KR20230019722A - Tetrasulfide derivative, modified conjugated diene-based polymer comprising the derivative, method of preparing the polymer and rubber composition comprising the polymer - Google Patents

Abstract

The present invention provides a tetrasulfide derivative that is easily used as a polymer modifier, a modified conjugated diene-based polymer having excellent affinity with a filler by containing a functional group derived therefrom, a method for preparing the polymer, and a rubber composition comprising the polymer. More specifically, provided are a tetrasulfide derivative represented by chemical formula 1, a modified conjugated diene-based polymer comprising a functional group derived therefrom, a preparation method of the polymer and a rubber composition comprising the polymer.

Description

Tetrasulfide derivative, modified conjugated diene-based polymer containing the same, method for preparing the polymer, and rubber composition containing the polymer POLYMER}

The present invention relates to a tetrasulfide derivative that is easy to use as a polymer modifier, a modified conjugated diene-based polymer containing a functional group derived therefrom and having excellent affinity with a filler, a method for preparing the polymer, and a rubber composition containing the polymer.

In accordance with the recent demand for low fuel consumption for automobiles, conjugated diene-based polymers with low rolling resistance, excellent abrasion resistance and tensile properties, and adjustment stability represented by wet skid resistance are required as rubber materials for tires. there is.

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

Natural rubber, polyisoprene rubber, polybutadiene rubber and the like are known as rubber materials with low hysteresis loss, but these have a problem of low wet skid resistance. Recently, conjugated diene-based (co)polymers such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) are produced by emulsion polymerization or solution polymerization and are used as rubber for tires. .

In the case of using BR or SBR as a rubber material for tires, fillers such as silica or carbon black are typically blended together to obtain required tire properties. However, since the affinity between the BR or SBR and the filler is not good, physical properties including wear resistance, crack resistance, or workability are deteriorated.

Therefore, as a method for increasing the dispersibility of BR and a filler such as silica or carbon black, in a living polymer obtained by coordinate polymerization using a catalyst composition containing a lanthanum series rare earth element compound, the living active end is modified by a specific modifier. A method of denaturation has been developed. However, in the case of a polymer having a terminal modification, affinity with a filler is improved and compounding properties, such as tensile properties and viscoelastic properties, are improved.

In addition, when mixing SBR or BR with a filler such as silica or carbon black to prepare a rubber composition tank, a coupling agent having a functional group such as a silane group, an amine group, or an azo group is mixed together to increase the affinity between the SBR or BR and the filler Although the blending properties and blending processability were improved by increasing the dispersibility of the filler, the effect of improving the blending properties was not obtained.

JP 5172663 B2

The present invention has been made to solve the problems of the prior art, and by containing a tetrasulfide unit in the molecule, it can react with the active site of the polymer to introduce a functional group into the polymer, and by containing a filler affinity group, the physical properties of the polymer can be improved. It is an object of the present invention to provide novel tetrasulfide derivatives useful as polymer modifiers that can be used.

In addition, an object of the present invention is to provide a modified conjugated diene-based polymer having improved compounding properties including a functional group derived from a tetrasulfide derivative.

In addition, an object of the present invention is to provide a method for producing a modified conjugated diene-based polymer using a tetrasulfide derivative.

Furthermore, an object of the present invention is to provide a rubber composition comprising a modified conjugated diene-based polymer.

In order to solve the above problems, the present invention provides a tetrasulfide derivative represented by Formula 1 below:

[Formula 1]

In Formula 1,

R ₁ and R ₂ are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms,

n and m are independently of each other an integer of 2 to 6;

In addition, the present invention is a repeating unit derived from a conjugated diene-based monomer; and a modified conjugated diene-based polymer including a functional group derived from the tetrasulfide derivative represented by Chemical Formula 1.

In addition, the present invention comprises the steps of preparing 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 (S1); and a step (S2) of reacting the active polymer with a tetrasulfide derivative represented by Formula 1 below.

[Formula 1]

In Formula 1,

R ₁ and R ₂ are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms,

n and m are independently of each other an integer of 2 to 6;

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

The tetrasulfide derivative according to the present invention contains a tetrasulfide unit in the molecule, so it has high reaction activity with the active site of the polymer, so that it reacts smoothly with the active site of the polymer, and it is easy to group the filler affinity functional group derived from the tetrasulfide derivative into the polymer. can be introduced.

In addition, the modified conjugated diene-based polymer according to the present invention may have excellent filler affinity by including a functional group derived from the tetrasulfide derivative, particularly a filler affinity functional group such as carbon black.

In addition, the method for preparing a modified conjugated diene-based polymer according to the present invention prepares an active polymer and reacts the active polymer with a tetrasulfide derivative, thereby introducing a modified conjugated diene-based polymer with a filler affinity functional group derived from the tetrasulfide derivative. can be easily manufactured.

Furthermore, since the rubber composition according to the present invention includes the modified conjugated diene-based polymer, the affinity between the polymer and the filler is excellent, and compounding properties can be improved, thereby greatly improving running resistance.

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

Terms or words used in this specification and claims should not be construed as being limited to ordinary or dictionary meanings, and the inventor may appropriately define the concept of terms in order to explain his or her invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of the present invention based on the principle that there is.

Terms

As used herein, the term 'substitution' may mean that hydrogen of a functional group, atomic group, or compound is substituted with a specific substituent, and when hydrogen of a functional group, atomic group, or compound is substituted with a specific substituent, it is present in the functional group, atomic group, or compound. One or two or more substituents may be present depending on the number of hydrogens to be present. In addition, when a plurality of substituents are present, each substituent may be the same as or different from each other.

The term 'alkyl group' used in the present invention may mean a monovalent aliphatic saturated hydrocarbon, and includes linear alkyl groups such as methyl, ethyl, propyl, and butyl, isopropyl, and sec-butyl. , branched alkyl groups such as tert-butyl and neo-pentyl.

The term 'cycloaklyl group' used in the present invention may mean a cyclic saturated hydrocarbon.

The term 'aryl group' used in the present invention may mean an aromatic hydrocarbon, and may also refer to a monocyclic aromatic hydrocarbon in which one ring is formed or a polycyclic aromatic hydrocarbon in which two or more rings are bonded. ) may mean including all.

The term 'alkylene group' used in the present invention may mean divalent aliphatic saturated hydrocarbons such as methylene, ethylene, propylene and butylene.

The terms 'derived unit' and 'derived functional group' used in the present invention may indicate a component or structure derived from a certain material or the material itself.

measurement method

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

tetrasulfide derivatives

The present invention provides novel compounds capable of introducing filler affinity functional groups into polymers.

The tetrasulfide derivative according to an embodiment of the present invention is characterized in that it is a compound represented by Formula 1 below:

[Formula 1]

In Formula 1,

R ₁ and R ₂ are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms,

n and m are independently of each other an integer of 2 to 6;

The tetrasulfide derivative according to an embodiment of the present invention may be a modifier for modifying polymers, specifically, a modifier for conjugated diene-based polymers. It reacts smoothly and can easily introduce a filler affinity functional group into the polymer.

