Method for preparing modified conjugated diene polymer

Abstract

The present invention relates to a method for manufacturing a modified conjugated diene-based polymer having excellent formulation properties and improved processability.

Description

Technology Field

[0001] The present invention relates to a method for manufacturing a modified conjugated diene-based polymer having excellent formulation properties and improved processability. Background Technology

[0003] Recently, in response to the demand for lower fuel consumption in automobiles, conjugated diene polymers are required as rubber materials for tires that possess low driving resistance, excellent wear resistance and tensile properties, and handling stability represented by wet skid resistance. To reduce the driving resistance of tires, methods to minimize hysteresis loss in vulcanized rubber are employed, and rebound elasticity, Tanδ, and Goodrich exothermic reaction at 50 to 80°C are used as evaluation indicators for such vulcanized rubber. In other words, rubber materials with high rebound elasticity at the above temperatures or low Tanδ or Goodrich exothermic reaction are preferred.

[0004] Natural rubber, polyisoprene rubber, or polybutadiene rubber are known as rubber materials with low hysteresis loss, but they have the problem of low wet skid resistance. Accordingly, recently, conjugated diene (co)polymers such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) are manufactured by emulsion polymerization or solution polymerization and are used as rubber for tires.

[0005] When the above-mentioned BR or SBR is used as a rubber material for tires, fillers such as silica or carbon black are typically blended together to obtain the required physical properties of the tire. However, there is a problem in that the affinity between the above-mentioned BR or SBR and the filler is poor, which actually leads to a decrease in physical properties such as wear resistance, crack resistance, and processability.

[0006] Accordingly, as a method to improve the dispersibility of SBR and fillers such as silica or carbon black, a method has been proposed to modify the polymerization active site of a conjugated diene polymer obtained by anionic polymerization using organic lithium to a functional group capable of interacting with the filler. For example, methods have been proposed to modify the polymerization active end of the conjugated diene polymer to a tin-based compound, to introduce an amino group, or to modify it to an alkoxysilane derivative.

[0007] In addition, as a method to improve the dispersibility of BR and fillers such as silica or carbon black, a method has been developed to modify the living active end of a living polymer obtained by coordination polymerization using a catalyst composition containing a lanthanide rare earth element compound by using a specific coupling agent or modifying agent. Meanwhile, in the case of a polymer with modified ends, the affinity with the filler is improved, which has the advantage of improving compounding properties, such as tensile and viscoelastic properties; however, on the other hand, the compounding processability is significantly reduced, resulting in poor processability.

[0008] In addition, when manufacturing by solution polymerization, in order to recover the polymer contained in the polymer solution produced by solution polymerization, the polymer solution must be washed with water and catalyst residues decomposed and removed, and then devolvulated to remove volatile components such as solvent, unreacted monomer, or a small amount of residual water from the polymer solution. For such devolvulation treatment, desolvation by stripping, such as steam stripping, is mainly used.

[0009] The above stripping method involves contacting a stripping solution (e.g., stripping steam) with a polymer solution to desolvate it. However, the system tends to be in an equilibrium state, making efficient desolvation difficult. Accordingly, a method has been proposed to contact the polymer solution with the stripping solution using a gas-liquid mixer, but there is a problem in that smooth desolvation is not achieved. Prior art literature

[0011] (Patent Document 0001) JP 3175350 B2 The problem to be solved

[0012] The objective of the present invention is to produce a modified conjugated diene polymer exhibiting excellent processability, tensile properties, and viscoelastic properties by efficiently removing the solvent from a modified polymer produced by solution polymerization and drying it at a high temperature. means of solving the problem

[0014] To solve the above problem, the present invention provides a method for preparing a modified conjugated diene polymer, comprising: (S1) a step of preparing a polymer containing an active polymer by polymerizing a conjugated diene monomer in the presence of a catalyst composition containing a neodymium compound in a hydrocarbon solvent; (S2) a step of preparing a modified polymer by reacting the polymer with a modifying agent represented by the following chemical formula 1; and (S3) a step of desolvating the modified polymer and drying it at a temperature of 130°C or higher.

[0015] [Chemical Formula 1]

[0016]

[0017] In the above chemical formula 1,

[0018] R 1 to R 3 Each independently comprises a halogen group, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and -R 6 COOR 7 A trivalent hydrocarbon group substituted with one or more substituents selected from the group consisting of; or an unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, and

[0019] However, R 1 to R 3 All of these are simultaneously trivalent hydrocarbon groups; or not divalent hydrocarbon groups,

[0020] R 4is a single bond; a linear or branched alkylene group having 1 to 20 carbon atoms; or a cycloalkylene group having 3 to 20 carbon atoms, and

[0021] R 5 is a silyl group substituted or unsubstituted with a linear or branched alkyl group having 1 to 20 carbon atoms; a halogen; a cyano group; or -COR 8 And,

[0022] R 6 is a single bond; a linear or branched alkylene group having 1 to 20 carbon atoms; or a cycloalkylene group having 3 to 20 carbon atoms, and

[0023] R 7 is a linear or branched alkyl group having 1 to 20 carbon atoms; or a cycloalkyl group having 3 to 20 carbon atoms, and

[0024] R 8 It is one type selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a heterocycloalkyl group having 2 to 10 carbon atoms, a heteroamine group having 2 to 10 carbon atoms, and a disilylamino group having 3 to 10 carbon atoms. Effects of the invention

[0026] The modified conjugated diene polymer produced by the manufacturing method of the present invention has excellent affinity with fillers using a modifying agent represented by Chemical Formula 1, which improves the physical properties of the formulation, and also has excellent processability as it is produced with a high degree of branching through drying at a high temperature. Specific details for implementing the invention

[0028] Hereinafter, the present invention will be described in more detail to aid in understanding the invention.

[0029] Terms and words used in the description and claims of the present invention should not be interpreted as being limited to their ordinary or dictionary meanings, and should be interpreted in a meaning and concept consistent with the technical spirit of the present invention, based on the principle that the inventor can appropriately define the concept of the terms to best describe his invention.

[0031] The method for preparing a modified conjugated diene-based polymer according to the present invention comprises: (S1) a step of preparing a polymer containing an active polymer by polymerizing a conjugated diene-based monomer in the presence of a catalyst composition containing a neodymium compound in a hydrocarbon solvent; (S2) a step of preparing a modified polymer by reacting the polymer with a modifying agent represented by the following chemical formula 1; and (S3) a step of desolvating the modified polymer and drying it at a temperature of 130°C or higher.

[0032] [Chemical Formula 1]

[0033]

[0034] In the above chemical formula 1,

[0035] R 1 to R 3 Each independently comprises a halogen group, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and -R 6 COOR 7 A trivalent hydrocarbon group substituted with one or more substituents selected from the group consisting of; or an unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, and

[0036] However, R 1 to R 3 All of these are simultaneously trivalent hydrocarbon groups; or not divalent hydrocarbon groups,

[0037] R 4 is a single bond; a linear or branched alkylene group having 1 to 20 carbon atoms; or a cycloalkylene group having 3 to 20 carbon atoms, and

[0038] R 5 is a silyl group substituted or unsubstituted with a linear or branched alkyl group having 1 to 20 carbon atoms; a halogen; a cyano group; or -COR 8 And,

[0039] R 6 is a single bond; a linear or branched alkylene group having 1 to 20 carbon atoms; or a cycloalkylene group having 3 to 20 carbon atoms, and

[0040] R 7 is a linear or branched alkyl group having 1 to 20 carbon atoms; or a cycloalkyl group having 3 to 20 carbon atoms, and

[0041] R 8 It is one type selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a heterocycloalkyl group having 2 to 10 carbon atoms, a heteroamine group having 2 to 10 carbon atoms, and a disilylamino group having 3 to 10 carbon atoms.

[0043] Step (S1)

[0044] A step of preparing a polymer containing an active polymer by polymerizing a conjugated diene monomer in the presence of a catalyst composition containing a neodymium compound in a hydrocarbon solvent, wherein the active polymer may be a polymer of the conjugated diene monomer containing an organometallic group. Additionally, since the polymerization is performed as a solution polymerization in a hydrocarbon solvent, the polymer may contain not only the active polymer but also the hydrocarbon solvent, unreacted monomer, etc.

