KR20220023455A - Conjugated diene-based polymer, method of preparing the polymer and rubber composition comprising the polyemr - Google Patents

Abstract

The present invention relates to a conjugated diene-based polymer having excellent running resistance properties which comprises a high molecular weight polymer chain in a controlled content, a preparation method thereof, and a rubber composition comprising the same. The present invention provides a conjugated diene-based polymer which comprises a repeating unit derived from a conjugated diene-based monomer, comprises 20 wt% or more of the polymer chain having a weight average molecular weight of 1,000,000 g/mol or more, and has a molecular weight distribution of 2.8 or more and 3.4 or less, a preparation method thereof, and a rubber composition comprising the same.

Description

Conjugated diene-based polymer, manufacturing method thereof, and rubber composition comprising the polymer

The present invention relates to a conjugated diene-based polymer comprising a high molecular weight polymer chain in a controlled content and having a molecular weight distribution in a specific range, excellent running resistance and improved processability, a method for preparing the same, and a rubber composition comprising the same .

In response to the recent demand for fuel economy reduction in automobiles, a conjugated diene-based polymer having low running resistance, excellent abrasion resistance and tensile properties, and adjustment stability typified by wet skid resistance is required as a rubber material for tires.

In order to reduce the running resistance of the tire, there is a method of reducing the hysteresis loss of the vulcanized rubber, and rebound elasticity of 50°C to 80°C, tan δ, Goodrich heat, etc. are used as evaluation indicators of the vulcanized rubber. That is, a rubber material having a large rebound elasticity at the above temperature or a small tan δ or Goodrich heat generation is preferable.

As a rubber material having a small hysteresis loss, natural rubber, polyisoprene rubber, polybutadiene rubber, etc. are known, but these have a problem of low wet skid resistance. Accordingly, recently, conjugated diene-based (co)polymers such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) have been manufactured by emulsion polymerization or solution polymerization and are used as rubber for tires. .

When the BR or SBR is used as a rubber material for a tire, a filler such as silica or carbon black is usually blended together to obtain the required physical properties of the tire. However, the affinity of the BR or SBR with the filler is not good, so there is a problem in that physical properties including abrasion resistance, crack resistance or workability are rather deteriorated.

On the other hand, in BR, compounding properties and processability such as running resistance were improved by controlling the molecular weight distribution, but compounding properties and processability are trade-off. On the contrary, when the molecular weight distribution is widened, the processability is improved, but there is a problem in that the compounding properties are lowered.

Accordingly, the BR having a narrow molecular weight distribution was modified to introduce a long-chian branch (LCB) to improve compounding properties and processability at the same time, but a sufficient effect was not obtained.

JP 2013-507510 A (2013. 03. 04.)

The present invention has been devised to solve the problems of the prior art, and contains a high molecular weight polymer chain in a specific ratio, and has a molecular weight distribution in a specific range, thereby having excellent compounding properties and improved processability characteristics. It aims to provide a polymer.

Another object of the present invention is to provide a method for preparing the conjugated diene-based polymer using a catalyst composition prepared by mixing a first alkylating agent and a second alkylating agent in a specific ratio.

In addition, an object of the present invention is to provide a rubber composition comprising the conjugated diene-based polymer and a filler.

In order to solve the above problems, the present invention includes a repeating unit derived from a conjugated diene-based monomer, 20% by weight or more of a polymer chain having a weight average molecular weight of 1,000,000 g/mol or more, and a conjugated diene having a molecular weight distribution of 2.8 or more and 3.4 or less to provide a polymer.

In addition, the present invention comprises the step of polymerizing a conjugated diene-based monomer in the presence of a catalyst composition comprising a neodymium compound in a hydrocarbon solvent, wherein the catalyst composition is a neodymium compound, a first alkylating agent, a second alkylating agent and a halide mixture to prepare a catalyst mixture, and aging the prepared catalyst mixture, wherein the first alkylating agent and the second alkylating agent are mixed in a molar ratio of 5:1 to 3:1. Method for producing the conjugated diene-based polymer provides

In addition, the present invention provides a rubber composition comprising the modified conjugated diene-based polymer.

The conjugated diene-based polymer according to the present invention contains 20% by weight or more of a polymer chain having a weight average molecular weight of 1,000,000 g/mol or more, and has a molecular weight distribution of 2.8 or more and 3.4 or less, thereby having excellent compounding properties and improving processability characteristics. there is.

In addition, in the method for producing a conjugated diene-based polymer according to the present invention, a polymer having a weight average molecular weight of 1,000,000 g/mol or more by mixing a first alkylating agent and a second alkylating agent in a specific ratio and polymerizing a monomer in the presence of a catalyst composition prepared by aging It is possible to prepare a conjugated diene-based polymer including a chain in an amount of 20 wt% or more, and having a broad molecular weight distribution controlled to a specific range.

In addition, the rubber composition according to the present invention has excellent compounding properties and processability by including the conjugated diene-based polymer.

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

The terms or words used in the present specification and claims should not be construed as being limited to ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. Based on the principle that there is, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.

measurement method

In the present invention, 'cis-1,4-bond content and vinyl bond content' refers to the FT-IR transmittance spectrum of a carbon disulfide solution of a conjugated diene-based polymer prepared at a concentration of 5 mg/mL using carbon disulfide in the same cell as a blank. After the measurement, the maximum peak value near 1130 cm ^-1 of the measurement spectrum (a, baseline), the minimum peak value near 967 cm ^-1 indicating trans-1,4 bond (b), and 911 cm indicating the vinyl bond Each content was calculated using the minimum peak value (c) near ^-1 and the minimum peak value (d) near 736 cm ^-1 indicating cis-1,4 bond.

Conjugated diene polymer

The present invention includes a polymer chain having a weight average molecular weight of 1,000,000 g/mol or more in a specific range, and has a wide molecular weight distribution controlled in a specific range, so that the compounding properties are excellent and the processability properties are improved at the same time, so that the compounding properties and the processability properties are balanced To provide an excellent conjugated diene-based polymer.

The conjugated diene-based polymer according to an embodiment of the present invention includes a repeating unit derived from a conjugated diene-based monomer, 20% by weight or more of a polymer chain having a weight average molecular weight of 1,000,000 g/mol or more, and a molecular weight distribution of 2.8 or more 3.4 It is characterized by the following.

