KR102653221B1 - Modified conjugated diene polymer and preparation method thereof - Google Patents

Abstract

The present invention relates to a modified conjugated diene polymer with excellent compound properties and improved processability and a method for producing the same. The resulting modified conjugated diene polymer has a linearity of less than 0.6 at 100°C, which not only has a high degree of branching and excellent blending processability, but also has excellent compatibility with fillers, resulting in excellent blending properties such as tensile properties and viscoelastic properties. can do.

Description

Modified conjugated diene polymer and preparation method thereof}

The present invention relates to a modified conjugated diene polymer with excellent compound properties and improved processability and a method for producing the same.

Recently, in response to the demand for lower fuel consumption for automobiles, conjugated diene-based polymers are required as rubber materials for tires, which have low running resistance, excellent abrasion resistance and tensile properties, and also have steering stability as represented by wet skid resistance.

In order to reduce the running resistance of a tire, there is a way to reduce the hysteresis loss of vulcanized rubber, and the rebound elasticity of 50°C to 80°C, tan δ, and Goodrich heat generation are used as evaluation indicators for vulcanized rubber. That is, a rubber material with high rebound elasticity at the above temperature or low tan δ or Goodrich heat generation is preferable.

Natural rubber, polyisoprene rubber, and polybutadiene rubber are known as rubber materials with low hysteresis loss, but these have the problem of low wet skid resistance. Accordingly, recently, conjugated diene-based (co)polymers such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) are manufactured by emulsion polymerization or solution polymerization and are used as tire rubber. .

When the BR or SBR above is used as a rubber material for tires, it is usually blended with fillers such as silica or carbon black to obtain the required physical properties of the tire. However, since the affinity between the BR or SBR and the filler is not good, there is a problem in that physical properties including wear resistance, crack resistance, or processability are lowered.

Accordingly, as a method to increase the dispersibility of SBR and fillers such as silica or carbon black, a method of modifying the polymerization active site of the conjugated diene polymer obtained by anionic polymerization using organic lithium into a functional group capable of interacting with the filler was proposed. . For example, methods of modifying the polymerization active terminal of the conjugated diene polymer with a tin-based compound, introducing an amino group, or modifying the polymerization active terminal with an alkoxysilane derivative have been proposed.

In addition, in the living polymer obtained by coordination polymerization using a catalyst composition containing a lanthanum-based rare earth element compound as a method to increase the dispersibility of fillers such as BR and silica or carbon black, the living active end is treated with a specific coupling agent or A method of denaturing using denaturing agents has been developed.

On the other hand, in the case of polymers with modified ends, there is an advantage in that the affinity with the filler is improved and the mixing properties, such as tensile properties and viscoelastic properties, are improved. However, on the other hand, the mixing processability is greatly reduced, so there is a problem of poor processability.

Therefore, when manufacturing SBR or BR, there is a need for a method that can improve processability while providing excellent mixing properties.

JP 3175350 B2

The present invention was developed to solve the problems of the prior art, and its purpose is to provide a modified conjugated diene polymer with excellent compounding properties and improved processability.

Additionally, the present invention aims to provide a method for producing the above-described modified conjugated diene polymer.

In order to solve the above problems, the present invention provides a modified conjugated diene-based polymer having a linearity (-S/R) of less than 0.6 at 100°C and containing a functional group derived from a denaturant represented by the following formula (1):

[Formula 1]

In Formula 1,

R ¹ to R ³ are each independently one or more substituents selected from the group consisting of a halogen group, an alkyl group with 1 to 20 carbon atoms, a cycloalkyl group with 3 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, and -R ⁶ COOR ⁷ Substituted trivalent hydrocarbon group; An unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms; A tetravalent silyl group substituted with two types of substituents selected from the group consisting of an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 20 carbon atoms; A trivalent silyl group substituted with one type of substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 20 carbon atoms; Unsubstituted divalent silyl group; or one hetero atom selected from the group consisting of O and S,

However, R ¹ to R ³ are all trivalent hydrocarbon groups; divalent hydrocarbon group; Tetravalent group; trivalent hydroxyl group; It is not a divalent silyl group or a heteroatom, but at least one of R ¹ to R ³ is a tetravalent silyl group; trivalent hydroxyl group; or divalent silyl group,

R ⁴ is a single bond, an alkylene group having 1 to 20 carbon atoms, or a cycloalkylene group having 3 to 20 carbon atoms,

R ⁵ is a silyl group unsubstituted or substituted with an alkyl group having 1 to 20 carbon atoms; halogen; or -COR ⁸ ,

R ⁶ is a single bond, an alkylene group having 1 to 20 carbon atoms, or a cycloalkylene group having 3 to 20 carbon atoms,

R ⁷ is an alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms,

R ⁸ is an alkoxy group with 1 to 10 carbon atoms, an aryl group with 6 to 30 carbon atoms, a heteroaryl group with 2 to 30 carbon atoms, a heterocycloalkyl group with 2 to 10 carbon atoms, a heteroamine group with 2 to 10 carbon atoms and 3 to 10 carbon atoms. It is a type selected from the group consisting of a disilylamino group.

In addition, the present invention includes the steps of preparing an active polymer by polymerizing a conjugated diene monomer in a hydrocarbon solvent in the presence of a catalyst composition (step 1); Preparing a first polymer by reacting the active polymer with a denaturant represented by Formula 1 (step 2); And the step of adding and mixing a sulfur halide to the first polymer (step 3), wherein the sulfur halide is added in an amount of 0.1 to 0.6 parts by weight based on 100 parts by weight of the first polymer. A method for preparing diene-based polymers is provided:

[Formula 1]

In Formula 1,

R ¹ to R ³ are each independently one or more substituents selected from the group consisting of a halogen group, an alkyl group with 1 to 20 carbon atoms, a cycloalkyl group with 3 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, and -R ⁶ COOR ⁷ Substituted trivalent hydrocarbon group; An unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms; A tetravalent silyl group substituted with two types of substituents selected from the group consisting of an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 20 carbon atoms; A trivalent silyl group substituted with one type of substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 20 carbon atoms; Unsubstituted divalent silyl group; or one hetero atom selected from the group consisting of O and S,

However, R ¹ to R ³ are all trivalent hydrocarbon groups; divalent hydrocarbon group; Tetravalent group; trivalent hydroxyl group; It is not a divalent silyl group or a heteroatom, but at least one of R ¹ to R ³ is a tetravalent silyl group; trivalent hydroxyl group; or divalent silyl group,

R ⁴ is a single bond, an alkylene group having 1 to 20 carbon atoms, or a cycloalkylene group having 3 to 20 carbon atoms,

R ⁵ is a silyl group unsubstituted or substituted with an alkyl group having 1 to 20 carbon atoms; halogen; or -COR ⁸ ,

R ⁶ is a single bond, an alkylene group having 1 to 20 carbon atoms, or a cycloalkylene group having 3 to 20 carbon atoms,

R ⁷ is an alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms,

R ⁸ is an alkoxy group with 1 to 10 carbon atoms, an aryl group with 6 to 30 carbon atoms, a heteroaryl group with 2 to 30 carbon atoms, a heterocycloalkyl group with 2 to 10 carbon atoms, a heteroamine group with 2 to 10 carbon atoms and 3 to 10 carbon atoms. It is a type selected from the group consisting of a disilylamino group.

The modified conjugated diene polymer according to the present invention has a linearity of less than 0.6 at 100°C, which not only has a high degree of branching and excellent mixing processability, but also has excellent affinity with fillers by containing a functional group derived from the modifier of Formula 1. The compound properties such as tensile properties and viscoelastic properties can be excellent.

In addition, the method for producing the modified conjugated diene-based polymer according to the present invention prepares a first polymer containing a functional group using a denaturing agent represented by Formula 1, and mixes the first polymer with a sulfur halide to form a polymer chain. By easily introducing functional groups derived from the modifier, the degree of branching of the polymer chain can be increased, and thus a modified conjugated diene-based polymer with excellent tensile and viscoelastic properties and excellent mixing processability can be manufactured.

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

Terms or words used in this specification and claims should not be construed as limited to their usual or dictionary meanings, and the inventor may appropriately define the concept of terms in order to explain his or her invention in the best way. It must be interpreted with meaning and concept consistent with the technical idea of the present invention based on the principle that it is.

In the present invention, linearity (-S/R), unless otherwise specified, is measured using a Mooney viscometer, for example, a large rotor of Monsanto's MV2000E, at 100°C and a rotor speed of 2±0.02rpm, measuring the polymer. After leaving it at room temperature (23±5°C) for more than 30 minutes, 27±3g is collected, filled inside the die cavity, and the Mooney viscosity is measured while operating the platen and applying torque. Mooney viscosity appears as the torque is released. This is a value obtained by measuring the slope of the change in viscosity and taking its absolute value.

In the present invention, unless otherwise specified, the Mooney viscosity is measured by measuring the polymer at room temperature (23±5°C) using a Mooney viscometer, for example, a large rotor of Monsanto's MV2000E, under conditions of 100°C and a rotor speed of 2±0.02rpm. ), after leaving it for more than 30 minutes, 27 ± 3g was collected, filled inside the die cavity, and measured by operating the platen and applying torque.

In the present invention, unless otherwise specified, the weight average molecular weight, number average molecular weight, and molecular weight distribution are determined by dissolving the polymer in tetrahydrofuran (THF) for 30 minutes at 40°C and then using gel permeation chromatography (GPC). It was measured by loading and flowing. At this time, the column used was a combination of two PLgel Olexis columns and one PLgel mixed-C column from Polymer Laboratories, and all newly replaced columns were mixed bed type columns. And polystyrene was used as a gel permeation chromatography standard material (GPC standard material).

In the present invention, unless otherwise specified, the tensile strength and 300% modulus are the tensile strength and modulus at 300% elongation (M-300%) of the vulcanized product in accordance with ASTM D412 after vulcanizing the rubber composition containing the polymer at 150°C for t90 minutes. ) was measured.

In the present invention, unless otherwise specified, the viscoelastic properties are measured by measuring the viscoelastic coefficient (Tan δ) at 60°C at a frequency of 10 Hz, Prestrain of 3%, and Dynamic Strain of 3% using DMTS 500N from Gabo, Germany.

The present invention provides a modified conjugated diene polymer with excellent blend properties such as tensile properties and viscoelastic properties, and improved blend processability due to a high degree of branching.

