KR20220066672A - Diimine derivative compound, modified conjugated diene-based polymer comprising a functional group derived from the same, method of preparing the polymer and rubber composition comprising the polymer - Google Patents

Abstract

The present invention relates to a diimine derivative compound comprising an amide group and an imine group useful as a polymer modifier, 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. The present invention provides the diimine derivative compound represented by chemical formula 1, the modified conjugated diene-based polymer comprising a functional group derived therefrom, a preparation method of the polymer, and the rubber composition comprising the polymer.

Description

A diimine derivative compound, a modified conjugated diene-based polymer comprising a functional group derived therefrom, a method for producing the polymer, and a rubber composition comprising the polymer TECHNICAL FIELD METHOD OF PREPARING THE POLYMER AND RUBBER COMPOSITION COMPRISING THE POLYMER}

The present invention relates to a diimine derivative compound containing an imine group and an amide group useful as a polymer modifier, a modified conjugated diene-based polymer containing a functional group derived therefrom, a method for preparing the polymer, and a rubber composition comprising the polymer.

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

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

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

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

Accordingly, in a living polymer obtained by coordination polymerization using a catalyst composition containing a lanthanum-based rare earth element compound as a method for increasing the dispersibility of BR and fillers such as silica or carbon black, the living active ends are treated with a specific modifier A method of denaturation has been developed. However, in the case of the terminal-modified polymer, the affinity with the filler is improved to improve compounding properties, such as tensile properties and viscoelastic properties.

In addition, when preparing a rubber composition by mixing SBR or BR with a filler such as silica or carbon black, 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. An attempt was made to improve the compounding properties and compounding processability by increasing the dispersibility of the filler, but the compounding property improvement effect was not obtained.

JP 5172663 B2

The present invention has been devised to solve the problems of the prior art, and by containing an imine group and an amide group in the molecule, it reacts with the polymer active site to introduce a functional group into the polymer, thereby improving the physical properties of the polymer such as filler affinity. An object of the present invention is to provide a useful diimine derivative compound.

Another 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 diimine derivative compound.

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

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 diimine derivative compound represented by the following formula (1):

[Formula 1]

In Formula 1,

R ₁ to R ₃ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms substituted or unsubstituted with a substituent,

R ₄ and R ₅ are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms, or a divalent heterohydrocarbon group having 1 to 20 carbon atoms including at least one hetero element selected from N, O and S,

R ₆ to R ₉ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms substituted or unsubstituted with a substituent, or R ₆ and R ₇ and R ₈ and R ₉ are each connected to each other and saturated with 3 to 20 carbon atoms Or to form an unsaturated ring group,

The substituents are an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 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, an alkylaryl group having 7 to 20 carbon atoms. , a C 1 to C 20 heteroalkyl group, or a C 2 to C 20 heterocyclic group.

In addition, the present invention is a repeating unit derived from a conjugated diene-based monomer; And it provides a modified conjugated diene-based polymer comprising a functional group derived from the diimine derivative compound represented by the 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 comprising a neodymium compound in a hydrocarbon solvent (S1); And it provides a method for producing the modified conjugated diene-based polymer comprising the step (S2) of reacting the active polymer with a diimine derivative compound represented by the following formula (1):

[Formula 1]

In Formula 1,

R ₁ to R ₃ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms substituted or unsubstituted with a substituent,

R ₄ and R ₅ are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms, or a divalent heterohydrocarbon group having 1 to 20 carbon atoms including at least one hetero element selected from N, O and S,

R ₆ to R ₉ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms substituted or unsubstituted with a substituent, or R ₆ and R ₇ and R ₈ and R ₉ are each connected to each other and saturated with 3 to 20 carbon atoms Or to form an unsaturated ring group,

The substituents are an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 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, an alkylaryl group having 7 to 20 carbon atoms. , a C 1 to C 20 heteroalkyl group, or a C 2 to C 20 heterocyclic group.

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

The diimine derivative compound according to the present invention has a high reactive activity with the polymer active site, including an active polymer reactive functional group and a filler affinity functional group in the molecule, and thus smoothly reacts with the polymer active site to easily introduce a filler affinity functional group into the polymer and to improve the physical properties by modifying the polymer.

