.) MU) of the second compounded mixture obtained in 1) the preparation of the rubber sample, in which case the lower the Mooney viscosity measurement, the better the processability.

Specifically, each second compounded mixture was left at room temperature (23 ± 3 ℃) for 30 minutes or more by using a large rotor at a rotor speed of 2 ± 0.02rpm at 100 ℃ with MV-2000(Alpha Technologies Co.), and 27 ± 3g was collected, put into a mold cavity, and then, the press plate was operated for 4 minutes to measure.

[ Table 3]

As shown in table 3, examples 1 to 3 according to the embodiments of the present invention show excellent viscoelastic properties, tensile properties, and processability in balance when compared to comparative examples 1 to 5. Specifically, examples 1 to 3 showed excellent tensile properties, viscoelastic properties and processability as a whole when compared with comparative examples 1 to 3; examples 1 to 3 show significantly improved tensile properties and processability when compared to comparative examples 1 and 3; and examples 1 to 3 showed significantly improved rolling resistance when compared with comparative example 2.

In addition, examples 1 to 3 showed excellent tensile properties, viscoelastic properties and processability as a whole, as compared with comparative examples 4 and 5; examples 1 to 3 showed significantly improved tensile properties and processability compared to comparative example 4; examples 1 to 3 showed significantly improved tensile properties and rolling resistance when compared to comparative example 5. In this case, comparative examples 1 and 3 are polymers prepared without using an epoxy-based modifier, do not contain a functional group derived from the epoxy-based modifier in the molecule, and have a mooney large relaxation area of less than 1500 MU-s; while comparative example 2 is a polymer prepared without using an aminoalkoxysilane-based modifier, does not contain a functional group derived from the aminoalkoxysilane-based modifier in the molecule, and has a mooney large relaxation area of less than 1500 MU-s. Meanwhile, comparative examples 4 and 5 are polymers prepared using two types of modifiers (but using two types of modifiers that are not a combination of an aminoalkoxysilane-based modifier and an epoxy-based modifier as proposed in the present invention), and have a mooney large relaxation area of less than 1500 MU-s.

From the results of tables 1 to 3, it can be confirmed that the modified conjugated diene-based polymer according to the present invention has a high molecular weight and a high branching property and exhibits a mooney large relaxation area of 1500MU-s or more, and therefore, if applied to a rubber composition, can exhibit excellent tensile properties and viscoelastic properties and remarkably improved processability.