[0045] The above organometallic region may be an activated organometallic region at the end of the polymer (an activated organometallic region at the end of the molecular chain), an activated organometallic region in the main chain, or an activated organometallic region in the side chain (side chain), and among these, when an activated organometallic region of the copolymer is obtained by anionic polymerization or coordination anionic polymerization, the organometallic region may represent an activated organometallic region at the end.

[0046] The above polymerization can be carried out by a batch method, a continuous method, or a semi-continuous method. As a specific example, the polymerization for preparing the active polymer can be carried out by introducing and contacting a conjugated diene monomer with the catalyst composition in a hydrocarbon solvent.

[0047] In addition, the polymerization may be a temperature-increasing polymerization, an isothermal polymerization, or a constant temperature polymerization (adiabatic polymerization).

[0048] Here, constant temperature polymerization refers to a polymerization method comprising the step of polymerizing using the reaction heat itself without arbitrarily applying heat after the introduction of the catalyst composition, the temperature-increasing polymerization refers to a polymerization method in which the temperature is increased by arbitrarily applying heat after the introduction of the catalyst composition, and the isothermal polymerization refers to a polymerization method in which the temperature of the reactants is maintained constant by increasing or removing heat after the introduction of the catalyst composition.

[0050] The polymerization may be performed in a temperature range of -20 to 200°C, specifically at 50 to 150°C, more specifically at 10 to 120°C, or at 60 to 90°C for 15 minutes to 3 hours. If the temperature exceeds 200°C during the polymerization, it is difficult to sufficiently control the polymerization reaction, and there is a risk that the cis-1,4 bond content of the resulting conjugated diene polymer will be lowered, and if the temperature is below -20°C, there is a risk that the polymerization reaction rate and efficiency will decrease.

[0051] In addition, the polymerization can be carried out for 5 minutes to 1 hour within the temperature range mentioned above until a 100% conversion rate of the conjugated diene polymer is reached, specifically for 15 minutes to 1 hour.

[0053] The above conjugated diene monomer may be used without special restrictions as long as it is commonly used in the manufacture of conjugated diene polymers. Specifically, the above conjugated diene monomer may be 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 any one or more of these may be used. More specifically, the above conjugated diene monomer may be 1,3-butadiene.

[0054] In addition, other monomers copolymerizable with the conjugated diene monomer may be used in consideration of the physical properties of the active polymer finally produced during the polymerization reaction. Specifically, these may be aromatic vinyl monomers such as styrene, p-methyl styrene, α-methylstyrene, 1-vinylnaphthalene, 3-vinyltoluene, ethylvinylbenzene, divinylbenzene, 4-cyclohexylstyrene, 2,4,6-trimethylstyrene, etc., and any one or more of these may be used. The other monomers may be used in an amount of 20% by weight or less relative to the total weight of the monomers used in the polymerization reaction.

[0055] At this time, the conjugated diene monomer used for the manufacture of a conjugated diene polymer is not used by dissolving the entire amount in the solvent, but rather a portion of the total amount is dissolved in the polymerization solvent and polymerized, and then, depending on the polymerization conversion rate, it may be divided and added one or more times, specifically two or more times, and more specifically two to four times.

[0057] The above hydrocarbon solvent may be a non-polar solvent. Specifically, the hydrocarbon solvent may be one or more selected from the group consisting of aliphatic hydrocarbon solvents such as pentane, hexane, isopentane, heptane, octane, isooctane, etc.; cycloaliphatic hydrocarbon solvents such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, etc.; or aromatic hydrocarbon solvents such as benzene, toluene, ethylbenzene, xylene, etc. As a specific example, the hydrocarbon solvent may be an aliphatic hydrocarbon solvent such as hexane, etc. When using the above polymerization solvent, the concentration of the monomer is not particularly limited, but may be 3% by weight to 80% by weight, more specifically 10% by weight to 30% by weight.

[0059] The above catalyst composition may be used in an amount such that the neodymium compound is 0.03 to 0.15 mmol based on a total of 100 g of conjugated diene monomers, and specifically, the neodymium compound may be used in an amount such that the neodymium compound is 0.05 to 0.15 mmol based on a total of 100 g of conjugated diene monomers.

[0060] The above neodymium compound is activated by the first alkylating agent and the second alkylating agent described below, and then forms a catalytic active species for the polymerization of conjugated diene monomers.

[0061] The above neodymium compound is its carboxylate (e.g., neodymium acetate, neodymium acrylate, neodymium methacrylate, neodymium gluconate, neodymium citrate, neodymium fumarate, neodymium sulfate, neodymium maleate, neodymium oxalate, neodymium 2-ethylhexanoate, neodymium neodecanoate, etc.); organic phosphate (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, etc.); organic phosphinates (e.g., neodymium butyl phosphinate, neodymium pentyl phosphinate, neodymium hexyl phosphinate, neodymium heptyl phosphinate, neodymium octyl phosphinate, neodymium (1-methyl heptyl) phosphinate or neodymium (2-ethylhexyl) phosphinate, etc.); Carbamate (e.g., neodymium dimethyl carbamate, neodymium diethyl carbamate, neodymium diisopropyl carbamate, neodymium dibutyl carbamate or neodymium dibenzyl carbamate, etc.); dithiocarbamate (e.g., neodymium dimethyl dithiocarbamate, neodymium diethyl dithiocarbamate, neodymium diisopropyl dithiocarbamate or neodymium dibutyl dithiocarbamate, etc.); xantogenate (e.g., neodymium methyl xantogenate, neodymium ethyl xantogenate, neodymium isopropyl xantogenate, neodymium butyl xantogenate, or neodymium benzyl xantogenate, etc.);β-diketonates (e.g., neodymium acetylacetonate, neodymium trifluoroacetylacetonate, neodymium hexafluoroacetylacetonate, or neodymium benzoylacetonate, etc.); alkoxides or allyl oxides (e.g., 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 (e.g., neodymium oxyfluoride, neodymium oxychloride, or neodymium oxybromide, etc.); Or, organic neodymium-containing compounds comprising one or more neodymium element-carbon bonds (e.g., Cp3Nd, Cp2NdR, Cp2NdCl, CpNdCl2, CpNd(cyclooctatetraene), (C5Me5)2NdR, NdR3, Nd(allyl)3, or Nd(allyl)2Cl, etc., where R is a hydrocarbyl group), etc., may be included, and any one or more of these may be included.;

[0063] Specifically, the neodymium compound may be a compound represented by the following chemical formula 3.

[0064] [Chemical Formula 3]

[0065]

[0066] In the above chemical formula 3,

[0067] R a to R c are independently hydrogen or an alkyl group having 1 to 12 carbon atoms, provided that R a to R c Not all of them are hydrogen at the same time.

[0068] Furthermore, considering the excellent solubility in solvents without concerns regarding oligomerization, the conversion rate to catalytically active species, and the resulting excellent effect of improving catalytic activity, the neodymium compound is, more specifically, R in Chemical Formula 3. a ga 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 It could be something that is not hydrogen at the same time.

[0069] As a more specific example, in the above chemical formula 3, R a is an alkyl group having 6 to 8 carbon atoms, and R b and R c Each may independently be hydrogen or an alkyl group having 2 to 6 carbon atoms, wherein R b and R c It may not be hydrogen at the same time.

[0070] More specifically, in the above chemical formula 3, the R a is an alkyl group having 6 to 8 carbon atoms, and R b and R c Each can independently be an alkyl group having 2 to 6 carbon atoms.

[0071] As such, the neodymium compound represented by Chemical Formula 3 contains a carboxylate ligand comprising alkyl groups of various lengths with two or more carbon atoms as substituents at the α (alpha) position, thereby inducing a steric change around the neodymium central metal to block aggregation between compounds and, accordingly, has the effect of inhibiting oligomerization. In addition, such a neodymium compound has high solubility in solvents and a high conversion rate to catalytic active species because the proportion of neodymium located in the central part, which is difficult to convert to catalytic active species, is reduced.

