KR20160073924A

KR20160073924A - Modified conjugated diene polymer and rubber composition comprising the same

Info

Publication number: KR20160073924A
Application number: KR1020150179880A
Authority: KR
Inventors: 김원희; 배효진; 김철재; 안정헌; 최원문
Original assignee: 주식회사 엘지화학
Priority date: 2014-12-17
Filing date: 2015-12-16
Publication date: 2016-06-27
Also published as: KR101770482B1

Abstract

The present invention provides a modified conjugated polymer comprising a modifier-derived functional group represented by the following chemical formula 1, having a high linearity and high modification ratio corresponding to a stress/relaxation (S/R) value of 0.8 or more at 100°C, showing high affinity to an inorganic filler in a rubber composition, and thus capable of improving the physical properties, such as wear resistance, and processability of a rubber composition when applied to the rubber composition. The present invention also relates to a rubber composition comprising the modified conjugated polymer. In chemical formula 1, Cy, R^1 and R^2 are the same as defined in the specification.

Description

MODIFIED CONJUGATED DIENE POLYMER AND RUBBER COMPOSITION COMPRISING THE SAME [0002]

The present invention relates to a modified conjugated diene polymer having a high modifying ratio with excellent linearity and exhibiting excellent affinity to an inorganic filler in a rubber composition and capable of improving the physical properties and processability of the rubber composition, &Lt; / RTI >

Recently, interest in energy conservation and environmental issues has increased, and fuel economy of automobiles has been demanded. As a method for realizing this, a method of lowering the heat generation in a tire by using an inorganic filler such as silica or carbon black in the rubber composition for tire formation has been proposed. However, the above-mentioned inorganic filler is not easily dispersed in the rubber composition, and there is a problem that the physical properties of the rubber composition, including abrasion resistance, crack resistance or workability, are lowered.

As a method for solving such a problem and improving the dispersibility of an inorganic filler such as silica or carbon black in a rubber composition, a polymerizable active site of a conjugated diene polymer obtained by anionic polymerization using organolithium is reacted with a functional group capable of interacting with an inorganic filler Was developed. Specifically, a method of modifying the polymerization active terminal of the conjugated diene-based polymer with a tin-based compound, a method of introducing an amino group, or a method of modifying the polymerization terminal with an alkoxysilane derivative have been proposed.

However, when the modified conjugated diene polymer modified by the above-mentioned method is used, low heat build-up can be ensured in the production of the rubber composition, but the effect of improving the physical properties of the rubber composition such as abrasion resistance and workability is not sufficient.

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

Japanese Patent Publication No. 1994-057767 (registered on August 3, 1994) Japanese Patent Publication No. 3230532 (registered on September 14, 2001) International Patent Publication No. WO2003-029299 (published Apr. 10, 2003)

A first technical problem to be solved by the present invention is to provide a rubber composition which exhibits excellent linearity and a high modifying ratio and exhibits excellent affinity for an inorganic filler in a rubber composition, And a conjugated diene polymer.

A second technical problem to be solved by the present invention is to provide a process for producing the modified conjugated diene polymer.

A third object of the present invention is to provide a polymer composition and a rubber composition containing the modified conjugated diene polymer.

A fourth object of the present invention is to provide a rubber molded article and a tire produced using the rubber composition.

However, the technical problem to be solved by the present invention is not limited to the above-mentioned problems, and other matters not mentioned can be clearly understood by those skilled in the art from the following description.

According to one embodiment of the present invention, there is provided a modified conjugated diene polymer comprising a modifier-derived functional group represented by the following formula (1) and having a value of -S / R (stress / relaxation) to provide.

[Chemical Formula 1]

(Wherein Cy in the formula (1) is substituted with at least one substituent selected from the group consisting of a halogen group, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms hwandoen, a group of the aromatic hydrocarbon having 6 to 20 carbon atoms, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms containing one or more heteroatoms selected from the group consisting of N, S and O, and R ² are carbon atoms, 11 to 30 aliphatic monovalent hydrocarbon groups)

According to another embodiment of the present invention, a conjugated diene-based polymer is polymerized in a polymerization solvent using a polymerization catalyst containing a neodymium compound of the following formula (2) Preparing; And a step of reacting the conjugated diene polymer having the active metal organic moiety with the modifier of the above formula (1).

(2)

(Wherein R _a is a linear or branched alkyl group having 6 to 12 carbon atoms, R _b and R _c are each independently a hydrogen atom or a linear or branched alkyl group having 2 to 8 carbon atoms, provided that R _b And R < _c > are not simultaneously hydrogen atoms)

According to another embodiment of the present invention, there is provided a conjugated diene-based polymer having an active organometallic moiety obtained by polymerizing a conjugated diene monomer in a polymerization solvent using a polymerization catalyst containing a neodymium compound of Formula 2, There is provided a polymer composition comprising a modified conjugated diene polymer prepared by modifying a conjugated diene polymer having an active metal organic moiety with a modifier of the above formula (1).

Still further, according to another embodiment of the present invention, there is provided a rubber composition comprising the modified conjugated diene polymer.

According to still another embodiment of the present invention, there is provided a rubber molded article and a tire produced using the rubber composition.

Other details of the embodiments of the present invention are included in the following detailed description.

The modified conjugated diene polymer according to the present invention can be produced by using a neodymium catalyzed conjugated diene polymer having excellent linearity by using a polymerization catalyst containing a neodymium compound having high solubility in a polymerization solvent and high conversion to a catalytically active species And has excellent linearity and high modifying ratio and shows excellent affinity for an inorganic filler in a rubber composition by being produced by modifying it with a modifier including an inorganic filler affinity functional group and a solvent affinity functional group at the same time. As a result, it is possible to improve the physical properties and workability of the rubber composition including abrasion resistance when applied to the rubber composition.

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

The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.

Modified conjugated diene polymer

The modified conjugated diene polymer according to one embodiment of the present invention comprises a modifier-derived functional group represented by the following formula (1), and the value of -S / R (stress / relaxation) at 100 캜 is 0.8 or more.

[Chemical Formula 1]

(In the formula 1,

Cy is a group selected from the group consisting of a halogen group, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms, 20 aromatic divalent hydrocarbon group,

R ¹ is a hydrocarbon group of 1 to 20 carbon atoms containing at least one heteroatom selected from the group consisting of N, S and O, and

And R < ² > is an aliphatic monovalent hydrocarbon group having from 11 to 30 carbon atoms)

Specifically, the modified conjugated diene polymer according to one embodiment of the present invention is obtained by polymerizing a conjugated diene monomer in a polymerization solvent using a polymerization catalyst containing a neodymium compound of the following formula (2) And then modifying the conjugated diene polymer with the modifier of the above formula (1).

(2)

(In the formula (2)

R _a is a linear or branched alkyl group having 6 to 12 carbon atoms,

R _b and R _c are each independently a hydrogen atom or a linear or branched alkyl group having from 2 to 8 carbon atoms with the proviso that R _b and R _c are not simultaneously hydrogen atoms)

In the present invention, the active site of the conjugated diene polymer may be an active terminal site (active site at the molecular chain terminal) of the conjugated diene polymer, an active site in the main chain or an active site in the side chain, When the active site of the conjugated diene polymer is obtained by anionic polymerization, it may be an active terminal site.

Specifically, the modified conjugated diene polymer is produced by using a catalyst for polymerization containing a neodymium compound of Formula 2, which has a high solubility in a polymerization solvent and a high conversion ratio to a catalytically active species, whereby a living end, that is, Catalyzed conjugated diene-based polymer having excellent activity at the site, the terminal modification ratio is high and the effect of improving the physical properties of the rubber composition is excellent.

The modified conjugated diene polymer is modified by using the modifier of the above formula (1) simultaneously containing an inorganic filler affinity functional group and a solvent affinity functional group. In the conjugated diene polymer, specifically, Derived functional groups.

Thus, the modifier of the above-mentioned formula (1) can be obtained by subjecting a conjugated diene-based polymer, specifically, a conjugated diene-based polymer having an active organometallic moiety, to a functional group To denature the polymer.

Specifically, the modifier of the above formula (1) is a functional group capable of improving the physical properties of the butadiene polymer, together with an imino group which is a reactive functional group for the butadiene polymer in the molecule, a functional group for improving the dispersibility of the inorganic filler, A filler affinity functional group and a solvent affinity functional group. Specifically, in the above modifier, the imino group exhibits high reactivity with respect to the active site of the conjugated diene polymer, so that the conjugated diene polymer can be modified with a high modification ratio, and as a result, a functional group substituted with a modifying agent Can be introduced into the conjugated diene polymer at a high yield. The imino group may be further converted to a secondary amino group by reacting with the conjugated diene-based polymer to improve the affinity with the inorganic filler. In addition, the aliphatic hydrocarbon group, more specifically, the linear aliphatic hydrocarbon group, increases the affinity to the polymerization solvent to increase the solubility of the modifier, and as a result, the modification ratio to the conjugated diene polymer can be improved. In addition, in the above modifier, a hydrocarbon group containing a hetero atom, specifically a tertiary amino group, improves the affinity of the modified denatured diene polymer in the rubber composition with the filler. For example, the tertiary amino group prevents the hydrogen bonding between the hydroxyl groups present on the surface of the inorganic filler, thereby preventing the aggregation between the inorganic fillers, thereby improving the dispersibility of the inorganic filler in the rubber composition. As such, the modifier has an optimized structure capable of maximizing the affinity with an inorganic filler and a solvent, thereby efficiently producing a modified conjugated diene polymer capable of improving the abrasion resistance, the low fuel consumption characteristic and the workability of the rubber composition in a good balance can do.

