KR20210035543A - Method for preparing conjugated diene polymer by continuous polymerization - Google Patents

Abstract

The present invention relates to a method for producing a conjugated diene-based polymer while preventing gelation by using a polymerization reactor including two or more reactors.

Description

Manufacturing method of conjugated diene polymer by continuous polymerization {METHOD FOR PREPARING CONJUGATED DIENE POLYMER BY CONTINUOUS POLYMERIZATION}

The present invention relates to a method of preparing a conjugated diene-based polymer while preventing gelation by using a polymerization reactor including two or more reactors.

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

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

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

As another method, in a living polymer obtained by coordination polymerization using a catalyst containing a lanthanum-based rare earth element compound, a method for improving processability and physical properties by modifying the living active end with a specific coupling agent or modifying agent has been developed. .

As an example, in the method disclosed in U.S. Patent No. 5,557,784, in the document, 1,4-cis polybutadiene was prepared in a non-polar solvent using a catalyst consisting of a combination of a neodymium carboxyl group salt compound, an alkyl aluminum compound, and a halogen-containing compound. After stopping the reaction with a reaction stopper and an antioxidant, sulfur chloride is added to introduce a branched structure.

On the other hand, modified conjugated diene-based polymers have been widely used for modification of resins and in various industrial articles, but modified conjugated diene-based polymers cause gel formation and discoloration during long-term storage at high temperatures or under thermal shear stability. When used for modification, the presence of a gel in the polymer and discoloration of the polymer adversely affects the final resin product.

Therefore, the appearance of a conjugated diene polymer composition having excellent thermal stability under high temperature and shear heat stability and very little gel formation and discoloration has been urgently desired. For these problems, phenolic stabilizers, phosphorus type stabilizers, etc. have been used as stabilizers for preventing gelation until now, but a more effective method is to prevent the gelation of the conjugated diene-based polymer and the resulting deterioration of the properties of the polymer. There is still a need for a way to do it.

JP 3175350 B2

An object of the present invention is to control the concentration of the coupling agent within a certain range when performing the coupling process of the active polymer in the last reactor while applying continuous polymerization and coupling using a polymerization reactor including two or more reactors. It is to provide a method for producing a conjugated diene-based polymer capable of efficiently performing a coupling reaction of an active polymer and preventing a gelation phenomenon by using it as a separate inlet separate from a line in which the active polymer is transferred.

In order to solve the above problems, the present invention is a continuous production method carried out in a polymerization reactor including two or more reactors, (S1) in the presence of a catalyst composition containing a lanthanum-based rare earth element-containing compound, a conjugated diene-based monomer Polymerizing to prepare an active polymer; And (S2) reacting the active polymer with a mixed solution containing a tin chloride compound or a sulfur chloride compound, and a hydrocarbon solvent; and, the (S2) step is performed in the last reactor among the reactors included in the polymerization reactor. And, the mixed solution of step (S2) is introduced into the last reactor through a transfer line and a separate line for transferring the active polymer prepared in step (S1) to the last reactor, and chlorination included in the mixed solution The content of the tin compound or the sulfur chloride compound is 0.05 to 0.3% by weight relative to the mixed solution, providing a method of preparing a conjugated diene-based polymer.

By using the production method according to the present invention to control the reactivity and reaction rate of the coupling agent and the active polymer, it is possible to effectively prevent the occurrence of gelation when preparing the conjugated diene-based polymer.

In addition, the manufacturing method of the present invention prevents gelation by controlling the concentration of a coupling agent, such as a tin chloride compound and a sulfur chloride compound, in a certain numerical range so that the coupling process can be most effectively performed when the same amount is used. As a result, there is an effect of improving the economy and efficiency of the entire process by increasing the use efficiency of the coupling agent.

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

The terms or words used in the description and claims of the present invention should not be construed as being limited to a conventional or dictionary meaning, and the inventor appropriately defines the concept of terms in order to describe his own invention in the best way. Based on the principle that it can be done, it should be interpreted as a meaning and concept consistent with the technical idea of the present invention.

Terms

The term "continuous polymerization" used in the present invention may refer to a process of continuously supplying a substance participating in polymerization into a reactor and continuously discharging a product produced by polymerization.

The term "reactant" used in the present invention refers to a material in which polymerization is performed in each reactor during polymerization before polymerization is completed to obtain an active polymer or a conjugated diene-based polymer. For example, a catalyst composition, a conjugated diene-based monomer, and It may include at least one of the resulting polymer type intermediates.

Method for producing conjugated diene-based polymer

The production method of the present invention is a continuous production method carried out in a polymerization reactor including two or more reactors, and a conjugated diene-based monomer is continuously polymerized in one or two or more reactors to prepare an active polymer, and the active polymer is A step of reacting the active polymer and a coupling agent, such as a tin chloride compound or a sulfur chloride compound, is performed in the last reactor connected to the prepared reactor (hereinafter, it is mixed with the'coupling reactor'). At this time, the reactivity of the active polymer and the coupling agent can be controlled by dissolving the coupling agent in a hydrocarbon solvent and adjusting the concentration in a certain range. It has the effect of maximizing the efficiency of the ring agent.

In addition, in the present invention, the mixed solution in which the tin chloride compound or sulfur chloride compound is dissolved in a hydrocarbon solvent is a line connecting the reactor and the coupling reactor in which the active polymer has been prepared, that is, transfer for transferring the active polymer to the last reactor. It is not put into the line, but is directly put into the inlet of the last reactor through a separate line from the transfer line, through which the active polymer is transferred to the last reactor and mixed with the coupling agent to prevent some gelation from proceeding, By directly injecting the coupling agent into the last reactor equipped with a stirrer, the coupling agent and the active polymer are evenly mixed and reacted at a controlled rate, thereby preventing gel formation as much as possible.

