KR20210036082A - Modified conjugated diene polymer, preparation method thereof and rubber composition comprising the same - Google Patents

Abstract

The present invention relates to a neodymium-catalyzed modified conjugated diene-based polymer with excellent compounding properties and high modification rate, a method for preparing the same, and a rubber composition comprising the same. Provided is a neodymium-catalyzed modified conjugated diene-based polymer, comprising: a repeating unit derived from a conjugated diene-based monomer; and a denaturant-derived functional group represented by chemical formula 1, wherein the denaturation rate is more than 30%, and the cis 1,4-linkage content is at least 96 wt%.

Description

Modified conjugated diene polymer, preparation method thereof and rubber composition comprising the same}

The present invention relates to a neodymium catalyzed modified conjugated diene-based polymer having a high degree of modification excellent in blending properties, a method for preparing the same, and a rubber composition comprising the same.

In recent years, as interest in energy saving and environmental issues has increased, there is a demand for low fuel consumption of automobiles. As one of the methods for realizing this, a method of lowering the heat generation property of a tire by using an inorganic filler such as silica or carbon black in the rubber composition for forming a tire has been proposed, but it is not easy to disperse the inorganic filler in the rubber composition. There is a problem that the physical properties of the rubber composition, including abrasion resistance, crack resistance, or processability, are deteriorated as a whole.

In order to solve such a problem, the polymerization active site of the conjugated diene-based polymer obtained by anionic polymerization using organic lithium is a method to increase the dispersibility of inorganic fillers such as silica or carbon black in the rubber composition. A method for transforming into a functional group has been developed. Specifically, a method of modifying the polymerization active terminal of the conjugated diene-based polymer with a tin-based compound, introducing an amino group, or modifying it with an alkoxysilane derivative has been proposed.

However, when preparing a rubber composition using the conjugated diene-based polymer modified by the above-described method, low heat generation properties can be ensured, but the effect of improving physical properties on the rubber composition such as abrasion resistance and processability was not sufficient.

As another method, in a living polymer obtained by coordination polymerization using a catalyst containing a lanthanum-based rare earth element compound, a method of modifying the living active end with a specific coupling agent or modifying agent has been developed. However, in the conventionally known catalyst containing a lanthanum-based rare earth element compound, the activity of the resulting living terminal is weak and the terminal modification rate is low, so that the effect of improving the physical properties of the rubber composition is insignificant.

JP 5340556 B2

The present invention has been devised to solve the problems of the prior art, and an object of the present invention is to provide a neodymium catalyzed modified conjugated diene polymer having a high modification rate and improved blending properties.

In addition, an object of the present invention is to provide a method for producing the above neodymium catalyzed modified conjugated diene polymer.

In addition, an object of the present invention is to provide a rubber composition comprising the neodymium catalyzed modified conjugated diene polymer.

In order to solve the above problems, the present invention is a repeating unit derived from a conjugated diene-based monomer; And it provides a neodymium catalyzed modified conjugated diene-based polymer comprising a denaturant-derived functional group represented by the following formula (1), a denaturation rate of 30% or more, and a cis 1,4-bond content of 96% by weight or more:

[Formula 1]

In Formula 1,

R ¹ and R ² are each independently a divalent hydrocarbon group having 1 to 10 carbon atoms substituted or unsubstituted with a substituent,

R ³ and R ⁴ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms unsubstituted or substituted with a substituent,

R ⁵ is a monovalent to hexavalent hydrocarbon group having 1 to 10 carbon atoms unsubstituted or substituted with a substituent,

n is an integer from 1 to 6,

The substituent is at least one selected from an ether group, a tertiary amine group, an epoxy group, a carbonyl group and a halogen group.

In addition, the present invention comprises the steps of preparing an active polymer by polymerizing a conjugated diene-based monomer in the presence of a catalyst composition containing a neodymium compound in a hydrocarbon solvent (S1); And reacting the active polymer with a denaturant represented by the following formula (1) (S2), wherein the neodymium catalyzed modified conjugated diene has a denaturation rate of 30% or more and a cis 1,4-bond content of 96% by weight or more. Provides a method for preparing a polymer based:

[Formula 1]

In Formula 1,

R ¹ to R ⁵ and n are as previously defined.

The neodymium catalyzed modified conjugated diene-based polymer according to the present invention has a high rate of modification and has excellent affinity with a filler, so that when applied to a rubber composition, it may have excellent blending properties.

In addition, in the method for preparing the neodymium catalyzed modified conjugated diene-based polymer according to the present invention, a neodymium catalyzed modified conjugated diene-based polymer having excellent filler affinity can be prepared by performing a modification reaction using a modifier represented by Formula 1.

In addition, in the above production method, when polymerization is performed using a catalyst composition containing a neodymium compound, a first alkylating agent, a second alkylating agent, a halide, and a conjugated diene-based monomer in a specific ratio, the catalyst composition may exhibit high activity. Accordingly, it is possible to more easily form an active polymer and to perform a subsequent modification reaction more easily, and as a result, a neodymium catalyzed modified conjugated diene-based polymer having a high modification rate can be prepared.

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

The terms or words used in the specification and claims should not be construed as being limited to their usual or dictionary meanings, and the inventor may appropriately define the concept of terms in order to describe his own invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

Hereinafter, the terms and measurement methods used in the present invention may be defined as follows unless otherwise defined.

[Terms]

The term "substitution" used in the present invention may mean that hydrogen of a functional group, atomic group or compound is substituted with a specific substituent, and exists in a functional group, atomic group or compound when hydrogen of a functional group, atomic group or compound is substituted with a specific substituent. One or two or more substituents may be present depending on the number of hydrogens. In addition, when a plurality of substituents are present, each of the substituents may be the same as or different from each other.

The term “alkyl group” used in the present invention may mean a monovalent saturated aliphatic hydrocarbon, and linear alkyl groups such as methyl, ethyl, propyl and butyl, and isopropyl, sec-butyl , Tert-butyl, and a branched alkyl group such as neo-pentyl may be included.

In the present invention, the term'alkylene group' may mean a divalent saturated aliphatic hydrocarbon such as methylene, ethylene, propylene, and butylene.

In the present invention, the terms "derived repeating unit", "derived unit" and "derived functional group" may refer to a component, structure, or the substance itself derived from a substance.

In the present invention, the term'modification rate (%)' may mean the ratio of the modified polymer to the unmodified polymer when modified with a modifier for the polymer in which the polymerization active site is present, which is modified It can be expressed as a percentage (%) of the total polymer and unmodified polymer.

[How to measure]

In the present invention, the'denaturation rate (%)' is a value calculated according to Equation 1 below using a chromatogram obtained from chromatography measurement, and the chromatographic measurement is performed by dissolving a polymer in cyclohexane to obtain a sample. (Preparation at 1.0 mg/ml) was stored in a mobile phase reservoir, and tetrahydrofuran (THF) was stored in another mobile phase reservoir. Each of the mobile phase reservoirs was connected to a dual-head pump, and a solution of the mobile phase reservoir in which the polymer was dissolved was first injected into a column filled with a silica adsorbent through the pump and an injector having a loop volume of 100 μl. At this time, the pressure of the pump was 450 psi, and the injection flow rate was 0.7 ml/min. Subsequently, it was confirmed that the unmodified butadiene polymer unit in the polymer was no longer detected from the detector (ELSD, Waters), and the tetrahydrofuran was injected into the column through a pump based on 5 minutes from the start of injection. At this time, the pressure of the pump was 380 psi, and the injection flow rate was 0.7 ml/min. When tetrahydrofuran was injected from the detector, it was confirmed that the modified butadiene polymer unit in the polymer was no longer detected, and the injection of the second solvent was terminated. Then, the denaturation rate (%) was calculated according to Equation 1 below from the detected chromatogram result.

