KR20170075662A - Modified conjugated diene polymer, preparation method of the same and modifying agent - Google Patents

Abstract

The present invention relates to a modified conjugated diene polymer containing a functional group derived from a modifier, a process for producing the modified conjugated diene polymer, and a modifier capable of easily modifying the conjugated diene polymer. The resulting modified conjugated diene polymer may have an excellent affinity with a filler, and as a result, a processed product (for example, a tire) produced from a rubber composition containing the polymer has excellent tensile strength, abrasion resistance and wet road surface resistance .

Description

TECHNICAL FIELD [0001] The present invention relates to a modified conjugated diene polymer, a modified conjugated diene polymer, a preparation method of the same and a modifying agent,

The present invention relates to a modified conjugated diene polymer containing a functional group derived from a modifier, a process for producing the modified conjugated diene polymer, and a modifier capable of easily modifying the conjugated diene polymer.

In recent years, there has been a demand for a conjugated diene polymer having a low running resistance, excellent abrasion resistance and tensile properties as a rubber material for a tire, and also having adjustment stability represented by wet skid resistance.

In order to reduce the running resistance of the tire, there is a method of reducing the hysteresis loss of the vulcanized rubber. As the evaluation index of such vulcanized rubber, repulsive elasticity of 50 DEG C to 80 DEG C, tan delta, Goodrich heat is used. That is, a rubber material having a large rebound resilience at that temperature or a small tan δ or Goodrich heating is preferable.

Natural rubbers, polyisoprene rubbers, polybutadiene rubbers, and the like are known as rubber materials having a small hysteresis loss, but these have a problem of low wet skid resistance. Recently, a conjugated diene (co) polymer such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) is prepared by emulsion polymerization or solution polymerization and is used as a rubber for a tire . Of these, the greatest advantage of solution polymerization over emulsion polymerization is that vinyl structure content and styrene content, which define rubber properties, can be arbitrarily controlled and molecular weight and physical properties, etc., can be controlled by coupling, It can be adjusted. Therefore, it is easy to change the structure of the finally prepared SBR or BR rubber, and it is possible to reduce the movement of chain ends due to bonding or modification of chain ends and to increase the bonding force with a filler such as silica or carbon black, It is widely used as rubber material for tires.

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

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

For example, US Pat. No. 4,397,994 discloses a technique in which an active anion at the chain terminal of a polymer obtained by polymerizing styrene-butadiene in a nonpolar solvent using alkyllithium, a monofunctional initiator, is bonded using a binder such as a tin compound Respectively.

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 property and wet skid resistance are improved. However, silica having a hydrophilic surface compared to carbon black on the hydrophobic surface has a disadvantage that the affinity with the rubber is low and the dispersibility is poor. Therefore, in order to improve the dispersibility or to provide the bond between the silica and the rubber, It is necessary to use a lingering agent.

Accordingly, a method of introducing a functional group having affinity or reactivity with silica to the end of the rubber molecule has been attempted, but the effect is insufficient.

Therefore, it is necessary to develop a rubber having high affinity with a filler including silica.

US 4,397,994 A

SUMMARY OF THE INVENTION The present invention has been conceived to solve the problems of the prior art, and it is an object of the present invention to provide a modifier for rubber that can provide a filler, particularly a silica-based filler affinity functional group.

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

Still another object of the present invention is to provide a process for producing a modified conjugated diene polymer using the above modifier.

It is still another object of the present invention to provide a rubber composition comprising the modified conjugated diene polymer.

Still another object of the present invention is to provide a tire made from the rubber composition.

In order to solve the above problems, the present invention provides a modified conjugated diene polymer comprising at least one functional group derived from a modifying agent selected from the following formulas (1) and (2).

[Chemical Formula 1]

(2)

In the above formulas (1) and (2)

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

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

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

The present invention also relates to a process for producing an active polymer having at least one terminal thereof bonded with an alkali metal by polymerizing a conjugated diene monomer or an aromatic vinyl monomer and a conjugated diene monomer in the presence of an organic alkali metal compound in a hydrocarbon solvent ); And a step (step 2) of reacting the active polymer with at least one modifier selected from the following formulas (1) and (2).