Specifically, the method for preparing a conjugated diene-based polymer of the present invention is carried out in a continuous production method in a polymerization reactor including two or more reactors, and (S1) in the presence of a catalyst composition containing a lanthanum-based rare earth element-containing compound, conjugated Polymerizing a diene-based monomer to prepare an active polymer; And (S2) reacting the active polymer with a mixed solution containing a tin chloride compound or a sulfur chloride compound, and a hydrocarbon solvent; and, the (S2) step is performed in the last reactor among the reactors included in the polymerization reactor. And, the mixed solution of step (S2) is introduced into the last reactor through a transfer line and a separate line for transferring the active polymer prepared in step (S1) to the last reactor, and chlorination included in the mixed solution The content of the tin compound or the sulfur chloride compound is characterized in that it is 0.05 to 0.3% by weight compared to the mixed solution.

Step (S1)

The step (S1) is a step of polymerizing a conjugated diene-based monomer in the presence of a catalyst composition containing a lanthanum-based rare earth element-containing compound to prepare an active polymer, wherein the active polymer is a conjugated diene-based polymer and contains an organometallic moiety. Can indicate what to do.

As the conjugated diene-based monomer, it may be used without particular limitation as long as it is usually used for preparing a conjugated diene-based polymer. Specifically, the conjugated diene monomer is 1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3- Butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, or 2,4-hexadiene, and the like, any one of these Or a mixture of two or more may be used. More specifically, the conjugated diene-based monomer may be 1,3-butadiene, but is not limited thereto.

In addition, other monomers copolymerizable with the conjugated diene-based monomer may be further used in consideration of the physical properties of the conjugated diene-based polymer finally prepared during the polymerization reaction, and the other monomers are specifically styrene and p-methyl styrene. , α-methylstyrene, 1-vinylnaphthalene, 3-vinyltoluene, ethylvinylbenzene, divinylbenzene, 4-cyclohexylstyrene, and aromatic vinyl monomers such as 2,4,6-trimethylstyrene, etc., any of these One or a mixture of two or more may be used. The other monomers may be used in an amount of 20% by weight or less based on the total weight of the monomers used in the polymerization reaction.

The step (S1) may be performed in one reactor, or may be continuously performed in two or more reactors. That is, the polymerization reaction of the conjugated diene-based monomer is all completed in the first reactor to complete the preparation of the active polymer, or it may be carried out by continuous polymerization in at least two or more reactors including the first reactor. The number of reactors to be used can be flexibly adjusted according to the reaction conditions and environment.

The continuous polymerization method may refer to a reaction process in which a reactant is continuously supplied to a reactor and the produced reaction product is continuously discharged. In the case of the continuous polymerization method, there may be an effect of excellent productivity and processability, and excellent uniformity of the polymer to be produced.

When the step (S1) is performed alone in one reactor, the polymerization reaction may be carried out until the polymerization conversion rate is finally 95% or more in the reactor, and the step (S1) is a continuous polymerization in two or more reactors. When carried out as, the polymerization product polymerized in the first reactor is sequentially transferred to the polymerization reactor before the coupling reactor, so that the polymerization can be carried out until the polymerization conversion rate becomes 95% or more, and after polymerization in the first reactor, The polymerization conversion rate for each reactor from the second reactor or the second reactor to the polymerization reactor before the coupling reactor may be appropriately adjusted for each reactor in order to control the molecular weight distribution.

In this case, the polymerization conversion rate may be adjusted according to the reaction temperature, the residence time of the reactor, and the like.

The polymerization conversion rate may be determined, for example, by measuring the solid concentration in a polymer solution containing a polymer during polymerization. Specifically, a cylindrical container is mounted at the outlet of each polymerization reactor to secure the polymer solution to obtain a certain amount of polymer solution. After filling the cylindrical container, the cylindrical container is separated from the reactor, the weight (A) of the cylinder filled with the polymer solution is measured, and the polymer solution filled in the cylindrical container is transferred to an aluminum container (e.g., an aluminum dish). ) And measuring the weight (B) of the cylindrical container from which the polymer solution was removed, and then drying the aluminum container containing the polymer solution in an oven at 140° C. for 30 minutes and measuring the weight (C) of the dried polymer. It may be calculated according to Equation 1.

[Equation 1]

In this case, the residence time of the polymer in the first reactor may be 1 minute to 40 minutes, 1 minute to 30 minutes, or 5 minutes to 30 minutes, but is not limited thereto. Within this range, it is easy to control the polymerization conversion rate, and accordingly, it is possible to narrow the molecular weight distribution of the polymer, and accordingly, there may be an effect of improving physical properties.

Here, the polymer may refer to an intermediate in the form of a polymer that is being polymerized in each reactor during step (S1) prior to obtaining the active polymer by completing step (S1), and polymerization is carried out in the reactor. It may mean a polymer having a polymerization conversion rate of less than 95% being carried out.

The polymerization in step (S1) may be elevated temperature polymerization, isothermal polymerization, or constant temperature polymerization (insulation polymerization).

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

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

On the other hand, the polymerization in step (S1) may be preferably carried out at a temperature of -20 to 200 ℃, specifically 20 to 150 ℃, more specifically 10 to 120 ℃, or a temperature of 60 to 90 ℃ It can be carried out for 15 minutes to 3 hours. When the polymerization temperature exceeds 200°C, it is difficult to sufficiently control the polymerization reaction, and the content of cis 1,4 bonds of the resulting conjugated diene-based polymer may be lowered, and when the polymerization temperature is less than -20°C, the polymerization reaction rate And there is a concern that the efficiency may decrease.

In addition, the polymerization reaction may be performed for 5 minutes to 1 hour within the above-described temperature range until a conversion rate of 95% or more of the conjugated diene-based polymer is reached, and specifically, may be performed for 15 minutes to 1 hour.

