WO2017115996A1 - Polymerization initiator, modified conjugated diene-based polymer, and preparation methods therefor - Google Patents

Abstract

The present invention relates to a polymerization initiator represented by chemical formula 1, a modified conjugated diene-based polymer obtained by using the same, preparation methods therefor, a rubber composition containing the same, and a tire manufactured from the rubber composition. [Chemical formula 1] [Chemical formula 2] In chemical formula 1, Cy is a cyclic saturated hydrocarbon group having 5 to 8 carbon atoms, substituted or unsubstituted with an alkyl group having 1 to 4 carbon atoms; and A1 and A2 each are independently a functional group represented by chemical formula 2. In chemical formula 2, R is a linear hydrocarbon group having 1 to 20 carbon atoms or a monocyclic or multicyclic saturated hydrocarbon group having 3 to 20 carbon atoms; X is a divalent hydrocarbon group having 1 to 5 carbon atoms; M is an alkali metal; and a is 0 or 1.

Description

Polymerization Initiator, Modified Conjugated Diene-Based Polymer, and Method for Producing the Same

Citation with Related Applications

This application claims the benefit of priority based on Korea Patent Application No. 10-2015-0187677 dated December 28, 2015 and Korea Patent Application No. 10-2016-0143543 dated October 31, 2016. All content disclosed in the literature is included as part of this specification.

Technical Field

The present invention relates to a polymerization initiator, a modified conjugated diene-based polymer, a preparation method thereof, a rubber composition comprising the same, and a tire made from the rubber composition.

At present, there is a demand for conjugated diene-based polymers having low running resistance and excellent wear resistance and wet road resistance as rubber materials for tires. In order to reduce the running resistance of the tire, the hysteresis loss of the vulcanized rubber may be reduced. Although natural rubber and the like are known as a rubber material having such a low hysteresis loss, they have a problem of low wet road resistance. Recently, conjugated diene-based polymers such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) produced by emulsion polymerization or solution polymerization have been used as rubbers for tires.

On the other hand, the solution polymerization SBR is prepared using an anionic polymerization initiator, at this time, mainly used as the anionic polymerization initiator alkyllithium.

However, the rubbers for tires do not yet have sufficient improvement in hysteresis loss or abrasion resistance, and also have little improvement effect due to blending, and rather have poor workability.

Therefore, there is a need for development of a polymerization initiator having sufficient improvement in wear resistance and excellent workability, and a rubber having excellent heat generation property and excellent physical properties such as tensile strength, wear resistance, and wet road resistance when using silica.

The present invention has been made to solve the problems of the prior art, and an object thereof is to provide a modified polyfunctional polymerization initiator.

Another object of the present invention is to provide a method for producing the polymerization initiator.

Still another object of the present invention is to provide a method for producing a modified conjugated diene polymer using the polymerization initiator.

It is still another object of the present invention to provide a modified conjugated diene-based polymer prepared by the above method, which has excellent exothermicity and can improve tensile strength, wear resistance, and wet road resistance.

In order to solve the above problems, the present invention provides a polymerization initiator comprising a compound represented by the following formula (1):

[Formula 1]

[Formula 2]

In Formula 1, Cy may be a cyclic saturated hydrocarbon group having 5 to 8 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 4 carbon atoms, A ¹ and A ² may be independently a functional group represented by Formula 2 ,

In Formula 2, R may be a linear hydrocarbon group having 1 to 20 carbon atoms, or a cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, X may be a divalent hydrocarbon group having 1 to 5 carbon atoms, and M may be an alkali metal. , a may be 0 or 1.

In addition, the present invention comprises the steps of preparing a compound represented by the formula (1b) by reacting the compound represented by the formula (1a) and the compound represented by the formula (4) in a solvent (S1); And reacting the compound represented by Chemical Formula 1b with an alkali metal or a compound represented by Chemical Formula 5 (S2):

[Formula 1a]

[Formula 1b]

In Chemical Formulas 1a and 1b,

Cy may be a cyclic saturated hydrocarbon group having 5 to 8 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 4 carbon atoms, A ^{1 '} and A ^2' may each independently be a functional group represented by Formula 2a, A ^{1 ”} And A ^2” may be each independently a functional group represented by Formula 2b,

[Formula 2a]

[Formula 2b]

[Formula 4]

In Chemical Formulas 2a, 2b, and 4,

R may be a linear hydrocarbon group having 1 to 20 carbon atoms or a mono-cyclic or multicyclic saturated hydrocarbon group having 3 to 20 carbon atoms, and X 'may be a divalent hydrocarbon group having 1 to 5 carbon atoms A 'may be 0 or 1, X ¹ and X ² may each independently be a halogenated compound,

[Formula 5]

In Chemical Formula 5,

R 'may be a hydrocarbyl group having 1 to 20 carbon atoms, M may be an alkali metal, x may be an integer selected from 1 to 4.

The present invention also provides a modified conjugated diene-based polymer comprising a functional group derived from a polymerization initiator represented by Chemical Formula 1 at one end thereof, and a method for preparing the same.

Furthermore, the present invention provides a rubber composition comprising the modified conjugated diene-based polymer and a tire manufactured using the same.

By applying the modified multifunctional polymerization initiator represented by Chemical Formula 1 according to the present invention, a conjugated diene polymer having high vinyl content and excellent physical properties can be obtained.

The polymerization initiator may have a plurality of functional groups to form a polymer having a plurality of active sites, thereby improving the reactivity with the denaturant to prepare a modified conjugated diene-based polymer having a high modification rate. In addition to improving affinity with the filler added in the tire rubber composition, physical properties such as tensile strength, wear resistance and wet road resistance can be further improved.

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 to illustrate the present invention, but the scope of the present invention is not limited only to them.

Preparation Example: Preparation of Polymerization Initiator of Formula 3-1

8 mol (1105.68 g) of potassium carbonate was added to a 3 L four-necked flask connected with a stirrer, a thermometer, a dropping funnel and a shrink line to remove moisture by depressurization, and then 1-bromo-3-chloro under argon atmosphere. 4 mol (629.76 g) of propane, 1 mol (88.15 g) of t-butyl methyl ether, and 1 mol (84.16 g) of cyclohexane were added thereto, and the mixture was stirred at 0 ° C. at 300 rpm. 2.4 mol (341.38 g) of N, N'-dimethyl-1,2-cyclohexanediamine was added thereto over 1 hour using a dropping funnel, and the reaction was performed by raising the temperature to room temperature after completion of the addition. After the reaction was completed, 400 ml of cyclohexane was added thereto, followed by stirring sufficiently, and then the remaining HBr was removed using a saturated aqueous sodium hydrogen carbonate solution. Since salt was removed using distilled water and brine (Brine), the remaining water was removed with sodium sulfate. Sodium sulfate was removed using a filter, and the solvent was removed using a rotary concentrator. Then purified intermediate was obtained through distillation.

In an argon atmosphere, a small-cut lithium metal was placed in a three-necked round flask, and a thermometer, a dropping funnel, and a shrink line were connected to each other. After adding the solvent, heated to a predetermined temperature and the intermediate diluted in the solvent was slowly added. After the reaction was completed, the lithium chloride was removed through a filter and the solvent was removed under reduced pressure to prepare a polymerization initiator represented by Chemical Formula 3-1.

