KR100780478B1 - Copolymer of styrene-butadiene polymer with high 1,4-cis polybutadiene and preparation method thereof - Google Patents

Abstract

The present invention relates to a copolymer of styrene-butadiene polymer and high 1,4-cis polybutadiene, and to a method of manufacturing the same. More particularly, the present invention relates to a copolymer having a high mechanical properties and excellent mechanical properties. The present invention relates to a copolymer of styrene-butadiene polymer and high 1,4-cis polybutadiene and a method for preparing the same.

Copolymer of styrene-butadiene polymer and high 1,4-cis polybutadiene

Description

Copolymerization of styrene-butadiene polymer with high 1,4-cis polybutadiene and its preparation method {Copolymerization of SBR and High cis Polybutadiene, and its Preparation}

FIG. 1 shows NMR spectrum results of a copolymer of styrene-butadiene polymer and high 1,4-cis polybutadiene according to Example 1. FIG.

FIG. 2 shows NMR spectral results of a copolymer of styrene-butadiene polymer and high 1,4-cis polybutadiene according to Example 2. FIG.

3 shows NMR spectrum results of a copolymer of styrene-butadiene polymer and high 1,4-cis polybutadiene according to Example 3. FIG.

The present invention relates to a copolymer of styrene-butadiene polymer and high 1,4-cis polybutadiene, and to a method of manufacturing the same. More particularly, the present invention relates to a copolymer having a high mechanical properties and excellent mechanical properties. The present invention relates to a copolymer of styrene-butadiene polymer and high 1,4-cis polybutadiene and a method for preparing the same.

Examples of preparing a styrene-butadiene copolymer using an anion catalyst, in particular organolithium, as an initiator include Japanese Patent Application Laid-Open No. 57-87407, Japanese Patent Application Laid-Open 58-162605, US Patent No. 3,281,383, and Japanese Patent Application Laid-Open No. 54-15994. It is introduced. Examples of the method for preparing 1,4-cis polybutadiene using a niodimium catalyst include the methods disclosed in European Patent Nos. 11,184, 652,240 and US Pat. Nos. 4,260,707 and 5,017,539. 1,4-cis polybutadiene was prepared under a nonpolar solvent through a combination of a magnesium carboxyl salt compound, an alkylaluminum compound, and a Lewis acid. The process disclosed in U.S. Patent No. 5,428,119 discloses rare earth carboxyl salts with R ¹ AlCl ₂ , R ¹ ₂ AlCl or R ¹ ₃ Al ₂ Cl ₃ (R ¹ = alkyl groups having 8 to 12 carbon atoms) and R ² ₂ AlH (R ² = A method for producing 1,4-cis polybutadiene using an alkyl group having 2 to 6 carbon atoms is disclosed.

On the other hand, the combination of styrene-butadiene rubber and butadiene rubber used in the tread is well shown in US Patent Nos. 6,815,473 and 6,747,085. In general, however, the styrene-butadiene rubber and butadiene rubber are compounded in the blender during tire production. At this time, due to the butadiene rubber takes a long time to blend, the processing state is likely to be poor.

Accordingly, the present inventors have made efforts to solve the above problems, and as a result, the copolymer of a new styrene-butadiene polymer and a high 1,4-cis polybutadiene through a covalent bond of styrene-butadiene rubber and butadiene rubber in the molecular unit The present invention has been completed by improving the problems of the existing styrene-butadiene rubber and butadiene rubber.

Accordingly, an object of the present invention is to provide a copolymer of styrene-butadiene polymer and 1,4-cis polybutadiene and a preparation method thereof.

The present invention features a copolymer in which a polymer portion having a styrene-butadiene polymer repeating unit and a polymer portion having a high 1,4-cis polybutadiene repeating unit are bonded by a binding material;

In addition, the present invention

1) preparing a styrene-butadiene copolymer with an anionic catalyst in a nonpolar solvent;

2) 95% or more of high 1,4-cis polybutadiene is prepared by polymerizing a 1,3-butadiene or butadiene derivative using a catalyst composed of a rare earth organic acid salt, a Lewis acid containing halogen, and an organoaluminum compound in a nonpolar solvent. Doing;

3) adding and reacting the styrene-butadiene polymer prepared in steps 1) and 2) with a binding compound having a functional group of 2 or more to high 1,4-cis polybutadiene; And

4) combining and reacting the two polymers prepared in step 3)

It is represented by the formula (1) comprising a, characterized by another method for producing a copolymer consisting of repeating units of styrene-butadiene polymer and repeating units of high 1,4-cis polybutadiene.