In addition, the modified conjugated diene-based polymer according to the present invention includes a functional group derived from the diimine derivative compound, for example, a filler affinity functional group, so that it can be excellent in filler dispersibility and filler affinity when blended with a filler.

In addition, in the method for producing a modified conjugated diene-based polymer according to the present invention, an active polymer is prepared, and the active polymer is reacted with a diimine derivative compound. The modified conjugated diene-based polymer into which the derived filler affinity functional group is introduced can be easily prepared.

Furthermore, since the rubber composition according to the present invention includes the modified conjugated diene-based polymer including the functional group derived from the diimine derivative compound, the filler dispersibility is excellent, and the affinity between the polymer and the filler is excellent, resulting in tensile properties and viscoelastic properties There is an effect of improving the compounding properties such as

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

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

Terms

The term 'substitution' used in the present invention 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, the functional group, atomic group, or compound is present One or two or more plural substituents may be present depending on the number of hydrogens to be used. In addition, when a plurality of substituents exist, each substituent may be the same as or different from each other.

The term 'monovalent hydrocarbon group' used in the present invention refers to a monovalent substituent derived from a hydrocarbon group, for example, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkyl group having one or more unsaturated bonds, an aryl group, etc. It may represent a monovalent atomic group in which carbon and hydrogen are bonded, and the monovalent atomic group may have a linear or branched structure depending on the structure of the bond.

The term 'divalent hydrocarbon group' used in the present invention refers to a divalent substituent derived from a hydrocarbon group, for example, an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, or a cycloalkyl containing one or more unsaturated bonds. It may represent a divalent atomic group in which carbon and hydrogen are bonded, such as a lene group and an arylene group, and the divalent atomic group may have a linear or branched structure depending on the structure of the bond.

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

The term 'cycloalkyl 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 also 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 of them.

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

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

How to measure

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

diimine derivative compounds

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

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

[Formula 1]

In Formula 1,

R ₁ to R ₃ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms substituted or unsubstituted with a substituent,

R ₄ and R ₅ are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms, or a divalent heterohydrocarbon group having 1 to 20 carbon atoms including at least one hetero element selected from N, O and S,

R ₆ to R ₉ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms substituted or unsubstituted with a substituent, or R ₆ and R ₇ and R ₈ and R ₉ are each connected to each other and saturated with 3 to 20 carbon atoms Or to form an unsaturated ring group,

The substituents are an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 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, an alkylaryl group having 7 to 20 carbon atoms. , a C 1 to C 20 heteroalkyl group, or a C 2 to C 20 heterocyclic group.

The diimine derivative compound according to an embodiment of the present invention may be a modifier for modifying a polymer, and the polymer may be a polymer including a repeating unit derived from a conjugated diene-based monomer, for example, a butadiene homopolymer such as polybutadiene, or It may be a diene-based copolymer such as a butadiene-isoprene copolymer.

In addition, the diimine derivative compound contains a polymer reactive functional group and a filler affinity functional group having high reactivity with the polymer active site in the molecule, and can react smoothly with the polymer active site by the polymer reactive functional group, and thus the polymer The polymer can be modified by easily introducing a filler affinity functional group derived from the diimine derivative compound into the molecule.

Specifically, the diimine derivative compound contains an imine group, a tertiary amine group, and an amide group in a molecule, and the diimine derivative compound reacts with an active site of the polymer by an imine group in its molecule to bond with the polymer, and thereby the polymer It is possible to introduce a tertiary amine group and an amide group, which are functional groups derived from the diimine derivative compound, into the compound, and then, when the polymer and the filler are mixed, the dispersibility of the filler can be improved by the tertiary amine group and the amide group. In addition, after the imine group reacts with the polymer active site, a secondary amine group exists in the polymer to improve the filler affinity of the polymer. It can be converted to primary amine groups in the process to improve the compounding properties of the polymer, such as tensile properties and viscoelastic properties.

Specifically, in Formula 1, R ₁ to R ₃ are each independently a hydrogen atom or an unsubstituted or substituted C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C3 to C20 cycloalkyl group, 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, R ₄ and R ₅ are each independently an alkylene group having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms Rene group or a C 1 to C 20 heteroalkylene group containing at least one hetero element selected from N, O and S, R ₆ to R ₉ are each independently a C 1 to C 20 alkyl group unsubstituted or substituted with a substituent, carbon number an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, or R ₆ and R ₇ and R ₈ and R ₉ are each linked to each other to a saturated cyclic group having 6 to 20 carbon atoms, or It may be to form an unsaturated ring group having 6 to 20 carbon atoms.