In general, in a conjugated diene-based polymer, compounding properties and processability characteristics are physical properties in a trade-off relationship, and it is known that it is difficult to simultaneously exhibit excellent properties in compounding properties and processability characteristics. In addition, when the molecular weight distribution of the conjugated diene-based polymer is narrow, the compounding properties may be excellent, but the processability characteristics are deteriorated. However, the modified conjugated diene-based polymer according to the present invention is prepared by the manufacturing method described below, thereby including a high molecular weight polymer chain having a weight average molecular weight in the polymer of 1,000,000 g/mol or more in a specific content, and at the same time a molecular weight distribution in a specific range can have, and there is an effect of greatly improving processability characteristics while maintaining excellent compounding properties.

Specifically, the conjugated diene-based polymer includes a polymer chain including a repeating unit derived from a conjugated diene-based monomer, and a polymer chain having a weight average molecular weight of 1,000,000 g/mol or more among the polymer chain is 20 based on 100% by weight of the total polymer Weight % or more, more specifically, it may be included in an amount of 20 wt% or more and 30 wt% or less.

On the other hand, as a means for limiting that the weight average molecular weight of the polymer chain is a high molecular weight above a specific value, all polymer chains having a weight average molecular weight or more as presented above may be included, but in terms of a more preferable effect, the weight average molecular weight of the polymer chain may be 1,000,000 g/mol or more and 2,000,000 g/mol or less.

As another example, the conjugated diene-based polymer may include 20% by weight or more of the polymer chain having the above-mentioned weight average molecular weight and at the same time have a molecular weight distribution of 2.8 or more and 3.4 or less, specifically, the conjugated diene-based polymer has a weight average molecular weight This 1,000,000 g/mol or more of the polymer chain may be included in an amount of 20 wt% or more and 30 wt% or less, and a molecular weight distribution of 2.8 or more and 3.2 or less. In this case, the workability characteristics, the tensile characteristics, and the running resistance may be superior at the same time.

In the present invention, the molecular weight distribution of the modified conjugated diene-based polymer may be calculated from the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn). In this case, the number average molecular weight (Mn) is a common average of individual polymer molecular weights calculated by measuring the molecular weights of n polymer molecules, obtaining the sum of these molecular weights, and dividing by n, and the weight average molecular weight (Mw) is the polymer The molecular weight distribution of the composition is shown. All molecular weight averages can be expressed in grams per mole (g/mol). In addition, the weight average molecular weight and the number average molecular weight may mean a polystyrene equivalent molecular weight analyzed by gel permeation chromatography (GPC), respectively.

The conjugated diene-based polymer according to an embodiment of the present invention may have a weight average molecular weight (Mw) of 500,000 to 1,500,000 g/mol, and a number average molecular weight (Mn) of 100,000 to while satisfying the molecular weight distribution conditions described above. It may be 500,000 g/mol, and when applied to a rubber composition within this range, it has excellent tensile properties and excellent processability, so it is easy to knead due to the improvement of workability of the rubber composition, and the mechanical and physical properties balance of the rubber composition is excellent It works. The weight average molecular weight may be, for example, 500,000 to 1,200,000 g/mol, or 500,000 to 800,000 g/mol, and the number average molecular weight may be, for example, 150,000 to 350,000 g/mol, or 200,000 to 270,000 g/mol.

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

In addition, the conjugated diene-based polymer may be a butadiene homopolymer such as polybutadiene, or a diene-based copolymer such as a butadiene-isoprene copolymer.

As a specific example, the conjugated diene-based polymer may contain 80 to 100% by weight of 1,3-butadiene monomer-derived units, and 20% by weight or less of other conjugated diene-based monomer-derived units that are optionally copolymerizable with 1,3-butadiene. There is an effect that the content of 1,4-cis bonds in the polymer is not lowered within the above range. In this case, the 1,3-butadiene monomer includes 1,3-butadiene or derivatives thereof, such as 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, or 2-ethyl-1,3-butadiene. and other conjugated diene-based monomers copolymerizable with 1,3-butadiene include 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 mentioned, and any one or two or more compounds of these may be used.

In addition, the conjugated diene-based polymer according to an embodiment of the present invention may be a neodymium-catalyzed liquid diene-based polymer. That is, the modified conjugated diene-based polymer may be a conjugated diene-based polymer including an organometallic moiety activated from a catalyst composition including a neodymium compound.

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

In the present invention, the Mooney viscosity was measured using a Mooney viscometer, for example, a Large Rotor of Monsanto's MV2000E at 100° C. and a rotor speed of 2±0.02 rpm. Specifically, after leaving the polymer at room temperature (23±5° C.) for more than 30 minutes, 27±3 g was collected, filled in the die cavity, and the Mooney viscosity was measured while applying a torque by operating a platen.

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

In addition, in the modified conjugated diene-based polymer, the vinyl content of the conjugated diene part measured by Fourier transform infrared spectroscopy may be 5% or less, more specifically, 2% or less. When the vinyl content in the polymer exceeds 5%, there is a fear that the abrasion resistance, crack resistance, and ozone resistance of the rubber composition including the same may be deteriorated. Here, the vinyl content represents the mass (or weight) percentage of butadiene contained in positions 1 and 2 in the polymer chain based on the conjugated diene monomer (butadiene, etc.) portion (total amount of polymerized butadiene) in the polymer. .

Method for producing conjugated diene-based polymer

In addition, the present invention provides a method for producing the conjugated diene-based polymer.

The manufacturing method according to an embodiment of the present invention comprises polymerizing a conjugated diene-based monomer in the presence of a catalyst composition containing a neodymium compound in a hydrocarbon solvent (step A), and the catalyst composition is a neodymium compound, It is prepared by mixing the first alkylating agent, the second alkylating agent and the halide and then aging, and the first alkylating agent and the second alkylating agent are mixed in a molar ratio of 5:1 to 3:1.

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

In the present invention, in the active polymer including the organometallic moiety, the organometallic moiety is an activated organometallic moiety at the end of the conjugated diene-based polymer (an activated organometallic moiety at the end of the molecular chain), and an activated organometallic moiety in the main chain. Alternatively, it may be an activated organometallic moiety in a side chain (side chain), and among them, when an activated organometallic moiety of a conjugated diene-based polymer is obtained by anionic polymerization or coordination anionic polymerization, the organometallic moiety is an activated organometallic moiety at the terminal may indicate

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

The conjugated diene-based monomer is not particularly limited, for example, 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl The group consisting of -1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene and 2,4-hexadiene, etc. It may be at least one selected from

In the catalyst composition, the neodymium compound may be used in an amount of 0.02 g to 1.0 g based on a total of 100 g of the conjugated diene-based monomer, and specifically, 0.05 g of the neodymium compound based on a total of 100 g of the conjugated diene-based monomer to 0.5 g, more specifically, 0.05 g to 0.25 g may be used.