[Chemical Formula 1]

(2)

In the above formulas (1) and (2)

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

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

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

In addition, the present invention provides a modifier represented by the following general formula (1) or (2).

[Chemical Formula 1]

(2)

In the above formulas (1) and (2)

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

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

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

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

The modified conjugated diene polymer according to the present invention is a modified conjugated diene polymer in which the functional group derived from at least one modifier selected from the modifiers represented by the general formulas (1) and (2), for example, ethylene glycol groups are bonded to the polymer chain, Can be excellent.

Further, the production method according to the present invention can easily produce the modified conjugated diene polymer by using at least one modifier selected from the modifiers represented by the formulas (1) and (2).

In addition, the modifier represented by the formula (1) or (2) according to the present invention is used as a modifier for rubber, particularly a modifier of a conjugated diene polymer, and is capable of being easily bonded to the conjugated diene polymer chain to easily introduce a filler- have.

 Further, the rubber composition according to the present invention may have excellent processability by including a modified conjugated diene polymer having excellent affinity with the filler. As a result, a work product (for example, a tire) produced using the rubber composition Tensile strength and running resistance can be excellent.

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

The terms and words used in the present specification and claims should not be construed in an ordinary or dictionary sense and the inventor can properly define the concept of the term to describe its invention in the best possible way It should be construed as meaning and concept consistent with the technical idea of the present invention.

The present invention provides a modified conjugated diene polymer excellent in affinity with a filler, particularly a silica filler.

The modified conjugated diene polymer according to one embodiment of the present invention is characterized by containing at least one functional group derived from a denaturant selected from the denaturing agents represented by the following general formulas (1) and (2).

[Chemical Formula 1]

(2)

In the above formulas (1) and (2)

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

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

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

The modified conjugated diene polymer according to one embodiment of the present invention is a modified conjugated diene polymer having a functional group derived from the modifier represented by the formula 1, a functional group derived from the modifier represented by the formula 2 or a functional group derived from the modifier represented by the formula 1 and a modifier derived from the formula 2 Functional group at the same time. That is, the modified conjugated diene polymer may be modified by the modifier represented by the formula (1) or may be modified by the modifier represented by the formula (2), and the modifier represented by the formula (1) and the modifier represented by the formula . ≪ / RTI >

Specifically, in Formula 1, R ₁ to R ₅ are 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. Further, in the formula 2 R ₇ to R ₉ are independently an alkoxy group having 1 to 6 carbon atoms from each other, R ₉ and R ₁₀ are independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms from each other, R ₁₂ is C 1 -C 6 < / RTI >

More specifically, in Formula 1, R ₁ to R ₅ are 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 the above formula (2), R ₇ to R ₉ independently represent an alkoxy group having 1 to 3 carbon atoms, R ₉ and R ₁₀ independently represent an alkyl group having 1 to 3 carbon atoms, and R ₁₂ denotes an alkyl group having 1 to 3 carbon atoms It can be a ringgit.

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

(3)

[Chemical Formula 4]

Meanwhile, the modified conjugated diene polymer according to an embodiment of the present invention may be a homopolymer or a copolymer, and may be one produced by a production method described later.

Specifically, when the modified conjugated diene polymer is a homopolymer, the modified conjugated diene polymer may be a modified conjugated diene polymer, and when the modified conjugated diene polymer is a copolymer, the modified conjugated diene polymer preferably contains a conjugated diene monomer derived unit and an aromatic vinyl monomer And may include a derived unit. When the modified conjugated diene polymer is a copolymer, the copolymer may be a random copolymer.

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

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

The modified conjugated diene polymer has siloxane groups and ethylene glycol groups bonded to the polymer chain, and thus can have excellent affinity with a filler, particularly a silica filler. Thus, the rubber composition containing the modified conjugated diene polymer can have excellent processability because of its excellent compounding property with the filler, and consequently the molded article produced using the rubber composition, such as the tensile strength, Wear resistance and wet road surface resistance can be improved.