As another example, in Formula 1, R ₁ to R ₃ are each independently a hydrogen atom or an unsubstituted C 1 to C 10 alkyl group, 2 to 20 C alkenyl group, 3 to 10 C cycloalkyl group, or 6 to 12 C atoms of an aryl group, R ₄ and R ₅ are each independently an alkylene group having 1 to 10 carbon atoms, or a heteroalkylene group having 1 to 10 carbon atoms including at least one hetero element selected from N, O and S, and R ₆ to R ₉ is independently of each other an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, or R ₆ and R unsubstituted or substituted with a substituent ₇ and R ₈ and R ₉ may be connected to each other to form a saturated ring group having 6 to 10 carbon atoms or an unsaturated ring group having 6 to 12 carbon atoms.

As another example, the diimine derivative compound represented by Formula 1 may be 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]

On the other hand, the diimine derivative compound according to an embodiment of the present invention is prepared by reacting a compound represented by Formula A with a compound represented by Formula B to prepare a compound represented by Formula C, and the compound represented by Formula C and It can be prepared by reacting the compound represented by the formula (D).

[Formula A]

[Formula B]

[Formula C]

[Formula D]

In Formulas A to D,

R ₁ to R ₉ are the same as described in Formula 1,

R _4a is a divalent hydrocarbon group having 1 to 20 carbon atoms, or a divalent heterohydrocarbon group having 1 to 20 carbon atoms including at least one hetero element selected from N, O and S;

R _6a and R _7a are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms that is substituted or unsubstituted with a substituent, or R ₆ and R ₇ and R ₈ and R ₉ are each connected to each other and saturated with 3 to 20 carbon atoms Or to form an unsaturated ring group,

The substituents are an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 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, an alkylaryl group having 7 to 20 carbon atoms. , a heteroalkyl group having 1 to 20 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.

On the other hand, the compound represented by the formula A and the compound represented by the formula B, and the compound represented by the formula C and the compound represented by the formula D are reacted in an appropriate ratio to facilitate the reaction in consideration of the stoichiometric ratio, respectively. In some embodiments, the compound represented by Formula A and the compound represented by Formula B may be reacted in a molar ratio of 1:2 to 1:10, or 1:2 to 1:6, and represented by Formula C The compound represented by the compound and the compound represented by Formula D may be reacted in a molar ratio of 1:1 to 1:3, or 1:1 to 1:2.

In addition, the compound represented by Formula C and the compound represented by Formula D may be carried out in the presence of a base in an organic solvent, wherein the organic solvent is not particularly limited, for example, tetrahydrofuran, anhydrous tetrahydro It may be at least one selected from the group consisting of furan, dichloromethane, chloroform, ethanol, acetic acid and dimethylformamide.

In addition, the base may be a nitrogen-based base, such as trimethylamine.

Modified conjugated diene-based polymer

The present invention provides a conjugated diene-based polymer having excellent compounding properties by including a functional group derived from the diimine derivative compound represented by Formula 1 and having excellent filler affinity.

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

In addition, the 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 from a catalyst composition including 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 within the aforementioned range.

As another example, the modified conjugated diene polymer may have a Mooney stress relaxation rate measured at 100° C. of 0.9 or less, specifically 0.1 or more and 0.8 or less, and more specifically, 0.1 or more and 0.5 or less.

Here, the Mooney stress relaxation rate can be used as an index of the branching structure of the polymer. For example, when comparing polymers having the same Mooney viscosity, the more branches there are, the smaller the Mooney relaxation rate. Therefore, it can be used as an index of the branching degree. The modified conjugated diene polymer according to the present invention may have the above-described Mooney viscosity and the Mooney stress relaxation rate, thereby having excellent processability and, at the same time, excellent tensile properties and viscoelastic properties.