The step (S1) may be performed in a hydrocarbon solvent. The hydrocarbon solvent may be a non-polar solvent. Specifically, the hydrocarbon solvent is an aliphatic hydrocarbon solvent such as pentane, hexane, isopentane, heptane, octane, isooctane, and the like; Cycloaliphatic hydrocarbon solvents such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, and the like; Alternatively, at least one selected from the group consisting of aromatic hydrocarbon solvents such as benzene, toluene, ethylbenzene, and xylene may be used. As a specific example, the hydrocarbon solvent may be an aliphatic hydrocarbon solvent such as hexane. When the polymerization solvent is used, the concentration of the conjugated diene-based monomer is not particularly limited, but may be 3 to 80% by weight, more specifically 10 to 30% by weight.

The catalyst composition includes a lanthanum-based rare-earth element-containing compound, and in this case, the lanthanum-based rare-earth element-containing compound is 0.01 to 0.5 mmol, specifically 0.03 to 0.4 mmol, more specifically based on 100 g of the conjugated diene monomer. May be contained in 0.04 to 0.25 mmol.

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

In addition, the lanthanum-based rare-earth element-containing compound includes the above-described rare-earth element-containing carboxylate (e.g., neodymium acetate, neodymium acrylate, neodymium methacrylate, neodymium acetate, neodymium gluconate, neodymium citrate, neodymium fumarate, Neodymium sulfate, neodymium maleate, neodymium oxalate, neodymium 2-ethylhexanoate, neodymium neodecanoate, etc.); Organophosphates (e.g., neodymium dibutyl phosphate, neodymium dipentyl phosphate, neodymium dihexyl phosphate, neodymium diheptyl phosphate, neodymium dioctyl phosphate, neodymium bis(1-methylheptyl) phosphate, neodymium bis(2-ethylhexyl) Phosphate, or neodymium didecyl phosphate, etc.); Organic phosphonates (e.g., neodymium butyl phosphonate, neodymium pentyl phosphonate, neodymium hexyl phosphonate, neodymium heptyl phosphonate, neodymium octyl phosphonate, neodymium (1-methyl heptyl) phosphonate, Neodymium (2-ethylhexyl) phosphonate, neodymium disyl phosphonate, neodymium dodecyl phosphonate or neodymium octadecyl phosphonate); Organic phosphinates (e.g., neodymium butylphosphinate, neodymium pentylphosphinate, neodymium hexyl phosphinate, neodymium heptyl phosphinate, neodymium octyl phosphinate, neodymium (1-methylheptyl) phosphinate, or Neodymium (2-ethylhexyl) phosphinate, etc.); Carbamates (eg, neodymium dimethyl carbamate, neodymium diethyl carbamate, neodymium diisopropyl carbamate, neodymium dibutyl carbamate or neodymium dibenzyl carbamate); Dithiocarbamate (eg, neodymium dimethyldithiocarbamate, neodymium diethyldithiocarbamate, neodymium diisopropyl dithiocarbamate or neodymium dibutyldithiocarbamate); Xanthogenates (eg, neodymium methyl xanthogenate, neodymium ethyl xanthogenate, neodymium isopropyl xanthogenate, neodymium butyl xanthogenate, or neodymium benzyl xanthogenate); 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 pseudo halides (neodymium fluoride, neodymium chloride, neodymium bromide, neodymium iodide, neodymium cyanide, neodymium cyanate, neodymium thiocyanate, or neodymium azide, etc.); Oxyhalides (eg, neodymium oxyfluoride, neodymium oxy chloride, or neodymium oxy bromide, etc.); Or an organic lanthanum-based rare earth element-containing compound containing at least one rare earth element-carbon bond (e.g., Cp ₃ Ln, Cp ₂ LnR, Cp ₂ LnCl, CpLnCl ₂ , CpLn (cyclooctatetraene), (C ₅ Me ₅ ) ₂ LnR, LnR ₃ , Ln (allyl) ₃ , or Ln (allyl) ₂ Cl, etc., wherein Ln is a rare earth metal element, R is a hydrocarbyl group), and the like, any one of them or It may contain a mixture of two or more.

Specifically, the lanthanum-based rare earth element-containing compound may include a neodymium compound represented by Formula 1 below.

[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, _{not all of R a} to R _c are hydrogen at the same time.

Considering the excellent solubility in the solvent, the conversion rate to the catalytically active species, and the resulting catalytic activity improvement effect without concern for oligomerization, in Formula 1, R _a is an alkyl group having 4 to 12 carbon atoms, and R _b and R _c is 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.

More specifically, in Formula 1, R _a is an alkyl group having 6 to 8 carbon atoms, and R _b and R _c may each independently be an alkyl group having 2 to 6 carbon atoms.

As such, the neodymium compound represented by Formula 1 includes a carboxylate ligand containing an alkyl group having a variable length of 2 or more carbon atoms as a substituent at the α (alpha) position, thereby inducing a three-dimensional change around the center of the neodymium metal. It is possible to block agglomeration phenomenon, and accordingly, there is an effect of suppressing oligomerization. In addition, such a neodymium-based compound has a high solubility in a solvent and a reduction in the proportion of neodymium located in a central portion where conversion to the catalytically active species is difficult, thereby increasing the conversion rate to the catalytically active species.

Specifically, the neodymium compound is 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 octano 8) ₃ , Nd(2-ethyl-2-propyl octanoate) ₃ , Nd(2-ethyl-2-hexyl octanoate) ₃ , Nd(2,2-diethyl nonanoate) ₃ , Nd( 2,2-dipropyl nonanoate) ₃ , Nd (2,2-dibutyl nonanoate) ₃ , Nd (2,2-dihexyl nonanoate) ₃ , Nd (2-ethyl-2-propyl no It may be one or more selected from the group consisting of nanoate) ₃ and Nd(2-ethyl-2-hexyl nonanoate) _3.