[Formula 3-1]

Example 1 Preparation of Modified Conjugated Diene-Based Polymer

Into a 20 L autoclave reactor, 270 g of styrene, 710 g of 1,3-butadiene, 5000 g of normal hexane, and 0.9 g of 2,2-bis (2-oxoranyl) propane were added as a polar additive, and the temperature inside the reactor was raised to 40. When the internal temperature of the reactor reached 40, 4.3 mmol of the compound represented by Chemical Formula 1-1 prepared in Example 1 was added to the reactor to perform an adiabatic heating reaction. After 20 minutes of the adiabatic heating reaction, 20 g of 1,3-butadiene was added thereto. After 5 minutes, 4.3 mmol of bis (diethoxymethylsilylpropyl) -N-methylamine was added and reacted for 15 minutes. Then, the polymerization reaction was stopped using ethanol, and 45 ml of a solution in which 0.3 wt% of BHT (butylated hydroxytoluene), an antioxidant, was dissolved in hexane was added. The resulting polymer was placed in hot water heated with steam, stirred to remove the solvent, and then dried in rolls to remove residual solvent and water to prepare a modified conjugated diene-based polymer. The analysis results of the modified conjugated diene-based polymer thus prepared are shown in Table 1 below.

Example 2: Preparation of Modified Conjugated Diene-Based Polymer

Modification was carried out in the same manner as in Example 1, except that N, N-bis (triethoxysilylpropyl) aminopropyl-1-imidazole was used instead of bis (diethoxymethylsilylpropyl) -N-methylamine. A conjugated diene-based polymer was prepared.

Comparative Example 1: Preparation of Modified Conjugated Diene-Based Polymer

A modified conjugated diene-based polymer was prepared in the same manner as in Example 1, except that n-butyllithium was used instead of the compound represented by Chemical Formula 3-1.

Comparative Example 2: Preparation of Modified Conjugated Diene-Based Polymer

Modification was carried out in the same manner as in Comparative Example 1, except that N, N-bis (triethoxysilylpropyl) aminopropyl-1-imidazole was used instead of bis (diethoxymethylsilylpropyl) -N-methylamine. A conjugated diene-based polymer was prepared.

Comparative Example 3: Preparation of Modified Conjugated Diene-Based Polymer

A modified conjugated diene-based polymer was prepared in the same manner as in Comparative Example 1, except that the compound represented by the following Formula 26 was used instead of the compound represented by the formula 3-1.

[Formula 26]

Experimental Example 1

The weight average molecular weight (Mw), the number average molecular weight (Mn), the molecular weight distribution (MWD) and the pattern viscosity (MV) were respectively measured for each of the modified conjugated diene-based polymers prepared in Examples and Comparative Examples. The results are shown in Table 1 below.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by gel permeation chromatohraph (GPC) analysis, and the molecular weight distribution (MWD, Mw / Mn) was calculated from the respective measured molecular weights. Specifically, the GPC used a combination of two PLgel Olexis (Polymer Laboratories Co.) column and one PLgel mixed-C (Polymer Laboratories Co.) column, all of the newly replaced column was a mixed bed column, The GPC standard material was calculated using polystyrene (PS) when calculating the molecular weight.

The pattern viscosity (MV, (ML1 + 4, @ 100 ℃) MU) was measured using a Rotor Speed 2 ± 0.02 rpm, Large Rotorfmf at 100 ℃ using MV-2000 (ALPHA Technologies, Inc.), the sample used After leaving at room temperature (23 ± 3 ℃) for 30 minutes or more, 27 ± 3 g was collected and filled into the die cavity, and the platen was operated for 4 minutes.

division		Example		Comparative example
		One	2	One	2	3
Molecular Weight (X10 3 )	Number average molecular weight (g / mol)	305	386	301	384	307
	Weight average molecular weight (g / mol)	397	555	390	553	397
Molecular weight distribution		1.3	1.4	1.3	1.4	1.3
Pattern viscosity		68	89	68	88	88

Experimental Example 2

In order to compare and analyze the physical properties of the rubber composition and the molded article prepared from each of the modified conjugated diene-based copolymers prepared in Examples and Comparative Examples, tensile properties, wear resistance and wet road resistance were respectively 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. At this time, the amount of the substance except the modified conjugated diene copolymer is shown based on 100 parts by weight of the modified conjugated diene copolymer. In the first stage kneading, 137.5 parts by weight of each modified conjugated diene copolymer, 70 parts by weight of silica, bis (3-triethoxysilylpropyl) tetrasulfate as a silane coupling agent using a half-variety mixer equipped with a temperature controller. 11.2 parts by weight of feed, 25 parts by weight of process oil (TDAE), 2 parts by weight of TMDQ, 3 parts by weight of zinc oxide (ZnO), 2 parts by weight of stearic acid and 1 part by weight of wax Kneaded. At this time, the temperature of the kneader was controlled and the primary blend was obtained at an outlet temperature of 150 ° C. In the second stage kneading, after cooling the first blend to room temperature, 1.75 parts by weight of rubber accelerator (CZ), 1.5 parts by weight of sulfur powder, and 2 parts by weight of vulcanization accelerator are added to the kneader, followed by curing for 150 to 20 minutes. A rubber composition was prepared. In this case, the silica had a nitrogen adsorption specific surface area of 175 m 2 / g and a CTAB adsorption of 160 m 2 / g.

2) tensile properties

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

3) wear resistance

Using an Akron abrasion tester, the load was measured at 6 pounds and 1000 revolutions and indexed. The smaller the index value, the better the wear resistance.

4) viscoelastic properties

Viscoelastic properties were measured by using a dynamic mechanical analyzer (TA Co., Ltd.) to determine the tan δ by varying the strain at a frequency of 10 Hz and each measurement temperature (-60 ° C. to 60 ° C.) in a torsion mode. Payne effect is expressed as the difference between the minimum and maximum values at 0.28% to 40% strain. The higher the low temperature 0 [deg.] C tan δ, the better the wet road resistance. The lower the high temperature 60 [deg.] C tan δ, the lower the hysteresis loss, and the lower the running resistance (fuelability).

5) Vulcanization Characteristics

The vulcanization characteristic (t90) was measured using MDF (moving die rheometer) for 50 minutes of vulcanization at 150 ° C., MH (maximum torque) value and retention time (t90) until 90% vulcanization.

division		Example		Comparative example
		One	2	One	2	3
Vulcanization characteristics (t90 minutes)		21.1	21.4	21.7	21.9	21.1
Viscoelastic	tanδ @ 0 ℃	1.12+	1.126	0.998	1.003	1.021
	tanδ @ 60 ℃	0.094	0.099	0.108	0.109	0.104
Tensile Properties	300% modulus (kgf / cm 2 )	161	170	151	156	151
	Tensile Strength (kgf / cm 2 )	189	187	177	174	179
Wear resistance		92	89	100	98	99

As shown in Table 2, the curing time of the rubber composition comprising the modified conjugated diene-based polymer of Examples 1 and 2 prepared using an initiator containing an amine according to an embodiment of the present invention It was confirmed that it was about 0.5 minutes short compared with 1 and the comparative example 2.

In addition, the tensile properties and viscoelastic properties of the rubber composition comprising the modified conjugated diene-based polymers of Examples 1 and 2 prepared using the modifying agent according to an embodiment of the present invention of the comparative examples 1 to 3 It was confirmed that it is superior to the rubber composition comprising a.