Meanwhile, in the present invention, the Mooney viscosity was measured at 100° C. and a rotor speed of 2±0.02 rpm using a Mooney viscometer, for example, a Large Rotor manufactured by Alpha Technologies MV2000E. Specifically, after leaving the polymer at room temperature (23±5° C.) for more than 30 minutes, 27±3 g was collected, filled in the die cavity, and the Mooney viscosity was measured while applying torque by operating the platen. In addition, the Mooney stress relaxation rate is expressed as an absolute value by measuring the Mooney viscosity and then measuring the slope value of the Mooney viscosity change appearing as the torque is released.

In addition, the modified conjugated diene-based polymer may have a molecular weight distribution (Mw/Mn) of 1.3 to 5.0, specifically, a molecular weight distribution of 1.5 to 5.0, 1.7 to 3.5, or 2.0 to 3.2, more specifically, a molecular weight distribution of 2.5 to 3.2 can have

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

The modified conjugated diene-based polymer according to an embodiment of the present invention may have a weight average molecular weight (Mw) of 1.3 X 10 ⁵ to 2.5 X 10 ⁶ g/mol, while satisfying the molecular weight distribution conditions described above, 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, it has excellent tensile properties and excellent processability, resulting in improved workability of the rubber composition. It is easy, there is an excellent effect of the mechanical properties and the balance of physical properties of the rubber composition. The weight average molecular weight may be, for example, 2.0 X 10 ⁵ to 1.2 X 10 ⁶ g/mol, or 3.0 X 10 ⁵ to 1.0 X 10 ⁶ g/mol, and the number average molecular weight is, for example, 1.5 X 10 ⁵ to 4.5 X 10 ⁵ g/mol, or 2.0 X 10 ⁵ to 4.0 X 10 ⁵ g/mol.

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

In addition, the conjugated diene-based polymer may have a cis-1,4 bond content of 95% or more, more specifically 96% or more, of the conjugated diene part measured by Fourier transform infrared spectroscopy (FT-IR). Accordingly, when applied to the rubber composition, the abrasion resistance, crack resistance and ozone resistance of the rubber composition may be improved.

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

Method for producing a modified conjugated diene-based polymer

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

The manufacturing method according to an embodiment of 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 reacting the active polymer with the diimine derivative compound represented by Formula 1 (S2).

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

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

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

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

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

The neodymium compound may be a compound represented by the following formula (2).

[Formula 2]

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

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

In addition, as another example, considering the excellent solubility in solvents, conversion to catalytically active species, and thus the catalytic activity improvement effect without concerns about oligomerization, the neodymium compound is more specifically, R _a in Formula 2 an alkyl group having 4 to 12 carbon atoms, and R _b and R _c are each independently a hydrogen atom or an alkyl group having 2 to 8 carbon atoms, provided that R _b and R _c are not hydrogen atoms 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 a hydrogen atom or an alkyl group having 2 to 6 carbon atoms, in which case R _b and R _c may not be hydrogen atoms 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) ate) 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- 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 nonanoate) ₃ , Nd(2-ethyl-2-propyl nonanoate) ₃ and Nd(2-ethyl-2-hexyl nonanoate) ₃ may be at least one selected from the group consisting of, among them The neodymium-based compound is Nd (2,2-diethyl decanoate) ₃ , Nd (2,2-dipropyl decanoate) ₃ , Nd (2,2-dibutyl decanoate) ₃ , Nd (2 ,2-dihexyl decanoate) ₃ , and Nd(2,2-dioctyl decanoate) ₃ It may be at least one selected from the group consisting of.

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

As such, the neodymium-based compound represented by Formula 2 includes a carboxylate ligand including an alkyl group having various lengths of 2 or more carbon atoms as a substituent at the α (alpha) position, thereby inducing a steric change around the neodymium central metal compound It is possible to block the clumping phenomenon 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 ratio of neodymium located in a central portion having difficulty in conversion to a catalytically active species is reduced, thereby increasing the conversion rate to a catalytically active species.

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

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

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

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

(a) alkylating agent

The alkylating agent is an organometallic compound capable of transferring a hydrocarbyl group to another metal, and may serve as a co-catalyst. The alkylating agent may be used without particular limitation as long as it is used as an alkylating agent in the production of a diene-based polymer, for example, it 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 be an organometallic compound containing.