In addition, the modified conjugated diene 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 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 polymer may have a molecular weight distribution of 1.0 to 3.0, specifically 1.0 to 2.5.

Herein, the weight average molecular weight and the number average molecular weight are respectively polystyrene-reduced molecular weights analyzed by gel permeation chromatography (GPC), molecular weight distribution (Mw / Mn) is also called polydispersity and weight average molecular weight (Mw ) And the number average molecular weight (Mn) (Mw / Mn).

The modified conjugated diene polymer may have a vinyl content of 5% by weight or more, specifically 10% by weight or more, more specifically 10% by weight to 50% by weight. When the vinyl content is in the above range, Can be adjusted to an appropriate range. Therefore, when the tire is applied to a tire, it is excellent in physical properties required for a tire such as a running resistance and a braking force, and also has an effect of reducing fuel consumption.

At this time, the vinyl content indicates the content of the 1,2-added conjugated diene monomer, not 1,4-added to 100% by weight of the conjugated diene-based polymer composed of the vinyl group-containing monomer or the conjugated diene-based monomer.

The present invention also provides a process for producing the above-mentioned modified conjugated diene polymer.

The production method according to an embodiment of the present invention is a method of polymerizing an aromatic vinyl monomer or an aromatic vinyl monomer and a conjugated diene monomer in the presence of an organic alkali metal compound in a hydrocarbon solvent and polymerizing an active polymer having at least one terminal thereof with an alkali metal (Step 1); And a step (step 2) of reacting the active polymer with at least one modifier selected from the following formulas (1) and (2).

[Chemical Formula 1]

(2)

In the above formulas (1) and (2)

R ₁ to R ₅ and R ₇ to R ₁₁ independently represent 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 independently represent an alkylene group having 1 to 10 carbon atoms,

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

Specifically, the modifiers represented by the above-mentioned formulas (1) and (2) are as described above.

The above step 1 is a step for producing an active polymer having at least one terminal thereof bound with an alkali metal and is carried out by polymerizing a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer in the presence of an organic alkali metal compound in a hydrocarbon solvent .

The polymerization of step 1 may be carried out using a conjugated diene monomer alone or a conjugated diene monomer and an aromatic vinyl monomer as monomers. That is, the polymer produced by the above production method according to one embodiment of the present invention may be a homopolymer derived from a conjugated diene monomer, or a copolymer derived from a conjugated diene monomer and an aromatic vinyl 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 above-mentioned "random copolymer" may indicate that constituent units constituting the copolymer are randomly arranged.

Examples of the conjugated diene monomer include, but are not limited to, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, -1,3-butadiene, and the like.

When the conjugated diene-based monomer and the aromatic vinyl-based monomer are used together as the monomer, the conjugated diene-based monomer has a unit derived from the conjugated diene-based monomer in the finally produced modified conjugated diene-based polymer in an amount of 60% by weight or more, May be used in an amount of 60 wt% to 100 wt%, more specifically 60 wt% to 85 wt%.

Examples of the aromatic vinyl monomer include, but not limited to, styrene,? -Methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- -Methylphenyl) styrene and 1-vinyl-5-hexyl naphthalene.

When the conjugated diene-based monomer and the aromatic vinyl-based monomer are used together as the monomer, the amount of the aromatic vinyl-based monomer-derived unit in the finally produced modified conjugated diene-based polymer is 40% by weight or less, , And 0% by weight to 40% by weight, more specifically 15% by weight to 40% by weight.

Here, the "derived unit" may be an element, a structure, or the substance itself due to 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 100 g of the total monomer.

 The organic alkali metal compound is not particularly limited and includes, for example, methyl lithium, ethyl lithium, propyl lithium, n-butyl lithium, s-butyl lithium, t- Phenyl lithium, 1-naphthyl lithium, n-eicosyllithium, 4-butylphenyl lithium, 4-tolyl lithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, At least one member selected from the group consisting of lithium, sodium, potassium, sodium, potassium, sodium, sodium, potassium, sodium, sodium, potassium and alkaline earth metals. .

