KR20140127726A - Method of preparing conjugated-diene polymer, composition comprising the polymer and tires comprising the composition - Google Patents

Abstract

The present invention relates to manufacture of a modified conjugated-diene polymer having a silyl group where one terminal is substituted to amine and the other terminal is substituted to one or more alkoxy groups, and nitrogen atoms by synthesizing an initiator where a negative ion terminal including amine and a positive ion terminal including alkali metal exist, polymerizing combination with an aromatic vinyl monomer using the initiator, synthesizing a polymer where one terminal is modified, and coupling or reacting a compound including one or more silyl groups substituted to the alkoxy group and nitrogen atoms to the polymer. The present invention has excellent progenic properties and shows tensile strength, wear resistance, and wet surface resistance when mixing the polymer to silica as a reinforcing agent.

Description

[0001] The present invention relates to a method for preparing a conjugated diene polymer, a composition comprising the polymer and a tire comprising the composition,

The present invention relates to a process for producing a conjugated diene polymer, a rubber composition comprising the polymer, and a tire comprising the composition, and more particularly to a tire comprising an amine terminal An initiator is synthesized and a combination of an aromatic vinyl monomer and an aromatic vinyl monomer is polymerized to synthesize a polymer modified at one end thereof and then a compound containing at least one silyl group substituted with an alkoxy group and a nitrogen atom Or by reacting the resulting mixture with an amine at one end thereof and a silyl group and a nitrogen atom at the other end thereof substituted with at least one alkoxy group and has excellent exothermicity when silica is mixed with a reinforcing agent At the same time, tensile strength, abrasion resistance, wet road surface resistance To a non-composition.

In recent years, consideration for the environment, such as suppression of carbon dioxide emission, has become a social request, and the demand for fuel economy for automobiles is increasing. Development of a material having a small rolling resistance as a material for an automobile tire, particularly a tire tread in contact with the ground is required, and development of a material having excellent wet skid resistance and sufficient wear resistance and fracture characteristics is required.

On the other hand, carbon black, silica and the like are used as reinforcing fillers for tire treads. When silica is used as a reinforcing filler, there is an advantage that low hysteresis loss property and wet skid resistance are improved. Silica on the hydrophilic surface has a low affinity with the conjugated diene rubber and has a disadvantage that the dispersibility is poor compared with the carbon black. Therefore, it is possible to improve the dispersibility or to improve the dispersibility of the silica- It is necessary to include a separate silane coupling agent in order to impart the bond between the silane coupling agent.

Considering the problem with silica, the functional group having affinity or reactivity with silica is introduced into the end portion of the rubber molecule having high mobility to improve the dispersibility of the silica in the conjugated diene rubber material, Attempts have been made to reduce the hysteresis loss by sealing with bonding with the particles.

The present inventors have conducted intensive studies to solve the problems of the prior art, and as a result, they have found that a diene rubber having excellent heat resistance when blended with silica as a reinforcing agent and having tensile strength, abrasion resistance and wet road surface resistance is included And the present inventors have completed the present invention by confirming the prescription of the rubber composition containing the rubber component and the reinforcing agent.

An object of the present invention is to provide a method for producing a modified conjugated diene having a silyl group substituted with at least one alkoxy group and a silyl group substituted with at least one alkoxy group by coupling or reacting a compound containing at least one silyl group substituted with an alkoxy group and a nitrogen atom at an active- And to provide a method for producing the polymer.

Another object of the present invention is to provide a modified conjugated diene polymer produced by the above process for producing a modified conjugated diene polymer.

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

According to the present invention there is provided a process for the preparation of a compound of formula

[Chemical Formula 1]

(Wherein R ₁ to R ₅ are each independently hydrogen or an alkyl group having 1 to 21 carbon atoms, and at least one of them is an alkyl group having 1 to 21 carbon atoms) with an organometallic compound to prepare an initiator ; b) polymerizing the initiator with a conjugated diene monomer or conjugated diene monomer and its comonomer to form an active polymer; And c) reacting the active polymer with aminosilane to produce a modified conjugated diene polymer. The present invention also provides a method for preparing a modified conjugated diene polymer.

In Formula 1, R ₁ and R ₅ are independently a methyl group or an ethyl group, and R ₂ to R ₄ may be hydrogen.

The molar ratio of the compound represented by Formula 1 to the organometallic compound is, for example, 1: 0.001 to 1: 5.

The molar ratio of the compound represented by Formula 1 to the aminosilane is, for example, 1: 0.01 to 1: 2.

The comonomer of b) is, for example, a vinyl aromatic monomer.

The aminosilane in step c) is, for example, aminotrialkoxysilane.

