KR102185353B1 - Polymer compound, preparation method of modified conjugated diene polymer using the polymer compound and modified conjugated diene polymer - Google Patents

Abstract

The present invention relates to a rubber modifier polymer compound, a modified conjugated diene polymer containing a functional group derived therefrom, and a method for preparing the modified conjugated diene polymer. The resulting polymer compound is used as a modifier for rubber, particularly as a modifier for a conjugated diene-based polymer, and is bonded to the conjugated diene-based polymer chain, so that a filler affinity functional group can be easily introduced. Therefore, the modified conjugated diene-based polymer prepared using the rubber modifier polymer compound may contain a plurality of functional groups.

Description

Polymer compound, preparation method of modified conjugated diene polymer using the polymer compound and modified conjugated diene polymer}

The present invention relates to a polymer compound for a rubber modifier, a modified conjugated diene polymer containing a functional group derived from the polymer compound, and a method for preparing the modified conjugated diene polymer.

In recent years, in accordance with the demand for low fuel consumption for automobiles, a conjugated diene-based polymer having low rolling resistance, excellent abrasion resistance, and tensile properties as a rubber material for tires, and also having adjustment stability typified by wet skid resistance is required.

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

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

When such a solution-polymerized SBR is used as a rubber material for tires, the glass transition temperature of the rubber can be increased by increasing the vinyl content in the SBR, so that the required properties of the tire such as running resistance and braking force can be adjusted, as well as the glass transition temperature appropriately. By adjusting it, you can reduce fuel consumption.

The solution polymerization SBR is prepared by using an anionic polymerization initiator, and the chain ends of the formed polymer are bonded or modified using various modifiers.

For example, U.S. Patent No. 4,397,994 proposes a technique in which the active anion at the chain end of the polymer obtained by polymerizing styrene-butadiene in a non-polar solvent using alkyllithium, which is a monofunctional initiator, is bound using a binder such as a tin compound. I did.

On the other hand, carbon black and silica are used as reinforcing fillers for tire treads. When silica is used as a reinforcing filler, low hysteresis loss and wet skid resistance are improved. However, silica on a hydrophilic surface compared to carbon black on a hydrophobic surface has a drawback of poor dispersibility due to low affinity with rubber, so a separate silane couple is used to improve dispersibility or to impart a silica-rubber bond. It is necessary to use a ring agent.

Accordingly, a method of introducing a functional group having affinity or reactivity with silica at the end of the rubber molecule has been made, but the effect is not sufficient.

Accordingly, there is a need to develop rubber having high affinity with fillers including silica.

US 4,397,994 A

The present invention has been devised to solve the problems of the prior art, and an object of the present invention is to provide a polymer compound for a rubber modifier capable of providing a functional group according to an object.

Another object of the present invention is to provide a modified conjugated diene-based polymer comprising a functional group derived from the polymer compound.

Another object of the present invention is to provide a method for preparing the modified conjugated diene-based polymer using the polymer compound for a rubber modifier.

In order to solve the above problems, it provides a polymer compound comprising a structural unit represented by the following formula (1).

[Formula 1]

In Formula 1,

X ₁ is a substituent derived from a silane group-containing compound,

X ₂ is a substituent derived from an aromatic vinyl compound,

X ₃ is a substituent derived from an acrylic group-containing compound,

X ₄ is a substituent derived from an amine group-containing compound,

k, l, m, and n represent the molar ratio of each repeating unit, and k+l+m+n is 100,

k is 1 to 50,

l is from 0 to 50,

m is from 0 to 50,

n is 1 to 70,

A ₁ to A ₄ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms.

In addition, the present invention provides a modified conjugated diene-based polymer comprising a functional group derived from the polymer compound comprising a structural unit represented by the following formula (1).

[Formula 1]

In Formula 1,

X ₁ is a substituent derived from a silane group-containing compound,

X ₂ is a substituent derived from an aromatic vinyl compound,

X ₃ is a substituent derived from an acrylic group-containing compound,

X ₄ is a substituent derived from an amine group-containing compound,

k, l, m, and n represent the molar ratio of each repeating unit, and k+l+m+n is 100,

k is 1 to 50,

l is from 0 to 50,

m is from 0 to 50,

n is 1 to 70,

A ₁ to A ₄ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms.

In addition, the present invention is a step of polymerizing a conjugated diene-based monomer or an aromatic vinyl-based monomer and a conjugated diene-based monomer in a hydrocarbon solvent in the presence of an organic alkali metal compound to prepare an active polymer in which an alkali metal is bonded to at least one terminal (Step 1 ); And it provides a method for producing a modified conjugated diene-based polymer comprising the step (step 2) of reacting the active polymer with a polymer compound containing a constituent unit represented by Formula 1 above.

The polymer compound containing the constituent unit represented by Formula 1 according to the present invention is used as a modifier for rubber, particularly as a modifier for a conjugated diene polymer, and is bonded to the conjugated diene polymer chain to provide a plurality of functional groups.

In addition, the modified conjugated diene-based polymer according to the present invention has a functional group derived from a polymer compound, such as a siloxane group and an amine group, which includes a structural unit represented by Formula 1 in the polymer chain, so that it has affinity with a filler, particularly a silica-based filler. This can be excellent.

In addition, the manufacturing method according to the present invention can easily prepare a modified conjugated diene-based polymer having an excellent modification rate by using a polymer compound containing a structural unit represented by Formula 1.

Furthermore, the rubber composition containing the modified conjugated diene-based polymer according to the present invention may have excellent processability, and as a result, the processed product (eg, tire) manufactured using the rubber composition has tensile strength, abrasion resistance, and wet road surface resistance properties. This can be excellent.

