KR20170075671A - Preparation method of conjugated diene polymer and conjugated diene polymer produced by the same - Google Patents

Abstract

The present invention relates to a process for producing a conjugated diene polymer capable of producing a conjugated diene polymer having a shortened production time and a controlled structure ratio, a conjugated diene polymer prepared therefrom, a rubber composition comprising the conjugated diene polymer .

Description

The present invention relates to a conjugated diene polymer and a conjugated diene polymer prepared by the method.

The present invention relates to a process for producing a conjugated diene polymer capable of producing a conjugated diene polymer having a shortened production time and a controlled structure ratio, a conjugated diene polymer prepared therefrom, a rubber composition comprising the conjugated diene polymer .

In recent years, there has been a demand for a conjugated diene polymer having a low running resistance, excellent abrasion resistance and tensile properties as a rubber material for a tire, and also having adjustment stability represented by wet skid resistance.

The conjugated diene polymer is generally prepared by preparing a catalyst composition and then polymerizing the conjugated diene monomer in the presence of the catalyst composition. At this time, the catalyst composition contains an alkylating agent for catalytic activation, which contributes to the formation of the catalytically active species and affects the structure of the conjugated diene-based polymer. In addition, the alkylating agent also performs a role of controlling the Mooney viscosity in the polymerization reaction. Therefore, it takes a long time to prepare the conjugated diene polymer after the additional injection for controlling the target Mooney viscosity, and the process efficiency is lowered as the manufacturing time becomes longer.

Therefore, there is a need for a method capable of easily producing a conjugated diene-based polymer having excellent process efficiency and desired physical properties.

JP 2002-030107 A

SUMMARY OF THE INVENTION The present invention has been made in order to solve the problems of the prior art, and it is an object of the present invention to provide a method for producing a conjugated diene polymer.

Another object of the present invention is to provide a conjugated diene polymer produced from the above-mentioned production process.

It is still another object of the present invention to provide a rubber composition comprising the conjugated diene-based polymer.

In addition, another object of the present invention is to provide a rubber molded article made from the rubber composition.

In order to solve the above problems, the present invention relates to a method for preparing a catalyst mixture, comprising the step of polymerizing a conjugated diene monomer in the presence of a catalyst composition, wherein the catalyst composition comprises a) a first mixture of a rare earth metal compound and a first alkylating agent, ; And b) adding a second alkylating agent and a halogen compound to the first catalyst mixture and secondarily mixing the first catalyst and the second alkylating agent, wherein the first alkylating agent and the second alkylating agent have a weight ratio of 1: 1 to 19: 1 And the secondary mixing is performed under a relatively low temperature condition as compared with the primary mixing. The present invention also provides a method for producing a conjugated diene-based polymer.

The present invention also provides the conjugated diene polymer produced from the above-mentioned production process.

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

Further, the present invention provides a rubber molded article produced from the rubber composition.

The production process according to the present invention can reduce the time required for the process by preparing an alkylating agent in a divided manner during the production of the catalyst composition, and can provide a conjugated diene polymer in which the amount of cis, trans, Can be manufactured.

The rubber composition according to the present invention can be excellent in tensile strength and running resistance by including the conjugated diene polymer, and thus the rubber molded article produced from the rubber composition can have excellent fuel consumption characteristics and abrasion resistance.

Therefore, the process for producing the conjugated diene polymer according to the present invention and the conjugated diene polymer prepared therefrom can be easily applied to an industry in which the conjugated diene polymer is required, such as the tire industry.

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 in an ordinary or dictionary sense and the inventor can properly define the concept of the term to describe its invention in the best possible way It should be construed as meaning and concept consistent with the technical idea of the present invention.

The present invention provides a process for producing a conjugated diene polymer capable of producing a conjugated diene polymer having controlled cis, trans and vinyl bond ratios.