The aminotrialkoxysilane is at least one selected from the group consisting of compounds represented by the following general formulas (2), (3) and (4).

 (2)

(Wherein R ¹ and R ² are independently an alkyl group or an alkylsilyl group having 1 to 12 carbon atoms, R ³ and R ⁴ are an alkyl group having 1 to 12 carbon atoms, a is an integer of 0 to 2, 1 < / RTI > to 3)

Wherein R ¹ is an alkyl group having 1 to 3 carbon atoms or 1 to 2 carbon atoms, R ² is an alkylene group having 1 to 5 carbon atoms or 2 to 4 carbon atoms, R ³ and R ⁴ are independently an alkyl group having 1 to ³ carbon atoms, 3, or 1 to 2, and n may be 1 or 2.

(3)

(Wherein R ₁ is an alkyl or alkylsilyl group having 1 to 12 carbon atoms, R ₂ and R ₃ are independently an alkyl group having 1 to 12 carbon atoms, a is an integer of 1 to 3, and n is an integer of 0 to 2 When n is 2, two R ₁ groups bonded to nitrogen may be the same or different from each other, and when 3-n is 2 or more in the same manner, corresponding groups may be the same or different from each other Can be)

In formula (3), R ₁ to R ₃ may be an alkyl group having 1 to 3 carbon atoms or 1 to 2 carbon atoms, and n may be 2 or 3.

[Chemical Formula 4]

(Wherein R ₁ , R ₂ and R ₃ are each independently an alkylene group having 1 to 15 carbon atoms, and R ₄ , R ₅ , R ₆ , R ₇ and R ₉ are each independently an alkyl group having 1 to 15 carbon atoms Or an alkylsilyl group, R ₈ is an alkyl group having 1 to 15 carbon atoms, and m is an integer of 0 to 2)

In Formula 4, R ⁴ to R ⁷ are alkyl groups having 1 to 3 carbon atoms or 1 to 2 carbon atoms, R ² and R ³ are alkylene groups having 1 to 3 carbon atoms or 1 to 2 carbon atoms, R ⁸ and R ⁹ Is an alkyl group having 1 to 3 carbon atoms or 1 to 2 carbon atoms, and m may be 0 or 1.

Examples of the aminotrialkoxysilane include bis (methyldimethoxysilylpropyl) -N-methylamine, tris (trimethoxysilyl) amine and 3-dimethylamino-2 ((dimethylaminomethyl) propyl) trimethoxysilane And at least one selected from the group consisting of

Also, according to the present invention, there is provided a modified conjugated diene polymer which is produced according to the above-mentioned production method.

Further, according to the present invention,

 [Chemical Formula 5]

Wherein R ₁ is hydrogen, an alkyl group having 1 to 21 carbon atoms, or R'-PA, R ₂ to R ₄ are independently hydrogen or an alkyl group having 1 to 21 carbon atoms, and R ' 21 is an alkylene group, P is a conjugated diene-based polymer chain, A is an aminosilane group, and n is an integer of 1 to 5. The present invention also provides a modified conjugated diene polymer.

The aminosilane group of the present invention means a group remaining after 1 to 4 atoms or atoms bonded to a silicon (Si) atom in the aminosilane are eliminated and, for example, the atomic group to be eliminated is an alkoxy group bonded to silicon .

In Formula 5, R ₁ to R ₄ are independently hydrogen, a methyl group, or an ethyl group, and R 'may be a methylene group or an ethylene group.

As another example, in Formula 5, R ₁ is a methyl group or an ethyl group, R 'is a methylene group or an ethylene group, and R ₂ to R ₄ may be hydrogen.

The conjugated diene polymer chain is, for example, a styrene-butadiene copolymer chain.

The aminosilane group is, for example, aminotrialkoxysilane.

The modified conjugated diene polymer has a pattern viscosity of 30 to 90 as an example.

The modified conjugated diene polymer has a vinyl aromatic monomer content of 5 to 50% by weight, for example.

The modified conjugated diene polymer has a vinyl content of 5 to 60% by weight, for example.

The modified conjugated diene polymer has a molecular weight distribution (PDI) of 1.0 to 4.0 as an example.

According to the present invention, there is also provided a rubber composition characterized by comprising 100 parts by weight of the modified conjugated diene polymer and 1 to 200 parts by weight of a silica-based inorganic filler.

Further, according to the present invention, there is provided a tire comprising the rubber composition.

The rubber composition comprising the modified conjugated diene polymer according to the present invention has an effect of exhibiting excellent low fuel consumption when blended with silica as a reinforcing agent, and exhibiting tensile strength, abrasion resistance and wet road surface resistance.