In the present invention, the solubility of the modifier means a degree of dissolution that is clear without visual phenomenon when observed visually.

Specifically, the modified conjugated diene polymer may have a cis-1,4 bond content of not less than 95%, more specifically not less than 98%, as measured by Fourier transform infrared spectroscopy (FT-IR). As described above, since the cis-1,4 bond content in the 1,3-butadiene monomer unit is high and the vinyl bond content is low as compared with the conventional butadiene polymer, the elongation crystallinity is remarkably high. As a result, The abrasion resistance, crack resistance and ozone resistance of the composition can be improved.

The modified conjugated diene polymer may have a vinyl content of not more than 5%, more specifically not more than 2%, as measured by Fourier transform infrared spectroscopy. When the vinyl content in the polymer is more than 5%, the elongation crystallinity is insufficient, and the abrasion resistance, crack resistance and ozone resistance of the rubber composition containing the rubber composition may be deteriorated.

In the present invention, the content of cis-1,4 bond and the content of vinyl in the polymer by FT-IR were measured by using a carbon disulfide of the same cell as a blank, and a concentration of 5 mg / After the FT-IR transmittance spectrum was measured, the maximum peak value (a, baseline) near 1130 cm ^-1 of the measurement spectrum, the minimum peak value (b) near 967 cm ^-1 indicating trans- for using the minimum peak value (c), and the minimum peak value of the 736cm ^-1 near showing a cis-1,4 bond (d) the near 911cm ^-1 was determined for each of the content shown.

The modified conjugated diene polymer may have a molecular weight distribution with a molecular weight distribution (MWD) of from 2.5 to 3.5, specifically from 2.8 to 3.2, by the specific production method. If the molecular weight distribution of the modified conjugated diene polymer is less than 2.5, the workability of the rubber composition containing the diene polymer tends to deteriorate, so that it is difficult to sufficiently perform the physical properties of the rubber composition, and the molecular weight distribution of the modified conjugated diene polymer If it is more than 3.5, there is a fear that the physical properties such as hysteresis loss of the rubber composition may be lowered.

In the present invention, the molecular weight distribution (MWD) of the modified butadiene polymer is also called polydispersity and can be calculated as the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) . The weight-average molecular weight and the number-average molecular weight are molecular weight in terms of polystyrene analyzed by gel permeation chromatography (GPC), and all molecular weight averages can be expressed in grams (g / mol) per mole.

Further, the modified conjugated diene-based polymer has a weight average molecular weight (Mw) under conditions which satisfy the above-described molecular weight distribution 5X10 ⁵ g / mol to about ⁶ 1.2X10 g / mol, more specifically, 6X10 ⁵ g / mol to about 1.0X10 specifically, ⁶ g / mol, more addition number-average molecular weight (Mn) of 1.5X10 ⁵ g / mol to about 4.5X10 ⁵ g / mol, it may be one of 2.0X10 ⁵ g / mol to about 3.2X10 ⁵ g / mol.

When the weight average molecular weight of the modified conjugated diene polymer is less than 500,000 g / mol, or when the number average molecular weight is less than 150,000 g / mol, the modulus of elasticity of the vulcanized product is decreased to increase the hysteresis loss and deteriorate the abrasion resistance. If the average molecular weight exceeds 1,200,000 g / mol or the number average molecular weight exceeds 450,000 g / mol, the workability of the rubber composition containing the modified conjugated diene polymer is deteriorated and the kneading becomes difficult, The physical properties can not be sufficiently improved.

The modified conjugated diene polymer may have a Mooney viscosity (MV) of 40 to 70 MU, more specifically 45 to 65 MU at 100 ° C. As the Mooney viscosity increases, it means an increase in the degree of branching in the conjugated diene polymer. The modified conjugated diene polymer according to the present invention has a relatively low Mooney viscosity as described above, and can exhibit excellent linearity and an improvement in processability of the rubber composition.

According to one embodiment of the present invention, the Mooney viscosity can be measured using, for example, Monsanto MV2000E at 100 ° C using Rotor Speed 2 0.02 rpm, Large Rotor. The sample used is allowed to stand at room temperature (23 ± 3 ° C) for more than 30 minutes, and 27 ± 3 g can be collected, filled in the die cavity, and the platen can be measured.

In addition, the modified conjugated diene polymer according to one embodiment of the present invention is a polymer having high linearity with a value of -S / R (stress / relaxation) at 100 ° C of 0.8 or more.

-S / R is the index of the linearity of the polymer, which indicates the change in stress caused by the reaction of the same amount of strain generated in the material. Generally, the lower the -S / R value means the lower the linearity of the polymer, and the lower the linearity, the greater the rolling resistance or the rolling resistance when applied to the rubber composition. From the above-S / R value, the degree of branching of the polymer and the molecular weight distribution can be predicted. The lower the S / R value, the higher the degree of branching, the broader the molecular weight distribution, and consequently the better the processability of the polymer, while the lower the mechanical properties. On the other hand, the modified conjugated diene polymer according to an embodiment of the present invention has a high-S / R value of 0.8 or more at 100 ° C through optimization of the catalyst composition and the manufacturing method using the modified conjugated diene polymer according to an embodiment of the present invention, Resistance characteristics and fuel consumption characteristics can be improved. More specifically, the -S / R value of the modified conjugated diene-based polymer may be 0.8 to 1.2, more specifically 0.9 to 1.0.

In the present invention, the -S / R value can be measured using a Mooney viscometer, for example, a large rotor of Monsanto's MV2000E at 100 ° C and a rotor speed of 2 ± 0.02 rpm. Specifically, the polymer was allowed to stand at room temperature (23 ± 5 ° C) for 30 minutes or more, 27 ± 3 g was collected, filled in the die cavity, and the platen was operated to measure the Mooney viscosity while applying the torque. The -S / R value can be determined by measuring the slope value of the Mooney viscosity change appearing when the torque is released.

Method for producing modified conjugated diene polymer

The modified conjugated diene polymer according to an embodiment of the present invention may be prepared by polymerizing a conjugated diene monomer in a polymerization solvent using a polymerization catalyst containing a neodymium compound of Formula 2 to form an active organometallic moiety (Step 1) of preparing a conjugated diene polymer having an active organometallic moiety and a step (step 2) of reacting the conjugated diene polymer having the active organometallic moiety with the modifier of the above formula (1) &Lt; / RTI > Thus, according to another embodiment of the present invention, there is provided a process for producing the modified conjugated diene polymer.

Describe each step below

(Step 1)

Step 1 is a step of preparing a conjugated diene polymer having an active organometallic moiety using a polymerization catalyst comprising a neodymium compound represented by the following formula 2:

(2)

In Formula 2,

R _a is a linear or branched alkyl group having 6 to 12 carbon atoms,

R _b and R _c are each independently a hydrogen atom or a linear or branched alkyl group having from 2 to 8 carbon atoms, provided that R _b and R _c are not simultaneously hydrogen atoms.

As the neodymium compound used as a catalyst in the conventional diene polymerization process, Nd (neodecanoate) ₃ containing a carboxylate ligand in which two methyl groups are substituted at the? Compounds were used. However, the above Nd (neodecanoate) ₃ Compounds have a disadvantage in that they are present in large amounts in the form of oligomers in the polymerization process, resulting in lowering of the efficiency of conversion into catalytically active species, and thus the catalytic activity is low.

In contrast, the neodymium-based compound of Formula 2 used in the present invention includes a carboxylate ligand that contains, as a ligand, an alkyl group having various lengths at the? -Position instead of the conventional neodecanoate group, There is no fear of oligomerization due to blockage of entanglement between the compounds due to steric changes. In addition, the neodymium compound of Formula 2 has a high solubility in a polymerization solvent and has a low neodymium ratio in a central portion, which is difficult to convert to a catalytically active species, and thus has a high conversion ratio to a catalytically active species.

More specifically, in the neodymium compound of Formula 2, R _a is a linear or branched alkyl group having 6 to 8 carbon atoms, R _b and R _c are each independently a hydrogen atom, or a linear Or a branched alkyl group, wherein R _b and R _c are not simultaneously hydrogen atoms.