The polymerization of step 1 may be carried out by adding a polar additive if necessary, and the polar additive may be added in an amount of 0.001 part by weight to 10 parts by weight based on 100 parts by weight of the total amount of the monomers. Specifically, it may be added in an amount of 0.001 part by weight to 1 part by weight, and more desirably 0.005 part by weight to 0.1 part by weight based on 100 parts by weight of the total amount of monomers.

The polar additive may be selected from the group consisting of tetrahydrofuran, ditetrahydrofuryl propane, diethyl ether, cycloalcohol ether, dipropyl ether, ethylenedimethyl ether, ethylene dimethyl ether, diethyl glycol, dimethyl ether, tertiary butoxyethoxyethane, bis (3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine and tetramethylethylenediamine.

In the production method according to an embodiment of the present invention, when the conjugated diene-based monomer and the aromatic vinyl-based monomer are copolymerized by using the polar additive, the random copolymer can be easily formed .

The polymerization of the step 1 may be carried out through adiabatic polymerization or by isothermal polymerization.

Herein, the adiabatic polymerization represents a polymerization method comprising the step of polymerizing an organic alkali metal compound into a self-reaction heat without any heat, after the introduction of the organic alkali metal compound, wherein the isothermal polymerization is carried out by arbitrarily introducing heat Or the heat is taken to keep the temperature of the polymerizer constant.

The polymerization may be carried out in a temperature range of -20 캜 to 200 캜, specifically, in a temperature range of 0 캜 to 150 캜, more specifically, 10 캜 to 120 캜.

Step 2 is a step of reacting the active polymer with at least one modifier selected from the group consisting of the modifiers represented by the formulas (1) and (2) to produce the modified conjugated diene polymer.

Specifically, the step 2 is a step of adding a denaturant to the active polymer and reacting the denaturant to react the denaturant, the denaturant represented by the general formula (1), the denaturant represented by the general formula (2) 2 < / RTI >

If the modifier is a mixture of the modifier represented by the general formula (1) and the modifier represented by the general formula (2), the mixture may contain the modifier represented by the general formula (1) and the modifier represented by the general formula (2) in a molar ratio of 1: 1 to 2: . ≪ / RTI >

The modifier may be used in a proportion of 0.1 to 2.0 equivalents relative to the total molar amount of the organic alkali metal compound. The amount of the denaturant used in the reaction represents the total amount of the denaturant used in the reaction. If one of the denaturants represented by the general formulas (1) and (2) is used in the reaction, In the case of using the mixture of the modifier represented by the general formulas (1) and (2), it may indicate the amount of the mixture used.

The reaction of Step 2 according to an embodiment of the present invention may be a modification reaction for introducing a functional group into the polymer, and each of the reactions may be performed at a temperature ranging from 10 ° C to 120 ° C for 10 minutes to 5 hours.

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

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

The modifier according to one embodiment of the present invention is characterized by being represented by the following general formula (1) or (2).

[Chemical Formula 1]

(2)

In the above formulas (1) and (2)

R ₁ to R ₅ and R ₇ to R ₁₁ independently represent 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 independently represent an alkylene group having 1 to 10 carbon atoms,

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

The modifier represented by the above formula (1) or (2) may be a modifier for a conjugated diene 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.

Further, 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 the modified conjugated diene polymer in an amount of 0.1 to 100% by weight, specifically 10 to 100% by weight, more specifically 20 to 90% % ≪ / RTI > by weight. If the content of the modified conjugated diene polymer is less than 0.1% by weight, the effect of improving the abrasion resistance and crack resistance of a molded article produced from the rubber composition containing the modified conjugated diene polymer may be insufficient.

In addition, the rubber composition may further include other rubber components, if necessary, in addition to the modified conjugated diene polymer, wherein the rubber component may be contained in an amount of 90 wt% or less based on the total weight of the rubber composition. Specifically, the rubber component may be contained in an amount of 1 part by weight to 900 parts by weight based on 100 parts by weight of the modified conjugated diene polymer.