A process for producing a modified conjugated diene polymer of the present invention comprises: a)

[Chemical Formula 1]

(Wherein R ₁ to R ₅ are each independently hydrogen or an alkyl group having 1 to 21 carbon atoms, and at least one of them is an alkyl group having 1 to 21 carbon atoms) with an organometallic compound to prepare an initiator ; b) polymerizing the initiator with a conjugated diene monomer or conjugated diene monomer and its comonomer to form an active polymer; And c) reacting the active polymer with aminosilane to prepare a modified conjugated diene polymer.

The method for producing the modified conjugated diene polymer includes, for example, (a) synthesizing an initiator in which an anionic end containing an amine and a cation end containing an alkali metal are present; (b) polymerizing a homopolymer of a conjugated diene monomer or a copolymer of a vinyl aromatic monomer and a conjugated diene monomer in the presence of the initiator to form an active polymer modified at one end of the following formula (6); And (b) coupling or reacting the active polymer having the alkali metal terminal with a compound represented by any of the following general formulas (2) to (4) to produce a modified polymer.

[Chemical Formula 6]

(Wherein R ¹ and R ² are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms, and n is an integer of 2 to 5)

(2)

(Wherein R ¹ and R ² are independently an alkyl group or an alkylsilyl group having 1 to 12 carbon atoms, R ³ and R ⁴ are an alkyl group having 1 to 12 carbon atoms, a is an integer of 0 to 2, 1 < / RTI > to 3)

(3)

(Wherein R ₁ is an alkyl or alkylsilyl group having 1 to 12 carbon atoms, R ₂ and R ₃ are independently an alkyl group having 1 to 12 carbon atoms, a is an integer of 1 to 3, and n is an integer of 0 to 2 When n is 2, two R ₁ groups bonded to nitrogen may be the same or different from each other, and when 3-n is 2 or more in the same manner, corresponding groups may be the same or different from each other Can be)

[Chemical Formula 4]

(Wherein R ₁ , R ₂ and R ₃ are each independently an alkylene group having 1 to 15 carbon atoms, and R ₄ , R ₅ , R ₆ , R ₇ and R ₉ are each independently an alkyl group having 1 to 15 carbon atoms Or an alkylsilyl group, R ₈ is an alkyl group having 1 to 15 carbon atoms, and m is an integer of 0 to 2)

The modified conjugated diene polymer may be, for example, one kind or a mixture of two kinds of polymers represented by the following general formula (7).

(7)

Wherein R ¹ and R ² are each independently an alkyl or alkylsilyl group having 1 to 12 carbon atoms, R ⁴ is an alkyl group, P 1 is a conjugated diene polymer, a is an integer of 0 to 2, n is 1 < / RTI >

Initiator  synthesis

The initiator of (a) may be prepared by reacting a compound capable of providing a cationic terminal comprising an amine (a compound represented by the formula (1)) with a compound capable of providing a cationic terminal containing an alkali metal (an organometallic compound) And the reaction of the example is shown in the following Reaction Scheme 1.

[Reaction Scheme 1]

2,6-dimethylpyridine and n-propyllithium are reacted to synthesize an initiator as a product.

The molar ratio of the compound represented by Formula 1 to the organometallic compound is, for example, 1: 0.001 to 1: 5, 1: 0.1 to 1: 2, or 1: 0.4 to 1: .

The alkali metal-containing cation terminal is preferably selected from the group consisting of methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, Group consisting of lithium, 1-naphthyllithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolylithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium and 4-cyclopentyllithium , But are not limited thereto. Particularly preferred are n-butyllithium and sec-butyllithium, and they can be used not only as one kind but also as a mixture of two or more kinds. Other organic alkali metal alkali metal compounds include organic sodium compounds, organic potassium compounds, organic rubidium compounds, and organic cesium compounds. Specific examples thereof include sodium naphthalene and potassium naphthalene. In addition, alkoxides, sulfonates and amides of lithium, sodium and potassium are used. It can also be used in combination with other organometallic compounds.