Specifically, the rubber composition comprising the modified conjugated diene-based polymers of Examples 1 and 2 prepared using the modifying agent according to an embodiment of the present invention includes the conjugated diene-based polymers of Comparative Examples 1 and 2 Tan δ value at 0 ° C. was increased (about 13% level increase) and Tan δ value at 60 ° C. was decreased (about 13% and 10% level decrease) compared to the rubber composition. In addition, compared to the rubber composition comprising the modified conjugated diene-based polymer of Comparative Example 3, the Tan δ value at 0 ° C is increased (about 6% level increase), and the Tan δ value at 60 ° C is decreased (about 10%). Level decrease). This is a result that the modified conjugated diene-based polymer according to an embodiment of the present invention is excellent in resistance and running resistance characteristics on the wet road surface, fuel efficiency can be high.

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

The terms or words used in this specification and claims are not to be construed as limiting in their usual or dictionary meanings, and the inventors may appropriately define the concept of terms in order to best describe their invention. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that the present invention.

The present invention provides a polymerization initiator comprising a compound represented by the following formula (1).

[Formula 1]

In Chemical Formula 1, Cy may be a cyclic saturated hydrocarbon group having 5 to 8 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 4 carbon atoms, and A ¹ and A ² may each independently be a functional group represented by Formula 2 below. ,

[Formula 2]

In Formula 2, R may be a linear hydrocarbon group having 1 to 20 carbon atoms, or a mono-cyclic or multicyclic saturated hydrocarbon group having 3 to 20 carbon atoms, and X may be 2 to 1 carbon atoms. Can be a hydrocarbon group, M can be an alkali metal, and a can be 0 or 1.

As a specific example, in Chemical Formula 1, Cy may be an unsubstituted cyclic saturated hydrocarbon group having 5 to 8 carbon atoms, A ¹ and A ² may each independently be a functional group represented by Chemical Formula 2, in Chemical Formula 2, R may be a linear hydrocarbon group having 1 to 6 carbon atoms, or a mono-cyclic or multicyclic saturated hydrocarbon group having 4 to 8 carbon atoms, X may be a divalent hydrocarbon group having 1 to 5 carbon atoms, and , M may be an alkali metal and a may be 0 or 1.

The compound represented by Formula 1 may be, for example, a compound represented by Formula 3 below.

[Formula 3]

In Chemical Formula 3,

R ¹ and R ² are each independently a linear hydrocarbon group having 1 to 20 carbon atoms, or may be a mono-cyclic or multicyclic saturated hydrocarbon group having 4 to 20 carbon atoms, and M ¹ and M ² are Each independently may be an alkali metal, m and n may each independently be an integer selected from 0 to 5.

As a specific example, R ¹ and R ² may be each independently a linear hydrocarbon group having 1 to 6 carbon atoms, or may be combined with each other to form a mono-cyclic or multicyclic saturated hydrocarbon group having 4 to 8 carbon atoms. , M ¹ and M ² may be each independently selected from Li, Na, K, Rb and Cs.

More specifically, in Formula 3, R ¹ and R ² may be each independently an alkyl group having 1 to 6 carbon atoms, M ¹ and M ² may be each independently selected from Li, Na and K.

According to an embodiment of the present invention, the compound represented by Chemical Formula 3 may be one selected from the group consisting of compounds represented by Chemical Formulas 3-1 to 3-4.

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

The polymerization initiator can be used to initiate the polymerization of various polymers. In particular, the polymerization initiator has high activity when used for conjugated diene-based polymer and can ensure sufficient randomization of monomers.

In addition, the present invention provides a method for producing a polymerization initiator for producing a polymerization initiator comprising a compound represented by the formula (1).

The method for preparing a polymerization initiator according to the present invention comprises the steps of preparing a compound represented by Chemical Formula 1b by reacting a compound represented by Chemical Formula 1a with a compound represented by Chemical Formula 4 in a solvent (S1); And reacting the compound represented by Formula 1b with an alkali metal or a compound represented by Formula 5 below (S2).

[Formula 1a]

[Formula 1b]

In Formulas 1a and 1b, Cy may be a cyclic saturated hydrocarbon group having 5 to 8 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 4 carbon atoms, and A ^{1 '} and A ^2' are each independently represented by Formula 2a It may be a functional group, A ^{1 "} and A ^2" may each independently be a functional group represented by the formula (2b),

[Formula 2a]

[Formula 2b]

[Formula 4]

In Formulas 2a, 2b, and 4, R may be a linear hydrocarbon group having 1 to 20 carbon atoms, or a mono-cyclic or multicyclic saturated hydrocarbon group having 3 to 20 carbon atoms, and X 'may be a carbon atom. It may be a divalent hydrocarbon group of 1 to 5, a 'may be 0 or 1, X ¹ and X ² may be each independently a halogenated compound,

[Formula 5]

In Formula 5, R 'may be a hydrocarbyl group having 1 to 20 carbon atoms, M may be an alkali metal, x may be an integer selected from 1 to 4.

As a specific example, in Chemical Formulas 1a and 1b, Cy may be an unsubstituted cyclic saturated hydrocarbon group having 5 to 8 carbon atoms, and A ^{1 '} and A ^2' may each independently be a functional group represented by Formula 2a, and A ^{1 ”} and A ^2” may each independently be a functional group represented by Formula 2b, and in Formulas 2a, 2b and 4, R may be a linear hydrocarbon group having 1 to 6 carbon atoms, or a monocyclic ring having 4 to 8 carbon atoms ( mono-cyclic) or polycyclic saturated hydrocarbon group, X 'may be a divalent hydrocarbon group of 1 to 5 carbon atoms, a' may be 0 or 1, X ¹ and X ² are each independently It may be one halogen atom selected from the group consisting of F, Br, Cl and I, in Formula 5, R 'may be a hydrocarbyl group having 1 to 20 carbon atoms, M is Li, Na, K, It may be selected from Rb and Cs, x is from 1 to 4 It may be an integer selected.

In the method for preparing a polymerization initiator according to an embodiment of the present invention, the step (S1) may be, for example, reacting at a reaction temperature of 0 to 50 ° C., 0 to 40 ° C., or 0 to 35 ° C. There is an effect of minimizing side reactions within the range.

The reaction time of the step (S1) may be 12 minutes to 48 hours, there is an effect that the side reaction is minimized within this range.

In the step (S1), the molar ratio of the compound represented by Formula 1a and the compound represented by Formula 4 may be 1: 1 to 1: 4, 1: 1 to 1: 3, or 1: 1 to 1: 1.8. In this case, there is an effect that side reactions are minimized within this range.

In addition, the solvent may be a nonpolar solvent, and a polar solvent may be further added to increase the solubility. In this case, there is an effect of increasing the solubility of the solute to promote the reaction.

Examples of suitable polar solvents include tetrahydrofuran, ditetra hydroprilpropane, diethyl ether, thibutylmethyl ether, cycloamal ether, dipropyl ether, ethylene dimetal ether, ethylene dimethyl ether, diethylene glycol, dimethyl ether, An ether-based solvent selected from the group consisting of tertiary butoxyethoxyethane bis (2-dimethylaminoethyl) ether and (dimethylaminoethyl) ethyl ether can be used, preferably diethyl ether or thibutylmethyl ether is used. Can be used.

