KR20210109897A - Modified conjugated diene copolymer and rubber composition comprising the same - Google Patents

Abstract

The present invention relates to a modified conjugated diene copolymer having excellent abrasion resistance and driving resistance while having improved wet road resistance; and a rubber composition comprising the same. Provided are a modified conjugated diene copolymer comprising: a first copolymer unit, a second copolymer unit, and a functional group derived from a modifier, and satisfying the conditions (i) to (vi) at the same time; and a rubber composition comprising the same.

Description

Modified conjugated diene-based copolymer and rubber composition comprising the same

The present invention relates to a modified conjugated diene-based copolymer having excellent abrasion resistance and driving resistance while improving wet road resistance and processability, and a rubber composition comprising the same.

In response to the recent demand for low fuel consumption for automobiles, a conjugated diene-based polymer with low running resistance, excellent abrasion resistance and tensile properties, and adjustment stability typified by wet road resistance is required as a rubber material for tires.

In order to reduce the running resistance of the tire, there is a method of reducing the hysteresis loss of the vulcanized rubber, and rebound elasticity of 50°C to 80°C, tan δ, Goodrich heat, etc. are used as evaluation indicators of the vulcanized rubber. That is, a rubber material having a large rebound elasticity at the above temperature or a small tan δ and Goodrich heat generation is preferable.

As a rubber material with a small hysteresis loss, natural rubber, polyisoprene rubber, polybutadiene rubber and the like are known, but these have a problem of low resistance to wet road surfaces. Accordingly, recently, conjugated diene polymers or copolymers such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) have been manufactured by emulsion polymerization or solution polymerization and are used as rubber for tires. . Among them, the greatest advantage of solution polymerization compared to emulsion polymerization is that the content of vinyl structure and styrene content defining rubber properties can be arbitrarily adjusted, and molecular weight and physical properties can be adjusted by coupling or modification. that it can be adjusted. Therefore, it is easy to change the structure of the finally manufactured SBR or BR, and it is possible to reduce the movement of the chain ends by bonding or modifying the chain ends, and to increase the binding force with fillers such as silica or carbon black. It is widely used as a rubber material for

The solution polymerization SBR is prepared by using an anionic polymerization initiator, and a technique of introducing a functional group at the end by binding or modifying the chain end of the formed polymer using various modifiers is used. For example, U.S. Patent No. 4,397,994 discloses a technique in which an active anion at the chain end of a polymer obtained by polymerizing styrene-butadiene in a non-polar solvent using alkyllithium, a monofunctional initiator, is combined using a binder such as a tin compound. did.

In addition, when the solution-polymerized SBR is used as a rubber material, the required physical properties of the tire such as running resistance can be adjusted by increasing the vinyl content in the SBR. However, when the vinyl content is high, braking performance and abrasion resistance are disadvantageous, so Although the styrene content in SBR should be maintained above a certain level, there is a problem in that the effect expressed from the high vinyl content does not appear in this case.

Accordingly, an attempt was made to improve running resistance, wet road resistance, and abrasion resistance in a balanced way by using a block copolymer SBR including two block copolymer units having a gradient in styrene and vinyl contents as a solution polymerization SBR, but the level of improvement was not achieved. It was only marginal.

JP 08193147 A (July 30, 1996) US 4397994 A (1983. 08. 09.)

The present invention has been devised in order to solve the problems of the prior art, each comprising a repeating unit derived from a conjugated diene-based monomer and a repeating unit derived from an aromatic vinyl-based monomer having a gradient in the styrene defect content and the 1,2-vinyl bond content An object of the present invention is to provide a modified conjugated diene-based copolymer that includes first and second copolymer units, and satisfies specific conditions defined by (i) to (vi).

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

According to one embodiment of the present invention for solving the above problems, the present invention includes a first copolymer unit, a second copolymer unit, and a functional group derived from a modifier, the first copolymer unit and the second copolymer unit Each includes a repeating unit derived from a conjugated diene-based monomer and a repeating unit derived from an aromatic vinyl-based monomer, and provides a modified conjugated diene-based copolymer satisfying the following conditions (i) to (vi):

(i) the molecular weight distribution curve by gel permeation chromatography is unimodal,

(ii) the molecular weight distribution is 1.0 or more and less than 1.7;

(iii) a styrene bond content of at least 15% by weight and less than 25% by weight;

(iv) 1,2-vinyl bond content is greater than or equal to 45% by weight and less than 55% by weight;

(v) a weight average molecular weight of 100,000 g/mol or more and less than 3,000,000 g/mol,

(vi) the first copolymer unit and the second copolymer unit satisfy the following Equations 1 and 2,

[Equation 1]

|SM ₁ -SM ₂ |< 10% by weight

In Equation 1, SM ₁ is the styrene bond content in the first copolymer unit, SM ₂ is the styrene bond content in the second copolymer unit,

[Equation 2]

VN ₁ -VN ₂ ≥ 20 wt%

In Equation 2, VN ₁ is the content of 1,2-vinyl bonds in the first copolymer unit, and VN ₂ is the content of 1,2-vinyl bonds in the second copolymer unit.

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

The modified conjugated diene-based copolymer according to the present invention includes a first copolymer unit having a gradient in a styrene defect content and a 1,2-vinyl bond content, a second copolymer unit, and a functional group derived from a modifier, (i) to ( By satisfying the specific conditions defined by vi), there is an effect of improving the wet road resistance and workability while having excellent driving resistance and abrasion resistance.

In addition, since the rubber composition according to the present invention includes the modified conjugated diene-based copolymer, there is an excellent effect in well-balanced wet road resistance, abrasion resistance and driving resistance.

The following drawings attached to the present specification illustrate specific embodiments of the present invention, and serve to further understand the technical spirit of the present invention together with the above-described content of the present invention, so the present invention is limited to the matters described in those drawings should not be construed as limited.
1 shows molecular weight distribution curves by gel permeation chromatography (GPC) of the modified conjugated diene-based polymers of Example 1 and Comparative Example 1 according to an embodiment of the present invention.

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

The terms or words used in the description and claims of the present invention should not be construed as being limited to their ordinary or dictionary meanings, and the inventor should properly understand the concept of the term in order to best describe his invention. Based on the principle that can be defined, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.

Justice

As used herein, the term 'copolymer' refers to a polymer compound prepared by polymerizing two or more different types of monomers.

As used herein, the term '1,2-vinyl bond content' refers to 1,2-numbers in the polymer chain of the copolymer based on the portion (total amount of polymerized butadiene) derived from the conjugated diene-based monomer (butadiene, etc.) in the copolymer. Refers to the mass (or weight) percentage of butadiene contained in the position.

As used herein, the term 'styrene bond content' refers to the percentage by mass (or weight) of styrene contained in the copolymer chain of the copolymer derived from an aromatic vinylic monomer (styrene, etc.) in the copolymer.

In the present specification, the term 'modification rate (%)' refers to the ratio of the modified copolymer chain to the unmodified copolymer chain when modified with a modifier for the copolymer having the polymerization active site. and it is expressed as a percentage (%) of the total copolymer including the modified copolymer chain and the unmodified copolymer chain.

As used herein, the term 'substitution' may mean that hydrogen of a functional group, atomic group, or compound is substituted with a specific substituent, and when hydrogen of a functional group, atomic group or compound is substituted with a specific substituent, within the functional group, atomic group or compound One or two or more plural substituents may be present depending on the number of hydrogens present, and when plural substituents are present, each substituent may be the same as or different from each other.