The present invention will be described in more detail as follows.

The present invention is a copolymer of a styrene-butadiene polymer and a high 1,4-cis polybutadiene having a structure represented by the formula (1) and having a significantly lower compounding viscosity related to improving workability in manufacturing a tire and having excellent mechanical properties. It is about.

The present invention includes a copolymer represented by the following formula (1).

[Formula 1]

A _n -QB _m

In Chemical Formula 1, A is a branch repeating unit (SBR) of a styrene-butadiene polymer prepared by anionic polymerization, and B is prepared using a catalyst composed of a rare earth organic acid salt, a Lewis acid containing halogen, and an organoaluminum compound. Is a repeating unit (PBD) of 95% or more of high 1,4-cis polybutadiene polymer by polymerizing 1,3-butadiene or butadiene derivative, n and m represent an integer of 1 to 5, and Q is a binding substance. It is a binding compound in which a functional group capable of simultaneously binding to a high 1,4-cis polybutadiene polymer active species made of anionic terminal polymer active species and rare earth organic acid salts is present.

1) In the compound in the form of MX ₄ , M is silicon, germanium and tin, and X is chloride, bromide and iodine among the halogen elements.

2) In the compound in the form of R- (NCO) _n , R is an alkyl and allyl group having 1 to 20 carbon atoms, and n is an integer of 3 or more. Among them, hexyl triisocyanate, octyl triisocyanate, dodecyl tetraisocyanate, methylene triphenyl triisocyanate, 1,2,5,7-tetraisocyanate naphthalin, 1,3,7 containing 3 or more isocyanate groups in the compound. Preferred are -triisocyanate naphthalin, tris- (p-isocyanatephenyl) -thiophosphate, carbodiimide-isocyanate cyclic derivative compounds or methylene diphenyl diisocyanate, high molecular compound of polystyryl isocyanate.

의 형태를 취하는 아실할라이드 화합물로서, n은 3 ~ 6의 정수이다. 3)

As an acyl halide compound which takes the form of, n is an integer of 3-6.

The present invention for achieving the above object is largely composed of four steps.

The first step is to prepare a styrene-butadiene copolymer with an anion catalyst in a nonpolar solvent, wherein 1,3-butadiene and styrene are polymerized with an anion catalyst under a nonpolar solvent. At this time, the catalyst and the solvent used in the styrene-butadiene copolymer are as follows.

As the anion catalyst, an organic sodium, organomagnesium, organolithium catalyst, or the like can be used. Preferably it is an organolithium catalyst, and as an organolithium catalyst, it is a hydrocarbon which couple | bonded with at least 1-10 lithium atoms, For example, ethyl lithium, propyl lithium, n-butyl lithium, sec-butyl lithium, tert- butyl lithium, Phenyl lithium, propenyl lithium, hexyl lithium, 1,4-dirithio-n-butane, 1,3-di (2-lithio-2-hexyl) benzene, and the like. More preferably, they are n-butyl lithium and sec-butyl lithium. The organolithium catalyst can be used not only as one kind but also as a mixture of two or more kinds. The amount of the organolithium catalyst used depends on the target molecular weight of the resulting polymer, but is preferably 0.1 to 5 mmol, preferably 0.3 to 4 mmol per 100 g of the monomer. At this time, when the amount of the organic lithium catalyst is less than 0.1 mmol, the polymerization reaction does not occur, and there is a problem that a polymer having a macromolecular weight is polymerized. When the amount of the organic lithium catalyst exceeds 5 mmol, there is a problem that a low molecular weight polymer is produced.