The nonpolar solvent may be, for example, a saturated hydrocarbon-based solvent selected from the group consisting of hexane, heptane, octane, nonane, decane, cyclopentane, cyclohexane and cycloheptane, preferably May use hexane or cyclohexane.

The step (S2) may be for example to react at a reaction temperature of 0 to 70 ℃, there is an effect that the side reaction is minimized within this range.

In addition, the reaction time of the step (S2) may be 0.5 hours to 6 hours, there is an effect that the side reaction is minimized within this range.

On the other hand, when reacting the compound represented by the formula (1b) and the alkali metal in the step (S2), the molar ratio of the compound represented by the formula (1b) and the alkali metal may be 1:10 to 1:40, (S2) When the compound represented by Formula 1b and the compound represented by Formula 5 are reacted in the step, the molar ratio of the compound represented by Formula 1b and the compound represented by Formula 5 may be 1: 1.9 to 1: 2.2, Within this range, side reactions are minimized, and there is an effect of obtaining a compound represented by Chemical Formula 1 with a high conversion rate.

On the other hand, when the reaction of step b may cause a problem in that the side reaction increases when a polar solvent is present, it may be to react in the absence of a polar solvent.

In addition, the present invention provides a method for producing a modified conjugated diene-based polymer using a polymerization initiator containing a compound represented by the formula (1).

The method for preparing the modified conjugated diene-based polymer is an alkali metal is bonded by polymerizing a conjugated diene monomer, an aromatic vinyl monomer and a conjugated diene monomer in a hydrocarbon solvent including a polymerization initiator containing a compound represented by the following formula (1): Preparing an active polymer (S3); And it may include a step (S4) of reacting the active polymer prepared in the step (S3) with a denaturing agent.

[Formula 1]

Definitions for each substituent of Formula 1 are as defined above.

The step (S3) is a step for preparing an active polymer combined 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 the compound of Formula 1 in a hydrocarbon solvent. can do. The active polymer may refer to a polymer in which a polymer anion and an organic metal cation are bonded.

The aromatic vinyl monomer may be included in an amount of 0.0001 to 50 wt% based on a total of 100 wt% of the conjugated diene monomer and the aromatic vinyl monomer.

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

The polymerization initiator including the compound represented by Chemical Formula 1 may be used in an amount of 0.01 mmol to 10 mmol based on 100 g of the total monomer. Specifically, the polymerization initiator may be used in 0.05 mmol to 5 mmol, more specifically 0.1 mmol to 2 mmol, and more specifically 0.1 mmol to 1 mmol, based on 100 g of the total monomers.

The polymerization of the step (S3) may be carried out by further adding a polar additive as needed, the polar additive is 0.001 g to 50 g, specifically 0.001 g to 10 g, more based on a total of 100 g monomer Specifically, it may be added at 0.005 g to 0.1 g.

The polar additive may be added in an amount of 0.001 g to 10 g, specifically 0.005 g to 1 g, and more specifically 0.005 g to 0.1 g based on 1 mmol of the total organometallic compound.

The polar additives may be salts, ethers, amines or mixtures thereof, specifically tetrahydrofuran, ditetrahydrofurylpropane, diethyl ether, cycloamal ether, dipropyl ether, ethylene dimethyl ether, ethylene dimethyl ether, di From the group consisting of ethylene glycol, dimethyl ether, tertiary butoxyethoxyethane bis (3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine and tetramethylethylenediamine It may be one or more selected. More specifically, it may be ditetrahydropropylpropane, triethylamine or tetramethylethylenediamine.

The preparation method according to an embodiment of the present invention is a random copolymer by compensating for the difference in reaction rate when copolymerizing a conjugated diene monomer, or a conjugated diene monomer and an aromatic vinyl monomer by using the polar additives described above. It can be induced to be easily formed.

The polymerization of the step (S3) may be anionic polymerization, specifically, it may be a living anion polymerization to obtain an active site by a growth reaction by anion.

In addition, the polymerization may be elevated temperature polymerization, isothermal polymerization or constant temperature polymerization (thermal insulation polymerization).

Here, the constant temperature polymerization refers to a polymerization method including the step of polymerizing with the heat of reaction itself without adding any heat after the addition of the alkali metal compound, and the temperature rising polymerization is a temperature by optionally applying heat after the addition of the alkali metal compound The isothermal polymerization refers to a polymerization method of increasing the heat by adding heat after the addition of the alkali metal compound or taking away the heat to maintain a constant temperature of the polymerization product.

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

The step (S4) is a step of reacting the active polymer with a modifier to prepare a modified conjugated diene-based polymer.

The denaturant may have high anion reactivity and thus may easily act with the active site of the polymer, and thus, a denaturant that may easily perform denaturation may be preferable.

The modifier according to the embodiment of the present invention may include a compound represented by the following Formula 6.

[Formula 6]

In Formula 6, R ³ may be an alkyl group or alkylsilyl group having 1 to 20 carbon atoms, R ⁴ may be an alkylene group having 1 to 20 carbon atoms, and R ⁵ and R ⁶ are each independently an alkyl group having 1 to 20 carbon atoms. K may be 0, 1 or 2, and d may be 1, 2 or 3.

As a specific example, the compound represented by Formula 6 may be one selected from the group consisting of compounds represented by Formulas 6-1 and 6-2.

[Formula 6-1]

[Formula 6-2]

In this case, the modified conjugated diene-based polymer includes a modifier-derived functional group containing a compound represented by the formula (6) at the other end in addition to one end containing a functional group derived from a polymerization initiator, thereby excellent interaction with the inorganic filler, the modifier The linearity between the modified conjugated diene-based polymer coupled by the has a high wear resistance effect.

As another example, the denaturant according to one embodiment of the present invention may include a compound represented by the following Chemical Formula 7.

[Formula 7]

In Formula 7, R ⁷ , R ^8, and R ¹¹ may each independently be an alkylene group having 1 to 10 carbon atoms, and R ⁹ , R ¹⁰ , R ^12, and R ¹³ may each independently be an alkyl group having 1 to 10 carbon atoms. R ¹⁴ may be hydrogen or an alkyl group having 1 to 10 carbon atoms, b and c may be each independently 0, 1, 2 or 3, b + c ≧ 1, and A is

or

In this case, R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ may be each independently hydrogen or an alkyl group having 1 to 10 carbon atoms.

As a specific example, the compound represented by Formula 7 may be one selected from the group consisting of compounds represented by Formulas 7-1 and 7-2.

[Formula 7-1]

[Formula 7-2]

In this case, the modified conjugated diene-based polymer includes a modifier-derived functional group containing a compound represented by the formula (7) at the other end in addition to one end containing a functional group derived from a polymerization initiator, so that the interaction with the inorganic filler is very excellent, tensile Properties and viscoelastic properties have excellent effects.

As another example, the denaturant according to an embodiment of the present invention may include a compound represented by the following Formula 8.