The amine compound may be at least one selected from the group consisting of 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2,3-dimethylpyridine, 2,4-dimethylpyridine, 2,5-dimethylpyridine, -Dimethylpyridine, 3,5-dimethylpyridine, 2,3,4-trimethylpyridine, 2,4,5-trimethylpyridine, 2,4,6-trimethylpyridine, 2,3,4,5-tetramethylpyridine, 2,3,4,6-tetramethylpyridine, 2,3,5,6-tetramethylpyridine, 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, 2,3- -Diethylpyridine, 2,5-diethylpyridine, 2,6-diethylpyridine, 3,4-diethylpyridine, 3,5-diethylpyridine, 2,3,4-triethylpyridine, 2,4 , 5-triethylpyridine, 2,4,6-triethylpyridine, 2,3,4,5-tetraethylpyridine, 2,3,4,6-tetraethylpyridine, and 2,3,5,6- And examples thereof include tetraethylpyridine, 2-propylpyridine, 3-propylpyridine, 4-propylpyridine, 2,3-dipropylpyridine, 2,4-dipropylpyridine, , 3,4-dipropyl Pyridine, 2,3,4-tribopropylpyridine, 2,4,5-tripropylpyridine, 2,4,6-tripropylpyridine, 2,3,4,5-tetrapropylpyridine, Pyridine, 2,3,4,6-tetrapropylpyridine, and 2,3,5,6-tetrapropylpyridine, but the present invention is not limited thereto.

Modification and polymerization at one end

The conjugated diene polymer in a state before the modification of the modified conjugated diene polymer is obtained by polymerizing a conjugated diene monomer or copolymerizing a conjugated diene monomer and a vinyl aromatic monomer with a comonomer.

The comonomer is not particularly limited when it is a comonomer to be used together with a conjugated diene monomer in the technical field of the present invention.

In the polymerization step of the conjugated diene polymer, a polymerization initiator may be supplied to a reactor for carrying out the polymerization of the conjugated diene compound or copolymerization of the conjugated diene compound and the aromatic vinyl compound to carry out the polymerization reaction. The polymerization of the conjugated diene-based polymer can be carried out by a batch mode or a continuous polymerization mode such as one reactor or two or more connected reactors.

The conjugated diene monomer may be at least one selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene and 2- At least one selected from the group consisting of 1,3-butadiene, but is not limited thereto.

Also, the vinyl aromatic monomers may be styrene,? -Methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (p- -Vinyl-5-hexynaphthalene, and more specifically, styrene or? -Methylstyrene is used, but the present invention is not limited thereto.

The above polymerization method is preferably an anion polymerization, and it is particularly preferable to obtain an active terminal by a growth reaction by living anion polymerization. The polymerization may be a temperature-raising polymerization or a regular-temperature polymerization, and the polymerization temperature is preferably -20 占 폚 to 200 占 폚, more preferably 0 占 폚 to 150 占 폚, particularly preferably 10 占 폚 to 120 占 폚.

Optionally, a polar solvent may also be added to the non-protonic solvent to increase the rate of polymerization or to modify the polymer structure. Examples of suitable polar solvents include ethers such as tetrahydrofuran, ditetrahydrofuryl propane, diethyl ether, cycloamal ether, dipropyl ether, ethylene dimethyl ether, diethylene glycol, dimethyl ether, tertiary butoxyethoxyethane, bis (2-dimethylaminoethyl) ether and (dimethylaminoethyl) ethyl ether, or an ether-based solvent selected from the group consisting of trimethylamine, triethylamine, tripropylamine and tetramethylethylenediamine Tertiary amines which can be used in the present invention may be used, and preferred examples thereof include tetrahydrofurfuryl propionate, triethylamine or tetramethylethylenediamine.

In addition, although the block copolymer is generally produced due to the difference in reaction rate between the conjugated diene compound and the vinyl aromatic compound of the copolymer, the reaction rate of the vinyl aromatic compound with a slow reaction rate is increased when the polar solvent is added, Such as a block copolymer, into a random copolymer. The polar solvent used to modify the polymer structure is generally used in an amount of 0.1 to 40 mol, preferably 0.1 to 10 mol, per 1 mol of the polymerization initiator.

Denaturation reaction

The modified conjugated diene polymer according to the present invention is obtained by reacting a polymer modified with an amine (for example, a compound represented by the formula (1)) at one end with a compound having a nitrogen atom (aminosilane) with a silyl group substituted with at least one alkoxy group Can be obtained.

The molar ratio of the compound represented by Formula 1 to the aminosilane is, for example, 1: 0.01 to 1: 2, 1: 0.1 to 1: 2, or 1: 0.1 to 1: have.

The aminosilane in step c) may be, for example, aminotrialkoxysilane.

The aminotrialkoxysilane may be at least one selected from the group consisting of compounds represented by the following formulas (2), (3) and (4).