As used herein, the term 'alkyl group' may refer to a monovalent aliphatic saturated hydrocarbon, and may include linear alkyl groups such as methyl, ethyl, propyl and butyl; branched alkyl groups such as isopropyl, sec-butyl, tert-butyl and neo-pentyl; and cyclic saturated hydrocarbons, or cyclic unsaturated hydrocarbons including one or two or more unsaturated bonds.

As used herein, the term 'alkylene group' may mean a divalent aliphatic saturated hydrocarbon such as methylene, ethylene, propylene, and butylene.

In the present invention, the term 'cycloalkyl group' may mean a cyclic saturated hydrocarbon.

As used herein, the term 'aryl group' may mean a cyclic aromatic hydrocarbon, and also a monocyclic aromatic hydrocarbon in which one ring is formed, or a polycyclic aromatic hydrocarbon in which two or more rings are bonded. It may mean including all hydrocarbons.

As used herein, the term 'aralkyl' is also called aralkyl, and may refer to a combination group of an alkyl group and an aryl group formed by substituting an aryl group in which a hydrogen atom bonded to a carbon constituting the alkyl group is substituted.

As used herein, the term 'single bond' may refer to a single covalent bond that does not include a separate atom or molecular group.

As used herein, the terms 'derived unit', 'derived repeating unit' and 'derived functional group' may refer to a component, structure, or substance itself derived from a certain substance.

The terms 'comprising', 'having' and their derivatives herein are not intended to exclude the presence of any additional component, step or procedure, whether or not they are specifically disclosed. . For the avoidance of any doubt, all compositions claimed through use of the term "comprising", unless stated to the contrary, contain any additional additives, adjuvants, or compounds, whether polymeric or otherwise. may include In contrast, the term 'consisting essentially of' excludes from the scope of any subsequent description any other component, step or procedure, except as 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' and 'styrene bond content' measure the vinyl (Vinyl) content and styrene content in the copolymer and the first and second copolymer units using Varian VNMRS 500 MHz NMR, it will be analyzed For NMR measurement, 1,1,2,2-tetrachloroethane was used as the solvent, and the solvent peak was calculated as 6.0 ppm, 7.2 to 6.9 ppm for random styrene, 6.9 to 6.2 ppm for block styrene, and 5.8 to 5.1 ppm for 1,4-vinyl and 1,2-vinyl, 5.1 to 4.5 ppm are measured by calculating the 1,2-vinyl bond content and the styrene defect content in the entire polymer, respectively, using the peak of 1,2-vinyl.

In the present specification, 'weight average molecular weight (Mw)', 'molecular weight distribution (MWD)' and 'unimodal characteristics' are measured by measuring molecular weight through gel permeation chromatograph (GPC) analysis and obtaining a molecular weight distribution curve. In addition, molecular weight distribution (PDI, MWD, Mw/Mn) is calculated from each of the measured molecular weights. Specifically, the GPC uses a combination of two PLgel Olexis (Polymer Laboratories) columns and one PLgel mixed-C (Polymer Laboratories) column, and when calculating molecular weight, the GPC standard material is PS (polystyrene). The GPC measurement solvent is prepared by mixing 2 wt% of an amine compound with tetrahydrofuran.

In the present specification, the 'denaturation rate (%)' is a value calculated according to the following Equation 3 using a chromatogram obtained from chromatographic measurement, and the chromatographic measurement is, for example, by dissolving a copolymer in cyclohexane. Samples (prepared at 1.0 mg/ml) were stored in a mobile phase reservoir, and tetrahydrofuran (THF) was stored in another mobile phase reservoir. Each of the mobile phase reservoirs was connected to a dual-head pump, and first, a solution of the mobile phase reservoir in which the copolymer was dissolved was injected into the column filled with the silica adsorbent through the pump and the injector having a loop volume of 100 μl. At this time, the pressure of the pump was 450 psi, and the injection flow rate was 0.7 ml/min. Then, it was confirmed from the detector (ELSD, Waters) that the unmodified copolymer unit in the copolymer was no longer detected, and based on 5 minutes from the start of the injection, the tetrahydrofuran was injected into the column through a pump. At this time, the pressure of the pump was 380 psi, and the injection flow rate was 0.7 ml/min. According to the injection of tetrahydrofuran from the detector, it was confirmed that the modified copolymer unit in the polymer was no longer detected, and the injection of the second solvent was terminated. Then, the denaturation rate (%) was calculated according to Equation 1 below from the detected chromatogram results.

[Equation 3]

In Equation 3, the peak area of the unmodified copolymer unit is the peak area of the chromatogram for the first solution transferred to the detector, and the peak area of the modified copolymer unit is the second solution transferred to the detector is the peak area of the chromatogram for

Modified conjugated diene-based copolymer

The modified conjugated diene-based copolymer according to the present invention includes a first copolymer unit, a second copolymer unit, and a functional group derived from a modifier, and the first copolymer unit and the second copolymer unit are repeats derived from the conjugated diene-based monomer, respectively. It contains a unit and a repeating unit derived from an aromatic vinylic monomer, and is characterized in that it satisfies the following conditions (i) to (vi):

(i) the molecular weight distribution curve by gel permeation chromatography is unimodal,

(ii) the molecular weight distribution is 1.0 or more and less than 1.7;

(iii) a styrene bond content of at least 15% by weight and less than 25% by weight;

(iv) 1,2-vinyl bond content is greater than or equal to 45% by weight and less than 55% by weight;

(v) a weight average molecular weight of 100,000 g/mol or more and less than 3,000,000 g/mol,

(vi) the first copolymer unit and the second copolymer unit satisfy the following Equations 1 and 2,

[Equation 1]

|SM ₁ -SM ₂ | < 10% by weight

In Equation 1, SM ₁ is the styrene bond content in the first copolymer unit, SM ₂ is the styrene bond content in the second copolymer unit,

[Equation 2]

VN ₁ -VN ₂ ≥ 20% by weight

In Equation 2, VN ₁ is the content of 1,2-vinyl bonds in the first copolymer unit, and VN ₂ is the content of 1,2-vinyl bonds in the second copolymer unit.

According to an embodiment of the present invention, the modified conjugated diene-based copolymer is derived from a first copolymer unit and a second copolymer unit and a modifier having a gradient under specific conditions in the styrene bond content and the 1,2-vinyl bond content. By including functional groups and satisfying conditions (i) to (vi) at the same time, mechanical properties such as tensile properties, viscoelasticity, and compounding processability can be excellent at the same time, and wet road resistance, abrasion resistance and running resistance can be excellent in balance have.

Specifically, the first copolymer unit and the second copolymer unit may satisfy Equations 1 and 2. That is, the first copolymer unit and the second copolymer unit may have a difference in the content of styrene bonds in the copolymer unit of 10% by weight or less in absolute value and a difference in the content of 1,2-vinyl bonds of 20% by weight or more, in this case The first copolymer unit may have a higher 1,2-vinyl bond content than the second copolymer unit.

Specifically, in Equation 1, |SM ₁ -SM ₂ | may be 5 wt% or less, and VN ₁ -VN ₂ in Equation 2 may be 30 wt% or more and 50 wt% or less. That is, in the first copolymer unit and the second copolymer unit, the difference in the styrene bond content in each copolymer unit is 5 wt% or less in absolute value, and the difference in the 1,2-vinyl bond content is 30 wt% or more and 50 wt% or less, and in this case, it may be advantageous to improve the wet road resistance, abrasion resistance, and running resistance in a balanced way.

