KR102153473B1 - Modified conjugated diene polymer, preparation method of the same and modifying agent - Google Patents

Abstract

The present invention relates to a modified conjugated diene-based polymer containing a functional group derived from a modifying agent, a method for preparing the modified conjugated diene-based polymer, and a modifying agent capable of easily modifying the conjugated diene-based polymer. Accordingly, the modified conjugated diene-based polymer may have excellent affinity with the filler, and as a result, the processed product (e.g., tire) manufactured from the rubber composition containing the polymer will have excellent tensile strength, abrasion resistance, and resistance to wet road surfaces. I can.

Description

Modified conjugated diene polymer, preparation method of the same and modifying agent {Modified conjugated diene polymer, preparation method of the same and modifying agent}

The present invention relates to a modified conjugated diene-based polymer containing a functional group derived from a modifying agent, a method for preparing the modified conjugated diene-based polymer, and a modifying agent capable of easily modifying the conjugated diene-based polymer.

In recent years, in accordance with the demand for low fuel consumption for automobiles, a conjugated diene-based polymer having low running 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 running resistance of the tire, there is a method of reducing the hysteresis loss of the vulcanized rubber. As an evaluation index of the vulcanized rubber, repulsive elasticity of 50°C to 80°C, tan δ, Goodrich heat, and the like are used. That is, a rubber material having high repulsion elasticity 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 with low wet skid resistance. In recent years, 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 technology in which the active anion at the chain end of a polymer obtained by polymerizing styrene-butadiene in a non-polar solvent using alkyllithium, a monofunctional initiator, is 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.

Therefore, there is a need to develop a 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 filler, particularly a modifier for rubber capable of providing a silica-based filler affinity functional group.

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

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

In addition, another object of the present invention is to provide a rubber composition comprising the modified conjugated diene polymer.

Furthermore, another object of the present invention is to provide a tire manufactured from the rubber composition.

In order to solve the above problems, the present invention provides a modified conjugated diene-based polymer comprising a functional group derived from one or more denaturants selected from denaturants represented by the following Chemical Formulas 1 and 2.

[Formula 1]

[Formula 2]

In Formula 1 and Formula 2,

R ₁ to R ₅ and R ₇ to R ₁₁ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, but at least one of R ₁ to R ₅ is an alkoxy group having 1 to 10 carbon atoms And, at least one of R ₇ to R ₁₁ is an alkoxy group having 1 to 10 carbon atoms,

R ₆ and R ₁₂ are each independently an alkylene group having 1 to 10 carbon atoms,

a, b, c and d are each independently an integer of 0 to 3, but a+b is 1 to 6, and c+d is an integer of 1 to 6.

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 the presence of an organic alkali metal compound in a hydrocarbon solvent 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 one or more modifiers selected from modifiers represented by the following Formulas 1 and 2 below.

[Formula 1]

[Formula 2]

In Formula 1 and Formula 2,

R ₁ to R ₅ and R ₇ to R ₁₁ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, but at least one of R ₁ to R ₅ is an alkoxy group having 1 to 10 carbon atoms And, at least one of R ₇ to R ₁₁ is an alkoxy group having 1 to 10 carbon atoms,

R ₆ and R ₁₂ are each independently an alkylene group having 1 to 10 carbon atoms,

a, b, c and d are each independently an integer of 0 to 3, but a+b is 1 to 6, and c+d is an integer of 1 to 6.

In addition, the present invention provides a denaturant represented by the following Chemical Formula 1 or Chemical Formula 2.

[Formula 1]

[Formula 2]

In Formula 1 and Formula 2,

R ₁ to R ₅ and R ₇ to R ₁₁ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, but at least one of R ₁ to R ₅ is an alkoxy group having 1 to 10 carbon atoms And, at least one of R ₇ to R ₁₁ is an alkoxy group having 1 to 10 carbon atoms,

R ₆ and R ₁₂ are each independently an alkylene group having 1 to 10 carbon atoms,

a, b, c and d are each independently an integer of 0 to 3, but a+b is 1 to 6, and c+d is an integer of 1 to 6.

Furthermore, the present invention provides a rubber composition comprising the modified conjugated diene polymer and a tire manufactured from the rubber composition.