The modified conjugated diene-based polymer according to an embodiment of the present invention can have characteristics such as molecular weight distribution, linearity, and Mooney viscosity optimized to have excellent blending properties and blending processability by being manufactured through a manufacturing method described later. , it may be a lanthanum-based rare earth element-catalyzed modified conjugated diene-based polymer.

Specifically, the modified conjugated diene polymer according to an embodiment of the present invention has a linearity (-S/R) of less than 0.6 at 100°C and contains a functional group derived from a denaturant represented by the following formula (1): do.

[Formula 1]

In Formula 1,

R ¹ to R ³ are each independently one or more substituents selected from the group consisting of a halogen group, an alkyl group with 1 to 20 carbon atoms, a cycloalkyl group with 3 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, and -R ⁶ COOR ⁷ Substituted trivalent hydrocarbon group; An unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms; A tetravalent silyl group substituted with two types of substituents selected from the group consisting of an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 20 carbon atoms; A trivalent silyl group substituted with one type of substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 20 carbon atoms; Unsubstituted divalent silyl group; or one hetero atom selected from the group consisting of O and S,

However, R ¹ to R ³ are all trivalent hydrocarbon groups; divalent hydrocarbon group; Tetravalent group; trivalent hydroxyl group; It is not a divalent silyl group or a heteroatom, but at least one of R ¹ to R ³ is a tetravalent silyl group; trivalent hydroxyl group; or divalent silyl group,

R ⁴ is a single bond, an alkylene group having 1 to 20 carbon atoms, or a cycloalkylene group having 3 to 20 carbon atoms,

R ⁵ is a silyl group unsubstituted or substituted with an alkyl group having 1 to 20 carbon atoms; halogen; or -COR ⁸ ,

R ⁶ is a single bond, an alkylene group having 1 to 20 carbon atoms, or a cycloalkylene group having 3 to 20 carbon atoms,

R ⁷ is an alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms,

R ⁸ is an alkoxy group with 1 to 10 carbon atoms, an aryl group with 6 to 30 carbon atoms, a heteroaryl group with 2 to 30 carbon atoms, a heterocycloalkyl group with 2 to 10 carbon atoms, a heteroamine group with 2 to 10 carbon atoms and 3 to 10 carbon atoms. It is a type selected from the group consisting of a disilylamino group.

The term 'trivalent hydrocarbon group substituted with a substituent' as used in the present invention refers to a hydrocarbon group that is trivalently substituted from the bond within the ring containing the N atom (divalent) and the bond with the substituent defined above (monovalent). The substituted trivalent hydrocarbon group may be a trivalent hydrocarbon group having 1 to 10 or 1 to 5 carbon atoms forming a ring with the N atom, excluding the carbon number of the substituent defined above.

In addition, unless otherwise defined in the present invention, a 'tetravalent silyl group substituted with a substituent' refers to the total number of bonds (divalent) in the ring containing the N atom and each bond (total divalent) with the substituents defined above. It may mean a tetravalently substituted silyl group.

In addition, unless otherwise defined in the present invention, 'trivalent silyl group substituted with a substituent' is a total of trivalent groups from the bond within the ring containing the N atom (divalent) and the bond with the substituent defined above (monovalent). It may mean a substituted silyl group.

The term 'single bond' used in the present invention may mean a single covalent bond itself, not containing separate atoms or molecular groups.

As used in the present invention, the term 'silyl group substituted or unsubstituted with an alkyl group having 1 to 20 carbon atoms' refers to a type selected from the group consisting of an unsubstituted monovalent silyl group and a divalent to tetravalent silyl group substituted with the alkyl group. can do.

The denaturant according to the present invention may be the compound represented by Formula 1, or may contain another compound capable of denaturing the conjugated diene polymer together with the compound represented by Formula 1.

In addition, the modifier according to the present invention includes a cyclized tertiary amine derivative like the compound represented by Formula 1, and thus has the activity in the conjugated diene polymer, specifically, the conjugated diene polymer having an active organic metal moiety. The conjugated diene-based polymer can be modified by imparting a functional group to the conjugated diene-based polymer through a substitution or addition reaction with an organometallic moiety.

Meanwhile, the modifier according to an embodiment of the present invention can improve the blending properties between the polymer and the filler by including a functional group in the molecule that can increase the affinity with the filler, and furthermore, as described above, the cyclized tertiary amine By including the derivative, the dispersibility of the filler can be improved by preventing agglomeration between fillers in the rubber composition. For example, when silica, a type of inorganic filler, is used as a filler, aggregation is likely to occur due to hydrogen bonding between hydroxyl groups present on the surface of silica, and the cyclized tertiary amino group interferes with the hydrogen bonding between hydroxyl groups of silica, thereby dispersibility can be improved. In this way, the modifier has a structure capable of maximizing the blending properties of the modified conjugated diene-based polymer, and thus a modified conjugated diene-based polymer with an excellent balance of mechanical properties such as wear resistance and processability of the rubber composition can be efficiently manufactured.

According to one embodiment of the present invention, in Formula 1, R ¹ to R ³ are each independently a trivalent hydrocarbon group substituted with -R ⁶ COOR ⁷ ; An unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms; A tetravalent silyl group substituted with an alkyl group having 1 to 20 carbon atoms; A trivalent silyl group substituted with an alkyl group having 1 to 20 carbon atoms; or O, provided that R ¹ to R ³ are all trivalent hydrocarbon groups; divalent hydrocarbon group; Tetravalent group; trivalent hydroxyl group; or O, but at least one of R ¹ to R ³ is a tetravalent silyl group; trivalent hydroxyl group; Or it may be a divalent silyl group, R ⁴ may be a single bond or an alkylene group having 1 to 20 carbon atoms, and R ⁵ may be a silyl group substituted with an alkyl group having 1 to 20 carbon atoms; halogen; or -COR ⁸ , R ⁶ may be a single bond, R ⁷ may be an alkyl group of 1 to 20 carbon atoms, and R ⁸ may be an alkoxy group of 1 to 10 carbon atoms, an aryl group of 6 to 30 carbon atoms, or a carbon number of It may be one selected from the group consisting of a heteroaryl group with 2 to 30 carbon atoms, a heterocycloalkyl group with 2 to 10 carbon atoms, a heteroamine group with 2 to 10 carbon atoms, and a disilylamino group with 3 to 10 carbon atoms.

Additionally, the denaturant represented by Formula 1 may be a compound represented by Formula 2 below:

[Formula 2]

In Formula 2, R ² is a trivalent hydrocarbon group substituted with one or more substituents selected from the group consisting of a halogen group, an alkyl group with 1 to 20 carbon atoms, a cycloalkyl group with 3 to 20 carbon atoms, and an aryl group with 6 to 30 carbon atoms; Or, it may be an unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, R ⁴ may be an alkylene group having 1 to 20 carbon atoms, or a cycloalkylene group having 3 to 20 carbon atoms, and R ⁵ may be an alkyl group having 1 to 20 carbon atoms. Substituted or unsubstituted silyl group; halogen; Or it may be -COR ⁸ , and R ⁸ is an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a heterocycloalkyl group having 2 to 10 carbon atoms, or a COR group having 2 to 10 carbon atoms. It may be one selected from the group consisting of a heteroamine group and a disilylamino group having 3 to 10 carbon atoms, and R ¹² to R ¹⁵ may each independently be hydrogen or an alkyl group having 1 to 20 carbon atoms.

As another example, in Formula 2, R ² may be an unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, R ⁴ may be an alkylene group having 1 to 20 carbon atoms, and R ⁵ may be an alkyl group having 1 to 20 carbon atoms. A substituted or unsubstituted silyl group; halogen; Or it may be -COR ⁸ , and R ⁸ is an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a heterocycloalkyl group having 2 to 10 carbon atoms, or a COR group having 2 to 10 carbon atoms. It may be one selected from the group consisting of a heteroamine group and a disilylamino group having 3 to 10 carbon atoms, and R ¹² to R ¹⁵ may each independently be hydrogen or an alkyl group having 1 to 20 carbon atoms.

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

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

In addition, the modified conjugated diene-based polymer according to an embodiment of the present invention may have a linearity (-S/R) of less than 0.6 at 100°C, specifically, 0.4 or more and less than 0.6, or 0.44 or more and less than 0.58. .

The linearity (-S/R: stress/relaxation) represents the change in stress in response to the same amount of strain generated in the material. Through the linearity, the degree of stress of the modified conjugated diene polymer The degree of branching can be predicted. For example, the lower the linearity, the higher the degree of branching. Additionally, the above numerical values represent absolute values.

On the other hand, if the linearity is too low, that is, if the degree of branching is too high, processability is improved when applied to a rubber composition, but problems such as increased rotational resistance and decreased mechanical properties may occur.

However, the modified conjugated diene-based polymer according to an embodiment of the present invention has a linearity in the above range, so that when applied to a rubber composition, both the blend properties such as tensile properties and viscoelasticity and the blend processability are excellent.

In addition, the modified conjugated diene-based polymer according to an embodiment of the present invention may have a Mooney viscosity (MV) of 20 or more and 100 or less at 100°C, specifically, 30 or more and 80 or less, 35 or more and 75 or less. Or it may be 40 or more and 70 or less. The modified conjugated diene-based polymer according to the present invention may have excellent processability by having a Mooney viscosity in the above-mentioned range.

In the present invention, the Mooney viscosity was measured using a Mooney viscometer, for example, a large rotor of Monsanto's MV2000E, at 100°C and a rotor speed of 2±0.02rpm. Specifically, after leaving the polymer at room temperature (23 ± 5°C) for more than 30 minutes, 27 ± 3 g was collected, filled inside the die cavity, and the Mooney viscosity was measured while operating the platen and applying torque. In addition, the linearity (-S/R) was obtained by measuring the slope of the Mooney viscosity change that appears as the torque is released after measuring the Mooney viscosity and taking its absolute value.

In addition, the modified conjugated diene-based polymer may have a molecular weight distribution (Mw/Mn) of 2.0 to 3.5, and more specifically, may have a molecular weight distribution of 2.5 to 3.5, 2.5 to 3.2, or 2.6 to 3.0.