[Formula 8]

In Formula 8, R ¹⁹ and R ²⁰ may be each independently an alkyl group having 1 to 20 carbon atoms, R ²¹ may be one functional group selected from the group consisting of Formula 9 to 12, e is 1 or 2 F may be an integer selected from 0 to 2, but e and f may not be 2 at the same time,

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

In Formulas 9 to 12, R ²² , R ²³ , R ²⁷ , R ²⁸ , R ²⁹ , R ^32, and R ³⁵ may each independently be a linear or branched alkylene group having 1 to 20 carbon atoms, and R ²⁴ , R ²⁵ , R ²⁶ , R ³⁰ , R ³³ , R ³⁴ , R ³⁶ and R ³⁷ may each independently be an alkyl or alkylsilyl group having 1 to 20 carbon atoms, and R ³¹ may be a trivalent hydrocarbon group having 1 to 20 carbon atoms. .

As a specific example, the compound represented by Chemical Formula 8 may be one selected from the group consisting of compounds represented by the following Chemical Formulas 13 to 17.

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

In Formulas 13 to 17, Me is a methyl group, Et is an ethyl group.

In this case, the modified conjugated diene-based polymer includes a modifier-derived functional group containing the compound represented by Formula 8 at the other end in addition to one end including the functional group derived from the polymerization initiator, thereby excellent in interaction with the inorganic filler and excellent in tensile There is an effect that the properties and viscoelastic properties are improved.

The modifying agent according to an embodiment of the present invention may be used in the reaction by mixing one or two or more kinds.

The modifying agent including at least one selected from the group consisting of the compounds represented by Formulas 6 to 8 may be used in an amount of 0.1 mol to 10 mol relative to 1 mol of the polymerization initiator including the compound represented by Formula 1. . Specifically, the modifier may be used in 0.3 mol to 2 mol relative to 1 mole of the polymerization initiator. If the denaturant is used in an amount within the ratio range, it is possible to perform a modification reaction of optimum performance, thereby obtaining a conjugated diene polymer having a high modification rate.

The reaction of the step (S4) is a modification reaction for introducing a functional group into the polymer, it may be to perform the reaction for 1 minute to 5 hours at 0 ℃ to 90 ℃.

In addition, the modified conjugated diene-based polymer manufacturing method according to an embodiment of the present invention may be carried out by a batch polymerization (batch) or a continuous polymerization method comprising one or more reactors.

The preparation method according to an embodiment of the present invention may further include one or more steps of recovering and drying the solvent and the unreacted monomer, if necessary, after the step (S4).

In addition, the denaturant may be a solubility of at least 10 g in a nonpolar solvent, such as 100 g of hexane at 25 ° C., 1 atmosphere. Here, the solubility of the denaturant means the degree of clear dissolution without a hazy phenomenon when observed by the naked eye. By exhibiting such high solubility, it is possible to exhibit excellent denaturation rate for the polymer.

Meanwhile, the polymerization initiator and the denaturant according to the present invention have an optimized functional group capable of maximizing affinity for inorganic fillers and solvents, and thus are used as polymerization initiators and modifiers of conjugated diene-based polymers. It has an effect that can impart excellent viscoelasticity, tensile properties, wet road resistance and workability.

Accordingly, the present invention provides a modified conjugated diene-based polymer comprising a functional group derived from a polymerization initiator represented by the following Formula 1 at one end.

[Formula 1]

Definitions for each substituent of Formula 1 are as defined above.

As a specific example, the modified conjugated diene-based polymer may include a conjugated diene-based polymer chain (P) including a polymerization initiator-derived functional group represented by Chemical Formula 1 at one end thereof, and be represented by the form of a compound represented by the following Chemical Formula 18: Can be.

[Formula 18]

In Formula 18, R ⁷⁰ may be an alkyl group or alkylsilyl group having 1 to 20 carbon atoms, R ³⁸ may be an alkylene group having 1 to 20 carbon atoms, and R ³⁹ and R ⁴⁰ are each independently an alkyl group having 1 to 20 carbon atoms. K may be 0, 1 or 2, k + j may be 1, 2 or 3, and d 'may be 1, 2 or 3.

As another example, the modified conjugated diene-based polymer includes a conjugated diene-based polymer chain (P) including a polymerization initiator-derived functional group represented by Chemical Formula 1 at one end thereof, and is represented by the form of a compound represented by the following Chemical Formula 19: Can be.

[Formula 19]

In Formula 19, R ⁴¹ , R ^42, and R ⁴⁵ may each independently be an alkylene group having 1 to 10 carbon atoms, and R ⁴³ , R ⁴⁴ , R ^46, and R ⁴⁷ may each independently be an alkyl group having 1 to 10 carbon atoms. R ⁴⁸ may be hydrogen or an alkyl group having 1 to 10 carbon atoms, b and c may be each independently 0, 1 or 2, y and q may be each independently 1, 2 or 3, b + y and c + q can each independently be 1, 2 or 3, and A is

or

In this case, R ⁴⁹ , R ⁵⁰ , R ⁵¹ and R ⁵² may be each independently hydrogen or an alkyl group having 1 to 10 carbon atoms.

More specifically, the compound represented by Formula 19 may be one selected from the group consisting of compounds represented by Formulas 19-1 and 19-2.

[Formula 19-1]

[Formula 19-2]

In Formulas 19-1 and 19-2, R ⁵⁵ , R ⁵⁶ , R ⁵⁸ , R ⁵⁹ , R ⁶² , R ⁶³ , R ⁶⁵ and R ⁶⁶ may each independently be an alkyl group having 1 to 10 carbon atoms, R ⁵³ , R ⁵⁴ , R ⁵⁷ , R ⁶⁰ , R ⁶¹ and R ⁶⁴ may each independently be an alkylene group having 1 to 10 carbon atoms, b and c may each independently be 0, 1 or 2, and y and q May be independently 1, 2 or 3, and b + y and c + q may be independently 1, 2 or 3, respectively.

As another example, the modified conjugated diene-based polymer includes a conjugated diene-based polymer chain (P) including a polymerization initiator-derived functional group represented by Chemical Formula 1 at one end thereof, and is represented by the form of a compound represented by the following Chemical Formula 20: Can be.

[Formula 20]

In Formula 20, R ⁶⁷ and R ⁶⁸ may each independently be an alkyl group having 1 to 20 carbon atoms, R ⁶⁹ may be one functional group selected from the group consisting of Formulas 9 to 12, e is 1 or 2 May be, f may be 0 or 1, g may be an integer selected from 1 to 3,

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

In Formulas 9 to 12, R ²² , R ²³ , R ²⁷ , R ²⁸ , R ²⁹ , R ^32, and R ³⁵ may each independently be a linear or branched alkylene group having 1 to 20 carbon atoms, and R ²⁴ , R ²⁵ , R ²⁶ , R ³⁰ , R ³³ , R ³⁴ , R ³⁶ and R ³⁷ may each independently be an alkyl or alkylsilyl group having 1 to 20 carbon atoms, and R ³¹ may be a trivalent hydrocarbon group having 1 to 20 carbon atoms. .

More specifically, the compound represented by Chemical Formula 20 may be one selected from the group consisting of compounds represented by the following Chemical Formulas 21 to 25.

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

[Formula 25]

In Formulas 21 to 25, Me is a methyl group, Et is an ethyl group, z may be 0, 1 or 2, and r may be 1 or 2.

The conjugated diene polymer chain may be derived from a homopolymer of a conjugated diene monomer or a copolymer of a conjugated diene monomer and an aromatic vinyl monomer. Therefore, the conjugated diene polymer according to an embodiment of the present invention may include a conjugated diene monomer derived unit and an aromatic vinyl monomer derived unit.

