KR102627378B1 - Modified conjugated diene polymer and rubber composition comprising the same - Google Patents

Abstract

The present invention relates to a modified conjugated diene polymer, and more specifically, to a modified conjugated diene polymer manufactured by continuous polymerization and having a unique polymer structure, molecular weight distribution, and shape, thereby providing excellent processability and excellent physical properties due to a narrow molecular weight distribution. It relates to a diene polymer and a rubber composition containing the same.

Description

Modified conjugated diene polymer and rubber composition containing the same {MODIFIED CONJUGATED DIENE POLYMER AND RUBBER COMPOSITION COMPRISING THE SAME}

The present invention relates to a modified conjugated diene polymer having excellent processability and excellent tensile and viscoelastic properties, and a rubber composition containing the same.

Recently, in response to the demand for lower fuel consumption for automobiles, conjugated diene-based polymers are required as rubber materials for tires, which have low rolling resistance, excellent abrasion resistance and tensile properties, and also have steering stability, such as resistance to wet road surfaces.

In order to reduce the rolling resistance of a tire, there is a way to reduce the hysteresis loss of vulcanized rubber, and as evaluation indicators for such vulcanized rubber, rebound elasticity at 50°C to 80°C, tan δ, and Goodrich heat generation are used. That is, a rubber material with high rebound elasticity at the above temperature or low tan δ and Goodrich heat generation is preferable.

Natural rubber, polyisoprene rubber, and polybutadiene rubber are known as rubber materials with low hysteresis loss, but these have the problem of low wet road surface resistance. 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) are manufactured by emulsion polymerization or solution polymerization and are used as tire rubber. . Among these, the biggest advantage of solution polymerization over emulsion polymerization is that the vinyl structure content and styrene content that define the rubber properties can be arbitrarily adjusted, and the molecular weight and physical properties can be adjusted through coupling or modification. The point is that it can be adjusted. Therefore, it is easy to change the structure of the final manufactured SBR or BR, and bonding or modification of the chain ends can reduce the movement of the chain ends and increase the bonding strength with fillers such as silica or carbon black, so SBR by solution polymerization can be used in tires. It is widely used as a rubber material.

When this solution-polymerized SBR is used as a rubber material for tires, by increasing the vinyl content in the SBR, the glass transition temperature of the rubber can be raised to adjust the tire's required physical properties such as running resistance and braking force, as well as lowering the glass transition temperature. By adjusting appropriately, fuel consumption can be reduced. The solution polymerization SBR is manufactured using an anionic polymerization initiator, and is used by bonding or denaturing the chain ends of the formed polymer using various denaturants. For example, U.S. Patent No. 4,397,994 proposes a technique in which active anions at the chain ends of a polymer obtained by polymerizing styrene-butadiene in a non-polar solvent using a monofunctional initiator, alkyl lithium, are combined using a binder such as a tin compound. did.

Meanwhile, the polymerization of SBR or BR can be carried out by batch or continuous polymerization. In the case of batch polymerization, the molecular weight distribution of the produced polymer is narrow, so there is an advantage in terms of improving physical properties, but productivity is low and , there is a problem in that processability is poor, and in the case of continuous polymerization, polymerization is performed continuously and productivity is excellent, and there is an advantage in terms of improved processability, but there is a problem in that the physical properties are poor due to the wide molecular weight distribution. Accordingly, when manufacturing SBR or BR, research to simultaneously improve productivity, processability, and physical properties is continuously required.

US 4397994 A J.P. 1994-271706 A

The present invention was made to solve the problems of the prior art, and is manufactured by continuous polymerization, and has excellent processability, excellent physical properties such as tensile properties, and excellent viscoelastic properties, and a modified conjugated diene polymer containing the same. The object is to provide a rubber composition.

According to one embodiment of the present invention to solve the above problem, the present invention has a molecular weight distribution curve by gel permeation chromatography (GPC) that has a unimodal form and a molecular weight distribution (PDI; A modified conjugated diene-based polymer having an MWD) of 1.0 or more and less than 1.7, including a functional group derived from a modified initiator represented by Formula 1 below at one end, and a functional group derived from a denaturant represented by Formula 2 or Formula 3 below at the other end. Provides:

[Formula 1]

In Formula 1,

Cy is a divalent cyclic saturated hydrocarbon or aromatic hydrocarbon having 5 to 12 carbon atoms,

A is -NR ₃ or -CR ₄ R ₅ , where R ₃ to R ₅ are independently hydrogen, a linear hydrocarbon group having 1 to 20 carbon atoms, or a monocyclic or polycyclic ring having 4 to 20 carbon atoms. It is a hydrocarbon group,

R ₁ and R ₂ are independently an alkylene group having 1 to 5 carbon atoms,

M ₁ and M ₂ are independently alkali metals,

[Formula 2]

In Formula 2,

R ₂₀ is a single bond or an alkylene group having 1 to 10 carbon atoms,

R ₂₁ and R ₂₂ are independently an alkyl group having 1 to 10 carbon atoms, or -[R ₄₂ O] _d -R ₄₃ ,

R ₂₃ is a single bond, an alkylene group having 1 to 10 carbon atoms, or -[R ₄₂ O] _d -,

R ₂₄ is hydrogen, an alkyl group having 1 to 10 carbon atoms,

R ₄₂ is an alkylene group having 1 to 10 carbon atoms,

R ₄₃ is an alkyl group having 1 to 10 carbon atoms,

a is 2 or 3, c is an integer from 1 to 3, b is an integer from 0 to 2, b+c=3, d is an integer from 1 to 30,

At least one of R ₂₁ to R ₂₃ necessarily includes the -[R ₄₂ O] _d - unit,

[Formula 3]

In Formula 3, Cy is a trivalent aromatic hydrocarbon group having 6 to 20 carbon atoms or a trivalent heteroaromatic hydrocarbon group having 3 to 20 carbon atoms,

R ₃₀ is a single bond, -NR ₄₄ -, -O-, -S-, or an alkylene group having 1 to 10 carbon atoms,

R ₃₁ and R ₃₂ are independently an alkyl group having 1 to 10 carbon atoms,

R ₃₃ is -[R ₄₂ O] _d -,

R ₃₄ is hydrogen, an alkyl group having 1 to 10 carbon atoms,

R ₄₂ is an alkylene group having 1 to 10 carbon atoms,

R ₄₄ is hydrogen or an alkyl group having 1 to 10 carbon atoms,

m is an integer from 0 to 3, k and n are integers from 1 or 2, where k+n=3, and d is an integer from 1 to 30.

Additionally, the present invention provides a rubber composition comprising the modified conjugated diene polymer and a filler.

The modified conjugated diene polymer according to the present invention is manufactured by continuous polymerization with the polymerization conversion rate controlled, so that the molecular weight distribution curve by gel permeation chromatography has a unimodal form and the molecular weight distribution is narrow to less than 1.7, thereby improving processability. It has excellent tensile properties and viscoelastic properties. In addition, the modified conjugated diene polymer according to the present invention includes a functional group derived from a modification initiator at one end and a functional group derived from the modifier at the other end, thereby improving the viscoelastic properties. It can be improved.

The following drawings attached to this specification illustrate specific embodiments of the present invention, and serve to further understand the technical idea of the present invention together with the contents of the above-described invention. Therefore, the present invention is limited to the matters described in such drawings. It should not be interpreted in a limited way.
Figure 1 shows the molecular weight distribution curve of the modified conjugated diene polymer of Example 1 according to an embodiment of the present invention by gel permeation chromatography (GPC).
Figure 2 shows the molecular weight distribution curve by gel permeation chromatography (GPC) of the modified conjugated diene polymer of Comparative Example 1 according to an embodiment of the present invention.
Figure 3 shows the molecular weight distribution curve of the modified conjugated diene polymer of Reference Example 1 according to an embodiment of the present invention by gel permeation chromatography (GPC).
Figure 4 shows the molecular weight distribution curve of the modified conjugated diene polymer of Reference Example 2 according to an embodiment of the present invention by gel permeation chromatography (GPC).

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

Terms or words used in the description and claims of the present invention should not be construed as limited to their usual or dictionary meanings, and the inventor should appropriately use the concepts of terms to explain his invention in the best way. Based on the principle of definability, it must be interpreted with meaning and concept consistent with the technical idea of the present invention.

In the present invention, 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 it may be meant to include both cyclic saturated hydrocarbons and cyclic unsaturated hydrocarbons containing one or two or more unsaturated bonds.

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

In the present invention, the terms 'derived unit' and 'derived functional group' may refer to a component or structure derived from a certain substance, or the substance itself.

In the present invention, the term 'single bond' may mean a single covalent bond itself that does not include separate atoms or molecular groups.

The present invention provides a modified conjugated diene polymer produced by continuous polymerization and having excellent processability and excellent physical properties due to its narrow molecular weight distribution.

The modified conjugated diene-based polymer according to an embodiment of the present invention has a unimodal molecular weight distribution curve determined by gel permeation chromatography (GPC), and a molecular weight distribution (PDI; MWD) of 1.0 or more. It is less than 1.7 and is characterized in that it contains a functional group derived from a denaturing initiator represented by the following formula (1) at one end, and a functional group derived from a denaturing agent represented by the formula (2) or formula (3) shown at the other end.