In the present invention, the molecular weight distribution of the modified conjugated diene polymer can be calculated from the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn). At this time, the number average molecular weight (Mn) is the common average of the molecular weights of individual polymers calculated by measuring the molecular weight of n polymer molecules, calculating the total of these molecular weights, and dividing by n, and the weight average molecular weight (Mw) is the polymer Indicates the molecular weight distribution of the composition. All molecular weight averages can be expressed in grams per mole (g/mol). In addition, the weight average molecular weight and number average molecular weight may each refer to polystyrene conversion molecular weight analyzed by gel permeation chromatography (GPC).

The modified conjugated diene-based polymer according to an embodiment of the present invention satisfies the above- ^described molecular weight distribution conditions and may have ^a weight average molecular weight (Mw) of 3 The ^molecular weight (Mn) may be ^1.0 It is easy to use and has excellent mechanical properties and property balance of the rubber composition. The weight average ^{molecular weight} may ^be , for example ^{, 5} It may be ^{10 5} g/mol, or ^2.0

More specifically, when the modified conjugated diene-based polymer according to an embodiment of the present invention satisfies the weight average molecular weight (Mw) and number average molecular weight conditions along with the molecular weight distribution described above, it is applied to a rubber composition. It has excellent tensile properties, viscoelasticity, and processability, and has an excellent balance of physical properties between them.

In addition, the conjugated diene-based polymer may have a cis-1,4 bond content of the conjugated diene portion measured by Fourier transform infrared spectroscopy (FT-IR) of 95% or more, more specifically, 98% or more. Accordingly, when applied to a rubber composition, the wear resistance, crack resistance, and ozone resistance of the rubber composition can be improved.

In addition, the modified conjugated diene-based polymer may have a vinyl content of the conjugated diene portion measured by Fourier transform infrared spectroscopy of 5% or less, more specifically, 2% or less. If the vinyl content in the polymer exceeds 5%, there is a risk that the wear resistance, crack resistance, and ozone resistance of the rubber composition containing it may deteriorate.

Here, the cis-1,4 bond content and vinyl content in the polymer by Fourier transform infrared spectroscopy (FT-IR) are obtained from the conjugated diene-based polymer prepared at a concentration of 5 mg/mL using carbon disulfide in the same cell as a blank. After measuring the FT-IR transmittance spectrum of a carbon disulfide solution, the maximum peak value (a, baseline) around 1130 cm ^-1 of the measured spectrum, and the minimum peak around 967 cm ^-1 indicating trans-1,4 bond. Each content was calculated using the value (b), the minimum peak value (c) around 911 cm ^-1 indicating a vinyl bond, and the minimum peak value (d) around 736 cm ^-1 indicating a cis-1,4 bond. It was saved.

Additionally, the present invention provides a method for producing the above modified conjugated diene polymer.

The production method according to an embodiment of the present invention includes preparing an active polymer by polymerizing a conjugated diene monomer in a hydrocarbon solvent in the presence of a catalyst composition (step 1); Preparing a first polymer by reacting the active polymer with a denaturant represented by the following formula (1) (step 2); And adding a sulfur halide to the first polymer and mixing for at least 15 minutes (step 3), wherein the sulfur halide is added in an amount of 0.1 to 0.6 parts by weight based on 100 parts by weight of the first polymer. do.

[Formula 1]

In Formula 1, R ¹ to R ⁵ are as defined above.

Step 1 is a step for preparing an active polymer containing an activated organometallic moiety derived from a catalyst composition, and can be performed by polymerizing a conjugated diene monomer in the presence of the catalyst composition in a hydrocarbon solvent.

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

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 catalyst composition may include a lanthanum-based rare earth element-containing compound.

The catalyst composition may be used in an amount such that the lanthanum series rare earth element-containing compound is 0.1 mmol to 0.5 mmol based on a total of 100 g of conjugated diene monomer. Specifically, the lanthanum series rare earth element-containing compound may be used in the conjugated diene. It may be used in an amount of 0.1 mmol to 0.4 mmol, more specifically 0.1 mmol to 0.25 mmol, based on a total of 100 g of monomers.

The lanthanum-based rare earth element-containing compound is not particularly limited, but may be any one or two or more compounds of rare earth metals with atomic numbers 57 to 71, such as lanthanum, neodymium, cerium, gadolinium, or praseodymium, and more specifically, neodymium. It may be a compound containing one or more selected from the group consisting of , lanthanum, and gadolinium.

In addition, the lanthanum-based rare earth element-containing compound is the rare earth element-containing carboxylate (e.g., neodymium acetate, neodymium acrylate, neodymium methacrylate, neodymium gluconate, neodymium citrate, neodymium fumarate, neodymium lactate, neodymium maleate, neodymium oxalate, neodymium 2-ethylhexanoate, neodymium neodecanoate, etc.); Organophosphates (e.g. neodymium dibutyl phosphate, neodymium dipentyl phosphate, neodymium dihexyl phosphate, neodymium diheptyl phosphate, neodymium dioctyl phosphate, neodymium bis(1-methylheptyl) phosphate, neodymium bis(2-ethylhexyl) phosphate, or neodymium didecyl phosphate, etc.); Organic phosphonates (e.g. neodymium butyl phosphonate, neodymium pentyl phosphonate, neodymium hexyl phosphonate, neodymium heptyl phosphonate, neodymium octyl phosphonate, neodymium (1-methyl heptyl) phosphonate, neodymium (2-ethylhexyl) phosphonate, neodymium disyl phosphonate, neodymium dodecyl phosphonate or neodymium octadecyl phosphonate, etc.); Organic phosphinates (e.g. neodymium butylphosphinate, neodymium pentylphosphinate, neodymium hexyl phosphinate, neodymium heptyl phosphinate, neodymium octyl phosphinate, neodymium (1-methylheptyl) phosphinate, or neodymium (2-ethylhexyl) phosphinate, etc.); Carbamates (e.g. neodymium dimethyl carbamate, neodymium diethyl carbamate, neodymium diisopropyl carbamate, neodymium dibutyl carbamate or neodymium dibenzyl carbamate, etc.); dithiocarbamate (e.g., neodymium dimethyldithiocarbamate, neodymium diethyldithiocarbamate, neodymium diisopropyl dithiocarbamate, or neodymium dibutyldithiocarbamate, etc.); xanthogenates (e.g., neodymium methyl xanthogenate, neodymium ethyl xanthogenate, neodymium isopropyl xanthogenate, neodymium butyl xanthogenate, or neodymium benzyl xanthogenate, etc.); β-diketonates (e.g. neodymium acetylacetonate, neodymium trifluoroacetyl acetonate, neodymium hexafluoroacetyl acetonate or neodymium benzoyl acetonate, etc.); Alkoxides or allyloxides (e.g. neodymium methoxide, neodymium ethoxide, neodymium isopropoxide, neodymium phenoxide or neodymium nonyl phenoxide, etc.); Halides or pseudohalides (such as neodymium fluoride, neodymium chloride, neodymium bromide, neodymium iodide, neodymium cyanide, neodymium cyanate, neodymium thiocyanate, or neodymium azide); Oxyhalides (e.g., neodymium oxyfluoride, neodymium oxychloride, or neodymium oxybromide, etc.); or an organic lanthanide rare earth element-containing compound containing one or more rare earth element-carbon bonds (e.g., Cp ₃ Ln, Cp ₂ LnR, Cp ₂ LnCl, CpLnCl ₂ , CpLn (cyclooctatetraene), (C ₅ Me ₅ ) ₂ LnR, LnR ₃ , Ln (allyl) ₃ , or Ln (allyl) ₂ Cl, wherein Ln is a rare earth metal element and R is a hydrocarbyl group), any one of these or It may contain mixtures of two or more.

Specifically, the lanthanum-based rare earth element-containing compound may include a neodymium compound represented by the following formula (3).

[Formula 3]

In Formula 3, Ra to Rc are independently hydrogen or an alkyl group having 1 to 12 carbon atoms, but Ra to Rc are not all hydrogen at the same time.

More specifically, the neodymium compound is Nd (2-ethylhexanoate) ₃ , Nd (2,2-dimethyl decanoate) ₃ , Nd (2,2-diethyl decanoate) ₃ , Nd (2, 2-dipropyl decanoate) ₃ , Nd (2,2-dibutyl decanoate) ₃ , Nd (2,2-dihexyl decanoate) ₃ , Nd (2,2-dioctyl decanoate) ₃ , Nd(2-ethyl-2-propyl decanoate) ₃ , Nd(2-ethyl-2-butyl decanoate) ₃ , Nd(2-ethyl-2-hexyl decanoate) ₃ , Nd(2 -Propyl-2-butyl decanoate) ₃ , Nd (2-propyl-2-hexyl decanoate) ₃ , Nd (2-propyl-2-isopropyl decanoate) ₃ , Nd (2-butyl-2 -hexyl decanoate) ₃ , Nd (2-hexyl-2-octyl decanoate) ₃ , Nd (2,2-diethyl octanoate) ₃ , Nd (2,2-dipropyl octanoate) ₃ , Nd(2,2-dibutyl octanoate) ₃ , Nd(2,2-dihexyl octanoate) ₃ , Nd(2-ethyl-2-propyl octanoate) ₃ , Nd(2-ethyl- 2-hexyl octanoate) ₃ , Nd (2,2-diethyl nonanoate) ₃ , Nd (2,2-dipropyl nonanoate) ₃ , Nd (2,2-dibutyl nonanoate) ₃ , Nd (2,2-dihexyl nonanoate) ₃ , Nd (2-ethyl-2-propyl nonanoate) ₃ and Nd (2-ethyl-2-hexyl nonanoate) ₃ 1 selected from the group consisting of It may be more than one species.

In addition, as another example, considering the excellent solubility in solvents without concerns about oligomerization, the conversion rate to catalytically active species, and the resulting excellent effect of improving catalytic activity, the lanthanum-based rare earth element-containing compound is more specifically Formula 3 where R _a is an alkyl group having 4 to 12 carbon atoms, and R _b and R _c are independently hydrogen or an alkyl group having 2 to 8 carbon atoms, provided that R _b and R _c may be neodymium-based compounds that are not hydrogen at the same time.