[Equation 1]

In Equation 1, the peak area of the unmodified polymer unit is the peak area of the chromatogram for the first solution transferred to the detector, and the peak area of the modified polymer unit is for the second solution transferred to the detector. It is the peak area of the chromatogram.

In the present invention, '1,4-cis bond content' and '1,2-vinyl bond content' can be measured by Fourier transform infrared spectroscopy (FT-IR), for example, 5 mg of carbon disulfide in the same cell as a blank. After measuring the FT-IR transmittance spectrum of the carbon disulfide solution of the conjugated diene-based polymer prepared at a concentration of /mL, ^{the maximum peak value around 1130 cm -1} of the measurement spectrum (a, baseline), trans-1,4 binding The minimum peak value around 967 cm ^-1 (b) representing 1,2-vinyl bonds, ^{the minimum peak value around 911 cm -1} representing 1,2-vinyl bonds, and around ^{736 cm -1} representing cis-1,4 bonds. Each content was calculated using the minimum peak value (d) of.

The present invention provides a neodymium catalyzed modified conjugated diene polymer having a high modification rate and excellent blending properties.

The neodymium catalyzed modified conjugated diene-based polymer according to an embodiment of the present invention may have a high denaturation rate by being prepared through a manufacturing method described below, and thus it may have improved blending properties due to excellent filler affinity. have.

Specifically, the neodymium catalyzed modified conjugated diene-based polymer according to an embodiment of the present invention includes a repeating unit derived from a conjugated diene-based monomer; And a functional group derived from a denaturant represented by the following Formula 1, a denaturation rate of 30% or more, and a cis 1,4-bond content of 96% by weight or more.

[Formula 1]

In Formula 1,

R ¹ and R ² are each independently a divalent hydrocarbon group having 1 to 10 carbon atoms substituted or unsubstituted with a substituent, and R ³ and R ⁴ are each independently a hydrogen atom or 1 to 20 carbon atoms unsubstituted or substituted with a substituent Is a monovalent hydrocarbon group of, R ⁵ is a monovalent to hexavalent hydrocarbon group having 1 to 10 carbon atoms substituted or unsubstituted with a substituent, n is an integer of 1 to 6, and the substituent is an ether group, a tertiary amine group , At least one selected from an epoxy group, a carbonyl group, and a halogen group.

The modifier according to the present invention may be a compound represented by Formula 1 itself, or may include another compound capable of denaturing a conjugated diene-based polymer together with the compound represented by Formula 1.

In addition, the modifier according to the present invention includes an amine group as in the modifier represented by Formula 1, so that in the conjugated diene polymer, specifically, in the conjugated diene polymer having an active organic metal moiety, The conjugated diene-based polymer may be modified by imparting a functional group to the conjugated diene-based polymer through a substitution or addition reaction.

Meanwhile, the denaturant according to an embodiment of the present invention includes a functional group capable of increasing affinity with the filler in the molecule, thereby improving the blending properties between the polymer and the filler, and further, includes a tertiary amine group as described above. By doing so, it is possible to improve the dispersibility of the filler by preventing agglomeration between the fillers in the rubber composition. For example, in the case of using silica, which is a kind of inorganic filler, as a filler, aggregation is likely to occur due to hydrogen bonds between hydroxyl groups present on the surface of the silica, but the tertiary amine group interferes with hydrogen bonds between the hydroxyl groups of the silica and thus dispersibility of silica. Can improve. As such, the modifier has a structure capable of maximizing the blending properties of the modified conjugated diene polymer, and a modified conjugated diene polymer having excellent balance of mechanical properties such as abrasion resistance and processability of the rubber composition can be efficiently produced.

Specifically, in Formula 1, R ¹ and R ² are each independently an unsubstituted C 1 to C 10 alkylene group, and R ³ and R ⁴ are each independently a hydrogen atom or an unsubstituted C 1 to C 10 alkyl group. , R ⁵ may be an unsubstituted divalent to hexavalent aliphatic hydrocarbon cyclic group having 6 to 10 carbon atoms or an aromatic hydrocarbon cyclic group, and more specifically, the modifier represented by Chemical Formula 1 is the following Chemical Formula 1-1 or Chemical Formula 1- It may be a compound represented by 2.

[Formula 1-1]

[Formula 1-2]

.

.

In addition, the neodymium catalyzed modified conjugated diene-based polymer has a cis-1,4 bond content of the conjugated diene portion measured by Fourier transform infrared spectroscopy (FT-IR) of 96% by weight or more, specifically 97% by weight or more, more specifically It may be 98% by weight or more. Accordingly, when applied to a rubber composition, abrasion resistance, crack resistance, and ozone resistance of the rubber composition may be improved.

In addition, the neodymium catalyzed modified conjugated diene-based polymer has a 1,2-vinyl bond content of the conjugated diene part measured by Fourier transform infrared spectroscopy of 4% by weight or less, specifically 3% by weight or less, and more specifically 2% by weight. It can be below. When the 1,2-vinyl bond content in the polymer exceeds 4% by weight, there is a concern that the abrasion resistance, crack resistance, and ozone resistance of the rubber composition including the same may be deteriorated.

In addition, the modified conjugated diene-based polymer of the present invention may have a modification rate (%) calculated from Equation 1 defined above, 30% or more, specifically 40% or more and 60% or less, and the filler affinity within this range. As it is excellent, it can have excellent compounding properties when applied to a rubber composition.

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 0.7 at 100°C, specifically 0.4 or more and less than 0.7, or 0.44 or more and 0.6 or less. .

The linearity (-S/R: stress/relaxation) represents the change in stress that occurs in response to the same amount of strain generated in the material. The degree of branching can be predicted. For example, the lower the linearity, the higher the degree of branching. In addition, the said numerical value represents an absolute value.

On the other hand, when the linearity is too low, that is, the branching degree is too high, the processability is improved when applied to the rubber composition, but rotational resistance is increased and mechanical properties are decreased.

However, since the modified conjugated diene-based polymer according to an embodiment of the present invention has a linearity within the above range, when applied to a rubber composition, both blending properties such as tensile properties and viscoelasticity and blending 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, and 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 aforementioned range.

In the present invention, the Mooney viscosity was measured at 100° C. and a Rotor Speed of 2±0.02 rpm using a Mooney viscometer, for example, a Large Rotor of Monsanto's MV2000E. Specifically, after allowing the polymer to stand at room temperature (23±5°C) for 30 minutes or more, 27±3g was collected and filled in the die cavity, and the Mooney viscosity was measured while applying a torque by operating a platen. In addition, the linearity (-S/R) was obtained by measuring the slope value of the Mooney viscosity change that appears as the torque is released after the Mooney viscosity measurement and is obtained as an 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, 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-based 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 weights of n polymer molecules and dividing the total molecular weights by n, and the weight average molecular weight (Mw) is a polymer It shows 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 mean a molecular weight in terms of polystyrene 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 condition and may have a weight average molecular weight (Mw) of 3 X 10 ⁵ to 1.5 X 10 ⁶ g/mol, and a number average Molecular weight (Mn) may be 1.0 X 10 ⁵ to 5.0 X 10 ⁵ g/mol, and when applied to a rubber composition within this range, it has excellent tensile properties and excellent processability. It is easy, and there is an effect of excellent balance of mechanical properties and properties of the rubber composition. The weight average molecular weight may be, for example, 5 X 10 ⁵ to 1.2 X 10 ⁶ g/mol, or 5 X 10 ⁵ to 8 X 10 ⁵ g/mol, and the number average molecular weight is 1.5 X 10 ⁵ to 3.5 X, for example 10 ⁵ g/mol, or 2.0 X 10 ⁵ to 2.7 X 10 ⁵ g/mol.