Specifically, as the organoaluminum compound, trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentyl Alkyl aluminum, such as aluminum, trihexyl aluminum, tricyclohexyl aluminum, and trioctylaluminum; diethylaluminum hydride, di-n-propylaluminum hydride, diisopropylaluminum hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride (DIBAH), di-n-octylaluminum hydride, Diphenylaluminum hydride, di-p-tolylaluminum hydride, dibenzylaluminum hydride, phenylethylaluminum hydride, phenyl-n-propylaluminum hydride, phenylisopropylaluminum hydride, phenyl-n-butylaluminum hydride Ride, phenylisobutylaluminum hydride, phenyl-n-octylaluminum hydride, p-tolylethylaluminum hydride, p-tolyl-n-propylaluminum hydride, p-tolylisopropylaluminum hydride, p-tolyl- n-butylaluminum hydride, p-tolylisobutylaluminum hydride, p-tolyl-n-octylaluminum hydride, benzylethylaluminum hydride, benzyl-n-propylaluminum hydride, benzylisopropylaluminum hydride, benzyl dihydrocarbylaluminum hydride such as -n-butylaluminum hydride, benzylisobutylaluminum hydride or benzyl-n-octylaluminum hydride; Hydrocarbylaluminum dihydride such as ethylaluminum dihydride, n-propylaluminum dihydride, isopropylaluminum dihydride, n-butylaluminum dihydride, isobutylaluminum dihydride or n-octylaluminum dihydride, etc. A hydride etc. are mentioned. Examples of the organic magnesium compound include alkyl magnesium compounds such as diethyl magnesium, di-n-propyl magnesium, diisopropyl magnesium, dibutyl magnesium, dihexyl magnesium, diphenyl magnesium, or dibenzyl magnesium, and the like. Examples of the organolithium compound include alkyl lithium compounds such as n-butyllithium.

In addition, the organoaluminum compound may be aluminoxane.

The aluminoxane may be prepared by reacting a trihydrocarbyl aluminum-based compound with water, and specifically may be a linear aluminoxane of the following Chemical Formula 3a or a cyclic aluminoxane of the following Chemical Formula 3b.

[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 each independently an integer of 1 or more, specifically 1 to 100 , more specifically, may be an integer of 2 to 50.

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

In addition, the modified methylaluminoxane may be a compound in which the methyl group of methylaluminoxane is substituted with a modifying group (R), specifically, a hydrocarbon group having 2 to 20 carbon atoms, specifically, a compound represented by the following formula (4).

[Formula 4]

In Formula 4, R is as defined above, and m and n may be each independently an integer of 2 or more. In addition, in Formula 4, 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, isobutyl group, hexyl group or octyl group having 2 carbon atoms. to 10, and more specifically, may be an isobutyl group.

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

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

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 molar ratio, and more specifically 1 to 20 molar ratio with respect to 1 mole of the neodymium compound. have. If the alkylating agent is included in an amount exceeding 200 molar ratio, it is not easy to control the catalytic reaction during the preparation of the polymer, and there is a risk that an excessive amount of the alkylating agent may cause side reactions.

(b) halides

The halide is not particularly limited, but may include, 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, and any of these One or a mixture of two or more may be used. Among them, any one or a mixture of two or more selected from the group consisting of organic halides, metal halides, and organometallic halides may be used as the halide in consideration of the excellent effect of improving catalytic activity and thus improving reactivity.

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

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

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

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

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

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

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

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

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

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

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

(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 catalyst composition for polymerization in advance to perform pre-polymerization or pre-polymerization. By using it in the form of a premix catalyst composition, it is possible not only to improve the catalyst composition activity, but also to stabilize the active polymer to be prepared.

In the present invention, the "preforming" means a catalyst composition including a neodymium compound, an alkylating agent and a halide, that is, diisobutylaluminum hydride (DIBAH) in a catalyst system. In order to reduce the possibility of generating active species in the catalyst composition, a small amount of a conjugated diene-based monomer such as 1,3-butadiene is added. have. In addition, "premix (premix)" may mean a state in which each compound is uniformly mixed without polymerization in the catalyst composition system.

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

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

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

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

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

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

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

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

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

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

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

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

Step S2 is a step of preparing a modified conjugated diene-based polymer including a functional group by modifying or coupling the active polymer, and may be carried out by reacting the active polymer with the diimine derivative compound represented by Formula 1.