The solubility of the lanthanum-based rare earth element-containing compound may be about 4 g or more per 6 g of the hydrocarbon solvent at room temperature (25° C.). The solubility refers to a degree of clear dissolution without a cloudy phenomenon, and excellent catalytic activity may be exhibited by exhibiting such high solubility.

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

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

(a) alkylating agent

The alkylating agent is an organometallic compound capable of transferring a hydrocarbyl group to another metal and may serve as a cocatalyst. The alkylating agent may be used without particular limitation as long as it is used as an alkylating agent in the production of a diene-based polymer, and is soluble in a polymerization solvent, such as an organic aluminum compound, an organic magnesium compound, or an organic lithium compound, and has a metal-carbon bond. It may be an organometallic compound containing.

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

In addition, the organic aluminum compound may be aluminoxane.

The aluminoxane may be prepared by reacting water with a trihydrocarbyl aluminum-based compound, and specifically, may be a straight-chain aluminoxane represented by the following Formula 2a or a cyclic aluminoxane represented by the following 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 independently an integer of 1 or more, specifically 1 to 100. , More specifically, it may be an integer of 2 to 50.

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

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

[Formula 3]

In Formula 3, R is as defined above, and m and n may be an integer of 2 or more independently of each other. In addition, in Formula 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, 2 carbon atoms such as an ethyl group, an isobutyl group, a hexyl group or an octyl group. It is an alkyl group of to 10, and more specifically, it may be an isobutyl group.

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

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

The catalyst composition may include 1 to 200 moles, specifically 1 to 100 moles, and more specifically 3 to 20 moles of the alkylating agent per 1 mole of the lanthanum-based rare earth element-containing compound. If more than 200 moles of the alkylating agent are included, it is not easy to control the catalytic reaction during the production of the polymer, and there is a concern that an excess of the alkylating agent may cause side reactions.

(b) halide

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

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

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

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

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

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

In addition, as the metal halide, tin tetrachloride, tin tetrabromide, aluminum trichloride, aluminum tribromide, antimony trichloride, antimony pentachloride, antimony tribromide, aluminum trifluoride, gallium trichloride, gallium tribromide, gallium trifluoride, indium trichloride, Indium tribromide, indium trifluoride, titanium tetrachloride, titanium tetrabromide, zinc dichloride, zinc dibromide, zinc difluoride, aluminum triiodide, gallium triiodide, indium triiodide, titanium tetraiodide, zinc iodide, tetraiodide Germanium, tin sayodine, tin iodide, antimony triiodide, or magnesium iodide.

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

According to an embodiment of the present invention, the catalyst composition contains 1 to 20 moles, more specifically 1 to 5 moles, and more specifically 2 to 3 moles of the halide based on 1 mole of the lanthanum-based rare earth element-containing compound. Can include. If it contains more than 20 moles of the halide, it is not easy to remove the catalytic reaction, and there is a fear that an excess halide may cause side reactions.

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

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

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

(c) conjugated diene monomer

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

The "preforming" means a catalyst composition containing a lanthanum-based rare earth element-containing compound, an alkylating agent, and a halide, that is, when the catalyst system includes diisobutylaluminum hydride (DIBAH), etc., various catalysts A small amount of a conjugated diene-based monomer such as 1,3-butadiene is added to reduce the possibility of generating active species in the composition, and it may mean that pre-polymerization is performed in the catalyst composition system with the addition of 1,3-butadiene. . In addition, "premix" may mean a state in which polymerization is not performed in the catalyst composition system and each compound is uniformly mixed.

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

According to an embodiment of the present invention, the catalyst composition is at least one of the above-described lanthanum-based rare earth element-containing compound and alkylating agent, halide and conjugated diene-based monomer in an organic solvent, specifically, a lanthanum-based rare earth element-containing compound, an alkylating agent, and It can be produced by mixing a halide and optionally a conjugated diene-based monomer. In this case, the organic solvent may be a hydrocarbon solvent that is not reactive with the constituents of the catalyst composition. Specifically, the hydrocarbon 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; Mixed solvents 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 solvent such as benzene, toluene, ethylbenzene, xylene, or the like, and any one or a mixture of two or more of them may be used. More specifically, the hydrocarbon solvent may be a linear, branched or cyclic C 5 to C 20 aliphatic hydrocarbon or a mixed solvent of an aliphatic hydrocarbon, and more specifically n-hexane, cyclohexane, or a mixture thereof. I can.

The organic solvent may be appropriately selected depending on the constituent components constituting the catalyst composition, particularly the type of alkylating agent.

Specifically, as the alkylating agent, an aromatic hydrocarbon solvent may be appropriately used because an alkylaluminoxane such as methylaluminoxane (MAO) or ethylaluminoxane is not easily dissolved in an aliphatic hydrocarbon solvent.

Further, when modified methylaluminoxane is used as the alkylating agent, an aliphatic hydrocarbon solvent may be appropriately used. In this case, since it is possible to implement a single solvent system together with an aliphatic hydrocarbon 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 solvent can promote catalytic activity, and the reactivity can be further improved by such catalytic activity.

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

In addition, according to an embodiment of the present invention, antioxidants such as 2,6-di-t-butylparacresol, etc., before starting step (S2) after step (S1), or during step (S1) Further additives can be used. In addition, additives to facilitate solution polymerization in general, specifically, additives such as a chelating agent, a dispersing agent, a pH adjusting agent, a deoxygenating agent, or an oxygen scavenger may be optionally further used.

In addition, in the polymerization reaction, in order not to deactivate the catalyst composition and the polymer, for example, it may be preferable to prevent the incorporation of a compound having a deactivating action such as oxygen, water, and carbon dioxide gas into the polymerization reaction system.

After the step (S1) and before the start of step (S2), a polymerization terminator may be added to stop the polymerization, and the polymerization terminator may be used without limitation as long as it is a polymerization terminator used in the conjugated diene-based polymerization process. , Specifically, a phosphate ester-based polymerization terminator may be used. The polymerization terminator may be added in an amount of 0.01 to 0.4 parts by weight based on 100 parts by weight of a conjugated diene-based monomer.