The process according to one embodiment of the present invention comprises polymerizing a conjugated diene monomer in the presence of a catalyst composition, wherein the catalyst composition comprises a) a first mixture of a rare earth metal compound and a first alkylating agent to form a catalyst mixture Producing; And b) adding a second alkylating agent and a halogen compound to the first catalyst mixture and secondarily mixing the first catalyst and the second alkylating agent, wherein the first alkylating agent and the second alkylating agent have a weight ratio of 1: 1 to 19: 1 And the secondary mixing is performed under a relatively low temperature condition as compared with the primary mixing.

The method for producing the conjugated diene-based polymer according to an embodiment of the present invention may be one produced by polymerizing a conjugated diene-based monomer in the presence of a catalyst composition comprising a rare earth metal compound, an alkylating agent and a halogen compound, A metal compound, an alkylating agent, and a halogen compound.

Specifically, the catalyst composition according to one embodiment of the present invention may be prepared by the following steps:

Step a: The primary mixture of the rare earth metal compound and the first alkylating agent to prepare a catalyst mixture; And

Step b: The second alkylating agent and the halogen compound are added to the catalyst mixture and the second mixture is mixed.

In the present invention, 'first' and 'second' in the first alkylating agent and the second alkylating agent may be used to distinguish the time of injection, or may be different from each other at the time of injection. For example, the first alkylating agent and the second alkylating agent may be the same substance or different injection timing, or they may be different from each other and have different dosing points.

The step (a) may be carried out by first mixing the rare earth metal compound and the first alkylating agent to prepare a catalyst mixture. For example, the rare earth metal compound and the first alkylating agent may be sequentially introduced into the reactor and the first mixture may be mixed.

The rare earth metal compound may be a compound containing any one or more of the rare earth metals of atomic number 57 to 71 such as lanthanum, neodymium, cerium, gadolinium or praseodymium, and specifically may be a compound selected from the group consisting of neodymium, lanthanum and gadolinium Or a compound containing at least one rare earth metal.

The rare earth metal compound may be at least one selected from the group consisting of the rare earth metal containing carboxylate, organic phosphate, phosphate, organic phosphonate, phosphonate, organic phosphinate, carbamate, dithiocarbamate, xanthogenate, an organic rare earth metal compound including at least one rare earth metal-carbon bond, at least one rare earth metal compound, at least one rare earth metal compound, at least one rare earth metal compound, at least one rare earth metal compound, at least one compound selected from the group consisting of β-diketonates, alkoxides, allyl oxides, halides,

Specifically, the rare earth metal compound may be a neodymium compound represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1,

R _a to R _c are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.

Specifically, in Formula 1, R _a is an alkyl group having 6 to 12 carbon atoms, and R _b and R _c are independently an alkyl group having 2 to 8 carbon atoms.

More specifically, the rare earth metal compound is Nd (neodecanoate) _3, Nd (2- ethylhexanoate) _3, Nd (2,2- diethyl decanoate) _3, Nd (2,2- di propyl decanoate) _3, Nd (2,2- di-butyl decanoate) _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-propyl- 2-butyl decanoate) _3, Nd (2-propyl-2-hexyl decanoate) _3, Nd (2-propyl-2-isopropyl decanoate) _3, Nd (2-butyl-2-hexyl de decanoate) _3, Nd (2- cyclohexyl-2-octyl decanoate) _3, Nd (2-t- butyl decanoate) _3, Nd (2,2- diethyl octanoate) _3, Nd (2 , 2-dipropyloctanoate) ₃ , Nd (2,2-dibutyloctanoate) ₃ , Nd (2,2-dihexyloctanoate) ₃ , Nd Eight) _3, Nd (2- ethyl-2-hexyl-octanoic Eight) _3, Nd (2,2- diethyl-no nano-benzoate) _3, Nd (2,2- dipropyl no nano-benzoate) _3, Nd (2,2- dibutyl no nano-benzoate) _3, Nd (2, 2-dihexyl no nano-benzoate) _3, may be at least one selected from Nd (2-ethyl-2-propyl-no nano-benzoate) ₃ and Nd (2-ethyl-2-hexyl-no nano-benzoate) the group consisting of ₃ .