In addition, the tetrasulfide derivative contains an ethylene glycol-derived group and an ethylene glycol ether group in a molecule, and the ethylene glycol-derived group and ethylene glycol ether group are introduced into the polymer molecule by a reaction between the terrasulfide unit and the active site of the polymer, , thereby improving the filler affinity of the polymer.

Specifically, in Formula 1, R ₁ and R ₂ are each independently selected from an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. to 13, and n and m may be each independently an integer of 2 to 4.

More specifically, in Formula 1, R ₁ and R ₂ are each independently an alkyl group having 1 to 6 carbon atoms or an aralkyl group having 7 to 13 carbon atoms, and n and m may independently be integers of 2 to 4.

More specifically, the tetrasulfide derivative represented by Chemical Formula 1 may be at least one selected from compounds represented by Chemical Formulas 1-1 to 1-4 below.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

.

.

Meanwhile, the tetrasulfide derivative according to the present invention is prepared by reacting a compound represented by the following Chemical Formula 3 with thionyl chloride to prepare a compound represented by the Chemical Formula 4 (step a), and a compound represented by the Chemical Formula 4 It may be prepared by reacting (step b) with disodium tetrasulfide.

[Formula 3]

[Formula 4]

In Formula 3 and Formula 4,

R _3a is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms, and o is 2 to 6 carbon atoms; is an integer

The compound represented by Chemical Formula 3 and thionyl chloride may be reacted by adjusting the amount used in consideration of an appropriate stoichiometric ratio that enables the compound represented by Chemical Formula 4 to be easily prepared. An excessive amount of thionyl chloride may be used relative to the compound, and specifically, the compound represented by Chemical Formula 3 and thionyl chloride may be used in a molar ratio of 1:1 to 1:2.

In addition, the compound represented by Chemical Formula 4 and disodium tetrasulfide may be reacted by adjusting the amount used in consideration of an appropriate stoichiometric ratio that allows the tetrasulfide derivative represented by Chemical Formula 1 to be easily prepared. For example, The compound represented by Formula 4 may be used in an excess amount compared to disodium tetrasulfide, and specifically, the compound represented by Formula 4 and disodium tetrasulfide are used in a molar ratio of 2:1 to 2.5:1 can

In addition, the reaction of step a may be carried out at a temperature of -10 ° C to 0 ° C for 30 minutes to 3 hours, and the reaction of step b is carried out at a temperature of 60 ° C to 90 ° C for 3 hours to 24 hours. it may be

Modified conjugated diene polymer

The present invention provides a modified conjugated diene-based polymer containing a tetrasulfide derivative-derived functional group represented by Chemical Formula 1 and having excellent filler affinity and thus excellent compounding properties.

The modified conjugated diene-based polymer according to an embodiment of the present invention includes a repeating unit derived from a conjugated diene-based monomer; and a functional group derived from the tetrasulfide derivative represented by Formula 1 above.

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

As a specific example, the modified conjugated diene-based polymer contains 80% to 100% by weight of 1,3-butadiene monomer-derived units, and optionally 20% by weight or less of other conjugated diene-based monomer-derived units copolymerizable with 1,3-butadiene. It may be included, and there is an effect that the content of 1,4-cis bonds in the polymer is not reduced within the above range. In this case, examples of the 1,3-butadiene monomer include 1,3-butadiene or derivatives thereof such as 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, or 2-ethyl-1,3-butadiene. and other conjugated diene-based monomers copolymerizable with the 1,3-butadiene include 2-methyl-1,3-pentadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 4 -Methyl-1,3-pentadiene, 1,3-hexadiene or 2,4-hexadiene, and the like, any one or two or more compounds of these may be used.

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

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

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

In addition, the modified conjugated diene-based polymer may have a molecular weight distribution (Mw / Mn) of 2.0 to 3.5, more specifically, may have a molecular weight distribution of 2.5 to 3.5, 2.5 to 3.2 or 2.6 to 3.0.

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

The modified conjugated diene-based polymer according to an embodiment of the present invention satisfies the above molecular weight distribution conditions, and has a weight average molecular weight (Mw) of 3 X 10 ⁵ to 1.5 X 10 ⁶ g/mol, and a number average The molecular weight (Mn) may be 1.0 X 10 ⁵ to 5.0 X 10 ⁵ g/mol, and when applied to a rubber composition within this range, excellent tensile properties and excellent processability improve the workability of the rubber composition, resulting in reduced kneading. It is easy, and there is an effect of excellent balance of mechanical properties and physical properties of the rubber composition. The weight average molecular weight may be, for example, 5 X 10 ⁵ to 1.2 X 10 ⁶ g/mol, or 5 X 10 ⁵ to 8 X 10 ⁵ g/mol, and the number average molecular weight may be, for example, 1.5 X 10 ⁵ to 3.5 X 10 ⁵ g/mol, or between 2.0 X 10 ⁵ and 2.7 X 10 ⁵ g/mol.

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

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

In addition, the modified conjugated diene-based polymer may have a vinyl content of 5% or less, more specifically, 2% or less, as measured by Fourier transform infrared spectroscopy. When the vinyl content in the polymer exceeds 5%, there is a concern that the abrasion resistance, crack resistance, and ozone resistance of the rubber composition including the vinyl content may be deteriorated.

Manufacturing method of modified conjugated diene-based polymer

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

The preparation method according to an embodiment of the present invention includes preparing 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 (S1); and reacting the active polymer with a tetrasulfide derivative represented by Chemical Formula 1 (S2).

[Formula 1]

In Formula 1, R ₁ , R ₂ , n and m are as defined above.

S1 phase

The step S1 is a step of preparing an active polymer including an organometallic moiety by polymerizing a conjugated diene-based monomer, and may be performed by polymerizing the conjugated diene-based monomer in the presence of a catalyst composition containing a neodymium compound in a hydrocarbon solvent.

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

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

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

The catalyst composition may be used in an amount such that the neodymium compound is 0.1 mmol to 0.5 mmol based on the total 100 g of the conjugated diene-based monomers, and specifically, the neodymium compound is used based on the total 100 g of the conjugated diene-based monomers. It may be used in an amount of 0.1 mmol to 0.4 mmol, more specifically 0.1 mmol to 0.25 mmol.

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

The neodymium compound may be a compound represented by Formula 2 below.

[Formula 2]

In Formula 2, R _a to R _c are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms, provided that R _a to R _c are not all hydrogen at the same time.