[Formula 1]

In Formula 1,

Cy is a divalent cyclic saturated hydrocarbon or aromatic hydrocarbon having 5 to 12 carbon atoms, and A is -NR ₃ or -CR ₄ R ₅ , where R ₃ to R ₅ are independently hydrogen or have 1 to 20 carbon atoms. is a linear hydrocarbon group or a monocyclic or polycyclic hydrocarbon group having 4 to 20 carbon atoms, R ₁ and R ₂ are independently an alkylene group having 1 to 5 carbon atoms, and M ₁ and M ₂ are independently an alkali group. It is metal,

[Formula 2]

In Formula 2, R ₂₀ is a single bond or an alkylene group having 1 to 10 carbon atoms, and R ₂₁ and R ₂₂ are independently an alkyl group having 1 to 10 carbon atoms, or -[R ₄₂ O] _d -R ₄₃ , R ₂₃ is a single bond, an alkylene group with 1 to 10 carbon atoms, or -[R ₄₂ O] _d -, R ₂₄ is hydrogen, an alkyl group with 1 to 10 carbon atoms, and R ₄₂ is an alkylene group with 1 to 10 carbon atoms, R ₄₃ is an alkyl group having 1 to 10 carbon atoms, a is 2 or 3, c is an integer of 1 to 3, b is an integer of 0 to 2, b+c=3, and d is an integer of 1 to 30. And, at least one of R ₂₁ to R ₂₃ necessarily includes the -[R ₄₂ O] _d - unit,

[Formula 3]

In Formula 3, Cy is a trivalent aromatic hydrocarbon group having 6 to 20 carbon atoms or a trivalent heteroaromatic hydrocarbon group having 3 to 20 carbon atoms, and R ₃₀ is a single bond, -NR ₄₄ -, -O-, -S-, or an alkylene group having 1 to 10 carbon atoms, R ₃₁ and R ₃₂ are independently an alkyl group having 1 to 10 carbon atoms, R ₃₃ is -[R ₄₂ O] _d -, and R ₃₄ is hydrogen, an alkyl group having 1 to 10 carbon atoms. is an alkyl group, R ₄₂ is an alkylene group having 1 to 10 carbon atoms, R ₄₄ is hydrogen or an alkyl group having 1 to 10 carbon atoms, m is an integer from 0 to 3, k and n are integers of 1 or 2, and k+ n=3, and d is an integer from 1 to 30.

According to one embodiment of the present invention, the modified conjugated diene-based polymer may include a repeating unit derived from a conjugated diene-based monomer, a functional group derived from a modification initiator, and a functional group derived from a modifying agent. The repeating unit derived from the conjugated diene monomer may refer to a repeating unit formed by the conjugated diene monomer during polymerization, and the functional group derived from the denaturing initiator and the functional group derived from the denaturing agent are each derived from the denaturing initiator or the denaturing agent present at the end of the polymer chain. It may mean a functional group.

In addition, according to another embodiment of the present invention, the modified conjugated diene-based polymer may be a copolymer containing a repeating unit derived from a conjugated diene-based monomer, a repeating unit derived from an aromatic vinyl monomer, a functional group derived from a modification initiator, and a functional group derived from a denaturant. . Here, the repeating unit derived from the aromatic vinyl monomer may refer to the repeating unit that the aromatic vinyl monomer forms during polymerization.

According to one embodiment of the present invention, the conjugated diene monomer is 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, 2 -It may be one or more types selected from the group consisting of phenyl-1,3-butadiene and 2-halo-1,3-butadiene (halo refers to a halogen atom).

The aromatic vinyl monomer includes, for example, styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, 1 -Vinyl-5-hexylnaphthalene, 3-(2-pyrrolidino ethyl)styrene (3-(2-pyrrolidino ethyl)styrene), 4-(2-pyrrolidino ethyl)styrene (4-(2-pyrrolidino ethyl) )styrene) and 3-(2-pyrrolidino-1-methyl ethyl)-α-methylstyrene (3-(2-pyrrolidino-1-methyl ethyl)styrene).

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

According to one embodiment of the present invention, the copolymer may be a random copolymer, and in this case, excellent balance between physical properties is achieved. The random copolymer may mean that the repeating units that make up the copolymer are arranged in a disorderly manner.

The modified conjugated diene-based polymer according to an embodiment of the present invention has a number average molecular weight (Mn) of 1,000 g/mol to 2,000,000 g/mol, 10,000 g/mol to 1,000,000 g/mol, or 100,000 g/mol to 800,000 g. /mol, the weight average molecular weight (Mw) may be 1,000 g/mol to 3,000,000 g/mol, 10,000 g/mol to 2,000,000 g/mol, or 100,000 g/mol to 2,000,000 g/mol, and the peak average molecular weight (Mp) may be from 1,000 g/mol to 3,000,000 g/mol, from 10,000 g/mol to 2,000,000 g/mol, or from 100,000 g/mol to 2,000,000 g/mol. Within this range, rolling resistance and wet road resistance are excellent.

As another example, the modified conjugated diene polymer has a molecular weight distribution (PDI; MWD; Mw/Mn), as the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn), of 2.5 or less, 2.3 or less, particularly preferably 1.7. It may be less than 1.0 to less than 1.7, or more than 1.1 to less than 1.7, and within this range, the tensile properties and viscoelastic properties are excellent, and the balance between each physical property is excellent.

At the same time, the modified conjugated diene-based polymer has a unimodal molecular weight distribution curve determined by gel permeation chromatography (GPC), which is the molecular weight distribution shown in the polymer polymerized by continuous polymerization. This may mean that the modified conjugated diene-based polymer has uniform characteristics. That is, the modified conjugated diene-based polymer according to an embodiment of the present invention may be manufactured by continuous polymerization and have a unimodal molecular weight distribution curve while having a molecular weight distribution of less than 1.7.

In general, when a conjugated diene-based polymer is manufactured by a batch polymerization method and subjected to a modification reaction, the molecular weight distribution curve of the prepared modified conjugated diene-based polymer has a bimodal or more multimodal molecular weight distribution curve. Specifically, in the case of batch polymerization, the polymerization reaction is initiated after all of the raw materials are added, and chain growth can occur simultaneously from the starting point generated by multiple initiators, so the growth of each chain can be generally uniform, and accordingly, The molecular weight of the produced polymer chains is constant, so the molecular weight distribution may be in a fairly narrow unimodal form. However, when a denaturing agent is added to carry out a denaturation reaction, two cases may occur: 'no denaturation' and 'denaturation and coupling', and as a result, there is a large difference in molecular weight between polymer chains. Two groups can be formed, ultimately forming a multimodal molecular weight distribution curve with two or more peaks. Meanwhile, in the case of the continuous polymerization method according to an embodiment of the present invention, unlike batch polymerization, the initiation of the reaction and the input of raw materials are performed continuously, and the point in time at which the starting point at which the reaction begins is created is different, and accordingly, the polymerization Since the initiation varies from early in the reaction, in the middle of the reaction, and at the end of the reaction, polymer chains with various molecular weights are produced when the polymerization reaction is completed. Accordingly, a specific peak does not predominate in the curve representing the molecular weight distribution, so the molecular weight distribution curve appears as a single peak and is wide, and even if the chain where polymerization started at the end of the reaction is coupled, the molecular weight will be similar to the molecular weight of the chain where polymerization started at the beginning of the reaction. Since the diversity of molecular weight distribution can be maintained the same, it is generally the case that the unimodal distribution curve is still maintained.

However, even when manufacturing and modifying a polymer using a batch polymerization method, the modification conditions can be adjusted to have a unimodal form; however, in this case, the entire polymer must be uncoupled or the entire polymer must be coupled. And in other cases, the unimodal molecular weight distribution curve cannot be expressed.

At this time, in the case of a polymer that is not fully coupled or fully coupled, a problem may occur in which the Mooney relaxation rate and shrinkage factor of the polymer itself are significantly reduced.

In addition, even though it was manufactured by the batch polymerization method as described above, the molecular weight distribution curve of the modified conjugated diene polymer shows a unimodal distribution, and when all the polymers are coupled, only polymers with the same molecular weight exist, making processability difficult. This may be poor, and the functional groups that can interact with fillers such as silica or carbon black may be reduced due to coupling, resulting in poor blending properties. Conversely, if not all of the polymer is coupled, processing When the functional groups at the ends of the polymer that need to interact with fillers such as silica or carbon black interact with each other, the interaction between the functional groups at the end of the polymer becomes dominant, which can lead to a phenomenon that interferes with the interaction with the fillers, resulting in significantly poorer processability. Therefore, if the polymer is manufactured using the batch polymerization method and adjusted to have a unimodal molecular weight distribution curve, there may be problems with the processability and compounding properties of the produced modified conjugated diene polymer, and in particular, the processability may be significantly reduced. there is.

Meanwhile, the coupling of the modified conjugated diene polymer can be confirmed by the coupling number (C.N.), where the coupling number is determined by the number of functional groups that the polymer present in the modifier can bind to after modification of the polymer. It is a dependent figure. In other words, it represents the ratio of a polymer with no coupling between polymer chains and only terminal modifications and a polymer with multiple polymer chains coupled to one modifier, and can have a range of 1=C.N≤=F, where F is In a denaturant, it refers to the number of functional groups that can react with the terminal of the active polymer. In other words, a modified conjugated diene-based polymer with a coupling number of 1 means that not all polymer chains are coupled, and a modified conjugated diene-based polymer with a coupling number of F means that all polymer chains are coupled.

Therefore, the modified conjugated diene-based polymer according to an embodiment of the present invention may have a unimodal molecular weight distribution curve and a coupling number greater than 1 and less than the number of functional groups of the modifier used (1<C.N<F).

As another example, the modified conjugated diene polymer may have a Si content of 50 ppm or more, 100 ppm or more, 100 ppm to 10,000 ppm, or 100 ppm to 5,000 ppm, based on weight, and is modified within this range. The rubber composition containing the conjugated diene polymer has excellent mechanical properties such as tensile properties and viscoelastic properties. The Si content may refer to the content of Si atoms present in the modified conjugated diene polymer. Meanwhile, the Si atom may be derived from a functional group derived from a denaturant.