In the present invention, the term "derived unit" may refer to a component, a structure, or the substance itself resulting from a substance.

On the other hand, the modified conjugated diene-based polymer may be a homopolymer or a copolymer, when the modified conjugated diene-based polymer is a homopolymer may be a modified conjugated diene polymer, when the modified conjugated diene-based polymer is a copolymer The conjugated diene polymer may include a conjugated diene monomer derived unit and an aromatic vinyl monomer derived unit. In addition, when the modified conjugated diene-based polymer is a copolymer, the copolymer may be a random copolymer.

In the present invention, the term "random copolymer" may indicate that the structural units constituting the copolymer are randomly arranged.

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

When the modified conjugated diene-based polymer is a copolymer, the conjugated diene-based monomer derived unit may be at least 50% by weight, specifically 60% by weight to 90% by weight, more specifically 60% by weight to 85% by weight. have.

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

When the modified conjugated diene-based polymer is a copolymer, the aromatic vinyl monomer-derived unit comprises 50 wt% or less, specifically 0.0001 wt% to 50 wt%, more specifically 15 wt% to 40 wt%. It may be.

In addition, the modified conjugated diene-based polymer has a number average molecular weight of 10,000 g / mol to 10,000,000 g / mol, specifically 100,000 g / mol to 2,000,000 g / mol, more specifically 120,000 g / mol to 1,500,000 g / mol days Can be.

The modified conjugated diene-based polymer may have a molecular weight distribution (Mw / Mn) of 1.0 to 8.0, specifically 1.0 to 4.0, more specifically 1.0 to 3.5. When the modified conjugated diene-based polymer has the above molecular weight distribution, the processability of the rubber composition including the same may be improved, and as a result, mechanical properties, low fuel consumption characteristics, and wear resistance of the manufactured molded article may be improved.

In addition, the modified conjugated diene-based polymer may have a vinyl content of 5% by weight or more, specifically 10% by weight or more, and more specifically 14% by weight to 70% by weight. If the modified conjugated diene-based polymer exhibits a vinyl content in the above range, the glass transition temperature can be adjusted to an appropriate range, thereby not only satisfying the properties required for the tire such as running resistance and braking force when applied to the tire. This has the effect of reducing fuel consumption.

Herein, the vinyl content refers to the content of 1,2-added conjugated diene monomer, not 1,4-addition, based on 100% by weight of the conjugated diene copolymer composed of a monomer having a vinyl group and an aromatic vinyl monomer. .

In addition, the modified conjugated diene-based polymer has a characteristic of viscoelasticity, and when measured at 10 Hz through DMA after silica blending, the Tan δ value (Tanδ at 0 ° C.) at O ° C. is 0.4 to 1, or 0.5 to 1 Within this range, there is an effect that the road surface resistance or the wet resistance is greatly improved compared to the conventional invention.

In addition, the Tan δ value (Tan δ at 60 ° C.) at 60 ° C. may be 0.3 to 0.2, or 0.15 to 0.1, and within this range, running resistance, wet road resistance, or rolling resistance (RR) is significantly higher than that of the conventional invention. The effect is improved.

In addition, the modified conjugated diene-based polymer may include 0.00001% to 0.001% by weight of silyl groups based on the total moles of the polymer.

The present invention also provides a rubber composition comprising the modified conjugated diene-based polymer.

The rubber composition according to an embodiment of the present invention comprises a modified conjugated diene-based polymer in an amount of 10% by weight or more, specifically 10% by weight to 100% by weight, more specifically 20% by weight to 90% by weight. It may be. If the content of the modified conjugated diene-based polymer is less than 10% by weight, the effect of improving the wear resistance and crack resistance of a molded article, for example, a tire manufactured using the rubber composition 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, wherein the rubber components may be included in an amount of 90% by weight or less based on the total weight of the rubber composition. Specifically, the modified conjugated diene polymer may be included in an amount of 1 part by weight to 900 parts by weight based on 100 parts by weight.

The rubber component may be natural rubber or synthetic rubber, for example, the rubber component may include natural rubber (NR) including cis-1,4-polyisoprene; Modified natural rubbers such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber obtained by modifying or refining 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., and any one or a mixture of two or more thereof may be used. have.

In addition, the rubber composition may include 0.1 parts by weight to 200 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene-based polymer, and specifically, may include 10 parts by weight to 120 parts by weight of a filler.

The filler may be a silica-based filler, the silica-based filler is not particularly limited, but may be, for example, wet silica (silicate silicate), dry silica (silicate anhydride), calcium silicate, aluminum silicate or colloidal silica. More specifically, the filler may be a wet silica having the most remarkable effect of improving the breaking characteristics and wet grip (wet grip).

In addition, the rubber composition according to an embodiment of the present invention may further include a carbon black-based filler as needed.

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

Specific examples of the silane coupling agent include 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-dimethylthiocarbamoyl tetrasul Feed, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilyl Propylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzolyl tetrasulfide, 3-triethoxysilylpropyl methacrylate Monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide or dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide, and the like, and any one or a mixture of two or more thereof may be used. More specifically, in consideration of the reinforcing improvement effect, the silane coupling agent may be bis (3-triethoxysilylpropyl) polysulfide or 3-trimethoxysilylpropylbenzothiazyl tetrasulfide.

In addition, in the rubber composition according to one embodiment of the present invention, since the modified conjugated diene-based polymer in which a functional group having high affinity with silica is introduced into the active site as the rubber component, the amount of the silane coupling agent used is It can be reduced than usual. 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 silica. When used in the above range, the 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 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 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 parts by weight to 10 parts by weight based on 100 parts by weight of the rubber component. When included in the content range, it is possible to ensure the required elastic modulus and strength of the vulcanized rubber composition, and at the same time obtain a low fuel consumption.

In addition, the rubber composition according to an embodiment of the present invention, in addition to the above components, various additives commonly used in the rubber industry, in particular, vulcanization accelerators, process oils, plasticizers, anti-aging agents, anti-scoring agents, zinc white (zinc white) ), Stearic acid, a thermosetting resin, or a thermoplastic resin may be further included.

The said vulcanization accelerator is not specifically limited, Specifically, M (2-mercapto benzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2- benzothiazyl sulfenamide), etc. Thiazole compounds, or guanidine compounds such as DPG (diphenylguanidine) can be used. The vulcanization accelerator may be included in an amount of 0.1 parts by weight 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, specifically, may be a paraffinic, naphthenic, or aromatic compound, and more specifically, aromatic process oil, hysteresis loss in consideration of tensile strength and wear resistance. And naphthenic or paraffinic process oils may be used when considering low temperature properties. The process oil may be included in an amount of 100 parts by weight or less with respect to 100 parts by weight of the rubber component, when included in the content, it is possible to prevent the degradation of tensile strength, low heat generation (low fuel consumption) of the vulcanized rubber.

In addition, as the anti-aging agent, specifically N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, 6- Methoxy-2,2,4-trimethyl-1,2-dihydroquinoline, or a high temperature condensate of diphenylamine and acetone. The anti-aging agent may be used in an amount of 0.1 parts by weight 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 kneading machine such as a Banbury mixer, a roll, an internal mixer, etc. by the above formulation, and also has low heat resistance and abrasion resistance by a vulcanization process after molding. This excellent rubber composition can be obtained. Accordingly, the rubber composition may be used for tire members such as tire treads, under treads, sidewalls, carcass coated rubbers, belt coated rubbers, bead fillers, pancreapers, or bead coated rubbers, dustproof rubbers, belt conveyors, hoses, and the like. It may be useful for the production of various industrial rubber products.