The diimine derivative compound 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 diimine derivative compound may be used in an amount of 1 mol to 15 mol relative to 1 mol of the neodymium compound in the catalyst composition, and more specifically, 1 mol to 10 mol relative to 1 mol of the neodymium compound in the catalyst composition.

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

After completion of the above-described modification reaction, a solution of 2,6-di-t-butyl-p-cresol (BHT) in isopropanol or the like may be added to the polymerization reaction system to stop the polymerization reaction.

In the manufacturing method according to an embodiment of the present invention, after step S2, solvent removal treatment such as steam stripping to lower the partial pressure of the solvent through supply of water vapor, vacuum drying treatment, or drying with a 100 ° C roll mill (Hot Roll mill) A modified conjugated diene-based polymer can be obtained. In addition, an unmodified active polymer may be included in the reaction product obtained as a result of the above-mentioned reaction together with the above-mentioned modified conjugated diene polymer.

rubber composition

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

The rubber composition according to an embodiment of the present invention contains the modified conjugated diene-based polymer in an amount of 0.1 wt% to 100 wt%, specifically 10 wt% to 100 wt%, 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 improvement effect of abrasion resistance and crack resistance of a molded article manufactured using the rubber composition, such as a tire, may be insignificant.

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

The rubber component may be natural rubber or synthetic rubber, for example, the rubber component may include natural rubber (NR) containing cis-1,4-polyisoprene; Modified natural rubbers such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber that are modified or refined of the general natural rubber; Styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, polyisobutylene-co-isoprene, neoprene, poly(ethylene-co-) propylene), poly(styrene-co-butadiene), poly(styrene-co-isoprene), poly(styrene-co-isoprene-co-butadiene), poly(isoprene-co-butadiene), poly(ethylene-co-propylene) -co-diene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, or a synthetic rubber such as halogenated butyl rubber, and any one or a mixture of two or more thereof may be used.

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

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

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

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

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

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

The vulcanizing agent may be specifically sulfur powder, and may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the rubber component. When included in the above content range, it is possible to secure the required elastic modulus and strength of the vulcanized rubber composition, and at the same time to obtain low fuel economy.

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

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

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

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

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

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

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

Example

Hereinafter, the present invention will be described in more detail by way of Examples and Experimental Examples. However, the following Examples and Experimental Examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereto.

Preparation Example 1

(1) Preparation of bis(2-(cyclohexylideneamino)ethyl)amine (bis(2-(cyclohexylideneamino)ethyl)amine)

20.0 g (193.86 mmol) of 1,2-ethanediamine was added to a 250 ml round-bottom flask, and 114.16 g (1.16 mol) of cyclohexanone was added thereto. The reaction proceeded while the temperature was raised to 150° C., and water generated during the reaction was removed using a Dean-Stark type extractor. The reaction was terminated after 12 hours, and the remaining cyclohexanone was removed by distillation to prepare 48.50 g (yield 95%) of bis(2-(cyclohexylideneamino)ethyl)amine. By observing ¹ H nuclear magnetic resonance spectroscopy spectrum, it was confirmed that bis(2-(cyclohexylideneamino)ethyl)amine was prepared.

¹ H NMR (500 MHz, CDCl ₃ ) δ 2.64-2.60 (m, 4H), 2.55-2.51 (m, 8H), 1.66-1.62 (t, 4H), 1.60-1.54 (m, 13H).

(2) Preparation of N,N-bis(2-(cyclohexylideneamino)ethyl)acrylamide (N,N-bis(2-(cyclohexylideneamino)ethyl)acrylamide)

In an ice bath, 10.0 g (37.96 mmol) of the bis(2-(cyclohexylideneamino)ethyl)amine prepared in (1) above was placed in a 100 ml round-bottom flask, 20 ml of dichloromethane and trimethyl After adding 7.94 ml (56.94 mmol) of the amine, the temperature was reduced under a nitrogen atmosphere. After 10 minutes, 4.12 g (45.55 mmol) of acryloyl chloride was slowly added dropwise and reacted at room temperature for 8 hours. After completion of the reaction, 30 ml of MTBE (Methyl Tertiary Butyl Ether) was added to remove the salt, filtered to collect the filtrate, and concentrated to N,N-bis(2-(cyclohexylideneamino) represented by the following formula 1-1 Ethyl) acrylamide 11.23 g (yield 93.2%) was prepared. By observing ¹ H nuclear magnetic resonance spectroscopy spectrum, it was confirmed that N,N-bis(2-(cyclohexylideneamino)ethyl)acrylamide was prepared.