The modified conjugated diene-based polymer according to the present invention has at least one functional group derived from a denaturant selected from the denaturants represented by Formula 1 and Formula 2, such as an ethylene glycol group, bound to the polymer chain, so that it has affinity with a filler, especially a silica-based filler. This can be excellent.

In addition, the production method according to the present invention can easily prepare a modified conjugated diene-based polymer by using at least one type of denaturant selected from the denaturing agents represented by Chemical Formulas 1 and 2.

In addition, the modifier represented by Formula 1 or Formula 2 according to the present invention is used as a modifier for rubber, particularly a modifier for a conjugated diene polymer, and is bonded to the conjugated diene polymer chain to easily introduce a filler affinity functional group. have.

Furthermore, the rubber composition according to the present invention may have excellent processability by including a modified conjugated diene-based polymer having excellent affinity with the filler, and as a result, the processed product (eg, tire) manufactured using the rubber composition It can have excellent tensile strength and running resistance.

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 modified conjugated diene-based polymer having excellent affinity with a filler, particularly a silica-based filler.

The modified conjugated diene-based polymer according to an embodiment of the present invention is characterized in that it contains at least one type of denaturant-derived functional group selected from the denaturing agents represented by the following Chemical Formulas 1 and 2.

[Formula 1]

[Formula 2]

In Formula 1 and Formula 2,

R ₁ to R ₅ and R ₇ to R ₁₁ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, but at least one of R ₁ to R ₅ is an alkoxy group having 1 to 10 carbon atoms And, at least one of R ₇ to R ₁₁ is an alkoxy group having 1 to 10 carbon atoms,

R ₆ and R ₁₂ are each independently an alkylene group having 1 to 10 carbon atoms,

a, b, c and d are each independently an integer of 0 to 3, but a+b is 1 to 6, and c+d is an integer of 1 to 6.

The modified conjugated diene-based polymer according to an embodiment of the present invention is derived from a denaturant-derived functional group represented by Formula 1, a denaturant-derived functional group represented by Formula 2, or a denaturant-derived functional group represented by Formula 1 It may contain functional groups at the same time. That is, the modified conjugated diene-based polymer may be modified by a denaturant represented by Formula 1, or modified by a denaturant represented by Formula 2, and also a denaturant represented by Formula 1 and a denaturant represented by Formula 2. It may be denatured by

Specifically, in Formula 1, R ₁ to R ₅ may be each independently an alkoxy group having 1 to 6 carbon atoms, and R ₆ may be an alkylene group having 1 to 6 carbon atoms. In addition, in Formula 2, R ₇ to R ₉ are each independently an alkoxy group having 1 to 6 carbon atoms, R ₉ and R ₁₀ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ₁₂ is a C 1 to C It may be an alkylene group of 6.

More specifically, in Formula 1, R ₁ to R ₅ may be each independently an alkoxy group having 1 to 3 carbon atoms, and R ₆ may be an alkylene group having 1 to 3 carbon atoms. In addition, in Formula 2, R ₇ to R ₉ are each independently an alkoxy group having 1 to 3 carbon atoms, R ₉ and R ₁₀ are each independently an alkyl group having 1 to 3 carbon atoms, and R ₁₂ is an alkyl group having 1 to 3 carbon atoms It could be Rengi.

More specifically, the modifier represented by Formula 1 may be represented by the following Formula 3, and the modifier represented by Formula 2 may be represented by the following Formula 4.

[Formula 3]

[Formula 4]

Meanwhile, the modified conjugated diene-based polymer according to an embodiment of the present invention may be a homopolymer or a copolymer, and may be prepared by a method described below.

Specifically, when the modified conjugated diene-based polymer is a homopolymer, it may be a modified conjugated diene polymer, and when the modified conjugated diene-based polymer is a copolymer, the modified conjugated diene-based polymer is a unit derived from a conjugated diene-based monomer and an aromatic vinyl-based monomer. It may include a derived unit. In addition, when the modified conjugated diene-based polymer is a copolymer, the copolymer may be a random copolymer.