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

The terms or words used in the specification and claims should not be construed as being limited to their usual or dictionary meanings, and the inventor may appropriately define the concept of terms in order to describe his own invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

The present invention provides a polymer compound for a rubber modifier capable of providing a plurality of functional groups. The polymer compound according to an embodiment of the present invention is characterized in that it contains a structural unit represented by the following formula (1).

[Formula 1]

In Formula 1,

X ₁ is a substituent derived from a silane group-containing compound,

X ₂ is a substituent derived from an aromatic vinyl compound,

X ₃ is a substituent derived from an acrylic group-containing compound,

X ₄ is a substituent derived from an amine group-containing compound,

k, l, m, and n represent the molar ratio of each repeating unit, and k+l+m+n is 100,

k is 1 to 50,

l is from 0 to 50,

m is from 0 to 50,

n is 1 to 70,

A ₁ to A ₄ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms.

The polymer compound may be a compound having a structure in which a plurality of functional groups-containing substituents, such as X ₁ , X ₂ , X ₃ and X ₄ are bonded to the main chain, as shown in Formula 1, and the substituents derived from the plurality of functional groups are bonded. By having it, when it is used as a rubber modifier, a functional group can be provided according to the purpose.

In this case, the polymer compound may be a block copolymer in which each repeating unit having a molar ratio of k, l, m, and n forms a block, or a random copolymer in which each repeating unit is arranged in a disorder.

The term "derived substituent" as used in the present invention may refer to a structure derived from a substance, a substance, a derived functional group, or the substance itself. For example, a substituent derived from a silane group-containing compound may be a structure generated from a silane group-containing compound, It may represent a functional group or the silane group-containing compound itself.

Specifically, in Chemical Formula 1, X ₁ may be a substituent derived from a silane group-containing compound as described above, and may provide a silane functional group to the polymer compound, and may be represented by the following Chemical Formula 2.

[Formula 2]

In Formula 2, R ₁ is an ester group, an arylene group having 6 to 10 carbon atoms, or a secondary amine group, and R ₂ to R ₄ are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, At this time, at least one of R ₂ to R ₄ is an alkoxy group having 1 to 10 carbon atoms, and a may be an integer of 1 to 8. Here, it may be a portion bonded to the main chain of the polymer compound.

More specifically, in Formula 2, R ₁ is an ester group, R ₂ to R ₄ are each independently an alkoxy group having 1 to 6 carbon atoms, and a may be an integer of 1 to 6.

In addition, in Formula 1, X ₂ is a substituent derived from an aromatic vinyl compound as described above, and specifically, X ₂ is an unsubstituted or substituted with an alkyl group having 1 to 3 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms. It may be an aryl group of 10. More specifically, X ₂ may be an aryl group having 6 to 10 carbon atoms.

In addition, X ₃ in Chemical Formula 1 is a substituent derived from an acrylic group-containing compound as described above, and may be represented by Chemical Formula 3 below.

[Formula 3]

In Formula 3, R ₅ is an ester group, R ₆ is an alkyl group having 1 to 20 carbon atoms, and b may be an integer of 0 to 10.

Specifically, in Formula 3, R ₅ is an ester group, R ₆ is an alkyl group having 1 to 20 carbon atoms, and b may be an integer of 0 to 3. More specifically, when b is 0 in Formula 3, R ₅ is an ester group, R ₆ is an alkyl group having 6 to 20 carbon atoms, and when b is not 0, R ₅ is an ester group, and R ₆ may be an alkyl group having 1 to 6 carbon atoms. Here, R ₅ may be a moiety bonded to the main chain of the polymer compound.

In addition, in Formula 1, X ₄ is a substituent derived from an amine group-containing compound as described above, and may be represented by the following Formula 4.

[Formula 4]

In Formula 4, R ₇ is an alkylene group having 1 to 6 carbon atoms, an ester group, or an arylene group having 6 to 10 carbon atoms, and R ₈ and R ₉ are each independently an alkyl group having 1 to 10 carbon atoms, or are linked to each other to have 3 carbon atoms. To form a ring structure of 10, c may be an integer of 1 to 8.

Specifically, in Formula 4, R ₇ may be an arylene group having 6 to 10 carbon atoms, and R ₈ and R ₉ may be independently an alkyl group having 1 to 6 carbon atoms. Here, R ₇ may be a portion bonded to the main chain of the polymer compound.

More specifically, the polymer compound including the constituent unit represented by Formula 1 may include the constituent unit represented by the following Formula 5 or Formula 6. That is, the structural unit represented by Formula 1 may be represented by Formula 5 or Formula 6.

[Formula 5]

[Formula 6]

In Formula 5, k, l, m, and n represent the molar ratio of each repeating unit, where k+l+m+n is 100, k is 1 to 50, l is 0 to 50, and m is 0 To 50, and n may be 1 to 70.

In addition, the polymer compound including the structural unit represented by Formula 1 may be a rubber modifier as described above.

Specifically, the polymer compound represented by Formula 1 may be a modifier for a conjugated diene-based polymer. Here, the conjugated diene-based polymer may be a conjugated diene-based monomer homopolymer or a copolymer of an aromatic vinyl-based monomer and a conjugated diene-based monomer.

In addition, the present invention provides a modified conjugated diene-based polymer containing a functional group derived from a polymer compound containing a structural unit represented by the following formula (1).

[Formula 1]

In Formula 1,

X ₁ is a substituent derived from a silane group-containing compound,

X ₂ is a substituent derived from an aromatic vinyl compound,

X ₃ is a substituent derived from an acrylic group-containing compound,

X ₄ is a substituent derived from an amine group-containing compound,

k, l, m, and n represent the molar ratio of each repeating unit, and k+l+m+n is 100,

k is 1 to 50,

l is from 0 to 50,

m is from 0 to 50,

n is 1 to 70,

A ₁ to A ₄ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms.