More specifically, in the neodymium compound of Formula 2, R _a is a linear or branched alkyl group having 6 to 8 carbon atoms, R _b and R _c are each independently a linear or branched alkyl group having 2 to 6 carbon atoms Lt; / RTI > Since R _a has an alkyl group having 6 or more carbon atoms and R _b and R _c each have an alkyl group having 2 or more carbon atoms, it is possible to further improve the efficiency of conversion into a catalytically active species without worrying about oligomerization during the polymerization step , It can exhibit better catalytic activity.

The neodymium-based compound of Formula 2 is specifically Nd (2,2-diethyldecanoate) ₃ , Nd (2,2-dipropyldecanoate) ₃ , Nd (2,2-dibutyldecanoate) _3, Nd (2,2- di-hexyl 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- butyl-2-propyl decanoate) _3, Nd (2- propyl-2-hexyl de decanoate) _3, Nd (2- propyl-2-isopropyl decanoate) _3, Nd (2- butyl-2-hexyl decanoate) _3, Nd (2- cyclohexyl-2-octyl decanoate) ₃ , Nd (2,2- diethyl octanoate) _3, Nd (2,2- dipropyl octanoate) _3, Nd (2,2- dibutyltin octanoate) _3, Nd (2,2- di hexyl octanoate) _3, Nd (2- ethyl-2-propyl-octanoate) _3, Nd (2- ethyl-hexyl-2-octanoate) _3, Nd (2,2- diethyl-no nano-benzoate) ₃ , Nd (2,2-dipropylnonanoate) ₃ , Nd (2,2- dibutyl no nano-benzoate) _3, Nd (2,2- dihexyl no nano-benzoate) _3, Nd (2- ethyl-2-propyl-no nano-benzoate) ₃ or Nd (2- ethyl-2 -Hexyl nanoate) _3, etc., and any one or a mixture of two or more thereof may be used. More specifically, the neodymium-based compound Nd (2,2- diethyl decanoate) _3, Nd (2,2- dipropyl decanoate) _3, Nd (2,2- di-butyl decanoate _{3) 3,} Nd (2,2-dihexyldecanoate) ₃ , or Nd (2,2-dioctyldecanoate) ₃ , and any one or a mixture of two or more thereof may be used.

The solubility of the neodymium compound of Formula 2 may be at least about 4 g per 6 g of nonpolar solvent, specifically n-hexane at 25 ° C and 1 atm. In the present invention, the solubility of a neodymium compound means a degree of dissolution without cloudiness. By exhibiting such high solubility, excellent catalytic activity can be exhibited.

The neodymium compound of Formula 2 may be a reaction product with a Lewis base. The Lewis base improves solubility of the neodymium compound in the solvent and can be stored stably for a long period of time. The Lewis base used for easily solubilizing the neodymium compound in a solvent and for stable storage for a long period of time may be used in a proportion of 30 moles or less, more specifically 1 to 10 moles per 1 mole of neodymium element. Examples of the Lewis base include acetylacetone, tetrahydrofuran, pyridine, N, N-dimethylformamide, thiophene, diphenylether, triethylamine, organic phosphorus compounds or monovalent or divalent alcohols .

The neodymium compound having the above structure can be prepared by substituting a carboxyl group for a hydrate of neodymium (III) chloride using a ligand substitution reaction.

Preparing a first mixed solution containing an organic acid and an organic base, and a second mixed solution containing neodymium chloride hydrate, respectively; Preparing a third mixed solution by mixing the first and second mixed solutions; And distilling the third mixed solution under reduced pressure, and then extracting, separating and drying the organic layer.

In the preparation of the neodymium compound, the solvent which can be used in the production of the first and second mixed solutions may be organic solvents such as ethanol, tetrahydrofuran and the like.

Further, in the production of the neodymium compound, the organic acid is not particularly limited as long as it can provide a carboxylate ligand component bonded to the neodymium center metal. Specifically, it may be a carboxylic acid-based compound represented by the following formula (3)

(3)

(In the formula 3, Ra to Rc are the same as defined above)

Specifically, the carboxylic acid-based compound may be an alkylnonanoic acid; Or an alkyldecanoic acid such as 2,2-diethyldecanoic acid, 2,2-dipropyldecanoic acid, 2,2-butyldecanoic acid, 2,2-dihexyldecanoic acid or 2,2- have. One or a mixture of two or more of them may be used.

In the preparation of the neodymium-based compound of Formula 2, the organic base may be sodium hydroxide as a component that converts an organic acid into an organic acid salt. The organic base may be used in the form of an aqueous solution dissolved in water.

The organic acid and the organic base may be used in a mixing molar ratio of 1: 0.97 to 1: 1. If the content of the organic base is more than about 1.0 or less than about 0.97, a large amount of by-products may be produced, thereby reducing the yield of the neodymium compound.

In the preparation of the neodymium compound of Formula 2, the organic acid and neodymium chloride hydrate may be used in a molar ratio of 1: 0.33 to 1: 0.34. If the content of the neodymium chloride hydrate is less than 0.33 mol or more than 0.34 mol, the yield of the byproduct may be increased and the yield of the neodymium compound may be decreased.

In the preparation of the neodymium-based compound of Formula 2, the extraction of the organic layer may be carried out using water; And a non-polar solvent such as hexane.

The neodymium compound of Formula 2 may be used in an amount of 0.1 to 0.5 mmol, more specifically 0.1 to 0.2 mmol, per 100 g of the diene monomer. If the amount of the neodymium compound of Formula 2 is less than 0.1 mmol, the catalyst activity for polymerization is low. If the amount of neodymium compound exceeds 0.5 mmol, the catalyst concentration becomes too high, and a demineralization process is required.

On the other hand, the catalyst for polymerization includes an alkylating agent and a halogen compound together with the neodymium compound of the formula (2).

In the catalyst for polymerization, the alkylating agent serves as a cocatalyst as an organometallic compound capable of transferring a hydrocarbyl group to another metal. The alkylating agent is not particularly limited as long as it is used as an alkylating agent in the production of a diene-based polymer. Specifically, the alkylating agent may be an organometallic compound soluble in a polymerization solvent, such as an organoaluminum compound, an organomagnesium compound, or an organolithium compound, and containing a metal-carbon bond.

More specifically, the organoaluminum compounds include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri- Alkyl aluminum such as aluminum, trihexyl aluminum, tricyclohexyl aluminum and trioctyl aluminum; Di-n-propyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride (DIBAH) 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-propyl aluminum hydride, p-tolyl isopropyl aluminum hydride, p-tolyl-isopropyl aluminum hydride, p-tolyl isopropyl aluminum hydride, n-butyl aluminum hydride, p-tolyl isobutyl aluminum hydride, p-tolyl-n-octyl aluminum N-propyl aluminum hydride, benzyl isopropyl aluminum hydride, benzyl-n-butyl aluminum hydride, benzyl isobutyl aluminum hydride or benzyl-n-octyl aluminum hydride, etc. Dihydrocarbyl aluminum hydride; Hydrocarbylaluminum di-hydrides such as ethylaluminum dihydride, n-propylaluminum dihydride, isopropylaluminum dihydride, n-butylaluminum dihydride, isobutylaluminum dihydride or n- Hydride, and the like.

More specifically, examples of the organomagnesium compound include alkylmagnesium compounds such as diethylmagnesium, di-n-propylmagnesium, diisopropylmagnesium, dibutylmagnesium, dihexylmagnesium, diphenylmagnesium or dibenzylmagnesium. And examples of the organic lithium compound include alkyl lithium compounds such as n-butyl lithium and the like.

Any one or a mixture of two or more of the organoaluminum compounds, organomagnesium compounds, and organolithium compounds described above may be used. More specifically, the alkylating agent may be DIBAH, wherein the DIBAH may serve as a molecular weight regulator during polymerization.

The alkylating agent may be used in an amount of 1 to 100 mol, more preferably 3 to 20 mol, per mol of the neodymium compound.

In the above-mentioned catalyst for polymerization, the kind of the halogen compound is not particularly limited, but can be used without particular limitation, as long as it is generally used as a halogenating agent in the production of a diene-based polymer. Specifically, the halogen compound may be an aluminum halogen compound or an inorganic halogen compound in which aluminum is substituted with boron, silicon, tin or titanium in the aluminum halogen compound, or an organic halogen compound such as a t-alkylhalogen compound (alkyl having 4 to 20 carbon atoms) Halogen compounds.