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

On the other hand, in the present invention, the neodymium catalyzed modified conjugated diene-based polymer may represent a modified conjugated diene-based polymer derived from a catalyst composition containing a neodymium compound, that is, including an organometallic moiety activated from the catalyst, and the modified conjugated The diene polymer may be a butadiene homopolymer such as a modified polybutadiene or a modified butadiene copolymer such as a butadiene-isoprene copolymer.

Specifically, the neodymium catalyzed modified conjugated diene-based polymer includes a repeating unit derived from a conjugated diene-based monomer, and in this case, when the neodymium catalyzed modified conjugated diene-based polymer is a modified butadiene copolymer, together with the repeating unit derived from a conjugated diene-based monomer It may include repeating units derived from other conjugated diene-based monomers.

More specifically, the neodymium catalyzed modified conjugated diene-based polymer is a repeating unit derived from a conjugated diene-based monomer other than 80% to 100% by weight of a repeating unit derived from a 1,3-butadiene monomer and optionally copolymerizable with 1,3-butadiene. It may include 20% by weight or less, and within the above range, the cis 1,4-bond content may be adjusted within the above-described range. In this case, the 1,3-butadiene monomer includes 1,3-butadiene or a derivative thereof such as 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, or 2-ethyl-1,3-butadiene. Conjugated diene-based monomers other than those capable of copolymerizing with 1,3-butadiene are 2-methyl-1,3-pentadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 4 -Methyl-1,3-pentadiene, 1,3-hexadiene or 2,4-hexadiene may be included, and any one or two or more compounds of these may be used.

More specifically, in the present invention, the neodymium catalyzed modified conjugated diene polymer may be a neodymium catalyzed modified butadiene polymer including a repeating unit derived from a 1,3-butadiene monomer.

In the present invention, the activated organometallic moiety of the conjugated diene-based polymer is an activated organometallic moiety at the end of the conjugated diene-based polymer (activated organometallic moiety at the molecular chain end), an activated organometallic moiety or side chain in the main chain. In the case of obtaining an activated organometallic portion of the conjugated diene-based polymer by anionic polymerization or coordination anion polymerization, the activated organometallic portion may be an activated organometallic portion of the terminal. .

In addition, the present invention provides a method for preparing the neodymium catalyzed modified conjugated diene polymer.

The method for preparing the neodymium catalyzed modified conjugated diene-based polymer having a modification rate of 30% or more and a cis 1,4-bond content of 96 wt% or more according to an embodiment of the present invention includes a neodymium compound in a hydrocarbon solvent Preparing an active polymer by polymerizing a conjugated diene-based monomer in the presence of a catalyst composition (S1); It characterized in that it comprises a step (S2) of reacting the active polymer with a denaturant represented by the following formula (1).

[Formula 1]

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

The step S1 is a step for preparing an active polymer containing an activated organometallic moiety derived from the catalyst composition, and may be performed by polymerizing a conjugated diene-based monomer in the presence of a catalyst composition containing a neodymium compound in a hydrocarbon solvent. .

Here, the conjugated diene-based monomer may include a 1,3-butadiene monomer defined above and a conjugated diene-based monomer other than copolymerizable therewith, for example, 1,3-butadiene, 2,3-dimethyl-1,3- Butadiene or 2-ethyl-1,3-butadiene, or 1,3-butadiene, 2,3-dimethyl-1,3-butadiene or 2-ethyl-1,3-butadiene and 2-methyl-1,3-penta Diene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3-hexadiene or 2,4-hexadiene.

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 be used in an amount such that a neodymium compound is 0.1 mmol to 0.5 mmol based on a total of 100 g of conjugated diene-based monomers, and specifically, the neodymium compound is based on a total of 100 g of conjugated diene-based monomers. It may be used in an amount of 0.1 mmol to 0.4 mmol, more specifically 0.1 mmol to 0.25 mmol.

The neodymium compound may be a compound represented by Formula 2 below.

[Formula 2]

In Formula 2, R _a to R _c are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms, provided _{that all of R a} to R _c are not 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 1 selected from the group consisting of, Nd (2,2-dihexyl nonanoate) ₃ , Nd (2-ethyl-2-propyl nonanoate) ₃ and Nd (2-ethyl-2-hexyl nonanoate) ₃ It can be more than a species.

In addition, as another example, in consideration of excellent solubility in a solvent, conversion to catalytically active species, and excellent effect of improving catalytic activity without concern for oligomerization, the neodymium compound is more specifically represented by R _{a in Formula 2} It is an alkyl group having 4 to 12 carbon atoms, and R _b and R _c are each independently hydrogen or an alkyl group having 2 to 8 carbon atoms, provided that R _b and R _c are not hydrogen at the same time, but may be a neodymium-based compound.

For a more specific example, in Formula 2, 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 It may not be hydrogen at the same time, and specific examples thereof 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 Hexyl nonanoate) ₃ , Nd (2-ethyl-2-propyl nonanoate) ₃ and Nd (2-ethyl-2-hexyl nonanoate) _{3 It} may be one or more selected from the group consisting of 3, among which Neodymium-based compounds are Nd (2,2-diethyl decanoate) ₃ , Nd (2,2-dipropyl decanoate) ₃ , Nd (2,2-dibutyl decanoate) ₃ , Nd (2, 2-dihexyl decanoate) ₃ , and Nd (2,2-dioctyl decanoate) _{3 It} may be one or more selected from the group consisting of.

More specifically, in Formula 2, 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.

As described above, the neodymium-based compound represented by Formula 2 includes a carboxylate ligand containing an alkyl group having a length of 2 or more carbon atoms as a substituent at the α (alpha) position, thereby inducing a three-dimensional change around the central neodymium metal. It is possible to block the coagulation phenomenon of the liver, and accordingly, there is an effect of suppressing oligomerization. In addition, such a neodymium-based compound has a high solubility in a solvent and a reduction in the proportion of neodymium located in a central portion where conversion to the catalytically active species is difficult, thereby increasing the conversion rate to the catalytically active species.

In addition, the solubility of the neodymium compound according to an embodiment of the present invention may be about 4 g or more per 6 g of the non-polar solvent at room temperature (25° C.).

In the present invention, the solubility of a neodymium-based compound refers to a degree of clear dissolution without a cloudy phenomenon, and excellent catalytic activity may be exhibited by exhibiting such high solubility.

In addition, the neodymium compound according to an embodiment of the present invention may be used in the form of a reactant with a Lewis base. This reaction product has the effect of improving the solubility of the neodymium compound in a solvent by Lewis base and allowing it to be stored in a stable state for a long period of time. The Lewis base may be used in a ratio of 30 moles or less, or 1 to 10 moles per 1 mole of neodymium, for example. The Lewis base may be, for example, acetylacetone, tetrahydrofuran, pyridine, N,N-dimethylformamide, thiophene, diphenyl ether, triethylamine, an organophosphorus compound, or a monohydric or dihydric alcohol.