Specifically, the polymer compound including the structural unit represented by Chemical Formula 1 is as described above.

The modified conjugated diene-based polymer according to an embodiment of the present invention may include a functional group derived from a polymer compound containing the structural unit represented by Formula 1 above. That is, the modified conjugated diene-based polymer may be modified by a polymer compound containing a constituent unit represented by Formula 1.

Specifically, the modified conjugated diene-based polymer may include 0.1 to 10 moles of siloxane groups relative to the total 1 mole of the polymer, and the polymer may include 0.1 to 100 moles of amine groups relative to the total 1 mole of the polymer. .

The modified conjugated diene-based polymer may have excellent affinity with a filler, particularly a silica-based filler, since a siloxane group and an amine group are bonded to the polymer chain. Accordingly, the blending properties with the filler may be excellent, so that the processability of the rubber composition including the modified conjugated diene polymer may be excellent, and as a result, the tensile strength of a molded article manufactured using the rubber composition, such as a tire, Wear resistance and wet road surface resistance can be improved.

In addition, the modified conjugated diene-based polymer may have a number average molecular weight of 10,000 g/mol to 2,000,000 g/mol, and specifically 100,000 g/mol to 1,000,000 g/mol.

The modified conjugated diene-based polymer may have a weight average molecular weight of 10,000 g/mol to 10,000,000 g/mol, and specifically 200,000 g/mol to 2,000,000 g/mol.

The modified conjugated diene-based polymer may have a molecular weight distribution of 1.1 to 10, specifically 1.4 to 3.5.

Here, the weight average molecular weight and number average molecular weight are each molecular weight in terms of polystyrene analyzed by gel permeation chromatography (GPC), and the molecular weight distribution (Mw/Mn) is also called polydispersity, and the weight average molecular weight (Mw) It was calculated as the ratio (Mw/Mn) to the number average molecular weight (Mn).

In addition, the modified conjugated diene-based polymer may have a vinyl content of 5% by weight or more, specifically 10% by weight or more, more specifically 10% to 50% by weight, and the glass transition temperature when the vinyl content is within the above range. When applied to a tire, it has excellent physical properties such as driving resistance and braking force, as well as reducing fuel consumption.

In this case, the vinyl content refers to the content of 1,2-added conjugated diene-based monomer, not 1,4-added, based on 100% by weight of a conjugated diene-based polymer composed of a monomer having a vinyl group or a conjugated diene-based monomer.

On the other hand, the modified conjugated diene-based polymer may be prepared by a manufacturing method described below, and may be a conjugated diene-based monomer homopolymer or a copolymer of a vinyl-based aromatic monomer and a conjugated diene-based monomer, and the polymer is a copolymer It may be one containing 40% by weight or less of a substituent derived from an aromatic vinyl-based monomer.

In addition, the present invention provides a method for preparing the modified conjugated diene-based polymer using a polymer compound containing a structural unit represented by the following formula (1).

The preparation method according to an embodiment of the present invention is an active polymer in which an alkali metal is bonded to at least one terminal by polymerizing a conjugated diene-based monomer or an aromatic vinyl-based monomer and a conjugated diene-based monomer in the presence of an organic alkali metal compound in a hydrocarbon solvent. Manufacturing a step (step 1); And reacting the active polymer with a polymer compound containing a structural unit represented by the following formula (1) (step 2).

[Formula 1]

In Formula 1,

X ₁ is a substituent derived from a silane group-containing compound,

X ₂ is a substituent derived from an aromatic vinyl compound,

X ₃ is a substituent derived from an acrylic group-containing compound,

X ₄ is a substituent derived from an amine group-containing compound,

k, l, m, and n represent the molar ratio of each repeating unit, and k+l+m+n is 100,

k is 1 to 50,

l is from 0 to 50,

m is from 0 to 50,

n is 1 to 70,

A ₁ to A ₄ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms.

Specifically, the polymer compound including the structural unit represented by Chemical Formula 1 is as described above.

Step 1 is a step for preparing an active polymer in which an alkali metal is bonded to at least one terminal, and is performed by polymerizing a conjugated diene-based monomer or an aromatic vinyl-based monomer and a conjugated diene-based monomer in the presence of an organic alkali metal compound in a hydrocarbon solvent. I can.

The polymerization in step 1 may be a combination of a conjugated diene-based monomer or an aromatic vinyl-based monomer and a conjugated diene-based monomer as a monomer. That is, the polymer prepared through the production method according to an embodiment of the present invention may be a homopolymer derived from a conjugated diene-based monomer or a copolymer derived from an aromatic vinyl-based monomer and a conjugated diene-based monomer.

In this case, the copolymer may be a random copolymer.

Here, the "random copolymer" may indicate that the constituent units constituting the copolymer are randomly arranged.

The conjugated diene-based monomer is not particularly limited, but, for example, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene and 2-phenyl It may be one or more selected from the group consisting of -1,3-butadiene.

When the modified conjugated diene-based polymer is a copolymer, the conjugated diene-based monomer has a unit derived from the conjugated diene-based monomer in the finally prepared modified conjugated diene-based polymer is 60% by weight or more, specifically 60% to 90% by weight , More specifically, it may be used in an amount contained in 60% by weight to 85% by weight.

The aromatic vinyl monomer is not particularly limited, for example, styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p -Methylphenyl) styrene and 1-vinyl-5-hexylnaphthalene may be one or more selected from the group consisting of.