 As described above, the neodymium compound of Formula 1 includes a carboxylate ligand containing an alkyl group having various lengths of at least 2 carbon atoms as a substituent at the alpha -position, thereby inducing a three-dimensional change around the neodymium center metal, And as a result, oligomerization can be suppressed. In addition, the neodymium compound has a high solubility in a polymerization solvent, and may have a low neodymium ratio in a central portion, which is difficult to convert to a catalytically active species, and thus may have a high conversion rate to a catalytically active species.

In addition, the solubility of the rare earth metal compound may be about 4 g or more per 6 g of non-polar solvent at room temperature (25 캜). In the present invention, the solubility of the neodymium compound may be meant to be such that it dissolves clearly without cloudy phenomenon.

The first alkylating agent may be the same as or different from the second alkylating agent described later. The alkylating agent used in the preparation of the catalyst composition according to an embodiment of the present invention may be one which acts as a cocatalyst as an organometallic compound capable of transferring a hydrocarbyl group to another metal. Here, the alkylating agent may be any alkylating agent including a first alkylating agent and a second alkylating agent.

The first alkylating agent is not particularly limited, but may be an organometallic compound soluble in a non-polar solvent and containing a metal-carbon bond, such as an organoaluminum compound, an organomagnesium compound, or an organolithium compound.

Specifically, the organoaluminum compound is selected from the group consisting of trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri- Alkyl aluminum such as 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 hydrogen Dihydrocarbylaluminum hydride; Hydrocarbylaluminum such as ethylaluminum dihydride, n-propylaluminum dihydride, isopropylaluminum dihydride, n-butylaluminum dihydride, isobutylaluminum dihydride or n-octylaluminum dihydride, Dihydride and the like.

Examples of the organomagnesium compound include alkylmagnesium compounds such as diethylmagnesium, di-n-propylmagnesium, diisopropylmagnesium, dibutylmagnesium, dihexylmagnesium, diphenylmagnesium and dibenzylmagnesium .

Examples of the organic lithium compound include alkyl lithium compounds such as n-butyl lithium and the like.

The first alkylating agent may be at least one selected from the group consisting of the organoaluminum compounds, the organomagnesium compounds, and the organolithium compounds. Specifically, diisobutylaluminum Hydride (DIBAH) may be used.

In addition, the first alkylating agent may be used in an amount having a weight ratio of 1: 1 to 19: 1 with a second alkylating agent used in secondary mixing, which will be described later. Specifically, the first alkylating agent and the second alkylating agent may be used in an amount having a weight ratio of 3: 2 to 9: 1.

On the other hand, the total content of the alkylating agent used in the preparation of the catalyst composition may be 5 to 200 moles relative to 1 mole of the rare earth metal compound, specifically 5 to 100 moles. Here, the total amount of the alkylating agent represents the total amount of the first alkylating agent and the second alkylating agent.

Meanwhile, in the production method according to an embodiment of the present invention, one or more selected from the group consisting of a conjugated dienic monomer and a reaction solvent may be further used in the primary mixing of the step a.

When the conjugated diene-based monomer is further used in the first mixing step, the mixture may be mixed with the components (the rare earth metal compound and the first alkylating agent) constituting the catalyst composition to form a premixing type catalyst or a preforming type catalyst Thereby improving not only the activity of the catalyst composition but also the stability of the conjugated diene polymer prepared using the catalyst composition.

The conjugated diene-based monomer may be the same as the conjugated diene-based monomer used in the later-described conjugated diene-based polymer producing step, and examples thereof include 1,3-butadiene, isoprene, 1,3- 1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl 1,3-pentadiene, and 2,4-hexadiene.