As a more specific example, in Formula 3, R _a is an alkyl group having 6 to 8 carbon atoms, and R _b and R _c may each independently be hydrogen or an alkyl group having 2 to 6 carbon atoms, wherein R _b and R _c are At the same time, it may not be hydrogen, and specific examples include Nd (2,2-diethyl decanoate) ₃ , Nd (2,2-dipropyl decanoate) ₃ , Nd (2,2-dibutyl decanoate) ) ₃ , Nd (2,2-dihexyl decanoate) ₃ , Nd (2,2-dioctyl decanoate) ₃ , Nd (2-ethyl-2-propyl decanoate) ₃ , Nd (2- Ethyl-2-butyl decanoate) ₃ , Nd (2-ethyl-2-hexyl decanoate) ₃ , Nd (2-propyl-2-butyl decanoate) ₃ , Nd (2-propyl-2-hexyl Decanoate) ₃ , Nd (2-propyl-2-isopropyl decanoate) ₃ , Nd (2-butyl-2-hexyl decanoate) ₃ , Nd (2-hexyl-2-octyl decanoate) ₃ , Nd (2-t-butyl decanoate) ₃ , Nd (2,2-diethyl octanoate) ₃ , Nd (2,2-dipropyl octanoate) ₃ , Nd (2,2-di Butyl octanoate) ₃ , Nd (2,2-dihexyl octanoate) ₃ , Nd (2-ethyl-2-propyl octanoate) ₃ , Nd (2-ethyl-2-hexyl octanoate) ₃ , Nd (2,2-diethyl nonanoate) ₃ , Nd (2,2-dipropyl nonanoate) ₃ , Nd (2,2-dibutyl nonanoate) ₃ , Nd (2,2-di It may be one or more selected from the group consisting of hexyl nonanoate) ₃ , Nd (2-ethyl-2-propyl nonanoate) ₃ , and Nd (2-ethyl-2-hexyl nonanoate) ₃ , among which the above Neodymium-based compounds include Nd (2,2-diethyl decanoate) ₃ , Nd (2,2-dipropyl decanoate) ₃ , Nd (2,2-dibutyl decanoate) ₃ , Nd (2, It may be one or more selected from the group consisting of 2-dihexyl decanoate) ₃ , and Nd (2,2-dioctyl decanoate) ₃ .

More specifically, in Formula 3, R _a is an alkyl group having 6 to 8 carbon atoms, and R _b and R _c may each independently be an alkyl group having 2 to 6 carbon atoms.

In this way, the neodymium-based compound represented by Formula 3 includes a carboxylate ligand containing an alkyl group of various lengths of 2 or more carbon atoms at the α (alpha) position as a substituent, thereby inducing a steric change around the neodymium center metal to form a compound. It can block liver aggregation, and thus has the effect of suppressing oligomerization. In addition, such neodymium-based compounds have high solubility in solvents and have the effect of increasing the conversion rate to catalytically active species by reducing the proportion of neodymium located in the central portion where conversion to catalytically active species is difficult.

Additionally, the solubility of the lanthanum-based rare earth element-containing compound according to an embodiment of the present invention may be about 4 g or more per 6 g of non-polar solvent at room temperature (25°C).

In the present invention, the solubility of a lanthanum-based rare earth element-containing compound refers to the degree to which it dissolves clearly without clouding, and by exhibiting such high solubility, it can exhibit excellent catalytic activity.

Additionally, the lanthanum-based rare earth element-containing compound according to an embodiment of the present invention may be used in the form of a reactant with a Lewis base. This reactant has the effect of improving the solubility of compounds containing lanthanum rare earth elements in solvents by using a Lewis base and enabling them to be stored in a stable state for a long period of time. For example, the Lewis base may be used in an amount of 30 moles or less, or 1 to 10 moles per mole of rare earth element. The Lewis base may be, for example, acetylacetone, tetrahydrofuran, pyridine, N,N-dimethylformamide, thiophene, diphenyl ether, triethylamine, an organophosphorus compound, or a monovalent or divalent alcohol.

Meanwhile, the catalyst composition may further include at least one of an alkylating agent, a halide, and a conjugated diene monomer along with a lanthanum-based rare earth element-containing compound.

That is, the catalyst composition according to an embodiment of the present invention may include a lanthanum-based rare earth element-containing compound, and may further include at least one of an alkylating agent, a halide, and a conjugated diene-based monomer.

Hereinafter, the (a) alkylating agent, (b) halide, and (c) conjugated diene monomer will be separately described in detail.

(a) Alkylating agent

The alkylating agent is an organometallic compound capable of transferring a hydrocarbyl group to another metal and may serve as a cocatalyst. The alkylating agent may be used without particular limitation as long as it is commonly used as an alkylating agent in the production of diene polymers. For example, an organoaluminum compound, an organomagnesium compound, or an organolithium compound, it is soluble in the polymerization solvent and forms a metal-carbon bond. It may be an organometallic compound containing.

Specifically, the organic aluminum compounds include trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, triisopropyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, tri-t-butyl aluminum, and tripentyl. Alkyl aluminum such as aluminum, trihexyl aluminum, tricyclohexyl aluminum, and trioctyl aluminum; Diethylaluminum hydride, di-n-propyl aluminum hydride, diisopropyl aluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride (DIBAH), di-n-octyl aluminum hydride, Diphenyl aluminum hydride, di-p-tolyl aluminum hydride, dibenzyl aluminum hydride, phenylethyl aluminum hydride, phenyl-n-propyl aluminum hydride, phenyl isopropyl aluminum hydride, phenyl-n-butylaluminum hydride. hydride, phenyl isobutylaluminum hydride, phenyl-n-octyl aluminum hydride, p-tolylethylaluminum hydride, p-tolyl-n-propylaluminum hydride, p-tolylisopropyl aluminum hydride, p-tolyl- n-butyl aluminum hydride, p-tolyl isobutyl aluminum hydride, p-tolyl-n-octyl aluminum hydride, benzyl ethyl aluminum hydride, benzyl-n-propyl aluminum hydride, benzyl isopropyl aluminum hydride, benzyl Dihydrocarbyl aluminum hydrides such as -n-butyl aluminum hydride, benzylisobutyl aluminum hydride, or benzyl-n-octyl aluminum hydride; Hydrocarbylaluminum dihydride, such as ethyl aluminum dihydride, n-propyl aluminum dihydride, isopropyl aluminum dihydride, n-butyl aluminum dihydride, isobutyl aluminum dihydride, or n-octyl aluminum dihydride. Hydride, etc. can be mentioned. The organic magnesium compounds include alkyl magnesium compounds such as diethyl magnesium, di-n-propyl magnesium, diisopropyl magnesium, dibutyl magnesium, dihexyl magnesium, diphenyl magnesium, or dibenzyl magnesium, and the like. Examples of the organic lithium compound include alkyl lithium compounds such as n-butyllithium.

Additionally, the organoaluminum compound may be aluminoxane.

The aluminoxane may be prepared by reacting water with a trihydrocarbyl aluminum compound. Specifically, it may be a straight-chain aluminoxane of the formula 4a below or a cyclic aluminoxane of the formula 4b below.

[Formula 4a]

[Formula 4b]

In Formulas 4a and 4b, R is a monovalent organic group bonded to an aluminum atom through a carbon atom and may be a hydrocarbyl group, and x and y are independently an integer of 1 or more, specifically 1 to 100. , more specifically, it may be an integer from 2 to 50.

More specifically, the aluminoxane is methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethyl aluminoxane, n-propyl aluminoxane, isopropyl aluminoxane, butyl aluminoxane, isobutyl aluminoxane, n -Pentyl aluminoxane, neopentyl aluminoxane, n-hexyl aluminoxane, n-octyl aluminoxane, 2-ethylhexyl aluminoxane, cyclohexyl aluminoxane, 1-methylcyclopentyl aluminoxane, phenyl aluminoxane or 2,6- It may be dimethylphenyl aluminoxane, etc., and any one or a mixture of two or more of these may be used.

In addition, the modified methylaluminoxane is obtained by replacing the methyl group of methylaluminoxane with a modification group (R), specifically a hydrocarbon group having 2 to 20 carbon atoms, and may be a compound represented by the following formula (5).

[Formula 5]

In Formula 5, R is as defined above, and m and n may be independently integers of 2 or more. Additionally, in Formula 5, Me represents a methyl group.

Specifically, in Formula 5, R is an alkyl group with 2 to 20 carbon atoms, a cycloalkyl group with 3 to 20 carbon atoms, an alkenyl group with 2 to 20 carbon atoms, a cycloalkenyl group with 3 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, It may be an arylalkyl group with 7 to 20 carbon atoms, an alkylaryl group with 7 to 20 carbon atoms, an allyl group, or an alkynyl group with 2 to 20 carbon atoms, and more specifically, a 2-carbon atom group such as an ethyl group, isobutyl group, hexyl group, or octyl group. It may be an alkyl group of 10 to 10, and more specifically, it may be an isobutyl group.

More specifically, the modified methylaluminoxane may be one in which about 50 mol% to 90 mol% of the methyl group of methylaluminoxane is replaced with the hydrocarbon group described above. When the content of substituted hydrocarbon groups in modified methylaluminoxane is within the above range, alkylation can be promoted and catalytic activity can be increased.

Such modified methylaluminoxane can be manufactured according to conventional methods, and specifically, it can be manufactured using trimethylaluminum and alkyl aluminum other than trimethylaluminum. At this time, the alkyl aluminum may be triisobutyl aluminum, triethyl aluminum, trihexyl aluminum, or trioctyl aluminum, and any one or a mixture of two or more of these may be used.

In addition, the catalyst composition according to an embodiment of the present invention contains the alkylating agent at a molar ratio of 1 to 200, specifically 1 to 100 molar ratio, and more specifically 3 to 20 molar ratio with respect to 1 mole of the lanthanum-based rare earth element-containing compound. It may include If the alkylating agent is included in a molar ratio exceeding 200, it is not easy to control the catalytic reaction during polymer production, and there is a risk that an excessive amount of alkylating agent may cause side reactions.

(b) Halides

The halogenide is not particularly limited, but includes, for example, a single halogen, an interhalogen compound, a hydrogen halide, an organic halide, a non-metal halide, a metal halide, or an organometallic halide, any of these. One or a mixture of two or more may be used. Among these, considering the excellent effect of improving catalyst activity and thereby improving reactivity, any one or a mixture of two or more selected from the group consisting of organic halides, metal halides and organometallic halides may be used as the halide.

The halogen group may include fluorine, chlorine, bromine, or iodine.

In addition, the interhalogen compound may include iodine monochloride, iodine monobromide, iodine trichloride, iodine pentafluoride, iodine monofluoride, or iodine trifluoride.