In addition, the first copolymer unit may have a styrene bond content of 15 parts by weight to 25 parts by weight, and a 1,2-vinyl bond content of 40 parts by weight to 60 parts by weight relative to 100 parts by weight of the first copolymer unit, The modified conjugated diene-based copolymer may include 5 wt% or more and less than 30 wt% of the first copolymer unit, specifically, 10 wt% or more and 25 wt% or less. In this case, the wet road resistance may be improved without fear of deterioration in wear resistance and driving resistance.

Meanwhile, the first copolymer unit and the second copolymer unit may be first and second copolymer blocks each including a repeating unit derived from a conjugated diene-based monomer and a repeating unit derived from an aromatic vinyl-based monomer. In addition, each of the first and second copolymer units may be a random copolymer, and the random copolymer means that the repeating units constituting the copolymer are disorderly arranged.

The repeating unit derived from the conjugated diene-based monomer may mean a repeating unit formed during polymerization of the conjugated diene-based monomer, and the repeating unit derived from the aromatic vinyl-based monomer may mean a repeating unit formed during polymerization of the aromatic vinyl-based monomer.

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) may be at least one selected from the group consisting of.

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 at least one selected from the group consisting of -vinyl-5-hexylnaphthalene.

As another example, each of the first and second copolymer units may be a copolymer further comprising a repeating unit derived from a diene-based monomer having 1 to 10 carbon atoms together with a repeating unit derived from a conjugated diene-based monomer. The repeating unit derived from the 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. . When each of the first and second copolymer units is a copolymer further comprising a diene-based monomer, the amount of the repeating unit derived from the diene-based monomer is greater than 0% by weight to 1% by weight, greater than 0% by weight to 0.1% by weight, and greater than 0% by weight % to 0.01% by weight, or more than 0% by weight to 0.001% by weight, there is an effect of preventing gel formation within this range.

In addition, the modified conjugated diene-based copolymer according to an embodiment of the present invention may include a functional group derived from a modifier, and may have a modification rate of 80% or more, or 85% or more and 100% or less. Here, the denaturant-derived functional group may refer to a functional group derived from the denaturant present at one end of the active polymer through a reaction or coupling between the active polymer and the denaturant. Meanwhile, in an example of the present invention, the functional group derived from the modifier may be located at one end of the first copolymer unit.

In addition, the denaturation rate may be affected by the extent to which coupling occurs by the denaturant in the denaturation reaction, and the amount of denaturant added during manufacture, the amount of polar additive, the reaction time, the mixing time and mixing of the denaturant and the active polymer It can be controlled according to the degree and the like.

On the other hand, the modifier may be a modifier for modifying the ends of the 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, particularly a silica-based filler, and thus a silica-based filler and It may refer to a functional group capable of interaction between functional groups derived from the denaturant.

The modifier may be, for example, an alkoxysilane-based compound, and a specific example may be an alkoxysilane-based compound containing at least one hetero atom such as a nitrogen atom, an oxygen atom, or a sulfur atom. When the alkoxysilane-based compound is used as a modifier, through a substitution reaction between an anionic active site located at one end of the active polymer and the alkoxy group of the alkoxysilane-based compound, one end of the active polymer is modified to be bonded to a silyl group. Accordingly, the affinity of the modified conjugated diene-based copolymer including the first copolymer unit from the modifier-derived functional group present at one end of the first copolymer unit to the inorganic filler and the like can be improved. There is an effect that the viscoelasticity of the rubber composition containing the modified conjugated diene-based copolymer is further improved. In addition, when the alkoxysilane-based compound contains a nitrogen atom, in addition to the effect derived from the silyl group, an additional synergistic effect of physical properties derived from the nitrogen atom can be expected.

According to an embodiment of the present invention, the modifier may include a compound represented by the following formula (1).

[Formula 1]

In Chemical Formula 1, R ¹ may be a single bond or an alkylene group having 1 to 10 carbon atoms, R ² and R ³ may each independently be an alkyl group having 1 to 10 carbon atoms, R ⁴ is hydrogen, or an alkylene group having 1 to 10 carbon atoms. It may be a 10 alkyl group, 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, R ²¹ is a single bond, an alkylene group having 1 to 10 carbon atoms , or -[R ⁴² O] _j - may be, R ⁴² may be an alkylene group having 1 to 10 carbon atoms, a and m may each independently be an integer selected from 1 to 3, n is 0, 1, Alternatively, it may be an integer of 2, and j may be an integer selected from 1 to 30.

As a specific example, in Formula 1, R ¹ may be a single bond or an alkylene group having 1 to 5 carbon atoms, R ² and R ³ may each independently be hydrogen or an alkyl group having 1 to 5 carbon atoms, and R ⁴ is It may be hydrogen, 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 ²¹ is a single bond, or an alkylene group having 1 to 5 carbon atoms. , or -[R ⁴² O] _j may be -, R ⁴² may be an alkylene group having 1 to 5 carbon atoms, a may be an integer of 2 or 3, m may be an integer selected from 1 to 3, n may be an integer of 0, 1, or 2, in this case, m+n=3, and j may be an integer selected from 1 to 10.

In Formula 1, when R ⁴ is a heterocyclic group, the heterocyclic group may be unsubstituted or substituted with a trisubstituted alkoxysilyl group, and when the heterocyclic group is substituted with a trisubstituted alkoxysilyl group, the trisubstituted alkoxysilyl group It may be substituted by being connected to 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.

As a more specific example, the compound represented by Formula 1 may be 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), tri(trimethoxysilyl)amine, tri(3-(tri Methoxysilyl)propyl)amine (tri-(3-(trimethoxysilyl)propyl)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-imidazol-1-yl)propyl)-(tri Ethoxysilyl)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-(trimethoxysi lyl)propyl)propan-1-amine), 3-(trimethoxysilyl)-N-(3-trimethoxysilyl)propyl)-N-(3-(1-(3-(trimethoxysilyl) propyl)-1H-1,2,4-triazol-3-yl)propyl)propan-1-amine(3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)-N-(3-(1) -(3-(trimehtoxysilyl)propyl)-1H-1,2,4-triazol-3-yl)propyl)propan-1-amine), N,N-bis(2-(2-methoxyethoxy)ethyl )-3-(triethoxysilyl)propan-1-amine (N,N-bis(2-(2-methoxyethoxy)ethyl)-3-(triethoxysilyl)propna-1-amine), N,N-bis( 3-(triethoxysilyl)propyl)-2,5,8,11,14-pentaoxahexadecan-16-amine (N,N-bis(3-(triethoxysilyl)propyl)-2,5,8, 11,14-pentaoxahexadecan-16-amine), N-(2,5,8,11,14-pentaoxahexadecan-16-yl)-N-(3-(triethoxysilyl)propyl)-2, 5,8,11,14-pentaoxahexadecan-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-tetraoxahexadecyl)-N-(3-(triethoxysilyl)propyl)-3,6, 9,12-tetraoxahexadecan-1-amine(N-(3,6,9,12-tetraoxahexadecyl)-N-(3-(triethoxysilyl)propyl)-3,6,9,12-tetraoxahexadecan-1- amine) may be one selected from the group consisting of.

As another example, the modifier may include a compound represented by the following formula (2).