In addition, the present invention provides a tire manufactured using the rubber composition. The tire may include a tire or a tire tread.

Claims (20)

1. A polymerization initiator comprising a compound represented by the following formula (1):

   [Formula 1]

   

   In Chemical Formula 1,

   Cy is a cyclic saturated hydrocarbon group of 5 to 8 carbon atoms unsubstituted or substituted with an alkyl group of 1 to 4 carbon atoms, A ¹ and A ² are each independently a functional group represented by the formula (2),

   [Formula 2]

   

   In Chemical Formula 2,

   R is a linear hydrocarbon group having 1 to 20 carbon atoms or a mono-cyclic or multicyclic saturated hydrocarbon group having 3 to 20 carbon atoms, X is a divalent hydrocarbon group having 1 to 5 carbon atoms, M Is an alkali metal and a is 0 or 1.
2. The method of claim 1,

   The compound represented by Chemical Formula 1 is a polymerization initiator represented by Chemical Formula 3 below:

   [Formula 3]

   

   In Chemical Formula 3,

   R ¹ and R ² are each independently a linear hydrocarbon group having 1 to 20 carbon atoms, or a mono-cyclic or multicyclic saturated hydrocarbon group having 4 to 20 carbon atoms, and M ¹ and M ² are each Independently an alkali metal, m and n are each independently an integer selected from 0-5.
3. The method of claim 2,

   In Chemical Formula 3,

   R ¹ and R ² are each independently an alkyl group having 1 to 6 carbon atoms, and M ¹ and M ² are each independently selected from Li, Na, and K.
4. The method of claim 2,

   The compound represented by the formula (3) is a polymerization initiator selected from the group consisting of compounds represented by the following formulas 3-1 to 3-4.

   [Formula 3-1]

   

   [Formula 3-2]

   

   [Formula 3-3]

   

   [Formula 3-4]

   
5. Preparing a compound represented by Chemical Formula 1b by reacting the compound represented by Chemical Formula 1a with the compound represented by Chemical Formula 4 in a solvent (S1); And

   Method of preparing a polymerization initiator comprising the step (S2) of reacting with a compound represented by the formula (1b) and an alkali metal or a compound represented by the formula (5):

   [Formula 1a]

   

   [Formula 1b]

   

   In Chemical Formulas 1a and 1b,

   Cy is a cyclic saturated hydrocarbon group of 5 to 8 carbon atoms unsubstituted or substituted with an alkyl group of 1 to 4 carbon atoms, A ^{1 '} and A ^2' are each independently a functional group represented by the formula (2a), A ^{1 "} and A ^{2 ”} are each independently a functional group represented by the following formula (2b),

   [Formula 2a]

   

   [Formula 2b]

   

   [Formula 4]

   

   In Chemical Formulas 2a, 2b, and 4,

   R is a linear hydrocarbon group having 1 to 20 carbon atoms or a mono-cyclic or multicyclic saturated hydrocarbon group having 3 to 20 carbon atoms, X 'is a divalent hydrocarbon group having 1 to 5 carbon atoms, a 'is 0 or 1, X ¹ and X ² are each independently a halogenated compound,

   [Formula 5]

   

   In Chemical Formula 5,

   R 'is a C1-C20 hydrocarbyl group, M is an alkali metal, and x is an integer selected from 1-4.
6. The method of claim 5,

   The molar ratio of the compound represented by the formula (1a) and the compound represented by the formula (4) in the step (S1) is 1: 1 to 1: 4 method for producing a polymerization initiator.
7. The method of claim 5,

   The molar ratio of the compound represented by the formula (1b) and the alkali metal in the step (S2) is 1:10 to 1:40 method of producing a polymerization initiator.
8. The method of claim 5,

   The molar ratio of the compound represented by the formula (1b) and the compound represented by the formula (5) in the step (S2) is 1: 1.9 to 1: 2.2 method for producing a polymerization initiator.
9. Step (S3) to prepare an active polymer combined with an alkali metal by polymerizing a conjugated diene monomer, or an aromatic vinyl monomer and a conjugated diene monomer in a hydrocarbon solvent comprising a polymerization initiator comprising a compound represented by the formula (1) ; And

   Method of producing a modified conjugated diene-based polymer comprising the step (S4) of reacting the active polymer prepared in the step (S3) with a modifier:

   [Formula 1]

   

   In Chemical Formula 1,

   Cy is a cyclic saturated hydrocarbon group of 5 to 8 carbon atoms unsubstituted or substituted with an alkyl group of 1 to 4 carbon atoms, A ¹ and A ² are each independently a functional group represented by the formula (2),

   [Formula 2]

   

   In Chemical Formula 2,

   R is a C1-C20 linear hydrocarbon group or a C3-C20 cyclic saturated hydrocarbon group, X is a C1-C5 divalent hydrocarbon group, M is an alkali metal, and a is 0 or 1.
10. The method of claim 9,

    Method for producing a modified conjugated diene-based polymer wherein the modifier comprises a compound represented by the following formula (6) or (7):

    [Formula 6]

    

    In Chemical Formula 6,

    R ³ is an alkyl group or alkylsilyl group having 1 to 20 carbon atoms,

    R ⁴ is an alkylene group having 1 to 20 carbon atoms,

    R ⁵ and R ⁶ are each independently an alkyl group having 1 to 20 carbon atoms,

    k is 0, 1 or 2,

    d is 1, 2 or 3,

    [Formula 7]

    

    In Chemical Formula 7,

    R ⁷ , R ⁸ and R ¹¹ are each independently an alkylene group having 1 to 10 carbon atoms,

    R ⁹ , R ¹⁰ , R ¹² and R ¹³ are each independently an alkyl group having 1 to 10 carbon atoms,

    R ¹⁴ is hydrogen or an alkyl group having 1 to 10 carbon atoms,

    b and c are each independently 0, 1, 2 or 3, b + c ≧ 1,

    A is

    

    or

    

    Is,

    At this time, R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms.
11. The method of claim 10,

    Compound represented by the formula (6) is a method for producing a modified conjugated diene-based polymer is one selected from the group consisting of compounds represented by the formula 6-1 and 6-2:

    [Formula 6-1]

    

    [Formula 6-2]

    
12. The method of claim 10,

    Compound represented by the formula (7) is a method for producing a modified conjugated diene-based polymer is one selected from the group consisting of compounds represented by the formula 7-1 and 7-2:

    [Formula 7-1]

    

    [Formula 7-2]

    
13. Step (S3) to prepare an active polymer combined with an alkali metal by polymerizing a conjugated diene monomer, or an aromatic vinyl monomer and a conjugated diene monomer in a hydrocarbon solvent comprising a polymerization initiator comprising a compound represented by the formula (1) ; And

    Reacting the active polymer prepared in the step (S3) with a denaturing agent (S4),

    The modifying agent is a method for producing a modified conjugated diene polymer, characterized in that the compound represented by the formula (8):

    [Formula 1]

    

    In Chemical Formula 1,

    Cy is a cyclic saturated hydrocarbon group of 5 to 8 carbon atoms unsubstituted or substituted with an alkyl group of 1 to 4 carbon atoms, A ¹ and A ² are each independently a functional group represented by the formula (2),