Non-polar solvents used for the polymerization include butane, pentane, hexane, isopentane, heptane, octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, benzene, toluene, ethylbenzene, Xylene etc. are mentioned, Especially preferably, hexane, heptane, cyclohexane, etc. are mentioned. It is preferable to use 1 to 20 parts by weight per 1 part by weight of the monomer. At this time, when the solvent is less than 1 part by weight, there is a problem that a high solution viscosity polymer is polymerized during the polymerization, and when it exceeds 20 parts by weight, the yield of the polymer in the system is low.

The second step is to polymerize 1,3-butadiene or butadiene derivatives using a catalyst consisting of rare earth organic acid salts, halogen-containing Lewis acids and organoaluminum compounds in a non-polar solvent to produce at least 95% high 1,4-cis polybutadiene. In the preparing step, a 1,3-butadiene or butadiene derivative is polymerized with a Ziegler-Natta catalyst formed by mixing a rare earth organic acid salt, a Lewis acid containing a halogen, and an organoaluminum compound in a predetermined ratio to obtain 95% or more of high 1,4- Cis polybutadiene is prepared.

As the rare earth organic acid salt, a compound having a carboxyl group having a high solubility in a nonpolar solvent as a ligand and having 8 to 20 carbon atoms in the carboxyl group is preferable. Specifically, for example, niodymium vertate, niodymium octoate, niodymium naphthenate and the like.

The halogen-containing Lewis acid is an aluminum halogen compound (AlX _n R ¹ _3-n (R ¹ is alkyl, aryl, or hydrogen atom having 1 to 10 carbon atoms, X = F, Cl, Br, I, n = 3) Or inorganic halogen compounds such as boronhalogen, silicon halogen, tin halogen, titanium halogen, and the like, and organic halogen compounds such as t-butyl chloride.

In addition, the organoaluminum compound is typically an alkylaluminum compound represented by AlR ² ₃ (R ² is an alkyl, aryl, or hydrogen atom having 1 to 10 carbon atoms), specifically trimethylaluminum, triethylaluminum, and tripropyl. Aluminum, tributylaluminum, triisobutylaluminum, trihexyl aluminum, diisobutylaluminum hydride, etc. are preferable, and alkyl lithium and alkylmagnesium are also replaceable.

Although these three catalyst components are used in a constant ratio mixture, it is preferable to mix rare earth organic acid salts, Lewis acids containing halogens, and organoaluminum compounds in a molar ratio of 1: 1 to 10: 5 to 40. Outside the above range, there is a problem that the polymerization of the polymer does not occur or 1,4-cis polybutadiene having a Cis content of 95% or less is polymerized.

On the other hand, the polymerization solvent used in this step should be used in the state of removing oxygen and water, non-polar solvents such as cyclohexane, hexane, heptane and toluene is preferred. At this time, the nonpolar solvents used are aliphatic hydrocarbons such as butane, pentane, hexane, isopentane, heptane, octane, isooctane, and the like, and cycloaliphatic solvents include cyclopentane, methylcyclopentane, Cyclohexane, methylcyclohexane, ethylcyclohexane and the like, and aromatic hydrocarbons include, for example, benzene, toluene, ethylbenzene and xylene. It can be used directly for 1,3-butadiene polymerization only when oxygen and water are removed. At this time, the amount of the polymerization solvent is preferably 1 to 20 parts by weight based on 1 part by weight of the monomer, and if less than 1 part by weight, there is a problem due to the high solution viscosity during the polymerization, when more than 20 parts by weight the yield of the polymer in the system is low There is a problem.

The third step is a step of adding and reacting a binding material having two or more functional groups to the styrene-butadiene polymer and the high 1,4-cis polybutadiene, and is a silicone group halogen compound, an isocyanate compound or an acyl halide compound having two or more functional groups. It is added to styrene-butadiene polymer and high 1,4-cis polybutadiene.

The silicon group halogen compound is a compound represented by the following formula (2).

MX ₄

In Formula 2, M is silicon, germanium, and tin, and X is chloride, bromide, or iodine in a halogen element.

The isocyanate compound is a compound represented by the following formula (3).

R- (NCO) _n

In Formula 3, R is an alkyl and allyl group having 1 to 20 carbon atoms, and n is an integer of 3 or more.