The aromatic vinyl-based monomer has a substituent derived from the aromatic vinyl-based monomer in the finally prepared modified conjugated diene-based polymer is 40% by weight or less, specifically 10% to 40% by weight, more specifically 15% to 40% by weight It may be used in an amount included in %.

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

The organic alkali metal compound may be used in an amount of 0.01 mmol to 10 mmol based on a total of 100 g of monomers.

The organic alkali metal compound is not particularly limited, for example, methyllithium, ethyllithium, propyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octyllithium, Phenyllithium, 1-naphthyllithium, n-ecosyllithium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naph Tyl sodium, naphthyl potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide, lithium isopropyl amide. I can.

The polymerization of step 1 may be performed by adding a polar additive as necessary, and the polar additive may be added in an amount of 0.001 parts by weight to 10 parts by weight based on a total of 100 parts by weight of the monomer. Specifically, it may be added in an amount of 0.001 parts by weight to 1 part by weight, more specifically 0.003 parts by weight to 0.5 parts by weight, based on 100 parts by weight of the total monomer.

The polar additives are tetrahydrofuran, ditetrahydrofurylpropane, diethyl ether, cycloamal ether, dipropyl ether, ethylene dimethyl ether, ethylene dimethyl ether, diethyl glycol, dimethyl ether, tertiary butoxyethoxyethane, bis It may be one or more selected from the group consisting of (3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine, and tetramethylethylenediamine.

The manufacturing method according to an embodiment of the present invention is to make it easier to form a random copolymer by compensating for the difference in reaction rate when the conjugated diene-based monomer and the aromatic vinyl-based monomer are copolymerized by using the polar additive. You can induce.

The polymerization of step 1 may be performed through adiabatic polymerization or isothermal polymerization.

Here, the adiabatic polymerization refers to a polymerization method comprising the step of polymerization by self-reaction heat without arbitrarily applying heat after adding the organic alkali metal compound, and the isothermal polymerization is performed by adding the organic alkali metal compound. It represents a polymerization method that maintains a constant temperature of a polymer by adding or taking away heat.

The polymerization may be performed at a temperature range of -20°C to 200°C, specifically 0°C to 150°C, more specifically 10°C to 120°C.

Step 2 is a step of reacting the active polymer with a polymer compound containing a structural unit represented by Formula 1 in order to prepare a modified conjugated diene polymer.

The polymer compound may be used in a ratio of 0.1 mol to 5 mol relative to 1 mol of the organic alkali metal compound.

The reaction of step 2 according to an embodiment of the present invention is a denaturation reaction for introducing a functional group into the polymer, and each reaction may be performed for 10 minutes to 5 hours at a temperature range of 10°C to 120°C.

The manufacturing method according to an embodiment of the present invention may further include at least one step of recovering and drying the solvent and the unreacted monomer as necessary after step 2 above.

Furthermore, the present invention provides a rubber composition comprising the modified conjugated diene polymer.

The rubber composition according to an embodiment of the present invention may contain a modified conjugated diene-based polymer in an amount of 10 wt% or more, specifically 10 wt% to 100 wt%, and more specifically 20 wt% to 90 wt% have. If the content of the modified conjugated diene-based polymer is less than 10% by weight, as a result, the effect of improving abrasion resistance and crack resistance of a molded article manufactured using the rubber composition, such as a tire, may be insignificant.

In addition, the rubber composition may further include other rubber components as necessary in addition to the modified conjugated diene-based polymer, in which 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. Specifically, it may be included in an amount of 1 part by weight to 900 parts by weight based on 100 parts by weight of the modified conjugated diene-based copolymer.

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

In addition, the rubber composition may include 0.1 to 200 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene polymer, and the filler may be a silica-based filler, a carbon black-based filler, or a combination thereof.

Meanwhile, when a silica-based filler is used as the filler, a silane coupling agent may be used together to improve reinforcement and low heat generation.

Specifically, as the silane coupling agent, bis(3-triethoxysilylpropyl)tetrasulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis (2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, 3-mercaptopropyltrimethoxysilane , 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfur Feed, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilyl Propylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzolyltetrasulfide, 3-triethoxysilylpropylmethacrylate monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, bis (3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide or dimethoxymethylsilylpropylbenzothiazolyl Tetrasulfide and the like, and any one or a mixture of two or more of them may be used. More specifically, when considering the effect of improving reinforcing properties, the silane coupling agent may be bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide.

In addition, in the rubber composition according to an embodiment of the present invention, a modified conjugated diene-based polymer in which a functional group having high affinity with a silica-based filler is introduced at the active site as a rubber component is used, so that the silane coupling agent The blending amount can be reduced than in the usual case. Specifically, the silane coupling agent may be used in an amount of 1 to 20 parts by weight based on 100 parts by weight of the silica-based filler. When used in the above range, gelation of the rubber component can be prevented while the effect as a coupling agent is sufficiently exhibited. More specifically, the silane coupling agent may be used in an amount of 5 to 15 parts by weight based on 100 parts by weight of silica.

In addition, the rubber composition according to an embodiment of the present invention may be sulfur crosslinkable, and thus may further include a vulcanizing agent.

The vulcanizing agent may be specifically sulfur powder, and may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the rubber component. When included in the above content range, it is possible to secure the necessary elastic modulus and strength of the vulcanized rubber composition, and at the same time, low fuel economy can be obtained.

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

The vulcanization accelerator is not particularly limited, and specifically, M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazylsulfenamide), etc. A thiazole-based compound or a guanidine-based compound such as DPG (diphenylguanidine) may be used. The vulcanization accelerator may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the rubber component.