The rubber component may be natural rubber or synthetic rubber, for example natural rubber (NR) comprising cis-1,4-polyisoprene; Modified natural rubbers such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber, which are modified or refined with the general natural rubber; Butadiene copolymers (SBR), polybutadiene (BR), polyisoprenes (IR), butyl rubbers (IIR), ethylene-propylene copolymers, polyisobutylene-co-isoprene, neoprene, poly Butadiene), poly (styrene-co-butadiene), poly (styrene-co-butadiene) Synthetic rubber such as polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, butyl rubber, halogenated butyl rubber and the like may be used, and any one or a mixture of two or more thereof may be used have.

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. The filler may be a silica filler, a carbon black 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 filler may have a dibutyl phthalate oil absorption (DBP) of 80 cc / 100 g to 200 cc / 100 g. If the nitrogen adsorption specific surface area of the carbon black filler exceeds 250 m ² / g, the workability of the rubber composition may decrease. If it is less than 20 m ² / g, the reinforcing performance by the carbon black filler may be insufficient. If the DBP oil absorption of the carbon black filler exceeds 200 cc / 100 g, the processability of the rubber composition may be lowered. If it is less than 80 cc / 100 g, the reinforcing performance by the carbon black filler may be insufficient.

The silica-based filler is not particularly limited, but may be, for example, wet silica (hydrated silicic acid), dry silica (silicic anhydride), calcium silicate, aluminum silicate or colloidal silica. Specifically, the silica may be a wet silica having the most remarkable effect of improving the destructive property and the wet grip. The silica has a nitrogen surface area per gram (N 2 SA) of 120 m 2 / g to 180 m 2 / g and a specific surface area of CTAB (cetyl trimethyl ammonium bromide) of 100 m 2 / g to 200 m 2 / g Lt; / RTI > If the nitrogen adsorption specific surface area of the silica is less than 120 m < 2 > / g, the reinforcing performance by silica may be lowered. If it exceeds 180 m < 2 > / g, If 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 lowered, and if it exceeds 200 m &

On the other hand, when silica is used as the filler, a silane coupling agent may be used together to improve the reinforcing property and the low heat build-up. Specific examples of the silane coupling agent include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane , 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide Triethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilyl Propylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzyltetrasulfide, 3-triethoxysilylpropylmethacrylate Monosulfide, monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl- N-dimethylthiocarbamoyltetrasulfide, or dimethoxymethylsilylpropylbenzothiazolyltetrasulfide. Any one or a mixture of two or more of them may be used. More specifically, the silane coupling agent may be bis (3-triethoxysilylpropyl) polysulfide or 3-trimethoxysilylpropylbenzotriazetetrasulfide in consideration of the effect of improving the reinforcing property. In the rubber composition according to one embodiment of the present invention, since the modified conjugated diene polymer in which a functional group having a high affinity for the filler is introduced into the active site as a rubber component is used, the amount of the silane coupling agent to be blended is usually Can be reduced. Specifically, the silane coupling agent may be used in an amount of 1 part by weight to 20 parts by weight based on 100 parts by weight of the filler. When used in the above-mentioned range, gelation of the rubber component can be prevented while sufficiently exhibiting the effect as a coupling agent. More specifically, the silane coupling agent may be used in an amount of 5 parts by weight 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 may further include a vulcanizing agent.

The vulcanizing agent may be specifically a 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 contained in the above content range, the required elastic modulus and strength of the vulcanized rubber composition can be ensured, and at the same time, the low fuel consumption ratio can be obtained.

In addition, the rubber composition according to one embodiment of the present invention may contain various additives commonly used in the rubber industry, such as a vulcanization accelerator, a process oil, a plasticizer, an antioxidant, a scorch inhibitor, zinc white ), Stearic acid, a thermosetting resin, or a thermoplastic resin.

The vulcanization accelerator is not particularly limited and specifically includes M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazyl sulfenamide) Based compound, or a guanidine-based compound such as DPG (diphenylguanidine) can 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.

The process oil may be a paraffinic, naphthenic, or aromatic compound. More specifically, considering the tensile strength and abrasion resistance, the process oil may be an aromatic process oil, a hysteresis loss And naphthenic or paraffinic process oils may be used in view of the low temperature characteristics. The process oil may be contained in an amount of 100 parts by weight or less based on 100 parts by weight of the rubber component. When the content is included in the above amount, the tensile strength and low heat build-up (low fuel consumption) of the vulcanized rubber can be prevented from lowering.