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

In addition, the modified conjugated diene-based polymer may contain 0.3 equivalents to 6.0 equivalents of siloxane groups relative to the total number of moles of the polymer, and the polymer may include 0.2 equivalents to 4.0 equivalents of ethylene glycol groups based on the total moles of polymer.

The modified conjugated diene-based polymer may have excellent affinity with a filler, especially a silica-based filler, since a siloxane group and an ethylene glycol 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 100,000 g/mol to 500,000 g/mol, and specifically, 200,000 g/mol to 500,000 g/mol.

The modified conjugated diene-based polymer may have a weight average molecular weight of 200,000 g/mol to 1,500,000 g/mol, and specifically 300,000 g/mol to 1,200,000 g/mol.

The modified conjugated diene-based polymer may have a molecular weight distribution of 1.0 to 3.0, specifically 1.0 to 2.5.

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 called even polydispersity, and the weight average molecular weight (Mw ) And the number average molecular weight (Mn) and the ratio (Mw/Mn).

In addition, the modified conjugated diene-based polymer may have a vinyl content of 5 wt% or more, specifically 10 wt% or more, and more specifically 10 wt% to 50 wt%, and when the vinyl content is within the above range, the glass transition temperature 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.

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

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 at least one denaturant selected from denaturants represented by the following Chemical Formulas 1 and 2 (Step 2).

[Formula 1]

[Formula 2]

In Formula 1 and Formula 2,

R ₁ to R ₅ and R ₇ to R ₁₁ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms,

R ₆ and R ₁₂ are each independently an alkylene group having 1 to 10 carbon atoms,

a, b, c and d are each independently an integer of 0 to 3, but a+b is 1 to 6, and c+d is an integer of 1 to 6.

Specifically, the denaturant represented by Chemical Formula 1 and Chemical Formula 2 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 a conjugated diene-based monomer and an aromatic vinyl-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 conjugated diene-based monomer alone or a conjugated diene-based monomer and an aromatic vinyl-based monomer used together as a monomer. That is, the polymer prepared through the manufacturing 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 a conjugated diene-based monomer and an aromatic vinyl-based monomer.

When the modified conjugated diene-based polymer is a copolymer of a conjugated diene-based monomer and an aromatic vinyl-based monomer, 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 conjugated diene-based monomer and the aromatic vinyl-based monomer are used together as the monomer, the conjugated diene-based monomer contains 60% by weight or more of the unit derived from the conjugated diene-based monomer in the finally prepared modified conjugated diene-based polymer, specifically It may be used in an amount contained in 60% by weight to 100% by weight, more specifically 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.

When a conjugated diene-based monomer and an aromatic vinyl-based monomer are used together as the monomer, the aromatic vinyl-based monomer contains 40% by weight or less of the unit derived from the aromatic vinyl-based monomer in the finally prepared modified conjugated diene-based polymer, specifically It may be used in an amount of 0% to 40% by weight, more specifically 15% to 40% by weight.

Here, the "derived unit" may represent a component, structure, or the substance itself derived from a substance.

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 15 mg to 90 mg 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 and lithium isopropylamide. 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 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 0.005 parts by weight to 0.1 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 easy 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 one or more modifiers selected from modifiers represented by Formulas 1 and 2 in order to prepare a modified conjugated diene polymer.

Specifically, step 2 is a step of performing a denaturation reaction by adding and reacting a denaturant to the active polymer, wherein the denaturant is a denaturant represented by Formula 1, a denaturant represented by Formula 2, or a denaturant represented by Formula 1 and a formula It may be a mixture of denaturants represented by 2.

If, as the denaturing agent, a mixture of a denaturant represented by Formula 1 and a denaturant represented by Formula 2 is used, the mixture may include a denaturant represented by Formula 1 and a denaturant represented by Formula 2 in a molar ratio of 1:1 to 2:1. It may be mixed with.

The modifier may be used in a ratio of 0.1 to 2.0 equivalents based on the total number of moles of the organic alkali metal compound. The amount of denaturant used at this time indicates the total amount of the denaturant used in the reaction, and if one of the denaturants represented by Formula 1 and Formula 2 is used in the reaction, it may represent the amount of one used denaturant. When using a mixture of the denaturing agent represented by Formula 1 and Formula 2, it may indicate the amount of the mixture.