In addition, the hydrogen halide may include hydrogen fluoride, hydrogen chloride, hydrogen bromide, or hydrogen iodide.

In addition, the organic halides include t-butyl chloride (t-BuCl), t-butyl bromide, allyl chloride, allyl bromide, benzyl chloride, benzyl bromide, chloro-di-phenylmethane, bromo-di-phenylmethane, and tri-phenylmethane. Phenylmethyl chloride, triphenylmethyl bromide, benzylidene chloride, benzylidene bromide, methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, trimethylchlorosilane (TMSCl), benzoyl chloride, benzoyl bromide, propylene Onyl chloride, propionyl bromide, methyl chloroformate, methyl bromoformate, iodomethane, diiodomethane, triiodomethane (also called 'iodoform'), tetraiodomethane, 1-iodomethane Dopropane, 2-iodopropane, 1,3-diiodopropane, t-butyl iodide, 2,2-dimethyl-1-iodopropane (also called 'neopentyl iodide'), allyl iodide Odide, iodobenzene, benzyl iodide, diphenylmethyl iodide, triphenylmethyl iodide, benzylidene iodide (also called 'benzal iodide'), trimethylsilyl iodide, triethyl Silyl iodide, triphenylsilyl iodide, dimethyldiiodosilane, diethyldiiodosilane, diphenyldiiodosilane, methyltriiodosilane, ethyltriiodosilane, phenyltriiodosilane, Benzoyl iodide, propionyl iodide, or methyl iodoformate may be mentioned.

In addition, the non-metal halide includes phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride, phosphorus oxybromide, boron trifluoride, boron trichloride, boron tribromide, silicon tetrafluoride, silicon tetrachloride (SiCl ₄ ), and silicon tetrabromide. , arsenic trichloride, arsenic tribromide, selenium tetrachloride, selenium tetrabromide, tellurium tetrachloride, tellurium tetrabromide, silicon tetraiodide, arsenic triiodide, tellurium tetraiodide, boron triiodide, phosphorus triiodide, phosphorus oxyiodide or selenium tetraiodide, etc. can be mentioned.

In addition, the metal halide includes tin tetrachloride, tin tetrabromide, aluminum trichloride, aluminum tribromide, antimony trichloride, antimony pentachloride, antimony tribromide, aluminum trifluoride, gallium trichloride, gallium tribromide, gallium trifluoride, indium trichloride, Indium tribromide, indium trifluoride, titanium tetrachloride, titanium tetrabromide, zinc dichloride, zinc dibromide, zinc difluoride, aluminum triiodide, gallium triiodide, indium triiodide, titanium tetraiodide, zinc diiodide, tetraiodide Examples include germanium, tin tetraiodide, tin diiodide, antimony triiodide, or magnesium diiodide.

In addition, the organometallic halides include dimethyl aluminum chloride, diethylaluminum chloride, dimethyl aluminum bromide, diethylaluminum bromide, dimethyl aluminum fluoride, diethylaluminum fluoride, methylaluminum dichloride, ethyl aluminum dichloride, and methylaluminum dichloride. Bromide, Ethyl Aluminum Dibromide, Methyl Aluminum Difluoride, Ethyl Aluminum Difluoride, Methyl Aluminum Sesquichloride, Ethyl Aluminum Sesquichloride (EASC), Isobutyl Aluminum Sesquichloride, Methyl Magnesium Chloride, Methyl Magnesium Bromide, Ethyl Magnesium chloride, ethylmagnesium bromide, n-butylmagnesium chloride, n-butylmagnesium bromide, phenylmagnesium chloride, phenylmagnesium bromide, benzylmagnesium chloride, trimethyltin chloride, trimethyltin bromide, triethyltin chloride, triethyltin bromide, di -t-Butyltin dichloride, di-t-butyltin dibromide, di-n-butyltin dichloride, di-n-butyltin dibromide, tri-n-butyltin chloride, tri-n-butyltin bromide. , Methyl magnesium iodide, dimethyl aluminum iodide, diethylaluminum iodide, di-n-butylaluminum iodide, diisobutyl aluminum iodide, di-n-octyl aluminum iodide, methylaluminum Diiodide, ethyl aluminum diiodide, n-butyl aluminum diiodide, isobutyl aluminum diiodide, methyl aluminum sesqui iodide, ethyl aluminum sesqui iodide, isobutyl aluminum sesqui iodide, ethyl magnesium Odide, n-butylmagnesium iodide, isobutylmagnesium iodide, phenylmagnesium iodide, benzylmagnesium iodide, trimethyltin iodide, triethyltin iodide, tri-n-butyltin iodide. odide, di-n-butyltin diiodide, or di-t-butyltin diiodide.

In addition, the catalyst composition according to an embodiment of the present invention contains the halide in an amount of 1 mole to 20 mole, more specifically 1 mole to 5 mole, more specifically 2 mole, per 1 mole of the lanthanum-based rare earth element-containing compound. It may contain from mol to 3 mol. If the halide is contained in a molar ratio exceeding 20, it is not easy to remove the catalytic reaction, and there is a risk that the excess halide may cause a side reaction.

Additionally, the catalyst composition according to an embodiment of the present invention may include a non-coordinating anion-containing compound or a non-coordinating anion precursor compound instead of or together with the halide.

Specifically, in the compound containing the non-coordinating anion, the non-coordinating anion is a sterically bulky anion that does not form a coordination bond with the active center of the catalyst system due to steric hindrance, and is a tetraaryl borate anion or tetraaryl fluoride. It may be a borate anion, etc. In addition, the compound containing the non-coordinating anion may include a carbonium cation such as a triaryl carbonium cation along with the non-coordinating anion; It may include an ammonium cation such as an N,N-dialkyl anilinium cation, or a counter cation such as a phosphonium cation. More specifically, the compound containing the non-coordinating anion is triphenyl carbonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenyl carbonium tetra It may be kiss[3,5-bis(trifluoromethyl)phenyl]borate, or N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate.

In addition, the non-coordinating anion precursor is a compound capable of forming a non-coordinating anion under reaction conditions, such as a triaryl boron compound (BE ₃ , where E is a pentafluorophenyl group or a 3,5-bis (trifluoromethyl) phenyl group, etc. (an aryl group with the same strong electron-attracting properties) can be mentioned.

(c) Conjugated diene monomer

In addition, the catalyst composition may further include a conjugated diene-based monomer, and pre-polymerization or pre-polymerization is performed by mixing a portion of the conjugated diene-based monomer used in the polymerization reaction with the catalyst composition for polymerization in advance. By using it in the form of a premix catalyst composition, not only can the activity of the catalyst composition be improved, but also the produced active polymer can be stabilized.

In the present invention, the "preforming" refers to a catalyst composition containing a lanthanum rare earth element-containing compound, an alkylating agent, and a halogenide, that is, when the catalyst system includes diisobutylaluminum hydride (DIBAH), etc. , In addition, in order to reduce the possibility of generating active species in various catalyst compositions, a small amount of conjugated diene monomer such as 1,3-butadiene is added, and pre-polymerization occurs within the catalyst composition system with the addition of 1,3-butadiene. It can mean. Additionally, “premix” may mean a state in which each compound is uniformly mixed without polymerization occurring in the catalyst composition system.

At this time, the conjugated diene-based monomer used in the production of the catalyst composition may be used in a partial amount within the total amount of conjugated diene-based monomer used in the polymerization reaction, for example, the lanthanum-based rare earth element-containing compound 1 It may be used in an amount of 1 mole to 100 mole, specifically 10 mole to 50 mole, or 20 mole to 50 mole per mole.

The catalyst composition according to an embodiment of the present invention contains at least one of the above-described lanthanum rare earth element-containing compound and an alkylating agent, a halide, and a conjugated diene monomer, specifically, a lanthanum rare earth element-containing compound, an alkylating agent, and a halogen in an organic solvent. It can be manufactured by mixing cargo and, optionally, conjugated diene monomers. At this time, the organic solvent may be a non-polar solvent that is not reactive with the components of the catalyst composition. Specifically, the nonpolar solvent is n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, isopentane, isohexane, isopentane, isooctane, 2,2-dimethylbutane, cyclo linear, branched or cyclic aliphatic hydrocarbons having 5 to 20 carbon atoms, such as pentane, cyclohexane, methylcyclopentane or methylcyclohexane; A mixed solvent of aliphatic hydrocarbons having 5 to 20 carbon atoms, such as petroleum ether, petroleum spirits, or kerosene; Alternatively, it may be an aromatic hydrocarbon-based solvent such as benzene, toluene, ethylbenzene, or xylene, and any one or a mixture of two or more of these may be used. More specifically, the non-polar solvent may be a linear, branched, or cyclic aliphatic hydrocarbon having 5 to 20 carbon atoms or a mixed solvent of aliphatic hydrocarbons, and more specifically, n-hexane, cyclohexane, or a mixture thereof. You can.

Additionally, the organic solvent may be appropriately selected depending on the type of components constituting the catalyst composition, especially the alkylating agent.

Specifically, in the case of alkylaluminoxane such as methylaluminoxane (MAO) or ethyl aluminoxane as an alkylating agent, since it does not easily dissolve in aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent can be appropriately used.

Additionally, when modified methylaluminoxane is used as the alkylating agent, an aliphatic hydrocarbon-based solvent may be appropriately used. In this case, it can be more advantageous for the polymerization reaction because it is possible to implement a single solvent system with an aliphatic hydrocarbon-based solvent such as hexane, which is mainly used as a polymerization solvent. Additionally, aliphatic hydrocarbon-based solvents can promote catalytic activity, and this catalytic activity can further improve reactivity.

Meanwhile, the organic solvent may be used in an amount of 20 to 20,000 mol, more specifically, 100 to 1,000 mol, per 1 mol of the lanthanum-based rare earth element-containing compound.

Meanwhile, the polymerization in Step 1 may be performed as a continuous polymerization in a polymerization reactor containing at least two reactors, or may be performed in a batch reactor.

Additionally, the polymerization may be elevated temperature polymerization, isothermal polymerization, or constant temperature polymerization (adiabatic polymerization).