The neodymium compound is a carboxylate salt thereof (eg, neodymium acetate, neodymium acrylate, neodymium methacrylate, neodymium gluconate, neodymium citrate, neodymium fumarate, neodymium lactate, neodymium maleate, neodymium oxalate, neodymium 2 -ethylhexanoate, neodymium neodecanoate, etc.); organophosphates (e.g., neodymium dibutyl phosphate, neodymium dipentyl phosphate, neodymium dihexyl phosphate, neodymium diheptyl phosphate, neodymium dioctyl phosphate, neodymium bis(1-methyl heptyl) phosphate, neodymium bis(2-ethylhexyl) phosphate, or neodymium didecyl phosphate, etc.); organic phosphonates (e.g., neodymium butyl phosphonate, neodymium pentyl phosphonate, neodymium hexyl phosphonate, neodymium heptyl phosphonate, neodymium octyl phosphonate, neodymium (1-methyl heptyl) phosphonate, neodymium (2-ethylhexyl) phosphonate, neodymium disyl phosphonate, neodymium dodecyl phosphonate, or neodymium octadecyl phosphonate); organic phosphinates (e.g., neodymium butylphosphinate, neodymium pentylphosphinate, neodymium hexyl phosphinate, neodymium heptyl phosphinate, neodymium octyl phosphinate, neodymium (1-methyl heptyl) phosphinate, or neodymium (2-ethylhexyl) phosphinate, etc.); carbamates (eg, neodymium dimethyl carbamate, neodymium diethyl carbamate, neodymium diisopropyl carbamate, neodymium dibutyl carbamate, or neodymium dibenzyl carbamate, etc.); dithiocarbamate (eg, neodymium dimethyldithiocarbamate, neodymium diethyldithiocarbamate, neodymium diisopropyl dithiocarbamate, or neodymium dibutyldithiocarbamate); xanthogenates (eg, neodymium methyl xanthogen, neodymium ethyl xanthogen, neodymium isopropyl xanthogen, neodymium butyl xanthogen, or neodymium benzyl xanthogen, etc.); β-diketonate (eg, neodymium acetylacetonate, neodymium trifluoroacetyl acetonate, neodymium hexafluoroacetyl acetonate or neodymium benzoyl acetonate, etc.); alkoxides or allyloxides (eg, neodymium methoxide, neodymium ethoxide, neodymium isopropoxide, neodymium phenoxide or neodymium nonyl phenoxide, etc.); halides or pseudohalides (such as neodymium fluoride, neodymium chloride, neodymium bromide, neodymium iodide, neodymium cyanide, neodymium cyanate, neodymium thiocyanate, or neodymium azide); oxyhalides (eg, neodymium oxyfluoride, neodymium oxy chloride, or neodymium oxy bromide, etc.); or an organic neodymium containing compound comprising one or more elemental neodymium-carbon bonds (eg, Cp ₃ Nd, Cp ₂ NdR, Cp ₂ NdCl, CpNdCl ₂ , CpNd(cyclooctatetraene), (C ₅ Me ₅ ) ₂ ) NdR, NdR ₃ , Nd(allyl) ₃ , or Nd(allyl) ₂ Cl, etc., wherein R is a hydrocarbyl group), and the like, may include any one or a mixture of two or more thereof.

The neodymium compound may be a compound represented by the following formula (1).

[Formula 1]

In Formula 1, R _a to R _c are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms, with the proviso that R _a to R _c are not all hydrogen at the same time.

More specifically, the neodymium compound is Nd(2-ethylhexanoate) ₃ , Nd(2,2-dimethyl decanoate) ₃ , Nd(2,2-diethyl decanoate) ₃ , Nd(2, 2-dipropyl decanoate) ₃ , Nd(2,2-dibutyl decanoate) ₃ , Nd(2,2-dihexyl decanoate) ₃ , Nd(2,2-dioctyl decanoate) ₃ , Nd(2-ethyl-2-propyl decanoate) ₃ , Nd(2-ethyl-2-butyl decanoate) ₃ , Nd(2-ethyl-2-hexyl decanoate) ₃ , Nd(2 -Propyl-2-butyl decanoate) ₃ , Nd(2-propyl-2-hexyl decanoate) ₃ , Nd(2-propyl-2-isopropyl decanoate) ₃ , Nd(2-butyl-2 -Hexyl decanoate) ₃ , Nd (2-hexyl-2-octyl decanoate) ₃ , Nd (2,2-diethyl octanoate) ₃ , Nd (2,2-dipropyl octanoate) ₃ , Nd(2,2-dibutyl octanoate) ₃ , Nd(2,2-dihexyl octanoate) ₃ , Nd(2-ethyl-2-propyl octanoate) ₃ , Nd(2-ethyl- 2-hexyl octanoate) ₃ , Nd(2,2-diethyl nonanoate) ₃ , Nd(2,2-dipropyl nonanoate) ₃ , Nd(2,2-dibutyl nonanoate) ₃ 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 may be more than a species.

In addition, as another example, considering the excellent solubility in solvents, conversion to catalytically active species, and thus the catalytic activity improvement effect without concerns about oligomerization, the neodymium compound is more specifically, R _a in Formula 1 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.

As a more specific example, in Formula 1, R _a is an alkyl group having 6 to 8 carbon atoms, 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 may be at least one selected from the group consisting of, among them, 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 may be at least one selected from the group consisting of.

More specifically, in Formula 2, R _a may be 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 such, the neodymium compound represented by Formula 1 includes a carboxylate ligand including an alkyl group of various lengths of 2 or more carbon atoms as a substituent at the α (alpha) position, thereby inducing a steric change around the neodymium central metal between the compounds It is possible to block the agglomeration phenomenon, and thus, there is an effect of suppressing oligomerization. In addition, such a neodymium-based compound has a high solubility in a solvent, and a ratio of neodymium located in a central portion having difficulty in conversion to a catalytically active species is reduced, thereby increasing the conversion rate to a 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 ℃).

In the present invention, the solubility of the neodymium compound refers to the degree of clear dissolution without turbidity, and by exhibiting such high solubility, excellent catalytic activity can be exhibited.