[Formula 2]

또는

일 수 있으며, 이 때, R¹³, R¹⁴, R¹⁵ 및 R¹⁶은 각각 독립적으로 수소, 또는 탄소수 1 내지 10의 알킬기일 수 있다.In Formula 2, R ⁵ , R ⁶ and R ⁹ may each independently be an alkylene group having 1 to 10 carbon atoms, and R ⁷ , R ⁸ , R ¹⁰ and R ¹¹ are each independently an alkyl group having 1 to 10 carbon atoms. may be, R ¹² may be hydrogen or an alkyl group having 1 to 10 carbon atoms, b and c are each independently 0, 1, 2 or 3, b + c ≥ 1, and A is

or

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

As a specific example, the compound represented by Formula 2 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-1-yl)-N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine) may be one selected from the group consisting of.

As another example, the modifier may include a compound represented by the following formula (3).

[Formula 3]

In Formula 3, A ¹ and A ² may each independently be a divalent hydrocarbon group having 1 to 20 carbon atoms including or not including an oxygen atom, and R ¹⁷ to R ²⁰ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms. 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 5 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 include 1 to 3 at least one hetero atom selected from the group consisting of N, O and S.

As a specific example, in Formula 3, A ¹ and A ² may each independently be an alkylene group ^{having 1 to 10, R 17} to R ²⁰ may each independently be an alkyl group having 1 to 10 carbon atoms, and L ¹ to L ⁴ is each independently a tetravalent alkylsilyl group substituted with an alkyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or L ¹ and L ² and L ³ and L ⁴ are connected to each other and a ring having 1 to 3 carbon atoms may form, 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 may contain one or more heteroatoms selected from the group consisting of N, O and S from 1 to It can contain three.

As a more specific example, the compound represented by Formula 3 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) 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-dipropylpropane- 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-dipropyl) Ropan-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-diethylmethan-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-dimethylmethan-1-amine)(3,3'-(1,1,3) ,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethan-1-amine)), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl) Bis(N,N-dipropylmethan-1-amine)(3,3'-(1,1,3,3-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-am ine)), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethan-1-amine)(3,3'- (1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethan-1-amine)), 3,3'-(1,1,3,3-tetraethoxydisiloxane -1,3-diyl)bis(N,N-dimethylmethan-1-amine)(3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethan) -1-amine)), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethan-1-amine) (3, 3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethan-1-amine)), N,N'-((1,1,3,3-tetra Methoxydisiloxane-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-tetraprotooxydisiloxane-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-phenyl Silanamine)(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-tetrapropoxydisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1- Trimethyl-N-phenylsilanamine)(N,N'-((1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1 -trimethyl-N-phenylsilanamine)), 1,3-bis (3- (1H-imidazol-1-yl) propyl) -1,1,3,3-tetramethoxydisiloxane (1,3-bis (3 -(1H-imidazol-1-yl)propyl)-1,1,3,3-tetramethoxydisiloxane), 1,3-bis(3-(1H-imidazol-1-yl)propyl)-1,1,3 ,3-tetraethoxydisiloxane (1,3-bis(3-(1H-imidazol-1-yl)propyl)-1,1,3,3-tetraethoxydisiloxane), and 1,3-bis(3-( 1H-imidazol-1-yl)propyl)-1,1,3,3-tetrapropoxydisiloxane (1,3-bis(3-(1H-imidazol-1-yl)propyl)-1,1, 3,3-tetrapropoxydisiloxane) may be one selected from the group consisting of.

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

[Formula 4]

In Formula 4, 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. , d and e are each independently 0, or an integer selected from 1 to 3, d+e may be an integer of 1 or more, and f may be an integer of 1 to 30.

Specifically, in Formula 4, 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 are each independently a carbon number 1 to 10 may be an alkyl group, 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 of 1 or more, and f may be an integer selected from 1 to 30.

More specifically, the compound represented by Formula 4 may be a compound represented by Formula 4a, Formula 4b, or Formula 4c.

[Formula 4a]

[Formula 4b]

[Formula 4c]

In Formulas 4a, 4b, and 4c, R ²² to R ²⁷ , d and e are the same as described above.

As a more specific example, the compound represented by Formula 4 is 1,4-bis(3-(3-(triethoxysilyl)propoxy)propyl)piperazine (1,4-bis(3-(3-(triethoxysilyl)propoxysilyl) ) 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)prop yl)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 modifier may include a compound represented by the following Chemical Formula 5.

[Formula 5]

In Formula 5, 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 are each independently 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 modifier may include a compound represented by the following formula (6).

[Formula 6]

In Formula 6, A ³ and A ⁴ may each independently be an alkylene group of 1 to 10, 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, , i may be an integer selected from 1 to 30.

In another example, the denaturant is 3,4-bis(2-methoxyethoxy)-N-(4-(triethoxysilyl)butyl)aniline (3,4-bis(2-methoxyethoxy)-N-( 4-(trimethylsilyl)butyl)aniline), N,N-diethyl-3-(7-methyl-3,6,8,11-tetraoxa-7-silatridecan-7-yl)propan-1-amine (N,N-diethyl-3-(7-methyl-3,6,8,11-tetraoxa-7-silatridecan-7-yl)propan-1-amine), 2,4-bis(2-methoxy oxy)-6-((trimethylsilyl)methyl)-1,3,5-triazine (2,4-bis(2-methoxyethoxy)-6-((trimethylsilyl)methyl)-1,3,5-triazine) and 3,14-dimethoxy-3,8,8,13-tetramethyl-2,14-dioxa-7,9-dithia-3,8,13-trisilapentadecane (3,14-dimtehosy- 3,8,8,13-tetramethyl-2,14-dioxa-7,9-dithia-3,8,13-trisilapentadecane) may include one or more selected from the group consisting of).

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

[Formula 7]

In Formula 7, 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.

As a more specific example, the compound represented by Formula 7 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), 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) and 8-butyl-3,3,13,13-tetramethoxy-8-((3-(trimethoxysilyl) Propyl)thio)-2,14-dioxa-7,9-dithia-3,13-disila-8-stanpentadecane (8-butyl-3,3,13,13-tetramethoxy-8-(( 3-(trimehtoxysilyl)propyl)thio)-2,14-dioxa-7,9-dithia-3,13-disila-8-stannapentadecane) may be selected from the group consisting of).

In addition, the modified conjugated diene-based copolymer according to an embodiment of the present invention includes the first copolymer unit and the second copolymer unit as described above and at the same time satisfies the conditions (i) to (v). can

Specifically, in the modified conjugated diene-based copolymer, a molecular weight distribution curve by gel permeation chromatography (GPC) is unimodal, and a molecular weight distribution may be 1.0 or more and less than 1.7, wherein the unimodal The curve shape and molecular weight distribution of can be simultaneously satisfied by continuous polymerization, which will be described later.

In addition, the modified conjugated diene-based copolymer has a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 100,000 g/mol to 3,000,000 g/mol, 200,000 g/mol to 2,000,000 g/ mol or 300,000 g/mol to 1,500,000 g/mol, within this range, there is an excellent effect in a better balance between running resistance and wet road resistance.

In addition, the modified conjugated diene-based copolymer has a styrene bond content of 15 wt% or more and less than 25 wt%, a 1,2-vinyl bond content of 45 wt% or more and less than 55 wt%, specifically a styrene bond content of 18 Weight % or more and 22 wt% or less, and the 1,2-vinyl bond content may be 48 wt% or more and 52 wt% or less. Since there is a possibility that wear resistance may become extremely poor depending on the content of styrene bonds and the content of 1,2-vinyl bonds in the modified conjugated diene-based copolymer, the content of styrene bonds and 1,2-vinyl bonds when preparing the modified conjugated diene-based copolymer It is necessary to pay attention to the reaction conditions so that the content can satisfy the above range, and when the above range is satisfied, wet road resistance and driving resistance can be excellently balanced without fear of deterioration of abrasion resistance.