For example, the Si content may be measured using an ICP analysis method, and the ICP analysis method may be measured using an inductively coupled plasma emission spectrometer (ICP-OES; Optima 7300DV). When using the inductively coupled plasma emission spectrometer, approximately 0.7 g of a sample is placed in a platinum crucible (Pt crucible), approximately 1 mL of concentrated sulfuric acid (98% by weight, Electronic grade) is added, heated at 300°C for 3 hours, and the sample is After conducting the conversation in an electric furnace (Thermo Scientific, Lindberg Blue M) using the program of steps 1 to 3 below,

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

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

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

Add 1 mL of concentrated nitric acid (48% by weight) and 20 ㎕ of concentrated hydrofluoric acid (50% by weight) to the residue, seal the platinum crucible, shake it for more than 30 minutes, and add 1 mL of boric acid to the sample. It may be measured by storing it at 0°C for more than 2 hours, diluting it with 30 mL of ultrapure water, and performing incineration. In addition, the sample must be placed in hot water heated with steam and stirred to remove the solvent, and residual monomers and residual denaturants must also be removed. If oil is added, the oil is also removed through extraction and measured. It could be.

As another example, the modified conjugated diene-based polymer has a unimodal polymer component with a molecular weight of 100,000 g/mol or more in terms of standard polystyrene equivalent molecular weight by gel permeation chromatography, a molecular weight distribution (PDI; MWD) of 2.0 or less, and a number average molecular weight. (Mn) is 250,000 g/mol to 700,000 g/mol, the vinyl content of the butadiene unit is 20 mol% to 80 mol% or less, the Si content is 100 ppm or more by weight, and the content of the polymer component having a functional group It may be 50% by weight or more, and may include a unit derived from a denaturing initiator represented by Formula 1 above at one end, and a unit derived from a denaturant represented by Formula 2 or Formula 3 above at the other end.

As another example, the modified conjugated diene-based polymer may have an N content of 50 ppm or more, 100 ppm or more, 100 ppm to 10,000 ppm, or 100 ppm to 5,000 ppm based on the total weight, and within this range, the modified conjugated diene-based polymer The rubber composition containing the polymer has excellent mechanical properties such as tensile properties and viscoelastic properties. The N content may refer to the content of N atoms present in the modified conjugated diene-based polymer, and in this case, the N atoms may be derived from a functional group derived from a denaturant.

For example, the N content may be measured using the NSX analysis method, and the NSX analysis method may be measured using a trace nitrogen quantitative analyzer (NSX-2100H). For example, when using the trace nitrogen quantitative analyzer, turn on the trace nitrogen quantitative analyzer (Auto sampler, Horizontal furnace, PMT & Nitrogen detector) and set Ar at 250 ml/min, O2 at 350 ml/min, and ozonizer at 300 ml/min. The carrier gas flow rate was set to , the heater was set to 800°C, and the analyzer was stabilized by waiting for about 3 hours. After the analyzer was stabilized, a calibration curve with a range of 5 ppm, 10 ppm, 50 ppm, 100 ppm and 500 ppm was created using Nitrogen standard (AccuStandard S-22750-01-5 ml) and the area corresponding to each concentration was obtained. Then, a straight line was drawn using the ratio of concentration to area. Afterwards, a ceramic boat containing 20 mg of sample was placed on the auto sampler of the analyzer and measured to obtain the area. N content was calculated using the area of the obtained sample and the above calibration curve.

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

As another example, the modified conjugated diene-based polymer may have a Mooney relaxation ratio measured at 100°C of 0.7 or more, 0.7 or more and 3.0 or less, 0.7 or more and 2.5 or less, or 0.7 or more and 2.0 or less.

Here, the Mooney relaxation rate represents a change in stress in response to the same amount of strain, and may be measured using a Mooney viscometer. Specifically, the Mooney relaxation rate was determined by using a large rotor of Monsanto's MV2000E at 100°C and a rotor speed of 2±0.02 rpm, and after leaving the polymer at room temperature (23±5°C) for more than 30 minutes, 27±3 g was obtained. The sample was collected and filled inside the die cavity, and the Mooney viscosity was measured while operating the platen and applying torque. Then, the slope of the Mooney viscosity change that appears as the torque was released was measured and obtained.

Meanwhile, the Mooney relaxation rate can be used as an indicator of the branched structure of the polymer. For example, when comparing polymers with equivalent Mooney viscosity, the more branches there are, the smaller the Mooney relaxation rate is, so it can be used as an index of the degree of branching.

In addition, the modified conjugated diene-based polymer may have a Mooney viscosity of 30 or more, 40 to 150, or 40 to 140 at 100°C, and within this range, it has excellent processability and productivity.

As another example, the modified conjugated diene polymer has a shrinkage factor (g') determined by gel permeation chromatography-light scattering measurement using a viscosity detector of 0.8 or more, preferably 1.0 or more, specifically 0.8 or more and 3.0 or less, More specifically, it may be 0.8 or more and 1.3 or less.

Here, the shrinkage factor (g') determined by the gel permeation chromatography-mineralization method is the ratio of the intrinsic viscosity of the branched polymer to the intrinsic viscosity of the linear polymer having the same absolute molecular weight. It can be used as an indicator of the branched structure of a polymer, that is, an indicator of the proportion of branches. For example, as the shrinkage factor decreases, the number of branches of the polymer tends to increase, and thus, comparing polymers with equivalent absolute molecular weights In this case, the more branches there are, the smaller the shrinkage factor is, so it can be used as an indicator of branching degree.

In addition, the shrinkage factor was calculated by measuring the chromatogram using a gel chromatography-light scattering measuring device equipped with a viscosity detector and calculated based on the solution viscosity and light scattering method, specifically, a column with polystyrene gel as a filler. Using a GPC-light scattering measurement device equipped with two connected light scattering detectors and a viscosity detector, obtain the absolute molecular weight and the intrinsic viscosity corresponding to each absolute molecular weight, and calculate the intrinsic viscosity of the linear polymer corresponding to the absolute molecular weight. , the shrinkage factor was calculated as the ratio of intrinsic viscosity corresponding to each absolute molecular weight. Illustratively, the shrinkage factor is obtained by injecting a sample into a GPC-light scattering measuring device (Viscotek TDAmax, Malvern) equipped with a light scattering detector and a viscosity detector, obtaining the absolute molecular weight from the light scattering detector, and obtaining the absolute molecular weight from the light scattering detector and the viscosity detector. After obtaining the intrinsic viscosity [η] for The average value of [η]0) was expressed as the shrinkage factor. At this time, the eluent is a mixed solution of tetrahydrofuran and N,N,N',N'-tetramethylethylenediamine (20 mL of N,N,N',N'-tetramethylethylenediamine is mixed with 1L of tetrahydrofuran) adjusted) was used, the column was used by PL Olexix (Agilent), and the measurement was performed under the conditions of an oven temperature of 40°C and a THF flow rate of 1.0 mL/min. The sample was prepared by dissolving 15 mg of polymer in 10 mL of THF. .

[Equation 3]

[η] ₀ =10 ^-3.883 M ^0.771

In Equation 3 above, M is the absolute molecular weight.

Additionally, the modified conjugated diene-based polymer may have a vinyl content of 5% by weight or more, 10% by weight or more, or 10% by weight to 60% by weight. Here, the vinyl content refers to the content of 1,2-added conjugated diene monomer rather than 1,4-addition based on 100% by weight of the conjugated diene-based copolymer consisting of a monomer having a vinyl group and an aromatic vinyl monomer. You can.

Meanwhile, the modification initiator represented by the following formula (1) according to an embodiment of the present invention may be capable of initiating polymerization and simultaneously introducing a functional group to one end of the polymer chain formed by polymerization.

[Formula 1]

In Formula 1,

Cy is a divalent cyclic saturated hydrocarbon or aromatic hydrocarbon having 5 to 12 carbon atoms, and A is -NR ₃ or -CR ₄ R ₅ , where R ₃ to R ₅ are independently hydrogen or have 1 to 20 carbon atoms. is a linear hydrocarbon group or a monocyclic or polycyclic hydrocarbon group having 4 to 20 carbon atoms, R ₁ and R ₂ are independently an alkylene group having 1 to 5 carbon atoms, and M ₁ and M ₂ are independently an alkali group. It's metal.

Specifically, in Formula 1, Cy is cyclohexylene or phenylene, and A is -NR ₃ or -CR ₄ R ₅ , where R ₃ to R ₅ are independently hydrogen. or a linear hydrocarbon group having 1 to 20 carbon atoms, or a monocyclic or polycyclic cyclic hydrocarbon group having 4 to 20 carbon atoms, R ₁ and R ₂ are independently alkylene groups having 1 to 5 carbon atoms, M ₁ and M ₂ may be independently selected from Li, Na and K.

More specifically, in Formula 1, when Cy is a cyclohexylene group, A is -NR ₃ , R ₃ is a linear hydrocarbon group having 1 to 6 carbon atoms, and R ₁ and R ₂ are each independently a cyclohexylene group having 1 to 5 carbon atoms. It is an alkylene group, and M ₁ and M ₂ may be independently selected from Li, Na, and K. When Cy is a phenylene group, A is -CR ₄ R ₅ , and R ₄ and R ₅ are hydrogen or carbon atoms of 1 to 1. It is a linear hydrocarbon group of 6, R ₁ and R ₂ are independently an alkylene group of 1 to 5 carbon atoms, and M ₁ and M ₂ may be independently selected from Li, Na and K.

More specifically, the modification initiator represented by Formula 1 may be selected from compounds represented by Formulas 1-1 to 1-8 below.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

Additionally, the denaturant according to the present invention may be a denaturant for denaturing the remaining end of the conjugated diene polymer, and a specific example may be a silica affinity denaturant. The silica affinity denaturant may refer to a denaturant containing a silica affinity functional group in a compound used as a denaturant, and the silica affinity functional group has excellent affinity with fillers, especially silica-based fillers, and can be used with silica-based fillers. It may refer to a functional group capable of interaction between functional groups derived from a denaturant.

Specifically, according to one embodiment of the present invention, the denaturant may be a compound represented by Formula 2, where R ₂₀ is a single bond or an alkylene group having 1 to 5 carbon atoms, and R ₂₁ and R ₂₂ are independently an alkyl group having 1 to 5 carbon atoms or -[R ₄₂ O] _d -R ₄₃ , and R ₂₃ is a single bond, an alkylene group having 1 to 5 carbon atoms or -[R ₄₂ O] _d -, and R ₂₄ is an alkyl group having 1 to 5 carbon atoms, R ₄₂ is an alkylene group having 1 to 5 carbon atoms, R ₄₃ is an alkyl group having 1 to 5 carbon atoms, and d may be an integer of 1 to 10.