As a result of the polymerization reaction as described above, an active polymer containing an organometallic moiety activated from the catalyst composition containing the rare earth metal compound, more specifically, a neodymium catalyzed conjugated diene system containing a 1,3-butadiene monomer unit A polymer is produced, and the prepared conjugated diene-based polymer may have pseudo-living properties.

Step (S2)

The step (S2) is a step of reacting the active polymer with a tin chloride compound or a sulfur chloride compound and is performed in a coupling reactor, which may mean the last reactor among the polymerization reactors. Here, the tin chloride compound or the sulfur chloride compound may act as a coupling agent capable of increasing the molecular weight by reacting with a portion of the terminal of the active polymer and coupling with the active polymer.

The tin chloride compound may be tin tetrachloride, monobutyl tin trichloride, isobutyl tin trichloride, methyl tin trichloride, dibutyl tin dichloride, diisobutyl tin dichloride or di(t-butyl tin) dichloride, and the sulfur chloride compound is It may be disulphur dichloride (S ₂ Cl ₂ ), sulfur dichloride (SCl ₂ ) or thionyl chloride (SOCl ₂ ), but is not limited thereto, and any material that can be used as a coupling agent as a tin chloride compound or a sulfur chloride compound is not limited. It can be applied to the present invention without.

The production method of the present invention is a continuous production method carried out in a polymerization reactor including two or more reactors, and according to an embodiment of the present invention, step (S2) is carried out in the last reactor among the polymerization reactors. When the production method of the present invention is carried out in a polymerization reactor including a first and a second reactor, the preparation of the active polymer in step (S1) is all completed in the first reactor, and in this case, the active polymer prepared in step (S1) is It is transferred to the second reactor and step (S2) is performed in the second reactor. In addition, when the production method of the present invention is carried out in a polymerization reactor including three or more reactors, step (S1) may be continuously carried out from the first reactor to the reactor before the last reactor, and the active polymer obtained therefrom is Step (S2) is carried out by being transferred to the last reactor and reacting with the mixed solution.

As described above, the polymerization reactor used in the present invention includes two or more reactors, all of which are connected in series to perform a continuous polymerization and coupling process, and a transfer line between each reactor is provided. The active polymer prepared in step (S1) is transferred to the last reactor as described above to perform step (S2), and a mixed solution containing a tin chloride compound or a sulfur chloride compound, and a hydrocarbon solvent is used in step (S2). In this case, the mixed solution is added to the last reactor, such as at the bottom of the reactor from which the active polymer prepared in step (S1) is discharged, or in the middle of a transfer line for transferring the active polymer to the last reactor. The active polymer is not added in advance before reaching, but is introduced into the last reactor through a separate line from the transfer line, through which the active polymer is transferred and does not react with the tin chloride compound or the sulfur chloride compound before being introduced into the last reactor. May not.

If, after obtaining the active polymer from the reactor before the last reactor, before being transferred to the last reactor, the mixed solution is added in advance, or when the mixed solution is added to the transfer line that transfers the active polymer to the last reactor, the active polymer is activated while flowing through the transfer line. The polymer and the tin chloride compound or the sulfur chloride compound (coupling agent) cause some reaction, which is carried out in a line without a stirrer, so that gelation will occur as they react in a state where they are not evenly mixed. In the present invention, by directly injecting the mixed solution into the last reactor through the transfer line and a separate line, the mixed solution injected into the last reactor and the transferred active polymer are evenly mixed and reacted at an appropriate rate to prevent gelation. Can be manufactured.

According to an embodiment of the present invention, it is preferable that the last reactor in which the step (S2) is performed has a stirrer, through which the active polymer and the mixed solution can be more uniformly mixed as described above, and gelation There is an aspect that can effectively prevent the from occurring.

The mixed solution in step (S2) is a solution obtained by dissolving a tin chloride compound or a sulfur chloride compound in a hydrocarbon solvent, and the content of the tin chloride compound or sulfur chloride compound contained in the mixed solution may be 0.05 to 0.3% by weight compared to the mixed solution. And, specifically, it may be 0.05 to 0.2% by weight, more specifically 0.05 to 0.1% by weight.

By diluting and using a tin chloride compound or a sulfur chloride compound as described above, in the present invention, the gelation phenomenon is prevented from occurring due to a rapid reaction between the active polymer and the tin chloride compound or the sulfur chloride compound, and while preventing the gelation phenomenon, the compound The coupling process due to the reaction was controlled to be efficiently performed. That is, in the present invention, a tin chloride compound or a sulfur chloride compound is used in the same amount, and the optimum concentration is newly derived to cause a coupling reaction while preventing a gelation phenomenon by mixing with a certain amount of a hydrocarbon solvent.

When the content of the tin chloride compound or sulfur chloride compound contained in the mixed solution is less than 0.05% by weight of the mixed solution, the content of the compound that can react with it is too low compared to the active polymer, so that coupling cannot occur efficiently. When the content of the compound or the sulfur chloride compound exceeds 0.3% by weight of the mixed solution, a gelation phenomenon may occur, and thus a problem in that the conjugated diene-based polymer with improved physical properties cannot be prepared may occur.

In addition, the tin chloride compound or the sulfur chloride compound satisfies the above concentration, and at the same time, the absolute content is 3 to 10 equivalents, specifically 4 to 9 equivalents, or 5 to 7 equivalents of 1 equivalent of the lanthanum-based rare earth element-containing compound. I can.

If the tin chloride compound or sulfur chloride compound is less than 3 equivalents of 1 equivalent of the lanthanum-based rare earth element-containing compound, the coupling reaction between polymers does not occur well, making it difficult to improve processability, and more than 10 equivalents compared to 1 equivalent of the lanthanum-based rare-earth element-containing compound In this case, the processability is improved due to excessive coupling, but tensile properties and viscoelastic properties may be extremely poor, and a gelation phenomenon may occur, thereby producing a polymer that is not suitable for industrial use.