Specific examples of the antioxidant include N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'- 2, 4-trimethyl-1,2-dihydroquinoline, or high-temperature condensates of diphenylamine and acetone. The antioxidant may be used in an amount of 0.1 part by weight to 6 parts by weight based on 100 parts by weight of the rubber component.

The rubber composition according to one embodiment of the present invention can be obtained by kneading by using a kneader such as Banbury mixer, roll, internal mixer or the like by the above compounding formula. Further, the rubber composition can be obtained by a vulcanization step after molding, This excellent rubber composition can be obtained.

Accordingly, the rubber composition can be applied to various members such as tire tread, under-tread, sidewall, carcass coated rubber, belt coated rubber, bead filler, pancake fur, or bead coated rubber, vibration proof rubber, belt conveyor, Can be useful for the production of various industrial rubber products.

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

The tire may be a tire or a tire tread.

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. However, the following examples and experimental examples are provided for illustrating the present invention, and the scope of the present invention is not limited thereto.

Example 1

270 g of styrene, 710 g of 1,3-butadiene and 5 kg of n-hexane, and 0.86 g of 2,2-bis (2-oxoranyl) propane as a polar additive were introduced into a 20 L autoclave reactor, Lt; 0 > C. When the internal temperature of the reactor reached 40 캜, 4 mmol of n-butyllithium was charged into the reactor to proceed the adiabatic temperature-rise reaction. After 20 minutes, 20 g of 1,3-butadiene was added and after 5 minutes, N, N-bis (2- (2-methoxyethoxy) ethyl) -3- (triethoxysilyl) 4.7 mmol of a modifier of the following formula (i), which is N, N-bis (2- (2-methoxyethoxy) ethyl) -3- (triethoxysilyl) propan-1-amine, was added thereto 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 BHT (butylated hydroxytoluene) as an antioxidant was dissolved in hexane was added. The resultant polymer was put into hot water heated with steam and stirred to remove the solvent. The solvent and water were removed to prepare a modified styrene-butadiene copolymer.

(i)

(i)

Example 2

(2-methoxyethoxy) - (2-methoxyethoxy) ethyl) -3- (triethoxysilyl) propan- The modifier of the following formula (ii), which is N- (3- (triethoxysilyl) propyl) aniline, was reacted with 4.7 mMolol of 3,4-bis (2-methoxyethoxy) -N- Modified styrene-butadiene copolymer was prepared in the same manner as in Example 1, except that the modified styrene-butadiene copolymer was added.

(ii)

(ii)

Comparative Example 1

270 g of styrene, 710 g of 1,3-butadiene and 5 kg of n-hexane, and 0.86 g of 2,2-bis (2-oxoranyl) propane as a polar additive were placed in a 20 L autoclave reactor, Lt; / RTI > When the internal temperature of the reactor reached 40 캜, 4 mmol of n-butyllithium was charged into the reactor to proceed the adiabatic temperature-rise reaction. After 20 minutes, 20 g of 1,3-butadiene was added. After 5 minutes, 4 mmol of dichlorodimethylsilane was added, and the reaction was continued for 15 minutes. Thereafter, the polymerization reaction was stopped using ethanol, and 45 ml of a solution in which 0.3 wt% of BHT (butylated hydroxytoluene) as an antioxidant was dissolved in hexane was added. The resultant polymer was put into hot water heated with steam and stirred to remove the solvent. The solvent was then removed by roll drying to remove residual solvent and water to prepare 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 above.

Comparative Example 2

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

Experimental Example 1

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

1) Styrene-derived units and vinyl content

The styrene derived unit (SM) and vinyl content in each copolymer were measured by 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 캜. In this case, two columns of PLgel Olexis manufactured by Polymer Laboratories and a PLgel mixed-C column were used in combination. Also, PS (polystyrene) was used as a GPC reference material in molecular weight calculation. The molecular weight distribution was calculated by the ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight measured by the above method.