Here, the styrene bond content and the 1,2-vinyl bond content of the modified conjugated diene-based copolymer are the difference between the styrene bond content of the first copolymer unit and the second copolymer unit in the modified conjugated diene-based copolymer and 1,2 -Can be adjusted according to the difference in the vinyl bond content, as another example, the content of the first copolymer unit in the modified conjugated diene-based copolymer, the difference in the styrene bond content between the first copolymer unit and the second copolymer unit, and 1,2 -Can be adjusted according to the difference in vinyl bond content. Here, the content of the first copolymer unit, the styrene bond content and the 1,2-vinyl bond content of the first copolymer unit and the second copolymer unit may depend on the ratio of the monomers, the polymerization method and conditions, for example, It may be affected by the initial polymerization conversion rate and the amount and time of input of the polar additive.

In addition, the modified conjugated diene-based copolymer according to an embodiment of the present invention must satisfy that the Mooney viscosity measured under ASTM D1646 is 10 to 120, specifically 30 to 110, preferably It may be 40 to 100. There may be various measures for evaluating the processability, but when the Mooney viscosity satisfies the above range, the processability may be quite excellent.

Method for producing a modified conjugated diene-based copolymer

The present invention provides a method for preparing a modified conjugated diene-based copolymer in order to prepare the modified conjugated diene-based copolymer.

The modified conjugated diene-based copolymer preparation method comprises the steps of preparing an active copolymer by polymerizing a conjugated diene-based monomer and an aromatic vinyl-based monomer in a hydrocarbon solvent in the presence of a polymerization initiator and a polar additive (S1); and a step (S2) of reacting the active copolymer prepared in step (S1) with a modifier, wherein the polymerization reaction (S1) and the modification reaction (S2) are carried out continuously, and the step (S1) is 2 It is carried out in a polymerization reactor of more than one group, and the polymerization conversion rate in the first polymerization reactor among the polymerization reactors may be 50% or less, and a polar additive and a conjugated diene-based monomer are added at a time point when the polymerization conversion rate is 70% to 90% after initiation of polymerization. It may be carried out by adding additionally.

Hereinafter, the characteristics of the modified conjugated diene-based copolymer and the modifier used in the reaction overlap with those described above, and thus description thereof will be omitted.

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

According to one 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 to 0.8 mmol based on 100 g of the total monomer. Can be used. The polymerization initiator is, for example, methyllithium, ethyllithium, propyllithium, isopropyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octyllithium, phenyllithium, 1-naphthyllithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolylithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naphthyl sodium, It may be at least one selected from the group consisting of naphthyl potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide and lithium isopropylamide.

The polymerization in step (S1) may be, for example, anionic polymerization, and as a specific example, living anionic polymerization having an anionic active site at the polymerization end by an anion-based growth polymerization reaction. In addition, the polymerization in step (S1) may be an elevated temperature polymerization, isothermal polymerization, or constant temperature polymerization (adiabatic polymerization), and the constant temperature polymerization includes a step of polymerizing by its own heat of reaction without optionally applying heat after the polymerization initiator is added. may refer to a polymerization method, and the temperature-rising polymerization may refer to a polymerization method in which the temperature is increased by optionally applying heat after the polymerization initiator is added, and the isothermal polymerization is heat by adding heat after the polymerization initiator is added It may refer to a polymerization method in which the temperature of the polymer is maintained constant by increasing the temperature or taking heat away.

In addition, according to an embodiment of the present invention, the polymerization in step (S1) may be carried out by further including a diene-based compound having 1 to 10 carbon atoms in addition to the conjugated diene-based monomer, and in this case, a gel is formed on the reactor wall during long-term operation. This has the effect of preventing its formation. The diene-based compound may be, for example, 1,2-butadiene.

In addition, according to one embodiment of the present invention, the polymerization in step (S1) is carried out in two or more polymerization reactors, the polymerization conversion in the first polymerization reactor of the polymerization reactor is 50% or less, specifically 10% It may be more than 50% or less, or 20% to 50%. That is, the polymerization in step (S1) may be performed only until the polymerization conversion rate in the first polymerization reactor is 50% or less, 10% or more and 50% or less, or 20% or more and 50% or less. After the polymerization reaction is initiated within this range, a polymer of a linear structure can be induced during polymerization by suppressing side reactions that occur while the polymer is formed, thus having the unimodal molecular weight distribution curve as described above. The molecular weight distribution may satisfy the above-mentioned range. In this case, the polymerization conversion rate may be adjusted according to the reaction temperature, the residence time of the reactor, and the like.

In addition, the polymerization of step (S1) may be carried out by additionally adding a polar additive and a conjugated diene-based monomer at a time when the polymerization conversion rate is 70% to 90% after the start of polymerization, in which case the modified conjugated diene-based monomer produced The content of the first copolymer unit in the copolymer and the difference between the styrene bond content and the 1,2-vinyl bond content between the first copolymer unit and the second copolymer unit can be adjusted as described above, and as a result, the modified conjugated diene It may be advantageous to adjust the styrene bond content and the 1,2-vinyl bond content of the copolymer based on the above-mentioned ranges.

More specifically, the polymerization of step (S1) is carried out in two or more polymerization reactors, and in the first polymerization reactor, in a hydrocarbon solvent, in the presence of a polymerization initiator and a first polar additive, a first conjugated diene-based monomer and an aromatic vinyl-based monomer The monomer is polymerized until the polymerization conversion rate is 50% or less, or from 10% to 50% to prepare an active polymer having the above polymerization conversion rate, and the polymerization is continued in the second polymerization reactor and the subsequent polymerization reactor, but the polymerization conversion rate after the start of polymerization is At a time of 70% to 90%, the second polar additive and the second conjugated diene-based monomer may be additionally added.

On the other hand, the second conjugated diene-based monomer may be used in an amount of more than 0 parts by weight to 30 parts by weight or less based on 100 parts by weight of the first conjugated diene-based monomer.

In addition, the total amount of the polar additive used in the polymerization of step (S1) may be used in a ratio of 0.001 g to 50 g, or 0.002 g to 1.0 g based on 100 g of the total monomer. As another example, the total amount of the polar additive may be used in a ratio of more than 0 g to 1 g, 0.01 g to 1 g, or 0.1 g to 0.9 g based on 100 g of the total polymerization initiator. Here, the total amount of the polar additive used means the total amount of the first polar additive and the second polar additive.

As another example, the second polar additive may be used in an amount of 2 to 1000 times that of the first polar additive, and specifically, the second polar additive may be used in an amount of 4 to 100 times compared to the first polar additive. have.

The polar additive is, for example, tetrahydrofuran, ditetrahydrofurylpropane, diethyl ether, cycloamyl ether, dipropyl ether, ethylene methyl ether, ethylene dimethyl ether, diethyl glycol, dimethyl ether, tertiary butoxyethoxyethane , bis(3-dimethylaminoethyl)ether, (dimethylaminoethyl)ethylether, trimethylamine, triethylamine, tripropylamine, and tetramethylethylenediamine may be at least one selected from the group consisting of, specifically, triethyl amine or tetramethylethylenediamine.