The conjugated diene-based monomer may be used in an amount within a total amount of the conjugated diene-based monomer used in Step 2 described later. Specifically, the conjugated diene-based monomer may be used in an amount of 1 to 100 molar equivalents relative to 1 mol of the rare earth metal compound Specifically 5 to 50 molar equivalents, and more particularly 10 to 40 molar equivalents.

The reaction solvent may be a nonpolar solvent which is not reactive with the components constituting the catalyst composition, and examples thereof include n-pentane, n-hexane, n-heptane, n-octane, Linear, branched or cyclic aliphatic hydrocarbons having 5 to 20 carbon atoms such as hexane, isooctane, 2,2-dimethylbutane, cyclopentane, 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; Or aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene and the like. Specifically, it may be n-hexane, cyclohexane, or a mixture thereof.

The step (b) is a step for preparing the catalyst composition. The step (b) may be carried out by adding a second alkylating agent and a halogen compound to the catalyst mixture prepared by the first mixing and then by secondary mixing.

The second alkylating agent may be the same as or different from the first alkylating agent described above, and specifically may be the same material.

For example, the halogen compound may be an aluminum halide compound or an aluminum halide compound in which aluminum is substituted with boron, silicon, tin or titanium , Or an organic halogen compound such as a t-alkylhalogen compound (alkyl having 4 to 20 carbon atoms).

Specifically, the inorganic halogen compound may be selected from the group consisting of dimethyl aluminum chloride, diethyl aluminum chloride (DEAC), dimethyl aluminum bromide, diethyl aluminum bromide, dimethyl aluminum fluoride, diethyl aluminum fluoride, methyl aluminum 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 dibromide, dibutyl tin dichloride, dibutyl tin dichloride, dibutyl tin dichloride, dibutyl tin dichloride, dibutyl tin dichloride, dibutyl tin dibromide, 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, bromo- 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.

The halogen compound may be any one or a mixture of two or more of the above-mentioned inorganic halogen compounds and organic halogen compounds. The halogen compound may be used in an amount of 1 to 20 mol, 5 mole, more specifically 2 mole to 3 mole.

Further, in the preparation of the catalyst composition according to an embodiment of the present invention, the secondary mixing in step b) may be performed under a relatively low temperature condition as compared with the primary mixing in step a).

Specifically, the primary mixing may be performed at a temperature of 50 DEG C or lower, more specifically, a temperature of 0 DEG C or higher and lower than 50 DEG C, or more specifically, a temperature condition of 0 DEG C to 30 DEG C.

Further, the secondary mixing may be carried out under a temperature condition of 30 DEG C or less, specifically, a temperature of -10 DEG C or more and 30 DEG C or less, more specifically, a temperature of -10 DEG C to 25 DEG C.

Here, the primary mixing and the secondary mixing may be performed under the temperature conditions described above, and the secondary mixing may be controlled so as to be a relatively low temperature condition relative to the primary mixing.

When the primary mixing and the secondary mixing are carried out under the above conditions, catalytically active species can be easily formed.

The production method according to an embodiment of the present invention is characterized in that, in the production of the catalyst composition, the rare-earth metal compound and the first alkylating agent are mixed and the second alkylating agent and the second alkylating agent are mixed, The addition ratio of the first alkylating agent and the second alkylating agent can be adjusted as desired and the formation of the catalytically active species can be controlled. Accordingly, the ratio of the cis bond, trans bond and vinyl bond structure in the conjugated diene polymer produced using the catalyst composition can be controlled.

Meanwhile, the conjugated diene-based polymer according to an embodiment of the present invention may be carried out by polymerization reaction of the conjugated diene-based monomer in the presence of the catalyst composition.

Specifically, the polymerization reaction may be performed by polymerizing the conjugated diene monomer in an organic solvent in the presence of the catalyst composition.