As a more specific example, the compound represented by Formula 2 is N,N-bis(3-(triethoxysilyl)propyl)-2,5,8,11,14-pentaoxahexadecane-16-amine (N, N-bis(3-(triethoxysilyl)propyl)-2,5,8,11,14-pentaoxahexadecan-16-amine), N,N-bis(3-(diethoxymethylsilyl)propyl)-2,5, 8,11,14-pentaoxahexadecan-16-amine (N,N-bis(3-(diethoxymethylsilyl)propyl)-2,5,8,11,14-pentaoxahexadecan-16-amine), N,N- Bis(3-(trimethoxysilyl)propyl)-3,6,9,12-tetraoxatetradecan-1-amine (N,N-bis(3-(trimethoxysilyl)propyl)-3,6,9, 12-tetraoxateradecan-1-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) It may be one type selected from the group consisting of.

Additionally, specifically, according to another embodiment of the present invention, the denaturant may be a compound represented by Formula 3, and in Formula 3, Cy is preferably a benzene ring, a pyridine ring, a pyrimidine ring, or a triazine ring. , R ₃₀ is -NR ₄₄ - or an alkylene group having 1 to 5 carbon atoms, R ₃₁ and R ₃₂ are independently an alkyl group having 1 to 5 carbon atoms, R ₃₄ is an alkyl group having 1 to 5 carbon atoms, and R ₄₂ is an alkylene group having 1 to 5 carbon atoms, R ₄₄ is hydrogen, an alkyl group having 1 to 3 carbon atoms, and d may be an integer of 1 to 10.

As a more specific example, the compound represented by Formula 3 is 3,4-bis(2-methoxyethoxy)-N-methyl-N-(3-(triethoxysilyl)propyl)aniline (3,4-bis (2-methoxyethoxy)-N-methyl-N-(3-(triethoxysilyl)propyl)aniline), 3,4-bis(2-methoxyethoxy)-N-(3-(triethoxysilyl)propyl) Aniline (3,4-bis(2-methoxyethoxy)-N-(3-(triethoxysilyl)propyl)aniline), N,N-bis(2-(2-methoxyethoxy)ethyl)-3-(triethoxysilyl)propyl)aniline) Toxysilyl)propan-1-amine (N,N-bis(2-(2-methoxyethoxy)ethyl)-3-(triethoxysilyl)propan-1-amine) and 2,4-bis(2-methoxyethoxy) -6-((triethoxylsilyl)methyl)-1,3,5-triazine (2,4-bis(2-methoxyethoxy)-6-((triethoxylsilyl)methyl)-1,3,5-triazine) It may be one type selected from the group consisting of.

As described above, the modified conjugated diene-based polymer according to an embodiment of the present invention may have a specific structure and a unique molecular weight distribution and shape. The structure of this polymer can be expressed in physical properties such as shrinkage factor, Mooney relaxation rate, and coupling number, and the molecular weight distribution and its shape can be expressed in the PDI value, the shape of the molecular weight distribution curve, and the coupling number, and the denaturant Modification of both ends by a modification initiator can affect the structure, molecular weight distribution, and shape. The parameters expressing the structure of this polymer and the characteristics related to the molecular weight distribution can be satisfied according to the manufacturing method described later, and it is preferable to manufacture it through this manufacturing method to satisfy the above-mentioned characteristics. If all are satisfied, the effect desired by the present invention can be achieved.

Additionally, the present invention provides a method for producing the modified conjugated diene polymer.

The method for producing the modified conjugated diene-based polymer according to an embodiment of the present invention is to polymerize a conjugated diene-based monomer or a conjugated diene-based monomer and an aromatic vinyl monomer in a hydrocarbon solvent in the presence of a modification initiator represented by the following formula (1). Preparing an active polymer into which a derived functional group is introduced (S1); And a step (S2) of reacting or coupling the active polymer prepared in step (S1) with a modifier represented by Formula 2 or Formula 3 below, wherein step (S1) is carried out continuously in two or more polymerization reactors. It is carried out, and the polymerization conversion rate in the first reactor among the polymerization reactors may be 50% or less.

[Formula 1]

[Formula 2]

[Formula 3]

In Formulas 1 to 3, each substituent and index are as previously defined.

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.

According to one embodiment of the present invention, the modification 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 a total of 100 g of monomer. You can use it.

The polymerization in the step (S1) may be, for example, anionic polymerization, and as a specific example, it may be living anionic polymerization with an anionic active site at the polymerization terminal through an anion-induced growth polymerization reaction. In addition, the polymerization in the step (S1) may be an elevated temperature polymerization, an isothermal polymerization, or a constant temperature polymerization (adiabatic polymerization), and the constant temperature polymerization includes the step of polymerizing with its own heat of reaction without arbitrarily adding heat after adding the modification initiator. It may refer to a polymerization method, and the elevated temperature polymerization may refer to a polymerization method in which the temperature is increased by arbitrarily applying heat after adding the modification initiator, and the isothermal polymerization may refer to a polymerization method in which heat is applied after adding the modification initiator. It may refer to a polymerization method that maintains a constant temperature of the polymer by increasing or taking away heat.

In addition, according to one embodiment of the present invention, the polymerization in the 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 may form on the wall of the reactor when operated for a long time. It has the effect of preventing this formation. An example of the diene-based compound may be 1,2-butadiene.

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

The active polymer prepared in step (S1) may refer to a polymer in which a polymer anion and an organic metal cation are combined.

According to one embodiment of the present invention, the method for producing the modified conjugated diene-based polymer may be carried out by a continuous polymerization method in a plurality of reactors including two or more polymerization reactors and a modification reactor. As a specific example, step (S1) may be carried out continuously in two or more polymerization reactors including a first reactor, and the number of polymerization reactors may be flexibly determined depending on reaction conditions and environment. The continuous polymerization method may refer to a reaction process in which reactants are continuously supplied to the reactor and the generated reaction products are continuously discharged. In the case of the continuous polymerization method, productivity and processability are excellent, and the polymer produced has excellent uniformity.

In addition, according to one embodiment of the present invention, when the active polymer is continuously produced in the polymerization reactor, the polymerization conversion rate in the first reactor may be 50% or less, 10% to 50%, or 20% to 50%, Within this range, after the polymerization reactor is started, side reactions that occur as the polymer is formed can be suppressed and a polymer with a linear structure can be induced during polymerization. Accordingly, it is possible to narrowly control the molecular weight distribution of the polymer, thereby improving the physical properties. The improvement is very effective.

At this time, the polymerization conversion rate can be adjusted depending on reaction temperature, reactor residence time, etc.

For example, the polymerization conversion rate may be determined by measuring the solid concentration in the polymer solution containing the polymer during polymerization. As a specific example, a cylindrical container is installed at the outlet of each polymerization reactor to secure the polymer solution to a constant level. A positive amount of polymer solution is filled in a cylindrical container, the cylindrical container is separated from the reactor, the weight (A) of the cylinder filled with the polymer solution is measured, and the polymer solution filled in the cylindrical container is placed in an aluminum container, For example, the weight (B) of a cylindrical container from which the polymer solution was removed was measured after being transferred to an aluminum dish, the aluminum container containing the polymer solution was dried in an oven at 140°C for 30 minutes, and the weight of the dried polymer (C) was measured. After measurement, it may be calculated according to Equation 1 below.

[Equation 1]

Meanwhile, 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 final polymerization conversion rate is 95% or more, and after polymerization in the first reactor, the polymerization may proceed in 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 molecular weight distribution.

Meanwhile, in the step (S1), when preparing the active polymer, the residence time of the polymer in the first reactor may be 1 minute to 40 minutes, 1 minute to 30 minutes, or 5 minutes to 30 minutes, and within this range, polymerization It is easy to control the conversion rate, and thus it is possible to narrowly control the molecular weight distribution of the polymer, which has the effect of improving physical properties.

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

According to one embodiment of the present invention, the molecular weight distribution (PDI, polydispersed index; MWD, molecular weight distribution; Mw/Mn) of the active polymer prepared in step (S1) is less than 1.5, 1.0 or more to less than 1.5, or 1.1. It may be from more than 1.5 to less than 1.5, and within this range, the molecular weight distribution of the modified conjugated diene-based polymer prepared through modification reaction or coupling with a modifier is narrow, resulting in excellent improvement of physical properties.

Meanwhile, the polymerization in the step (S1) may be carried out including a polar additive, and the polar additive is added at a rate of 0.001 g to 50 g, 0.001 g to 10 g, or 0.005 g to 0.1 g based on a total of 100 g of monomer. can do. As another example, the polar additive may be added at a rate of 0.001 g to 10 g, 0.005 g to 5 g, or 0.005 g to 4 g based on a total of 1 mmol of the modification initiator.

The polar additives include, for example, tetrahydrofuran, 2,2-di(2-tetrahydrofuryl)propane, diethyl ether, cycloamal ether, dipropyl ether, ethylene methyl ether, ethylene dimethyl ether, diethyl glycol, and dimethyl ether. , tertiary butoxyethoxyethane, bis(3-dimethylaminoethyl)ether, (dimethylaminoethyl)ethyl ether, trimethylamine, triethylamine, tripropylamine, N,N,N',N'-tetramethyl It may be at least one selected from the group consisting of ethylenediamine, sodium mentholate, and 2-ethyl tetrahydrofurfuryl ether, and is preferably 2,2-di(2-tetrahydrofuryl ether). It may be furyl) propane, triethylamine, tetramethylethylenediamine, sodium mentholate, or 2-ethyl tetrahydrofurfuryl ether, and if it contains the polar additive, it may be conjugated diene-based When copolymerizing monomers, or conjugated diene-based monomers and aromatic vinyl-based monomers, there is an effect of inducing easy formation of random copolymers by compensating for differences in reaction rates between them.