The hydrocarbon solvent used for the tin chloride compound or the sulfur chloride compound is applicable to the present invention as long as it is not reactive with the compound and thus stably dissolves the tin chloride compound or the sulfur chloride compound. Specifically, the hydrocarbon solvent may be an aliphatic hydrocarbon solvent such as pentane, hexane, isopentane, heptane, octane, and isooctane; Cycloaliphatic hydrocarbon solvents such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, and the like; Alternatively, at least one selected from the group consisting of aromatic hydrocarbon solvents such as benzene, toluene, ethylbenzene, and xylene may be used. As a specific example, the hydrocarbon solvent may be an aliphatic hydrocarbon solvent such as hexane.

According to an embodiment of the present invention, the gel content of the conjugated diene-based polymer prepared by the above production method may be 0 to 1000 ppm, specifically 0 to 800 ppm, more specifically 0 to 500 ppm, based on the weight. . As described above, the preparation method of the present invention can prevent gelation of the polymerization solution, and the conjugated diene-based polymer prepared through it contains a gel in a low content within the above range.

The gel content is determined by cutting the sample finely with scissors, adding 19 g to 400 ml of toluene, dissolving overnight, filtering through a 150 stainless steel mesh to separate the gel, washing and drying the residual gel remaining on the mesh, and measuring the weight. I did.

In addition, the (S2) step may be to perform the reaction for 1 minute to 5 hours at 0 to 90 ℃.

After the completion of step (S2), the polymerization reaction may be stopped by adding an isopropanol solution of 2,6-di-t-butyl-p-cresol (BHT) to the polymerization reaction system. Thereafter, a conjugated diene-based polymer may be obtained through vacuum drying treatment or desolvation treatment such as steam stripping to lower the partial pressure of the solvent through the supply of water vapor. Further, in the reaction product obtained from the result of the step (S2), an active polymer that is not coupled together with a conjugated diene-based polymer may be included.

Conjugated diene polymer

In addition, the present invention provides a conjugated diene-based polymer prepared by the above production method.

The conjugated diene-based polymer according to an embodiment of the present invention may have a number average molecular weight (Mn) of 1,000 to 2,000,000 g/mol, 10,000 to 1,000,000 g/mol, or 100,000 to 800,000 g/mol, and a weight average molecular weight ( Mw) may be 1,000 to 3,000,000 g/mol, 10,000 to 2,000,000 g/mol, or 100,000 to 2,000,000 g/mol.

In addition, the conjugated diene-based polymer may have a molecular weight distribution (MWD, Mw/Mn) of 1.5 or more and 4.0 or less, and thus tensile properties and viscoelastic properties may be improved when applied to a rubber composition.

In addition, the conjugated diene-based polymer may have a molecular weight distribution of 4.0 or less, a weight average molecular weight of 500,000 g/mol or more and 1,000,000 g/mol or less, and a number average molecular weight of 100,000 g/mol or more and 500,000 g/mol or less. The weight average molecular weight and number average molecular weight are respectively molecular weights in terms of polystyrene analyzed by gel permeation chromatography (GPC).

In addition, when the conjugated diene-based polymer is applied to a rubber composition, considering the effect of improving the balance of mechanical properties, elastic modulus, and processability of the rubber composition, the weight average molecular weight and number average molecular weight are simultaneously described above while having the above molecular weight distribution range. It may be one that satisfies a range of conditions.

The conjugated diene-based polymer according to an embodiment of the present invention may have a Mooney viscosity at 100° C., 30 or more, 40 to 150, or 40 to 140, and has excellent processability and productivity within this range. There is.

Rubber composition, molded article

Furthermore, 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 may include a conjugated diene-based polymer in an amount of 0.1 to 100% by weight, specifically 10 to 100% by weight, and more specifically 20 to 90% by weight. If the content of the conjugated diene-based polymer is less than 0.1% by weight, as a result, the effect of improving abrasion resistance and crack resistance of a molded article manufactured using the rubber composition, such as a tire, may be insignificant.

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

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

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

The carbon black-based filler is not particularly limited, but may have a nitrogen adsorption specific surface area (measured in accordance with N2SA, JIS K 6217-2:2001) of 20 m 2 /g to 250 m 2 /g. In addition, the carbon black may have a dibutylphthalate oil absorption (DBP) of 80 cc/100g to 200 cc/100g. When the nitrogen adsorption specific surface area of the carbon black ^{exceeds 250 m 2} /g, the processability of the rubber composition may be deteriorated, and when it is ^{less than 20 m 2} /g, the reinforcing performance by the carbon black may be insignificant. In addition, when the DBP oil absorption amount of the carbon black exceeds 200 cc/100 g, the processability of the rubber composition may be deteriorated, and when it is less than 80 cc/100 g, the reinforcing performance by the carbon black may be insignificant.

In addition, the silica is not particularly limited, but may be, for example, wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, or colloidal silica. Specifically, the silica may be a wet room silica having the most remarkable effect of improving fracture properties and having both wet grip properties. In addition, the silica has a nitrogen surface area per gram (N2SA) of 120 m2/g to 180 m2/g, and a specific surface area of CTAB (cetyl trimethyl ammonium bromide) adsorption from 100 m2/g to 200 m2/g Can be When the nitrogen adsorption specific surface area of the silica is less than 120 m 2 /g, the reinforcing performance by silica may be deteriorated, and when it exceeds 180 m 2 /g, the workability of the rubber composition may be deteriorated. In addition, when the CTAB adsorption specific surface area of the silica is less than 100 m 2 /g, the reinforcing performance by silica as a filler may be deteriorated, and when it exceeds 200 m 2 /g, the workability of the rubber composition may be reduced.