Among them, hexyl triisocyanate, octyl triisocyanate, dodecyl tetraisocyanate, methylene triphenyl triisocyanate, 1,2,5,7-tetraisocyanate naphthalin, 1,3,7 containing 3 or more isocyanate groups in the compound. -Triisocyanate naphthalin, tris- (p-isocyanatephenyl) -thiophosphate, a carbodiimide-isocyanate cyclic derivative compound, a high molecular form compound of methylene diphenyl diisocyanate, polystyryl isocyanate, etc. are mentioned.

The acyl halide compound is a compound represented by the following formula (4), the amount of the injection is effective 0.1 to 5.0 g per 100 g of polybutadiene polymer.

In Formula 4, n is an integer of 3 to 6.

The final step is the step of coupling the two polymers, and covalently linking the styrene-butadiene polymer and the high 1,4-cis polybutadiene with the silicon group halogen compound, the isocyanate compound or the acyl halide compound.

After the reaction, the product is obtained by adding a reaction terminator (polyoxyethylene glycol ether organic phosphoric acid) and 2,6-di-t-butyl paracresol, followed by precipitation in methyl alcohol or ethyl alcohol.

When adjusting the molecular weight and molecular weight distribution of 1,4-cis polybutadiene according to the above method, the average weight molecular weight can be adjusted to 100,000 to 5,000,000, the molecular weight distribution can be adjusted to 2.5 to 7.5, the Mooney viscosity ( ML1 + 4, 100 degreeC) can obtain about 10-150 degree.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the Examples.

Example 1

(1) A 10 liter stainless steel polymerization reactor was refluxed with dry nitrogen after washing and drying. Thereafter, 675 g of 1,3-butadiene, 225 g of styrene, 5400 g of cyclohexane solvent, 178 g of tetrahydrofuran (THF) and 3.8 mmol of n-butyllithium (0.5 mol cyclohexane solution) were added to the reaction vessel. Injected. The polymerization was started at 37 ° C., and the contents were stirred for 1 hour.

(2) The Ziegler-Natta catalysts used in the reaction are niodymium vertate (1.0% cyclohexane solution), diethylaluminum chloride and diisobutylaluminum hydride (15% n-hexane solution), and the molar ratio of each catalyst. Is 1: 3: 30, and 1.0 × 10 ^-4 mole of niodymium catalyst was used per 100 g of monomer molecules. At this time, the polymerization solvent is 5 times the monomer content. After nitrogen was sufficiently blown into a 10-L pressure glass reactor, cyclohexane polymerization solvent, monomer butadiene (500 g), diethylaluminum chloride and diisobutylaluminum hydride were added in a predetermined amount and aged at 40 ° C for 30 minutes. Next, the reaction was carried out for 2 hours after adding niodymium vertate.

(3) The above polymers (1) and (2) were stirred in reactor 1 at 60 ° C for 1 hour. Polymerization was carried out using tin tetrachloride (3.9 mmol) as the binding compound.

After the reaction, 2,6-di-t-butylparacresol as an antioxidant and polyoxyethylene phosphate and ethanol were added as a reaction terminator to terminate the reaction to prepare a copolymer of styrene-butadiene polymer and high 1,4-cis polybutadiene. It was. NMR analysis of the microstructure of the copolymer is shown in FIG.

Example 2

(1) A 10 liter stainless steel polymerization reactor was refluxed with dry nitrogen after washing and drying. Thereafter, 675 g of 1,3-butadiene, 225 g of styrene, 5400 g of cyclohexane solvent, 178 g of tetrahydrofuran (THF) and 3.8 mmol of n-butyllithium (0.5 mole cyclohexane solution) were added to the reaction vessel. Injected. The polymerization was started at 37 ° C., and the contents were stirred for 1 hour.

(2) The Ziegler-Natta catalysts used in the reaction are niodymium vertate (1.0% cyclohexane solution), diethylaluminum chloride and diisobutylaluminum hydride (15% n-hexane solution), and the molar ratio of each catalyst. Is 1: 3: 30, and 1.0 x 10 ^-4 mole of niodymium catalyst was used per 100 g of monomer molecules. At this time, the polymerization solvent is 5 times the monomer content. After nitrogen was sufficiently blown into a 10-L pressure glass reactor, cyclohexane polymerization solvent, monomer butadiene (500 g), diethylaluminum chloride and diisobutylaluminum hydride were added in a predetermined amount and aged at 40 ° C for 30 minutes. Next, the reaction was carried out for 2 hours after adding niodymium vertate.