On the other hand, the polymerization conversion rate can be determined by measuring the solid concentration of the copolymer solution containing the copolymer during polymerization, for example, and as a specific example, a cylindrical vessel at the outlet of each polymerization reactor to secure the copolymer solution. After mounting, a certain amount of copolymer solution is filled in a cylindrical container, the cylindrical container is separated from the reactor, the weight (A) of the cylinder filled with the copolymer solution is measured, and the air filled in the cylindrical container is Transfer the copolymer solution to an aluminum container, for example, an aluminum dish, measure the weight (B) of the cylindrical container from which the copolymer solution has been removed, and dry the aluminum container containing the copolymer solution in an oven at 140° C. for 30 minutes, and dry After measuring the weight (C) of the copolymer, it may be calculated according to Equation 4 below.

[Equation 4]

In Equation 4, the total solid content is the weight percentage of the solid content with respect to 100% of the copolymer solution as the total solid content in the copolymer solution separated in each reactor. Illustratively, when the total solid content is 20% by weight, when this is applied to Equation 4, it may be calculated by substituting 20/100, that is, 0.2.

On the other hand, the polymer polymerized in the first reactor may be sequentially transferred to the polymerization reactor before the modification reactor, and polymerization may proceed until the polymerization conversion ratio is 95% or more. After polymerization in the first reactor, the second reactor , or 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 to control the molecular weight distribution.

In addition, the active copolymer prepared by the step (S1) may refer to a polymer in which an anion of a copolymer and an organometallic cation of a polymerization initiator are bonded.

In addition, the polymerization in step (S1) may be carried out, for example, in a temperature range of 100° C. or less, 50° C. to 100° C., or 40° C. to 80° C., and the conversion rate of the polymerization reaction can be increased within this range.

In the present invention, the term 'polymer' means that (S1) step or (S2) step is completed, prior to obtaining an active polymer or a modified conjugated diene-based copolymer, during (S1) step, polymerization in each reactor It may mean an intermediate in the form of a polymer being carried out, and may mean a polymer having a polymerization conversion rate of less than 95% in which polymerization is being carried out in the reactor.

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 100 g of the total monomer. As another example, 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 1 mole of the polymerization initiator in step (S1).

In addition, according to an embodiment of the present invention, the denaturant may be introduced into the denaturation reactor, and step (S2) may be performed in the denaturation reactor. As another example, the modifier may be added to a transfer unit for transferring the active polymer prepared in step (S1) to a modification reactor for performing step (S2), and the active polymer and modifier are mixed in the transfer unit. The reaction may be proceeded by the denaturant, in which case the reaction may be a denaturation reaction in which the modifier is simply bound to the active polymer, or a coupling reaction in which the active polymer is connected based on the modifier.

According to the present invention, there is provided a rubber composition comprising the modified conjugated diene-based copolymer.

The rubber composition may include the modified conjugated diene-based copolymer in an amount of 10 wt% or more, 10 wt% to 100 wt%, or 20 wt% to 90 wt%, and tensile strength, abrasion resistance within this range It is excellent in mechanical properties, such as, and there is an effect excellent in the balance between each physical property.

In addition, the rubber composition may further include other rubber components as needed in addition to the modified conjugated diene-based copolymer, wherein 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 copolymer.

The rubber component may be, for example, natural rubber or synthetic rubber, and specific examples thereof include natural rubber (NR) including cis-1,4-polyisoprene; Modified natural rubbers such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber, which are modified or refined of 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, or a synthetic rubber such as halogenated butyl rubber, and any one or a mixture of two or more thereof 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 copolymer of the present invention. The filler may be, for example, a silica-based filler, and specific examples thereof include wet silica (hydrous silicic acid), dry silica (silicic anhydride), calcium silicate, aluminum silicate or colloidal silica, and preferably, the effect of improving the breaking properties and wet Wet silica may be the most excellent in compatibility with wet grip. 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 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 It may be silane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide or dimethoxymethylsilylpropylbenzothiazolyltetrasulfide, and any one or a mixture of two or more thereof may be used. Preferably, in consideration of the reinforcing improvement effect, it may be bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide.

In addition, in the rubber composition according to an embodiment of the present invention, as a rubber component, a modified conjugated diene-based copolymer in which a functional group with high affinity for silica is introduced is used as a rubber component, so the compounding amount of the silane coupling agent is usually may be reduced than in the case of It has the effect of preventing the gelation of the rubber component while sufficiently exhibiting.

The rubber composition according to an embodiment of the present invention may be crosslinkable with sulfur, and may further include a vulcanizing agent. The vulcanizing agent may be specifically 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. It has an excellent effect.

The rubber composition according to an embodiment of the present invention, in addition to the above components, 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, zinc white, It may further include stearic acid, a thermosetting resin, or a thermoplastic resin.

The vulcanization accelerator is, for example, a thiazole-based compound such as M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazyl sulfenamide), 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. Naphthenic or paraffinic process oils may be used. 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, for example, and has an effect of preventing deterioration of the tensile strength and low heat generation (low fuel efficiency) of the vulcanized rubber within this range.

The antioxidant 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 condensate of diphenylamine and acetone, etc., 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, an internal mixer, etc. according to the compounding prescription, and has low heat generation and wear resistance by a vulcanization process after molding processing. This excellent rubber composition can be obtained.

Accordingly, the rubber composition may be used for each member of the tire such as a tire tread, under tread, side wall, carcass coated rubber, belt coated rubber, bead filler, chaff, or bead coated rubber, vibration proof rubber, belt conveyor, hose, etc. It may be useful in the manufacture of various industrial rubber products of

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

The tire may include a tire or a tire tread.

Example

Hereinafter, examples will be given 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 explain the present invention to those of ordinary skill in the art.

Example 1

In the first reactor of five continuously stirred liquid phase reactors (CSTR), 4 kg/hr of n-hexane and a monomer solution in which a monomer mixture (80 wt% butadiene and 20 wt% of styrene) were dissolved in n-hexane at 60 wt% 1.31 kg/hr, 3.8 g/hr of an initiator solution in which 10 wt% of n-butyllithium is dissolved in n-hexane, and a first polar additive in which ditetrahydrofurylpropane is dissolved in n-hexane at 10 wt% 1 The polar additive solution was continuously added at a flow rate of 0.66 g/hr. At this time, the internal temperature of the reactor was maintained at 40° C., and when the polymerization conversion reached 35%, the polymer was transferred from the first reactor to the second reactor through a transfer pipe. The polymerization reaction was continued while maintaining the temperature of the second reactor at 50° C., and when the polymerization conversion reached 60%, the polymer was transferred from the second reactor to the third reactor through a transfer pipe. Thereafter, the polymerization reaction was continued while maintaining the temperature of the third reactor at 60° C., and when the polymerization conversion reached 80%, the polymer was transferred from the third reactor to the fourth reactor through a transfer pipe, and at the same time, the fourth reactor A 1,3-butadiene solution in which 60 wt% of 1,3-butadiene was dissolved in n-hexane was added to 0.05 kg/h and a second polar additive in which ditetrahydrofurylpropane was dissolved in n-hexane at 10 wt%. The second polar additive solution was continuously injected at a rate of 16.4 g/hr. Meanwhile, a portion of the polymer was collected while transferring the polymer from the third reactor to the fourth reactor, and then used as a microstructure analysis sample of the first copolymer unit. In addition, the temperature of the fourth reactor was maintained at 65° C., and when the polymerization conversion reached 99% or more, the polymer was transferred from the fourth reactor to the fifth reactor through a transfer pipe. The first polar additive and the second polar additive were used in a weight ratio of 1:25, and some of the polymer was collected while transferring the polymer from the fourth reactor to the fifth reactor, and then as a sample for microstructure analysis of the conjugated diene-based copolymer. was used. On the other hand, the polymerization conversion rate in each reactor was calculated based on the sum of the monomers initially added to the first reactor and the monomers additionally added to the fourth reactor.