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

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

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

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

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

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

In addition, the process oil acts as a softening agent in the rubber composition, and may be a paraffinic, naphthenic, or aromatic compound. More specifically, when considering tensile strength and abrasion resistance, the aromatic process oil price, hysteresis loss And in consideration of low-temperature characteristics, naphthenic or paraffinic process oil may be used. The process oil may be included in an amount of 100 parts by weight or less based on 100 parts by weight of the rubber component, and when included in the amount, it is possible to prevent a decrease in tensile strength and low heat generation (low fuel economy) of the vulcanized rubber.

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

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

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

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

Example

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

Example 1

A conjugated diene-based polymer was prepared using a polymerization reactor in which three 10L stainless reactors equipped with a stirrer and a jacket were connected in series.

_{Nd (2-ethylhexanoate) 3} through the top of the first reactor was added to 0.130 mmol/1,3-butadiene 100 g, and a 0.02 M solution was added at 13.6 g/hr, and n-hexane was added at 2500 g/hr. Then, 60% 1,3-butadiene was added at 500 g/hr. After staying in the first reactor for 30 minutes, the polymer was transferred to the second reactor. After staying in the second reactor for 20 minutes, it was transferred to the third reactor. Before entering the reactor, tin tetrachloride (SnCl ₄ ) as a tin chloride compound was mixed with n-hexane and diluted to 0.05% by weight to prepare a mixed solution, and the total amount of tin tetrachloride was Nd (2-ethylhexanoate) ₃ 1 equivalent. While putting the polymer to the top of the third reactor (a separate inlet from the line transferred from the second reactor) so as to have 5 equivalents of comparison, the polymer was retained in the third reactor for 30 minutes to prepare a butadiene polymer.

Examples 2 to 4

A butadiene polymer was prepared in the same manner as in Example 1, except that the tin tetrachloride concentration in the mixed solution was changed as shown in Table 1 below.

Comparative Examples 1 to 6

A butadiene polymer was prepared in the same manner as in Example 1, except that the concentration of tin tetrachloride in the mixed solution and the input position of the mixed solution were changed as shown in Table 1 below.

Example Comparative example One 2 3 4 One 2 3 4 5 6 Tin tetrachloride concentration
(% by weight based on the mixed solution) 0.05 0.1 0.2 0.3 0.05 0.1 0.2 0.3 0.03 1.5 Mixed solution input location Top of reactor 3 Top of reactor 3 Top of reactor 3 Top of reactor 3 The bottom of the second reactor The bottom of the second reactor The bottom of the second reactor The bottom of the second reactor Top of reactor 3 Top of reactor 3 Total amount of tin tetrachloride
(Equivalent based on 1 equivalent of Nd) 5 5 5 5 5 5 5 5 5 5

Experimental Example 1

Each of the physical properties of the butadiene polymers prepared in Examples and Comparative Examples was measured in the following manner, and the results are shown in Table 2.

(1) Mooney viscosity (RP, Raw polymer)

A butadiene polymer was obtained from each of the first to third reactors, and Mooney viscosity (ML1+4, @100℃) at 100℃ using a large rotor with Monsanto's MV2000E under the condition of 2±0.02rpm of a rotor speed at 100℃ for each polymer. ) (MU) was measured. At this time, the sample used was left at room temperature (23±3℃) for at least 30 minutes, then 27±3g was collected and filled in the die cavity, and the Mooney viscosity was measured while applying a torque by operating a platen.

(2) Gel content (ppm)

After cutting the finally obtained butadiene polymer latex finely with scissors, 19 g was added to 400 ml of toluene, dissolved overnight, filtered through a 150 stainless steel mesh to separate the gel, and the residual gel remaining on the mesh was washed and dried to determine its weight. It was measured.

Example Comparative example One 2 3 4 One 2 3 4 5 6 Mooney viscosity of the first reactor 38 35 35 37 36 37 33 34 37 35 Mooney viscosity of the second reactor 48 46 47 45 45 46 44 42 45 44 3rd reactor Mooney viscosity 90 87 89 91 109 120 119 122 50 132 Gel content (ppm) 261 350 414 475 1769 2317 2616 2561 10 7735

The polymer obtained in the first reactor and the second reactor undergoes polymerization of butadiene to generate the polymer, and the Mooney viscosity increases, and the polymer obtained in the third reactor uses tin tetrachloride to proceed with the second coupling reaction. Compared to the results of the reactor, the Mooney viscosity is greatly improved.

As shown in Table 2, Examples 1 to 4 in which a mixed solution containing a tin tetrachloride concentration of 0.05 to 0.3% by weight was prepared according to the production method of the present invention and added to the top of the third reactor to prepare a polymer. In the case of, it was confirmed that the Mooney viscosity of the butadiene polymer obtained in the third reactor was high, and the coupling reaction proceeded sufficiently, and at the same time, the gel content was low.

On the other hand, in the case of Comparative Examples 1 to 4 in which the input position of the mixed solution was changed to the bottom of the second reactor, gelation occurred while being transferred from the second reactor to the third reactor, so that the gel content increased very significantly.

In addition, in the case of Comparative Example 5, the concentration of tin tetrachloride was too low to sufficiently proceed with the coupling, and the Mooney viscosity of the polymers obtained in the second and third reactors, respectively, appeared almost similar, and in the case of Comparative Example 6, tin tetrachloride It was confirmed that the concentration was too high and the gel content appeared high.

Experimental Example 2

Raw rubber was prepared by mixing 37.5 phr of TDAE oil based on 100 parts by weight of the butadiene polymer with the butadiene polymers of Examples and Comparative Examples, and using this, a rubber composition and a rubber specimen were prepared according to the following method.