[0072] More specifically, the neodymium compound is Nd(2-ethylhexanoate)3, Nd(2,2-dimethyl decanoate)3, Nd(2,2-diethyl decanoate)3, Nd(2,2-dipropyl decanoate)3, Nd(2,2-dibutyl decanoate)3, Nd(2,2-dihexyl decanoate)3, Nd(2,2-dioctyl decanoate)3, Nd(2-ethyl-2-propyl decanoate)3, Nd(2-ethyl-2-butyl decanoate)3, Nd(2-ethyl-2-hexyl decanoate)3, Nd(2-propyl-2-butyl decanoate)3, Nd(2-propyl-2-hexyl decanoate)3, Nd(2-propyl-2-isopropyl decanoate)3, Nd(2-butyl-2-hexyl decanoate)3, Nd(2-hexyl-2-octyl decanoate)3, Nd(2,2-diethyl octanoate)3, Nd(2,2-dipropyl octanoate)3, Nd(2,2-dibutyl octanoate)3, Nd(2,2-dihexyl octanoate)3, Nd(2-ethyl-2-propyl octanoate)3, Nd(2-ethyl-2-hexyl octanoate)3, Nd(2,2-diethyl nonanoate)3, Nd(2,2-dipropyl nonanoate)3, Nd(2,2-dibutyl nonanoate)3, Nd(2,2-dihexyl It may be one or more selected from the group consisting of nonanoate)3, Nd(2-ethyl-2-propyl nonanoate)3 and Nd(2-ethyl-2-hexyl nonanoate)3.

[0073] In addition, the solubility of the above neodymium compound may be about 4g or more per 6g of non-polar solvent at room temperature (23±5℃). The solubility of the above neodymium compound refers to the degree of clear dissolution without turbidity, and excellent catalytic activity can be exhibited by showing such high solubility.

[0074] In addition, the neodymium compound may also be used in the form of a reactant with a Lewis base. This reactant has the effect of improving the solubility of the neodymium compound in a solvent and allowing it to be stored in a stable state for a long period of time through the Lewis base. The Lewis base may be used, for example, in a ratio of 30 moles or less, or 1 to 10 moles, per mole of neodymium element. The Lewis base may be, for example, acetylacetone, tetrahydrofuran, pyridine, N,N-dimethylformamide, thiophene, diphenyl ether, triethylamine, an organophosphorus compound, or a monovalent or divalent alcohol.

[0076] The catalyst composition may further include at least one of a first alkylating agent, a second alkylating agent, a halide, and a conjugated diene monomer together with the neodymium compound.

[0077] (a) First alkylating agent

[0078] The first alkylating agent may be aluminoxan, and the aluminoxan may be prepared by reacting water with a trihydrocarbyl aluminum-based compound. Specifically, the aluminoxan may be a straight-chain aluminoxan of the following chemical formula 4a or a cyclic aluminoxan of the chemical formula 4b.

[0079] [Chemical Formula 4a]

[0080]

[0081] [Chemical Formula 4b]

[0082]

[0083] In the above chemical formulas 4a and 4b, 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 may be integers of 1 or more independently, specifically 1 to 100, more specifically 2 to 50.

[0084] More specifically, the aluminoxan may be methylaluminoxan (MAO), modified methylaluminoxan (MMAO), ethylaluminoxan, n-propylaluminoxan, isopropylaluminoxan, butylaluminoxan, isobutylaluminoxan, n-pentylaluminoxan, neopentylaluminoxan, n-hexylaluminoxan, n-octylaluminoxan, 2-ethylhexylaluminoxan, cyclohexylaluminoxan, 1-methylcyclopentylaluminoxan, phenylaluminoxan, or 2,6-dimethylphenylaluminoxan, and any one or more of these may be used.

[0085] In addition, the modified methylaluminoxan may be a compound in which the methyl group of methylaluminoxan is substituted with a modifying group (R), specifically a hydrocarbon group having 2 to 20 carbon atoms, and specifically, may be a compound represented by the following chemical formula 5.

[0086] [Chemical Formula 5]

[0087]

[0088] In the above chemical formula 5, R is as previously defined, and m and n can be two or more integers independently of each other. Also, in the above chemical formula 5, Me represents a methyl group.

[0089] Specifically, in the above chemical formula 5, R may be 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, 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; more specifically, it may be an alkyl group having 2 to 10 carbon atoms, such as an ethyl group, an isobutyl group, a hexyl group, or an octyl group, and even more specifically, it may be an isobutyl group.

[0090] More specifically, the modified methylaluminoxane may be one in which about 50 mol% to 90 mol% of the methyl groups of methylaluminoxane are substituted with the hydrocarbon groups mentioned above. When the content of the substituted hydrocarbon groups in the modified methylaluminoxane is within the above range, alkylation can be promoted to increase catalytic activity.

[0091] Such modified methylaluminoxan can be manufactured according to conventional methods, specifically using trimethylaluminum and alkylaluminum other than trimethylaluminum. In this case, the alkylaluminum may be triisobutylaluminum, triethylaluminum, trihexylaluminum, or trioctylaluminum, and any one or a mixture of two or more of these may be used.

[0092] In addition, according to one embodiment of the present invention, the molecular weight distribution of the modified conjugated diene-based polymer being manufactured can be formed narrowly, and in terms of improving the physical properties of the polymer accordingly, the first alkylating agent may be methylaluminoxane or modified methylaluminoxane.

[0093] (b) Secondary alkylating agent

[0094] According to one embodiment of the present invention, the second alkylating agent may be hydrocarbylaluminum dihydride, and specifically, the second alkylating agent may be 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, phenylisobutylaluminum hydride, phenyl-n-octylaluminum hydride, p-tolylethylaluminum hydride, Dihydrocarbylaluminum hydride such as p-tolyl-n-propylaluminum hydride, p-tolyl-isopropylaluminum hydride, p-tolyl-n-butylaluminum hydride, p-tolyl-n-octylaluminum hydride, benzylethylaluminum hydride, benzyl-n-propylaluminum hydride, benzyl-isopropylaluminum hydride, benzyl-n-butylaluminum hydride, benzyl-isobutylaluminum hydride, or benzyl-n-octylaluminum hydride; It may be one or more selected from the group consisting of ethylaluminum dihydride, n-propylaluminum dihydride, isopropylaluminum dihydride, n-butylaluminum dihydride, isobutylaluminum dihydride, and n-octylaluminum dihydride.

[0095] In the above catalyst composition, the alkylating agent may be an organometallic compound capable of transferring hydrocarbyl groups to other metals and acting as a co-catalyst.

[0096] In addition, the catalyst composition of the present invention may further include, if necessary, a conventional alkylating agent used as an alkylating agent in the production of conjugated diene polymers in addition to the first and second alkylating agents above, and such alkylating agents may include alkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctylaminum, etc.; alkyl magnesium compounds such as diethylmagnesium, di-n-propylmagnesium, diisopropylmagnesium, dibutylmagnesium, dihexylmagnesium, diphenylmagnesium, or dibenzylmagnesium, etc., and the above organic lithium compounds may include alkyl lithium compounds such as n-butyllithium, etc.

[0097] (c) Halogen compounds

[0098] The above halogen compound is not particularly limited in type, but any compound commonly used as a halogen compound in the manufacture of diene-based polymers may be used without special restrictions.

[0099] Specifically, the above halogen compounds may include simple halogen substances, interhalogen compounds, hydrogen halides, organic halides, nonmetallic halides, metal halides, or organometallic halides, and any one or more of these may be used. Among these, considering the excellent effect of enhancing catalytic activity and consequently improving reactivity, any one or more of the above halogen compounds selected from the group consisting of organic halides, metal halides, and organometallic halides may be used.

[0100] More specifically, the above halogen elements may include fluorine, chlorine, bromine, or iodine.

[0101] In addition, specific examples of the above-mentioned halogen compounds include iodine monochloride, iodine monobromide, iodine trichloride, iodine pentafluoride, iodine monofluoride, or iodine trifluoride.

[0102] In addition, the above-mentioned hydrogen halides may specifically include hydrogen fluoride, hydrogen chloride, hydrogen bromide, or hydrogen iodide.

[0103] In addition, the above organic halides specifically include t-butyl chloride (t-BuCl), t-butyl bromide, allyl chloride, allyl bromide, benzyl chloride, benzyl bromide, chloro-diphenylmethane, bromo-diphenylmethane, triphenylmethyl chloride, triphenylmethyl bromide, benzylidene chloride, benzylidene bromide, methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, trimethylchlorosilane (TMSCl), benzoyl chloride, benzoyl bromide, propionyl chloride, propionyl bromide, methyl chloroformate, methyl bromoformate, iodomethane, diiodomethane, triiodomethane (also called iodoform), tetraiodomethane, 1-iodopropane, 2-iodopropane, Examples include 1,3-diiodopropane, t-butyl iodide, 2,2-dimethyl-1-iodopropane (also called 'neopentyl iodide'), allyl iodide, iodobenzene, benzyl iodide, diphenylmethyl iodide, triphenylmethyl iodide, benzylidene iodide (also called 'benzal iodide'), trimethylsilyl iodide, triethylsilyl iodide, triphenylsilyl iodide, dimethyldiiodosilane, diethyldiiodosilane, diphenyldiiodosilane, methyltriiodosilane, ethyltriiodosilane, phenyltriiodosilane, benzoyl iodide, propionyl iodide, or methyl iodoformate.