The conjugated diene-based monomer may be a 1,3-butadiene-based monomer, a 1,3-butadiene-based monomer, or a butadiene-based monomer copolymerizable therewith. The 1,3-butadiene monomer may be 1,3-butadiene or a derivative thereof such as 1,3-butadiene, 2,3-dimethyl-1,3-butadiene or 2-ethyl-1,3-butadiene. Other butadiene-based monomers copolymerizable with 1,3-butadiene may be 2-methyl-1,3-pentadiene, 1,3-pentadiene, 3-methyl- 1,3-pentadiene, 1,3-hexadiene or 2,4-hexadiene, and one or two or more of these compounds may be used.

The organic solvent used for preparing the conjugated diene polymer may include aliphatic hydrocarbon solvents such as pentane, hexane, isopentane, heptane, octane, isooctane and the like; Cyclic aliphatic hydrocarbon solvents such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane and the like; Or an aromatic hydrocarbon solvent such as benzene, toluene, ethylbenzene, xylene and the like, and one or a mixture of two or more of them may be used. The amount of the organic solvent to be used is not particularly limited. For example, the organic solvent may be used in an amount such that the concentration of the conjugated diene monomer in the organic solvent is 3% by weight to 80% by weight.

In addition, the polymerization reaction may be carried out by radical polymerization, for example, bulk polymerization, solution polymerization, suspension polymerization or emulsion polymerization. Specifically, the polymerization may be carried out in a solution, and the polymerization may be carried out by any of a batch process and a continuous process.

On the other hand, a reaction terminator such as polyoxyethylene glycol phosphate during the polymerization reaction; Or an antioxidant such as 2,6-di-t-butyl paracresol may be further used. In addition, an additive such as a chelating agent, a dispersing agent, a pH adjusting agent, a deoxidizing agent or an oxygen scavenger may be further used to facilitate the solution polymerization.

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

The present invention also provides the conjugated diene polymer produced from the above-mentioned production process.

The conjugated diene polymer according to an embodiment of the present invention is characterized in that the cis bond, the trans bond, and the vinyl bond ratio are 61.3: 1: 0.25 to 21.1: 1: 0.11. If the conjugated diene polymer exhibits the above-mentioned cis-bond, trans-bond and vinyl bond ratio, tensile strength and running resistance can be improved.

In addition, the conjugated diene polymer may have a narrow molecular weight distribution (Mw / Mn) of 2.0 to 3.5. When the molecular weight distribution of the conjugated diene polymer is more than 3.5 or less than 2.0, the tensile properties and the viscoelasticity of the rubber composition containing the conjugated diene polymer may deteriorate. Specifically, considering the remarkable effect of improving the tensile properties and the viscoelasticity by controlling the molecular weight distribution, the molecular weight distribution of the conjugated diene polymer may be 2.2 to 3.2.

Here, the molecular weight distribution can be calculated from the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn). The number average molecular weight (Mn) is a common average of the individual polymer molecular weights obtained by measuring the molecular weights of n polymer molecules and calculating the sum of the molecular weights and dividing by n, and the weight average molecular weight (Mw) Molecular weight distribution of the polymer composition. All molecular weight averages can be expressed in grams per mole (g / mol), and the weight average molecular weight and number average molecular weight can be polystyrene reduced molecular weight analyzed by gel permeation chromatography (GPC).

In addition, the conjugated diene polymer according to the embodiment of the present invention satisfies the above-mentioned molecular weight distribution condition and has a weight average molecular weight (Mw) of 5 x 10 ⁵ g / mol to 1.2 x 10 ⁶ g / mol, ^{May be} 6 x 10 < ⁵ > g / mol to 1.0 x 10 < ⁶ > g / mol. The conjugated diene polymer according to an embodiment of the present invention may have a number average molecular weight (Mn) of 1.5 × 10 ⁵ g / mol to 3.5 × 10 ⁵ g / mol, specifically 2.0 × 10 ⁵ g / mol 3.2 x 10 < ⁵ > g / mol. The tensile properties of the rubber composition containing the conjugated diene polymer are excellent in the range of the weight average molecular weight (Mw) and the number average molecular weight (Mn), and the processability of the conjugated diene polymer is excellent, Is improved, the kneading of the kneaded mixture is facilitated, and the physical properties of the rubber composition are sufficiently improved. Accordingly, the conjugated diene polymer according to an embodiment of the present invention satisfies both the weight average molecular weight (Mw) and the number average molecular weight condition together with the molecular weight distribution described above, and thereby the tensile property, the viscoelasticity and the workability Balance can be improved well.