More specifically, the neodymium compound is Nd(2-ethylhexanoate) ₃ , Nd(2,2-dimethyl decanoate) ₃ , Nd(2,2-diethyl decanoate) ₃ , Nd(2, 2-dipropyl decanoate) ₃ , Nd(2,2-dibutyl decanoate) ₃ , Nd(2,2-dihexyl decanoate) ₃ , Nd(2,2-dioctyl decanoate) ₃ , Nd(2-ethyl-2-propyl decanoate) ₃ , Nd(2-ethyl-2-butyl decanoate) ₃ , Nd(2-ethyl-2-hexyl decanoate) ₃ , Nd(2 -Propyl-2-butyl decanoate) ₃ , Nd(2-propyl-2-hexyl decanoate) ₃ , Nd(2-propyl-2-isopropyl decanoate) ₃ , Nd(2-butyl-2 -hexyl decanoate) ₃ , Nd(2-hexyl-2-octyl decanoate) ₃ , Nd(2,2-diethyl octanoate) ₃ , Nd(2,2-dipropyl octanoate) ₃ , Nd(2,2-dibutyl octanoate) ₃ , Nd(2,2-dihexyl octanoate) ₃ , Nd(2-ethyl-2-propyl octanoate) ₃ , Nd(2-ethyl- 2-hexyl octanoate) ₃ , Nd(2,2-diethyl nonanoate) ₃ , Nd(2,2-dipropyl nonanoate) ₃ , Nd(2,2-dibutyl nonanoate) _{3 1} selected from the group consisting of Nd(2,2-dihexyl nonanoate) ₃ , Nd(2-ethyl-2-propyl nonanoate) ₃ and Nd(2-ethyl-2-hexyl nonanoate) 3 There may be more than one species.

In addition, as another example, considering the excellent solubility in solvents without concern for oligomerization, the conversion rate to catalytically active species, and the excellent effect of improving catalytic activity, the neodymium compound is more specifically R _a in Formula 2 An alkyl group having 4 to 12 carbon atoms, and R _b and R _c are each independently hydrogen or an alkyl group having 2 to 8 carbon atoms, provided that R _b and R _c may not be hydrogen at the same time.

As a more specific example, in Formula 2, R _a is an alkyl group having 6 to 8 carbon atoms, R _b and R _c may each independently be hydrogen or an alkyl group having 2 to 6 carbon atoms, wherein R _b and R _c are It may not be hydrogen at the same time, and specific examples thereof include Nd(2,2-diethyl decanoate) ₃ , Nd(2,2-dipropyl decanoate) ₃ , Nd(2,2-dibutyl decanoate) ) ₃ , Nd(2,2-dihexyl decanoate) ₃ , Nd(2,2-dioctyl decanoate) ₃ , Nd(2-ethyl-2-propyl decanoate) ₃ , Nd(2- Ethyl-2-butyl decanoate) ₃ , Nd(2-ethyl-2-hexyl decanoate) ₃ , Nd(2-propyl-2-butyl decanoate) ₃ , Nd(2-propyl-2-hexyl Decanoate) ₃ , Nd(2-propyl-2-isopropyl decanoate) ₃ , Nd(2-butyl-2-hexyl decanoate) ₃ , Nd(2-hexyl-2-octyl decanoate) ₃ , Nd(2-t-butyl decanoate) ₃ , Nd(2,2-diethyl octanoate) ₃ , Nd(2,2-dipropyl octanoate) ₃ , Nd(2,2-diethyl octanoate) butyl octanoate) ₃ , Nd(2,2-dihexyl octanoate) ₃ , Nd(2-ethyl-2-propyl octanoate) ₃ , Nd(2-ethyl-2-hexyl octanoate) ₃ , Nd(2,2-diethyl nonanoate) ₃ , Nd(2,2-dipropyl nonanoate) ₃ , Nd(2,2-dibutyl nonanoate) ₃ , Nd(2,2-dibutyl nonanoate) 3 hexyl nonanoate) ₃ , Nd (2-ethyl-2-propyl nonanoate) ₃ and Nd (2-ethyl-2-hexyl nonanoate) ₃ may be at least one selected from the group consisting of Neodymium compounds are Nd(2,2-diethyl decanoate) ₃ , Nd(2,2-dipropyl decanoate) ₃ , Nd(2,2-dibutyl decanoate) ₃ , Nd(2, 2-dihexyl decanoate) ₃ , and Nd(2,2-dioctyl decanoate) ₃ .

More specifically, in Chemical Formula 2, 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-based compound represented by Chemical Formula 2 includes a carboxylate ligand including an alkyl group having a carbon number of 2 or more as a substituent at the α (alpha) position, thereby inducing a steric change around the neodymium central metal, thereby inducing a steric change in the compound. It is possible to block the coagulation of the liver, and thus, there is an effect of suppressing oligomerization. In addition, such a neodymium-based compound has a high solubility in a solvent and a high conversion rate to catalytically active species due to a reduced ratio of neodymium located in the central portion where conversion to catalytically active species is difficult.

Also, the solubility of the neodymium compound according to an embodiment of the present invention may be about 4 g or more per 6 g of the non-polar solvent at room temperature (25° C.).

In the present invention, the solubility of neodymium-based compounds means the degree of clear dissolution without turbidity, and excellent catalytic activity can be exhibited by exhibiting such high solubility.

In addition, the neodymium compound according to an embodiment of the present invention may be used in the form of a reactant with a Lewis base. This reactant has the effect of improving the solubility of the neodymium compound in a solvent by means of a Lewis base and being able to store it in a stable state for a long period of time. For example, the Lewis base may be used in an amount 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 organic phosphorus compound, or monohydric or dihydric alcohol.

Meanwhile, the catalyst composition may further include at least one of an alkylating agent, a halide, and a conjugated diene-based monomer together with a neodymium compound.

That is, the catalyst composition according to an embodiment of the present invention may include a neodymium compound and further include at least one of an alkylating agent, a halide, and a conjugated diene-based monomer.

Hereinafter, the (a) alkylating agent, (b) halide, and (c) conjugated diene-based monomer will be separately described in detail.

(a) an 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 usually used as an alkylating agent in the preparation of diene-based polymers, and is soluble in a polymerization solvent, such as an organoaluminum compound, an organomagnesium compound, or an organolithium compound, and forms a metal-carbon bond. It may contain organometallic compounds.

Specifically, the organic aluminum compounds include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminium, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, and 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-Tolylluminum Hydride, Dibenzylaluminum Hydride, Phenylethylaluminum Hydride, Phenyl-n-Propylaluminum Hydride, Phenylisopropylaluminium Hydride, Phenyl-n-Butylaluminum Hydride Ride, phenyl isobutyl aluminum hydride, phenyl-n-octyl aluminum hydride, p-tolylethyl aluminum hydride, p-tolyl-n-propyl aluminum hydride, p-tolyl isopropyl aluminum hydride, p-tolyl- n-butylaluminium hydride, p-tolylisobutylaluminium hydride, p-tolyl-n-octylaluminium hydride, benzylethylaluminium hydride, benzyl-n-propylaluminium hydride, benzylisopropylaluminium hydride, benzyl dihydrocarbyl aluminum hydride such as n-butylaluminum hydride, benzylisobutylaluminum hydride or benzyl-n-octylaluminum 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 A hydride etc. are mentioned. Examples of the organomagnesium compound include alkylmagnesium compounds such as diethylmagnesium, di-n-propylmagnesium, diisopropylmagnesium, dibutylmagnesium, dihexylmagnesium, diphenylmagnesium, or dibenzylmagnesium, and the like. Examples of the organolithium compound include alkyl lithium compounds such as n-butyllithium and the like.