In addition, the process oil acts as a softener in the rubber composition, and may be a paraffinic, naphthenic, or aromatic compound. More specifically, when considering tensile strength and abrasion resistance, the aromatic process oil price and hysteresis loss And when considering the low temperature characteristics, naphthenic or paraffinic process oil may be used. The process oil may be included in an amount of 100 parts by weight or less based on 100 parts by weight of the rubber component, and when included in the amount, it is possible to prevent a decrease in tensile strength and low heat generation (low fuel economy) of the vulcanized rubber.

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

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

Accordingly, the rubber composition may include tire treads, under treads, side walls, carcass coated rubbers, belt coated rubbers, bead fillers, pancreas, or bead coated rubbers, and other tire members, anti-vibration rubber, belt conveyors, hoses, etc. It may be useful in the manufacture of various industrial rubber products.

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

The tire may include a tire or a tire tread.

Hereinafter, the present invention will be described in more detail by examples and experimental examples. However, the following examples and experimental examples are for illustrative purposes only, and the scope of the present invention is not limited thereto.

The denaturants used in the preparation of the modified conjugated diene polymer are 3-(trimethoxysilyl)-propyl methacrylate (TMSPMA), styrene (SM), 2-methoxyethyl acrylate (MEA) and N,N-dimethylamino. Quaternary copolymers of methylstyrene (DMAMS) or 3-(trimethoxysilyl)propyl methacrylate (TMSPMA), styrene (SM), octadecyl methacrylate (ODMA) and N,N-dimethylaminomethylstyrene A quaternary copolymer of (DMAMS) was used.

Manufacturing example One

3-(trimethoxysilyl)-propyl methacrylate (TMSPMA) 74.9 g (0.26 mol), styrene (SM) 161.1 g (1.55 mol) in a 5 L reactor equipped with a temperature control jacket, solvent condensing device and stirring device. , 2-methoxyethyl acrylate (MEA) 163.0 g (1.25 mol) and N,N-dimethylaminomethyl styrene (DMAMS) 101.0 g (0.63 mol) and tetrahydrofuran (THF) 2 kg were added, and 65°C After heating up to, the mixture was stirred for 5 minutes. Thereafter, 33.6 g (0.20 mol) of azobisisobutyronitrile (AIBN) was dissolved in 168.0 g of tetrahydrofuran in a 500 ml beaker, and then injected into the reactor, followed by reaction with stirring at 65° C. for 12 hours, and the following formula ( Modifier A, which is a polymer compound containing a structural unit represented by i), was prepared.

(i)

(i)

In Formula (i), k is 7, l is 42, m is 34, and n is 17.

Manufacturing example 2

3-(trimethoxysilyl)-propyl methacrylate (TMSPMA) 145.7 g (0.51 mol), styrene (SM) 141.8 g (1.36 mol) in a 5 L reactor equipped with a temperature control jacket, solvent condensing device and stirring device. , 2-methoxyethyl acrylate (MEA) 125.9 g (0.97 mol) and N,N-dimethylaminomethyl styrene (DMAMS) 86.7 g (0.54 mol) and tetrahydrofuran (THF) 2 kg were added, and 65 °C After heating up to, the mixture was stirred for 5 minutes. Thereafter, 30.7 g (0.19 mol) of azobisisobutyronitrile (AIBN) was dissolved in 154.0 g of tetrahydrofuran in a 500 ml beaker, and then injected into the reactor and reacted with stirring at 65° C. for 12 hours Preparation Example 1 Including the constituent unit represented by the formula (i), k is 15, l is 40, m is 29, and n is 16 to prepare a polymeric compound denaturant B.

Manufacturing example 3

3-(trimethoxysilyl)-propyl methacrylate (TMSPMA) 61.3 g (0.21 mol), styrene (SM) 139.3 g (1.34 mol) in a 5 L reactor equipped with a temperature control jacket, solvent condensing device and stirring device , 2-methoxyethyl acrylate (MEA) 100.8 g (0.77 mol) and N,N-dimethylaminomethyl styrene (DMAMS) 198.6 g (1.23 mol) and tetrahydrofuran (THF) 2 kg were added, and 65°C After heating up to, the mixture was stirred for 5 minutes. Thereafter, 32.4 g (0.20 mol) of azobisisobutyronitrile (AIBN) was dissolved in 162.0 g of tetrahydrofuran in a 500 ml beaker, and then injected into the reactor, followed by reaction with stirring at 65° C. for 12 hours Preparation Example 1 Including the constituent unit represented by the formula (i) of, k is 6, l is 38, m is 22, and n is a polymer compound of 34 to prepare a denaturant C.

Manufacturing example 4

3-(trimethoxysilyl)-propylmethacrylate (TMSPMA) 47.6 g (0.16 mol), styrene (SM) 99.7 g (0.96 mol) in a 5 L reactor equipped with a temperature control jacket, solvent condensing device and stirring device , Octadecyl methacrylate (ODMA) 277.7 g (0.82 mol) and N,N-dimethylaminomethylstyrene (DMAMS) 74.9 g (0.46 mol) and tetrahydrofuran (THF) 2 kg were added, and the temperature was raised to 65°C. Then it was stirred for 5 minutes. Thereafter, 22.0 g (0.13 mol) of azobisisobutyronitrile (AIBN) was dissolved in 110.0 g of tetrahydrofuran in a 500 ml beaker, and then injected into the reactor, followed by reaction with stirring at 65° C. for 12 hours, and the following formula ( Modifier D, which is a polymer compound containing a structural unit represented by ii), was prepared.

(ii)

(ii)

In the formula (ii), k is 7, l is 40, m is 34, and n is 19.

It was confirmed that each of the polymer compounds prepared in Preparation Examples 1 to 4, the denaturant A to the denaturant D, was synthesized through molecular weight analysis, and the results are shown in Table 1 below.