In addition, the conjugated diene polymer according to an embodiment of the present invention may have a Mooney viscosity (MV) at 100 ° C of 20 to 60, specifically 30 to 50. It is possible to exhibit better processability when having the Mooney viscosity in the above-mentioned range.

Here, the Mooney viscosity can be measured by using a Mooney viscometer, for example, Monsanto MV2000E 100, Rotor Speed 2 0.02 rpm, Large Rotor. At this time, the used sample is allowed to stand at room temperature (23 ° C ± 3 ° C) for 30 minutes or more, and 27 ± 3 g can be collected, filled in the die cavity, and measured by operating a platen.

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

The rubber composition according to an embodiment of the present invention may contain 10% by weight or more, specifically 10% by weight to 100% by weight, of the conjugated diene polymer.

The rubber composition may further comprise 1 to 900 parts by weight of a rubber component with respect to 100 parts by weight of the conjugated diene-based polymer.

The rubber component may be a natural rubber or a synthetic rubber. Specifically, the rubber component may be a 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 may be any one or a mixture of two or more thereof .

The rubber composition may further comprise 10 parts by weight to 120 parts by weight of a filler based on 100 parts by weight of the conjugated diene polymer.

The filler may be a silica filler, a carbon black filler, or a combination thereof.

When the filler is a silica-based filler, a silane coupling agent may be used together with the filler to improve the reinforcing property and the low heat build-up.

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 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 and may be contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the conjugated diene polymer. 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, the rubber composition according to one embodiment of the present invention may contain, in addition to the above-mentioned components, various additives conventionally 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 conjugated diene polymer.

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 conjugated diene polymer. 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 conjugated diene polymer.

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, and the vulcanization step after the molding process, Excellent rubber compositions can be obtained.

Further, the present invention provides a rubber molded article produced from the rubber composition.

 The rubber molded article according to one embodiment of the present invention includes various rubber products for industrial use such as anti-vibration rubber, belt conveyor, hose, or the like, or may be used for a tire tread, under tread, sidewall, carcass- A bead filler, a pancake wheel, or a tire such as a bead coating rubber.

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples. However, the following examples and experimental examples are provided for illustrating the present invention, and the scope of the present invention is not limited thereto.

Production Example 1

1.65 g of a neodymium versatate (NdV) hexane solution, 1.05 g of diisobutylaluminum hydride (DIBAH) and 1.8 g of 1,3-butadiene were first mixed at a temperature of 30 ° C to prepare a catalyst mixture 0.29 g of diethylaluminum chloride and 0.26 g of diisobutylaluminum hydride were further added thereto, followed by secondary mixing at a temperature of 15 ° C to prepare a catalyst composition.

Production Example 2

Except that diisobutyl aluminum hydride (DIBAH) was used in an amount of 0.78 g in the first mixing step and 0.53 g in the second mixing step, to prepare a catalyst composition.

Production Example 3

Except that diisobutylaluminum hydride (DIBAH) was used in an amount of 1.18 g in the first mixing step and 0.13 g in the second mixing step, to prepare a catalyst composition.

Comparative Preparation Example 1

1.31 g of neodymium versatate (NdV) hexane solution, 1.31 g of diisobutylaluminum hydride (DIBAH), 1.8 g of 1,3-butadiene and 0.29 g of diethyl aluminum chloride were mixed at a temperature of 30 캜 To prepare a catalyst composition.

Comparative Production Example 2

Except that diisobutylaluminum hydride (DIBAH) was used in an amount of 0.53 g in the primary mixing and 0.78 g in the secondary mixing.