Here, constant temperature polymerization refers to a polymerization method that includes the step of polymerizing with its own reaction heat without arbitrarily applying heat after adding the catalyst composition, and the elevated temperature polymerization refers to a polymerization method in which the temperature is increased by arbitrarily applying heat after adding the catalyst composition. This indicates that the isothermal polymerization refers to a polymerization method in which the temperature of the reactant is kept constant by adding heat or taking heat away after adding the catalyst composition.

In addition, the polymerization may be performed using coordination anion polymerization or radical polymerization, and may specifically be bulk polymerization, solution polymerization, suspension polymerization, or emulsion polymerization, and more specifically, may be solution polymerization. .

The polymerization may be carried out in a temperature range of -20°C to 200°C, specifically in the temperature range of 50°C to 150°C, more specifically in the temperature range of 10°C to 120°C or 60°C to 90°C for 15 minutes. It may be performed for 3 hours. If the temperature during polymerization exceeds 200°C, it is difficult to sufficiently control the polymerization reaction, and there is a risk that the cis-1,4 bond content of the produced conjugated diene polymer may be lowered, and if the temperature is less than -20°C, polymerization There is a risk that reaction speed and efficiency may decrease.

In addition, the method for producing the modified conjugated diene-based polymer according to an embodiment of the present invention includes a reaction terminator for completing the polymerization reaction, such as polyoxyethylene glycol phosphate, after preparing the active polymer; Alternatively, it may include terminating the polymerization by further using additives such as antioxidants such as 2,6-di-t-butylparacresol. In addition, additives that facilitate solution polymerization, such as chelating agents, dispersants, pH adjusters, deoxidizers, or oxygen scavengers, can optionally be used along with the reaction terminator.

Step 2 is a step of preparing a first polymer containing a functional group by denaturing or coupling an active polymer, and can be performed by reacting the active polymer with a denaturing agent represented by Formula 1. That is, in one embodiment of the present invention, the first polymer may be a modified polymer in which the functional group derived from the denaturant is introduced into at least one end of the conjugated diene-based polymer chain.

The modifier may be used in an amount of 0.5 to 20 moles based on 1 mole of the lanthanum-based rare earth element-containing compound in the catalyst composition. Specifically, the modifier may be used in an amount of 1 to 10 moles per 1 mole of the lanthanum-based rare earth element-containing compound in the catalyst composition.

Additionally, the denaturation reaction may be performed at 0°C to 90°C for 1 minute to 5 hours.

After completion of the above-described modification reaction, the polymerization reaction can be stopped by adding an isopropanol solution of 2,6-di-t-butyl-p-cresol (BHT), etc. to the polymerization reaction system.

Step 3 is a step to increase the degree of branching of the first polymer, and can be performed by adding a sulfur halide to the first polymer and mixing for more than 15 minutes. Specifically, mixing by stirring for more than 15 minutes and less than 60 minutes. You can.

The production method according to one embodiment of the present invention is to prepare a first polymer containing a functional group derived from a denaturant and mix it with a sulfur halide to form a double bond in the polymer chain constituting the polymer and an electrophilic addition reaction (electrophilic addition reaction). addition) can occur to form long chain branches within the polymer chain, thereby lowering the linearity and increasing the degree of branching, and consequently improving the mixing processability of the prepared modified conjugated diene polymer.

In addition, the sulfur halide may be used in an amount of 0.1 to 0.6 parts by weight, specifically 0.1 to 0.3 parts by weight, based on 100 parts by weight of the first polymer. If the sulfur halide is used in the above ratio, long chain branches can be easily formed without adversely affecting the polymer chain.

In addition, the sulfur halide may be at least one selected from the group consisting of disulfur dichloride (S ₂ Cl ₂ ), sulfur dichloride (SCl ₂ ), and thionyl chloride (SOCl ₂ ).

Additionally, mixing in step 3 may be performed at a temperature that is 5°C to 20°C higher than the polymerization temperature in step 1. If the mixing in step 3 is performed under the above conditions, the viscosity of the polymer solution during the reaction can be lowered, the flow can be made easier, and branching between the polymer chains constituting the polymer can be easily induced.

In the production method according to an embodiment of the present invention, after step 3, a modified conjugated diene-based polymer can be obtained through desolvation treatment such as steam stripping or vacuum drying treatment to lower the partial pressure of the solvent through the supply of water vapor. . In addition, the reaction product obtained as a result of the above reaction may include an unmodified, active polymer along with the above-described modified conjugated diene polymer.

Furthermore, the present invention provides a rubber composition containing the conjugated diene polymer and a molded article manufactured from the rubber composition.

The rubber composition according to an embodiment of the present invention contains the modified conjugated diene polymer in an amount of 0.1% by weight or more and 100% by weight or less, specifically 10% by weight to 100% by weight, and more specifically 20% by weight to 90% by weight. It may include If the content of the modified conjugated diene polymer is less than 0.1% by weight, the effect of improving the wear resistance and crack resistance of molded products, such as tires, manufactured using the rubber composition may be minimal.

In addition, the rubber composition may further include other rubber components as needed in addition to the modified conjugated diene polymer. In this case, the rubber component may be included in an amount of 90% by weight or less based on the total weight of the rubber composition. Specifically, it may be included in an amount of 1 to 900 parts by weight based on 100 parts by weight of the modified conjugated diene-based copolymer.

The rubber component may be natural rubber or synthetic rubber. For example, the rubber component may include natural rubber (NR) containing cis-1,4-polyisoprene; Modified natural rubber such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber, which are obtained by modifying or refining the above 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, halogenated butyl rubber, etc., and any one or a mixture of two or more of these may be used.

Additionally, the rubber composition may include 0.1 to 150 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene polymer, and the filler may be silica-based, carbon black, or a combination thereof. Specifically, the filler may be carbon black.

The carbon black-based filler is not particularly limited, but may, for example, have a nitrogen adsorption specific surface area (N ₂ SA, measured in accordance with JIS K 6217-2:2001) of 20 m2/g to 250 m2/g. Additionally, the carbon black may have a dibutylphthalate oil absorption (DBP) of 80 cc/100g to 200 cc/100g. If the nitrogen adsorption specific surface area of the carbon black exceeds 250 m ² /g, the processability of the rubber composition may decrease, and if it is less than 20 m ² /g, the reinforcing performance by carbon black may be minimal. In addition, if the DBP oil absorption of the carbon black exceeds 200 cc/100g, the processability of the rubber composition may decrease, and if it is less than 80 cc/100g, the reinforcement performance by the carbon black may be minimal.

In addition, the silica is not particularly limited, but may be, for example, wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, or colloidal silica. Specifically, the silica may be wet silica, which has the most significant effect of improving fracture properties and wet grip. In addition, the silica has a nitrogen adsorption specific surface area per gram (N ₂ SA) of 120 m2/g to 180 m2/g, and a CTAB (cetyl trimethyl ammonium bromide) adsorption specific surface area of 100 m2/g to 200 m2. It can be /g. If the nitrogen adsorption specific surface area of the silica is less than 120 m2/g, there is a risk that the reinforcement performance by silica may be reduced, and if it exceeds 180 m2/g, there is a risk that the processability of the rubber composition may be reduced. In addition, if the CTAB adsorption specific surface area of the silica is less than 100 m2/g, there is a risk that the reinforcement performance by silica as a filler may be reduced, and if it exceeds 200 m2/g, there is a risk that the processability of the rubber composition may be reduced.

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

The silane coupling agent specifically includes bis(3-triethoxysilylpropyl)tetrasulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, and bis(3-triethoxysilylpropyl)disulfide. (2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, 3-mercaptopropyltrimethoxysilane , 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasul Feed, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilyl Propylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzolyl tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis. (3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide or dimethoxymethylsilylpropylbenzothiazolyl. Tetrasulfide, etc. may be mentioned, and any one or a mixture of two or more of these may be used. More specifically, considering the effect of improving reinforcing properties, the silane coupling agent may be bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide.

Additionally, the rubber composition according to one embodiment of the present invention may be sulfur crosslinkable and may further include a vulcanizing agent accordingly.

The vulcanizing agent may specifically be sulfur powder and may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the rubber component. When included in the above content range, the necessary elastic modulus and strength of the vulcanized rubber composition can be secured, and at the same time, low fuel efficiency can be obtained.

In addition, the rubber composition according to an embodiment of the present invention contains, in addition to the above components, various additives commonly used in the rubber industry, specifically, a vulcanization accelerator, process oil, plasticizer, anti-aging agent, anti-scorch agent, and zinc white. ), stearic acid, thermosetting resin, or thermoplastic resin may be further included.

The vulcanization accelerator is not particularly limited, and specifically includes M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazylsulfenamide), etc. A thiazole-based compound or a guanidine-based compound such as DPG (diphenylguanidine) may be used. The vulcanization accelerator may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the rubber component.

In addition, the process oil acts as a softener in the rubber composition, and may be a paraffin-based, naphthenic, or aromatic compound. More specifically, considering tensile strength and wear resistance, the aromatic process oil price and hysteresis loss And considering low-temperature characteristics, naphthenic or paraffin-based process oil may be used. The process oil may be included in an amount of 100 parts by weight or less based on 100 parts by weight of the rubber component, and when included in the above amount, it can prevent a decrease in the tensile strength and low heat generation (low fuel efficiency) of vulcanized rubber.

In addition, the anti-aging agent specifically includes N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 6- Toxi-2,2,4-trimethyl-1,2-dihydroquinoline, or a high-temperature condensate of diphenylamine and acetone, etc. The anti-aging agent may be used in an amount of 0.1 to 6 parts by weight based on 100 parts by weight of the rubber component.

The rubber composition according to an embodiment of the present invention can be obtained by kneading using a kneader such as a Banbury mixer, roll, or internal mixer according to the above mixing recipe, and has low heat generation and wear resistance through a vulcanization process after molding processing. This excellent rubber composition can be obtained.

Accordingly, the rubber composition is used for each member of a tire such as tire tread, undertread, side wall, carcass coating rubber, belt coating rubber, bead filler, filler, or bead coating rubber, anti-vibration rubber, belt conveyor, hose, etc. It can be useful in the manufacture of various industrial rubber products.

Molded articles manufactured using the rubber composition may include tires or tire treads.

Hereinafter, the present invention will be described in more detail through examples and experimental examples. However, the following examples and experimental examples are for illustrative purposes only and do not limit the scope of the present invention.