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 of Formula 3a below or a cyclic aluminoxane of Formula 3b below.

[Formula 3a]

[Formula 3b]

In Formulas 3a and 3b, 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 integers of 1 or more, specifically 1 to 100 , more specifically an integer from 2 to 50.

More specifically, the aluminoxane is methyl aluminoxane (MAO), modified methyl aluminoxane (MMAO), ethyl aluminoxane, n-propyl aluminoxane, isopropyl aluminoxane, butyl aluminoxane, isobutyl aluminoxane, n -Pentylaluminoxane, neopentylaluminoxane, n-hexylaluminoxane, n-octylaluminoxane, 2-ethylhexylaluminoxane, cyclohexylaluminoxane, 1-methylcyclopentylaluminoxane, phenylaluminoxane or 2,6- 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 (4).

[Formula 4]

In Formula 4, R is as defined above, and m and n may be independently integers of 2 or more. In addition, in Formula 5, Me represents a methyl group.

Specifically, in Formula 4, R is an alkyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, It may be an arylalkyl group having 7 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an allyl group, or an alkynyl group having 2 to 20 carbon atoms, and more specifically, an ethyl group, an isobutyl group, a hexyl group, or an octyl group having 2 carbon atoms such as to 10, and more specifically, it may be an isobutyl group.

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

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

In addition, the catalyst composition according to an embodiment of the present invention may include the alkylating agent in a molar ratio of 1 to 200, specifically, 1 to 100, and more specifically, 3 to 20, based on 1 mole of the neodymium compound. there is. If the alkylating agent is included in a molar ratio exceeding 200, it is not easy to control the catalytic reaction during polymer production, and there is a concern that an excessive amount of the alkylating agent may cause a side reaction.

(b) halides

The halide is not particularly limited, but includes, for example, a simple halogen, an interhalogen compound, a hydrogen halide, an organic halide, a non-metal halide, a metal halide, or an organometal halide. One or a mixture of two or more may be used. Among them, in view of 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 organic halides, metal halides and organometal halides may be used as the halide.

Examples of the halogen element include fluorine, chlorine, bromine, and iodine.

In addition, the interhalogen compound may include iodine monochloride, iodine monobromide, iodine trichloride, iodine pentafluoride, iodine monofluoride or iodine trifluoride.

In addition, hydrogen fluoride, hydrogen chloride, hydrogen bromide or hydrogen iodide may be mentioned as the hydrogen halide.

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

In addition, the non-metal halide includes phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, phosphorus oxychloride, phosphorus oxybromide, boron trifluoride, boron trichloride, boron tribromide, silicon tetrafluoride, silicon tetrachloride (SiCl ₄ ), silicon tetrabromide , arsenic trichloride, arsenic tribromide, selenium tetrachloride, selenium tetrabromide, tellurium tetrachloride, tellurium tetrabromide, silicon tetraiodide, arsenic triiodide, tellurium tetraiodide, boron triiodide, phosphorus triiodide, phosphorus oxyiodide or selenium tetraiodide, etc. can be heard

In addition, the metal halide is 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 diiodide, tetraiodide Germanium, tin tetraiodide, tin diiodide, antimony triiodide, or magnesium diiodide.

In addition, the organometallic halide includes dimethylaluminum chloride, diethylaluminum chloride, dimethylaluminum bromide, diethylaluminum bromide, dimethylaluminum fluoride, diethylaluminum fluoride, methylaluminum dichloride, ethylaluminum dichloride, methylaluminum dichloride Bromide, Ethylaluminium Dibromide, Methylaluminium Difluoride, Ethylaluminium Difluoride, Methylaluminum Sesquichloride, Ethylaluminium Sesquichloride (EASC), Isobutylaluminium Sesquichloride, Methylmagnesium Chloride, Methylmagnesium Bromide, Ethyl Magnesium chloride, ethylmagnesium bromide, n-butylmagnesium chloride, n-butylmagnesium bromide, phenylmagnesium chloride, phenylmagnesium bromide, benzylmagnesium chloride, trimethyltin chloride, trimethyltin bromide, triethyltin chloride, triethyltin bromide, di -t-butyltin dichloride, di-t-butyltin dibromide, di-n-butyltin dichloride, di-n-butyltin dibromide, tri-n-butyltin chloride, tri-n-butyltin bromide , methyl magnesium iodide, dimethyl aluminum iodide, diethyl aluminum iodide, di-n-butyl aluminum iodide, di-isobutyl 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 iodide Odide, n-butylmagnesium iodide, isobutylmagnesium iodide, phenylmagnesium iodide, benzylmagnesium iodide, trimethyltin iodide, triethyltin iodide, tri-n-butyltin iodide Odide, di-n-butyltin diiodide or di-t-butyltin diiodide, etc. are mentioned.

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

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

Specifically, in the compound containing the non-coordinating anion, the non-coordinating anion is a sterically bulky anion that does not form a coordination bond with the active center of the catalyst system due to steric hindrance, such as tetraarylborate anion or tetraaryl fluoride. borate anions and the like. In addition, the compound containing the non-coordinating anion may include a carbonium cation such as a triaryl carbonium cation together with the non-coordinating anion; It may contain an ammonium cation such as N,N-dialkyl anilinium cation, or a counter cation such as phosphonium cation. More specifically, the compound containing the non-coordinating anion is triphenyl carbonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) 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. aryl groups with the same strong electron-withdrawing properties).

(c) conjugated diene-based monomers

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

In the present invention, the "preforming" means a catalyst composition containing a neodymium compound, an alkylating agent and a halide, that is, when diisobutylaluminum hydride (DIBAH) is included in the catalyst system, various In order to reduce the possibility of generating active species in the catalyst composition, a small amount of conjugated diene-based monomers such as 1,3-butadiene are added, and it may mean that pre-polymerization is performed in the catalyst composition system together with the addition of 1,3-butadiene. there is. In addition, "premix" may mean a state in which each compound is uniformly mixed without polymerization in the catalyst composition system.

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, 1 to 1 mole of the neodymium compound. mol to 100 mol, specifically 10 mol to 50 mol, or 20 mol to 50 mol.