According to one embodiment of the present invention, the reaction or coupling of step (S2) may be performed in a denaturation reactor, and in this case, the denaturant may be used in an amount of 0.01 mmol to 10 mmol based on a total of 100 g of monomers. there is. As another example, the denaturant may be used at 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 denaturation initiator in step (S1).

Additionally, according to one embodiment of the present invention, the denaturing agent may be added to a denaturing reactor, and the step (S2) may be performed in the denaturing 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 the modifier may be mixed within the transfer unit. Reaction or coupling may proceed.

The method for producing the modified conjugated diene-based polymer according to an embodiment of the present invention is a method that can satisfy the characteristics of the modified conjugated diene-based polymer described above, and as described above, the effect to be achieved in the present invention is the above features. This can be achieved if the is satisfied, but at least in the above production method, the polymerization conversion rate when transferring from the first reactor to the second reactor under a continuous process needs to be satisfied, and other polymerization conditions are controlled in various ways, The physical properties of the modified conjugated diene polymer according to the present invention can be realized.

In addition, the present invention provides a rubber composition containing the above modified conjugated diene polymer.

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

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

The rubber component may be, for example, natural rubber or synthetic rubber, and specific examples include natural rubber (NR) containing cis-1,4-polyisoprene; Modified natural rubber such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber, which are obtained by modifying or refining the above 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, butyl rubber, halogenated butyl rubber, etc. Any one or a mixture of two or more of these may be used. there is.

For example, the rubber composition may include 0.1 to 200 parts by weight, or 10 to 120 parts by weight of filler based on 100 parts by weight of the modified conjugated diene polymer of the present invention. The filler may be, for example, a silica-based filler, and specific examples may be wet silica (hydrous silicic acid), dry silica (silicic anhydride), calcium silicate, aluminum silicate, or colloidal silica, and are preferably used to improve fracture properties and wet silica. It may be wet silica that has the best wet grip compatibility. Additionally, the rubber composition may further include carbon-based fillers, if necessary.

As another example, when silica is used as the filler, a silane coupling agent may be used together to improve reinforcing properties and low heat generation, 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-triethoxysilyl ethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzolyl tetrasulfide, 3-Triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate 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 of these may be used. Preferably, considering the effect of improving reinforcement, it may be bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide.

In addition, since the rubber composition according to an embodiment of the present invention uses a modified conjugated diene-based polymer into which a functional group with high affinity for silica is introduced into the active site as the rubber component, the mixing amount of the silane coupling agent is conventional. Accordingly, the silane coupling agent may be used in an amount of 1 to 20 parts by weight, or 5 to 15 parts by weight, based on 100 parts by weight of silica, and within this range, the effect as a coupling agent is It has the effect of preventing gelation of the rubber component while being sufficiently effective.

The rubber composition according to an embodiment of the present invention may be sulfur crosslinkable and may further include a vulcanizing agent. The vulcanizing agent may specifically be 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, and within this range, the necessary elastic modulus and strength of the vulcanized rubber composition are secured and low fuel efficiency is achieved. It has excellent effects.

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

The vulcanization accelerator is, for example, a thiazole-based compound such as M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazylsulfenamide), or DPG. Guanidine-based compounds 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 paraffin-based, naphthenic-based, or aromatic-based compound. Considering the tensile strength and wear resistance, the price of the aromatic-based process oil, hysteresis loss, and low-temperature characteristics Naphthenic or paraffinic process oils may be used. For example, the process oil may be included in an amount of 100 parts by weight or less per 100 parts by weight of the rubber component, and within this range, it is effective in preventing a decrease in the tensile strength and low heat generation (low fuel efficiency) of vulcanized rubber.

The antioxidants include, for example, 2,6-di-t-butylparacresol, dibutylhydroxytoluenyl, 2,6-bis((dodecylthio)methyl)-4-nonylphenol (2,6-bis( (dodecylthio)methyl)-4-nonylphenol) or 2-methyl-4,6-bis((octylthio)methyl)phenol (2-methyl-4,6-bis((octylthio)methyl)phenol), It can be used in an amount of 0.1 to 6 parts by weight based on 100 parts by weight of the rubber component.

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

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

Accordingly, the rubber composition is used for each member of a tire such as tire tread, undertread, side wall, carcass coating rubber, belt coating rubber, bead filler, filler, or bead coating rubber, anti-vibration rubber, belt conveyor, hose, etc. It can be useful in the manufacture of various industrial rubber products.

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

The tire may include a tire or tire tread.

Example

Hereinafter, the present invention will be described in detail with reference to examples. However, the embodiments according to the present invention may be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described in detail below. Examples of the present invention are provided to more completely explain the present invention to those with average knowledge in the art.

Example 1

In the first reactor of a series of three reactors connected in series, a styrene solution containing 60% by weight of styrene in n-hexane was fed at 3.6 kg/h and 60% by weight of 1,3-butadiene in n-hexane. 1,3-butadiene solution dissolved in 12.6 kg/h, n-hexane 47.2 kg/h, 1,2-butadiene solution dissolved in n-hexane at 2.0% by weight, 40 g/h , 125.0 g/h of a 10% by weight solution of 2,2-(di-2(tetrahydrofuryl)propane in n-hexane as a polar additive, and 59.0 g/h of a compound represented by the following formula (i) as a modification initiator. It was injected at a rate of g/h. At this time, the temperature of the first reactor was maintained at 50°C, and when the polymerization conversion rate reached 40%, the polymer was transferred from the first reactor to the second reactor through the transfer pipe. transferred.

Subsequently, a 1,3-butadiene solution containing 60% by weight of 1,3-butadiene dissolved in n-hexane was injected into the second reactor at a rate of 0.74 kg/h. At this time, the temperature of the second reactor was maintained at 65°C, and when the polymerization conversion rate reached 95% or more, the polymer was transferred from the second reactor to the third reactor through a transfer pipe.

The polymer was transferred from the second reactor to the third reactor, and N-(3,6,9,12-tetraoxahexadecyl)-N-(3-(triethoxysilyl)propyl)-3,6 as a denaturant. A solution containing 20% by weight of 9,12-tetraoxahexadecane-1-amine was added to the third reactor at a rate of 150.0 g/h. The temperature of the third reactor was maintained at 65°C.

Afterwards, a solution of IR1520 (BASF) dissolved at 30% by weight as an antioxidant was injected into the polymerization solution discharged from the third reactor at a rate of 167 g/h and stirred. The resulting polymer was placed in hot water heated with steam and stirred to remove the solvent to prepare a conjugated diene-based polymer modified at both ends.

(i)

Example 2

In Example 1, when the polymerization conversion rate reached 43%, the polymer was transferred from the first reactor to the second reactor through a transfer pipe, and N,N-bis(3-(triethoxysilyl)propyl) was used as a modifier. )-2,5,8,11,14-pentaoxahexadecane-16-amine was carried out as above except that a solution of 20% by weight dissolved in the solution was continuously supplied to the third reactor at a rate of 100.0 g/h. In the same manner as Example 1, a conjugated diene-based polymer modified at both ends was prepared.

Example 3

In Example 1, when the polymerization conversion rate reached 43%, the polymer was transferred from the first reactor to the second reactor through a transfer pipe, and 3,4-bis(2-methoxyethoxy)-N was used as a denaturant. -(3-(triethoxysilyl)propyl)aniline was carried out in the same manner as in Example 1, except that a solution containing 20% by weight of aniline was continuously supplied to the third reactor at a rate of 103.5 g/h. , a conjugated diene-based polymer modified at both ends was prepared.

Example 4

In the first reactor of a series of three reactors connected in series, a styrene solution containing 60% by weight of styrene in n-hexane was administered at 1.80 kg/h and 1,3-butadiene at 60% by weight in n-hexane. 1,3-butadiene solution dissolved in 14.2 kg/h, n-hexane 49.11 kg/h, 1,2-butadiene solution dissolved in n-hexane at 2.0% by weight 40 g/h , 51.0 g/h of a 10% by weight solution of 2,2-(di-2(tetrahydrofuryl)propane in n-hexane as a polar additive, and 90 g/h of a compound represented by the following formula (i) as a modification initiator. It was injected at a rate of g/h. At this time, the temperature of the first reactor was maintained at 50°C, and when the polymerization conversion rate reached 40%, the polymer was transferred from the first reactor to the second reactor through the transfer pipe. transferred.

Subsequently, a 1,3-butadiene solution containing 60% by weight of 1,3-butadiene dissolved in n-hexane was injected into the second reactor at a rate of 0.74 kg/h. At this time, the temperature of the second reactor was maintained at 65°C, and when the polymerization conversion rate reached 95% or more, the polymer was transferred from the second reactor to the third reactor through a transfer pipe.

The polymer was transferred from the second reactor to the third reactor, and N-(3,6,9,12-tetraoxahexadecyl)-N-(3-(triethoxysilyl)propyl)-3,6 as a denaturant. A solution containing 20% by weight of 9,12-tetraoxahexadecane-1-amine was added to the third reactor at a rate of 250.0 g/h. The temperature of the third reactor was maintained at 65°C.

Afterwards, a solution of IR1520 (BASF) dissolved at 30% by weight as an antioxidant was injected into the polymerization solution discharged from the third reactor at a rate of 167 g/h and stirred. The resulting polymer was placed in hot water heated with steam and stirred to remove the solvent to prepare a conjugated diene-based polymer modified at both ends.

(i)

Example 5

In Example 4, N,N-bis(3-(triethoxysilyl)propyl)-2,5,8,11,14-pentaoxahexadecan-16-amine was dissolved at 20% by weight as a denaturant. A conjugated diene-based polymer modified at both ends was prepared in the same manner as in Example 4, except that the solution was continuously supplied to the third reactor at a rate of 100.0 g/h.