Comparative Production Example 3

The catalyst composition was prepared in the same manner as in Preparation Example 1, except that the reaction was carried out at a temperature of 60 ° C in the primary mixing and at 40 ° C in the secondary mixing.

Example 1

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 elevated to 70 ° C., and the catalyst composition prepared in Preparation Example 1 was added and polymerized to prepare a 1,3-butadiene polymer. The conversion of 1,3-butadiene to polybutadiene was about 100%.

Example 2

A 1,3-butadiene polymer was prepared in the same manner as in Example 1 except that the catalyst composition prepared in Preparation Example 2 was used in place of the catalyst composition prepared in Preparation Example 1.

Example 3

A 1,3-butadiene polymer was prepared in the same manner as in Example 1 except that the catalyst composition prepared in Preparation Example 3 was used instead of the catalyst composition prepared in Preparation Example 1.

Comparative Example 1

Butadiene polymer was prepared in the same manner as in Example 1 except that the catalyst composition prepared in Comparative Preparation Example 1 was used instead of the catalyst composition prepared in Preparation Example 1. [

Comparative Example 2

Butadiene polymer was prepared in the same manner as in Example 1 except that the catalyst composition prepared in Comparative Preparation Example 2 was used instead of the catalyst composition prepared in Preparation Example 1. [

Comparative Example 3

Butadiene polymer was prepared in the same manner as in Example 1 except that the catalyst composition prepared in Comparative Preparation Example 3 was used instead of the catalyst composition prepared in Preparation Example 1. [

Experimental Example

The amounts of cis-bonds, trans-bonds, and vinyl bonds in each of the 1,3-butadiene polymers prepared in Examples 1 to 3 and Comparative Examples 1 to 3 were compared and analyzed.

The above bound amounts were analyzed by NMR. The results are shown in Table 1 below.

division Cis bond: trans bond: vinyl
(wt%) Time required for polymerization Example 1 48.4: 1: 0.2 50 Example 2 46.4: 1: 0.24 50 Example 3 40.8: 1: 0.22 50 Comparative Example 1 29.0: 1: 0.27 80 Comparative Example 2 20.1: 1: 0.17 100 Comparative Example 3 32.0: 1: 0.33 120

As shown in Table 1, the cis, trans, and vinyl bond ratios in the conjugated diene polymers of Examples 1 to 3 prepared through the production method according to one embodiment of the present invention were comparable to those of Comparative Examples 1 to 3 Of the conjugated diene polymer in Comparative Examples 1 to 3 was significantly different from the conjugated diene polymer in Comparative Examples 1 to 3 in the preparation time of the conjugated diene polymer of Examples 1 to 3 Respectively.

Specifically, Comparative Example 1 using the catalyst composition of Comparative Preparation Example 1 prepared by collectively introducing an alkylating agent in the preparation of the catalyst composition, Comparative Example 1 using an alkylating agent in a proportion of a higher proportion of the second alkylating agent than the first alkylating agent Comparative Example 2 using the prepared catalyst composition of Comparative Preparation Example 2 and comparison using the catalyst composition of Comparative Preparation Example 3 prepared by performing the primary mixing and secondary mixing at a temperature outside the temperature range suggested by the present invention The conjugated diene polymers of Examples 1 to 3, compared to the conjugated diene polymers of Example 3, showed a significant increase in the cis-bond ratio in the polymer.

This is because it is possible to control the structure in the polymer by preparing the conjugated diene polymer according to the production method of the present invention and thus to control the ratio of the structure as desired to achieve the desired effect more easily Results.