The catalyst composition according to an embodiment of the present invention is at least one of the aforementioned neodymium compound and an alkylating agent, a halide and a conjugated diene-based monomer in an organic solvent, specifically a neodymium compound, an alkylating agent and a halide, and optionally a conjugated diene-based monomer. It can be prepared by mixing monomers. In this case, the organic solvent may be a non-polar solvent having no reactivity with the components of the catalyst composition. Specifically, the non-polar solvent is n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, isopentane, isohexane, isopentane, isooctane, 2,2-dimethylbutane, cyclo linear, branched or cyclic aliphatic hydrocarbons having 5 to 20 carbon atoms such as pentane, cyclohexane, methylcyclopentane or methylcyclohexane; mixed solvents of aliphatic hydrocarbons having 5 to 20 carbon atoms, such as petroleum ether, petroleum spirits, or kerosene; Or it may be an aromatic hydrocarbon-based solvent such as benzene, toluene, ethylbenzene, xylene, etc., and any one or a mixture of two or more of these may be used. More specifically, the non-polar solvent may be a linear, branched or cyclic aliphatic hydrocarbon having 5 to 20 carbon atoms or a mixture of aliphatic hydrocarbons, more specifically n-hexane, cyclohexane, or a mixture thereof. can

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

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

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

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

Meanwhile, the polymerization of step 1 may be carried out in a continuous polymerization in a polymerization reactor including at least two reactors or in a batch reactor.

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

Here, the constant temperature polymerization refers to a polymerization method comprising the step of polymerizing with the reaction heat itself without optionally applying heat after the introduction of the catalyst composition, and the elevated temperature polymerization is a polymerization method in which the temperature is increased by arbitrarily applying heat after the introduction of the catalyst composition The isothermal polymerization represents a polymerization method in which the temperature of a reactant is kept constant by adding heat after adding the catalyst composition to increase the heat or to take away the heat.

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

The polymerization may be carried out at a temperature range of -20 ° C to 200 ° C, specifically 50 ° C to 150 ° C, more specifically 10 ° C to 120 ° C or 60 ° C to 90 ° C in a temperature range of 15 minutes to It can be done for 3 hours. If the temperature during the polymerization exceeds 200 ° C, it is difficult to sufficiently control the polymerization reaction, there is a concern that the cis-1,4 bond content of the resulting conjugated diene polymer may be lowered, and if the temperature is less than -20 ° C, polymerization There is a possibility that the reaction rate and efficiency may decrease.

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

S2 phase

The step S2 is a step of preparing a modified conjugated diene-based polymer having a functional group by modifying or coupling the active polymer, and may be performed by reacting the active polymer with a tetrasulfide derivative represented by Formula 1.

The tetrasulfide derivative may be used in an amount of 0.5 to 20 moles based on 1 mole of the neodymium compound in the catalyst composition. Specifically, the modifier may be used in an amount of 1 to 15 moles based on 1 mole of the neodymium compound in the catalyst composition, and more specifically, 1 to 10 moles based on 1 mole of the neodymium compound in the catalyst composition.

In addition, the reaction of step S2 may be performed at 0 ° C to 90 ° C for 1 minute to 5 hours.

After completion of the reaction in 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.

In the manufacturing method according to an embodiment of the present invention, a modified conjugated diene-based polymer can be obtained by desolvation treatment such as steam stripping or vacuum drying treatment to lower the partial pressure of the solvent through the supply of steam after step S2. . In addition, among the reaction products obtained as a result of the above reaction, an unmodified, active polymer may be included together with the above-described modified conjugated diene polymer.

rubber composition

Furthermore, the present invention provides a rubber composition containing the conjugated diene-based polymer and a molded article manufactured from the rubber composition.

In the rubber composition according to an embodiment of the present invention, the modified conjugated diene-based polymer is contained in an amount of 0.1 wt% or more and 100 wt% or less, specifically, 10 wt% to 100 wt%, and more specifically, 20 wt% to 90 wt%. may include If the content of the modified conjugated diene-based polymer is less than 0.1% by weight, as a result, the effect of improving the abrasion resistance and crack resistance of a molded product manufactured using the rubber composition, for example, a tire, may be insignificant.

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

The rubber component may be natural rubber or synthetic rubber, for example, natural rubber (NR) including cis-1,4-polyisoprene; Modified natural rubbers such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber obtained by modifying or refining 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, halogenated butyl rubber, and the like, and any one or a mixture of two or more of these may be used.

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

The carbon black-based filler is not particularly limited, but may have, for example, a nitrogen adsorption specific surface area (N ₂ SA, measured in accordance with JIS K 6217-2: 2001) of 20 m 2 /g to 250 m 2 /g. In addition, the carbon black may have a dibutyl phthalate oil absorption (DBP) of 80 cc/100g to 200 cc/100g. If the nitrogen adsorption specific surface area of the carbon black exceeds 250 m ² /g, the processability of the rubber composition may deteriorate, and if it is less than 20 m ² /g, the reinforcing performance of the carbon black may be insignificant. In addition, if the DBP oil absorption amount of the carbon black exceeds 200 cc/100g, the processability of the rubber composition may deteriorate, and if it is less than 80 cc/100g, the reinforcing performance by the carbon black may be insignificant.

In addition, the silica is not particularly limited, but may be, for example, wet silica (hydrous silicic acid), dry silica (silicic anhydride), calcium silicate, aluminum silicate or colloidal silica. Specifically, the silica may be wet-processed silica, which has the most remarkable effect of improving fracture characteristics and the effect of combining wet grip. In addition, the silica has a nitrogen adsorption surface area per gram (N ₂ SA) of 120 m 2 / g to 180 m 2 / g, and a cetyl trimethyl ammonium bromide (CTAB) adsorption specific surface area of 100 m 2 / g to 200 m2/g. If the nitrogen adsorption specific surface area of the silica is less than 120 m 2 /g, there is a fear that the reinforcing performance by silica may decrease, and if it exceeds 180 m 2 /g, the processability of the rubber composition may decrease. In addition, if the CTAB adsorption specific surface area of the silica is less than 100 m 2 / g, there is a possibility that the reinforcing performance by the silica filler may decrease, and if it exceeds 200 m 2 / g, the processability of the rubber composition may decrease.

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

The silane coupling agent is specifically 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-dimethylthiocarbamoyltetrasul 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 these may be used. More specifically, 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 a sulfur powder, and may be included in an amount of 0.1 part by weight to 10 parts by weight based on 100 parts by weight of the rubber component. When included in the above content range, it is possible to secure the necessary elastic modulus and strength of the vulcanized rubber composition, and at the same time, it is possible to obtain low fuel consumption.

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

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

In addition, the process oil acts as a softener in the rubber composition, specifically, it may be a paraffinic, naphthenic, or aromatic compound, and more specifically, considering tensile strength and abrasion resistance, aromatic process oil is a And considering low-temperature characteristics, naphthenic or paraffinic process oils may be used. The process oil may be included in an amount of 100 parts by weight or less with respect to 100 parts by weight of the rubber component, and when included in the above amount, it is possible to prevent a decrease in tensile strength and low heat generation (low fuel consumption) of vulcanized rubber.