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 reactant has the effect of improving the solubility of the neodymium compound in the solvent by the Lewis base and storing it in a stable state for a long period of time. The Lewis base may be used, for example, in a ratio of 30 moles or less, or 1 to 10 moles per mole of neodymium element. The Lewis base may be, for example, acetylacetone, tetrahydrofuran, pyridine, N,N-dimethylformamide, thiophene, diphenyl ether, triethylamine, an organophosphorus compound, or monovalent or divalent alcohol.

In addition, the catalyst composition according to an embodiment of the present invention may be prepared by mixing a neodymium compound, a first alkylating agent, a second alkylating agent, and a halide and then aging, wherein the first alkylating agent and the second alkylating agent are 5 It may be mixed in a molar ratio of :1 to 3:1, specifically, in a molar ratio of 4:1 to 3:1.

In addition, the aging can be carried out by standing still for 2 weeks or more and 6 weeks or less at a temperature of -20°C to 0°C, specifically, it is prepared by mixing at a temperature of -10°C to 0°C for 2 weeks or more and 4 weeks or less It can be carried out by allowing the catalyst mixture to stand still.

The first alkylating agent may be aluminoxane, and the aluminoxane may be prepared by reacting a trihydrocarbyl aluminum-based compound with water. Specifically, the aluminoxane may be a straight-chain aluminoxane of Formula 2a or a cyclic aluminoxane of Formula 2b.

[Formula 2a]

[Formula 2b]

In Formulas 2a and 2b, 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 each independently an integer of 1 or more, specifically 1 to 100 , more specifically, may be an integer of 2 to 50.

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

In addition, the modified methylaluminoxane may be a compound in which the methyl group of methylaluminoxane is substituted with a modifying group (R), specifically, a hydrocarbon group having 2 to 20 carbon atoms, specifically, a compound represented by the following formula (3).

[Formula 3]

In Formula 3, R is as defined above, and m and n may be each independently an integer of 2 or more. In addition, in Formula 3, Me represents a methyl group.

Specifically, in Formula 3, 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, an ethyl group, isobutyl group, hexyl group or octyl group having 2 carbon atoms. to 10, and more specifically, may be an isobutyl group.

More specifically, the modified methylaluminoxane may be obtained by substituting about 50 to 90 mol% of the methyl group of methylaluminoxane with the above-described hydrocarbon group. 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 alkylaluminum other than trimethylaluminum. In this case, the alkyl aluminum may be triisobutyl aluminum, triethyl aluminum, trihexyl aluminum or trioctyla aluminum, and any one or a mixture of two or more thereof may be used.

The second alkylating agent may be hydrocarbylaluminum dihydride, specifically diethylaluminum hydride, di-n-propylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, di Isobutylaluminum hydride, di-n-octylaluminum hydride, diphenylaluminum hydride, di-p-tolylaluminum hydride, dibenzylaluminum hydride, phenylethylaluminum hydride, phenyl-n-propylaluminum hydride , phenylisopropylaluminum hydride, phenyl-n-butylaluminum hydride, phenylisobutylaluminum hydride, phenyl-n-octylaluminum hydride, p-tolylethylaluminum hydride, p-tolyl-n-propylaluminum hydride Ride, p-tolylisopropylaluminum hydride, p-tolyl-n-butylaluminum hydride, p-tolylisobutylaluminum hydride, p-tolyl-n-octylaluminum hydride, benzylethylaluminum hydride, benzyl- It may be at least one selected from the group consisting of n-propylaluminum hydride, benzylisopropylaluminum hydride, benzyl-n-butylaluminum hydride, benzylisobutylaluminum hydride, and benzyl-n-octylaluminum hydride, Specifically, it may be diisobutylaluminum hydride.

For example, in the catalyst composition according to the present invention, if necessary, an alkylating agent used as an alkylating agent in the preparation of a conjugated diene-based polymer other than the first and second alkylating agents may be further used, and the alkylating agent is trimethylaluminum , triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, tri alkyl aluminum such as octylaluminum; and alkyl magnesium compounds such as diethyl magnesium, di-n-propyl magnesium, diisopropyl magnesium, dibutyl magnesium, dihexyl magnesium, diphenyl magnesium, and dibenzyl magnesium. and alkyl lithium compounds such as n-butyllithium.

In addition, the catalyst composition according to an embodiment of the present invention may include an alkylating agent in a molar ratio of 50 to 250 molar ratio, specifically 80 to 200 molar ratio, and more specifically 100 to 150 molar ratio with respect to 1 mole of the neodymium compound. . If the alkylating agent is included in an amount exceeding 200 molar ratio, it is not easy to control the catalytic reaction during the preparation of the polymer, and there is a risk that an excessive amount of the alkylating agent may cause side reactions. In this case, the amount of the alkylating agent used for the neodymium compound is the total amount of the first alkylating agent and the second alkylating agent.

In addition, the halide is not particularly limited, for example, a halogen simple substance, an interhalogen compound, a hydrogen halide, an organic halide, a non-metal halide, a metal halide, or an organometallic halide, and the like. Any one or a mixture of two or more may be used. Among them, any one or a mixture of two or more selected from the group consisting of organic halides, metal halides, and organometallic halides may be used as the halide in consideration of the excellent effect of improving catalytic activity and thus improving reactivity.

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

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

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

In addition, 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, propyi Onyl chloride, propionyl bromide, methyl chloroformate, methyl bromoformate, iodomethane, diiodomethane, triiodomethane (also called 'iodoform'), tetraiodomethane, 1-io Dopropane, 2-iodopropane, 1,3-diiodopropane, t-butyl iodide, 2,2-dimethyl-1-iodopropane (also called 'neopentyl iodide'), allyl iodine Odide, iodobenzene, benzyl iodide, diphenylmethyl iodide, triphenylmethyl iodide, benzylidene iodide (also called 'benzal iodide'), trimethylsilyl iodide, triethyl Silyl iodide, triphenylsilyl iodide, dimethyldiiodosilane, diethyldiiodosilane, diphenyldiiodosilane, methyltriiodosilane, ethyltriiodosilane, phenyltriiodosilane, benzoyl iodide, propionyl iodide or methyl iodoformate; and the like.

In addition, as the non-metal halide, phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride, phosphorus oxybromide, 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 tetraiodide, arsenic triiodide, tellurium tetraiodide, boron triiodide, phosphorus triiodide, phosphorus oxyiodide or selenium tetraiodide, etc. can be heard

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 tetraiodide, tin iodide, antimony triiodide, or magnesium iodide.