[Formula 1-1]

¹ H NMR (500 MHz, CDCl ₃ ) δ 6.62-6.59 (m, 1H), 6.08-6.06 (d, 1H), 5.82-5.80 (d, 1H), 2.65-2.61 (m, 4H), 2.54-2.50 (m, 8H), 1.66-1.62 (t, 4H), 1.58-1.52 (m, 12H).

Preparation Example 2

(1) Preparation of bis(2-(cyclohexylideneamino)ethyl)amine (bis(2-(cyclohexylideneamino)ethyl)amine)

48.50 g (yield 95%) of bis(2-(cyclohexylideneamino)ethyl)amine was prepared in the same manner as in Preparation Example 1 (1). By observing ¹ H nuclear magnetic resonance spectroscopy spectrum, it was confirmed that bis(2-(cyclohexylideneamino)ethyl)amine was prepared.

¹ H NMR (500 MHz, CDCl ₃ ) δ 2.64-2.60 (m, 4H), 2.55-2.51 (m, 8H), 1.66-1.62 (t, 4H), 1.60-1.54 (m, 13H).

(2) Preparation of N,N-bis(2-(cyclohexylideneamino)ethyl)methacrylamide (N,N-bis(2-(cyclohexylideneamino)ethyl)methacrylamide)

Put the bis(2-(cyclohexylideneamino)ethyl)amine prepared in (1) in a 100 ml round-bottom flask, and methacryloyl instead of acryloyl chloride in (2) of Preparation Example 1 N,N-bis(2-(cyclohexylideneamino) represented by the following Chemical Formula 1-2 in the same manner as (2) of Preparation Example 1, except that 45.55 mmol of methacryloyl chloride was used. Ethyl) methacrylamide 11.77 g (yield 93.5%) was prepared. By observing ¹ H nuclear magnetic resonance spectroscopy spectrum, it was confirmed that N,N-bis(2-(cyclohexylideneamino)ethyl)methacrylamide was prepared.

[Formula 1-2]

¹ H NMR (500 MHz, CDCl ₃ ) δ 6.08-6.06 (d, 1H), 5.82-5.80 (d, 1H), 2.65-2.61 (m, 4H), 2.54-2.50 (m, 8H), 1.78 (s) , 3H), 1.66-1.62 (t, 4H), 1.58-1.52 (m, 12H).

Preparation Example 3

(1) Preparation of bis(2-((4-methylpentan-2-ylidene)amino)ethyl)amine (bis(2-((t-methylpentan-2-ylidene)amino)ethyl)amine)

20.0 g (193.86 mmol) of 1,2-ethanediamine was added to a 250 ml round-bottom flask, and 116.50 g (1.16 mol) of methyl isobutyl ketone (MIBK) was added. The reaction proceeded while the temperature was raised to 150° C., and water generated during the reaction was removed using a Dean-Stark type extractor. The reaction was terminated after 12 hours, and the remaining methyl isobutyl ketone was removed by distillation to prepare 48.44 g of bis(2-((4-methylpentan-2-ylidene)amino)ethyl)amine (yield 93.4%). . By observing ¹ H nuclear magnetic resonance spectroscopy spectrum, it was confirmed that bis(2-((4-methylpentan-2-ylidene)amino)ethyl)amine was prepared.

¹ H NMR (500 MHz, CDCl ₃ ) δ 2.62-2.58 (m, 4H), 2.23-2.21 (m, 4H), 1.95 (s, 6H), 1.79-1.74 (m, 2H), 1.65-1.62 (t) , 4H), 1.56-1.52 (br, 1H), 0.96-0.94 (d, 12H).