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

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

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

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

Hereinafter, the present invention will be described in more detail by examples and experimental examples. However, the following examples and experimental examples are for exemplifying the present invention, and the scope of the present invention is not limited only to these.

Preparation Example 1

(1) Preparation of 1- (2- (2- (2-chloroethoxy) ethoxy) ethoxy) butane (1- (2- (2- (2-chloroethoxy) ethoxy) ethoxy) butane

In an ice bath, 20 g of triethylene glycol monobutyl ether was added to a 250 ml round bottom flask and dissolved in 100 ml of dichloromethane (DCM). Thereafter, 700 mg of dimethylformamide (DMF) was added as a catalytic amount and reacted while slowly adding 7 ml of thionyl chloride. When the reaction was completed, water was added to perform extraction, and after removing moisture from the organic layer with sodium sulfate, the mixture was filtered. Thereafter, the solvent was removed under reduced pressure to obtain 1-(2-(2-(2-chloroethoxy)ethoxy)ethoxy)butane as an intermediate (16 g, yield: 73%). %). It was confirmed that the intermediate was formed by observing the ¹ H nuclear magnetic resonance spectroscopy spectrum.

¹ H NMR (500 MHz, CDCl ₃ ) δ 4.05 (2H, m), 3.64 (2H, t), 3.62 (6H, m), 3.48 (2H, t), 3.36 (2H, t), 1.47 (2H, t), 1.27 (2H, q), 0.82 (3H, t).

(2) Preparation of a compound represented by Formula 1-1

5 g of the above intermediate was placed in a 50 ml round bottom flask and dissolved in 5 ml of ethanol. Thereafter, 1.8 g of disodium tetrasulfide was added and reacted at 85°C. After the reaction was completed, the solvent was removed under reduced pressure, dissolved in dichloromethane, and then filtered to remove sodium chloride. Thereafter, the solvent was removed under reduced pressure to obtain a compound represented by Formula 1-1 (5.3 g, yield 94%). By observing the ¹ H nuclear magnetic resonance spectroscopy spectrum, it was confirmed that the compound represented by Chemical Formula 1-1 was formed.

[Formula 1-1]

¹ H NMR (500 MHz, CDCl ₃ ) δ 3.72 (4H, m), 3.67 (12H, m), 3.61 (4H, m), 3.58 (4H, m), 3.46 (4H, t), 1.57 (4H, t), 1.36 (4H, q), 0.91 (9H, t).

Preparation Example 2

(1) Preparation of 1-chloro-2- (2- (2-ethoxy) ethoxy) ethoxy) ethane (1-chloro-2- (2- (2-ethoxy) ethoxy) ethoxy) ethane

In an ice bath, 10 g of triethylene glycol monoethyl ether was added to a 100 ml round bottom flask and 56 ml of dichloromethane (DCM) was added to dissolve the mixture. Thereafter, 410 mg of dimethylformamide (DMF) was added as a catalytic amount and reacted while slowly adding 4 ml of thionyl chloride. When the reaction was completed, water was added to perform extraction, and after removing moisture from the organic layer with sodium sulfate, the mixture was filtered. Thereafter, the solvent was removed under reduced pressure to obtain 1-chloro-2-(2-(2-ethoxy)ethoxy)ethoxy)ethane as an intermediate (5 g, yield: 45%). It was confirmed that the intermediate was formed by observing the ¹ H nuclear magnetic resonance spectroscopy spectrum.

¹ H NMR (500 MHz, CDCl ₃ ) δ 4.00 (2H, m), 3.64 (2H, t), 3.62 (6H, m), 3.48 (2H, t), 3.36 (2H, t), 1.47 (2H, t), 1.27 (2H, q), 0.82 (3H, t).

(2) Preparation of a compound represented by Formula 1-2

5 g of the above intermediate was placed in a 50 ml round bottom flask and dissolved in 5 ml of ethanol. Thereafter, 2.1 g of disodium tetrasulfide was added and reacted at 85°C. After the reaction was completed, the solvent was removed under reduced pressure, dissolved in dichloromethane, and then filtered to remove sodium chloride. Thereafter, the solvent was removed under reduced pressure to obtain a compound represented by Formula 1-2 (4.8 g, yield 83%). By observing the ¹ H nuclear magnetic resonance spectroscopy spectrum, it was confirmed that the compound represented by Chemical Formula 1-2 was formed.

[Formula 1-2]

¹ H NMR (500 MHz, CDCl ₃ ) δ 3.62 (4H, m), 3.54 (12H, m), 3.43 (4H, m), 3.36 (4H, m), 0.90 (6H, t).

Preparation Example 3

(1) Preparation of ((2- (2-chloroethoxy) ethoxy) methyl) benzene ((2- (2-chloroethoxy) ethoxy) methyl) benzene

In an ice bath, 20 g of diethylene glycol monobenzyl ether was added to a 250 ml round bottom flask and 100 ml of dichloromethane (DCM) was added to dissolve the mixture. Thereafter, 744 mg of dimethylformamide (DMF) was added as a catalytic amount and reacted while slowly adding 7.4 ml of thionyl chloride. When the reaction was completed, water was added to perform extraction, and after removing moisture from the organic layer with sodium sulfate, the mixture was filtered. Thereafter, the solvent was removed under reduced pressure to obtain an intermediate ((2-(2-chloroethoxy)ethoxy)methyl)benzene (20 g, yield: 91%). It was confirmed that the intermediate was formed by observing the ¹ H nuclear magnetic resonance spectroscopy spectrum.

¹ H NMR (500 MHz, CDCl ₃ ) δ 7.31 (5H, m), 4.57 (2H, s), 3.76 (2H, t), 3.70 (2H, t), 3.64 (4H, m).

(2) Preparation of a compound represented by Formula 1-3

10 g of the above intermediate was placed in a 50 ml round bottom flask and dissolved in 15 ml of ethanol. Thereafter, 3.9 g of disodium tetrasulfide was added and reacted at 85°C. After the reaction was completed, the solvent was removed under reduced pressure, dissolved in dichloromethane, and then filtered to remove sodium chloride. Thereafter, the solvent was removed under reduced pressure to obtain a compound represented by Formula 1-3 (9.8 g, yield 86%). By observing the ¹ H nuclear magnetic resonance spectroscopy spectrum, it was confirmed that the compound represented by Chemical Formula 1-3 was formed.

[Formula 1-3]

¹ H NMR (500 MHz, CDCl ₃ ) δ 7.36 (10H, m), 4.55 (4H, s), 3.75 (4H, t), 3.64 (8H, m), 3.20 (4H, m).