3) Mooney viscosity analysis

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

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 comparatively analyze the physical properties of the rubber composition comprising the respective copolymers of Example 1, Example 2 and Comparative Example 2 and the molded article produced therefrom, tensile and viscoelastic properties were measured. The results are shown in Table 2 below.

1) Preparation of rubber composition

Each rubber composition was manufactured through a first stage kneading and a second stage kneading process. In this case, the amount of the material except for the modified styrene-butadiene copolymer is shown 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 modified styrene-butadiene copolymers, 70 parts by weight of silica, and 100 parts by weight of bis (3-triethoxysilylpropyl) tetrasulfide as a silane coupling agent were mixed by using a Banbury mixer equipped with a temperature- 11.2 parts by weight of feed, 2 parts by weight of antioxidant (TMDQ), 3 parts by weight of zinc oxide (ZnO) and 2 parts by weight of stearic acid, 2 parts by weight of antioxidant and 1 part by weight of wax were kneaded. At this time, the temperature of the kneader was controlled and a primary blend was obtained at an outlet temperature of 145 ° C to 155 ° C. In the second stage kneading, after cooling the above-mentioned primary 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 were added to a kneader, Compound. Thereafter, each rubber composition was prepared by curing at 100 DEG C for 20 minutes.

2) Tensile properties

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

3) Viscoelastic properties

The viscoelastic properties were measured by using a dynamic mechanical analyzer (TA) at a frequency of 10 Hz in a twist mode at various measuring temperatures (0 ° C to 70 ° C) to measure Tan δ. The higher the temperature of 0 ° C Tan δ, the better the wet road surface resistance. The lower the tan δ of 60 ° C at higher temperatures, the lower the hysteresis loss and the better the resistance to low-flow 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 Viscoelastic Tan δ at 0 ° C 0.456 0.483 0.407 0.445 Tan δ at 60 ° C 0.103 0.107 0.131 0.113

As shown in Table 2, the tensile properties and the viscoelastic properties of the rubber compositions comprising the modified styrene-butadiene copolymers of Examples 1 and 2 prepared using the modifier according to one embodiment of the present invention were comparable to those of Comparative Example 1 And the rubber composition containing the unmodified or modified styrene-butadiene copolymer of Comparative Example 2.

Specifically, the rubber compositions comprising the modified styrene-butadiene copolymers of Examples 1 and 2 prepared using the modifier according to one embodiment of the present invention were compared with the unmodified or modified styrene -Butadiene copolymer, the tan δ value at 0 ° C was increased and the tan δ value at 60 ° C was decreased. This is because the modified styrene-butadiene copolymer according to one embodiment of the present invention contains a functional group derived from a modifier derived from a modifier of formula (1) or (2), for example, an ethyleneglycol-derived functional group so that the affinity with the filler is excellent, And physical coupling is improved. In addition, the above results show that the modified styrene-butadiene copolymer produced by using the modifier according to an embodiment of the present invention is excellent in resistance and rolling resistance characteristics on a small road surface and high in fuel efficiency .

Claims (20)

A modified conjugated diene polymer comprising at least one functional group derived from a modifier selected from the following formulas (1) and (2)
[Chemical Formula 1]

(2)

In the above formulas (1) and (2)
R ₁ to R ₅ and R ₇ to R ₁₁ independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, at least one of R ₁ to R ₅ is an alkoxy group having 1 to 10 carbon atoms , At least one of R ₇ to R ₁₁ is an alkoxy group having 1 to 10 carbon atoms,
R ₆ and R ₁₂ independently represent an alkylene group having 1 to 10 carbon atoms,
a, b, c and d are independently integers of 0 to 3, 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 independently represent an alkoxy group having 1 to 6 carbon atoms,
R ₆ is a conjugated diene-based polymer is modified due to an alkylene group having 1 to 6 carbon atoms.
The method according to claim 1,
In Formula 2,
R ₇ to R ₉ independently represent an alkoxy group having 1 to 6 carbon atoms,
R ₁₀ and R ₁₁ independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
And R < ₁₂ > is an alkylene group having 1 to 6 carbon atoms.
The method according to claim 1,
Wherein the modifier represented by the formula (1) is represented by the following formula (3):
(3)