Meanwhile, the catalyst composition may further include at least one of an alkylating agent, a halide, and a conjugated diene-based monomer in addition to the neodymium compound.

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

Hereinafter, (a) an alkylating agent, (b) a halide, and (c) a conjugated diene-based monomer will be 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 used as an alkylating agent in the production of a diene-based polymer, and is soluble in a polymerization solvent, such as an organic aluminum compound, an organic magnesium compound, or an organic lithium compound, and has a metal-carbon bond. It may be an organometallic compound containing.

Specifically, as the organic aluminum compound, trimethyl aluminum, triethyl aluminum, tri-n-propyl aluminum, triisopropyl aluminum, tri-n-butyl aluminum, triisobutyl aluminum, tri-t-butyl aluminum, tripentyl Alkyl aluminum, such as aluminum, trihexyl aluminum, tricyclohexyl aluminum, and trioctyl aluminum; Diethylaluminum hydride, di-n-propylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride (DIBAH), di-n-octylaluminum hydride, Diphenylaluminum hydride, di-p-tolylaluminum hydride, dibenzylaluminum hydride, phenylethylaluminum hydride, phenyl-n-propylaluminum hydride, phenylisopropylaluminum hydride, phenyl-n-butylaluminum hydride Ride, phenylisobutylaluminum hydride, phenyl-n-octyl aluminum hydride, p-tolylethylaluminum hydride, p-tolyl-n-propylaluminum hydride, p-tolylisopropylaluminum hydride, p-tolyl- n-butylaluminum hydride, p-tolylisobutylaluminum hydride, p-tolyl-n-octylaluminum hydride, benzylethylaluminum hydride, benzyl-n-propylaluminum hydride, benzylisopropylaluminum hydride, benzyl dihydrocarbyl aluminum hydride such as -n-butyl aluminum hydride, benzyl isobutyl aluminum hydride or benzyl-n-octyl aluminum hydride; Hydrocarbyl aluminum 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. are mentioned. Examples of the organic magnesium compound include diethyl magnesium, di-n-propyl magnesium, diisopropyl magnesium, dibutyl magnesium, dihexyl magnesium, diphenyl magnesium, or alkyl magnesium compounds such as dibenzyl magnesium, and the like. Examples of the organolithium compound include alkyl lithium compounds such as n-butyllithium.

In addition, the organic aluminum compound may be aluminoxane.

The aluminoxane may be prepared by reacting water with a trihydrocarbyl aluminum-based compound, and specifically, may be a straight-chain aluminoxane represented by the following Formula 3a or a cyclic aluminoxane represented by the following Formula 3b.

[Formula 3a]

[Formula 3b]

In Formulas 3a and 3b, 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 of 2 to 50.

More specifically, the aluminoxane is methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane, n-propylaluminoxane, isopropylaluminoxane, butylaluminoxane, isobutylaluminoxane, n -Pentyl aluminoxane, neopentyl aluminoxane, n-hexyl aluminoxane, n-octyl aluminoxane, 2-ethylhexyl aluminoxane, cyclohexyl aluminoxane, 1-methylcyclopentyl aluminoxane, phenylaluminoxane or 2,6- It may be dimethylphenyl aluminoxane and the like, and any one or a mixture of two or more of them may be used.

In addition, the modified methylaluminoxane is obtained by substituting the methyl group of methylaluminoxane with a modifier group (R), specifically a hydrocarbon group having 2 to 20 carbon atoms, and may be a compound represented by the following formula (4).

[Formula 4]

In Formula 4, R is as defined above, and m and n may be an integer of 2 or more independently of each other. In addition, in Formula 4, Me represents a methyl group.

Specifically, in Formula 4, R is an alkyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, It may be an arylalkyl group having 7 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an allyl group or an alkynyl group having 2 to 20 carbon atoms, and more specifically, 2 carbon atoms such as an ethyl group, an isobutyl group, a hexyl group or an octyl group. It is an alkyl group of to 10, and more specifically, it may be an isobutyl group.

More specifically, the modified methylaluminoxane may be obtained by substituting about 50 mol% to 90 mol% of the methyl group of methylaluminoxane with the hydrocarbon group described above. When the content of the substituted hydrocarbon group in the modified methylaluminoxane is within the above range, the catalytic activity may be increased by promoting alkylation.

Such modified methylaluminoxane may be prepared according to a conventional method, and specifically, may be prepared 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 them may be used.

(b) halide

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

Examples of the halogen alone include fluorine, chlorine, bromine or iodine.

Further, examples of the interhalogen compound include iodine monochloride, iodine monobromide, iodine trichloride, iodine pentafluoride, iodine monofluoride or iodine trifluoride.

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

In addition, as the organic halide, t-butyl chloride (t-BuCl), t-butyl bromide, allyl chloride, allyl bromide, benzyl chloride, benzyl bromide, chloro-di-phenylmethane, bromo-di-phenylmethane, tri Phenylmethyl chloride, triphenylmethyl bromide, benzylidene chloride, benzylidene bromide, methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, trimethylchlorosilane (TMSCl), benzoyl chloride, benzoyl bromide, propi Onyl chloride, propionyl bromide, methyl chloroformate, methyl bromoformate, iodomethane, diiodomethane, triiodomethane (also called'iodoform'), tetraiodomethane, 1-iodo Dopropane, 2-iodopropane, 1,3-diiodopropane, t-butyl iodide, 2,2-dimethyl-1-iodopropane (also called'neopentyl iodide'), allyl yo 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, methyl iodoformate, etc. are mentioned.

In addition, as the non-metal halide, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride, phosphorus oxychloride, boron trifluoride, boron trichloride, boron tribromide, silicon tetrafluoride, silicon tetrachloride (SiCl ₄ ), silicon tetrabromide , Arsenic trichloride, arsenic tribromide, selenium tetrachloride, selenium tetrabromide, tellurium tetrachloride, tellurium tetrabromide, silicon tetrachloride, arsenic triiodide, tellurium sayiodide, boron triiodide, phosphorus triiodide, selenium oxyiodide or phosphorus triiodide, etc. Can be mentioned.

In addition, as the metal halide, 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 iodide, tetraiodide Germanium, tin sayodine, tin iodide, antimony triiodide, or magnesium iodide.

In addition, the organometallic halide includes dimethyl aluminum chloride, diethyl aluminum chloride, dimethyl aluminum bromide, diethyl aluminum bromide, dimethyl aluminum fluoride, diethyl aluminum fluoride, methyl aluminum dichloride, ethyl aluminum dichloride, methyl aluminum 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, ethyl magnesium bromide, n-butyl magnesium chloride, n-butyl magnesium bromide, phenyl magnesium chloride, phenyl magnesium bromide, benzyl magnesium chloride, trimethyl tin chloride, trimethyl tin bromide, triethyl tin chloride, triethyl tin 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, diethyl aluminum iodide, di-n-butyl aluminum iodide, diisobutyl aluminum iodide, di-n-octyl aluminum iodide, methyl aluminum Diiodide, ethyl aluminum diiodide, n-butyl aluminum diiodide, isobutyl aluminum diiodide, methyl aluminum sesquiiodide, ethyl aluminum sesquiiodide, isobutyl aluminum sesquiiodide, ethyl magnesium required Odide, n-butyl magnesium iodide, isobutyl magnesium iodide, phenyl magnesium iodide, benzyl magnesium iodide, trimethyltin iodide, triethyltin iodide, tri-n-butyltin required Odide, di-n-butyltin diiodide, di-t-butyltin diiodide, etc. are mentioned.