(2)

(Wherein R ¹ and R ² are independently an alkyl group or an alkylsilyl group having 1 to 12 carbon atoms, R ³ and R ⁴ are an alkyl group having 1 to 12 carbon atoms, a is an integer of 0 to 2, 1 < / RTI > to 3)

(3)

(Wherein R ₁ is an alkyl or alkylsilyl group having 1 to 12 carbon atoms, R ₂ and R ₃ are independently an alkyl group having 1 to 12 carbon atoms, a is an integer of 1 to 3, and n is an integer of 0 to 2 When n is 2, two R ₁ groups bonded to nitrogen may be the same or different from each other, and when 3-n is 2 or more in the same manner, corresponding groups may be the same or different from each other Can be)

[Chemical Formula 4]

(Wherein R ₁ , R ₂ and R ₃ are each independently an alkylene group having 1 to 15 carbon atoms, and R ₄ , R ₅ , R ₆ , R ₇ and R ₉ are each independently an alkyl group having 1 to 15 carbon atoms Or an alkylsilyl group, R ₈ is an alkyl group having 1 to 15 carbon atoms, and m is an integer of 0 to 2)

Examples of the compound represented by the general formula (2) include bis (methyldimethoxysilylpropyl) -N-methylamine, bis (methyldiethoxysilylpropyl) (Ethyldimethoxysilylpropyl) -N-methylamine, bis (ethyldiethoxysilylpropyl) -N-methylamine, bis (ethyldiethoxysilylpropyl) (Methyldimethoxysilylpropyl) -N-ethylamine, bis (methyldimethoxysilylpropyl) -N-ethylamine, bis Ethylamine, bis (ethyldiethoxysilylpropyl) -N-ethylamine, bis (ethyldipropoxysilylpropyl) -N-ethylamine, bis (methyldimethoxysilylpropyl) N-propylamine, bis (methyldipropoxysilylpropyl) -N-propylamine, bis (ethyldimethoxysilylpropyl) (Ethyldiethoxysilylpropyl) -N-propylamine, bis (ethyldipropoxysilylpropyl) -N-propylamine, bis (trimethoxysilylpropyl) (Tripropoxysilylpropyl) -N-methylamine, trimethoxysilylpropyl-N-methylamine, triethoxysilylpropyl-N-methylamine, tripropoxysilyl Propylamine, trimethoxysilylpropyl-N-ethylamine, triethoxysilylpropyl-N-ethylamine, tripropoxysilylpropyl-N-ethylamine, trimethoxysilylpropyl- , Triethoxysilylpropyl-N-propylamine or tripropoxysilylpropyl-N-propylamine.

The compound represented by the general formula (3) may be, for example, tris (trimethoxysilyl) amine, tris (triethoxysilyl) amine or tris (tripropoxysilyl) amine.

Examples of the compound represented by Formula 4 include 3-dimethylamino-2 ((dimethylaminomethyl) propyl) trimethoxysilane, 3-dimethylamino- (dimethylaminomethyl) propyltriethoxysilane, 3- ((Dimethylaminomethyl) propyl) trimethoxysilane, 3-diethylamino-2 ((dimethylaminomethyl) propyl) (Dimethylaminomethyl) propyl) trimethoxysilane, 3-diethylamino-2 ((dimethylaminomethyl) propyl) Propylamino-2 ((dimethylaminomethyl) propyl) triethoxysilane, or 3-dipropylamino-2 ((dimethylaminomethyl) propyl) tripropoxysilane.

The modified conjugated diene polymer of the present invention is characterized in that it is produced according to the above-mentioned production method.

The modified conjugated diene polymer may have a pattern viscosity of 20 to 90, 40 to 90, or 50 to 90, for example.

The modified conjugated diene polymer may have a weight average molecular weight of 10,000 to 2,000,000 g / mol, 100,000 to 1,800,000 g / mol, or 400,000 to 1,700,000 g / mol, for example.

The modified conjugated diene polymer may have a molecular weight distribution (PDI) of 1.0 to 5.0, or 1.1 to 3.0, for example.

The modified conjugated diene-based polymer may be, for example,

[Chemical Formula 5]

(Wherein R ₁ is hydrogen, an alkyl group having 1 to 21 carbon atoms or R'-PA, wherein R ₂ to R ₄ are independently hydrogen or an alkyl group having 1 to 21 carbon atoms, and R ' , P is a conjugated diene polymer chain, A is an aminosilane group, and n is an integer of 1 to 3).

For example, the reaction between an active polymer and an aminosilane according to the present invention is shown in Reaction Scheme 2 below.

[Reaction Scheme 2]

The modified polymer obtained in the present invention may be a kind having the following general formula (3).

The reaction temperature, the reaction time, and the like when the aminosilane is reacted with the polymerization active end of the conjugated diene-based polymer are not particularly limited, but the reaction can be carried out at a temperature of 0 to 90 캜 for 1 minute to 5 hours.