The method according to claim 1,
Wherein the modifier represented by the formula (2) is represented by the following formula (4): < EMI ID =
[Chemical Formula 4]

.
The method according to claim 1,
Wherein the polymer is a copolymer of a conjugated diene-based monomer homopolymer or a conjugated diene-based monomer and an aromatic vinyl-based monomer.
The method according to claim 1,
Wherein the polymer has a number average molecular weight of 100,000 g / mol to 500,000 g / mol.
The method according to claim 1,
Wherein the polymer has a molecular weight distribution of 1.0 to 3.0.
The method according to claim 1,
Wherein the polymer has a vinyl content of 5 wt% or more.
1) polymerizing a conjugated diene monomer or an aromatic vinyl monomer and a conjugated diene monomer in the presence of an organic alkali metal compound in a hydrocarbon solvent to produce an active polymer having at least one terminal of which an alkali metal is bonded; And
2) a method for producing the modified conjugated diene polymer according to claim 1, comprising reacting the active polymer with at least one modifier selected from the following formulas (1) and (2)
[Chemical Formula 1]

(2)

In the above formulas (1) and (2)
R ₁ to R ₅ and R ₇ to R ₁₁ independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, at least one of R ₁ to R ₅ is an alkoxy group having 1 to 10 carbon atoms , At least one of R ₇ to R ₁₁ is an alkoxy group having 1 to 10 carbon atoms,
R ₆ and R ₁₂ independently represent an alkylene group having 1 to 10 carbon atoms,
a, b, c and d are independently integers of 0 to 3, a + b is 1 to 6, and c + d is an integer of 1 to 6.
The method of claim 10,
Wherein the organic alkali metal compound is used in an amount of 15 mg to 90 mg based on 100 g of the total of monomers.
The method of claim 10,
The organic alkali metal compound may be at least one selected from the group consisting of methyl lithium, ethyl lithium, propyl lithium, n-butyl lithium, s-butyl lithium, t- Lithium, n-octyl lithium, n-octyl lithium, n-eicosyllithium, 4-butylphenyl lithium, 4-tolyl lithium, cyclohexyllithium, Wherein the modified conjugated diene polymer is at least one selected from the group consisting of lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide and lithium isopropylamide Gt;
The method of claim 10,
Wherein the polymerization of step 1) is carried out by adding a polar additive.
14. The method of claim 13,
Wherein the polar additive is added in an amount of 0.001 part by weight to 10 parts by weight based on 100 parts by weight of the total of the monomers.
The method of claim 10,
Wherein the modifier represented by the formula (1) is represented by the following formula (3): < EMI ID =
(3)

The method of claim 10,
Wherein the modifier represented by the formula (2) is represented by the following formula (4): < EMI ID =
[Chemical Formula 4]

The method of claim 10,
Wherein the modifier is used in a proportion of 0.1 to 2.0 equivalents based on the number of moles of the organic alkali metal compound.
The method of claim 10,
Wherein said modifier is a mixture of modifiers represented by formulas (1) and (2)
Wherein the mixture contains a modifier represented by the formula (1) and a modifier represented by the formula (2) in a molar ratio of 1: 1 to 2: 1.
A modifier represented by the following formula (1) or (2):
[Chemical Formula 1]

(2)

In the above formulas (1) and (2)
R ₁ to R ₅ and R ₇ to R ₁₁ independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, at least one of R ₁ to R ₅ is an alkoxy group having 1 to 10 carbon atoms , At least one of R ₇ to R ₁₁ is an alkoxy group having 1 to 10 carbon atoms,
R ₆ and R ₁₂ independently represent an alkylene group having 1 to 10 carbon atoms,
a, b, c and d are independently integers of 0 to 3, a + b is 1 to 6, and c + d is an integer of 1 to 6.
The method of claim 19,
Wherein the modifying agent is a copolymer of a conjugated diene monomer homopolymer or a copolymer of a conjugated diene monomer and an aromatic vinyl monomer.