[0104] In addition, the above non-metallic halides may specifically include phosphorus trichloride, phosphorus tribromide, phosphorus chloride, phosphorus oxychloride, phosphorus oxybromide, boron trifluoride, boron trichloride, boron tribromide, silicon tetrafluoride, silicon tetrachloride (SiCl4), silicon tetrabromide, arsenic trichloride, arsenic tribromide, selenium tetrachloride, selenium tetrabromide, tellurium tetrachloride, tellurium tetrabromide, silicon tetraiodide, arsenic triiodide, tellurium tetraiodide, boron triiodide, phosphorus triiodide, phosphorus oxyiodide, or selenium tetraiodide.

[0105] In addition, the metal halides mentioned above may specifically include tin tetrachloride, tin tetrabromide, aluminum trichloride, aluminum tribromide, antimony trichloride, antimony chloride, 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 triiodide, zinc diiodide, germanium tetraiodide, tin tetraiodide, tin diiodide, antimony triiodide, or magnesium diiodide.

[0106] In addition, the organometallic halides specifically include dimethylaluminum chloride, diethylaluminum chloride, dimethylaluminum bromide, diethylaluminum bromide, dimethylaluminum fluoride, diethylaluminum fluoride, methylaluminum dichloride, ethylaluminum dichloride, methylaluminum dibromide, ethylaluminum dibromide, methylaluminum difluoride, ethylaluminum difluoride, methylaluminum sesquichloride, ethylaluminum sesquichloride (EASC), isobutylaluminum 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, trimethyltin chloride, Trimethyltin bromide, triethyltin chloride, triethyltin bromide, di-t-butyltin dichloride, di-t-butyltin dibromide, di-n-butyltin dichloride, di-n-butyltin dibromide, tri-n-butyltin chloride, tri-n-butyltin bromide, methylmagnesium iodide, dimethylaluminum iodide, diethylaluminum iodide, di-n-butylaluminum iodide, diisobutylaluminum iodide, di-n-octylaluminum iodide, methylaluminum diiodide, ethylaluminum diiodide, n-butylaluminum diiodide, isobutylaluminum diiodide, methylaluminum sesquiiodide, ethylaluminum Examples include sesquiiodide, isobutylaluminum sesquiiodide, ethyl magnesium iodide, n-butyl magnesium iodide, isobutyl magnesium iodide, phenyl magnesium iodide, benzyl magnesium iodide, trimethyltin iodide, triethyltin iodide, tri-n-butyltin iodide, di-n-butyltin diiodide, or di-t-butyltin diiodide.

[0108] In addition, the catalyst composition of the present invention may include a non-coordinating anion-containing compound or a non-coordinating anion precursor compound instead of or together with the halogen compound.

[0109] Specifically, in the compound containing the above-mentioned non-coordinating anion, the non-coordinating anion is a stereochemically bulky anion that does not form a coordinate bond with the active center of the catalytic system due to steric hindrance, and may be a tetraarylborate anion or a tetraarylborate fluoride anion. In addition, the compound containing the above-mentioned non-coordinating anion may include, together with the above-mentioned non-coordinating anion, a carbonium cation such as a triaryl carbonium cation; an ammonium cation such as an N,N-dialkylanilinium cation; or a phosphonium cation. More specifically, the compound containing the above-mentioned non-coordinating anion may be triphenyl carbonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenyl carbonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, or N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, etc.

[0110] In addition, as the above-mentioned non-coordinating anion precursor, a compound capable of forming a non-coordinating anion under reaction conditions may be a triaryl boron compound (BR3, where R is a strongly electron-withdrawing aryl group such as a pentafluorophenyl group or a 3,5-bis(trifluoromethyl)phenyl group).

[0111] (d) Conjugated diene monomer

[0112] In addition, the catalyst composition may further include a conjugated diene monomer, and by using a preforming or premixed catalyst composition in which a portion of the conjugated diene monomer used in the polymerization reaction is pre-mixed with the polymerization catalyst composition and pre-polymerized, not only can the activity of the catalyst composition be improved, but the active polymer produced can also be stabilized.

[0113] In the present invention, the term "preforming" may mean that when a catalyst composition comprising a neodymium compound, an alkylating agent, and a halide, i.e., a catalyst system, includes diisobutylaluminum hydride (DIBAH), a small amount of a conjugated diene monomer such as 1,3-butadiene is added to reduce the possibility of generating various active species of the catalyst composition, and pre-polymerization occurs within the catalyst composition system along with the addition of 1,3-butadiene. Additionally, the term "premix" may mean a state in which the compounds are uniformly mixed without polymerization occurring within the catalyst composition system.

[0114] At this time, the conjugated diene monomer used in the preparation of the catalyst composition may be used in a partial amount within the total usage range of the conjugated diene monomer used in the polymerization reaction, for example, 1 mole to 100 moles, specifically 10 moles to 50 moles, or 20 moles to 50 moles per mole of the neodymium compound.

[0116] The catalyst composition according to one embodiment of the present invention can be prepared by mixing at least one of the aforementioned neodymium compound, alkylating agent, halide, and conjugated diene monomer in an organic solvent, specifically, a neodymium compound, an alkylating agent, a halide, and optionally a conjugated diene monomer. At this time, the organic solvent may be a non-polar solvent that is not reactive with the components of the catalyst composition.

[0117] Specifically, the nonpolar solvent may be a linear, branched, or cyclic aliphatic hydrocarbon having 5 to 20 carbon atoms, such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, isopentane, isohexane, isopentane, isooctane, 2,2-dimethylbutane, cyclopentane, cyclohexane, methylcyclopentane, or methylcyclohexane; a mixed solvent of aliphatic hydrocarbon having 5 to 20 carbon atoms, such as petroleum ether or petroleum spirits, or kerosene; or an aromatic hydrocarbon solvent such as benzene, toluene, ethylbenzene, xylene, etc., and any one or more of these may be used. More specifically, the nonpolar solvent may be a linear, branched, or cyclic aliphatic hydrocarbon having 5 to 20 carbon atoms or a mixed solvent of aliphatic hydrocarbons, and more specifically, n-hexane, cyclohexane, or a mixture thereof.

[0118] In addition, the method for preparing a modified conjugated diene-based polymer of the present invention may include a step of terminating the polymerization after preparing the active polymer by further using an additive such as a reaction stopper to complete the polymerization reaction, such as polyoxyethylene glycol phosphate, or an antioxidant, such as 2,6-di-t-butyl paracresol. In addition, additives that facilitate solution polymerization, such as chelating agents, dispersing agents, pH adjusters, deoxidizing agents, or oxygen scavengers, may be optionally used together with the reaction stopper.

[0120] Step (S2)

[0121] A step of preparing a modified polymer by reacting the above polymer with a modifying agent represented by Chemical Formula 1, wherein the modified polymer may include a polymer in which a functional group derived from the modifying agent represented by Chemical Formula 1 is introduced at least one end of a conjugated diene polymer chain, an active polymer remaining in an unmodified state, an unreacted monomer, a hydrocarbon solvent, etc.

[0123] Unless otherwise defined in the present invention, "a trivalent hydrocarbon group substituted with a substituent" may mean a hydrocarbon group substituted with a total of trivalent from a bond (divalent) within a ring containing an N atom and a bond (monovalent) with the defined substituent, and the substituted trivalent hydrocarbon group may be a trivalent hydrocarbon group having 1 to 10 carbon atoms or 1 to 5 carbon atoms forming a ring together with the N atom, excluding the number of carbon atoms of the defined substituent.

[0124] Additionally, unless otherwise defined in the present invention, "single bond" may mean a single covalent bond itself that does not include a separate atomic or molecular group.

[0125] In addition, unless otherwise defined in the present invention, "silyl group substituted or unsubstituted with a linear or branched alkyl group having 1 to 20 carbon atoms" may mean one selected from the group consisting of an unsubstituted monovalent silyl group and a divalent to tetravalent silyl group substituted with said alkyl group.