Specifically, molecular weight analysis was measured by GPC analysis under 40°C conditions. At this time, as the column, two PLgel Olexis columns of Polymer Laboratories and one PLgel mixed-C column were combined, and all newly replaced columns were mixed bed type columns. In addition, polystyrene (PS) was used as a GPC standard material when calculating the molecular weight.

division Monomer used Composition (molar ratio) Number average molecular weight (g/mol) Molecular weight distribution Denaturant A TMSPMA/SM/MEA/DMAMS 7/42/34/17 6000 1.8 Denaturant B TMSPMA/SM/MEA/DMAMS 15/40/29/16 5600 2.2 Denaturant C TMSPMA/SM/MEA/DMAMS 6/38/22/34 6200 2.1 Denaturant D TMSPMA/SM/ODMA/DMAMS 7/40/34/19 7185 1.9

Example One

After adding 250 g of styrene, 750 g of 1,3-butadiene, 7 kg of cyclohexane, and 0.8 g of ditetrahydrofurylpropane as a polar additive in a 10 L autoclave reactor, the temperature inside the reactor was raised to 70°C. When the temperature inside the reactor reached 60°C, 0.5 g of a 1.53 wt% normal hexane solution of n-butyllithium was added to the reactor to proceed with an adiabatic heating reaction. After about 40 minutes of the adiabatic heating reaction, 20 g of the polymerization solution was aliquoted, added to 100 g of isopropyl alcohol, and precipitated, which was used to check the properties of the polymer before modification. Thereafter, 32.8 g of the denaturant A prepared in Preparation Example 1 was dissolved in 200 g of anhydrous tetrahydrofuran, added to the reactor, and the reaction was allowed to proceed for 30 minutes. Thereafter, the reaction was stopped using isopropyl alcohol, and 45 ml of a solution in which 0.3 wt% of an antioxidant BHT (butylated hydroxytoluene) was dissolved in hexane was added. The resulting polymer was put in hot water heated by steam, stirred to remove the solvent, and then roll-dried to remove the remaining amount of solvent and water, thereby preparing a modified styrene-butadiene copolymer.

Example 2

A modified styrene-butadiene copolymer was prepared in the same manner as in Example 1, except that the modifying agent B of Table 1 was used instead of the modifying agent A.

Example 3

A modified styrene-butadiene copolymer was prepared in the same manner as in Example 1, except that the modifying agent C of Table 1 was used instead of the modifying agent A.

Example 4

A modified styrene-butadiene copolymer was prepared in the same manner as in Example 1, except that the modifying agent D of Table 1 was used instead of the modifying agent A.

Comparative Example 1

After adding 250 g of styrene, 750 g of 1,3-butadiene, 7 kg of cyclohexane, and 0.8 g of ditetrahydrofurylpropane as a polar additive in a 10 L autoclave reactor, the temperature inside the reactor was raised to 70°C. When the temperature inside the reactor reached 60° C., 0.38 g of n-butyllithium 1.53% was added to the reactor to proceed with an adiabatic heating reaction. Thereafter, the reaction was stopped using isopropyl alcohol, and 45 ml of a solution in which 0.3 wt% of an antioxidant BHT (butylated hydroxytoluene) was dissolved in hexane was added. The resulting polymer was put in hot water heated with steam, stirred to remove the solvent, and then roll-dried to remove the remaining amount of solvent and water, thereby preparing a styrene-butadiene copolymer.

Comparative Example 2

A styrene-butadiene copolymer was prepared in the same manner as in Example 1, except that 2.8 g of a 10 wt% normal hexane solution of tetrachlorosilane was used as a coupling agent instead of the modifier A.

Comparative Example 3

Example except that 11.3 g of 3-(N,N-dimethylamino)propyl trimethoxysilane (3-(N,N-Dimethyl amino) propyl trimethoxy silane) 10 wt% normal hexane solution was used instead of denaturant A In the same manner as in 1, a modified styrene-butadiene copolymer was prepared.

Experimental Example 1

For each of the copolymers prepared in Examples 1 to 4 and Comparative Examples 1 to 3, weight average molecular weight (Mw), number average molecular weight (Mn), maximum peak molecular weight (Mp), molecular weight distribution (MWD) , Mw/Mn) and pattern viscosity (MV) were measured, respectively. The results are shown in Table 2 below.

1) molecular weight analysis

Weight average molecular weight (Mw, g/mol), number average molecular weight (Mn, g/mol) and maximum peak molecular weight (Mp, g/mol) were measured through GPC analysis under 40°C condition, and molecular weight distribution (Mw/Mn ) Is calculated as the ratio of the measured weight average molecular weight and number average molecular weight, and the number of couplings (Mp1/Mp2) is the value divided after measuring the maximum peak molecular weight after denaturation (Mp1) and the maximum peak molecular weight before denaturation (Mp2). I got it. At this time, as the column, two PLgel Olexis columns of Polymer Laboratories and one PLgel mixed-C column were combined, and all newly replaced columns were mixed bed type columns. In addition, polystyrene (PS) was used as a GPC standard material when calculating the molecular weight.

2) Mooney viscosity analysis

The Mooney viscosity (MV, (ML1+4, @100℃)) of each copolymer was measured using a Rotor Speed 2±0.02 rpm, Large Rotor using ALPHA Technologies' MV-2000, and the sample used at this time was After leaving for at least 30 minutes at room temperature (23±3°C), 27±3 g was collected and filled inside the die cavity, and the platen was operated, preheated at 100°C for 1 minute, and then measured for 4 minutes.

division GPC Mooney viscosity (MV) Mw(g/mol, X10 ⁴ ) Mn(g/mol, X10 ⁴ ) Molecular weight distribution (Mw/Mn) Number of couplings Example 1 63 37 1.7 2.7 74 Example 2 58 36 1.6 2.4 70 Example 3 47 31 1.5 2.2 66 Example 4 60 35 1.7 2.6 72 Comparative Example 1 39 35 1.1 - 55 Comparative Example 2 59 37 1.6 2.4 68 Comparative Example 3 40 31 1.3 1.8 58

In Table 2, the number of couplings indicates that the polymer chain is coupled or modified by a modifier, and the larger the number, the higher the coupling or modification ratio is.