(3) The above polymers (1) and (2) were stirred in reactor 1 at 60 ° C for 1 hour. Polymerization was carried out using methylene diisocyanate (3.9 mmol) as the binding compound.

After the reaction, 2,6-di-t-butylparacresol as an antioxidant and polyoxyethylene phosphate and ethanol were added as a reaction terminator to terminate the reaction to prepare a copolymer of styrene-butadiene polymer and high 1,4-cis polybutadiene. It was. NMR analysis of the microstructure of the copolymer is shown in FIG.

Example 3

(1) A 10 liter stainless steel polymerization reactor was refluxed with dry nitrogen after washing and drying. Thereafter, 675 g of 1,3-butadiene, 225 g of styrene, 5400 g of cyclohexane solvent, 178 g of tetrahydrofuran (THF) and 3.8 mmol of n-butyllithium (0.5 mole cyclohexane solution) were added to the reaction vessel. Injected. The polymerization was started at 37 ° C., and the contents were stirred for 1 hour.

(2) The Ziegler-Natta catalysts used in the reaction are niodymium vertate (1.0% cyclohexane solution), diethylaluminum chloride and diisobutylaluminum hydride (15% n-hexane solution), and the molar ratio of each catalyst. Is 1: 3: 30, and 1.0 x 10 ^-4 mole of niodymium catalyst was used per 100 g of monomer molecules. At this time, the polymerization solvent is 5 times the monomer content. After nitrogen was sufficiently blown into a 10-L pressure glass reactor, cyclohexane polymerization solvent, monomer butadiene (500 g), diethylaluminum chloride and diisobutylaluminum hydride were added in a predetermined amount and aged at 40 ° C for 30 minutes. Next, the reaction was carried out for 2 hours after adding niodymium vertate.

(3) The above polymers (1) and (2) were stirred in reactor 1 at 60 ° C for 1 hour. Triacylchlorobenzene (3.9 mmol) was used as the binding compound and the polymerization reaction was carried out.

After the reaction, 2,6-di-t-butylparacresol as an antioxidant and polyoxyethylene phosphate and ethanol were added as a reaction terminator to terminate the reaction to prepare a copolymer of styrene-butadiene polymer and high 1,4-cis polybutadiene. It was. NMR analysis of the microstructure of the copolymer is shown in FIG.

Example 4

Copolymer of styrene-butadiene and high 1,4-cis polybutadiene prepared in Example 1 (165 g), zinc acid (6.6 g), stearic acid (3.3 g), silica (82.7 g), Si69 (6.6 g), A # 2 oil (30.6 g), antioxidant (3.3 g) was mixed for 5 minutes at 120 ℃ using a 500cc lab mixer.

Example  5

Copolymer of styrene-butadiene and high 1,4-cis polybutadiene prepared in Example 2 (165 g), zinc acid (6.6 g), stearic acid (3.3 g), silica (82.7 g), Si69 (6.6 g), A # 2 oil (30.6 g) and antioxidant (3.3 g) were mixed at 120 ° C. for 5 minutes using a 500 cc lab mixer.

Comparative Example 1

Styrene-butadiene rubber with oil (83 g) and butadiene rubber (114 g), zinc acid (6.6 g), stearic acid (3.3 g), silica (82.7 g), Si69 (6.6 g), antioxidant (3.3 g) was mixed for 5 minutes at 120 ℃ using a 500cc lab mixer.

Comparative Example 2

Styrene-butadiene rubber with oil (83 g) and butadiene rubber (114 g), zinc acid (6.6 g), stearic acid (3.3 g), silica (82.7 g), Si69 (6.6 g), antioxidant (3.3 g) ) Was mixed at 120 ° C. for 5 minutes using a 500cc lab mixer.