The present invention also provides a rubber composition comprising 0.1 to 150 parts by weight of a silica-based inorganic filler based on 100 parts by weight of a rubber component containing 0.1 to 100% by weight of the modified conjugated diene polymer.

In addition, a molded article comprising the rubber composition, particularly a tire, is provided.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope and spirit of the invention as disclosed in the accompanying claims. Changes and modifications may fall within the scope of the appended claims.

[Example]

Example  One

1) Modified Polymerization Initiator Preparation

(2,6-dimethylpyridine, 0.33 g, 0.3 mmol), N, N, N ', N'-tetramethylethylenediamine (1.06 g 0.9 mmol) and 16.5 ml of hexane were added to a 250 ml round bottom flask And 2.5 M n-butyllithium (1.52 ml, 0.4 mmol) was added to the solution. At this time, the solution turned to a clear red color by having anion groups. The polymerization initiator was stirred for 1 hour to prepare 2,6-dimethylpyridine (lutidine) -substituted n-butyllithium.

2) Manufacture of SBR (styrene-butadiene rubber)

200 g of styrene, 600 g of 1,3-butadiene and 3200 g of n-hexane were placed in a 10 L reactor, and the temperature inside the reactor was adjusted to 60 캜 by stirring while stirring. When the temperature reached 60 占 폚, the modified polymerization initiator prepared above was fed into the reactor to proceed with the adiabatic heating reaction. After the reaction, the temperature was controlled to be raised to 70 캜. 20 g of 1,3-butadiene was added after 20 minutes after the adiabatic heating reaction was completed.

After 5 minutes, 5 mmol of bis (methyldimethoxysilylpropyl) -N-methylamine was added to the aminosilane and the reaction was carried out for 15 minutes. Thereafter, the polymerization reaction was stopped using ethanol, and 5 ml of a solution in which 0.3 wt% of BHT (butylated hydroxytoluene) as an antioxidant was dissolved in hexane was added.

The polymer was poured into warm water heated with steam and stirred to remove the solvent. The solvent was then removed by roll drying to remove the remaining solvent and water to prepare a modified conjugated diene polymer. The analytical results of the modified conjugated diene polymer thus prepared are shown in Table 1 below.

Example  2

A modified conjugated diene polymer was prepared in the same manner as in Example 1, except that tris (trimethoxysilyl) amine was used as the aminosilane in the preparation of the SBR of Example 1. The analytical results of the modified conjugated diene polymer thus prepared are shown in Table 1 below.

Example  3

A modified conjugated diene polymer was obtained in the same manner as in Example 1, except that 3-dimethylamino-2 - ((dimethylaminomethyl) propyl) trimethoxysilane was used as the aminosilane in the preparation of the SBR of Example 1 . The analytical results of the modified conjugated diene polymer thus prepared are shown in Table 1 below.

Example  4 to 6

A modified conjugated diene polymer was prepared in the same manner as in Example 1, except that aminosilane shown in the following Table 2 was used in the preparation of the SBR of Example 1. The analytical results of the modified conjugated diene polymer thus prepared are shown in Table 2 below.

Comparative Example  One

A denatured conjugated diene polymer was prepared in the same manner as in Example 1, except that aminosilane was not used in the preparation of SBR of Example 1. The analytical results of the modified conjugated diene polymer thus prepared are shown in Table 1 below.

Comparative Example  2

A conjugated diene polymer was prepared in the same manner as in Example 1, except that only 4 mol of N-butyllithium was used without using a denaturation initiator in Example 1 and no aminosilane was used. The analytical results of the conjugated diene polymer thus prepared are shown in Table 1 below.

Comparative Example  3

A denatured conjugated diene polymer was prepared in the same manner as in Example 1, except that the modifying initiator of Example 1 was not used and 4 mol of N-butyllithium was added. The analytical results of the modified conjugated diene polymer thus prepared are shown in Table 1 below.

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Initiator Modification initiator: Lutidine (2,6-dimethylpyridine) + n-butyllithium n-butyllithium Denaturant a b c - - a pattern 58 57 56 56 58 59 Tg (占 폚) -27 -29 -29 -28 -30 -30 Styrene (%) 26 27 27 25 26 26 vinyl(%) 39 39 39 40 41 40 GPC
(x 10 ⁴ ) Mn 28.7 29.9 29.9 26.0 27.9 29.3 Mw 41.1 45.5 44.8 32.5 31.2 38.8 PDI 1.43 1.52 1.50 1.25 1.12 1.33