Thereafter, the obtained polymer of the fourth reactor is continuously supplied to the fifth reactor, and as a modifier, N,N-bis(3-(dimethoxy(methyl)silyl)propyl)-methyl-1-amine is dissolved in 10% by weight. The modified solution was continuously supplied to proceed with the denaturation reaction (n-butyllithium: denaturant = 1:0.5 molar ratio). Thereafter, a solution of IR1520 (BASF Corporation) dissolved in 10% by weight as an antioxidant into the polymerization solution discharged from the fifth reactor was injected at a rate of 40 g/h and stirred. The resulting polymer was put into hot water heated with steam, stirred to remove the solvent, and then roll-dried to remove the remaining solvent and water, thereby preparing a modified conjugated diene-based copolymer. The analysis results for the modified conjugated diene-based copolymer thus prepared are shown in Table 1 below.

Example 2

In Example 1, a modified conjugated diene-based copolymer was prepared in the same manner as in Example 1, except that the polymerization conversion in the third reactor was maintained at 85%. The analysis results for the modified conjugated diene-based copolymer thus prepared are shown in Table 1 below.

Example 3

In Example 1, tri(3-(trimethoxysilyl)propyl)amine was used instead of N,N-bis(3-(dimethoxy(methyl)silyl)propyl)-methyl-1-amine as a modifier. Except for that, a modified conjugated diene-based copolymer was prepared in the same manner as in Example 1. The analysis results for the modified conjugated diene-based copolymer thus prepared are shown in Table 1 below.

Comparative Example 1

180 g of styrene, 684 g of 1,3-butadiene, 5000 g of n-hexane and 0.07 g of ditetrahydrofuryl propane as the first polar additive were put into a 20L autoclave reactor, and then the temperature inside the reactor was raised to 70°C. When the internal temperature of the reactor reached 70°C, 4.2 g of an initiator solution in which n-butyllithium was dissolved at 10% by weight in n-hexane was added to proceed adiabatic temperature increase, and the polymerization conversion rate was 80%. 2 As a polar additive, 1.8 g of ditetrahydrofuryl propane and 36 g of 1,3-butadiene were added, and after 15 minutes, N,N-bis(3-(dimethoxy(methyl)silyl)propyl) as a modifier for the modification reaction -Methyl-1-amine was added and reacted for 30 minutes (n-butyllithium: modifier = 1:0.3 molar ratio). On the other hand, a portion of the polymer was collected before adding the second polar additive and before adding the modifier, and then used as a sample for analyzing the microstructure of the first copolymer unit and the conjugated diene-based polymer. Then, 30 g of methanol was added to stop the polymerization reaction, and 45 ml of a solution in which an antioxidant IR1520 (BASF) was dissolved in hexane by 0.3 wt% was added. The resulting polymer was put into hot water heated by steam, stirred to remove the solvent, and then roll-dried to remove the remaining amount of solvent and water to prepare a modified conjugated diene-based copolymer. The analysis results for the modified conjugated diene-based copolymer thus prepared are shown in Table 1 below.

Comparative Example 2

According to Example 1, maintaining the internal temperature of the first reactor, the second reactor, the third reactor and the fourth reactor to be 65 ℃, 70 ℃, 75 ℃ and 75 ℃, respectively, the first polar additive and the second polarity The same as in Example 1, except that a polar additive solution in which 10 wt% of ditetrahydrofurylpropane was dissolved in n-hexane as an additive was continuously added at a flow rate of 1.0 g/hr and 24.6 g/hr, respectively. A modified conjugated diene-based copolymer was prepared by the method. The analysis results for the modified conjugated diene-based copolymer thus prepared are shown in Table 1 below.

Comparative Example 3

In Example 1, as in Example 1, except that a solution in which a monomer mixture containing 90 wt% of 1,3-butadiene and 10 wt% of styrene in n-hexane was dissolved at 60 wt% was used as the monomer solution. A modified conjugated diene-based copolymer was prepared in the same manner. The analysis results for the modified conjugated diene-based copolymer thus prepared are shown in Table 1 below.

Comparative Example 4

In Example 1, a polar additive solution in which 10% by weight of ditetrahydrofurylpropane was dissolved in n-hexane as the first and second polar additives, respectively, was added at 5.1 g/hr and 7.7 g/hr (first polarity) A modified conjugated diene-based copolymer was prepared in the same manner as in Example 1, except that the additive and the second polar additive were used in a weight ratio of 1:1.5. The analysis results for the modified conjugated diene-based copolymer thus prepared are shown in Table 1 below.

Experimental example

Experimental Example 1

Microstructure analysis (styrene bond content and 1,2-vinyl bond content), weight average molecular weight (Mw, X10 ³ g/mol), molecular weight distribution (PDI, MWD) for each copolymer prepared in Examples and Comparative Examples ) and molecular weight distribution curves were measured, respectively, and are shown in Table 1 below.

1) Microstructure analysis

Microstructure analysis of each copolymer prepared in Examples and Comparative Examples was analyzed by measuring the styrene and 1,2-vinyl bond contents of each copolymer using Varian VNMRS 500 MHz NMR.

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

In addition, during the preparation of the copolymer in Examples and Comparative Examples, the first copolymer unit and the unmodified conjugated diene-based copolymer through the NMR measurement using some polymers collected in advance before the input of the second polar additive and before the addition of the modifier as a sample. By measuring the styrene and 1,2-vinyl bond content of each and calculating the styrene and 1,2-vinyl bond content of the second copolymer unit from the difference between the first copolymer unit and the unmodified conjugated diene-based copolymer, A difference in styrene and 1,2-vinyl bond content between the first copolymer unit and the second copolymer unit was confirmed.

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

The weight average molecular weight (Mw) and number average molecular weight (Mn) were measured through gel permeation chromatohraph (GPC) analysis, a molecular weight distribution curve was obtained, and molecular weight distribution (PDI, MWD, Mw/Mn) was measured for each molecular weight. was calculated from Specifically, the GPC uses a combination of two PLgel Olexis (Polymer Laboratories) columns and one PLgel mixed-C (Polymer Laboratories) column, and when calculating molecular weight, the GPC standard material is PS (polystyrene). was used. The GPC measurement solvent was prepared by mixing 2 wt% of an amine compound in tetrahydrofuran.

division |SM ₁ -SM ₂ |
(weight%) VN ₁ -VN ₂
(weight%) GPC Styrene bond content
(weight%) 1,2-vinyl bond
(weight%) molecular weight distribution curve Mw (X10 ³ g/mol) MWD Example 1 3.5 34.0 unimodal 480 1.55 20.2 49.8 Example 2 3.3 33.3 unimodal 510 1.62 20.1 50.5 Example 3 2.5 36.5 unimodal 490 1.58 20.1 50.3 Comparative Example 1 1.0 31.0 bimodal 460 1.50 19.8 51.2 Comparative Example 2 4.5 36.5 unimodal 590 1.80 20.2 50.3 Comparative Example 3 3.5 35.0 unimodal 490 1.55 10.2 65.0 Comparative Example 4 2.5 16.5 unimodal 500 1.62 20.3 50.8

Experimental Example 2

In order to compare and analyze the physical properties of the rubber composition containing each modified conjugated diene-based copolymer prepared in Examples and Comparative Examples and molded articles prepared therefrom, tensile properties, viscoelastic properties and processability properties were measured respectively and the results were obtained. It is shown in Table 3 below.