[0126] The modifying agent according to the present invention includes a cyclized tertiary amine derivative such as the compound represented by Formula 1, thereby modifying the conjugated diene polymer, specifically the conjugated diene polymer having an active organometallic site, by imparting a functional group to the conjugated diene polymer through substitution or addition reaction with the active organometallic site.

[0127] Meanwhile, the above-mentioned modifying agent can improve the compounding properties between the polymer and the filler by including a functional group within the molecule that can increase affinity with the filler, and furthermore, by including a cyclized tertiary amine derivative as described above, it can prevent aggregation between fillers within the rubber composition and improve the dispersibility of the filler. For example, when using silica, a type of inorganic filler, aggregation is prone to occur due to hydrogen bonding between hydroxyl groups present on the surface of the silica; however, the above-mentioned cyclized tertiary amino group can improve the dispersibility of the silica by interfering with hydrogen bonding between the hydroxyl groups of the silica. In this way, the above-mentioned modifying agent has a structure that can maximize the compounding properties of the modified conjugated diene polymer, thereby enabling the efficient production of a modified conjugated diene polymer with an excellent balance of mechanical properties such as wear resistance and processability of the rubber composition.

[0128] However, when using a modifying agent as described above in the present invention, a problem may arise in which mechanical properties are improved as linearity increases but processability is reduced. In the present invention, as described below, a modified conjugated diene polymer with excellent properties that secures both the advantages of modification with a modifying agent represented by Chemical Formula 1 and processability is produced by drying at a high temperature, specifically at a temperature of 130°C or higher.

[0130] According to one embodiment of the present invention, in the above chemical formula 1, R 1 to R 3 -R each independently 6 COOR 7 A trivalent hydrocarbon group substituted with; or an unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, provided that R 1 to R 3 All of these may simultaneously be trivalent hydrocarbon groups; or may not be divalent hydrocarbon groups, and R 4 is a single bond; or may be a linear or branched alkylene group having 1 to 20 carbon atoms, and R 5is a silyl group substituted with a linear or branched alkyl group having 1 to 20 carbon atoms; a halogen; a cyano group; or -COR 8 It could be, R 6 can be a single bond, and R 7 can be a linear or branched alkyl group having 1 to 20 carbon atoms, and R 8 It may be one selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a heterocycloalkyl group having 2 to 10 carbon atoms, a heteroamine group having 2 to 10 carbon atoms, and a disilylamino group having 3 to 10 carbon atoms.

[0131] According to one embodiment of the present invention, the compound represented by Chemical Formula 1 may be a compound represented by the following Chemical Formula 2:

[0132] [Chemical Formula 2]

[0133]

[0134] In the above chemical formula 2, R 1 and R 3 Each may be a trivalent hydrocarbon group independently substituted with one or more substituents selected from the group consisting of a halogen group, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms; or an unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, and R 2 is -R 6 COOR 7 It may be a trivalent hydrocarbon group substituted with, and R 4 and R 6 can be a single bond, and R 7 ≠ may be a linear or branched alkyl group having 1 to 20 carbon atoms; or a cycloalkyl group having 3 to 20 carbon atoms, and R 9 to R 11 Each can independently be hydrogen or a linear or branched alkyl group having 1 to 20 carbon atoms.

[0135] As another example, in the above chemical formula 2, R 1 and R 3 Each may be an independently unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, and R 2 is -R 6 COOR 7 It may be a trivalent hydrocarbon group substituted with, and R 4 and R 6 can be a single bond, and R 7 can be a linear or branched alkyl group having 1 to 20 carbon atoms, and R 9 to R 11 Each can independently be a linear or branched alkyl group having 1 to 20 carbon atoms.

[0136] As a specific example, the compound represented by the above chemical formula 2 may be one or more selected from the group consisting of compounds represented by the following chemical formulas 2-1 to 2-3.

[0137] [Chemical Formula 2-1]

[0138]

[0139] [Chemical Formula 2-2]

[0140]

[0141] [Chemical Formula 2-3]

[0142]

[0143] The above-mentioned modifying agent may be used in an amount of 0.5 to 20 moles relative to 1 mole of the neodymium compound in the catalyst composition. Specifically, the above-mentioned modifying agent may be used in an amount of 1 to 10 moles relative to 1 mole of the neodymium compound in the catalyst composition.

[0144] In addition, the above denaturation reaction may be carried out at 0 to 90°C for 1 minute to 5 hours.

[0145] After the above-mentioned denaturation reaction is completed, the polymerization reaction can be stopped by adding an isopropanol solution of 2,6-di-t-butyl-p-cresol (BHT), etc., to the polymerization reaction system.

[0147] Step (S3)

[0148] The above modified polymer is desolvated and dried at a temperature of 130°C or higher, thereby removing residual hydrocarbon solvent, unreacted monomers, etc., that were used during the polymerization in step (S1), and obtaining the final product, a modified conjugated diene polymer.

[0149] The drying of the above step (S3) can be performed at a temperature of 130°C or higher, 170°C or lower, and 150°C or lower.

[0150] Additionally, the drying in step (S3) may be performed by one or more methods selected from the group consisting of a roll-mill, an expeller, and an expander, and specifically, it may be roll-mill drying. The roll-mill removes moisture from the polymer while two or more cylindrical rolls rotate at a high temperature.

[0151] In addition, the drying can be performed for a time of 3 minutes or more, 5 minutes or more, 10 minutes or more, 20 minutes or less, 15 minutes or less, or 10 minutes or less.

[0152] By performing drying under the above conditions, the unmodified polymer remaining due to high temperature conditions reacts further with the modified polymer, thereby lowering the linearity and increasing the degree of branching of the modified conjugated diene polymer contained within the modified polymer, and consequently, a modified conjugated diene polymer with improved processability can be produced.

[0154] The modified conjugated diene polymer produced by the manufacturing method of the present invention may have characteristics such as an optimized molecular weight distribution and Mooney viscosity, through the control of the catalyst composition and polymerization conditions during manufacturing, so as to improve the balance of physical properties such as viscoelasticity, tensile properties, and processability of the rubber composition.

[0155] Specifically, the modified conjugated diene polymer may have a narrow molecular weight distribution (Mw / Mn) of 2.0 to 4.0, and within this range, when applied to a rubber composition, it has excellent tensile properties and viscoelasticity. Specifically, the molecular weight distribution may be 2.0 or higher, 2.2 or higher, 4.0 or lower, or 3.0 or lower.

[0156] The above 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). In this case, the number-average molecular weight (Mn) is the common average of the individual polymer molecular weights calculated by measuring the molecular weights of n polymer molecules, finding the sum of these molecular weights, and dividing by n, and the weight-average molecular weight (Mw) represents the molecular weight distribution of the polymer composition. All molecular weight averages can be expressed in grams per mole (g / mol). Additionally, the weight-average molecular weight and the number-average molecular weight may each refer to the polystyrene equivalent molecular weight analyzed by gel permeation chromatography (GPC).

[0157] More specifically, when the modified conjugated diene polymer according to one embodiment of the present invention simultaneously satisfies the conditions of weight-average molecular weight and number-average molecular weight along with the molecular weight distribution described above, when applied to a rubber composition, it has the effect of having excellent tensile properties, viscoelasticity, and processability for the rubber composition, and an excellent balance of physical properties among them.

[0158] The modified conjugated diene polymer according to one embodiment of the present invention may have a Mooney viscosity (MV) of 20 or more and 100 or less at 100°C, specifically 30 or more, 40 or more, 50 or more, 80 or less, 70 or less, and 60 or less. The modified conjugated diene polymer according to the present invention may have excellent processability by having a Mooney viscosity within the aforementioned range.

[0159] In addition, the modified conjugated diene polymer according to one embodiment of the present invention may have a -S / R (stress / relaxation) at 100°C reduced by more than 10% compared to the -S / R before performing step (S3).

[0160] The above -S / R represents the change in stress resulting from the response to an equal amount of strain generated within the material, and is an index indicating the linearity of the polymer. The lower the -S / R value, the higher the degree of branching and the broader the molecular weight distribution; consequently, the processability of the polymer is excellent.

[0161] The modified conjugated diene polymer according to one embodiment of the present invention has a linearity within the above range, thereby providing excellent compounding processability when applied to a rubber composition.