More specifically, examples of the inorganic halogen compound include dimethylaluminum chloride, diethylaluminum chloride (DEAC), dimethylaluminum bromide, diethylaluminum bromide, dimethylaluminum fluoride, diethylaluminum fluoride, methylaluminum dichloride, ethylaluminum dichloride , Methylaluminum dibromide, ethylaluminum dibromide, methylaluminum difluoride, ethylaluminum difluoride, methylaluminum sesquichloride, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, methylmagnesium chloride, methylmagnesium bromide, Methylmagnesium iodide, ethylmagnesium chloride, ethylmagnesium bromide, butylmagnesium chloride, butylmagnesium bromide, phenylmagnesium chloride, phenylmagnesium bromide, Di-t-butyl tin dichloride, di-t-butyl tin dibromide, dibutyl tin dichloride, dibutyl tin dichloride, dibutyl tin dichloride, dibutyl tin dichloride, dibutyl tin dichloride, dibutyl tin dichloride, dibutyl tin dichloride, dibutyl tin dichloride, Tin dibromide, tributyltin chloride, tributyltin bromide, and the like.

Examples of the organic halogen compound include t-butyl chloride, t-butyl bromide, allyl chloride, allyl bromide, benzyl chloride, benzyl bromide, chloro- di- phenyl methane, There may be mentioned triphenylmethylbromide, benzylidene chloride, benzylidene bromide, methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, trimethylchlorosilane, benzoyl chloride, benzoyl bromide, propionyl chloride, propionyl bromide, Methyl chloroformate, methyl bromoformate and the like.

Any one or a mixture of two or more of the above-mentioned inorganic halogen compounds and organic halogen compounds may be used.

The halogen compound may be used in an amount of 1 to 20 moles, more preferably 1 to 5 moles, and more preferably 2 to 3 moles per 1 mole of the neodymium compound.

The catalyst for polymerization may further include a diene-based monomer.

As described above, a part of the diene-based monomer used in the present polymerization reaction is preliminarily mixed with a polymerization catalyst and used in the form of a pre-polymerized preforming catalyst, whereby not only the catalytic activity can be improved, The polymer can be stabilized.

In the present invention, the term "preforming" as used herein means that when DIBAH or the like is contained in a catalyst system comprising a neodymium compound, an alkylating agent, and a halogen compound, in order to reduce the possibility of generating various catalytically active species, a monomer such as butadiene May be added in a small amount, which means that pre-polymerization is carried out in the catalyst system together with butadiene addition. Also, the term "premix" may mean that the polymerization is not carried out in the catalyst system and each compound is uniformly mixed.

Specific examples of the diene monomer include 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, Butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene or 2,4-hexadiene. Any one or a mixture of two or more may be used.

The diene monomer which can be used in the production of the catalyst for polymerization may be used in an amount within a range of the total amount of the diene monomer used in the polymerization reaction. Specifically, the diene monomer may be used in an amount of 1 to 100 Molar ratio, more specifically from 10 to 50 molar ratio, and even more specifically from 20 to 40 molar ratio.

The catalyst for polymerization may be prepared by sequentially charging the neodymium compound, the alkylating agent, the halogen compound, and optionally the diene monomer into the polymerization non-polar solvent.

The nonpolar solvent for polymerization may be an aliphatic or alicyclic nonreactive solvent that is not reactive with the above-mentioned catalyst components. Specific examples thereof include aliphatic hydrocarbon solvents such as pentane, hexane, isopentane, heptane, octane, isooctane and the like; Or an alicyclic hydrocarbon-based solvent such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, etc., and any one or a mixture of two or more of them may be used. More specifically, it may be linear aliphatic hydrocarbon-based solvents having 4 to 8 carbon atoms such as n-pentane, n-hexane, n-heptane, or n-octane, and the nonpolar solvent may be n-hexane.

On the other hand, the polymerization reaction for producing the conjugated diene polymer can be carried out using coordination anion polymerization.

The polymerization reaction for producing the conjugated diene polymer may be carried out by radical polymerization. Specifically, it may be bulk polymerization, solution polymerization, suspension polymerization or emulsion polymerization, and more specifically, solution polymerization. More specifically, the polymerization reaction may be carried out by reacting the diene monomer for forming the conjugated diene polymer with the catalyst for polymerization in a polymerization solvent.

Examples of the conjugated diene monomer used in the conjugated diene polymer include 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, And any one or a mixture of two or more thereof may be used. More specifically, the conjugated diene monomer may be 1,3-butadiene.

In addition, the polymerization reaction can be carried out in a polymerization solvent.

The polymerization solvent may be the same as the nonpolar solvent for polymerization used in the production of the polymerization catalyst. Whereby a non-polar solvent can be added in addition to the amount of non-polar solvent for polymerization that can be used to prepare the catalyst for polymerization. When the polymerization solvent is used, the concentration of the monomer is not particularly limited, but may be 3 to 80% by weight, more specifically 10 to 30% by weight.

In addition, a reaction terminator for completing the polymerization reaction such as polyoxyethylene glycol phosphate or the like during the polymerization reaction; Or antioxidants such as 2,6-di-t-butyl paracresol and the like may further be used. In addition, an additive such as a chelating agent, a dispersing agent, a pH adjusting agent, an oxygen scavenger, or an oxygen scavenger may be further optionally added, which facilitates solution polymerization usually.

In addition, the polymerization reaction may be carried out by polymerization at a temperature of 20 ° C to 200 ° C, more specifically, at a temperature of 20 ° C to 100 ° C for 15 minutes to 3 hours, more specifically, for 30 minutes to 2 hours. If the temperature during the polymerization reaction exceeds 200 ° C, it is difficult to sufficiently control the polymerization reaction, and the content of cis-1,4 bond in the resultant diene polymer may be lowered. If the temperature is lower than 20 캜, the polymerization reaction rate and efficiency may be lowered.

In addition, the polymerization reaction may be carried out by any of a batch process and a continuous process.

In order to prevent deactivation of the neodymium compound and the polymer of formula (2), it is preferable that the above polymerization reaction be carried out to prevent the incorporation of compounds having inactivating action such as oxygen, water and carbon dioxide gas in the polymerization reaction system.

As a result of the polymerization reaction as described above, a conjugated diene-based polymer containing an active organometallic moiety derived from a catalyst containing the neodymium-based compound of Formula 2, more specifically, a neodymium-containing 1,3-butadiene monomer unit A catalyzed butadiene-based polymer is produced. The conjugated diene polymer may have a living property or a pseudo living property.

In addition, the above catalyst composition can uniformly produce catalytically active species having high catalytic activity, so that a polymer having excellent linearity can be produced. Which in turn can affect the linearity of the modified polymer and can further improve the physical properties of the rubber composition.

(Step 2)

Step 2 is a denaturation step of reacting a modifier of the following formula (1) to the active site of the conjugated diene-based polymer having the active organometallic moiety prepared in step 1 to perform denaturation.

[Chemical Formula 1]

Cy in the above formula (1) is substituted with at least one substituent selected from the group consisting of a halogen group, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms, Aromatic divalent hydrocarbon group having 6 to 20 carbon atoms. When the substituents are plural, two or more substituents may be connected to each other to form an aliphatic or aromatic ring. More specifically, Cy may be a phenylene group.

In formula (1), R ¹ may specifically be a hydrocarbon group having 1 to 20 carbon atoms including at least one heteroatom selected from the group consisting of N, S and O in the functional group, and specifically includes hetero An alkyl group or a heterocyclic group having 2 to 20 carbon atoms. More specifically, it may be a carboxylic acid ester group, an alkoxy group, an amino group, or an epoxy group, and more specifically, an amino group (-NR ¹¹ R ¹² , wherein R ¹¹ and R ¹² are each independently a hydrocarbon group having 1 to 20 carbon atoms Group, specifically a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms).

In the above formula (1), R ² is an aliphatic monovalent hydrocarbon group having from 11 to 30 carbon atoms, and specifically includes an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, Such as, for example, cyclopropyl, cyclopentyl, cyclopentyl, cyclohexyl, cyclopentyl, cyclohexyl, cyclopentyl, cyclohexyl, cyclohexyl, cyclohexyl, Of a linear aliphatic monovalent hydrocarbon group.

More specifically, the modifier is a (E) -4 - ((dodecylimino) methyl) -N, N-dimethylaniline N-dimethylaniline).

[Formula 1a]

The modifier may be used in a stoichiometric amount or more with respect to the active site of the conjugated diene polymer. More specifically, the modifier may be added to 1 mole of the neodymium compound of formula (2) used in the production of the conjugated diene polymer having the active site The modifier may be used in an amount of 0.5 to 20 molar equivalents, more specifically 0.1 to 10 molar equivalents.

Meanwhile, in the method for producing a modified conjugated diene polymer according to an embodiment of the present invention, the denaturation reaction may be performed by a solution reaction or a solid phase reaction, specifically, by a solution reaction.

The denaturation reaction may be carried out using a batch reactor, or may be carried out continuously using an apparatus such as a multi-stage continuous reactor or an inline mixer.

In addition, the above-mentioned denaturation reaction can be usually carried out under the same temperature and pressure conditions as the polymerization reaction, specifically, at a temperature of 20 ° C to 100 ° C. When the temperature is lowered, the viscosity of the polymer tends to increase, and when the temperature is higher, the polymerization active terminal is liable to be inactivated.