Production Example 4

(1) Preparation of 2- (2- (2- (2-chloroethoxy) ethoxy) ethoxy) propane (2- (2- (2- (2-chloroethoxy) ethoxy) ethoxy) propane)

In an ice bath, 10 g of triethylene glycol monoisopropyl ether was added to a 100 ml round bottom flask and 52 ml of dichloromethane (DCM) was added to dissolve the mixture. Thereafter, 380 mg of dimethylformamide (DMF) was added as a catalyst and reacted while slowly adding 3.8 ml of thionyl chloride. When the reaction was completed, water was added to perform extraction, and after removing moisture from the organic layer with sodium sulfate, the mixture was filtered. Thereafter, the solvent was removed under reduced pressure to obtain 2-(2-(2-(2-chloroethoxy)ethoxy)ethoxy)propane as an intermediate (8.2 g, yield: 74%). It was confirmed that the intermediate was formed by observing the ¹ H nuclear magnetic resonance spectroscopy spectrum.

¹ H NMR (500 MHz, CDCl ₃ ) δ 4.10 (2H, m), 3.80 (2H, t), 3.65 (7H, m), 3.57 (2H, t), 1.10 (6H, d).

(2) Preparation of a compound represented by Formula 1-4

8.2 g of the above intermediate was placed in a 50 ml round bottom flask and dissolved in 12 ml of ethanol. Thereafter, 3.2 g of disodium tetrasulfide was added and reacted at 85°C. After the reaction was completed, the solvent was removed under reduced pressure, dissolved in dichloromethane, and then filtered to remove sodium chloride. Thereafter, the solvent was removed under reduced pressure to obtain a compound represented by Formula 1-4 (8.9 g, yield 95%). By observing the ¹ H nuclear magnetic resonance spectroscopy spectrum, it was confirmed that the compound represented by Formula 1-4 was formed.

[Formula 1-4]

¹ H NMR (500 MHz, CDCl ₃ ) δ 3.85 (8H, m), 3.60 (14H, m), 3.55 (4H, t), 1.15 (12H, d).

Example 1

After putting 900 g of 1,3-butadiene and 6,600 g of n-hexane in a 20L autoclave reactor, the temperature inside the reactor was raised to 70°C. After the catalyst composition was added thereto, polymerization was performed for 60 minutes. At this time, the catalyst composition is added to neodymium versatate (Nd (2-ethylhexanoate) ₃ ), Solvay Co.) in n-hexane solvent, diisobutyl aluminum hydride (DIBAH), diethyl aluminum Chloride (DEAC) was sequentially added at a molar ratio of neodymium versatate:DIBAH:DEAC=1:16:2.4, and then mixed. After adding the ethylbenzene solution containing the compound of Formula 1-1 prepared in Preparation Example 1, denaturation was performed at 70° C. for 30 minutes (Nd: Formula 1 = 1: 0.5 molar ratio). Then, the reaction was terminated by adding a hexane solution containing 1.0 g of a polymerization terminator and a solution in which 30% by weight of WINGSTAY (Eliokem SAS, France), an antioxidant, was dissolved in hexane, and the resulting heavy compound was heated with steam. It was put in hot water and stirred to remove the solvent, and then roll dried to remove the remaining amount of solvent and water to prepare a modified butadiene polymer.

Example 2

In Example 1, a modified butadiene polymer was prepared in the same manner as in Example 1, except that the compound of Formula 1-2 prepared in Preparation Example 2 was added instead of the compound of Formula 1-1.

Example 3

In Example 1, a modified butadiene polymer was prepared in the same manner as in Example 1, except that the compound of Formula 1-3 prepared in Preparation Example 3 was added instead of the compound of Formula 1-1.

Example 4

In Example 1, a modified butadiene polymer was prepared in the same manner as in Example 1, except that the compound of Formula 1-4 prepared in Preparation Example 4 was added instead of the compound of Formula 1-1.

Comparative Example 1

As an unmodified butadiene polymer, CB25 (Lanxess Co.) was used as a comparative example.

Comparative Example 2

After putting 900 g of 1,3-butadiene and 6,600 g of n-hexane in a 20L autoclave reactor, the temperature inside the reactor was raised to 70°C. After the catalyst composition was added thereto, polymerization was performed for 60 minutes. At this time, the catalyst composition is added to neodymium versatate (Nd (2-ethylhexanoate) ₃ ), Solvay Co.) in n-hexane solvent, diisobutyl aluminum hydride (DIBAH), diethyl aluminum Chloride (DEAC) was sequentially added at a molar ratio of neodymium versatate:DIBAH:DEAC=1:16:2.4, and then mixed. Then, the reaction was terminated by adding a hexane solution containing 1.0 g of a polymerization terminator and a solution in which 30% by weight of WINGSTAY (Eliokem SAS, France), an antioxidant, was dissolved in hexane, and the resulting heavy compound was heated with steam. It was put in warm water and stirred to remove the solvent, and then roll dried to remove the residual amount of solvent and water to prepare an unmodified butadiene polymer.

Comparative Example 3

In Example 1, a modified butadiene polymer was prepared in the same manner as in Example 1, except that the compound of Formula a (CAS NO. 1807933-39-6) was added instead of the compound of Formula 1-1.

[Formula a]

Experimental Example 1

The physical properties of the polymers of Examples 1 to 4 and Comparative Examples 1 to 3 were measured in the following manner, and the results are shown in Table 1 below.

(1) weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (MWD)

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

(2) Mooney viscosity (RP, Raw polymer)

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

division Example comparative example One 2 3 4 One 2 3 GPC result Mn (x10 ⁵ g/mol) 2.50 2.72 1.99 2.25 2.64 2.13 2.30 Mw(x10 ⁵ g/mol) 5.12 5.55 5.43 5.31 6.18 4.92 5.50 MWD (Mw/Mn) 2.04 2.04 2.72 2.36 2.35 2.31 2.39 Mooney Viscosity (RP) (ML1+4, @100℃) (MU) 45 48 47 46 46 46 44

In Table 1, the weight average molecular weight of the modified butadiene polymers of Examples 1 to 4 was increased compared to the unmodified butadiene polymer of Comparative Example 2, and through this, the modified butadiene polymers of Examples 1 to 4 had Formula 1- 1, Chemical Formula 1-2, Chemical Formula 1-3 or 1-4 can be expected to be modified by the compound.

Experimental Example 2

After preparing rubber compositions and rubber specimens using the polymers of Examples 1 to 4 and Comparative Examples 1 to 3, Mooney viscosity, tensile stress, 300% modulus, wear resistance and viscoelastic properties were measured in the following manner, respectively. measured. The results are shown in Table 2 below.

Specifically, the rubber composition includes 70 parts by weight of carbon black, 22.5 parts by weight of process oil, 2 parts by weight of an anti-aging agent (TMDQ), 3 parts by weight of zinc oxide (ZnO) and stearic acid (with 100 parts by weight of each polymer). stearic acid) to prepare each rubber composition by mixing 2 parts by weight. Thereafter, 2 parts by weight of sulfur, 2 parts by weight of a vulcanization accelerator (CZ) and 0.5 parts by weight of a vulcanization accelerator (DPG) were added to each of the above rubber compositions, mixed gently at 50 ° C. for 1.5 minutes at 50 rpm, and then using a roll at 50 ° C. Thus, a vulcanized compound in the form of a sheet was obtained. The obtained vulcanized mixture was vulcanized at 160° C. for 25 minutes to prepare a rubber specimen.