Claims (19)

Polymerizing the conjugated diene-based monomer in the presence of the catalyst composition,
The catalyst composition
a) preparing a catalyst mixture by primary mixing the rare earth metal compound and the first alkylating agent; And
b) adding a second alkylating agent and a halogen compound to the first catalyst mixture and secondary mixing,
The first alkylating agent and the second alkylating agent are used in an amount having a weight ratio of 1: 1 to 19: 1,
Wherein the secondary mixing is performed under a relatively low temperature condition as compared with the primary mixing.
The method according to claim 1,
Wherein the first alkylating agent and the second alkylating agent are used in an amount having a weight ratio of 3: 2 to 9: 1.
The method according to claim 1,
Wherein the primary mixing of said step a) is carried out at a temperature of 0 ° C to 50 ° C.
The method according to claim 1,
Wherein the primary mixing of step (a) is carried out at a temperature of 0 ° C to 30 ° C.
The method according to claim 1,
Wherein the secondary mixing of step b) is carried out at a temperature of -10 ° C to 25 ° C.
The method according to claim 1,
Wherein the rare earth metal compound is a compound containing at least one rare earth metal selected from the group consisting of neodymium, lanthanum and gadolinium.
The method according to claim 1,
The rare earth metal compound may be at least one selected from the group consisting of a carboxylate, an organic phosphate, a phosphate, an organic phosphonate, a phosphonate, an organic phosphinate, a carbamate, a dithiocarbamate, a xanthogenate, Wherein the conjugated diene-based polymer is at least one member selected from the group consisting of a diketonate, an alkoxide, an allyl oxide, a halide, a pseudohalide, an oxyhalide, and an organic rare earth metal compound containing at least one rare earth metal- Gt;
The method according to claim 1,
Wherein the rare earth metal compound is a compound represented by the following general formula (1).
[Chemical Formula 1]

In Formula 1,
R _a to R _c are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
The method of claim 8,
In the above formula (1), R _a is an alkyl group having 6 to 12 carbon atoms,
And R _b and R _c are each independently an alkyl group having 2 to 8 carbon atoms.
The method according to claim 1,
The rare earth metal compound is Nd (2- ethylhexanoate) _3, Nd (2,2- diethyl decanoate) _3, Nd (2,2- dipropyl decanoate) _3, Nd (2,2- dibutyl decanoate) _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 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-t- butyl decanoate) _3, Nd (2,2- diethyl octanoate) _3, Nd (2,2- dipropyl octanoate) _3, Nd ( 2,2-dibutyl-octanoate) _3, Nd (2,2-hexyl 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 no nano-benzoate) _3, Nd (2,2- dibutyl no nano-benzoate) _3, Nd (2,2- dihexyl no nano-benzoate) _3, Nd (2- ethyl-2 Propynonanoate) ₃ and Nd (2-ethyl-2-hexylnonanoate) ₃ .
The method according to claim 1,
Wherein the first alkylating agent and the second alkylating agent each independently include at least one selected from the group consisting of an organoaluminum compound, an organomagnesium compound, and an organolithium compound.
The method according to claim 1,
The halogen compound may be an aluminum halogen compound; An inorganic halogen compound substituted with boron, silicon, tin or titanium; And at least one selected from the group consisting of organohalogen compounds.
The method according to claim 1,
Wherein the total content of the first alkylating agent and the second alkylating agent is 5 to 200 moles relative to 1 mole of the rare earth metal compound.
The method according to claim 1,
Wherein the halogen compound is used in an amount of 1 to 20 moles per mole of the rare earth metal compound.
The method according to claim 1,
Wherein at least one selected from the group consisting of a conjugated diene monomer and a reaction solvent is further used during the primary mixing of the step a).
16. The method of claim 15,
The conjugated diene monomer may be at least one monomer selected from the group consisting of 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, Methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, and 2,4-hexadiene. Based on the weight of the conjugated diene-based polymer.
16. The method of claim 15,
Wherein the reaction solvent comprises at least one member selected from the group consisting of linear, branched or cyclic aliphatic hydrocarbons having 5 to 20 carbon atoms.
A conjugated diene-based polymer produced from the process of claim 1.
19. The method of claim 18,
Wherein the conjugated diene polymer has a cis bond, a trans bond and a vinyl bond ratio of 61.3: 1: 0.25 to 21.1: 1: 0.1.