In addition, 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 tetraarylborate anion or fluorinated tetraaryl. It may be a borate anion and the like. Further, the compound containing the non-coordinating anion may include a carbonium cation such as a triaryl carbonium cation together 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 (pentafluoro phenyl) borate, N,N-dimethylanilinium tetrakis (pentafluoro phenyl) borate, triphenyl carbonium tetra Kiss[3,5-bis(trifluoromethyl)phenyl]borate, or N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, and the like.

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

(c) conjugated diene monomer

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

In another example, in the present invention, the catalyst composition may include a neodymium compound, a first alkylating agent, a second alkylating agent, a halide, and a conjugated diene-based monomer, and in this case, the neodymium compound, the first alkylating agent, the second alkylating agent, and a halogen The cargo and the conjugated diene-based monomer may have a molar ratio of 1:100 to 200:40 to 60:2 to 4:20 to 50, and specifically, a neodymium compound, a first alkylating agent, a second alkylating agent, a halide and a conjugated The diene-based monomer may have a molar ratio of 1:100 to 150:40 to 50:2 to 3:20 to 30.

Herein, the neodymium compound, the halide and the conjugated diene-based monomer are as defined above, and the first alkylating agent and the second alkylating agent are included in the above-described alkylating agent, and may indicate that two types of specific alkylating agents are mixed and used.

Exemplarily, the first alkylating agent is methyl aluminoxane, modified methyl aluminoxane, ethyl aluminoxane, n-propyl aluminoxane, isopropyl aluminoxane, butyl aluminoxane, isobutyl aluminoxane, n-pentyl aluminoxane, neopentyl alumino In the group consisting of noxane, n-hexyl aluminoxane, n-octyl aluminoxane, 2-ethylhexyl aluminoxane, cyclohexyl aluminoxane, 1-methylcyclopentyl aluminoxane, phenylaluminoxane, and 2,6-dimethylphenyl aluminoxane It may be one or more selected aluminoxanes, and the second alkylating agent is diethylaluminum hydride, di-n-propylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum Hydride, di-n-octyl aluminum hydride, diphenyl aluminum hydride, di-p-tolyl aluminum hydride, dibenzyl aluminum hydride, phenylethylaluminum hydride, phenyl-n-propylaluminum hydride, phenyliso Propyl aluminum hydride, phenyl-n-butylaluminum hydride, phenylisobutylaluminum hydride, phenyl-n-octyl aluminum hydride, p-tolylethylaluminum hydride, p-tolyl-n-propylaluminum hydride, p -Tolylisopropylaluminum hydride, p-tolyl-n-butylaluminum hydride, p-tolylisobutylaluminum hydride, p-tolyl-n-octylaluminum hydride, benzylethylaluminum hydride, benzyl-n-propyl It may be one or more selected from the group consisting of aluminum hydride, benzyl isopropyl aluminum hydride, benzyl-n-butyl aluminum hydride, benzyl isobutyl aluminum hydride, and benzyl-n-octyl aluminum hydride.

In addition, the catalyst composition is a mixture of a neodymium compound, a first alkylating agent, a second alkylating agent, a halide and a conjugated diene-based monomer in a hydrocarbon-based solvent at a temperature of -30°C to -20°C, and a temperature of -30°C to -20°C. It can be prepared by standing for 24 to 36 hours at.

Specifically, the catalyst composition may be prepared by sequentially adding and mixing a neodymium compound, a first alkylating agent, a second alkylating agent, a halogen compound, and optionally a conjugated diene-based monomer in a hydrocarbon-based solvent. In this case, the hydrocarbon-based solvent may be a non-polar solvent having no reactivity with the constituents of the catalyst composition. Specifically, the hydrocarbon-based solvent may include an aliphatic hydrocarbon-based solvent such as pentane, hexane, isopentane, heptane, octane, and isooctane; Cycloaliphatic hydrocarbon-based solvents such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane; Alternatively, one or more selected from the group consisting of aromatic hydrocarbon-based solvents such as benzene, toluene, ethylbenzene, xylene, and the like may be used. As a specific example, the hydrocarbon-based solvent may be an aliphatic hydrocarbon-based solvent such as hexane.

The catalyst composition according to an embodiment of the present invention may have the above-described composition and may have high activity by being prepared as described above, and thus an active polymer may be easily prepared.

In addition, by premixing a part of the conjugated diene-based monomer used in the polymerization reaction with the catalyst composition and using it in the form of a preforming catalyst composition, the catalytic activity is improved, and further, the prepared conjugated diene-based monomer is used in the form of a pre-polymerization catalyst composition. There is an effect of stabilizing the polymer.

In the present invention, the term "preforming" refers to a catalyst composition, that is, when the catalyst system includes diisobutylaluminum hydride (DIBAH), etc., in order to reduce the possibility of generating various catalytically active species together, A small amount of a conjugated diene-based monomer such as butadiene is added, and it may mean that pre-polymerization is performed in the catalyst system together with the addition of butadiene. In addition, "premix" may mean a state in which polymerization is not performed in a catalyst system and each compound is uniformly mixed.

In the present invention, the "preforming" means a catalyst composition comprising a neodymium compound, an alkylating agent, and a halide, that is, when the catalyst system includes diisobutylaluminum hydride (DIBAH), etc., various In order to reduce the possibility of generating active species in the catalyst composition, a small amount of conjugated diene monomers such as 1,3-butadiene are added, and it may mean that pre-polymerization is performed in the catalyst composition system with the addition of 1,3-butadiene. have. In addition, "premix" may mean a state in which polymerization is not performed in the catalyst composition system and each compound is uniformly mixed.

On the other hand, the polymerization of step S1 may be performed in a polymerization reactor including at least two reactors by continuous polymerization or in a batch reactor.

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

Here, the constant-temperature polymerization refers to a polymerization method comprising the step of polymerization by self-reaction heat without optionally applying heat after the addition of the catalyst composition, and the elevated temperature polymerization is a polymerization method in which heat is optionally applied after the catalyst composition is added to increase the temperature. The isothermal polymerization refers to a polymerization method in which heat is increased by adding heat after the catalyst composition is added or heat is taken to maintain a constant temperature of a reactant.

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

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

In addition, a method for preparing the modified conjugated diene-based polymer according to an embodiment of the present invention includes a reaction stopping agent for completing a polymerization reaction such as polyoxyethylene glycol phosphate after preparing the active polymer; Alternatively, it may include the step of terminating the polymerization by further using an additive such as an antioxidant such as 2,6-di-t-butylparacresol. In addition, additives such as a chelating agent, a dispersing agent, a pH adjusting agent, a deoxygenating agent, or an oxygen scavenger may be optionally further used.

The step S2 is a step of preparing a neodymium catalyzed modified conjugated diene-based polymer by modifying or coupling an active polymer, and may be performed by reacting the active polymer with a modifier represented by Formula 1. That is, in an embodiment of the present invention, the neodymium catalyzed modified conjugated diene polymer may be a modified polymer in which a functional group derived from the modifier is introduced at at least one end of a polymer chain.

The modifier may be used in an amount of 0.5 to 20 moles relative to 1 mole of the neodymium compound in the catalyst composition. Specifically, the modifier may be used in an amount of 1 to 10 moles relative to 1 mole of the neodymium compound in the catalyst composition.