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.

In addition, the present invention provides a reinforcing filler, particularly a modifier for rubber that can provide an affinity functional group with a silica-based filler.

The denaturant according to an embodiment of the present invention is characterized in that it is represented by the following Formula 1 or Formula 2.

[Formula 1]

[Formula 2]

In Formula 1 and Formula 2,

R ₁ to R ₅ and R ₇ to R ₁₁ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms,

R ₆ and R ₁₂ are each independently an alkylene group having 1 to 10 carbon atoms,

a, b, c and d are each independently an integer of 0 to 3, but a+b is 1 to 6, and c+d is an integer of 1 to 6.

In addition, the modifier represented by Formula 1 or Formula 2 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 a conjugated diene-based monomer and an aromatic vinyl-based monomer.

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 contains 0.1% by weight or more, 100% by weight or less, specifically 10% to 100% by weight, and more specifically 20% to 90% by weight of the modified conjugated diene-based polymer. It may be included in weight percent. If the content of the modified conjugated diene-based polymer is less than 0.1% by weight, as a result, the effect of improving abrasion resistance and cracking resistance of a molded article manufactured from a rubber composition including the same may be insignificant.

In addition, the rubber composition may further include other rubber components as needed in addition to the modified conjugated diene-based polymer, and 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, the rubber component may be included in an amount of 1 to 900 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer.

The rubber component may be 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.

The carbon black filler is not particularly limited, but may have a nitrogen adsorption specific surface area (measured according to N2SA, JIS K 6217-2:2001) of 20 m ² /g to 250 m ² /g. In addition, the carbon black-based filler may have a dibutylphthalate oil absorption (DBP) of 80 cc/100 g to 200 cc/100 g. When the nitrogen adsorption specific surface area of the carbon black filler exceeds 250 m ² /g, the processability of the rubber composition may be deteriorated, and when it is less than 20 m ² /g, the reinforcing performance by the carbon black filler may be insignificant. In addition, when the DBP oil absorption amount of the carbon black-based filler exceeds 200 cc/100 g, the processability of the rubber composition may be deteriorated, and when it is less than 80 cc/100 g, the reinforcing performance by the carbon black-based filler may be insignificant.

In addition, the silica-based filler is not particularly limited, but may be, for example, wet silica (hydrous silicic acid), dry silica (silicic anhydride), calcium silicate, aluminum silicate, or colloidal silica. Specifically, the silica may be a wet room silica having the most remarkable effect of improving fracture characteristics and both of wet grip. In addition, the silica has a nitrogen surface area per gram (N2SA) of 120 m2/g to 180 m2/g, and a specific surface area of CTAB (cetyl trimethyl ammonium bromide) adsorption from 100 m2/g to 200 m2/g Can be When the nitrogen adsorption specific surface area of the silica is less than 120 m 2 /g, the reinforcing performance by silica may be deteriorated, and when it exceeds 180 m 2 /g, the workability of the rubber composition may decrease. In addition, when the CTAB adsorption specific surface area of the silica is less than 100 m 2 /g, the reinforcing performance by silica as a filler may be deteriorated, and when it exceeds 200 m 2 /g, the workability of the rubber composition may be reduced.

On the other hand, when silica 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 reinforcement, the silane coupling agent may be bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide. In the rubber composition according to an embodiment of the present invention, since a modified conjugated diene polymer in which a functional group having high affinity with a filler is introduced into the active site as a rubber component is used, the amount of the silane coupling agent is usually It can be further reduced. 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 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 agent. ), 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 specifically be a paraffinic, naphthenic, or aromatic compound, and 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, the anti-aging agent specifically includes 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 condensation product 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.