(1) Mooney viscosity (FMB, Final Master Batch) and Mooney viscosity difference (ΔMV)

Mooney viscosity (ML1+4, @100°C) (MU) was measured using each of the vulcanized formulations prepared above. Specifically, Mooney viscosity (MV) was measured under the condition of a rotor speed of 2 ± 0.02 rpm at 100 ° C using a large rotor with Monsanto's MV2000E. The sample used at this time was left at room temperature (23±3℃) for more than 30 minutes, then 27±3g was taken and filled into the die cavity, and Mooney viscosity (FMB) was measured while applying torque by operating the platen. did

In addition, the difference (ΔMV, FMB-RP) between the Mooney viscosity (RP) of each polymer and the Mooney viscosity (FMB) of the blend shown in Table 1 was calculated. At this time, the smaller the Mooney viscosity difference, the better the processability.

(2) tensile stress and 300% modulus

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

(3) Wear resistance (DIN wear test)

For each rubber specimen, a DIN abrasion test was performed according to ASTM D5963, and it was expressed as a DIN loss index (loss volume index: ARIA (Abrasion resistance index, Method A)).

(4) Viscoelastic properties

For the tan δ property, which is most important for low fuel consumption characteristics, the viscoelastic modulus (Tan δ) was measured at -60 ° C to 60 ° C at a frequency of 10 Hz, a prestrain of 3%, and a dynamic strain of 3% using DMTS 500N from Gabo, Germany. At this time, the Tanδ value at 0°C represents wet road resistance, and the Tanδ value at 60°C represents driving resistance characteristics (fuel economy).

division Example comparative example One 2 3 4 One 2 3 Mooney Viscosity (FMB) 95 96 94 95 95 93 98 △MV 50 48 47 49 49 47 54 tensile properties M-300% 111 110 107 112 100 108 106 tensile stress 108 107 109 111 100 105 108 wear resistance 100 101 99 102 100 99 100 Viscoelastic properties Tanδ @ 0℃ 99 100 101 98 100 100 97 Tanδ @ 60℃ 115 110 112 113 100 103 106

In Table 2, the resulting values of the tensile properties, abrasion resistance, and Tanδ value at 0 ° C of Examples 1 to 4 and Comparative Examples 2 and 3 are calculated by Equation 2 below based on the measured values of Comparative Example 1 and indexed (index), and the Tanδ value at 60 ° C was calculated and indexed by Equation 3 below.

[Equation 2]

Index=(measured value/standard value)×100

[Equation 3]

Index=(standard value/measurement value)×100

As shown in Table 2, Examples 1 to 4 showed improved processability and wear resistance at the same level as Comparative Examples 1 to 3, and improved tensile properties and viscoelastic properties.

Specifically, Examples 1 to 4 exhibited significantly improved driving resistance characteristics by about 7% to 12% while exhibiting improved tensile properties compared to Comparative Example 2, and improved abrasion resistance and improved abrasion resistance at an equivalent level compared to Comparative Example 3 It showed significantly improved driving resistance of about 4% to 8% while showing processability, tensile properties and wet road resistance.

Here, Comparative Example 2 is an unmodified polymer prepared in the same manner as in Example 1, except that it is not modified with the tetrasulfide derivative presented in the present invention, and Comparative Example 3 is a tetrasulfide derivative, but the tetrasulfide derivative and the present invention It is a modified polymer produced by modifying a compound with a different molecular structure.

On the other hand, it is known that wet road resistance and driving resistance are physical properties in a trade-off relationship with each other, and it is very difficult to simultaneously exhibit excellent characteristics of the two properties.

Through the above results, it can be confirmed that the tetrasulfide derivative represented by Formula 1 of the present invention is applied as a polymer modifier and has an excellent effect of improving the physical properties of the polymer, and furthermore, the modified conjugated diene-based polymer according to the present invention It can be seen that the inclusion of a functional group derived from a sulfide derivative, particularly a functional group having affinity for fillers, has excellent filler affinity, thereby improving compounding properties and significantly improving driving resistance.

Claims (14)

A tetrasulfide derivative represented by Formula 1 below:
[Formula 1]

In Formula 1,
R ₁ and R ₂ are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms,
n and m are independently of each other an integer of 2 to 6;
According to claim 1,
In Formula 1,
R ₁ and R ₂ are each independently an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, or an alkylaryl group having 7 to 13 carbon atoms,
n and m are independently of each other an integer of 2 to 4, which is a tetrasulfide derivative.
According to claim 1,
In Formula 1,
R ₁ and R ₂ are each independently an alkyl group having 1 to 6 carbon atoms or an aralkyl group having 7 to 13 carbon atoms;
n and m are independently of each other an integer of 2 to 4, which is a tetrasulfide derivative.
According to claim 1,
The tetrasulfide derivative represented by Formula 1 is at least one selected from compounds represented by Formulas 1-1 to 1-4 below:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

.
According to claim 1,
A tetrasulfide derivative as a modifier for conjugated diene-based polymers.
Repeating units derived from conjugated diene-based monomers; and
A modified conjugated diene-based polymer containing a functional group derived from the tetrasulfide derivative represented by Formula 1 of claim 1.
According to claim 6,
A modified conjugated diene-based polymer having a cis-1,4 bond content of 95% or more and a vinyl bond content of 5% or less.
According to claim 6,
The modified conjugated diene-based polymer wherein the tetrasulfide derivative represented by Formula 1 is at least one selected from compounds represented by Formulas 1-1 to 1-4 below:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

.
1) preparing an active polymer by polymerizing a conjugated diene-based monomer in a hydrocarbon solvent in the presence of a catalyst composition containing a neodymium compound; and
2) A method for producing a modified conjugated diene-based polymer comprising reacting the active polymer with a tetrasulfide derivative represented by Formula 1 below:
[Formula 1]

In Formula 1,
R ₁ and R ₂ are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms,
n and m are independently of each other an integer of 2 to 6;
According to claim 9,
The method for producing a modified conjugated diene-based polymer wherein the catalyst composition is used in an amount such that the neodymium compound is 0.1 mmol to 0.5 mmol based on 100 g of the conjugated diene-based monomer.
According to claim 9,
Method for producing a modified conjugated diene-based polymer wherein the neodymium compound is a compound represented by Formula 2 below:
[Formula 3]

In Formula 2,
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.
According to claim 9,
Method for producing a modified conjugated diene-based polymer wherein the tetrasulfide derivative represented by Formula 1 is used in an amount of 0.5 to 20 moles based on 1 mole of the neodymium compound.
A rubber composition comprising the modified conjugated diene-based polymer according to claim 6 and a filler.
According to claim 13,
The filler is a rubber composition that is carbon black.