In addition, as the organometallic halide, 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, ethylaluminum dibromide, methylaluminum difluoride, ethylaluminum difluoride, methylaluminum sesquichloride, ethylaluminum sesquichloride (EASC), isobutylaluminum sesquichloride, methylmagnesium chloride, methylmagnesium bromide, ethyl Magnesium chloride, ethylmagnesium bromide, n-butylmagnesium chloride, n-butylmagnesium bromide, phenylmagnesium chloride, phenylmagnesium bromide, benzylmagnesium chloride, trimethyltin chloride, trimethyltin bromide, triethyltin chloride, triethyltin bromide, di -t-butyltin dichloride, di-t-butyltin dibromide, di-n-butyltin dichloride, di-n-butyltin dibromide, tri-n-butyltin chloride, tri-n-butyltin bromide , methylmagnesium iodide, dimethylaluminum iodide, diethylaluminum iodide, di-n-butylaluminum iodide, diisobutylaluminum iodide, di-n-octylaluminum iodide, methylaluminum Diiodide, ethylaluminum diiodide, n-butylaluminum diiodide, isobutylaluminum diiodide, methylaluminum sesquiiodide, ethylaluminum sesquiiodide, isobutylaluminum sesquiiodide, ethylmagnesium iodide Odide, n-butylmagnesium iodide, isobutylmagnesium iodide, phenylmagnesium iodide, benzylmagnesium iodide, trimethyltin iodide, triethyltin iodide, tri-n-butyltin iodide odide, di-n-butyltin diiodide, or di-t-butyltin diiodide;

In addition, the catalyst composition according to an embodiment of the present invention contains the halide in an amount of 1 to 20 moles, more specifically 1 to 5 moles, and more specifically 2 to 3 moles, based on 1 mole of the neodymium compound. may include If the halide is included in a molar ratio of more than 20, it is not easy to remove the catalytic reaction, and there is a fear that an excessive amount of the halide may cause a side reaction.

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 tetraaryl fluoride. borate anion, and the like. In addition, 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, or the like.

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

In addition, the catalyst composition may further include a conjugated diene-based monomer, and a portion of the conjugated diene-based monomer used in the polymerization reaction is mixed with the catalyst composition for polymerization in advance to perform pre-polymerization or pre-polymerization. By using it in the form of a premix catalyst composition, it is possible not only to improve the catalyst composition activity, but also to stabilize the active polymer to be prepared.

In the present invention, the "preforming" means a catalyst composition comprising a neodymium compound, first and second alkylating agents and a halide, that is, diisobutylaluminum hydride (DIBAH) in a catalyst system. In this case, a small amount of a conjugated diene-based monomer such as 1,3-butadiene is added to reduce the possibility of generating various active species in the catalyst composition, and pre-polymerization is performed in the catalyst composition system along with the addition of 1,3-butadiene. can mean done. In addition, "premix (premix)" may mean a state in which each compound is uniformly mixed without polymerization in the catalyst composition system.

In this case, the conjugated diene-based monomer used in the preparation of the catalyst composition may be used in an amount within the total amount of the conjugated diene-based monomer used in the polymerization, for example, 1 per mole of the neodymium compound. It may be used in an amount of from 10 moles to 100 moles, specifically from 10 moles to 50 moles, or from 20 moles to 50 moles.

The catalyst composition according to an embodiment of the present invention may be prepared by mixing a neodymium compound, a first alkylating agent, a second alkylating agent and a halide, and optionally a conjugated diene-based monomer in an organic solvent. In this case, the organic solvent may be a non-polar solvent that is not reactive with the components of the catalyst composition. Specifically, the non-polar solvent is n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, isopentane, isohexane, isopentane, isooctane, 2,2-dimethylbutane, cyclo linear, branched or cyclic aliphatic hydrocarbons having 5 to 20 carbon atoms, such as pentane, cyclohexane, methylcyclopentane or methylcyclohexane; a mixed solvent of aliphatic hydrocarbons having 5 to 20 carbon atoms, such as petroleum ether or petroleum spirits, or kerosene; Alternatively, it may be an aromatic hydrocarbon-based solvent such as benzene, toluene, ethylbenzene, and xylene, and any one or a mixture of two or more thereof may be used. More specifically, the non-polar solvent may be a linear, branched or cyclic aliphatic hydrocarbon having 5 to 20 carbon atoms or a mixed solvent of aliphatic hydrocarbons, and more specifically, n-hexane, cyclohexane, or a mixture thereof. can

In addition, the organic solvent may be appropriately selected according to the type of constituents constituting the catalyst composition, particularly, the first alkylating agent.

Specifically, in the case of alkylaluminoxane such as methylaluminoxane (MAO) or ethylaluminoxane as the first alkylating agent, since it is not easily dissolved in the aliphatic hydrocarbon-based solvent, an aromatic hydrocarbon-based solvent may be appropriately used.

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

In addition, the organic solvent may be used in an amount of 20 moles to 20,000 moles, more specifically, 100 moles to 1,000 moles, based on 1 mole of the neodymium compound.

On the other hand, the polymerization in step A may be carried out as a continuous polymerization in a polymerization reactor including at least two reactors, or may be carried out in a batch reactor.

In addition, the polymerization may be an elevated temperature polymerization, an isothermal polymerization, or a constant temperature polymerization (adiabatic polymerization).

Here, the constant temperature polymerization refers to a polymerization method comprising the step of polymerization with heat of reaction by itself without optionally applying heat after the catalyst composition is added. , and the isothermal polymerization refers to a polymerization method in which heat is applied after the catalyst composition is added to increase heat, or heat is taken away to maintain a constant temperature of the reactant.

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

The polymerization may be carried out 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 may be performed for 3 hours. If the polymerization temperature exceeds 200 ℃, it is difficult to sufficiently control the polymerization reaction, there is a risk that the cis-1,4 bond content of the resulting conjugated diene-based polymer may be lowered, and if the temperature is less than -20 ℃, polymerization There is a possibility that the reaction rate and efficiency may be lowered.

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

After completion of the polymerization reaction described above, 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.

In the manufacturing method according to an embodiment of the present invention, after step A, a conjugated diene-based polymer may be obtained through a solvent removal treatment such as steam stripping or vacuum drying treatment to lower the partial pressure of the solvent through supply of water vapor.

rubber composition

In addition, the present invention provides a rubber composition comprising the 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 wt% or more and 100 wt% or less of the conjugated diene-based polymer, specifically 10 wt% to 100 wt%, more specifically 20 wt% to 90 wt% may be doing If the content of the modified conjugated diene-based polymer is less than 0.1% by weight, as a result, the improvement effect of 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 needed in addition to the modified conjugated diene-based polymer, wherein the rubber component may be included in an amount of 90% by weight or less based on the total weight of the rubber composition. Specifically, it may be included in an amount of 1 to 900 parts by weight based on 100 parts by weight of the modified conjugated diene-based copolymer.