Example 1

In a 20 L autoclave reactor, 270 g of styrene, 710 g of 1,3-butadiene, and 5 kg of normal hexane, and 0.86 g of 2,2-bis(2-oxoranyl)propane as a polar additive were added, and the temperature inside the reactor was increased to 40 The temperature was raised to °C. When the temperature inside the reactor reached 40°C, 4 mmol of n-butyllithium was added to the reactor to proceed with an adiabatic heating reaction. After 20 minutes, 1,3-butadiene 20 g was added, and after 5 minutes N,N-bis(2-(2-methoxyethoxy)ethyl)-3-(triethoxysilyl)propane-1- 4.7 mmol of a denaturant of the following formula (i), which is an amine (N,N-bis(2-(2-methoxyethoxy)ethyl)-3-(triethoxysilyl)propan-1-amine), was added and reacted for 15 minutes. Thereafter, the polymerization reaction was stopped using ethanol, 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 and stirred to remove the solvent, and roll-dried to remove the remaining amount of solvent and water to prepare a modified styrene-butadiene copolymer.

(i)

(i)

Example 2

(N,N-bis(2-(2-methoxyethoxy)ethyl)-3-(triethoxysilyl)propan-1-amine) 3,4-bis(2-methoxyethoxy)- A denaturant of the following formula (ii), which is N-(3-(triethoxysilyl)propyl)aniline (3,4-bis(2-methoxyethoxy)-N-(3-(triethoxysilyl)propyl)aniline), to 4.7 mmnol Except for the addition, a modified styrene-butadiene copolymer was prepared in the same manner as in Example 1.

(ii)

(ii)

Comparative Example 1

In a 20 L autoclave reactor, 270 g of styrene, 710 g of 1,3 butadiene, and 5 kg of normal hexane, and 0.86 g of 2,2-bis(2-oxoranyl)propane as a polar additive were added, and the temperature inside the reactor was set to 40°C. It heated up. When the temperature inside the reactor reached 40° C., 4 mmol of n-butyllithium was added to the reactor to proceed with an adiabatic heating reaction. After about 20 minutes, 20 g of 1,3-butadiene was added, and after 5 minutes, 4 mmol of dichlorodimethylsilane was added, and the reaction was further performed for 15 minutes. Thereafter, the polymerization reaction was stopped using ethanol, and 45 ml of a solution in which 0.3% by weight of the antioxidant BHT (butylated hydroxytoluene) was dissolved in hexane was added. The resulting polymer was put in hot water heated with steam and stirred to remove the solvent, and then roll-dried to remove the remaining amount of solvent and water, thereby preparing a styrene-butadiene copolymer. Here, the dichlorodimethylsilane was used to obtain a styrene-butadiene copolymer having a molecular weight similar to that of Example 1.

Comparative Example 2

A commercially available modified styrene-butadiene copolymer HPR850 (JSR) was used.

Experimental Example 1

For each of the copolymers of Examples 1 and 2 and Comparative Examples 1 and 2, the content of styrene-derived units and vinyl, weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution in the copolymer, respectively. (Mw/Mn) and pattern viscosity (MV) were measured, respectively. The results are shown in Table 1 below.

1) Styrene-derived units and vinyl content

The content of styrene-derived units (SM) and vinyl in each copolymer was measured using NMR.

2) molecular weight analysis

The weight average molecular weight (Mw) and number average molecular weight (Mn) of each copolymer were measured by GPC (gel permeation chromatograph) analysis under the condition of 40°C. At this time, the column was used in combination with two PLgel Olexis from Polymer Laboratories and one PLgel mixed-C column. In addition, PS (polystyrene) was used as the GPC standard material (sTandard material) when calculating the molecular weight. The molecular weight distribution was calculated as the ratio (Mw/Mn) of the weight average molecular weight and the number average molecular weight measured by the above method.

3) Mooney viscosity analysis

The Mooney viscosity of each copolymer was measured at 100° C. for 4 minutes after preheating two samples with a weight of 15 g or more for 1 minute using MV-2000 (Alpha Technologies).

division Styrene
(wt%) vinyl
(wt%) GPC Mooney viscosity (MV) Mw(g/mol, ×10 ⁴ ) Mn(g/mol, ×10 ⁴ ) MW/Mn Example 1 27.8 42.9 45 35 1.30 55 Example 2 27.5 42.9 43 32 1.32 57 Comparative Example 1 27.0 43.0 48 31 1.54 63 Comparative Example 2 27 42.5 44.8 29.8 1.5 70

Experimental Example 2

In order to compare and analyze the physical properties of the rubber compositions including each of the copolymers of Examples 1 and 2 and Comparative Example 2 and a molded article prepared therefrom, tensile properties and viscoelastic properties were measured. The results are shown in Table 2 below.