Preparation example: Preparation of 1-(3-chloropropyl)-2,2,5,5-tetramethyl-1,2,5-azadisiloridine

1.1 g of 3-chloropropan-1-amine and 1,2-bis(chlorodimethylsilyl)ethane in dichloromethane (CH ₂ Cl ₂ ) ) To 1.82 g of the mixture, 2.3 ml of triethylamine (Et3N) was slowly added at 0°C, and the reaction mixture was stirred overnight at room temperature (25°C). After the reaction was completed, the volatile solvent was removed under reduced pressure and filtered. The residue was re-dissolved in hexane, and the remaining solid was filtered. The filtered crude material was obtained without further purification, and ^{the 1} H nuclear magnetic resonance spectroscopy spectrum was observed to confirm the compound of the following formula 2-6.

[Formula 2-6]

¹ H NMR (500 MHz, CDCl ₃ ) δ 3.48 (m, 2H), δ 2.86 (m, 2H), δ 1.79 (m, 2H), δ 0.82-0.64 (m, 7H), δ 0.37 (m, 7H) ), δ 0.15 (m, 3H), δ 0.00 (s, 12H).

Example 1

After adding 4.7 kg of a hexane solution containing 1,3-butadiene dissolved in a vacuum reactor, the internal temperature of the reactor was raised to 70°C. After adding the catalyst composition, polymerization was performed for 60 minutes. At this time, the catalyst composition was prepared by adding 0.719 mmol of neodymium versatate (Nd(2-ethylhexanoate) ₃ ), Solvay, to n-hexane solvent, diisobutyl aluminum hydride (DIBAH), and chloride. Diethylaluminum (DEAC) was sequentially added to the neodymium versatate:DIBAH:DEAC=1:9.5:2.4 in a molar ratio and then mixed. After adding the compound of Formula 2-6 prepared in the above Preparation Example, a denaturation reaction was performed for 30 minutes (denaturant: Nd = 5:1 equivalent). Afterwards, HPSS as a polymerization terminator and Wingstay-K as an antioxidant were added in amounts of 0.15 parts by weight and 0.4 parts by weight, respectively, based on 100 parts by weight of monomer, to prepare the first polymer. Afterwards, the internal temperature of the reactor was raised to 80°C, disulfur dichloride (S ₂ Cl ₂ ) was added, and stirred for 15 minutes to mix with the first polymer. At this time, disulfur dichloride was added in an amount of 0.1 parts by weight based on 100 parts by weight of the first polymer. Afterwards, the solvent was removed through steam stripping, and the modified butadiene polymer was prepared by drying for 4 minutes using a 6-inch hot roll (110°C).

Example 2

In Example 1, a modified butadiene polymer was prepared in the same manner as in Example 1, except that disulfur dichloride was added and stirred for 60 minutes to mix with the first polymer.

Example 3

In Example 1, a modified butadiene polymer was prepared in the same manner as in Example 1, except that 0.769 mmol of neodymium versatate was added when preparing the catalyst composition, and 0.3 parts by weight of disulfur dichloride was added relative to 100 parts by weight of the first polymer. was manufactured.

Example 4

In Example 2, when preparing the catalyst composition, neodymium versatate was added at 0.769 mmol, and disulfur dichloride was added at 0.30 parts by weight compared to 100 parts by weight of the first polymer, and the modified butadiene polymer was prepared in the same manner as Example 1. was manufactured.

Example 5

In Example 1, a modified butadiene polymer was prepared in the same manner as in Example 1, except that 0.781 mmol of neodymium versatate was added when preparing the catalyst composition, and 0.6 parts by weight of disulfur dichloride was added relative to 100 parts by weight of the first polymer. was manufactured.

Comparative Example 1

CB25 (Lanxess) was used as a comparative example as an unmodified butadiene polymer.

Comparative Example 2

After adding 4.7 kg of a hexane solution containing 1,3-butadiene dissolved in a vacuum reactor, the internal temperature of the reactor was raised to 70°C. After adding the catalyst composition, polymerization was performed for 60 minutes. At this time, the catalyst composition was prepared by adding 0.719 mmol of neodymium versatate (Nd(2-ethylhexanoate) ₃ ), Solvay, to n-hexane solvent, diisobutyl aluminum hydride (DIBAH), and chloride. Diethylaluminum (DEAC) was sequentially added to the neodymium versatate:DIBAH:DEAC=1:9.5:2.4 in a molar ratio and then mixed. After adding the compound of Formula 2-6 prepared in the above Preparation Example, a denaturation reaction was performed for 30 minutes (denaturant: Nd = 5:1 equivalent). Afterwards, HPSS as a polymerization terminator and Wingstay-K as an antioxidant were added at 0.15 parts by weight and 0.4 parts by weight, respectively, based on 100 parts by weight of monomer. Afterwards, the solvent was removed through steam stripping, and the modified butadiene polymer was prepared by drying for 4 minutes using a 6-inch hot roll (110°C).

Comparative Example 3

In Example 1, a modified butadiene polymer was prepared through the same method as Example 1, except that disulfur dichloride was added in an amount of 0.05 parts by weight based on 100 parts by weight of the first polymer.

Comparative Example 4

In Example 1, modified butadiene was prepared in the same manner as in Example 1, except that 0.805 mmol of neodymium versatate was added when preparing the catalyst composition, and 0.8 parts by weight of disulfur dichloride was added based on 100 parts by weight of the first polymer. The polymer was prepared.

Comparative Example 5

In Example 1, a modified butadiene polymer was prepared in the same manner as in Example 1, except that the compound of the formula (ii) below was added instead of the compound of formula 2-6 for a modification reaction.

(ii)

In the above formula (ii), Me represents a methyl group.

Experimental Example 1

The physical properties of the polymers of the examples and comparative examples were measured in the following manner, and the results are shown in Table 1 below.

1) Microstructure analysis

The amount of cis, trans, and vinyl defects in each polymer was measured using Varian VNMRS 500 Mhz NMR, and 1,1,2,2-tetrachloroethane D2 (Cambridge Isotope) was used as a solvent.

2) Weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (MWD)

Each polymer was dissolved in tetrahydrofuran (THF) for 30 minutes at 40°C and then loaded onto gel permeation chromatography (GPC). At this time, a combination of two PLgel Olexis columns and one PLgel mixed-C column from Polymer Laboratories was used. In addition, all newly replaced columns used mixed bed type columns, and polystyrene was used as a gel permeation chromatography standard material (GPC standard material).

3) Mooney viscosity (RP, Raw polymer) and -S/R values

For each polymer, Mooney viscosity (ML1+4, @100°C) (MU) was measured at 100°C using a large rotor using Monsanto's MV2000E at a rotor speed of 2±0.02 rpm. The sample used at this time was left at room temperature (23 ± 3°C) for more than 30 minutes, then 27 ± 3 g was collected, filled inside the die cavity, and the Mooney viscosity was measured while operating the platen and applying torque. In addition, after measuring the Mooney viscosity, the change in Mooney viscosity that appears as the torque is released was observed for 1 minute, and the -S/R value (absolute value) was determined from the slope value.

division Example Comparative example One 2 3 4 5 One 2 3 4 5 Microstructure (cis:vinyl:trans) 97.3:0/6:2/1 96.9:0.6:2.5 97.1:0.72:2 97.0:0.6:2.4 96.9:0.5:2.6 - 97.5:0.6:1.9 97.3:0.7:2.0 97.5:0.7:1.7 97.0:0.7:2.3 GPC results Mn(x10 ⁵ g/mol) 2.64 2.37 2.25 2.45 2.36 - 2.64 2.44 2.57 2.52 Mw(x10 ⁵ g/mol) 6.31 6.62 6.58 6.50 6.80 - 7.88 6.98 7.84 6.90 MWD (Mw/Mn) 2.70 2.79 2.92 2.65 2.86 - 2.99 2.86 3.05 2.73 Mooney viscosity (RP) (ML1+4, @100℃)(MU) 50 53 52 55 60 45 52 55 80 49 -S/R 0.5632 0.5324 0.4458 0.4342 0.4564 0.6585 0.9863 0.8563 0.3428 0.6562

As shown in Table 1, the modified conjugated diene polymers of Examples 1 to 5 according to an embodiment of the present invention showed a -S/R value of less than 0.6, which is similar to that of Comparative Examples 1 to 3 and Comparative Examples 1 to 3. Compared to Example 5, it can be seen that this value is significantly lower. These results mean that the modified conjugated diene-based polymer according to an embodiment of the present invention had a high degree of branching.

In addition, Examples 1 to 5 all had -S/R values of 0.4 or more and less than 0.6, which means that all properties are well balanced without disturbing the balance of tensile properties, viscoelastic properties, and processability due to excessive branching. This means that it is possible, and can be confirmed through the results of Experimental Example 2 described later.

On the other hand, in the case of Comparative Example 4, the -S/R value was less than 0.6, showing a high degree of branching, but excessive branching occurred at less than 0.4, resulting in a decrease in tensile properties, viscoelastic properties, and processability as confirmed in Experimental Example 2 described later. It has been done.

Experimental Example 2

After preparing a rubber composition and a rubber specimen using each of the polymers prepared in Examples 1 to 5 and Comparative Examples 1 to 5, Mooney viscosity, tensile strength, 300% modulus, and Viscoelastic properties (rotational resistance) were measured for each. The results are shown in Table 2 below.

Specifically, the rubber composition contains 70 parts by weight of carbon black, 22.5 parts by weight of process oil, 2 parts by weight of anti-aging agent (TMDQ), 3 parts by weight of zinc oxide (ZnO), and stearic acid ( Each rubber composition was prepared by mixing 2 parts by weight of stearic acid. Afterwards, 2 parts by weight of sulfur, 2 parts by weight of vulcanization accelerator (CZ), and 0.5 parts by weight of vulcanization accelerator (DPG) were added to each rubber composition, mixed gently at 50 rpm for 1.5 minutes at 50°C, and then mixed using a roll at 50°C. Thus, a vulcanized mixture in the form of a sheet was obtained. Rubber specimens were prepared by vulcanizing the obtained vulcanization mixture at 160°C for 25 minutes.

1) Mooney viscosity (FMB, Final Master Batch)

Mooney viscosity (ML1+4, @100°C) (MU) was measured using each vulcanization formulation prepared above. Specifically, Mooney viscosity (MV) was measured using a large rotor using Monsanto's MV2000E at 100°C and a rotor speed of 2±0.02 rpm. The sample used at this time was left at room temperature (23 ± 3°C) for more than 30 minutes, then 27 ± 3 g was collected, filled inside the die cavity, and the Mooney viscosity was measured while operating the platen and applying torque.