Example 6

In Example 4, when the polymerization conversion rate reached 43%, the polymer was transferred from the first reactor to the second reactor through a transfer pipe, and 3,4-bis(2-methoxyethoxy)-N was used as a denaturant. -(3-(triethoxysilyl)propyl)aniline was carried out in the same manner as in Example 6, except that a solution containing 20% by weight of aniline was continuously supplied to the third reactor at a rate of 170.0 g/h. , a conjugated diene-based polymer modified at both ends was prepared.

Comparative Example 1

100 g of styrene, 880 g of 1,3-butadiene, 5000 g of n-hexane, and 0.89 g of 2,2-di(2-tetrahydrofuryl)propane as a polar additive were added to a 20 L autoclave reactor, and the internal temperature of the reactor was adjusted to 50°C. The temperature was raised to °C. When the temperature inside the reactor reached 50°C, 4.7 mmol of the compound represented by the formula (i) was added as a modification initiator to proceed with an adiabatic temperature increase reaction. After 20 minutes, 20 g of 1,3-butadiene was added to cap the polymer chain ends with butadiene. After 5 minutes, N-(3,6,9,12-tetraoxahexadecyl)-N-(3-(triethoxysilyl)propyl)-3,6,9,12-tetraoxahexadecane-1- 4.7 mmol of amine was added and reacted for 15 minutes. Afterwards, the polymerization reaction was stopped using ethanol, and 45 ml of a solution containing 0.3% by weight of the antioxidant IR1520 (BASF) dissolved in n-hexane was added. The resulting polymer was placed in hot water heated with steam and stirred to remove the solvent to prepare a conjugated diene-based polymer modified at both ends.

Comparative Example 2

In the first reactor of a series of three reactors connected in series, a styrene solution containing 60% by weight of styrene in n-hexane was administered at 1.80 kg/h and 1,3-butadiene at 60% by weight in n-hexane. 1,3-butadiene solution dissolved in 14.2 kg/h, n-hexane 49.11 kg/h, 1,2-butadiene solution dissolved in n-hexane at 2.0% by weight 40 g/h , 78.0 g/h of a solution of 10% by weight of 2,2-(di-2(tetrahydrofuryl)propane dissolved in n-hexane as a polar additive, and 10% by weight of n-butyllithium dissolved in n-hexane. The n-butyllithium solution was injected at a rate of 59.0 g/h. At this time, the temperature of the first reactor was maintained at 50°C, and when the polymerization conversion rate reached 45%, the first reactor was injected through the transfer pipe. The polymer was transferred from the reactor to the second reactor.

Subsequently, a 1,3-butadiene solution containing 60% by weight of 1,3-butadiene dissolved in n-hexane was injected into the second reactor at a rate of 0.74 kg/h. At this time, the temperature of the second reactor was maintained at 65°C, and when the polymerization conversion rate reached 95% or more, the polymer was transferred from the second reactor to the third reactor through a transfer pipe.

The polymer was transferred from the second reactor to the third reactor, and a solution of 2% by weight dichlorodimethylsilane dissolved in n-hexane as a coupling agent was added to the third reactor at a rate of 150 g/h. The temperature of the third reactor was maintained at 65°C.

Afterwards, a solution of IR1520 (BASF) dissolved at 30% by weight as an antioxidant was injected into the polymerization solution discharged from the third reactor at a rate of 167 g/h and stirred. The resulting polymer was placed in hot water heated with steam and stirred to remove the solvent, thereby preparing an unmodified conjugated diene-based polymer.

Comparative Example 3

In Example 1, the reaction temperature was maintained at 75°C in the first reactor, 80°C in the second reactor, and 80°C in the third reactor, and when the polymerization conversion rate in the first reactor reached 68%, A conjugated diene-based polymer modified at both ends was prepared in the same manner as in Example 1, except that the polymer was transferred from the first reactor to the second reactor and polymerized.

Comparative Example 4

In Example 1, when the polymerization conversion rate reached 48%, the polymer was transferred from the first reactor to the second reactor through a transfer pipe and reacted without adding a denaturant to the third reactor. In the same manner as Example 1, a terminally modified conjugated diene polymer was prepared.

Comparative Example 5

In Example 1, instead of the modification initiator (i), an n-butyllithium solution containing 10% by weight of n-butyllithium dissolved in n-hexane was continuously introduced into the first reactor at a rate of 59.0 g/h, When the polymerization conversion rate reached 46%, a terminal-modified conjugated diene-based polymer was prepared in the same manner as in Example 1, except that the polymer was transferred from the first reactor to the second reactor through a transfer pipe.

Comparative Example 6

In the first reactor of a series of three reactors connected in series, a styrene solution containing 60% by weight of styrene dissolved in n-hexane was fed at 1.6 kg/h and 1,3-butadiene was added at 60% by weight in n-hexane. 1,3-butadiene solution dissolved in 14.2 kg/h, n-hexane 47.2 kg/h, 1,2-butadiene solution dissolved in n-hexane at 2.0% by weight was 40 g/h , 125.0 g/h of a solution of 10% by weight of 2,2-(di-2(tetrahydrofuryl)propane dissolved in n-hexane as a polar additive, and 10% by weight of n-butyllithium dissolved in n-hexane. The n-butyllithium solution was injected at a rate of 59.0 g/h. At this time, the temperature of the first reactor was maintained at 50°C, and when the polymerization conversion rate reached 45%, the first reactor was injected through the transfer pipe. The polymer was transferred from the reactor to the second reactor.

Subsequently, a 1,3-butadiene solution containing 60% by weight of 1,3-butadiene dissolved in n-hexane was injected into the second reactor at a rate of 0.74 kg/h. At this time, the temperature of the second reactor was maintained at 65°C, and when the polymerization conversion rate reached 95% or more, the polymer was transferred from the second reactor to the third reactor through a transfer pipe.

The polymer was transferred from the second reactor to the third reactor, and a solution of 2% by weight dichlorodimethylsilane dissolved in n-hexane as a coupling agent was added to the third reactor at a rate of 150 g/h. The temperature of the third reactor was maintained at 65°C.

Afterwards, a solution of IR1520 (BASF) dissolved at 30% by weight as an antioxidant was injected into the polymerization solution discharged from the third reactor at a rate of 167 g/h and stirred. The resulting polymer was placed in hot water heated with steam and stirred to remove the solvent, thereby preparing an unmodified conjugated diene-based polymer.

Comparative Example 7

In Example 4, the reaction temperature was maintained at 75°C in the first reactor, 80°C in the second reactor, and 80°C in the third reactor, and when the polymerization conversion rate in the first reactor reached 69%, through the transfer pipe. A conjugated diene-based polymer modified at both ends was prepared in the same manner as in Example 4, except that the polymer was transferred from the first reactor to the second reactor and polymerized.

Comparative Example 8

In Example 4, when the polymerization conversion rate reached 48%, the polymer was transferred from the first reactor to the second reactor through a transfer pipe and reacted without adding a denaturant to the third reactor. In the same manner as in Example 4, a terminally modified conjugated diene polymer was prepared.

Comparative Example 9

In Example 4, instead of the modification initiator (i), an n-butyllithium solution containing 10% by weight of n-butyllithium dissolved in n-hexane was continuously introduced into the first reactor at a rate of 59.0 g/h, When the polymerization conversion rate reached 46%, a terminal-modified conjugated diene-based polymer was prepared in the same manner as in Example 4, except that the polymer was transferred from the first reactor to the second reactor through a transfer pipe.

Reference example 1

A conjugated diene-based polymer modified at both ends was carried out in the same manner as in Comparative Example 1, except that 28 mmol of 3-(dimethoxymethylsilyl)-N,N-diethylpropan-1-amine was added as a modifier in Comparative Example 1. was manufactured.

Reference example 2

A conjugated diene-based polymer modified at both ends was carried out in the same manner as in Comparative Example 1, except that 1.6 mmol of 3-(dimethoxymethylsilyl)-N,N-diethylpropan-1-amine was added as a modifier in Comparative Example 1. was manufactured.

Experimental Example 1

The following physical properties were measured for each modified or unmodified conjugated diene polymer prepared in the Examples, Comparative Examples, and Reference Examples, and the results are shown in Tables 1 and 2 below.

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

Styrene unit (SM) and vinyl (Vinyl) contents in each polymer were measured and analyzed using Varian VNMRS 500 MHz NMR.

During the NMR measurement, 1,1,2,2-tetrachloroethane was used as a solvent, and the solvent peak was calculated to be 5.97 ppm, 7.2~6.9 ppm was random styrene, 6.9~6.2 ppm was block styrene, and 5.8~5.1 ppm was Styrene unit and vinyl content were calculated by considering 1,4-vinyl, 5.1~4.5 ppm as the peak of 1,2-vinyl.

2) Weight ^average molecular weight (Mw, X10 ³ g/mol), number average molecular weight (Mn, X10 ³ g/mol), maximum peak molecular weight (Mp, (PDI, MWD)

The weight average molecular weight (Mw), number average molecular weight (Mn), and maximum peak molecular weight (Mp) were measured through GPC (Gel permeation chromatography) analysis, and a molecular weight distribution curve was obtained. In addition, molecular weight distribution (PDI, MWD, Mw/Mn) was obtained by calculating 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 PS (polystyrene) is used as the GPC standard material when calculating molecular weight. It was carried out using. The GPC measurement solvent was prepared by mixing 2% by weight of an amine compound in tetrahydrofuran. At this time, the obtained molecular weight distribution curves are shown in Figures 1 to 4.

In addition, the coupling number was determined by collecting some polymers before adding the modifier or coupling agent in each Example and Comparative Example to obtain the peak molecular weight (Mp ₁ ) of the polymer, and then calculating the peak molecular weight (Mp ₂₎ of each modified conjugated diene polymer. ) was obtained and calculated using Equation 2 below.