    [Formula 2]

    

    In Chemical Formula 2,

    R is a linear hydrocarbon group having 1 to 20 carbon atoms or a cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, X is a divalent hydrocarbon group having 1 to 5 carbon atoms, M is an alkali metal, a is 0 or 1,

    [Formula 8]

    

    In Chemical Formula 8,

    R ¹⁹ and R ²⁰ are each independently an alkyl group having 1 to 20 carbon atoms, R ²¹ is one functional group selected from the group consisting of Formulas 9 to 12, e is 1 or 2, and f is selected from 0 to 2 Is an integer, but e and f are not simultaneously 2,

    [Formula 9]

    

    [Formula 10]

    

    [Formula 11]

    

    [Formula 12]

    

    In Chemical Formulas 9 to 12,

    R ²² , R ²³ , R ²⁷ , R ²⁸ , R ²⁹ , R ³² and R ³⁵ are each independently a linear or branched alkylene group having 1 to 20 carbon atoms, and R ²⁴ , R ²⁵ , R ²⁶ , R ³⁰ , R ³³ , R ³⁴ , R ³⁶ and R ³⁷ are each independently an alkyl or alkylsilyl group having 1 to 20 carbon atoms, and R ³¹ is a trivalent hydrocarbon group having 1 to 20 carbon atoms.
14. The method of claim 13,

    The compound represented by the formula (8) is a method for producing a modified conjugated diene-based polymer is one selected from the group consisting of compounds represented by the following formulas 13 to 17:

    [Formula 13]

    

    [Formula 14]

    

    [Formula 15]

    

    [Formula 16]

    

    [Formula 17]

    

    In Formulas 13 to 17, Me is a methyl group, Et is an ethyl group.
15. The method according to claim 9 or 13,

    A molar ratio of the compound represented by Formula 1 and the modifier is 1: 0.1 to 1:10, characterized in that the method for producing a modified conjugated diene polymer.
16. Modified conjugated diene-based polymer comprising a functional group derived from a polymerization initiator represented by the formula (1) at one end:

    [Formula 1]

    

    In Chemical Formula 1,

    Cy is a cyclic saturated hydrocarbon group of 5 to 8 carbon atoms unsubstituted or substituted with an alkyl group of 1 to 4 carbon atoms, A ¹ and A ² are each independently a functional group represented by the formula (2),

    [Formula 2]

    

    In Chemical Formula 2,

    R is a C1-C20 linear hydrocarbon group or a C3-C20 cyclic saturated hydrocarbon group, X is a C1-C5 divalent hydrocarbon group, M is an alkali metal, and a is 0 or 1.
17. The method of claim 16,

    The modified conjugated diene-based polymer is a modified conjugated diene-based polymer including a conjugated diene-based polymer chain (P) comprising a polymerization initiator-derived functional group represented by Formula 1 at one end, and represented by the following Formula 18 or 19 :

    [Formula 18]

    

    In Chemical Formula 18,

    R ⁷⁰ is an alkyl group or alkylsilyl group having 1 to 20 carbon atoms, R ³⁸ is an alkylene group having 1 to 20 carbon atoms, R ³⁹ and R ⁴⁰ are each independently an alkyl group having 1 to 20 carbon atoms, and k is 0, 1 or 2, k + j is 1, 2 or 3, d 'is 1, 2 or 3,

    [Formula 19]

    

    In Chemical Formula 19,

    R ⁴¹ , R ⁴² and R ⁴⁵ are each independently an alkylene group having 1 to 10 carbon atoms, R ⁴³ , R ⁴⁴ , R ⁴⁶ and R ⁴⁷ are each independently an alkyl group having 1 to 10 carbon atoms, and R ⁴⁸ is hydrogen or carbon number An alkyl group of 1 to 10, b and c are each independently 0, 1 or 2, y and q are each independently 1, 2 or 3, and b + y and c + q are each independently 1, 2 or 3,

    A is

    

    or

    

    In this case, R ⁴⁹ , R ⁵⁰ , R ⁵¹ and R ⁵² are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms.
18. The method of claim 17,

    The compound represented by the formula (19) is a modified conjugated diene polymer selected from the group consisting of compounds represented by the following formula 19-1 and formula 19-2:

    [Formula 19-1]

    

    [Formula 19-2]

    

    In Chemical Formula 19-1 and Chemical Formula 19-2,

    R ⁵⁵ , R ⁵⁶ , R ⁵⁸ , R ⁵⁹ , R ⁶² , R ⁶³ , R ⁶⁵ and R ⁶⁶ are each independently an alkyl group having 1 to 10 carbon atoms, and R ⁵³ , R ⁵⁴ , R ⁵⁷ , R ⁶⁰ , R ⁶¹ and R ⁶⁴ are each independently an alkylene group having 1 to 10 carbon atoms, b and c are each independently 0, 1 or 2, y and q are each independently 1, 2 or 3, and b + y and c + q Are each independently 1, 2 or 3.
19. A modified conjugated diene-based polymer comprising a conjugated diene-based polymer chain (P) comprising a polymerization initiator-derived functional group represented by Formula 1 at one end thereof, and represented by the following Formula 20:

    [Formula 1]

    

    In Chemical Formula 1,

    Cy is a cyclic saturated hydrocarbon group of 5 to 8 carbon atoms unsubstituted or substituted with an alkyl group of 1 to 4 carbon atoms, A ¹ and A ² are each independently a functional group represented by the formula (2),

    [Formula 2]

    

    In Chemical Formula 2,

    R is a linear hydrocarbon group having 1 to 20 carbon atoms or a cyclic saturated hydrocarbon group having 3 to 20 carbon atoms, X is a divalent hydrocarbon group having 1 to 5 carbon atoms, M is an alkali metal, a is 0 or 1,

    [Formula 20]

    

    In Chemical Formula 20,

    R ⁶⁷ and R ⁶⁸ are each independently an alkyl group having 1 to 20 carbon atoms, R ⁶⁹ is one functional group selected from the group consisting of Formulas 9 to 12, e is 1 or 2, f is 0 or 1, g is an integer selected from 1 to 3,

    [Formula 9]

    

    [Formula 10]

    

    [Formula 11]

    

    [Formula 12]

    

    In Chemical Formulas 9 to 12,

    R ²² , R ²³ , R ²⁷ , R ²⁸ , R ²⁹ , R ³² and R ³⁵ are each independently a linear or branched alkylene group having 1 to 20 carbon atoms, and R ²⁴ , R ²⁵ , R ²⁶ , R ³⁰ , R ³³ , R ³⁴ , R ³⁶ and R ³⁷ are each independently an alkyl or alkylsilyl group having 1 to 20 carbon atoms, and R ³¹ is a trivalent hydrocarbon group having 1 to 20 carbon atoms.
20. The method of claim 19,

    The compound represented by Formula 20 is a modified conjugated diene-based polymer selected from the group consisting of compounds represented by Formula 21 to 25:

    [Formula 21]

    

    [Formula 22]

    

    [Formula 23]

    

    [Formula 24]

    

    [Formula 25]

    

    In Chemical Formulas 21 to 25,

    Me is a methyl group, Et is an ethyl group, z is 0, 1 or 2, and r is 1 or 2.