[0162] In addition, the modified conjugated diene polymer according to one embodiment of the present invention may have a T80 value, which indicates the time when the stress applied to the sample is relieved by 80% after measuring Mooney viscosity, increase by more than 10% compared to the T80 before performing step (S3).

[0163] As the T80 time increases, it implies lower linearity and higher degree of branching; the copolymer of the present invention is characterized by a high degree of branching and improved processability as the T80 value increases at a high rate as described above.

[0164] In the present invention, the Mooney viscosity was measured using a Mooney viscometer, for example, the Large Rotor of the Monsanto MV2000E, under conditions of 100°C and a Rotor Speed ​​of 2 ± 0.02 rpm. Specifically, after leaving the polymer at room temperature (23 ± 5°C) for at least 30 minutes, 27 ± 3 g was collected and filled into the die cavity, and the Mooney viscosity was measured while applying torque by operating the platen. Furthermore, the linearity (-S / R) was obtained by measuring the slope of the change in Mooney viscosity that appears as the torque is released after the Mooney viscosity measurement, and as the absolute value thereof.

[0165] The above-mentioned modified conjugated diene polymer may have a beta value (β-value) of 0.220 or less, 0.200 or less, 0.190 or less, 0.150 or more, 0.170 or more, or 0.180 or more. The above beta value represents the change in viscoelastic modulus according to the change in frequency for the same amount of strain, and is an indicator of the linearity of the polymer. Generally, the lower the beta value, the lower the linearity of the polymer, which means that the processability is excellent.

[0166] The above beta value can be obtained by using a Rubber Process Analyzer (RPA2000, Alpha Technologies) to perform a frequency sweep on each polymer at 100°C with a strain of 7% to obtain the slope of Log(1 / tan delta) vs Log(Freq.), and then calculating it. At this time, the frequency was set to 2, 5, 10, 20, 50, 100, 200, 500, 1,000, and 2,000 cpm.

[0167] The above modified conjugated diene polymer may have an SGIC value of 35.0 or higher. SGIC (Solvent gradient interaction chromatography) is a method for measuring the amount of modified polymer in a polymer, and a higher SGIC value is interpreted as indicating a higher rate of modification.

[0168] The above SGIC can change the ratio of toluene and mixed solvent, pass 0.2 mg of a sample (the result of an example or comparative example) dissolved in 1 mL of toluene through a column having a polar packing agent, and distinguish between the modified polymer and the unmodified polymer through a detector to calculate the area ratio.

[0170] In addition, the modified conjugated diene polymer of the present invention is applicable to rubber compositions containing the same and molded articles made therefrom.

[0171] The above rubber composition may contain a modified conjugated diene polymer in an amount of 0.1% by weight or more and 100% by weight or less, specifically 10% by weight to 100% by weight, and more specifically 20% by weight to 90% by weight. If the content of the modified conjugated diene polymer is less than 0.1% by weight, the improvement effect on wear resistance and crack resistance of a molded product, such as a tire, manufactured using the above rubber composition may be negligible.

[0172] In addition, the rubber composition may further include other rubber components as needed in addition to the modified conjugated diene-based polymer, wherein the rubber components may be included in an amount of 90% by weight or less relative to the total weight of the rubber composition. Specifically, it may be included in an amount of 1 to 900 parts by weight per 100 parts by weight of the modified conjugated diene-based copolymer.

[0173] The above rubber component may be natural rubber or synthetic rubber, for example, the above rubber component may be natural rubber (NR) containing cis-1,4-polyisoprene; modified natural rubber such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), hydrogenated natural rubber, etc., which is obtained by modifying or purifying the above general natural rubber; It may be synthetic rubber such as 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, butyl halogenated rubber, etc., and any one or more of these may be used.

[0174] In addition, the rubber composition may comprise 0.1 to 150 parts by weight of a filler per 100 parts by weight of a modified conjugated diene polymer, and the filler may be silica-based, carbon black, or a combination thereof. Specifically, the filler may be carbon black.

[0176] The above carbon black-based filler is not specifically limited, but, for example, may have a nitrogen adsorption specific surface area (N2SA, measured in accordance with JIS K 6217-2:2001) of 20 m² / g to 250 m² / g. In addition, the above carbon black may have a dibutyl phthalate oil absorption (DBP) of 80 cc / 100g to 200 cc / 100g. If the nitrogen adsorption specific surface area of ​​the above carbon black exceeds 250 m² / g, there is a risk that the processability of the rubber composition will be reduced, and if it is less than 20 m² / g, the reinforcing performance by the carbon black may be negligible. In addition, if the DBP oil absorption of the above carbon black exceeds 200 cc / 100g, there is a risk that the processability of the rubber composition will be reduced, and if it is less than 80 cc / 100g, the reinforcing performance by the carbon black may be negligible.

[0178] In addition, the silica is not specifically limited, but may be, for example, wet silica (hydrated silica), dry silica (anhydrous silica), calcium silicate, aluminum silicate, or colloidal silica. Specifically, the silica may be wet silica, which exhibits the most significant effects in improving fracture characteristics and achieving wet grip. Additionally, the silica may have a nitrogen adsorption specific surface area per gram (N2SA) of 120 m² / g to 180 m² / g and a CTAB (cetyl trimethyl ammonium bromide) adsorption specific surface area of ​​100 m² / g to 200 m² / g. If the nitrogen adsorption specific surface area of ​​the silica is less than 120 m² / g, there is a risk that the reinforcing performance by the silica will be reduced, and if it exceeds 180 m² / g, there is a risk that the processability of the rubber composition will be reduced. In addition, if the CTAB adsorption specific surface area of ​​the silica is less than 100 m² / g, there is a risk that the reinforcing performance by the silica filler will be reduced, and if it exceeds 200 m² / g, there is a risk that the processability of the rubber composition will be reduced.

[0179] Meanwhile, when silica is used as the above-mentioned filler, a silane coupling agent may be used together to improve reinforcement and low heat generation.

[0180] Specifically, the above silane coupling agents include 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-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, Examples include 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilylpropylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylmethacrylate monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, bis(3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, or dimethoxymethylsilylpropylbenzothiazolyltetrasulfide, and any one or a mixture of two or more of these may be used. More specifically, considering the effect of improving reinforcement, the silane coupling agent may be bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide.

[0182] In addition, the rubber composition according to one embodiment of the present invention may be sulfur-crosslinkable and, accordingly, may further include a vulcanizing agent.

[0183] The above vulcanizing agent may specifically be sulfur powder and may be included in an amount of 0.1 to 10 parts by weight per 100 parts by weight of rubber component. When included within the above content range, the necessary elastic modulus and strength of the vulcanized rubber composition can be secured, and at the same time, low fuel consumption can be obtained.

[0184] In addition, a rubber composition according to one embodiment of the present invention may further include, in addition to the above-mentioned components, various additives commonly used in the rubber industry, specifically vulcanization accelerators, process oils, plasticizers, anti-aging agents, anti-scotch agents, zinc white, stearic acid, thermosetting resins, or thermoplastic resins.

[0185] The above vulcanization accelerator is not particularly limited, and specifically, thiazole compounds such as M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), and CZ (N-cyclohexyl-2-benzothiazylsulfenamide), or guanidine compounds such as DPG (diphenylguanidine) may be used. The above vulcanization accelerator may be included in an amount of 0.1 to 5 parts by weight per 100 parts by weight of the rubber component.

[0186] In addition, the process oil acts as a softener in the rubber composition and, specifically, may be a paraffinic, naphthenic, or aromatic compound; more specifically, an aromatic process oil may be used when considering tensile strength and wear resistance, and a naphthenic or paraffinic process oil may be used when considering hysteresis loss and low-temperature characteristics. The process oil may be included in an amount of 100 parts by weight or less per 100 parts by weight of the rubber component, and when included in the above amount, it can prevent a decrease in the tensile strength and low heat generation (low fuel consumption) of the vulcanized rubber.

[0187] In addition, specific examples of the above-mentioned anti-aging agents include N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, or high-temperature condensation products of diphenylamine and acetone. The above-mentioned anti-aging agent may be used in an amount of 0.1 to 6 parts by weight per 100 parts by weight of the rubber component.

[0189] A rubber composition according to one embodiment of the present invention can be obtained by mixing using a mixer such as a Banbury mixer, a roll mixer, or an internal mixer according to the above formulation, and a rubber composition with low heat generation and excellent wear resistance can be obtained by a vulcanization process after molding.