Specifically, the rubber specimen is kneaded through the first stage kneading and the second stage kneading. In the first stage kneading, 70 parts by weight of carbon black, 3 parts by weight of zinc oxide (ZnO) and 2 parts by weight of stearic acid based on 100 parts by weight of butadiene polymer in the raw rubber using a Banbari mixer attached with a temperature control device. Combined the wealth. At this time, the temperature of the kneader was controlled, and a first compound (CMB, compound master batch) was obtained at a discharge temperature of 145 to 155°C.

In the second stage kneading, after cooling the first blend (CMB) to room temperature, add the first blend (CMB), 1.5 parts by weight of sulfur, and 0.9 parts by weight of vulcanization accelerator (TBBS) to the kneader, and mix at a temperature of 100°C or less. To obtain a second blend. Finally, a rubber specimen (FMB, final master batch) was prepared through a curing process at 100°C for 20 minutes.

(1) Mooney viscosity (MV)

The Mooney viscosity of the raw rubber, the first compound (CMB) and the rubber specimen (FMB) was measured in the same manner as in Experimental Example 1.

(2) tensile properties

After vulcanizing each rubber composition at 150°C for t90 minutes, according to ASTM D412, the tensile strength of the vulcanized material (tensile strength, kg f/cm ² ), modulus at 300% elongation (M-300%, 300% modulus, kg· f/cm ² ) and the elongation (%) of the vulcanized material at break were measured.

(3) viscoelastic properties

For viscoelastic properties, tanδ was measured by changing the strain at a frequency of 10 Hz, Prestrain 3%, Dynamic Strain 3%, and each measurement temperature (-60℃~60℃) using DMTS 500N of Gabo, Germany. The higher the low temperature 0℃ tanδ, the better the wet road surface resistance, and the lower the high temperature 60℃ tanδ, the less hysteresis loss and the better low running resistance (fuel economy).

(4) Curing characteristics

The vulcanization characteristics were measured at 150° C. for 50 minutes using a moving die rheometer (MDF), and the MH (maximum torque) value and the time required until 90% vulcanization (t90, min) were measured.

Example Comparative example One 2 3 4 One 2 3 4 5 6 Mooney viscosity Raw rubber 39 39 39 40 48 51 51 53 23 58 CMB 82 82 86 97 72 74 74 77 53 93 FMB 77 75 76 82 61 64 63 65 50 63 Tensile properties The tensile strength 147 160 156 165 149 148 148 145 149 152 M-300% 68 68 66 68 68 68 67 68 65 68 Elongation 512 553 548 562 490 485 492 480 554 542 Viscoelastic properties tanδ @0℃ 0.248 0.245 0.251 0.238 0.280 0.277 0.276 0.280 0.259 0.238 tanδ @60℃ 0.204 0.199 0.204 0.194 0.219 0.221 0.222 0.225 0.215 0.218 Vulcanization characteristics MH 23.6 22.3 21.8 24.3 20.2 20.5 20.9 20.5 18.4 20.5 t90 13.5 12.9 13.1 12.9 13.1 13.0 13.0 13.1 13.4 13.1

As shown in Table 3, in the case of the rubber composition containing the butadiene polymer of Examples prepared according to the present invention, the rubber specimen exhibited improved tensile properties compared to the comparative example, and the Tan δ value at 60°C was reduced, as a result of viscoelasticity. It could be seen that this was improved.

Claims (11)

A continuous production method carried out in a polymerization reactor including two or more reactors,
(S1) preparing an active polymer by polymerizing a conjugated diene-based monomer in the presence of a catalyst composition containing a lanthanum-based rare earth element-containing compound; And
(S2) reacting the active polymer with a mixed solution containing a tin chloride compound or a sulfur chloride compound, and a hydrocarbon solvent; Including,
The (S2) step is performed in the last reactor among the reactors included in the polymerization reactor,
The mixed solution of the (S2) step is introduced into the last reactor through a transfer line and a separate line for transferring the active polymer prepared in the (S1) step to the last reactor, and the tin chloride compound contained in the mixed solution Or the content of the sulfur chloride compound is 0.05 to 0.3% by weight compared to the mixed solution, a method for producing a conjugated diene-based polymer.
The method according to claim 1,
The tin chloride compound is tin tetrachloride, monobutyl tin trichloride, isobutyl tin trichloride, methyl tin trichloride, dibutyl tin dichloride, diisobutyl tin dichloride or dichloride (t-butyl tin), a method for preparing a conjugated diene-based polymer .
The method according to claim 1,
The sulfur chloride compound is disulfur dichloride (S ₂ Cl ₂ ), sulfur dichloride (SCl ₂ ), or thionyl chloride (SOCl ₂ ), a method for producing a conjugated diene-based polymer.
The method according to claim 1,
The tin chloride compound or sulfur chloride compound is used in an amount of 3 to 10 equivalents relative to 1 equivalent of a lanthanum-based rare earth element-containing compound, a method for producing a conjugated diene-based polymer.
The method according to claim 1,
The last reactor in which the step (S2) is performed is equipped with a stirrer, a method for producing a conjugated diene-based polymer.
The method according to claim 1,
The gel content of the conjugated diene-based polymer prepared by the above production method is 0 to 2,000 ppm by weight, a method for producing a conjugated diene-based polymer.
The method according to claim 1,
The (S1) step is to be continuously carried out in two or more reactors, the method of producing a conjugated diene-based polymer.
The method according to claim 1,
The hydrocarbon solvent is one selected from the group consisting of pentane, hexane, isopentane, heptane, octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, benzene, toluene, ethylbenzene, and xylene Above, a method for producing a conjugated diene-based polymer.
The method according to claim 1,
The polymerization of the step (S1) is performed at a temperature of -20 to 200°C.
The method according to claim 1,
The final polymerization conversion rate of the step (S1) is 95% or more, a method for producing a conjugated diene-based polymer.
The method according to claim 1,
The lanthanum-based rare earth element-containing compound comprises a neodymium compound represented by the following formula (1), a method for preparing a conjugated diene-based polymer:
[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, _{not all of R a} to R _c are hydrogen at the same time.