Example n-BuLi concentration (mmol) Binding compound Binding Compound Concentration (mmol) Nd concentration (mol) Molar ratio ^* (Nd / Cl / Al) One 3.8 Tin tetrachloride 3.9 1.0 × 10 ^-4 1: 3.0: 30 2 3.8 Methylene diisocyanate 3.9 1.0 × 10 ^-4 1: 3.0: 30 3 3.8 Triacylchlorobenzene 3.9 1.0 × 10 ^-4 1: 3.0: 30 ^* Niodymium Burstate / Diethyl Aluminum Chloride / Diisobutyl Aluminum Hydride

Example Mw ⁽²⁾ Mooney viscosity ⁽³⁾ (ML @ 1 + 4, 100 ℃) Styrene Content (%) ⁽¹⁾ Vinyl content (%) ⁽¹⁾ Molecular Weight Distribution ⁽²⁾ yield(%)  One 302,000 30 13 21 4.5 92  2 395,000 41 13 22 5.1 93  3 495,000 55 12 18 4.9 93

Comparative example Coupling Rate (%) Coupling Number Mw ⁽²⁾ Pattern Viscosity (ML @ 1 + 4 100 ℃) Styrene Content (%) Vinyl content (%) ⁽¹⁾ Molecular Weight Distribution ⁽²⁾ One 51 3.8 630,000 49 30 34 2.18 2 50 3.7 620,000 43 25 62 2.20

(1) Measurement using nuclear magnetic resonance (H-NMR): Molecular microstructure measurement (styrene and vinyl content).

(2) Measurement using gel permeation chromatography (GPC): molecular weight (Mw), molecular weight distribution measurement, coupling rate, number of couplings.

(3) The Mooney viscosity of the rubber is measured using a Mooney viscometer.

Test Example: Checking Properties

[Measurement of physical properties]

Hardness was measured using a SHORE-A hardness tester, and the blendability was also measured through a rubber process analyzer (RPA). Tensile strength, 300% modulus and elongation of the compounded rubber were measured using a universal test machine (UTM) according to the ASTM 3189 Method B method.

Test Items Example 4 Example 5 Comparative Example 1 Comparative Example 2 Mooney viscosity (100 ℃) 30.0 41.0 49.0 43.0 Vulcanization Characteristics (145 ℃) ML (kgfcm) 1.1 1.2 3.0 2.9 MH (kgfcm) 12.9 13.0 19.1 18.5 T50 (min) 17.1 17.2 17.4 18.7 T90 (min) 20.7 20.9 19.9 22.1 Compounded Mooney Viscosity (100 ℃) 42.3 52.7 95.3 90.2 Tensile Properties Strength (Shore A) 61 62 63 62 300% -modulus (kgf / cm ² ) 53 70 65 68 Tensile Strength (kgf / cm ² ) 108 137 129 120 % Elongation 527 539 493 395

As shown in Table 4, in the case of the Example has a very low compounded Mooney viscosity, the tensile strength results equivalent to or greater than the comparative example.

As described in detail above, the copolymer of styrene-butadiene and high 1,4-cis polybutadiene prepared according to the present invention is a problem that occurs when blending styrene-butadiene and butadiene rubber (butadiene rubber does not mix well It is difficult to achieve, but it is expected to be useful in the tire tread compounding by overcoming the high viscosity and exhibiting excellent processability and tensile properties.

Claims (19)