a: bis (3-dimethoxymethylsilylpropyl) -N-methylamine

b: Tris (trimethoxysilyl) amine

c: 3-Dimethylamino-2 - ((dimethylaminomethyl) propyl) trimethoxysilane

PDI: polydispersity

division Example 4 Example 5 Example 6 Initiator Modification initiator: Lutidine (2,6-dimethylpyridine) + n-butyllithium Denaturant a-2 b-2 c-2 pattern 55 54 52 Tg (占 폚) -27 -29 -29 Styrene (%) 27 27 27 vinyl(%) 40 41 40 GPC
(x 10 ⁴ ) Mn 26.5 27.5 25.4 Mw 39.9 42.4 38.4 PDI 1.51 1.54 1.51

a-2: Synthesis of bis (3-diethoxymethylsilylpropyl) -N-methylamine

b-2: Tris (triethoxysilyl) amine

c-2: 3-Dimethylamino-2 - ((dimethylaminomethyl) propyl) triethoxysilane

[Test Example]

Rubber compositions were prepared from the samples (rubber) of Examples 1 to 6 and Comparative Examples 1 to 3 by the compounding method (component and content) shown in Table 3 below.

(Unit: parts by weight) S-1 Rubber 100.0 Silica 70.0 Coupling agent 11.02 oil 37.5 Zincification 3.0 Stearic acid 2.0 Antioxidant 2.0 Antioxidant 2.0 Wax 1.0 Rubber accelerator 1.75 sulfur 1.5 Vulcanization accelerator 2.0 Gross weight 230.2

The kneading was carried out in the same manner as in the kneading of the first stage using a chestnut mixer equipped with a temperature control device under the conditions of 80 rpm, using raw rubber, filler (silica and carbon black), organosilane coupling agent, oil, , An antioxidant, a wax and an accelerator.

At this time, the temperature of the kneader was controlled, and the composition was obtained at an outlet temperature of 140 to 150 ° C.

As the kneading in the second stage, the compound obtained above was cooled to room temperature, rubber, sulfur and a vulcanization accelerator were added to the kneader, and the composition was obtained at a discharge temperature of 45 to 60 캜.

As the kneading in the third stage, the obtained composition was molded and vulcanized by vulcanization press at 180 DEG C for T90 + 10 minutes to prepare a vulcanized rubber, and its properties were measured by the following measuring methods.

1) Tensile test

The tensile strength at the time of cutting the test piece and the tensile stress at 300% elongation (300%, modulus) were measured by the tensile test method of ASTM 412.

2) Viscoelastic properties

A dynamic mechanical analyzer from TA Corporation was used. Tan δ was measured by varying the strain at a frequency of 10 Hz and a measurement temperature (0 to 60 ° C) in a twist mode. The pannier effect is expressed as the difference between the minimum value and the maximum value at the strain of 0.2% to 40%. The smaller the pine needle effect, the better the overall dispersibility of the silica and the like. The lower the tan δ value at 60 ° C, the lower the hysteresis loss and the lower the rolling resistance of the tire, that is, the lower the fuel consumption.

division Example 7 Example 8 Example 9 Comparative Example 4 Comparative Example 5 Comparative Example 6 Rubber sample Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 300% modulus (Kgf / cm ² ) 131 128 133 125 104 123 Tensile strength (Kgf / cm ² ) 189 192 191 183 168 184 Tan δ at 0 ° C 0.990 0.988 0.991 0.635 0.542 0.986 Tan δ at 60 ° C 0.068 0.070 0.067 0.087 0.098 0.075 60 ° C? G '(Pheny effect) 0.33 0.33 0.32 0.53 0.74 0.34

division Example 10 Example 11 Example 12 Rubber sample Example 4 Example 5 Example 6 300% modulus (Kgf / cm ² ) 129 128 124 Tensile strength (Kgf / cm ² ) 185 187 182 Tan δ at 0 ° C 0.988 0.986 0.981 Tan δ at 60 ° C 0.070 0.073 0.069 60 ° C? G '(Pheny effect) 0.34 0.33 0.33

As shown in Tables 4 and 5, the rubber compositions (Examples 7 to 12) containing the modified conjugated diene-based polymer of the present invention can be obtained by copolymerizing a modified conjugated diene having no end modified with a pyridine- Tensile strength (300% modulus), tensile strength, road surface resistance (Tan δ at 0 ° C, higher, higher) and lower fuel consumption (Tan δ at 60 ° C) than the rubber compositions (Comparative Examples 4 to 6) ° C, the lower the better).