The rubber component may be natural rubber or synthetic rubber, for example, the rubber component may include natural rubber (NR) containing cis-1,4-polyisoprene; Modified natural rubbers such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber that are modified or refined of 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, or a synthetic rubber such as halogenated butyl rubber, and any one or a mixture of two or more thereof may be used.

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

The carbon black-based filler is not particularly limited, but may have, for example, a nitrogen adsorption specific surface area (N ₂ SA, measured in accordance with JIS K 6217-2:2001) of 20 m 2 /g to 250 m 2 /g. In addition, the carbon black may have a dibutyl phthalate 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 decrease, and if 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/100g, there is a fear that the processability of the rubber composition is reduced, and when it is less than 80 cc/100g, 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 (silicic anhydride), calcium silicate, aluminum silicate or colloidal silica. Specifically, the silica may be wet silica having the most remarkable effect of improving fracture properties and coexisting effects of wet grip properties. In addition, the silica has a nitrogen adsorption specific surface area (nitrogen surface area per gram, N ₂ SA) of 120 m / g to 180 m / g, and a cetyl trimethyl ammonium bromide (CTAB) adsorption specific surface area of 100 m / g to 200 m It can be /g. 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 silica may be lowered, and if it exceeds 180 m / g, there is a fear that the processability of the rubber composition may decrease. In addition, if the CTAB adsorption specific surface area of the silica is less than 100 m 2 /g, the reinforcing performance by the silica filler may decrease, and if it exceeds 200 m / g, the processability of the rubber composition may decrease.

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

Specifically, the silane coupling agent is 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 thereof may be used. More specifically, in consideration of the reinforcing improvement effect, the silane coupling agent may be bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide.

In addition, the rubber composition according to an embodiment according to the present invention may be crosslinkable with sulfur, 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, it is possible to secure the required elastic modulus and strength of the vulcanized rubber composition, and at the same time to obtain low fuel economy.

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

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

In addition, the process oil acts as a softener in the rubber composition. Specifically, it may be a paraffinic, naphthenic, or aromatic compound. More specifically, when considering tensile strength and abrasion resistance, aromatic process oil price, hysteresis loss And in consideration of low-temperature characteristics, a naphthenic or paraffin-based process oil may be used. The process oil may be included in an amount of 100 parts by weight or less based on 100 parts by weight of the rubber component.

In addition, the antioxidant is 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 condensate 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 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 also has low heat generation and wear resistance by a vulcanization process after molding processing. This excellent rubber composition can be obtained.

Accordingly, the rubber composition may be used for each member of the tire such as a tire tread, under tread, side wall, carcass coated rubber, belt coated rubber, bead filler, cheffer, or bead coated rubber, vibration proof rubber, belt conveyor, hose, etc. It may be useful in the manufacture of various industrial rubber products of

A 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 way of Examples and Experimental Examples. However, the following Examples and Experimental Examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereto.

Preparation Example 1

Under nitrogen condition, NdV (neodymium versatate, Nd(2-ethylhexanoate) ₃ ) was added in a hexane solvent, methylaluminoxane (MAO), diisobutylaluminum hydride (DIBAH), diethylaluminum chloride ( DEAC) and 1,3-butadiene were sequentially added in a molar ratio of NdV:MAO:DIBAH:DEAC:1,3-butadiene=1:100:20:3:30, and then mixed at 20° C. for 12 hours for chlorination. A reactant (preform catalyst composition) was prepared. The prepared chlorination reactant was aged for 14 days under nitrogen conditions at -10°C, and then used to prepare a polymer.

Preparation 2

In Preparation Example 1, methylaluminoxane (MAO), diisobutylaluminum hydride (DIBAH), diethylaluminum chloride (DEAC) and 1,3-butadiene were mixed with NdV:MAO:DIBAH:DEAC:1,3-butadiene = A chlorination reactant was prepared in the same manner as in Preparation Example 1, except that the molar ratio was 1:100:25:3:30, except that it was aged for 14 days under nitrogen conditions at -10°C, and then used to prepare a polymer. did

Preparation 3

In Preparation Example 1, methylaluminoxane (MAO), diisobutylaluminum hydride (DIBAH), diethylaluminum chloride (DEAC) and 1,3-butadiene were mixed with NdV:MAO:DIBAH:DEAC:1,3-butadiene = A chlorination reactant was prepared in the same manner as in Preparation Example 1, except that the molar ratio was added sequentially to a molar ratio of 1:100:33:3:30, and aged for 14 days under nitrogen conditions at -10 ° C. did

Comparative Preparation Example 1

In Preparation Example 1, methylaluminoxane (MAO), diisobutylaluminum hydride (DIBAH), diethylaluminum chloride (DEAC) and 1,3-butadiene were mixed with NdV:MAO:DIBAH:DEAC:1,3-butadiene = A chlorination reactant was prepared in the same manner as in Preparation Example 1, except that the molar ratio was 1:100:40:3:30 except that it was sequentially added, and after aging for 14 days under nitrogen conditions at -10°C, it was used to prepare a polymer did

Comparative Preparation Example 2

In Preparation Example 1, methylaluminoxane (MAO), diisobutylaluminum hydride (DIBAH), diethylaluminum chloride (DEAC) and 1,3-butadiene were mixed with NdV:MAO:DIBAH:DEAC:1,3-butadiene = A chlorination reactant was prepared in the same manner as in Preparation Example 1, except that the molar ratio was 1:100:50:3:30, except that it was aged for 14 days under nitrogen conditions at -10°C, and then used to prepare a polymer. did

Comparative Preparation Example 3

In Preparation Example 1, methylaluminoxane (MAO), diisobutylaluminum hydride (DIBAH), diethylaluminum chloride (DEAC) and 1,3-butadiene were mixed with NdV:MAO:DIBAH:DEAC:1,3-butadiene = A chlorination reactant was prepared in the same manner as in Preparation Example 1 except that the molar ratio was 1:100:17:3:30 except that it was sequentially added, and after aging for 14 days under nitrogen conditions at -10°C, it was used to prepare a polymer did

Comparative Preparation Example 4

In Preparation Example 1, without using methylaluminoxane, diisobutylaluminum hydride (DIBAH), diethylaluminum chloride (DEAC) and 1,3-butadiene were mixed with NdV:DIBAH:DEAC:1,3-butadiene = 1 A chlorination reactant was prepared in the same manner as in Preparation Example 1, except that the molar ratio of :20:3:30 was sequentially added, and after aging for 14 days under nitrogen conditions at -10°C, it was used to prepare a polymer.