As shown in Table 2, the number of co-fillings in Examples 1 to 4 according to an embodiment of the present invention exceeded 2, and it was confirmed that modification was made through this.

Experimental Example 2

The rubber compositions including each copolymer prepared in Examples 1 to 4 and Comparative Examples 1 to 3 and the physical properties of the molded articles prepared therefrom were compared and analyzed, and the results are shown in Table 3 below.

1) Preparation of rubber composition

Each rubber composition was prepared through a first stage kneading, a second stage kneading process, and a third stage kneading process. At this time, the amount of materials excluding the modified conjugated diene-based copolymer is expressed based on 100 parts by weight of the modified conjugated diene-based copolymer. In the first stage kneading, 100 parts by weight of each of the above modified conjugated diene-based copolymers, 70 parts by weight of silica, and bis(3-triethoxysilylpropyl)tetrasulfur as a silane coupling agent using a semi-bar remixer attached with a temperature control device. Feed 11.2 parts by weight, process oil (TDAE) 37.5 parts by weight, anti-aging agent (TMDQ) 2 parts by weight, antioxidant 2 parts by weight, zinc oxide (ZnO) 3 parts by weight and stearic acid (stearic acid) 2 parts by weight, 1 part by weight of wax was blended and kneaded. At this time, the temperature of the kneader was controlled and the first blend was obtained at a discharge temperature of 140°C to 150°C. In the second-stage kneading, after cooling the first blend to room temperature, 1.75 parts by weight of a rubber accelerator (CZ), 1.5 parts by weight of sulfur powder, and 2 parts by weight of a vulcanization accelerator are added to the kneader, and then mixed at 45 to 60°C. Got it. Thereafter, the second blend was molded in the third stage kneading, and vulcanized at 180° C. for t90+10 minutes with a vulcanizing press to prepare each vulcanized rubber.

2) Mooney viscosity

The Mooney viscosity (MV, (ML1+4, @100℃)) of each rubber composition was measured using a Rotor Speed 2±0.02 rpm, Large Rotor using ALPHA Technologies' MV-2000, and the sample used at this time was After leaving for at least 30 minutes at room temperature (23±3°C), 27±3 g was collected and filled inside the die cavity, and the platen was operated, preheated at 100°C for 1 minute, and then measured for 4 minutes.

3) Payne effect

Using ALPHA Technologies' RPA 2000, a specimen weight of 7 g or more was used, and a strain swip of 0.04-40.0% was measured at a rate of 1 Hz at 60°C.

4) Tensile characteristics

For tensile properties, each test piece was prepared according to the tensile test method of ASTM 412, and the tensile strength at the time of cutting and the tensile stress at the time of 300% elongation (300% modulus) were measured. Specifically, the tensile properties were measured at a rate of 50 cm/min at room temperature using a Universal Test Machin 4204 (Instron) tensile tester, and based on the measured value of the rubber composition including the copolymer of Comparative Example 2 100 Compared with the index value, the higher the index value, the better.

5) Viscoelastic properties (roll resistance (RR) and braking (wet grip))

Viscoelastic properties are measured using DMTS (Dynamic Mechanical Thermal Spectrometry; GABO, EPLEXOR 500N) in torsion mode, frequency 10 Hz, strain (static strain: 3%, dynamic strain: 0.25%), and each measurement temperature (-60℃~70℃). ) By changing the strain to measure Tan δ. The higher the low-temperature 0℃ Tan δ, the better the braking performance, the lower the high-temperature 60℃ Tan δ, the less hysteresis loss and the better low-cloud resistance (fuel economy). The result value was compared with the index value based on the measured value of the rubber composition including the copolymer of Comparative Example 2 based on 100, and the higher the index value, the better.

6) wear resistance

It was measured using a DIN wear meter. The result value was compared with the index value based on the measured value of the rubber composition including the copolymer of Comparative Example 3 as 100, and the higher the index value, the better.

In the results of Table 3, the rubber composition containing the modified styrene-butadiene copolymer of Examples 1 to 4 prepared using the polymer compound according to the present invention as a modifier was prepared using a conventional general modifier. Compared to the rubber composition containing the modified styrene-butadiene copolymer of Example 3, the modulus and tensile strength of 300% were equal or higher, while excellent braking resistance (0℃ Tan δ) on wet road surfaces and low rolling resistance (60℃ Tan δ) ) Was significantly improved.

On the other hand, the rubber composition containing the modified styrene-butadiene copolymer of Examples 1 to 4 according to an embodiment of the present invention is unmodified a rubber composition containing the conjugated diene polymer of Comparative Examples 1 and 2 In contrast, it was confirmed that it showed improved performance in all aspects such as resistance to wet road surfaces, fuel economy characteristics, and mechanical properties.