1) Preparation of rubber composition

Each rubber composition was prepared through a first stage kneading process and a second stage kneading process. In this case, the amount of materials excluding the modified styrene-butadiene copolymer is expressed based on 100 parts by weight of the modified styrene-butadiene copolymer. In the first stage kneading, 137.5 parts by weight of each of the above modified styrene-butadiene copolymers, 70 parts by weight of silica, and bis(3-triethoxysilylpropyl)tetrasulfate as a silane coupling agent using a semi-bar remixer attached with a temperature control device. 11.2 parts by weight of feed, 2 parts by weight of anti-aging agent (TMDQ), 3 parts by weight of zinc oxide (ZnO), 2 parts by weight of stearic acid, 2 parts by weight of antioxidant, and 1 part by weight of wax were mixed and kneaded. At this time, the temperature of the kneader was controlled and the first blend was obtained at a discharge temperature of 145°C to 155°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, followed by mixing at a temperature of 100° C. The formulation was obtained. Thereafter, each rubber composition was prepared through a curing process at 100° C. for 20 minutes.

2) tensile properties

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

3) Viscoelastic properties

For viscoelastic properties, Tan δ was measured by varying the strain at a frequency of 10 Hz and each measurement temperature (0°C to 70°C) in a twist mode using a dynamic mechanical analyzer (TA). The higher the low temperature 0℃ Tan δ is, the better the wet road surface resistance, the lower the high temperature 60℃ Tan δ, the less hysteresis loss and the better low running resistance (fuel economy).

division Example 1 Example 2 Comparative Example 1 Comparative Example 2 Tensile properties Tensile strength (kgf/cm ² ) 188 189 168 189 300% tensile stress (kgf/cm ² ) 158 156 104 145 Viscoelasticity Tan δ at 0℃ 0.456 0.483 0.407 0.445 Tan δ at 60℃ 0.103 0.107 0.131 0.113

As shown in Table 2, the tensile properties and viscoelastic properties of the rubber compositions including the modified styrene-butadiene copolymers of Examples 1 and 2 prepared using the modifier according to an embodiment of the present invention are Comparative Example 1 And it was confirmed to be superior to the rubber composition containing the unmodified or modified styrene-butadiene copolymer of Comparative Example 2.

Specifically, the rubber composition containing the modified styrene-butadiene copolymer of Examples 1 and 2 prepared using the denaturing agent according to an embodiment of the present invention is the unmodified or modified styrene of Comparative Examples 1 and 2 -It was confirmed that the Tan δ value at 0°C increased and the Tan δ value at 60°C decreased compared to the rubber composition containing the butadiene copolymer. This is because the modified styrene-butadiene copolymer according to an embodiment of the present invention contains a functional group derived from a denaturant of Formula 1 or Formula 2, for example, a functional group derived from ethylene glycol. And improved physical bonding. In addition, the above results are results showing that the modified styrene-butadiene copolymer prepared using the modifier according to an embodiment of the present invention is excellent in resistance and rolling resistance properties on a road surface with a small amount, and fuel efficiency may be high. .

Claims (20)

It includes a functional group derived from one or more denaturants selected from the denaturants represented by the following formulas 1 and 2,
A modified conjugated diene-based polymer which is a conjugated diene-based monomer homopolymer or a copolymer of a conjugated diene-based monomer and an aromatic vinyl-based monomer:
[Formula 1]

[Formula 2]