[0190] Accordingly, the above rubber composition can be useful for manufacturing various components of a tire, such as tire treads, undertreads, sidewalls, carcass coating rubber, belt coating rubber, bead fillers, choppers, or bead coating rubber, or various industrial rubber products such as anti-vibration rubber, belt conveyors, and hoses.

[0191] A molded article manufactured using the above rubber composition may include a tire or a tire tread.

[0193] Examples

[0194] The present invention will be explained in more detail below through examples. However, the following examples are intended to illustrate the present invention and do not limit the scope of the present invention.

[0196] Preparation Example 1

[0197] To a solution in which 2 g of ethyl piperidine-4-carboxylate was dissolved in dichloromethane (CH2Cl2), 1.77 ml of triethylamine (Et3N) and 1.62 ml of trimethylsilyl chloride (TMSCl) were added at 0°C, and the reaction mixture was stirred at 0°C for 5 hours. Subsequently, the solvent in the resulting solution was evaporated under reduced pressure and redissolved in hexane, followed by filtration to obtain a compound having the structure as described below. 1 The H NMR spectrum was observed.

[0198] [Chemical Formula 2-2]

[0199]

[0200] 1 H NMR (500 MHz, CDCl3): δ 4.11-4.08 (m, 2H), δ 3.13-3.11 (m, 2H), δ 2.61-2.54 (m, 2H), δ 2.34-2.32 (m, 1H), δ 1.74 (m, 2H), δ 1.42(m, 2H), δ 1.23-1.22(m, 3H), δ 0.05-0.00(m, 9H)

[0202] Comparative Manufacturing Example 1

[0203] To a solution in which 5 g of ethyl 6-aminohexanoate hydrochloride (ethyl 6-aminohexanoate HCl) was dissolved in dichloromethane (CH2Cl2), 18 ml of triethylamine (Et3N) and 13.8 g of 1,2-bis(chlorodimethylsilyl)ethane were added at 0°C, and the reaction mixture was heated to room temperature after 10 minutes and stirred overnight. Subsequently, hexane was added to the resulting solution, and the solvent was evaporated under reduced pressure. The residue was filtered through a solution of diethyl ether and hexane (1 / 1), and the solvent was evaporated again. The remaining solution was subjected to vacuum distillation to obtain a compound of the following structure.

[0204]

[0206] Example 1

[0207] (S1) Preparation of catalyst composition and polymerization of conjugated diene monomer

[0208] A catalyst composition was prepared by adding a neodymium carboxylic acid compound to a hexane solvent under nitrogen conditions, and then sequentially adding diisobutylaluminum hydride (DIBAH) and diethylaluminum chloride (DEAC) in a molar ratio of neodymium compound:DIBAH:DEAC = 1:9~10:2~3 and mixing. The prepared catalyst composition was used immediately or stored under nitrogen conditions at -30 to 20°C before use.

[0209] After alternately applying vacuum and nitrogen to a completely dried reactor, 4.7 kg of a 1,3-butadiene / hexane mixed solution was introduced into the reactor under vacuum, and after adding the catalyst composition, a polymerization reaction was carried out at 60 to 90°C for 15 to 60 minutes to produce a polymer containing a butadiene polymer having an activated aluminum group at the terminal. It was confirmed that the Mooney viscosity of the butadiene polymer before modification at 100°C was 30 to 45.

[0210] (S2) Denaturation reaction

[0211] After the polymerization reaction of 1,3-butadiene in step (S1) was completed, a hexane solution containing the modifying agent obtained in Preparation Example 1 was added to the polymer containing the active polymer, and the reaction was carried out for 30 to 60 minutes under the same temperature conditions as the polymerization. Afterwards, a hexane solution containing a polymerization stopping agent was added to terminate the reaction, and a hexane solution containing an antioxidant was added to produce a modified polymer containing the modified butadiene-based polymer.

[0212] (S3) Desolvent and drying

[0213] After recovering the modified butadiene-based polymer from the modified polymer obtained in step (S2) by steam stripping, it was dried in a roll mill at 130°C for 10 minutes.

[0215] Examples 2 and 3

[0216] A modified butadiene-based polymer was prepared in the same manner as in Example 1, except that the conditions of step (S3) were changed as shown in Table 1 below.

[0218] Comparative Examples 1 to 5

[0219] A modified butadiene-based polymer was prepared in the same manner as in Example 1, except that the type of modifying agent and the conditions of step (S3) were changed as shown in Table 1 below.

[0220] denaturant Roll-mill temperature (°C) Roll-mill time Example 1 Preparation Example 1 130 10 minutes Example 2 Preparation Example 1 160 5 minutes Example 3 Preparation Example 1 130 5 minutes Comparative Example 1 Preparation Example 1 100 10 minutes Comparative Example 2 Comparative Manufacturing Example 1 100 10 minutes Comparative Example 3 Comparative Manufacturing Example 1 130 10 minutes Comparative Example 4 Dibutyltin dichloride 100 10 minutes Comparative Example 5 Dibutyltin dichloride 130 10 minutes

[0222] Experimental Example 1

[0223] The physical properties of the above modified conjugated diene polymer were measured according to the following method.

[0224] (1) Molecular weight distribution (MWD)

[0225] Each polymer was dissolved in tetrahydrofuran (THF) at 40°C for 30 minutes and then loaded and flowed through a gel permeation chromatography (GPC). At this time, a combination of two PLgel Olexis columns and one PLgel mixed-C column from Polymer Laboratories was used. Additionally, all newly replaced columns were of the mixed-bed type, and polystyrene was used as the GPC standard material.

[0226] (2) Measurement of Mooney viscosity (MV, ML1+4, @100℃), -S / R and T80

[0227] For each polymer, Mooney viscosity (ML1+4, @100℃) (MU) was measured at 100℃ using a Monsanto MV2000E with a Large Rotor and a Rotor Speed ​​of 2±0.02 rpm. The sample used was left at room temperature (23±5℃) for at least 30 minutes, then 27±3g was taken and placed inside the die cavity, and the Mooney viscosity was measured while applying torque by operating the platen.

[0228] In addition, the change in Mooney viscosity that appears as the torque is released after measuring Mooney viscosity was observed for 1 minute, and the -S / R value was determined from the slope value.

[0229] The time taken for the stress applied to the sample to be relieved by 80% after measuring Mooney viscosity was measured as T80.

[0230] (3) Beta value (β-value)

[0231] The beta value (β-value) was measured using a measurement method developed by The Goodyear Tire & Rubber Company.

[0232] A Rubber Process Analyzer (RPA2000, Alpha Technologies) was used as the measurement instrument. Specifically, each polymer was subjected to a frequency sweep at 100°C with a strain of 7%. The frequency was set to 2, 5, 10, 20, 50, 100, 200, 500, 1,000, and 2,000 cpm, and the beta value was obtained by calculating the slope of Log(1 / tan delta) vs Log(Freq.).

[0233] (4) SGIC

[0234] A sample of 0.2 mg of the polymer from the above example or comparative example dissolved in 1 mL of toluene was passed through a column with a polar packing material while varying the ratio of toluene to the mixed solvent, and the modified polymer and the unmodified polymer were separated using a detector, and the SGIC value was calculated based on the area ratio. A higher SGIC value is interpreted as indicating a higher degree of modification.

[0235] division Examples Comparative example 1 2 3 1 2 3 4 5 MWD(Mw / Mn) 2.56 2.42 2.43 2.36 2.35 2.39 2.41 2.36 Moony point 59.4 56.3 59.7 59.4 62.2 63.0 47.3 46.5 -S / R 0.637 0.581 0.652 0.764 0.788 0.750 0.745 0.738 T80 2.65 3.23 2.68 2.23 2.36 2.43 2.05 2.08 β-Value 0.183 0.155 0.188 0.229 0.213 0.204 0.213 0.208 SGIC 37 41 35 30 25 26 ND ND

[0236] As shown in Table 2 above, although the same modifying agent was used, it was confirmed that Example 1, dried at 130°C, had a higher SGIC value and increased modification rate compared to Comparative Example 1, dried at 100°C, while the -S / R value and β-value were lower. Furthermore, Example 2, dried at a higher temperature of 160°C, showed a further decrease in the -S / R value and β-value. Additionally, since there was almost no change in Mooney viscosity and molecular weight distribution, it can be inferred that only linearity changed without any breakage of polymer chains due to heat. This indicates that by setting the drying temperature to 130°C or higher, the unmodified polymer reacted further, increasing the modification rate, and the degree of branching increased while linearity decreased, thereby improving the processability of the polymer.