Claims (20)

It includes a structural unit represented by the following formula (1),
A polymer compound that is a modifier for conjugated diene-based polymers:
[Formula 1]

In Formula 1,
X ₁ is a substituent represented by the following formula (2),
X ₂ is an aryl group having 6 to 10 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 3 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms,
X ₃ is a substituent represented by the following formula (3),
X ₄ is a substituent represented by the following formula (4),
k, l, m, and n represent the molar ratio of each repeating unit, and k+l+m+n is 100,
k is 1 to 50,
l is from 0 to 50,
m is from 0 to 50,
n is 1 to 70,
A ₁ to A ₄ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms,
[Formula 2]

In Chemical Formula 2,
R ₁ is an ester group, an arylene group having 6 to 10 carbon atoms, or a secondary amine group,
R ₂ to R ₄ are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, wherein at least one of R ₂ to R ₄ is an alkoxy group having 1 to 10 carbon atoms,
a is an integer from 1 to 8,
[Formula 3]

In Chemical Formula 3,
R ₅ is an ester group,
R ₆ is an alkyl group having 1 to 20 carbon atoms,
b is an integer from 0 to 10,
[Formula 4]

In Chemical Formula 4,
R ₇ is a C 1 to C 6 alkylene group, an ester group or a C 6 to C 10 arylene group,
R ₈ and R ₉ are each independently an alkyl group having 1 to 10 carbon atoms, or are linked to each other to form a ring structure having 3 to 10 carbon atoms,
c is an integer from 1 to 8.
delete The method according to claim 1,
In Chemical Formula 2,
R ₁ is an ester group,
R ₂ to R ₄ are each independently an alkoxy group having 1 to 6 carbon atoms,
a is a polymer compound that is an integer of 1 to 6.
delete delete delete The method according to claim 1,
The polymer compound comprising a structural unit represented by Formula 1 is a polymer compound comprising a structural unit represented by Formula 5 or Formula 6:
[Formula 5]

[Formula 6]

In Formulas 5 and 6,
k, l, m, and n represent the molar ratio of each repeating unit, and k+l+m+n is 100,
k is 1 to 50,
l is from 0 to 50,
m is from 0 to 50,
n is 1 to 70.
delete A modified conjugated diene-based polymer comprising the functional group derived from the polymer compound according to claim 1.
The method of claim 9,
The polymer is a modified conjugated diene polymer having a number average molecular weight of 10,000 g/mol to 2,000,000 g/mol.
The method of claim 9,
The polymer is a modified conjugated diene-based polymer containing 0.1 to 10 moles of siloxane groups relative to 1 mole of the polymer.
The method of claim 9,
The polymer is a modified conjugated diene-based polymer containing 0.1 to 100 mol of an amine group relative to 1 mol of the polymer.
The method of claim 9,
The polymer is a modified conjugated diene-based polymer containing 40% by weight or less of an aromatic vinyl-based monomer-derived unit.
1) polymerizing a conjugated diene-based monomer or an aromatic vinyl-based monomer and a conjugated diene-based monomer in a hydrocarbon solvent in the presence of an organic alkali metal compound to prepare an active polymer having an alkali metal bonded to at least one terminal; And
2) A method for preparing a modified conjugated diene-based polymer according to claim 9, comprising reacting the active polymer with a polymer compound containing a structural unit represented by the following formula (1):
[Formula 1]

In Formula 1,
X ₁ is a substituent represented by the following formula (2),
X ₂ is an aryl group having 6 to 10 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 3 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms,
X ₃ is a substituent represented by the following formula (3),
X ₄ is a substituent represented by the following formula (4),
k, l, m, and n represent the molar ratio of each repeating unit, and k+l+m+n is 100,
k is 1 to 50,
l is from 0 to 50,
m is from 0 to 50,
n is 1 to 70,
A ₁ to A ₄ are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms,
[Formula 2]

In Chemical Formula 2,
R ₁ is an ester group, an arylene group having 6 to 10 carbon atoms, or a secondary amine group,
R ₂ to R ₄ are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, wherein at least one of R ₂ to R ₄ is an alkoxy group having 1 to 10 carbon atoms,
a is an integer from 1 to 8,
[Formula 3]

In Chemical Formula 3,
R ₅ is an ester group,
R ₆ is an alkyl group having 1 to 20 carbon atoms,
b is an integer from 0 to 10,
[Formula 4]

In Chemical Formula 4,
R ₇ is a C 1 to C 6 alkylene group, an ester group or a C 6 to C 10 arylene group,
R ₈ and R ₉ are each independently an alkyl group having 1 to 10 carbon atoms or are linked to each other to form a ring structure having 3 to 10 carbon atoms,
c is an integer from 1 to 8.
The method of claim 14,
The method for producing a modified conjugated diene-based polymer wherein the polymer compound containing the constituent unit represented by Formula 1 includes the constituent unit represented by the following Formula 5 or Formula 6:
[Formula 5]

[Formula 6]

In Formulas 5 and 6,
k, l, m, and n represent the molar ratio of each repeating unit, and k+l+m+n is 100,
k is 1 to 50,
l is from 0 to 50,
m is from 0 to 50,
n is 1 to 70.
The method of claim 14,
The method for producing a modified conjugated diene-based polymer, wherein the organic alkali metal compound is used in an amount of 0.01 mmol to 10 mmol based on a total of 100 g of monomers.
The method of claim 14,
The organic alkali metal compound is methyllithium, ethyllithium, propyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octyllithium, phenyllithium, 1-naphthyl Lithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naphthyl sodium, naphthyl potassium, Lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide, lithium isopropyl amide of at least one selected from the group consisting of a modified conjugated diene polymer Manufacturing method.
The method of claim 14,
The polymerization of step 1) is a method of producing a modified conjugated diene-based polymer to be performed by further adding a polar additive.
The method of claim 18,
The method for producing a modified conjugated diene-based polymer is added in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the total monomer.
The method of claim 14,
The method for producing a modified conjugated diene-based polymer is used in a ratio of 0.1 mol to 5 mol relative to 1 mol of the organic alkali metal compound.