[Equation 2]

Number of couplings (CN)=Mp ₂ /Mp ₁

3) Mooney viscosity and Mooney relaxation rate

The Mooney viscosity (MV, (ML1+4, @100℃) MU) was measured at 100℃ using MV-2000 (ALPHA Technologies), Rotor Speed 2±0.02 rpm, Large Rotor, and the The sample was left at room temperature (23 ± 3°C) for more than 30 minutes, then 27 ± 3 g was collected, filled inside the die cavity, and the platen was activated and measured for 4 minutes.

After measuring the Mooney viscosity, the slope of the Mooney viscosity change that appears as the torque is released was measured to obtain the Mooney relaxation rate.

4) Si content

The Si content was measured using an inductively coupled plasma emission analyzer (ICP-OES; Optima 7300DV) using the ICP analysis method. Specifically, about 0.7 g of the sample was placed in a platinum crucible, about 1 mL of concentrated sulfuric acid (98% by weight, Electronic grade) was added, heated at 300°C for 3 hours, and the sample was placed in an electric furnace (Thermo Scientific, In Lindberg Blue M), after conducting the conversation using the program of steps 1 to 3 below,

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

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

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

Add 1 mL of concentrated nitric acid (48% by weight) and 20 ㎕ of concentrated hydrofluoric acid (50% by weight) to the residue, seal the platinum crucible, shake it for more than 30 minutes, and add 1 mL of boric acid to the sample. After being stored at 0°C for more than 2 hours, it was diluted in 30 mL of ultrapure water, and incineration was performed for measurement.

5) N content

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

6) Shrinkage factor (g')

The shrinkage factor is obtained by injecting a sample into a GPC-light scattering measuring device (Viscotek TDAmax, Malvern) equipped with a light scattering detector and a viscosity detector, obtaining the absolute molecular weight from the light scattering detector, and calculating the intrinsic viscosity [η] for the absolute molecular weight from the light scattering detector and the viscosity detector. After obtaining ], the intrinsic viscosity [η]0 of the linear polymer for the absolute molecular weight was calculated through Equation 3 below, and the ratio of intrinsic viscosity ([η]/[η]0) corresponding to each absolute molecular weight was calculated. The average value was expressed as the shrinkage factor. At this time, the eluent is a mixed solution of tetrahydrofuran and N,N,N',N'-tetramethylethylenediamine (20 mL of N,N,N',N'-tetramethylethylenediamine is mixed with 1L of tetrahydrofuran) adjusted) was used, the column was used by PL Olexix (Agilent), and the measurement was performed under the conditions of an oven temperature of 40°C and a THF flow rate of 1.0 mL/min. The sample was prepared by dissolving 15 mg of polymer in 10 mL of THF. .

[Equation 3]

[η] ₀ =10 ^-3.883 M ^0.771

In Equation 3 above, M is the absolute molecular weight.

division Example One 2 3 4 5 6 reaction conditions Polar additives DTP DTP DTP DTP DTP DTP initiator a a a a a a Denaturing agent or coupling agent A B C A B C M:PI 1:1 1:1 1:1 1:1 1:1 1:1 First reactor temperature (℃) 50 50 50 50 50 50 First reactor polymerization conversion rate (%) 40 43 43 40 40 43 NMR
(weight%) SM 21 21 21 10 10 10 Vinyl 50 50 50 38 38 38 GPC Mw(X10 ³ g/mol) 468 535 474 473 541 482 Mn(X10 ³ g/mol) 310 330 312 311 332 313 PDI 1.51 1.62 1.52 1.52 1.63 1.54 C.N. 1.64 2.12 1.64 1.62 2.13 1.61 molecular weight distribution curve UNI
modal UNI
modal UNI
modal UNI
modal UNI
modal UNI
modal Mooney viscosity (MV) 57 61 57 57 62 58 Mooney relaxation rate (-S/R) 1.01 0.75 1.00 1.01 0.75 1.02 Shrinkage factor (g') 1.09 0.85 1.09 1.10 0.84 1.10 Si content (ppm) 105 205 104 104 206 103 N content (ppm) 62 61 61 63 62 61

division Comparative example Reference example One 2 3 4 5 6 7 8 9 One 2 reaction conditions Polar additives DTP DTP DTP DTP DTP DTP DTP DTP DTP DTP DTP initiator a b a a b b a a b a a Denaturing agent or coupling agent A D A - A D A - A E E M:PI 1:1 1:1 1:1 - 1:1 1:1 1:1 1:1 - 5.1:1 0.3:1 First reactor temperature (℃) 50→80 50 75 50 50 50 75 50 50 50→80 50→80 First reactor polymerization conversion rate (%) arrangement 45 68 48 46 45 69 48 46 arrangement arrangement NMR
(weight%) SM 10 21 21 21 21 10 10 10 10 10 10 Vinyl 38 50 50 50 50 38 38 38 38 38 38 GPC Mw(X10 ³ g/mol) 421 481 550 387 465 473 556 383 460 300 490 Mn(X10 ³ g/mol) 270 310 250 265 300 305 255 264 295 250 350 PDI 1.56 1.55 2.20 1.46 1.55 1.55 2.08 1.45 1.56 1.20 1.40 C.N. 1.62 1.50 1.52 - 1.62 1.52 1.51 - 1.61 1.0 2.0 molecular weight distribution curve bisexual
modal UNI
modal UNI
modal UNI
modal UNI
modal UNI
modal UNI
modal UNI
modal UNI
modal UNI
modal UNI
modal Mooney viscosity (MV) 50 55 59 48 54 55 59 47 53 42 55 Mooney relaxation rate 1.01 1.10 0.55 0.82 0.75 1.11 0.56 0.81 0.85 1.02 1.05 Shrinkage factor (g') 1.02 1.12 0.65 0.95 1.01 1.10 0.64 0.99 0.95 1.03 1.02 Si content (ppm) 104 30 78 - 90 30 77 - 91 102 80 N content (ppm) 61 - 45 32 48 - 45 32 49 60 46

In Tables 1 and 2, specific materials of the initiator, denaturant, and coupling agent are shown in Table 3 below.

initiator a Compounds represented by formula (i) b n-butyllithium denaturant A N-(3,6,9,12-tetraoxahexadecyl)-N-(3-(triethoxysilyl)propyl)-3,6,9,12-
Tetraoxahexadecan-1-amine B N,N-bis(3-(triethoxysilyl)propyl)-2,5,8,11,14-pentaoxahexadecan-16-amine C 3,4-bis(2-methoxyethoxy)-N-(3-(triethoxysilyl)propyl)aniline D dichlorodimethylsilane E 3-(dimethoxy(methyl)silyl)-N,N-diethylpropan-1-amine

Referring to Tables 1 and 2 above, it can be confirmed that the modified conjugated diene-based polymers of Examples 1 to 6 prepared according to an embodiment of the present invention satisfy all required ranges of physical properties. Specifically, the molecular weight distribution curve is unimodal, and at the same time, the PDI value is less than 1.7, so it can be predicted that the processability is quite excellent and the mixing properties are also excellent, and the Mooney relaxation ratios are all 0.7 or more, preferably all 0.8 or more, so linearity. This excellence can be predicted, and as the shrinkage factor is over 0.8, it can be predicted that the balance between physical properties is excellent.

On the other hand, Comparative Examples 3 and 7, in which the polymerization conversion rate was not controlled when transferring from the first reactor to the second reactor, showed a high PDI value of 1.7 or more, and the Mooney relaxation rate and shrinkage factor were below a certain value. Through the evaluation, it can be confirmed that unsatisfactory results were obtained in terms of balance or linearity between physical properties.

In addition, when batch polymerization is applied, it can be predicted that the general modified conjugated diene-based polymer has a small PDI value of less than 1.7 as in Comparative Example 1, but has poor processability because it has a bimodal molecular weight distribution curve, and among the results of batch polymerization A unimodal molecular weight distribution curve may appear as in Reference Examples 1 and 2, but this corresponds to extreme cases where the coupling number is the minimum or maximum value, and the modified conjugated diene-based polymer of such batch polymerization suffers from deterioration of the blended properties. That this continues can be seen from the above-mentioned explanation and the evaluation results described later.

Figures 1 to 4 show the molecular weight distribution curves of Example 1, Comparative Example 1, and Reference Examples 1 and 2, and it can be confirmed that the shape of each molecular weight distribution curve appears as described above.

Experimental Example 2

In order to comparatively analyze the physical properties of the rubber compositions containing each modified or unmodified conjugated diene copolymer prepared in the above Examples, Comparative Examples, and Reference Examples and molded articles manufactured therefrom, the tensile properties and viscoelastic properties were measured, respectively. The results are shown in Tables 5 and 6 below.

1) Preparation of rubber specimens

Each modified or unmodified conjugated diene polymer of Examples, Comparative Examples, and Comparative Examples was used as a raw material rubber and mixed under the mixing conditions shown in Table 4 below. The content of the raw materials in Table 4 is each part by weight based on 100 parts by weight of raw material rubber.

division Raw material Content (parts by weight) 1st stage kneading rubber 100 silica 70 Coupling agent (X50S) 11.2 process oil 37.5 Zincifying 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 first-stage kneading and second-stage kneading. In the first stage kneading, raw rubber, silica (filler), organosilane coupling agent, process oil, zincating agent, stearic acid, antioxidant, anti-aging agent, and wax were kneaded using a Banbari mixer equipped with a temperature control device. At this time, the initial temperature of the kneader was controlled to 70°C, and the first blend was obtained at a discharge temperature of 145°C to 155°C after completion of mixing. In the second stage kneading, the primary blend was cooled to room temperature, then the primary blend, sulfur, rubber accelerator, and vulcanization accelerator were added to the kneader, and mixed at a temperature of 100°C or lower to obtain the secondary blend. Afterwards, a rubber specimen was manufactured through a curing process at 160°C for 20 minutes.

2) Tensile properties

For tensile properties, each test piece was manufactured in accordance with the tensile test method of ASTM 412, and the tensile strength when cut and the tensile stress (300% modulus) when stretched 300% were measured. Specifically, tensile properties were measured at room temperature at a speed of 50 cm/min using a Universal Test Machin 4204 (Instron) tensile tester.