Claims (19)

a)
[Chemical Formula 1]

(Wherein R ₁ to R ₅ are each independently hydrogen or an alkyl group having 1 to 21 carbon atoms, and at least one of them is an alkyl group having 1 to 21 carbon atoms) with an organometallic compound to prepare an initiator ;
b) polymerizing the initiator with a conjugated diene monomer or conjugated diene monomer and its comonomer to form an active polymer; And
and c) reacting the active polymer with aminosilane to prepare a modified conjugated diene polymer.
Wherein the modified conjugated diene polymer is obtained by the following method. The method according to claim 1,
Wherein the molar ratio of the compound represented by Formula 1 to the organometallic compound is 1: 0.001 to 1: 5
Wherein the modified conjugated diene polymer is obtained by the following method. The method according to claim 1,
Wherein the molar ratio of the compound represented by the formula (1) to the aminosilane is 1: 0.01 to 1: 2
Wherein the modified conjugated diene polymer is obtained by the following method. The method according to claim 1,
Wherein the comonomer of b) is a vinyl aromatic monomer
Wherein the modified conjugated diene polymer is obtained by the following method. The method according to claim 1,
Wherein the aminosilane in step c) is an aminotrialkoxysilane.
Wherein the modified conjugated diene polymer is obtained by the following method. 6. The method of claim 5,
Wherein the aminotrialkoxysilane is at least one selected from the group consisting of compounds represented by the following formulas (2), (3) and (4)
Wherein the modified conjugated diene polymer is obtained by the following method.
(2)

(Wherein R ¹ and R ² are independently an alkyl group or an alkylsilyl group having 1 to 12 carbon atoms, R ³ and R ⁴ are an alkyl group having 1 to 12 carbon atoms, a is an integer of 0 to 2, 1 < / RTI > to 3)
(3)

(Wherein R ₁ is an alkyl or alkylsilyl group having 1 to 12 carbon atoms, R ₂ and R ₃ are independently an alkyl group having 1 to 12 carbon atoms, a is an integer of 1 to 3, and n is an integer of 0 to 2 When n is 2, two R ₁ groups bonded to nitrogen may be the same or different from each other, and when 3-n is 2 or more in the same manner, corresponding groups may be the same or different from each other Can be)
[Chemical Formula 4]

(Wherein R ₁ , R ₂ and R ₃ are each independently an alkylene group having 1 to 15 carbon atoms, and R ₄ , R ₅ , R ₆ , R ₇ and R ₉ are each independently an alkyl group having 1 to 15 carbon atoms Or an alkylsilyl group, R ₈ is an alkyl group having 1 to 15 carbon atoms, and m is an integer of 0 to 2) The method according to claim 6,
The aminotrialkoxysilane is a group consisting of bis (methyldimethoxysilylpropyl) -N-methylamine, tris (trimethoxysilyl) amine and 3-dimethylamino-2 ((dimethylaminomethyl) propyl) trimethoxysilane And at least one selected from the group consisting of
Wherein the modified conjugated diene polymer is obtained by the following method. Characterized in that it is produced according to the process of any one of claims 1 to 7
Modified conjugated diene polymer. The following formula 5
[Chemical Formula 5]

(Wherein R ₁ is hydrogen, an alkyl group having 1 to 21 carbon atoms or R'-PA, wherein R ₂ to R ₄ are independently hydrogen or an alkyl group having 1 to 21 carbon atoms, and R ' , P is a conjugated diene-based polymer chain, A is an aminosilane group, and n is an integer of 1 to 5).
Modified conjugated diene polymer. 10. The method of claim 9,
Wherein R ₁ to R ₄ are independently hydrogen, a methyl group or an ethyl group, and R 'is a methylene group or an ethylene group
Modified conjugated diene polymer. 10. The method of claim 9,
Wherein the conjugated diene-based polymer chain is a styrene-butadiene copolymer chain
Modified conjugated diene polymer. 10. The method of claim 9,
Wherein the aminosilane group is an aminotrialkoxysilane.
Modified conjugated diene polymer. 10. The method of claim 9,
Wherein the modified conjugated diene polymer has a pattern viscosity of 30 to 90
Modified conjugated diene polymer. 10. The method of claim 9,
Wherein the modified conjugated diene polymer has a vinyl aromatic monomer content of 5 to 50% by weight
Modified conjugated diene polymer. 10. The method of claim 9,
Wherein the modified conjugated diene polymer has a vinyl content of 5 to 60% by weight
Modified conjugated diene polymer. 10. The method of claim 9,
Wherein the modified conjugated diene polymer has a molecular weight distribution (PDI) of 1.0 to 4.0
Modified conjugated diene polymer. 100 parts by weight of the modified conjugated diene polymer of any one of claims 9 to 16 and 1 to 200 parts by weight of a silica-based inorganic filler
Rubber composition. Characterized in that it comprises the rubber composition of claim 17
Shaped article. 19. The method of claim 18,
Characterized in that the molded article is a tire
Shaped article.