After completion of the above-mentioned 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 terminate the polymerization reaction. Thereafter, the modified conjugated diene polymer can be obtained through desolvation treatment or vacuum drying treatment such as steam stripping which lowers the partial pressure of the solvent through supply of water vapor. The reaction product obtained as a result of the above-mentioned denaturation reaction may contain a conjugated diene polymer having an active metal organic moiety that is not denatured together with the above-mentioned modified conjugated diene polymer. The content of the conjugated diene polymer having an active organometal part contained in the reaction product may vary depending on the modification ratio of the modified conjugated diene polymer.

Accordingly, the method for producing a modified conjugated diene-based polymer according to an embodiment of the present invention may further include precipitation and separation steps for the produced modified conjugated diene-based polymer. The filtration, separation and drying of the precipitated denatured conjugated diene polymer may be carried out according to a conventional method.

As described above, the method for producing a modified conjugated diene polymer according to one embodiment of the present invention can produce a modified conjugated diene polymer having both an inorganic filler affinity functional group and a solvent affinity functional group in the polymer simultaneously and having a high modification ratio do. The modified conjugated diene polymers contain intramolecular inorganic filler affinity functional groups and exhibit excellent affinity for inorganic fillers when applied to rubber compositions. As a result, it is possible to improve the physical properties and workability of the rubber composition including abrasion resistance when applied to the rubber composition.

Polymer compositions and rubber compositions

According to another embodiment of the present invention, there is provided a polymer composition and a rubber composition comprising the modified conjugated diene polymer.

Specifically, the polymer composition comprises a conjugated diene polymer having an active organometallic moiety obtained by polymerizing a conjugated diene monomer in a polymerization solvent using a polymerization catalyst containing a neodymium compound of Formula 2, And a modified conjugated diene polymer prepared by modifying the conjugated diene polymer having a moiety of the formula (1) with the modifier of the above formula (1).

More specifically, the polymer composition is prepared by mixing the conjugated diene polymer having the active metal organic moiety and the modified conjugated diene polymer in a weight ratio of from 0.01: 99.99 to 90: 10, more specifically from 10:90 to 40:60 .

The conjugated diene polymer having the active organometallic moiety is prepared using a polymerization catalyst containing a neodymium compound of Formula 2, and may include a neodymium compound-derived functional group of Formula 2 in the polymer.

More specifically, the conjugated diene polymer having the active metal organic moiety is prepared by using a catalyst for polymerization comprising a neodymium compound, an alkylating agent and a halogen compound of Formula 2, and the neodymium compound of Formula 2 Derived functional group (e.g., a neodymium-containing functional group (-Nd-COOR _a R _b R _c )), an alkylating agent-derived functional group (e.g., an alkyl group, an aluminum metal element, ). At this time, the contents of neodymium, aluminum and halogen elements contained in the conjugated diene polymer having the active organometallic moiety can be confirmed by inductively coupled plasma (ICP) analysis.

The modified conjugated diene polymer is the same as that described above.

The polymer composition may be one prepared by mixing the conjugated diene polymer having the active organometallic moiety and the modified conjugated diene polymer or may be one obtained by mixing the modified conjugated diene polymer and the modified conjugated diene polymer, Reaction product. When the polymer composition is a reaction product obtained as a result of the modification reaction, the content ratio of the conjugated diene polymer having the active metal organic moiety contained in the reaction product and the modified conjugated diene polymer is preferably such that the modification ratio of the modified conjugated diene polymer And the modification ratio can be variously changed by suitably controlling the production process of the conjugated diene polymer having the active organometallic moiety and the modification reaction conditions for the conjugated diene polymer having the active organometallic moiety.

By including the conjugated diene polymer having the active organometallic moiety and the modified conjugated diene polymer at the same time, the physical properties of the rubber composition such as abrasion resistance and workability can be more easily controlled according to the use thereof, and as a result, Rubber compositions and molded articles having excellent physical properties can be produced.

Meanwhile, the rubber composition according to another embodiment of the present invention includes the above-mentioned modified conjugated diene polymer.

Specifically, the rubber composition may contain 10 wt% or more, more specifically 10 wt% to 100 wt%, of the modified conjugated diene polymer. If the content of the modified conjugated diene polymer is less than 10% by weight, the abrasion resistance, crack resistance and ozone resistance improving effect of the rubber composition may be insignificant.

In addition, the rubber composition may further comprise a conjugated diene polymer having the above-mentioned active organometallic moiety together with the modified conjugated diene polymer. Herein, the conjugated diene polymer having the active metal organic moiety is the same as described in the polymer composition.

The rubber composition may further comprise a rubber component in an amount of 90% by weight or less based on the total weight of the rubber composition together with the modified conjugated diene polymer. More specifically, it may further comprise 1 to 900 parts by weight of a rubber component with respect to 100 parts by weight of the modified conjugated diene polymer.

The rubber component may be natural rubber or synthetic rubber. Specifically, the rubber component may be natural rubber (NR) including cis-1,4-polyisoprene; Modified natural rubbers such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber, which are modified or refined with the general natural rubber; Butadiene copolymers (SBR), polybutadiene (BR), polyisoprenes (IR), butyl rubbers (IIR), ethylene-propylene copolymers, polyisobutylene-co-isoprene, neoprene, poly Butadiene), poly (styrene-co-butadiene), poly (styrene-co-butadiene) Synthetic rubber such as polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, butyl rubber, halogenated butyl rubber and the like, and any one or a mixture of two or more thereof may be used have.

The rubber composition may further contain 10 parts by weight or more, more specifically 10 to 120 parts by weight, of a filler based on 100 parts by weight of the modified conjugated diene polymer. When the content of the filler is 10 parts by weight or more, the effect of improving the reinforcing property and other physical properties is sufficiently exhibited. When the amount is 100 parts by weight or less, workability and the like are good. Also, considering the more improved effects such as reinforcing property and workability, the content of the filler may be 20 to 80 parts by weight.

The filler may be specifically carbon black or silica, and any one or a mixture of two or more thereof may be used. More specifically, the filler may be carbon black.

In the filler, the carbon black is not particularly limited, and specifically, the carbon black preferably has a nitrogen adsorption specific surface area (measured in accordance with N2SA, JIS K 6217-2: 2001) of 20 to 250 m < / g. < / RTI > The carbon black may have a dibutyl phthalate oil absorption (DBP) of 80 cc / 100 g to 200 cc / 100 g. If the nitrogen adsorption specific surface area of the carbon black exceeds 250 m ² / g, the workability of the rubber composition for a tire may be deteriorated. If the specific surface area is less than 20 m ² / g, the reinforcing performance of carbon black as a filler may be deteriorated. If the DBP oil absorption of the carbon black exceeds 200 cc / 100 g, the workability of the rubber composition may be deteriorated. If it is less than 80 cc / 100 g, the reinforcing performance of the filler carbon black may be deteriorated.

The silica may specifically be wet silica (hydrated silicic acid), dry silica (silicic anhydride), calcium silicate, aluminum silicate or colloidal silica. More specifically, the filler may be a wet silica having the most remarkable effect of improving the fracture characteristics and the wet grip.

Also, the silica has a nitrogen surface area per gram (N 2 SA) of 120 m 2 / g to 180 m 2 / g and a specific surface area of CTAB (cetyl trimethyl ammonium bromide) of 100 m 2 / g to 200 m 2 / g Lt; / RTI > If the nitrogen adsorption specific surface area of the silica is less than 120 m < 2 > / g, there is a fear that the reinforcing performance by the silica as the filler is lowered, and if it exceeds 180 m & If 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.

In addition, the rubber composition may comprise an inorganic filler of one or more metals, metal oxides or metal hydroxides selected from aluminum, magnesium, titanium, calcium and zirconium. More specifically, the inorganic filler is alumina α-, γ- alumina, alumina-hydrate _{(Al 2 O 3 · H 2} 0), aluminum hydroxide [Al (OH) _3], aluminum carbonate [Al ₂ (CO ₃₎ ₂ ], magnesium hydroxide [Mg (OH) _2], magnesium oxide (MgO), magnesium carbonate (MgCO3), talc _{(3MgO · 4SiO 2 · H 2} O), Atta paljayi agent _{(5Mg0 · 8SiO 2 · 9H 2} O), (TiO ₂ ), titanium black, calcium oxide (CaO), calcium hydroxide [Ca (OH) ₂ ], magnesium aluminum oxide (MgO.Al ₂ O ₃ ), clay (Al ₂ O ₃ .2SiO ₂ ), kaolin Al ₂ O ₃ .2SiO ₂ .2H ₂ O), pyrophyllite (Al ₂ O ₃ .4SiO ₂ .H ₂ O), bentonite (Al ₂ O ₃ .4SiO ₂ .2H ₂ O) ₂ SiO ₅ , Al ₄ .3SiO ₄ .5H ₂ O, etc.), magnesium silicate (Mg ₂ SiO ₄ , MgSiO ₃ And the like), calcium silicate (Ca ₂ · SiO ₄ etc.), magnesium silicate, calcium _{(Al 2 O 3 · CaO ·} 2SiO 2 etc.), magnesium silicate, calcium (CaMgSiO _4), calcium carbonate (CaCO _3), zirconium oxide (ZrO ₂ , Zirconium hydroxide [ZrO (OH) ₂ .nH ₂ O], zirconium carbonate [Zr (CO ₃ ) ₂ ], or crystalline aluminosilicate, and any one or a mixture of two or more thereof may be used.