[0237] Meanwhile, in the case of Comparative Examples 2 and 3, which used the modifying agent of Comparative Manufacturing Example 1 not included in the present invention, when the drying temperature was generally increased to 130°C (Comparative Example 3), the -S / R value and β-value decreased slightly compared to the polymer dried at 100°C (Comparative Example 2), but the decrease was not significant. Therefore, it was found that a modified butadiene-based polymer with lower processability and higher linearity was produced compared to the example with a higher drying temperature. Likewise, in the case of Comparative Examples 4 and 5, which used dibutyltin dichloride as the modifying agent, the degree of decrease in linearity was not significant even when the drying temperature was increased to 130°C or higher. Therefore, a modified butadiene-based polymer with lower processability was produced compared to the example.

[0238] That is, it was confirmed that the effect of improving processability due to the high drying temperature is clearly evident by using the modifying agent of Manufacturing Example 1 as in the manufacturing method of the present invention and drying the temperature at 130°C or higher, and through this, it was found that a modified conjugated diene polymer with excellent physical properties and processability can be manufactured.

[0240] Experimental Example 2

[0241] In order to compare and analyze the physical properties of rubber compositions containing each modified conjugated diene polymer prepared in the above examples and comparative examples, and molded articles prepared therefrom, rubber specimens were prepared and physical properties were measured as follows.

[0242] Specifically, each rubber compound was prepared by mixing 60 parts by weight of graphite, 15 parts by weight of process oil, 2 parts by weight of anti-aging agent (TMDQ), 3 parts by weight of zinc oxide (ZnO), and 2 parts by weight of stearic acid with 100 parts by weight of the modified conjugated diene polymer prepared in the above examples and comparative examples as raw rubber. 2 parts by weight of sulfur, 2 parts by weight of vulcanization accelerator (CZ), and 0.5 parts by weight of vulcanization accelerator (DPG) were added to the prepared rubber compound, and rubber specimens were prepared by vulcanizing at 160°C for 25 minutes.

[0243] (1) Tensile properties

[0244] Modulus at 300% elongation according to ASTM D412 after vulcanization at 150°C for 90 minutes for a rubber composition (300% modulus, kg·f / cm²) 2 ), tensile strength of vulcanized material (kg·f / cm²) 2 ), and the elongation of the vulcanized material at break was measured.

[0245] (2) Viscoelastic properties

[0246] A dynamic mechanical analyzer from TA was used. Tanδ values ​​were measured by varying the deformation in torsional mode at a frequency of 10 Hz and at each measurement temperature (-70 to 70℃). A lower Tanδ value at high temperatures (50 to 70℃) indicates less hysteresis loss and superior low rolling resistance of the tire, i.e., low fuel consumption.

[0247] Example 1 Comparative Example 1 Comparative Example 2 Tensile properties tensile strength 197 190 192 M-300% 102 96 95 Shin Yul 487 502 496 Viscoelastic properties Tanδ at 50~70℃ 0.145 0.158 0.157

[0248] As shown in Table 3 above, it was confirmed that the rubber specimens prepared from the modified conjugated diene polymer of the example prepared according to the present invention showed significantly improved tensile and viscoelastic properties compared to the comparative example.

[0249] From these results, it was found that when a modified conjugated diene polymer is manufactured using the manufacturing method according to the present invention, the processability is improved as described above, and a modified conjugated diene polymer with excellent tensile and viscoelastic properties can be manufactured as shown in the results above.

Claims

Claim 1 (S1) a step of preparing a polymer containing an active polymer by polymerizing a conjugated diene monomer in the presence of a catalyst composition containing a neodymium compound in a hydrocarbon solvent; (S2) a step of preparing a modified polymer by reacting the polymer with a modifying agent represented by the following Chemical Formula 1; and (S3) a step of desolvating the modified polymer and drying it at a temperature of 130°C or higher; comprising a method for preparing a modified conjugated diene polymer: [Chemical Formula 1] In the above chemical formula 1, R 1 to R 3 Each independently comprises a halogen group, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and -R 6 COOR 7 A trivalent hydrocarbon group substituted with one or more substituents selected from the group consisting of; or an unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, provided that R 1 to R 3 All of these are simultaneously trivalent hydrocarbon groups; or not divalent hydrocarbon groups, R 4 is a single bond; a linear or branched alkylene group having 1 to 20 carbon atoms; or a cycloalkylene group having 3 to 20 carbon atoms, and R 5 is a silyl group substituted or unsubstituted with a linear or branched alkyl group having 1 to 20 carbon atoms; a halogen; a cyano group; or -COR 8 and, R 6 is a single bond; a linear or branched alkylene group having 1 to 20 carbon atoms; or a cycloalkylene group having 3 to 20 carbon atoms, and R 7 is a linear or branched alkyl group having 1 to 20 carbon atoms; or a cycloalkyl group having 3 to 20 carbon atoms, and R 8 It is one type selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a heterocycloalkyl group having 2 to 10 carbon atoms, a heteroamine group having 2 to 10 carbon atoms, and a disilylamino group having 3 to 10 carbon atoms. Claim 2 A method for manufacturing a modified conjugated diene-based polymer according to claim 1, wherein the drying in step (S3) is performed at a temperature of 130 to 170°C. Claim 3 A method for manufacturing a modified conjugated diene polymer according to claim 1, wherein the drying in step (S3) is performed using one or more selected from the group consisting of a roll-mill, an expeller, and an expander. Claim 4 A method for manufacturing a modified conjugated diene-based polymer according to claim 1, wherein the drying in step (S3) is performed for 3 to 20 minutes. Claim 5 A method for manufacturing a modified conjugated diene-based polymer according to claim 1, wherein the desolvation in step (S3) is performed by steam stripping. Claim 6 In claim 1, in the above formula 1, R 1 to R 3 -R each independently 6 COOR 7 A trivalent hydrocarbon group substituted with; or an unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, provided that R 1 to R 3 All of these are simultaneously trivalent hydrocarbon groups; or not divalent hydrocarbon groups, R 4 is a single bond; or a linear or branched alkylene group having 1 to 20 carbon atoms, R 5 is a silyl group substituted with a linear or branched alkyl group having 1 to 20 carbon atoms; a halogen; a cyano group; or -COR 8 is,R 6 is a single bond, and R 7 is a linear or branched alkyl group having 1 to 20 carbon atoms, and R 8 A method for preparing a modified conjugated diene polymer, wherein the polymer is selected from the group consisting of an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a heterocycloalkyl group having 2 to 10 carbon atoms, a heteroamine group having 2 to 10 carbon atoms, and a disilylamino group having 3 to 10 carbon atoms. Claim 7 Method for preparing a modified conjugated diene polymer according to claim 1, wherein the modifying agent represented by Chemical Formula 1 is a modifying agent represented by the following Chemical Formula 2: [Chemical Formula 2] In the above chemical formula 2, R 1 and R 3 Each is a trivalent hydrocarbon group independently substituted with one or more substituents selected from the group consisting of a halogen group, a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 30 carbon atoms; or an unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, and R 2 is -R 6 COOR 7 It is a trivalent hydrocarbon group substituted with, and R 4 and R 6 is a single bond, and R 7 is a linear or branched alkyl group having 1 to 20 carbon atoms; or a cycloalkyl group having 3 to 20 carbon atoms, and R 9 to R 11 Each is independently hydrogen; or a linear or branched alkyl group having 1 to 20 carbon atoms. Claim 8 A method for preparing a modified conjugated diene polymer according to claim 7, wherein the modifying agent represented by Chemical Formula 2 is one selected from compounds represented by Chemical Formulas 2-1 to 2-3 below. [Chemical Formula 2-1] [Chemical Formula 2-2] [Chemical Formula 2-3] Claim 9 A method for preparing a modified conjugated diene polymer according to claim 1, wherein the catalyst composition comprises a neodymium compound, a first alkylating agent, a second alkylating agent, and a halogen compound. Claim 10 A method for preparing a modified conjugated diene polymer according to claim 1, wherein the conjugated diene monomer is one or more selected from the group consisting of 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, and 2,4-hexadiene.

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