2) Tensile strength (kg·f/cm ² ) and 300% modulus (300% modulus, kg·f/cm ² )

After each rubber composition was vulcanized at 150°C for t90 minutes, the tensile strength and modulus at 300% elongation (M-300%) of the vulcanized product were measured according to ASTM D412. The measured value was indexed by calculating the result of Comparative Example 1 as 100 using Equation 1 below.

[Equation 1]

Index=(measured value/reference value)*100

3) Viscoelastic properties (Tanδ @ 60℃)

The Tan δ property, which is most important for low fuel efficiency characteristics, was measured at 60°C using DMTS 500N from Gabo, Germany, at a frequency of 10 Hz, Prestrain of 3%, and Dynamic Strain of 3%. At this time, the Tanδ value at 60°C indicates rolling resistance characteristics and fuel efficiency. The measured value was indexed by calculating the result of Comparative Example 1 as 100 using Equation 2 below.

[Equation 2]

Index=(reference value/measured value)*100

division Example Comparative example One 2 3 4 5 One 2 3 4 5 Mooney viscosity (FMB) 65 69 67 70 75 60 77 75 102 66 △MV 15 16 15 16 15 15 25 20 22 17 Tensile properties M-300% 109 107 108 106 106 100 101 99 96 95 tensile strength 101 100 102 103 103 100 103 102 99 101 Viscoelastic properties Tanδ @ 60℃ 111 108 103 106 105 100 106 103 95 98

As shown in Table 2, the rubber specimen manufactured from the rubber composition containing the polymer of Examples 1 to 5 according to an embodiment of the present invention had superior tensile properties and viscoelastic properties compared to Comparative Examples 1 to 5. It showed improved processability.

Specifically, each rubber specimen manufactured from the rubber composition containing the polymer of Comparative Example 3 and Comparative Example 4 showed similar tensile properties compared to Examples 1 and 5, respectively, but viscoelastic properties and processability were significantly reduced. It has been done. Through this, the manufacturing method according to an embodiment of the present invention includes the step of adding and mixing a sulfur halide in an amount of 0.1 to 0.6 parts by weight based on 100 parts by weight of the first polymer, thereby increasing the linearity (-S/R) at 100°C. ) is less than 0.6, preferably 0.4 or more and less than 0.6. It was confirmed that a polymer with a high degree of branching can be produced, and that such a polymer has excellent blend properties such as tensile properties and viscoelastic properties while also improving blend processability.

In addition, the rubber specimen manufactured from the rubber composition containing the polymer of Comparative Example 2 showed similar excellent tensile and viscoelastic properties compared to Example 1, but the processability was significantly reduced, and in this case, Comparative Example 2 was a sulfur halide It was prepared in the same manner as Example 1, except that the mixing step was not performed. Through this, the modified conjugated diene-based polymer according to an embodiment of the present invention contains a unit derived from a denaturant represented by Formula 1, and is manufactured by a manufacturing method including the step of mixing with a sulfur halide, so that the melting properties and viscoelastic properties are improved. It was confirmed that it was excellent and that processability could be greatly improved.

In addition, the rubber specimen manufactured from the rubber composition containing the polymer of Comparative Example 5 not only had lower tensile properties and processability compared to Example 1, but also significantly reduced viscoelastic properties. In this case, Comparative Example 5 used a conventional alkoxy as a modifier. It was prepared in the same manner as Example 1, except that a silane-based modifier was used. Through this, the modified conjugated diene-based polymer according to an embodiment of the present invention is manufactured by a manufacturing method including the step of mixing with a sulfur halide, and includes a functional group derived from the modifier represented by Chemical Formula 1, thereby improving tensile properties, viscoelastic properties, and It was confirmed that processability can be excellent in a balanced manner.

Claims (12)

The linearity (-S/R) at 100°C is 0.4 or more and less than 0.6,
Contains a functional group derived from a denaturant represented by the following formula (1) or formula (2-3),
Modified conjugated diene-based polymer, which is a lanthanum-based rare earth element-catalyzed modified conjugated diene-based polymer:
[Formula 1]

In Formula 1,
R ¹ to R ³ are each independently one or more substituents selected from the group consisting of a halogen group, an alkyl group with 1 to 20 carbon atoms, a cycloalkyl group with 3 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, and -R ⁶ COOR ⁷ Substituted trivalent hydrocarbon group; An unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms; A tetravalent silyl group substituted with two types of substituents selected from the group consisting of an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 20 carbon atoms; A trivalent silyl group substituted with one type of substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 20 carbon atoms; Unsubstituted divalent silyl group; or one hetero atom selected from the group consisting of O and S,
However, R ¹ to R ³ are all trivalent hydrocarbon groups; divalent hydrocarbon group; Tetravalent group; trivalent hydroxyl group; It is not a divalent silyl group or a heteroatom, but at least one of R ¹ to R ³ is a tetravalent silyl group; trivalent hydroxyl group; or divalent silyl group,
R ⁴ is a single bond, an alkylene group having 1 to 20 carbon atoms, or a cycloalkylene group having 3 to 20 carbon atoms,
R ⁵ is a silyl group unsubstituted or substituted with an alkyl group having 1 to 20 carbon atoms; halogen; or -COR ⁸ ,
R ⁶ is a single bond, an alkylene group having 1 to 20 carbon atoms, or a cycloalkylene group having 3 to 20 carbon atoms,
R ⁷ is an alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms,
R ⁸ is selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a heterocycloalkyl group having 2 to 10 carbon atoms, and a disilylamino group having 3 to 10 carbon atoms. There is 1 type,
[Formula 2-3]
.
delete In claim 1,
The denaturant represented by Formula 1 is a modified conjugated diene-based polymer represented by the following Formula 2:
[Formula 2]

In Formula 2,
R ² is a trivalent hydrocarbon group substituted with one or more substituents selected from the group consisting of a halogen group, an alkyl group with 1 to 20 carbon atoms, a cycloalkyl group with 3 to 20 carbon atoms, and an aryl group with 6 to 30 carbon atoms; or an unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms,
R ⁴ is an alkylene group having 1 to 20 carbon atoms, or a cycloalkylene group having 3 to 20 carbon atoms,
R ⁵ is a silyl group unsubstituted or substituted with an alkyl group having 1 to 20 carbon atoms; halogen; or -COR ⁸ ,
R ⁸ is selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a heterocycloalkyl group having 2 to 10 carbon atoms, and a disilylamino group having 3 to 10 carbon atoms. It is type 1,
R ¹² to R ¹⁵ are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms.
In claim 1,
The denaturing agent represented by Formula 1 is a modified conjugated diene polymer selected from the group consisting of compounds represented by Formulas 2-1, 2-2, and Formulas 2-4 to 2-6:
[Formula 2-1]

[Formula 2-2]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

delete 1) preparing an active polymer by polymerizing a conjugated diene monomer in a hydrocarbon solvent in the presence of a catalyst composition;
2) preparing a first polymer by reacting the active polymer with a denaturant represented by Formula 1 or Formula 2-3; and
3) adding a sulfur halide to the first polymer and mixing,
Method for producing a modified conjugated diene-based polymer, wherein the sulfur halide is added in an amount of 0.1 to 0.6 parts by weight based on 100 parts by weight of the first polymer:
[Formula 1]

In Formula 1,
R ¹ to R ³ are each independently one or more substituents selected from the group consisting of a halogen group, an alkyl group with 1 to 20 carbon atoms, a cycloalkyl group with 3 to 20 carbon atoms, an aryl group with 6 to 30 carbon atoms, and -R ⁶ COOR ⁷ Substituted trivalent hydrocarbon group; An unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms; A tetravalent silyl group substituted with two types of substituents selected from the group consisting of an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 20 carbon atoms; A trivalent silyl group substituted with one type of substituent selected from the group consisting of an alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 20 carbon atoms; Unsubstituted divalent silyl group; or one hetero atom selected from the group consisting of O and S,
However, R ¹ to R ³ are all trivalent hydrocarbon groups; divalent hydrocarbon group; Tetravalent group; trivalent hydroxyl group; It is not a divalent silyl group or a heteroatom, but at least one of R ¹ to R ³ is a tetravalent silyl group; trivalent hydroxyl group; or divalent silyl group,
R ⁴ is a single bond, an alkylene group having 1 to 20 carbon atoms, or a cycloalkylene group having 3 to 20 carbon atoms,
R ⁵ is a silyl group unsubstituted or substituted with an alkyl group having 1 to 20 carbon atoms; halogen; or -COR ⁸ ,
R ⁶ is a single bond, an alkylene group having 1 to 20 carbon atoms, or a cycloalkylene group having 3 to 20 carbon atoms,
R ⁷ is an alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 3 to 20 carbon atoms,
R ⁸ is selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a heterocycloalkyl group having 2 to 10 carbon atoms, and a disilylamino group having 3 to 10 carbon atoms. There is 1 type,
[Formula 2-3]
.
In claim 6,
A method for producing a modified conjugated diene-based polymer, wherein the sulfur halide is used in an amount of 0.1 to 0.3 parts by weight based on 100 parts by weight of the first polymer.
In claim 6,
The mixing in step 3) is performed by adding a sulfur halide to the first polymer and stirring for 15 minutes or more and 60 minutes or less.
In claim 6,
A method for producing a modified conjugated diene-based polymer, wherein the sulfur halide is at least one selected from the group consisting of disulfur dichloride, sulfur dichloride, and thionyl chloride.
In claim 6,
The catalyst composition includes a lanthanum-based rare earth element-containing compound,
A method for producing a modified conjugated diene-based polymer, wherein the lanthanum-based rare earth element-containing compound includes a neodymium compound represented by the following formula (3):
[Formula 3]

In Formula 3 above,
R _a to R _c are independently hydrogen or an alkyl group having 1 to 12 carbon atoms,
However, R _a to R _c are not all hydrogen at the same time.
In claim 6,
The catalyst composition is a method for producing a modified conjugated diene-based polymer, wherein the catalyst composition includes at least one of an alkylating agent, a halide, and a conjugated diene-based monomer.
A rubber composition comprising the modified conjugated diene polymer according to claim 1.