1) Preparation of rubber specimens

Each of the modified conjugated diene-based copolymers of Examples and Comparative Examples was compounded under the compounding conditions shown in Table 3 below as raw rubber. The raw materials in Table 3 are each part by weight based on 100 parts by weight of the raw rubber.

division Raw material Content (parts by weight) 1st stage kneading Rubber 100 silica 70 Coupling agent (X50S) 11.2 fair oil 37.5 Zincizing agent 3 stearic acid 2 antioxidant 2 anti-aging agent 2 wax One 2nd stage kneading sulfur 1.5 rubber accelerator 1.75 vulcanization accelerator 2

Specifically, the rubber specimen is kneaded through the first stage kneading and the second stage kneading. In the first stage kneading, raw rubber, silica (filler), organosilane coupling agent (X50S, Evonik), process oil (TDAE oil), zinc oxide (ZnO), stearic acid using a Banbari mixer with a temperature control device is used. , antioxidant (TMQ(RD) (2,2,4-trimethyl-1,2-dihydroquinoline polymer), antioxidant (6PPD ((dimethylbutyl)-N-phenyl-phenylenediamine) and wax (Microcrystaline Wax) ) was kneaded. At this time, the initial temperature of the kneader was controlled to 70° C., and after the mixing was completed, a first formulation was obtained at a discharge temperature of 145° C. to 155° C. In the second stage of kneading, the first formulation was cooled to room temperature. After mixing, the primary compound, sulfur, rubber accelerator (DPD (diphenylguanine)) and vulcanization accelerator (CZ (N-cytlohexyl-2-benzothiazylsulfenamide)) are added to the kneader, and the temperature is not higher than 100°C. A secondary formulation was obtained by mixing in. Then, a rubber specimen was prepared through a curing process at 160° C. for 20 minutes.

2) 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 the test piece and the tensile stress (300% modulus) at 300% elongation were measured. Specifically, the tensile properties were measured at room temperature at a speed of 50 cm/min using a Universal Test Machin 4204 (Instron Co., Ltd.) tensile tester.

3) Viscoelastic properties

For the 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°C to 60°C) in Film Tension mode using a dynamic mechanical analyzer (GABO). At this time, the higher the low temperature 0℃ tan value, the better the wet road resistance, and the lower the high temperature 60℃ tan δ value, the less the hysteresis loss and the better the low running resistance (fuel efficiency). Since the value was indexed based on the measurement result of Comparative Example 4, the higher the value, the better.

4) Wear resistance (DIN wear test)

For each rubber specimen, a DIN wear test was performed according to ASTM D5963, and it was expressed as DIN wt loss index (loss volume index): ARIA (Abration resistance index, Method A). The higher the number, the better. indicates.

5) Mixing processability

The compounding processability of each polymer was comparatively analyzed by measuring the Mooney viscosity (ML1+4, @100℃, MU) of the secondary compound obtained during 1) preparation of the rubber specimen. The lower the Mooney viscosity value, the better the compounding processability characteristics indicates.

Specifically, using MV-2000 (ALPHA Technologies) at 100°C, using a Rotor Speed of 2±0.02 rpm, and a Large Rotor, each secondary formulation was left at room temperature (23±3°C) for at least 30 minutes and then 27 ±3 g was collected and filled in the die cavity, and the platen was operated for measurement for 4 minutes.

In Table 3, the tensile properties of Examples 1 to 3 and Comparative Examples 1 to 3, tan δ and abrasion resistance at 0° C. were calculated by the following Equation 5 using the measured values of Comparative Example 4 as reference values, Example 1 To 3 and Comparative Examples 1 to 3, tan δ at 60° C. was calculated by the following Equation 6 using the measured value of Comparative Example 4 as a reference value.

[Equation 5]

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

[Equation 6]

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

As shown in Table 3, Examples 1 to 3 according to an embodiment of the present invention were superior in tensile properties, viscoelastic properties, abrasion resistance and compounding processability compared to Comparative Examples 1 to 4 in a well-balanced manner.

In this case, Examples 1 to 3 satisfied all of the conditions (i) to (vi) presented in the present invention, and Comparative Examples 1 to 4 did not satisfy any one or more of the above conditions.

As a result, the modified conjugated diene-based copolymer of the present invention includes a first copolymer unit having a gradient in a styrene defect content and a 1,2-vinyl bond content, a second copolymer unit, and a functional group derived from a modifier, (i ) to (vi), it has excellent compounding processability and is applied to a rubber composition to improve wet road resistance and abrasion resistance without deterioration of tensile properties and running resistance of the rubber composition, thereby improving the tensile properties, running resistance, wet This means that there is an effect of improving the road surface resistance and abrasion resistance in a balanced way.

Claims (11)

a first copolymer unit, a second copolymer unit, and a functional group derived from a modifier;
The first copolymer unit and the second copolymer unit each include a repeating unit derived from a conjugated diene-based monomer and a repeating unit derived from an aromatic vinyl-based monomer,
A modified conjugated diene-based copolymer satisfying the following conditions (i) to (vi):
(i) the molecular weight distribution curve by gel permeation chromatography is unimodal,
(ii) the molecular weight distribution is 1.0 or more and less than 1.7;
(iii) a styrene bond content of at least 15% by weight and less than 25% by weight;
(iv) 1,2-vinyl bond content is greater than or equal to 45% by weight and less than 55% by weight;
(v) a weight average molecular weight of 100,000 g/mol or more and less than 3,000,000 g/mol,
(vi) the first copolymer unit and the second copolymer unit satisfy the following Equations 1 and 2,
[Equation 1]
|SM ₁ -SM ₂ | < 10% by weight
In Equation 1, SM ₁ is the styrene bond content in the first copolymer unit, SM ₂ is the styrene bond content in the second copolymer unit,
[Equation 2]
VN ₁ -VN ₂ ≥ 20% by weight
In Equation 2, VN ₁ is the content of 1,2-vinyl bonds in the first copolymer unit, and VN ₂ is the content of 1,2-vinyl bonds in the second copolymer unit.
According to claim 1,
A modified conjugated diene-based copolymer comprising the first copolymer unit in an amount of 10% by weight or more and less than 25% by weight.
According to claim 1,
In Equation 1, |SM ₁ -SM ₂ | is 5 wt% or less of a modified conjugated diene-based copolymer. According to claim 1,
In Equation 2, VN ₁ -VN ₂ is 30 wt% or more and 50 wt% or less of a modified conjugated diene-based copolymer.
According to claim 1,
The first copolymer unit has a styrene bond content of 15 parts by weight to 25 parts by weight, and a 1,2-vinyl bond content of 40 parts by weight to 60 parts by weight relative to 100 parts by weight of the first copolymer unit. copolymer.
According to claim 1,
A modified conjugated diene-based copolymer having a modification rate of 80% or more.
According to claim 1,
The modifying agent is an alkoxysilane-based compound modified conjugated diene-based copolymer.
A rubber composition comprising the modified conjugated diene-based copolymer according to claim 1 and a filler.
9. The method of claim 8,
wherein the filler is a silica-based filler or a carbon black-based filler.
9. The method of claim 8,
A rubber composition comprising 0.1 parts by weight to 200 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene-based copolymer.
9. The method of claim 8,
The rubber composition further comprising a vulcanizing agent.

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