In addition, 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, an isopropanol solution of 2,6-di-t-butyl-p-cresol (BHT) or the like may be added to the polymerization reaction system to stop the polymerization reaction. Thereafter, a conjugated diene-based polymer may be obtained through vacuum drying treatment or desolvation treatment such as steam stripping to lower the partial pressure of the solvent through the supply of water vapor. In addition, in the reaction product obtained as a result of the above-described modification reaction, an unmodified, active polymer may be included in addition to the above-described modified conjugated diene polymer.

In the manufacturing method according to an embodiment of the present invention, after step S2, a modified conjugated diene-based polymer may be obtained through desolvation treatment such as steam stripping or vacuum drying treatment to lower the partial pressure of the solvent through supply of water vapor. . In addition, in the reaction product obtained as a result of the above reaction, an unmodified, active polymer may be included in addition to the above-described modified conjugated diene polymer.

Furthermore, the present invention provides a rubber composition comprising the neodymium catalyzed modified conjugated diene-based polymer and a molded article prepared from the rubber composition.

The rubber composition according to an embodiment of the present invention contains 0.1% by weight or more and 100% by weight or less, specifically 10% to 100% by weight, and more specifically 20% to 90% by weight of the modified conjugated diene-based polymer. It may be included as. If the content of the modified conjugated diene-based polymer is less than 0.1% by weight, as a result, the effect of improving abrasion resistance and crack resistance of a molded article manufactured using the rubber composition, such as a tire, may be insignificant.

In addition, the rubber composition may further include other rubber components as necessary in addition to the modified conjugated diene-based polymer, and 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 a natural rubber or a synthetic rubber, for example, the rubber component is a natural rubber (NR) including cis-1,4-polyisoprene; Modified natural rubber such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), hydrogenated natural rubber, etc. obtained by modifying or purifying the general natural rubber; Styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, polyisobutylene-co-isoprene, neoprene, poly(ethylene-co- Propylene), poly(styrene-co-butadiene), poly(styrene-co-isoprene), poly(styrene-co-isoprene-co-butadiene), poly(isoprene-co-butadiene), poly(ethylene-co-propylene -Co-diene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, halogenated butyl rubber, and the like, and any one or a mixture of two or more of them may be used.

In addition, the rubber composition may include 0.1 parts by weight to 200 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene-based polymer, and the filler may be silica-based, carbon black, or a combination thereof. Specifically, the filler may be carbon black.

The carbon black filler is not particularly limited, but may have a nitrogen adsorption specific surface area ( _{measured in accordance with N 2} SA, JIS K 6217-2:2001) of 20 m 2 /g to 250 m 2 /g. In addition, the carbon black may have a dibutylphthalate oil absorption (DBP) of 80 cc/100g to 200 cc/100g. When the nitrogen adsorption specific surface area of the carbon black ^{exceeds 250 m 2} /g, the processability of the rubber composition may be deteriorated, and when it is ^{less than 20 m 2} /g, the reinforcing performance by the carbon black may be insignificant. In addition, when the DBP oil absorption amount of the carbon black exceeds 200 cc/100 g, the processability of the rubber composition may be deteriorated, and when it is less than 80 cc/100 g, the reinforcing performance by the carbon black may be insignificant.

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 a wet silica having the most remarkable effect of improving fracture properties and having both wet grip properties. In addition, the silica has a nitrogen surface area per gram (N ₂ SA) of 120 m2/g to 180 m2/g, and a specific surface area of CTAB (cetyl trimethyl ammonium bromide) adsorption of 100 m2/g to 200 m2 May be /g. When the nitrogen adsorption specific surface area of the silica is less than 120 m 2 /g, the reinforcing performance by silica may be deteriorated, and when it exceeds 180 m 2 /g, the workability of the rubber composition may be deteriorated. In addition, when the CTAB adsorption specific surface area of the silica is less than 100 m 2 /g, the reinforcing performance by silica as a filler may be deteriorated, and when it exceeds 200 m 2 /g, the workability 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 reinforcement and low heat generation.

Specifically, as the silane coupling agent, bis(3-triethoxysilylpropyl)tetrasulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis (2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, 3-mercaptopropyltrimethoxysilane , 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfur Feed, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilyl Propylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzolyltetrasulfide, 3-triethoxysilylpropylmethacrylate monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, bis (3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide or dimethoxymethylsilylpropylbenzothiazolyl Tetrasulfide and the like, and any one or a mixture of two or more of them may be used. More specifically, when considering the effect of improving reinforcing properties, the silane coupling agent may be bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide.

In addition, the rubber composition according to an embodiment of the present invention may be sulfur crosslinkable, and thus may further include a vulcanizing agent.

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

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

The vulcanization accelerator is not particularly limited, and specifically, 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 softening agent in the rubber composition, and may be a paraffinic, naphthenic, or aromatic compound. More specifically, when considering tensile strength and abrasion resistance, the aromatic process oil price, hysteresis loss And in consideration of low-temperature characteristics, naphthenic or paraffinic 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 amount, it is possible to prevent a decrease in tensile strength and low heat generation (low fuel economy) of the vulcanized rubber.

In addition, as the anti-aging agent, specifically, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 6- And oxy-2,2,4-trimethyl-1,2-dihydroquinoline, or a high-temperature condensation product of diphenylamine and acetone. 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, a roll, or an internal mixer according to the above formulation, and has low heat generation and abrasion resistance by a vulcanization process after molding processing. This excellent rubber composition can be obtained.

Accordingly, the rubber composition is a tire tread, under tread, side wall, carcass coated rubber, belt coated rubber, bead filler, pancreas, or bead coated rubber, and other tire members, anti-vibration rubber, belt conveyor, hose, etc. It may be useful in the manufacture of various industrial rubber products.

The molded article manufactured using the rubber composition may include a tire or a tire tread.

Hereinafter, the present invention will be described in more detail by examples and experimental examples. However, the following Examples and Experimental Examples are for illustrative purposes only, and the scope of the present invention is not limited thereto.

Manufacturing example

In a hexane solvent under nitrogen conditions, NdV (neodymium versatate, Nd (2-ethyl hexanoate) ₃ ) was added, and methylaluminoxane (MAO), diisobutylaluminum hydride (DIBAH), diethylaluminum chloride (DEAC ) And 1,3-butadiene were sequentially added to a molar ratio of NdV:MAO:DIBAH:DEAC:1,3-butadiene=1:120:43:2-3:30, and then mixed at -20°C for 12 hours. The catalyst composition was prepared. The prepared catalyst composition was stored at -30°C to -20°C under nitrogen conditions for 24 hours and then used.

Example 1

After the vacuum and nitrogen were alternately added to the completely dried reactor, 4.2 kg hexane and 500 g of 1,3-butadiene were added to a 15 L reactor in a vacuum state, and the temperature was raised to 70°C. After the catalyst composition of Preparation Example was added thereto, polymerization was performed for 60 minutes to prepare an active polymer. Here, a denaturing agent represented by the following Formula 1-1 (TETRAD-X, MITSUBISHI GAS CHEMICAL CO., INC.) was added and the denaturation reaction was performed at the same temperature for 30 minutes (denaturant: Nd = 5: 1 molar ratio). Thereafter, a hexane solution containing 1.0 g of HPSS as a polymerization stopper and 2.0 g of Wingstay-K as an antioxidant was added to terminate the reaction, and a neodymium catalyzed modified butadiene polymer was prepared.

[Formula 1-1]

Example 2

In Example 1, a neodymium catalyzed modified butadiene polymer was prepared in the same manner as in Example 1, except that the modifier was used in the [modifier:Nd=20:1 molar ratio].