When the carbon black and the inorganic filler are mixed, the mixing weight ratio may be 95: 5 to 5:95 in consideration of an improvement in performance.

On the other hand, when silica is used as the filler, a silane coupling agent may be used together to improve the reinforcing property and the low exothermic property.

Specific examples of the silane coupling agent include bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane , 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide Triethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilyl Propylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzyltetrasulfide, 3-triethoxysilylpropylmethacrylate Monosulfide, monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl- N-dimethylthiocarbamoyltetrasulfide, or dimethoxymethylsilylpropylbenzothiazolyltetrasulfide. Any one or a mixture of two or more of them may be used. More specifically, in consideration of the reinforcing effect, the silane coupling agent may be bis (3-triethoxysilylpropyl) polysulfide or 3-trimethoxysilylpropyl benzothiazine tetrasulfide.

In the rubber composition according to the embodiment of the present invention, since a modified polymer having a functional group having a high affinity for silica is introduced into a molecular active site as a rubber component, the compounding amount of the silane coupling agent is usually Can be reduced. Specifically, the silane coupling agent may be used in an amount of 1 to 20 parts by weight based on 100 parts by weight of silica. When used in the above-mentioned range, gelation of the rubber component can be prevented while sufficiently exhibiting the effect as a coupling agent. More specifically, the silane coupling agent may be used in an amount of 5 to 15 parts by weight based on 100 parts by weight of silica.

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

The vulcanizing agent may be specifically a sulfur powder.

The vulcanizing agent 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 contained in the above content range, the required elastic modulus and strength of the vulcanized rubber composition can be ensured, and at the same time, the low fuel consumption ratio can be obtained.

In addition to the above-mentioned components, the rubber composition according to one embodiment of the present invention may contain various additives commonly used in the rubber industry, specifically vulcanization accelerators, process oils, plasticizers, antioxidants, scorch inhibitors, zinc white ), Stearic acid, a thermosetting resin, or a thermoplastic resin.

The vulcanization accelerator is not particularly limited and specifically includes M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazyl sulfenamide) Based compound, or a guanidine-based compound such as DPG (diphenylguanidine) can 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.

The process oil may be a paraffinic, naphthenic or aromatic compound. More specifically, considering the tensile strength and abrasion resistance, the process oil may be an aromatic process oil, a hysteresis loss And naphthenic or paraffinic process oils may be used in view of the low temperature characteristics. The process oil may be contained in an amount of 100 parts by weight or less based on 100 parts by weight of the rubber component. When the content is included in the above amount, the tensile strength and low heat build-up (low fuel consumption) of the vulcanized rubber can be prevented from lowering.

Specific examples of the antioxidant include N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'- 2, 4-trimethyl-1,2-dihydroquinoline, or high-temperature condensates of diphenylamine and acetone. The antioxidant 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 one embodiment of the present invention can be obtained by kneading by using a kneader such as Banbury mixer, roll, internal mixer or the like by the above compounding formula. Further, the rubber composition can be obtained by a vulcanization step after molding, This excellent rubber composition can be obtained.

Accordingly, the rubber composition can be applied to various members such as tire tread, under-tread, sidewall, carcass coated rubber, belt coated rubber, bead filler, pancake fur, or bead coated rubber, vibration proof rubber, belt conveyor, And is useful for the production of various industrial rubber products.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

Production Example 1-1: Nd (2,2-diethyl decanoate) ₃ Synthesis of

10 ml of ethanol was added to a 50 ml round flask containing 0.82 g (3.6 mmol) of 2,2-diethyldecanoic acid, and the mixture was stirred at room temperature for 10 minutes. 3.6 ml of a 1.0 M aqueous sodium hydroxide solution (3.6 mmol) was added to the solution, and the mixture was stirred at room temperature for 1 hour to prepare a first mixed solution.

0.43 g (1.20 mmol) of neodymium chloride hydrate was added to a 250 ml round-bottomed flask, and 20 ml of hexane and 10 ml of ethanol were added and dissolved to prepare a second mixed solution.

The first mixed solution was put in a dropping funnel and dropped into the second mixed solution at room temperature to prepare a third mixed solution. After completion of the addition, the mixture was stirred at room temperature for 15 hours.

The third mixed solution was distilled under reduced pressure to remove all of the solvent. 50 ml of hexane and 50 ml of distilled water were added to the third mixed solution, and the mixture was placed in a separating funnel. The organic layer was extracted three times. Sodium sulfate was added to the collected organic layer, and the mixture was stirred at room temperature for 10 minutes and then filtered to remove the solution by distillation under reduced pressure. As a result, 0.7 g (yield 80%) of the title compound represented by the following structural formula (2a) was obtained as a white solid dissolved in hexane.

(2a)

FT-IR: ν 2954, 2920, 2873, 2852, 1680, 1511, 1461, 1415, 1377, 1317, 1296, 1199 cm ^-1

Production Example 1-2: Nd (2,2-dipropyldecanoate) ₃ Synthesis of

10 ml of ethanol was added to a 50 ml round flask containing 1.0 g (3.9 mmol) of 2,2-dipropyldicarboxylic acid, and the mixture was stirred at room temperature for 10 minutes. 3.9 ml of a 1.0 M sodium hydroxide aqueous solution (3.9 mmol) was added to the solution, and the mixture was stirred at room temperature for 1 hour to prepare a first mixed solution.

0.47 g (1.30 mmol) of neodymium chloride hydrate was added to a 250 ml round-bottomed flask, and 20 ml of hexane and 10 ml of ethanol were added and dissolved to prepare a second mixed solution.

The third mixed solution was distilled under reduced pressure to remove all of the solvent. 50 ml of hexane and 50 ml of distilled water were added to the third mixed solution, and the mixture was placed in a separating funnel. The organic layer was extracted three times. Sodium sulfate was added to the collected organic layer, and the mixture was stirred at room temperature for 10 minutes and then filtered to remove the solution by distillation under reduced pressure. As a result, 1.1 g (yield: 98%) of the title compound represented by the following formula (2b) was obtained as a yellowish blue liquid dissolved in hexane.

(2b)

FT-IR: ν 2955, 2923, 2853, 1682, 1555, 1503, 1453, 1411, 1360, 1307, 1288, 1261, 1185 cm ^-1

Production Example 1-3: Nd (2,2-dibutyl decanoate) ₃ Synthesis of

20 ml of ethanol was added to a 50 ml round flask containing 1.42 g (5.0 mmol) of 2,2-dibutyldecanoic acid, and the mixture was stirred at room temperature for 10 minutes. 5.0 ml of a 1.0 M aqueous sodium hydroxide solution (5.0 mmol) was added to the solution, and the mixture was stirred at room temperature for 1 hour to prepare a first mixed solution.

0.67 g (1.67 mmol) of neodymium chloride hydrate was added to a 250 ml round-bottom flask, and 30 ml of hexane and 20 ml of ethanol were added and dissolved to prepare a second mixed solution.

The third mixed solution was distilled under reduced pressure to remove all of the solvent. 50 ml of hexane and 50 ml of distilled water were added to the third mixed solution, and the mixture was placed in a separating funnel. The organic layer was extracted three times. Sodium sulfate was added to the collected organic layer, and the mixture was stirred at room temperature for 10 minutes and then filtered to remove the solution by distillation under reduced pressure. As a result, 1.64 g (yield 99%) of the title compound represented by the following formula (2c) as a yellowish blue solid dissolved in hexane was obtained.

(2c)

FT-IR: ν 2954, 2923, 2855, 1669, 1553, 1504, 1457, 1410, 1306, 1263, 1235 cm ^-1

Production Example 1-4: Nd (2,2-dihexyldecanoate) ₃ Synthesis of

10 ml of ethanol was added to a 50 ml round flask containing 0.35 g (1.0 mmol) of 2,2-dihexyldecanoic acid, and the mixture was stirred at room temperature for 10 minutes. 1.0 ml of a 1.0 M sodium hydroxide aqueous solution (1.0 mmol) was added to this solution, and the mixture was stirred at room temperature for 1 hour to prepare a first mixed solution.

0.125 g (0.35 mmol) of neodymium chloride hydrate was added to a 250 ml round-bottomed flask, and 20 ml of hexane and 10 ml of ethanol were added and dissolved to prepare a second mixed solution.