delete A polymer part having a styrene-butadiene polymer repeating unit and a polymer part having a high 1,4-cis polybutadiene repeating unit bonded by a binding material, wherein the copolymer is represented by the following Chemical Formula 1; [Formula 1] A _n -QB _m In Chemical Formula 1, A is a branch repeating unit (SBR) of a styrene-butadiene polymer prepared by anionic polymerization, and B is prepared using a catalyst composed of a rare earth organic acid salt, a Lewis acid containing halogen, and an organoaluminum compound. Is a repeating unit (PBD) of 95% or more high 1,4-cis polybutadiene polymer by polymerizing 1,3-butadiene or butadiene derivative, n and m represent an integer of 1 to 5, and Q is a binding substance. . The copolymer according to claim 2, wherein the binding material is a silicon group halogen compound, an isocyanate compound or an acyl chloride compound having two or more functional groups bonded thereto. The method of claim 3, wherein the silicon compound is a copolymer, characterized in that the compound represented by the formula (2); [Formula 2] MX ₄ In Formula 2, M is silicon, germanium or tin, and X is chloride, bromide or iodine in a halogen element. The copolymer according to claim 3, wherein the isocyanate compound is a compound represented by the following Formula 3; [Formula 3] R- (NCO) _n In Formula 3, R is an alkyl or allyl group having 1 to 20 carbon atoms, and n is an integer of 3 or more. The method of claim 5, wherein the isocyanate compound is hexyl triisocyanate, octyl triisocyanate, dodecyl tetraisocyanate, methylene triphenyl triisocyanate, 1,2,5,7-tetraisocyanate naphthalin, 1,3,7-triisocyanate A copolymer characterized in that it is a high molecular compound of naphthalin, tris- (p-isocyanatephenyl) -thiophosphate, carbodiimide-isocyanate cyclic derivative compound or methylene diphenyl diisocyanate and polystyryl isocyanate. The method of claim 3, wherein the acyl chloride compound is a copolymer characterized in that the compound represented by the following formula (4); [Formula 4]

In Formula 4, n is an integer of 3 to 6. 1) preparing a styrene-butadiene copolymer with an anionic catalyst in a nonpolar solvent; 2) 95% or more of high 1,4-cis polybutadiene is prepared by polymerizing a 1,3-butadiene or butadiene derivative using a catalyst composed of a rare earth organic acid salt, a Lewis acid containing halogen, and an organoaluminum compound in a nonpolar solvent. Doing; 3) adding and reacting the styrene-butadiene polymer prepared in steps 1) and 2) with a binding material having a functional group of 2 or more to the high 1,4-cis polybutadiene; And 4) combining and reacting the two polymers prepared in step 3) A method for preparing a copolymer represented by Chemical Formula 1 comprising a repeating unit of styrene-butadiene polymer and a repeating unit of high 1,4-cis polybutadiene. The method of claim 8, wherein the anionic catalyst is organosodium, organomagnesium or organolithium. 9. The method of claim 8, wherein the rare earth organic acid salt is niodymium vertate, niodymium octoate or niodymium naphthenate. The method of claim 8, wherein the halogen-containing Lewis acid is AlX _n R ¹ _3-n (R ¹ is an alkyl, aryl, or hydrogen atom having 1 to 10 carbon atoms, X = F, Cl, Br, I, n + m = 3). 9. The method of claim 8, wherein the organoaluminum compound is AlR ² ₃ (R ² is an alkyl, aryl, or hydrogen atom having 1 to 10 carbon atoms). The method of claim 8, wherein the non-polar solvent is butane, pentane, hexane, isopentane, heptane, octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, benzene, toluene, ethylbenzene And xylene. The method of claim 8, wherein the binding material is a silicon group halogen compound, an isocyanate compound or an acyl chloride compound having two or more functional groups bonded thereto. The method of claim 14, wherein the silicon group compound is a compound represented by the following formula (2); [Formula 2] MX ₄ In Formula 2, M is silicon, germanium or tin, and X is chloride, bromide or iodine in a halogen element. 15. The method of claim 14, wherein the isocyanate compound is a compound represented by the following formula (3); [Formula 3] R- (NCO) _n In Formula 3, R is an alkyl or allyl group having 1 to 20 carbon atoms, and n is an integer of 3 or more. The method of claim 16, wherein the isocyanate compound is hexyl triisocyanate, octyl triisocyanate, dodecyl tetraisocyanate, methylene triphenyl triisocyanate, 1,2,5,7-tetraisocyanate naphthalin, 1,3,7- A triisocyanate naphthalin, a tris- (p-isocyanatephenyl) -thiophosphate, a carbodiimide-isocyanate cyclic derivative compound or a high molecular form compound of methylene diphenyl diisocyanate, polystyryl isocyanate. The method of claim 14, wherein the acyl chloride compound is a compound represented by the following formula (4); [Formula 4]

In Formula 4, n is an integer of 3 to 6. 10. The method of claim 9, wherein the organolithium is an alkyl compound having 1 to 10 carbon atoms bonded to each other.

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