Reference Preparation Example 1

In Preparation Example 1, the prepared chlorination reactant was aged for 10 days under nitrogen conditions at -10°C, and then used to prepare a polymer.

Reference Preparation Example 2

In Preparation Example 1, the prepared chlorination reactant was aged for 45 days under nitrogen conditions at -10°C, and then used to prepare a polymer.

Example 1

After vacuum and nitrogen were alternately applied to a completely dried 15L autoclave reactor, 4.2 kg of n-hexane and 500 g of 1,3-butadiene were put into the reactor in a vacuum state, and then the temperature inside the reactor was raised to 70°C. After the catalyst composition prepared in Preparation Example 1 was added thereto, polymerization was performed for 60 minutes to prepare an active polymer. At this time, the conversion rate of 1,3-butadiene to polybutadiene polymer was 100%. Thereafter, the reaction was terminated by adding a hexane solution containing 1.0 g of a polymerization terminator and a hexane solution containing 2.0 g of an antioxidant WINGSTAY (Eliokem SAS, France), and the resulting heavy content was placed in hot water heated with steam. The mixture was added and stirred to remove the solvent, and then roll-dried to remove the remaining amount of solvent and water to prepare a butadiene polymer.

Example 2

In Example 1, a butadiene polymer was prepared in the same manner as in Example 1, except that the catalyst composition prepared in Preparation Example 2 was added instead of the catalyst composition prepared in Preparation Example 1.

Example 3

In Example 1, a butadiene polymer was prepared in the same manner as in Example 1, except that the catalyst composition prepared in Preparation Example 3 was added instead of the catalyst composition prepared in Preparation Example 1.

Comparative Example 1

In Example 1, a butadiene polymer was prepared in the same manner as in Example 1, except that the catalyst composition prepared in Comparative Preparation Example 1 was added instead of the catalyst composition prepared in Preparation Example 1.

Comparative Example 2

In Example 1, a butadiene polymer was prepared in the same manner as in Example 1, except that the catalyst composition prepared in Comparative Preparation Example 2 was added instead of the catalyst composition prepared in Preparation Example 1.

Comparative Example 3

In Example 1, a butadiene polymer was prepared in the same manner as in Example 1, except that the catalyst composition prepared in Comparative Preparation Example 3 was added instead of the catalyst composition prepared in Preparation Example 1.

Comparative Example 4

In Example 1, a butadiene polymer was prepared in the same manner as in Example 1, except that the catalyst composition prepared in Comparative Preparation Example 4 was added instead of the catalyst composition prepared in Preparation Example 1.

Reference Example 1

In Example 1, a butadiene polymer was prepared in the same manner as in Example 1, except that the catalyst composition prepared in Reference Preparation Example 1 was added instead of the catalyst composition prepared in Preparation Example 1.

Reference Example 2

In Example 1, a butadiene polymer was prepared in the same manner as in Example 1, except that the catalyst composition prepared in Reference Preparation Example 2 was added instead of the catalyst composition prepared in Preparation Example 1.

Experimental Example 1

For the polymers of Examples 1 to 3, Comparative Examples 1 to 3, and Reference Examples 1 and 2, each physical property was measured in the following manner, and the results are shown in Table 1 below.

1) Microstructure analysis

The cis-1,4 bond content of the conjugated diene moiety was measured by Fourier transform infrared spectroscopy (FT-IR).

Specifically, after measuring the FT-IR transmittance spectrum of the carbon disulfide solution of the conjugated diene-based polymer prepared at a concentration of 5 mg/mL using carbon disulfide in the same cell as a blank, the maximum peak near 1130 cm ^-1 of the measurement spectrum value (a, baseline), the minimum peak value near 967 cm ^-1 indicating trans-1,4 bonds (b), the minimum peak value near 911 cm ^-1 indicating vinyl bonds (c), and cis-1 ,4 The content of each was calculated using the minimum peak value (d) near 736 cm ^-1 indicating the binding.

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 a condition of 40° C., and then loaded and flowed through gel permeation chromatography (GPC). At this time, as the column, two PLgel Olexis columns manufactured by Polymer Laboratories and one PLgel mixed-C column were used in combination. In addition, all of the newly replaced columns used a mixed bed type column, and polystyrene was used as a gel permeation chromatography standard material (GPC standard material).

3) Mooney viscosity (RP, Raw polymer)

For each polymer, Mooney viscosity (ML1+4, @100°C) (MU) was measured using a large rotor with a Monsanto MV2000E at 100°C and a rotor speed of 2±0.02 rpm. At this time, the sample used was left at room temperature (23±3° C.) for more than 30 minutes, then 27±3 g was collected, filled in the die cavity, and the Mooney viscosity was measured while applying a torque by operating the platen.

As shown in Table 1, the butadiene polymers of Examples 1 to 3 all contain 20% by weight or more of a polymer chain having a weight average molecular weight of 1,000,000 g/mol or more, and have a molecular weight distribution controlled to a specific range of 2.8 or more and 3.4 or less. It was confirmed that it has a molecular weight distribution.

Experimental Example 2

After preparing rubber compositions and rubber specimens using the polymers of Examples 1 to 3, Comparative Examples 1 to 3, and Reference Examples 1 and 2, Mooney viscosity, tensile stress, 300% modulus, abrasion resistance, and Each of the viscoelastic properties was measured. The results are shown in Table 2 below.

1) Preparation of rubber specimen

The rubber composition contains 70 parts by weight of carbon black, 22.5 parts by weight of process oil, 2 parts by weight of antioxidant (TMDQ), 3 parts by weight of zinc oxide (ZnO) and 2 parts by weight of stearic acid to 100 parts by weight of each polymer. Each rubber composition was prepared by blending parts by weight. Then, 2 parts by weight of sulfur, 2 parts by weight of a vulcanization accelerator (CZ) and 0.5 parts by weight of a vulcanization accelerator (DPG) were added to each rubber composition, and gently mixed at 50 rpm for 1.5 minutes at 50 ° C. Using a roll at 50 ° C. Thus, a vulcanized formulation in the form of a sheet was obtained. The obtained vulcanized mixture was vulcanized at 160° C. for 25 minutes to prepare a rubber specimen.