The third mixed solution was distilled under reduced pressure to remove all of the solvent. 50 ml of hexane and 50 ml of distilled water were added to the third mixed solution, and the mixture was placed in a separating funnel. The organic layer was extracted three times. Sodium sulfate was added to the collected organic layer, and the mixture was stirred at room temperature for 10 minutes and then filtered to remove the solution by distillation under reduced pressure. As a result, 0.38 g (yield 94%) of the title compound represented by the following formula (2d) dissolved in hexane was obtained as a yellowish blue solid.

(2d)

FT-IR: ν 2953, 2921, 2852, 1664, 1557, 1505, 1457, 1412, 1377, 1311, 1263 cm ^-1

Production Example 1-5: Nd (2,2-dioctyl decanoate) ₃ Synthesis of

10 ml of ethanol was added to a 50 ml round flask containing 0.99 g (2.50 mmol) of 2,2-dioctyldecanoic acid, and the mixture was stirred at room temperature for 10 minutes. 2.50 ml of a 1.0 M aqueous sodium hydroxide solution (2.50 mmol) was added to the solution, and the mixture was stirred at room temperature for 1 hour to prepare a first mixed solution.

0.298 g (0.83 mmol) of neodymium chloride hydrate was added to a 250 ml round-bottomed flask, and 20 ml of hexane and 10 ml of ethanol were added and dissolved to prepare a second mixed solution.

The third mixed solution was distilled under reduced pressure to remove all of the solvent. 50 ml of hexane and 50 ml of distilled water were added to the third mixed solution, and the mixture was placed in a separating funnel. The organic layer was extracted three times. Sodium sulfate was added to the collected organic layer, and the mixture was stirred at room temperature for 10 minutes and then filtered to remove the solution by distillation under reduced pressure. As a result, 0.89 g (yield 80%) of the title compound represented by the following formula (2e) was obtained in the form of a yellow-blue liquid dissolved in hexane.

(2e)

Example 1-1: Preparation of Modified Conjugated Diene Polymer

Under a nitrogen atmosphere, 4.2 kg of hexane and 500 g of 1,3-butadiene were charged into a 15 L reactor and the temperature was raised to 70 ° C. A solution of 0.20 mmol of the neodymium compound prepared in Preparation Example 1-1 in hexane, 1.84 mmol of diisobutylaluminum hydride (DIBAH), 0.48 mmol of diethylaluminum chloride, 6.6 mmol of 1,3-butadiene Was added to a 15 L reactor, and polymerization was carried out for 60 minutes. The conversion of 1,3-butadiene to polybutadiene was about 100%.

(E) -4 - ((dodecylimino) methyl) -N, N-dimethylaniline (E) -4 - N, N-dimethylaniline) modifier was added to the above polymerization solution, followed by denaturation at 70 ° C for 30 minutes. After addition of a hexane solution containing 1.0 g of a polymerization terminator and a nucleic acid solution containing 1.0 g of an antioxidant, the resulting reaction product was precipitated and separated to prepare a modified 1,3 butadiene polymer.

(1a)

Example 1-2: Preparation of modified conjugated diene polymer

The modified 1,3 butadiene polymer was prepared in the same manner as in Example 1-1 except that the neodymium compound (2b) prepared in Preparation Example 1-2 was used as the neodymium compound.

Example 1-3: Preparation of Modified Conjugated Diene Polymer

The modified 1,3 butadiene polymer was prepared in the same manner as in Example 1-1 except that the neodymium compound (2c) prepared in Preparation Example 1-3 was used as the neodymium compound.

Example 1-4: Preparation of Modified Conjugated Diene Polymer

The modified 1,3 butadiene polymer was prepared in the same manner as in Example 1-1 except that the neodymium compound (2d) prepared in Preparation Example 1-4 was used as the neodymium compound.

Example 1-5: Preparation of Modified Conjugated Diene Polymer

The modified 1,3 butadiene polymer was prepared in the same manner as in Example 1-1 except that the neodymium compound (2e) prepared in Preparation Example 1-5 was used as the neodymium compound.

Example 2: Preparation of polymer composition

The neodymium-catalyzed 1,3-butadiene polymer obtained as a result of the polymerization reaction in Example 1-1 and the modified 1,3-butadiene polymer prepared in Example 1-1 were mixed at a weight ratio of 10:90 to prepare a polymer composition Respectively.

Example 3-1: Preparation of rubber composition

100 parts by weight of butadiene rubber, 70 parts by weight of carbon black, 30 parts by weight of process oil, and 4 parts by weight of an antioxidant (TMDQ) were added to 100 parts by weight of the modified conjugated diene polymer prepared in Example 1-1, 3 parts by weight of zinc oxide (ZnO) and 2 parts by weight of stearic acid were mixed to prepare a rubber composition. 2 parts by weight of sulfur powder, 2 parts by weight of a vulcanization accelerator (CZ) and 2 parts by weight of a vulcanization accelerator (DPG) were added to the rubber composition and vulcanized at 150 캜 for 90 minutes to prepare rubber specimens. The carbon black had a nitrogen adsorption specific surface area of 180 m 2 / g and a dibutyl phthalate oil absorption amount (DBP) of 120 cc / 100 h.

Examples 3-2 to 3-5: Preparation of rubber composition

Except that the modified conjugated diene polymers prepared in Examples 1-2 to 1-5 were used in place of the modified conjugated diene polymers prepared in Example 1-1, To prepare a rubber composition and a rubber specimen using the rubber composition, respectively.

Example 3-6: Preparation of rubber composition

The procedure of Example 3-1 was repeated except that the polymer composition prepared in Example 2 was used in place of the modified conjugated diene polymer in Example 3-1 to prepare a rubber composition and a rubber specimen .

Comparative Example 1

A rubber composition and a rubber specimen using the rubber composition were prepared in the same manner as in Example 3-1, except that Buna CB24 (Lanxess) was used as the modified conjugated diene polymer.

Comparative Example 2

A rubber composition and a rubber specimen using the rubber composition were obtained in the same manner as in Example 3-1, except that the polybutadiene used in Example 1-1 was used instead of the modified conjugated diene polymer .

Comparative Example 3

A modified 1,3 butadiene polymer was prepared in the same manner as in Example 1-1 except that Nd (neodecanoate) ₃ was used as the neodymium compound.

A rubber composition and a rubber specimen using the rubber composition were prepared in the same manner as in Example 3-1, except that the modified 1,3-butadiene polymer was used.

Experimental Example 1: Evaluation of physical properties of modified conjugated diene polymer

The properties of the modified conjugated diene polymers prepared in Example 1-1 and Comparative Examples 1 and 2 were measured by the following methods, and the results are shown in Table 1 below.

1) weight average molecular weight (Mw), number average molecular weight (Mn), and polydispersity

The modified conjugated diene polymers prepared in Example 1-1 and Comparative Examples 1 and 2 were each dissolved in tetrahydrofuran (THF) for 30 minutes at 40 ° C, and then loaded on gel permeation chromatography (GPC) I gave it away. At this time, two columns of PLgel Olexis column and one column of PLgel mixed-C column of Polymer Laboratories were used in combination. In addition, a column of a mixed bed type was used as a new column, and polystyrene was used as a gel permeation chromatography (GPC) standard material.

2) Mooney viscosity and -S / R value

For the modified conjugated diene polymer prepared in Example 1-1 and Comparative Examples 1 and 2, MV2000E manufactured by Monsanto was used as a large rotor, and its Mooney viscosity (MV) was measured at 100 ° C. under a rotor speed of 2 ± 0.02 rpm Respectively. The sample used was allowed to stand at room temperature (23 ± 3 ° C) for more than 30 minutes, and then 27 ± 3 g was sampled and filled in the die cavity. Platen was operated to measure the Mooney viscosity by applying torque.

Further, a change in Mooney viscosity as the torque was released upon measurement of the Mooney viscosity was observed, and the -S / R value was determined from the slope value.

3) Cis-1,4 bond content

Fourier transform infrared spectroscopy analysis was carried out on the modified conjugated diene polymers prepared in Example 1-1 and Comparative Examples 1 and 2, and the content of the 1,4-cis-1,4 bonds in the 1,4-cis-polybutadiene was measured Respectively.

Comparative Example 1 Comparative Example 2 Comparative Example 3 Example 1-1 Type of denaturant S ₂ Cl ₂ - (1a) (1a) Denaturation denaturalization Unmodified denaturalization denaturalization GPC results Mn (x 10 ⁵ g / mol) 2.20 2.51 2.43 2.48 Mw (x10 ⁵ g / mol) 6.08 6.57 6.70 6.83 Mw / Mn 2.76 2.61 2.75 2.76 MV (ML1 + 4, @ 100 C) (MU) 45.1 42.9 43.5 45.3 -S / R 0.5666 0.7490 0.6599 0.9211 Cis-1,4 bond content (%) 96.8 96.7 96.8 97.2

As a result of the measurement, the modified conjugated diene polymer produced in Example 1-1 exhibited an equivalent level in terms of molecular weight distribution and Mooney viscosity as compared with the polymer of Comparative Example 1 which is a conventional modified polymer, but in terms of Mw and Mn , Respectively.