Example 3

In Example 1, through the same method as in Example 1, except that the denaturing reaction was performed using a denaturing agent represented by Formula 1-2 below (TETRAD-C, MITSUBISHI GAS CHEMICAL CO., INC.) as a denaturing agent. A neodymium catalyzed modified butadiene polymer was prepared.

[Formula 1-2]

Comparative Example 1

BR1208 (manufacturer LG Chem) was used as the unmodified Ni-BR.

Comparative Example 2

In Example 1, a neodymium catalyzed unmodified butadiene polymer was prepared in the same manner as in Example 1, except that the modification reaction was not performed.

Comparative Example 3

After the vacuum and nitrogen were alternately added to the completely dried reactor, 4.2 kg hexane and 500 g of 1,3-butadiene were added to a 15 L reactor in a vacuum state, and the temperature was raised to 70°C. Here, 0.4 g of n-butyllithium and 0.25 g of tetraethylenediamine were sequentially added to the reactor, and polymerization was performed for 60 minutes to prepare an active polymer. To this, a denaturant represented by Formula 1-1 (TETRAD-X, MITSUBISHI GAS CHEMICAL CO., INC.) was added and the denaturation reaction was performed at the same temperature for 30 minutes (denaturant: act. Li = 0.06:1 molar ratio). . Thereafter, a hexane solution containing 1.0 g of isopropyl alcohol and 2.0 g of Wingstay-K as an antioxidant was added to terminate the reaction, thereby preparing a modified butadiene polymer.

Experimental Example 1

Each of 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) cis 1,4-bond content

The cis 1,4-bond content 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 under the condition of 40° C., and then loaded and flowed through gel permeation chromatography (GPC). At this time, the column was used in combination with two PLgel Olexis columns and one PLgel mixed-C column manufactured by Polymer Laboratories. 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 value

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

4) Denaturation rate (%)

Each polymer was dissolved in cyclohexane and stored in a sample (prepared at 1.0 mg/ml) in a mobile phase reservoir, and tetrahydrofuran (THF) was stored in another mobile phase reservoir. Each of the mobile phase reservoirs was connected to a dual-head pump, and a solution of the mobile phase reservoir in which the polymer was dissolved was first injected into a column filled with a silica adsorbent through the pump and an injector having a loop volume of 100 μl. At this time, the pressure of the pump was 450 psi, and the injection flow rate was 0.7 ml/min. Subsequently, it was confirmed that the unmodified butadiene polymer unit in the polymer was no longer detected from the detector (ELSD, Waters), and the tetrahydrofuran was injected into the column through a pump based on 5 minutes from the start of injection. At this time, the pressure of the pump was 380 psi, and the injection flow rate was 0.7 ml/min. When tetrahydrofuran was injected from the detector, it was confirmed that the modified butadiene polymer unit in the polymer was no longer detected, and the injection of the second solvent was terminated. Then, the denaturation rate (%) was calculated according to Equation 1 below from the detected chromatogram result.

[Equation 1]

In Equation 1, the peak area of the unmodified polymer unit is the peak area of the chromatogram for the first solution transferred to the detector, and the peak area of the modified polymer unit is for the second solution transferred to the detector. It is the peak area of the chromatogram.

division Example Comparative example One 2 3 One 2 3 Cis 1,4-bond content (% by weight 96.4 96.2 96.5 96.6 96.5 34.5 GPC results Mn (×10 ⁶ g/mol) 2.36 2.75 2.22 1.57 2.58 3.89 Mw (×10 ⁶ g/mol) 6.49 7.03 6.40 5.01 6.61 7.58 MWD(Mw/Mn) 2.75 2.56 2.88 3.19 2.56 1.95 Mooney viscosity (RP)
(ML1+4, @100℃)(MU) 50 68 58 48 44 68 -S/R 0.642 0.467 0.614 0.594 0.865 0.745 Denaturation rate (%) 35 46 37 - - 65

As shown in Table 1, Examples 1 to 3 all had a high denaturation rate of 30% or more, and a cis 1,4-bond content of 96% by weight. On the other hand, Comparative Example 3 was prepared under the same conditions except that the catalyst composition presented in the present invention was not used, but the cis 1,4-bond content was less than 50% by weight. Through these results, it can be confirmed that the cis 1,4-bond content is a physical property expressed by the catalyst composition.

Experimental Example 2

After preparing a rubber composition and a rubber specimen using each of the polymers prepared in the Examples and Comparative Examples, Mooney viscosity, tensile strength, 300% modulus, and viscoelastic properties (rotation resistance) were measured by the following methods. . The results are shown in Table 2 below.

Specifically, the rubber composition comprises 100 parts by weight of each polymer, 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 ( 2 parts by weight of stearic acid) were added to prepare respective rubber compositions. Thereafter, 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 of the rubber compositions, and gently mixed at 50 rpm for 1.5 minutes at 50° C., and then a roll of 50° C. was used. Thus, a vulcanized formulation in the form of a sheet was obtained. The obtained vulcanized compound was vulcanized at 160° C. for 25 minutes to prepare a rubber specimen.

1) Mooney viscosity (FMB, Final Master Batch)

Mooney viscosity (ML1+4, @100°C) (MU) was measured using each of the vulcanized formulations prepared above. Specifically, Mooney viscosity (MV) was measured under the condition of Rotor Speed 2±0.02 rpm at 100°C using a large rotor with Monsanto's MV2000E. At this time, the sample used was left at room temperature (23±3℃) for at least 30 minutes, then 27±3g was collected and filled in the die cavity, and the Mooney viscosity was measured while applying a torque by operating a platen.

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

After vulcanizing each rubber composition at 150° C. for t90 minutes, the tensile strength of the vulcanized material, the modulus at 300% elongation (M-300%), and the elongation of the vulcanized material at break were measured according to ASTM D412.

3) Viscoelastic properties (Tanδ @ 60℃)

The most important properties of Tan δ for low fuel efficiency were measured by using DMTS 500N from Gabo, Germany, and the viscoelastic modulus (Tan δ) at 60°C at a frequency of 10 Hz, Prestrain 3%, and Dynamic Strain 3%. At this time, the Tanδ value at 60°C represents the rolling resistance characteristic (fuel economy).

4) Wear resistance (DIN abrasion test)

For each rubber specimen using a DIN abrasion device, a DIN abrasion test was performed according to ASTM D5963, and DIN wt loss index (loss volume index): ARIA based on the measured value of Comparative Example 2 (Abration resistance index, Method A) The higher the value, the better.

division Example Comparative example One 2 3 One 2 3 Mooney viscosity (FMB) 74 89 80 65 68 94 △MV 24 21 22 17 24 24 Tensile properties M-300% 109 110 108 98 100 80 The tensile strength 105 113 107 99 100 90 Viscoelastic properties Tanδ @ 60℃ 105 113 108 95 100 84 Wear resistance (DIN wt loss Index) 105 104 103 99 100 50

In Table 2, the tensile properties of Examples 1 to 3, Comparative Example 1, and Comparative Example 3 were indexed (Index, %) by using the measured value of Comparative Example 2 as a reference value and calculated by Equation 2 below, and viscoelastic properties and abrasion resistance Was calculated by the following equation (3) and indexed.

[Equation 1]

Index(%)=(measured value/reference value)X100

[Equation 2]

Index(%)=(reference value/measured value)X100

As shown in Table 2, Examples 1 to 3 exhibited superior processability characteristics equal to or higher than those of Comparative Examples 1 to 3, while improving abrasion resistance and remarkably improving tensile characteristics and rolling resistance characteristics.