2) tensile stress and 300% modulus

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

3) Driving resistance

The most important property of Tan δ for low fuel efficiency was measured using Gabo's DMTS 500N from Germany at a frequency of 10 Hz, Prestrain 3%, and Dynamic Strain 3% at -60°C to 60°C (Tan δ). At this time, the Tanδ value at 60° C. represents the driving resistance characteristic (fuel efficiency), and is expressed by indexing the result value of Comparative Example 1 as a standard.

4) Machinability characteristics

1) Mooney viscosity (MV, (ML1+4, @100°C) MU) of the vulcanized mixture obtained during 1) preparation of the rubber composition was measured to compare and analyze the processability characteristics of each polymer, and the results in Table 3 below are Comparative Example 1 It is an index value based on the measurement result of , and the higher the value, the better.

Specifically, using MV-2000 (ALPHA Technologies) at 100°C, using a Rotor Speed of 2±0.02 rpm, and a Large Rotor, each secondary formulation was left at room temperature (23±3°C) for at least 30 minutes and then 27 ±3 g was collected and filled inside the die cavity, and the platen was operated and torque was applied while measuring for 4 minutes.

In Table 2, the Tanδ value (running resistance) and processability characteristics at 60° C. of Examples 1 to 3, Comparative Examples 1 and 4, and Reference Examples 1 and 2 were calculated and indexed by Equation 1 below.

[Equation 1]

Index=(reference value/measurement value)×100

As shown in Table 2, Examples 1 to 3 were excellent in tensile properties and running resistance compared to Comparative Examples 1 to 4 and improved workability properties, and it was confirmed that the tensile properties, running resistance and workability properties were well balanced.

Specifically, Examples 1 to 3 showed excellent tensile properties at the same level as Comparative Examples 1 to 3, improved running resistance and significantly improved workability characteristics, and tensile properties while exhibiting excellent workability characteristics at the same level as Comparative Example 4 Characteristics and driving resistance were significantly improved. That is, Comparative Examples 1 to 4 exhibited disproportionate properties in that tensile properties, running resistance, and workability properties were not balanced and excellent at the same time, and when one property was excellent, the other property was greatly reduced. In this case, Comparative Examples 1 to 3 are polymers prepared in the same manner as in Example 1, except that the catalyst composition including the first alkylating agent and the second alkylating agent outside the mixing ratio of the present invention was used. As confirmed in Table 1, at least one of the polymer chain content and molecular weight distribution having a weight average molecular weight of 1,000,000 g/mol in the polymer did not satisfy the conditions set forth in the present invention.

In addition, in Reference Examples 1 and 2, the processability characteristics were significantly lowered compared to Examples 1 to 3, and in this case, Reference Examples 1 and 2 were prepared in the same manner as in Example 1, except that the aging conditions of the catalyst composition were different. As a polymer that has been used as a polymer, as confirmed in Table 1 above, the polymer chain content and molecular weight distribution having a weight average molecular weight of 1,000,000 g/mol in the polymer do not meet the conditions presented in the present invention, or 1,000,000 g/mol in the polymer It contained a polymer chain content having a weight average molecular weight of 34% by weight, and the molecular weight distribution was 3.31.

Through the above results, the conjugated diene-based polymer according to the present invention contains 20% by weight or more of a polymer chain having a weight average molecular weight of 1,000,000 g/mol or more, and a molecular weight distribution of 2.8 or more and 3.4 or less, particularly, a weight average molecular weight of 1,000,000 g/mol 20 wt% or more and 30 wt% or less of the polymer chain is included, and the molecular weight distribution is 2.8 or more and 3.2 or less. It can be seen that there is an excellent effect in a balanced way.

Claims (12)

It contains a repeating unit derived from a conjugated diene-based monomer, and contains 20% by weight or more of a polymer chain having a weight average molecular weight of 1,000,000 g/mol or more,
A conjugated diene-based polymer having a molecular weight distribution of 2.8 or more and 3.4 or less.
According to claim 1,
A conjugated diene-based polymer comprising 20 wt% or more and 30 wt% or less of a polymer chain having a weight average molecular weight of 1,000,000 g/mol or more.
According to claim 1,
A conjugated diene-based polymer having a weight average molecular weight of 500,000 g/mol to 1,500,000 g/mol, and a number average molecular weight of 100,000 g/mol to 500,000 g/mol.
According to claim 1,
A conjugated diene-based polymer having a cis-1,4 bond content of 95% or more and a vinyl bond content of 5% or less.
In a hydrocarbon solvent, comprising the step of polymerizing a conjugated diene-based monomer in the presence of a catalyst composition comprising a neodymium compound,
The catalyst composition is prepared by mixing a neodymium compound, a first alkylating agent, a second alkylating agent and a halide, and then aging,
The method of claim 1 , wherein the first alkylating agent and the second alkylating agent are mixed in a molar ratio of 5:1 to 3:1.
6. The method of claim 5,
The method for producing a conjugated diene-based polymer, wherein the catalyst composition is used in an amount such that the neodymium compound is 0.1 mmol to 0.5 mmol based on 100 g of the conjugated diene-based monomer.
6. The method of claim 5,
The neodymium compound is a method for producing a conjugated diene-based polymer that is a compound represented by the following formula (1):
[Formula 1]

In Formula 1,
R _a to R _c are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms,
However, R _a to R _c are not all hydrogen at the same time.
6. The method of claim 5,
The first alkylating agent is methylaluminoxane, modified methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, isopropylaluminoxane, butylaluminoxane, isobutylaluminoxane, n-pentylaluminoxane, neopentylaluminoxane, n -Hexyl aluminoxane, n-octylaluminoxane, 2-ethylhexyl aluminoxane, cyclohexyl aluminoxane, 1-methylcyclopentyl aluminoxane, phenyl aluminoxane and 2,6-dimethylphenyl aluminoxane A method for producing a conjugated diene-based polymer of the above aluminoxane.
6. The method of claim 5,
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-octylaluminum 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-octylaluminum hydride A method for producing a conjugated diene-based polymer of at least one selected from the group consisting of hydride.
6. The method of claim 5,
The aging is a method for producing a conjugated diene-based polymer that is performed by allowing the catalyst mixture to stand at a temperature of -20°C to 0°C for 2 weeks or more and 6 weeks or less.
Claim 1 is a conjugated diene-based polymer; And a rubber composition comprising a filler.
12. The method of claim 11,
The rubber composition is that the filler is carbon black.