In addition, the modified conjugated diene polymer produced in Example 1-1 exhibited a significantly increased value of -S / R of 0.9 or more as compared with Comparative Examples 1 and 2. From this, it can be expected that the modified conjugated diene polymer of Example 1-1 exhibits very high linearity, and as a result, when applied to a tire, it can reduce rolling resistance and improve fuel consumption characteristics.

Experimental Example 2: Evaluation of physical properties of rubber composition

The rubber composition (Example 3-1) comprising the modified conjugated diene polymer prepared in Example 1-1 and the rubber compositions of Comparative Examples 1 and 2 were evaluated for viscosity characteristics, Mooney viscosity, Payne effect (payne effect), 300% modulus, tensile strength, elongation and viscoelasticity, respectively. The 300% modulus, tensile strength, elongation and viscoelasticity were indexed with the measured value of Comparative Example 1 at 100. The results are shown in Table 2 below.

The pattern viscosity (ML1 + 4) was measured by using Monsanto MV2000E with a large rotor at 100 ° C under a rotor speed of 2 ± 0.02 rpm. MV was determined from the Mooney viscosity difference with the rubber composition after measuring the Mooney viscosity of the raw rubber.

The payout effect (G ') was evaluated by measuring the carbon black dispersibility (Payne effect) after the standard combination of carbon black. In detail, the difference between the strain of the uncured rubber specimen at 0.28% and the dynamic elastic value of G 'and the strain at 40% was measured. In this case, the smaller the number, the better the dispersibility of carbon black.

The tensile strength (tensile strength, kg · f / cm 2), 300% modulus (300% modulus, kg · f / cm 2), elongation (elongation,%): after t90 minutes to the respective rubber compositions at 150 ℃ vulcanization ASTM The tensile strength of the vulcanizate, the modulus at 300% elongation (M-300%) and the elongation at break of the vulcanizate were measured according to D412.

Viscoelasticity (tanδ @ 60 ℃): The most important tan δ property for low fuel efficiency characteristics is the viscoelastic coefficient (tan δ) at 60 ℃ at 10Hz frequency, Prestrain 5% and Dynamic Strain 3% using DMTS 500N from Germany Gabo Respectively.

Comparative Example 1 Comparative Example 2 Example 3-1 FMB
(Final Master batch) ML1 + 4 57.3 58.2 76.5 G ' 0.31 0.43 0.29 MV 12 15.3 31 Tensile index M-300% 100 94 99 The tensile strength 100 95 112 Elongation 100 100 107 DMTS Index tanδ @ 60 ° C 100 94 111

As a result of the test, the rubber composition of Example 3-1 containing the modified butadiene polymer of Example 1-1 contained the rubber composition of Comparative Example 1 containing the conventional modified butadiene polymer and Comparative Example 1 containing the unmodified polymer Lt; RTI ID = 0.0 > G < / RTI > From this, it can be seen that the dispersibility of the carbon black filler in the rubber composition of Example 3-1 is better.

In addition, the rubber composition of Example 3-1 including the modified butadiene polymer of Example 1-1 exhibited excellent tensile properties and viscoelasticity as compared with the rubber compositions of Comparative Examples 1 and 2. From this, it can be seen that the rubber composition including the modified butadiene polymer of Example 3-1 has better tensile properties and processability, and that it is expected to exhibit improved rolling resistance and low fuel consumption characteristics when applied to a rubber composition for a tire .

Claims

A modifier-derived functional group represented by the following formula (1)
And a value of -S / R (stress / relaxation) at 100 占 폚 is not less than 0.8.
[Chemical Formula 1]

(In the formula 1,
Cy is a group selected from the group consisting of a halogen group, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms, 20 aromatic divalent hydrocarbon group,
R ¹ is a hydrocarbon group of 1 to 20 carbon atoms containing at least one heteroatom selected from the group consisting of N, S and O, and
And R < ² > is an aliphatic monovalent hydrocarbon group having from 11 to 30 carbon atoms)

The method according to claim 1,
A conjugated diene polymer having a cis-1,4 bond content of not less than 95% as measured by Fourier transform infrared spectroscopy.

The method according to claim 1,
And a molecular weight distribution (Mw / Mn) of 2.5 to 3.5.

The method according to claim 1,
Wherein the modified conjugated diene polymer has a molecular weight distribution (Mw / Mn) of 2.5 to 3.5, a weight average molecular weight (Mw) of ⁵ × 10 ⁵ g / mol to 1.2 × 10 ⁶ g / mol, X10 ⁵ g / mol to 4.5X10 ⁵ g / mol.

The method according to claim 1,
Wherein the modified conjugated diene polymer has a Mooney viscosity at 100 占 폚 of 40 to 70 MU.

The method according to claim 1,
Wherein the modified conjugated diene polymer is obtained by polymerizing a conjugated diene polymer having an active organometallic moiety obtained by polymerizing a conjugated diene monomer in a polymerization solvent using a polymerization catalyst containing a neodymium compound of the following formula Wherein the modified conjugated diene polymer is produced by modifying with a modifying agent.
(2)

The method according to claim 6,
Wherein R _a is a linear or branched alkyl group having 6 to 8 carbon atoms, and R _b and R _c are each independently a linear or branched alkyl group having 2 to 6 carbon atoms.

The method according to claim 6,
Wherein the catalyst for polymerization further comprises an alkylating agent and a halogen compound together with the neodymium compound of Formula 2 above.

The method according to claim 6,
Wherein the catalyst for polymerization further comprises a diene-based monomer.

The method according to claim 6,
Wherein the conjugated diene polymer having the active metal organic moiety is a terminal active polymer.

The method according to claim 6,
Wherein the conjugated diene-based polymer having the active metal organic moiety is a neodymium-catalyzed butadiene-based polymer containing a 1,3-butadiene monomer-derived repeating unit.

The method according to claim 6,
Wherein the polymerization solvent is an aliphatic hydrocarbon-based organic solvent having 4 to 12 carbon atoms.

The method according to claim 1,
Wherein Cy is a phenylene group, R ¹ is -NR ¹¹ R ¹² (wherein R ¹¹ and R ¹² are each independently a hydrocarbon group having 1 to 20 carbon atoms), and R ² is a linear Wherein the aliphatic monovalent hydrocarbon group is an aliphatic monovalent hydrocarbon group.

The method according to claim 1,
Wherein the modifier comprises (E) -4 - ((dodecylimino) methyl) -N, N-dimethylaniline.

Polymerizing a conjugated diene monomer in a polymerization solvent using a polymerization catalyst comprising a neodymium compound of the following formula 2 to prepare a conjugated diene polymer having an active organometal part;
Reacting the conjugated diene polymer having the active organometallic moiety with a modifier of the following formula
Based on the weight of the modified conjugated diene-based polymer.
[Chemical Formula 1]

(Wherein Cy in the formula (1) is substituted with at least one substituent selected from the group consisting of a halogen group, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms hwandoen, a group of the aromatic hydrocarbon having 6 to 20 carbon atoms, R ¹ is a hydrocarbon group having 1 to 20 carbon atoms containing one or more heteroatoms selected from the group consisting of N, S and O, and R ² are carbon atoms, 11 to 30 aliphatic monovalent hydrocarbon groups)
(2)

16. The method of claim 15,
The step of preparing a neodymium compound of Formula 2 by a ligand substitution reaction with neodymium chloride hydrate to a carboxylic acid compound of Formula 3 before preparing the conjugated diene polymer having the active organometallic moiety, Wherein the conjugated diene-based polymer is a conjugated diene polymer.
(3)

A modified conjugated diene polymer according to any one of claims 1 to 14, and
A conjugated diene polymer having an active organometallic moiety obtained by polymerizing a conjugated diene monomer in a polymerization solvent using a polymerization catalyst containing a neodymium compound of the following formula
&Lt; / RTI >
(2)

A rubber composition comprising the modified conjugated diene polymer according to any one of claims 1 to 14.

19. The method of claim 18,
And a conjugated diene polymer having an active organometallic moiety obtained by polymerizing a conjugated diene monomer in a polymerization solvent using a polymerization catalyst comprising a neodymium compound of the following formula (2).
(2)

19. The method of claim 18,
With respect to 100 parts by weight of the modified conjugated diene polymer,
1 to 900 parts by weight of a rubber component and 10 to 120 parts by weight of a filler.

21. The method of claim 20,
Wherein the filler is carbon black.

A rubber-molded article produced using the rubber composition according to claim 18.

A tire produced using the rubber composition according to claim 18.