Specifically, Examples 1 to 3 were improved abrasion resistance by 3% or more compared to Comparative Example 2, and the tensile properties and rolling resistance properties were each significantly improved from as little as 5% to as much as 10% or more. It was prepared in the same manner as in Example 1, except that the denaturant represented by 1 was not used.

In addition, in the case of Comparative Example 3, compared to Examples 1 to 3, the tensile properties and rolling resistance characteristics were significantly reduced to about 70-80% level, and the abrasion resistance was sharply decreased to half the level, wherein Comparative Example 3 was presented in the present invention. It was prepared in the same manner as in Example 1, except that n-butyllithium was used instead of the catalyst composition.

Through this, the neodymium catalyzed modified conjugated diene-based polymer according to the present invention contains a functional group derived from a modifier represented by Formula 1, and is prepared in the presence of a catalyst composition containing a neodymium compound, thereby having excellent filler affinity and consequently tensile properties. , It was confirmed that the wear resistance and rolling resistance properties are both improved.

Claims (15)

A repeating unit derived from a conjugated diene-based monomer; And
It includes a functional group derived from a denaturant represented by the following formula (1),
The denaturation rate is more than 30%,
A neodymium catalyzed modified conjugated diene polymer having a cis 1,4-bond content of 96% by weight or more:
[Formula 1]

In Formula 1,
R ¹ and R ² are each independently a divalent hydrocarbon group having 1 to 10 carbon atoms substituted or unsubstituted with a substituent,
R ³ and R ⁴ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms unsubstituted or substituted with a substituent,
R ⁵ is a monovalent to hexavalent hydrocarbon group having 1 to 10 carbon atoms unsubstituted or substituted with a substituent,
n is an integer from 1 to 6,
The substituent is at least one selected from an ether group, a tertiary amine group, an epoxy group, a carbonyl group and a halogen group.
The method of claim 1,
In Formula 1,
R ¹ and R ² are each independently an unsubstituted C 1 to C 10 alkylene group,
R ³ and R ⁴ are each independently a hydrogen atom or an unsubstituted C 1 to C 10 alkyl group,
R ⁵ is an unsubstituted divalent to hexavalent C6-C10 aliphatic hydrocarbon cyclic group or an aromatic hydrocarbon cyclic group,
n is an integer of 2 to 6 neodymium catalyzed modified conjugated diene polymer.
The method of claim 1,
The denaturing agent represented by Formula 1 is a compound represented by Formula 1-1 or Formula 1-2, which is a neodymium catalyzed modified conjugated diene polymer:
[Formula 1-1]

[Formula 1-2]

The method of claim 1,
A neodymium catalyzed modified conjugated diene polymer having a 1,2-vinyl bond content of 4% by weight or less.
The method of claim 1,
A neodymium catalyzed modified conjugated diene polymer having a modification rate of 40% or more and 60% or less.
Preparing an active polymer by polymerizing a conjugated diene-based monomer in the presence of a catalyst composition containing a neodymium compound in a hydrocarbon solvent (S1); And
Including the step (S2) of reacting the active polymer with a denaturant represented by the following formula (1),
The denaturation rate is more than 30%,
The method for preparing the neodymium catalyzed modified conjugated diene polymer of claim 1 having a cis 1,4-bond content of 96% by weight or more:
[Formula 1]

In Formula 1,
R ¹ and R ² are each independently a divalent hydrocarbon group having 1 to 10 carbon atoms substituted or unsubstituted with a substituent,
R ³ and R ⁴ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms unsubstituted or substituted with a substituent,
R ⁵ is a monovalent to hexavalent hydrocarbon group having 1 to 10 carbon atoms unsubstituted or substituted with a substituent,
n is an integer from 1 to 6,
The substituent is at least one selected from an ether group, a tertiary amine group, an epoxy group, a carbonyl group and a halogen group.
The method of claim 6,
The method for producing a neodymium catalyzed modified conjugated diene-based polymer wherein the modifier represented by Formula 1 is a compound represented by Formula 1-1 or Formula 1-2:
[Formula 1-1]

[Formula 1-2]

.
The method of claim 6,
The neodymium compound is a neodymium catalyzed modified conjugated diene polymer which is a compound represented by the following formula (2):
[Formula 2]

In Chemical Formula 2,
R _a to R _c are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms,
However, _{not all of R a} to R _c are hydrogen at the same time.
The method of claim 6,
The catalyst composition is a neodymium catalyzed modified conjugated diene-based polymer further comprising at least one of an alkylating agent, a halide and a conjugated diene-based monomer.
The method of claim 6,
The catalyst composition includes a neodymium compound, a first alkylating agent, a second alkylating agent, a halide and a conjugated diene-based monomer,
The neodymium compound, the first alkylating agent, the second alkylating agent, the halide and the conjugated diene-based monomer have a molar ratio of 1:100 to 200:40 to 60:2 to 4:20 to 50 Method of making a polymer.
The method of claim 10,
The catalyst composition is a mixture of a neodymium compound, a first alkylating agent, a second alkylating agent, a halide, and a conjugated diene-based monomer in a hydrocarbon-based solvent at a temperature of -30°C to -20°C, and 24 at a temperature of -30°C to -20°C. A method for producing a neodymium catalyzed modified conjugated diene-based polymer prepared by standing for a period of time to 36 hours.
The method of claim 10,
The first alkylating agent is methyl aluminoxane, modified methyl aluminoxane, ethyl aluminoxane, n-propyl aluminoxane, isopropyl aluminoxane, butyl aluminoxane, isobutyl aluminoxane, n-pentyl aluminoxane, neopentyl aluminoxane, n -One selected from the group consisting of hexyl aluminoxane, n-octyl aluminoxane, 2-ethylhexyl aluminoxane, cyclohexyl aluminoxane, 1-methylcyclopentyl aluminoxane, phenyl aluminoxane, and 2,6-dimethylphenyl aluminoxane A method for producing a neodymium catalyzed modified conjugated diene-based polymer that is the above aluminoxane.
The method of claim 10,
The second alkylating agent is diethylaluminum hydride, di-n-propylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride, di-n-octylaluminum hydride. Ride, diphenylaluminum hydride, di-p-tolylaluminum hydride, dibenzylaluminum hydride, phenylethylaluminum hydride, phenyl-n-propylaluminum hydride, phenylisopropylaluminum hydride, phenyl-n-butyl Aluminum hydride, phenylisobutylaluminum hydride, phenyl-n-octyl aluminum hydride, p-tolylethylaluminum hydride, p-tolyl-n-propylaluminum hydride, p-tolylisopropylaluminum hydride, p- Tolyl-n-butylaluminum hydride, p-tolylisobutylaluminum hydride, p-tolyl-n-octylaluminum hydride, benzylethylaluminum hydride, benzyl-n-propylaluminum hydride, benzylisopropylaluminum hydride , Benzyl-n-butylaluminum hydride, benzylisobutylaluminum hydride, and benzyl-n-octyl aluminum hydride, one or more selected from the group consisting of a neodymium catalyzed modified conjugated diene-based polymer production method.
A rubber composition comprising the neodymium catalyzed modified conjugated diene polymer of claim 1 and a filler.
The method of claim 14,
A rubber composition comprising 100 parts by weight of the neodymium catalyzed modified conjugated diene-based polymer and 0.1 parts by weight to 200 parts by weight of a filler.