3) Viscoelastic properties

The viscoelastic properties were measured using a dynamic mechanical analyzer (GABO) in Film Tension mode at a frequency of 10 Hz and each measurement temperature (-60℃~60℃) to measure the viscoelastic behavior against dynamic deformation and confirm the tan δ value. In the results, 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 smaller the hysteresis loss and the better the low driving resistance (fuel efficiency).

4) Processability characteristics

The processability characteristics of each polymer were compared and analyzed by measuring the Mooney viscosity (MV, (ML1+4, @100°C) MU) of the secondary mixture obtained during the manufacture of the rubber specimen above. In this case, the lower the Mooney viscosity measured value, the lower the Mooney viscosity. It shows excellent processability characteristics.

Specifically, using MV-2000 (ALPHA Technologies), Rotor Speed 2±0.02 rpm, Large Rotor at 100℃, each secondary mixture was left at room temperature (23±3℃) for more than 30 minutes and then 27 ±3 g was collected, filled inside the die cavity, operated platen, and measured for 4 minutes.

division Example Comparative example One 2 3 2 3 4 5 Tensile properties tensile strength
(kgf/ ^cm2 ) 183 183 184 170 180 172 170 300% modulus
(kgf/ ^cm2 ) 122 123 121 100 118 110 110 Viscoelastic properties tan δ
(at 0℃) 102 101 101 100 99 101 101 tan δ
(at 60℃) 123 121 122 100 108 112 105 Machinability characteristics 80 82 81 70 88 80 81

In Table 5, the results of viscoelastic properties of Examples 1 to 3 and Comparative Examples 3 to 5 are expressed as an index (%) based on the measured value of Comparative Example 2, with higher values indicating better results.

Referring to Table 5, as predicted through the measured physical properties of the polymer in Experimental Example 1, in the tensile properties of Examples 1 to 3, the tensile strength was at a level equal to or higher than that of the comparative examples, and the modulus was significantly superior. It can be confirmed that, in terms of viscoelastic properties, the tan δ value at low temperature is maintained at the same level or higher, while the tan δ value at high temperature is greatly improved, confirming that the fuel efficiency characteristics are greatly improved without loss of road resistance. I was able to.

In addition, in the case of Comparative Example 3, as a result of not following the manufacturing method of the present invention, not only did it not satisfy the ranges of PDI value, shrinkage factor, and Mooney relaxation rate as described above, but the viscoelastic properties were noticeably inferior to those of the Example. You can see that it stands out. And in the case of Comparative Examples 2, 4, and 5 in which the modifier and modification initiator according to the present invention were not applied, poor viscoelastic properties were similarly confirmed.

division Example Comparative example Reference example 4 5 6 One 6 7 8 9 One 2 Tensile properties tensile strength
(kgf/ ^cm2 ) 165 168 168 155 162 163 162 163 155 156 300% modulus
(kgf/ ^cm2 ) 102 101 102 92 85 92 93 92 85 90 Viscoelastic properties tan δ
(at 0℃) 101 102 102 100 100 100 100 100 100 101 tan δ
(at 60℃) 123 121 122 110 100 108 112 105 105 103 Machinability characteristics 80 82 81 90 70 88 80 81 95 90

In Table 6, the results of viscoelastic properties of Examples 4 to 6, Comparative Examples 1, 6 to 9, and Reference Examples 1 and 2 are expressed by indexing (%) based on the measured value of Comparative Example 6. The higher the value, the better. This means that Table 6 is a set of results evaluated by varying the content of comonomers from the set in Table 5, and it can be seen from Table 6 that the effect does not change even if the content of the monomers is changed. Table 6 It can be seen that the same results as the physical property improvement results confirmed in 5 were obtained.

Furthermore, in the case where the polymer prepared through batch polymerization has a unimodal molecular weight distribution curve as in Reference Examples 1 and 2, the poor processability inherent in batch polymerization can be maintained while still being realized as an advantage in batch polymerization. It was confirmed that excellent mixing properties were not achieved. On the other hand, the poor processability inherent in batch polymerization can be confirmed in Comparative Example 1 in which the number of couplings was applied in the same range as the examples according to the present invention.

Claims (12)

The molecular weight distribution curve by gel permeation chromatography (GPC) has a unimodal shape,
The molecular weight distribution (PDI; MWD) is 1.0 or more and less than 1.7,
Comprising a functional group derived from a denaturing initiator represented by the following formula (1) at one end, and a functional group derived from a denaturing agent represented by the formula (2) or formula (3) shown at the other end,
A modified conjugated diene-based polymer whose Coupling Number (CN) is 1 < CN < F, where F is the number of functional groups of the denaturant:
[Formula 1]

In Formula 1,
Cy is a divalent cyclic saturated hydrocarbon or aromatic hydrocarbon having 5 to 12 carbon atoms,
A is -NR ₃ or -CR ₄ R ₅ , where R ₃ to R ₅ are independently hydrogen, a linear hydrocarbon group having 1 to 20 carbon atoms, or a monocyclic or polycyclic saturated hydrocarbon group having 4 to 20 carbon atoms. It is a hydrocarbon group,
R ₁ and R ₂ are independently an alkylene group having 1 to 5 carbon atoms,
M ₁ and M ₂ are independently alkali metals,
[Formula 2]

In Formula 2,
R ₂₀ is a single bond or an alkylene group having 1 to 10 carbon atoms,
R ₂₁ and R ₂₂ are independently an alkyl group having 1 to 10 carbon atoms, or -[R ₄₂ O] _d -R ₄₃ ,
R ₂₃ is a single bond, an alkylene group having 1 to 10 carbon atoms, or -[R ₄₂ O] _d -,
R ₂₄ is hydrogen, an alkyl group having 1 to 10 carbon atoms,
R ₄₂ is an alkylene group having 1 to 10 carbon atoms,
R ₄₃ is an alkyl group having 1 to 10 carbon atoms,
a is 2 or 3, c is an integer from 1 to 3, b is an integer from 0 to 2, b+c=3, d is an integer from 1 to 30,
At least one of R ₂₁ to R ₂₃ necessarily includes the -[R ₄₂ O] _d - unit,
[Formula 3]

In Formula 3 above,
Cy is a trivalent aromatic hydrocarbon group having 6 to 20 carbon atoms or a trivalent heteroaromatic hydrocarbon group having 3 to 20 carbon atoms,
R ₃₀ is a single bond, -NR ₄₄ -, -O-, -S-, or an alkylene group having 1 to 10 carbon atoms,
R ₃₁ and R ₃₂ are independently an alkyl group having 1 to 10 carbon atoms,
R ₃₃ is -[R ₄₂ O] _d -,
R ₃₄ is hydrogen, an alkyl group having 1 to 10 carbon atoms,
R ₄₂ is an alkylene group having 1 to 10 carbon atoms,
R ₄₄ is hydrogen or an alkyl group having 1 to 10 carbon atoms,
m is an integer from 0 to 3, k and n are integers from 1 or 2, where k+n=3, and d is an integer from 1 to 30.
In claim 1,
In Formula 1,
Cy is a cyclohexylene group or a phenylene group,
A is -NR ₃ or -CR ₄ R ₅ , where R ₃ to R ₅ are independently hydrogen, a linear hydrocarbon group having 1 to 6 carbon atoms, or a monocyclic or polycyclic saturated hydrocarbon group having 4 to 8 carbon atoms. It is a hydrocarbon group,
R ₁ and R ₂ are independently an alkylene group having 1 to 5 carbon atoms.
M ₁ and M ₂ are each independently selected from Li, Na and K, a modified conjugated diene polymer.
In claim 1,
In Formula 2,
R ₂₀ is a single bond or an alkylene group having 1 to 5 carbon atoms,
R ₂₁ and R ₂₂ are independently an alkyl group having 1 to 5 carbon atoms or -[R ₄₂ O] _d -R ₄₃ ,
R ₂₃ is a single bond, an alkylene group having 1 to 5 carbon atoms, or -[R ₄₂ O] _d -,
R ₂₄ is an alkyl group having 1 to 5 carbon atoms,
R ₄₂ is an alkylene group having 1 to 5 carbon atoms, R ₄₃ is an alkyl group having 1 to 5 carbon atoms,
d is a modified conjugated diene-based polymer, wherein d is an integer of 1 to 10.
In claim 1,
In Formula 3 above,
Cy is a benzene ring, pyridine ring, pyrimidine ring, or triazine ring,
R ₃₀ is -NR ₄₄ -, or an alkylene group having 1 to 5 carbon atoms,
R ₃₁ and R ₃₂ are independently an alkyl group having 1 to 5 carbon atoms,
R ₃₄ is an alkyl group having 1 to 5 carbon atoms,
R ₄₂ is an alkylene group having 1 to 5 carbon atoms,
R ₄₄ is hydrogen, an alkyl group having 1 to 3 carbon atoms,
d is a modified conjugated diene-based polymer, wherein d is an integer of 1 to 10.
In claim 1,
The modified conjugated diene-based polymer has a number average molecular weight (Mn) of 1,000 g/mol to 2,000,000 g/mol and a weight average molecular weight (Mw) of 1,000 g/mol to 3,000,000 g/mol.
In claim 1,
The modified conjugated diene-based polymer is a modified conjugated diene-based polymer whose Si content and N content are each 50 ppm or more based on weight.
In claim 1,
The modified conjugated diene-based polymer has a Mooney relaxation ratio measured at 100°C of 0.7 to 3.0.
In claim 1,
The modified conjugated diene-based polymer has a shrinkage factor of 0.8 to 3.0, as determined by gel permeation chromatography-light scattering method equipped with a viscosity detector.
delete A rubber composition comprising the modified conjugated diene polymer and a filler according to claim 1.
In claim 10,
The rubber composition includes 0.1 to 200 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene polymer.
In claim 10,
A rubber composition wherein the filler is a silica-based filler or a carbon-based filler.