In Formula 1 and Formula 2,
R ₁ to R ₅ and R ₇ to R ₁₁ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, but at least one of R ₁ to R ₅ is an alkoxy group having 1 to 10 carbon atoms And, at least one of R ₇ to R ₁₁ is an alkoxy group having 1 to 10 carbon atoms,
R ₆ and R ₁₂ are each independently an alkylene group having 1 to 10 carbon atoms,
a, b, c and d are each independently an integer of 0 to 3, but a+b is 1 to 6, and c+d is an integer of 1 to 6.
The method according to claim 1,
In Formula 1,
R ₁ to R ₅ are each independently an alkoxy group having 1 to 6 carbon atoms,
R ₆ is a modified conjugated diene polymer which is an alkylene group having 1 to 6 carbon atoms.
The method according to claim 1,
In Formula 2,
R ₇ to R ₉ are each independently an alkoxy group having 1 to 6 carbon atoms,
R ₁₀ and R ₁₁ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
R ₁₂ is a modified conjugated diene-based polymer that is an alkylene group having 1 to 6 carbon atoms.
The method according to claim 1,
The modified conjugated diene polymer represented by the following formula (3):
[Formula 3]

The method according to claim 1,
The modifier represented by Formula 2 is a modified conjugated diene polymer represented by the following Formula 4:
[Formula 4]

.
delete The method according to claim 1,
The polymer is a modified conjugated diene-based polymer having a number average molecular weight of 100,000 g/mol to 500,000 g/mol.
The method according to claim 1,
The polymer is a modified conjugated diene polymer having a molecular weight distribution of 1.0 to 3.0.
The method according to claim 1,
The polymer is a modified conjugated diene polymer having a vinyl content of 5% by weight or more.
1) 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 to prepare an active polymer in which an alkali metal is bonded to at least one terminal; And
2) A method for producing a modified conjugated diene-based polymer according to claim 1, comprising reacting the active polymer with at least one modifier selected from modifiers represented by the following Formulas 1 and 2:
[Formula 1]

[Formula 2]

In Formula 1 and Formula 2,
R ₁ to R ₅ and R ₇ to R ₁₁ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, but at least one of R ₁ to R ₅ is an alkoxy group having 1 to 10 carbon atoms And, at least one of R ₇ to R ₁₁ is an alkoxy group having 1 to 10 carbon atoms,
R ₆ and R ₁₂ are each independently an alkylene group having 1 to 10 carbon atoms,
a, b, c and d are each independently an integer of 0 to 3, but a+b is 1 to 6, and c+d is an integer of 1 to 6.
The method of claim 10,
The method for producing a modified conjugated diene-based polymer, wherein the organic alkali metal compound is used in an amount of 15 mg to 90 mg based on a total of 100 g of monomers.
The method of claim 10,
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, and lithium isopropyl amide of at least one selected from the group consisting of modified conjugated diene polymer Manufacturing method.
The method of claim 10,
The polymerization of step 1) is a method for producing a modified conjugated diene-based polymer that is performed by adding a polar additive.
The method of claim 13,
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 10,
The method for producing a modified conjugated diene-based polymer wherein the modifier represented by Formula 1 is represented by the following Formula 3:
[Formula 3]

The method of claim 10,
The method for producing a modified conjugated diene-based polymer wherein the modifier represented by Formula 2 is represented by the following Formula 4:
[Formula 4]

The method of claim 10,
The method for producing a modified conjugated diene-based polymer is used in a ratio of 0.1 to 2.0 equivalents relative to the number of moles of the organic alkali metal compound.
The method of claim 10,
The denaturant is a mixture of a denaturant represented by Formula 1 and Formula 2,
The mixture is a method for producing a modified conjugated diene-based polymer comprising a denaturant represented by Formula 1 and a denaturant represented by Formula 2 in a molar ratio of 1:1 to 2:1.
It is represented by the following formula 1 or formula 2,
Modifier for modifying a conjugated diene-based monomer homopolymer or a copolymer of a conjugated diene-based monomer and an aromatic vinyl-based monomer:
[Formula 1]

[Formula 2]

In Formula 1 and Formula 2,
R ₁ to R ₅ and R ₇ to R ₁₁ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, but at least one of R ₁ to R ₅ is an alkoxy group having 1 to 10 carbon atoms And, at least one of R ₇ to R ₁₁ is an alkoxy group having 1 to 10 carbon atoms,
R ₆ and R ₁₂ are each independently an alkylene group having 1 to 10 carbon atoms,
a, b, c and d are each independently an integer of 0 to 3, but a+b is 1 to 6, and c+d is an integer of 1 to 6. delete