(2) N,N-bis(2-((4-methylpentan-2-ylidene)amino)ethyl)acrylamide (N,N-bis(2-((4-methylpentan-2-ylidene)amino) Preparation of ethyl)acrylamide)

In an ice bath, 10.0 g (37.39 mmol) of the bis(2-((4-methylpentan-2-ylidene)amino)ethyl)amine prepared in (1) above was placed in a 100 ml round-bottom flask, and , 20 ml of dichloromethane and 7.82 ml (56.08 mmol) of trimethylamine were added, and the temperature was reduced under a nitrogen atmosphere. After 10 minutes, 4.06 g (44.87 mmol) of acryloyl chloride was slowly added dropwise, and reacted at room temperature for 8 hours. After completion of the reaction, 30 ml of MTBE (Methyl Tertiary Butyl Ether) was added to remove the salt, filtered to collect the filtrate, and concentrated to N,N-bis(2-((4-methylpentane-) 11.28 g (yield 93.8%) of 2-ylidene)amino)ethyl)acrylamide was prepared. By observing ¹ H nuclear magnetic resonance spectroscopy spectrum, it was confirmed that N,N-bis(2-((4-methylpentan-2-ylidene)amino)ethyl)acrylamide was prepared.

[Formula 1-3]

¹ H NMR (500 MHz, CDCl ₃ ) δ 6.62-6.59 (m, 1H), 6.08-6.06 (d, 1H), 5.82-5.80 (d, 1H), 2.62-2.58 (m, 4H), 2.23-2.21 (d, 4H), 1.95 (s, 6H), 1.79-1.74 (m, 2H), 1.65-1.62 (t, 4H), 0.96-0.94 (d, 12H).

Preparation Example 4

(1) Preparation of bis(2-((4-methylpentan-2-ylidene)amino)ethyl)amine (bis(2-((t-methylpentan-2-ylidene)amino)ethyl)amine)

Bis(2-((4-methylpentan-2-ylidene)amino)ethyl)amine 48.44 g (yield 93.4%) was prepared in the same manner as in Preparation Example 3 (1). By observing ¹ H nuclear magnetic resonance spectroscopy spectrum, it was confirmed that bis(2-((4-methylpentan-2-ylidene)amino)ethyl)amine was prepared.

¹ H NMR (500 MHz, CDCl ₃ ) δ 2.62-2.58 (m, 4H), 2.23-2.21 (m, 4H), 1.95 (s, 6H), 1.79-1.74 (m, 2H), 1.65-1.62 (t) , 4H), 1.56-1.52 (br, 1H), 0.96-0.94 (d, 12H).

(2) N,N-bis(2-((4-methylpentan-2-ylidene)amino)ethyl)acrylamide (N,N-bis(2-((4-methylpentan-2-ylidene)amino) Preparation of ethyl)acrylamide)

Bis(2-((4-methylpentan-2-ylidene)amino)ethyl)amine prepared in (1) above was put in a 100 ml round-bottom flask, and acryloyl in (2) of Preparation Example 3 above In the same manner as in (2) of Preparation Example 3, except that 44.87 mmol of methacryloyl chloride was used instead of the chloride, N,N-bis(2-(( 11.40 g of 4-methylpentan-2-ylidene)amino)ethyl)acrylamide (yield 90.9%) was prepared. By observing ¹ H nuclear magnetic resonance spectroscopy spectrum, it was confirmed that N,N-bis(2-((4-methylpentan-2-ylidene)amino)ethyl)acrylamide was prepared.

[Formula 1-4]

¹ H NMR (500 MHz, CDCl ₃ ) δ 6.07-6.05 (d, 1H), 5.81-5.79 (d, 1H), 2.62-2.58 (m, 4H), 2.23-2.21 (d, 4H), 1.95 (s) , 6H), 1.81 (s, 3H), 1.79-1.74 (m, 2H), 1.65-1.62 (t, 4H), 0.96-0.94 (d, 12H).

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 Nd (2,2-diethyl decanoate) ₃ 0.10 mmol, diisobutylaluminum hydride (DIBAH) 0.89 mmol, diethylaluminum chloride (DEAC) 0.24 mmol and 1,3-butadiene 3.3 It was prepared by mixing mmol. Thereafter, 0.23 mmol of the compound of Formula 1-1 prepared in Preparation Example 1 was added, and then a denaturation reaction was performed at 70° C. for 30 minutes. Thereafter, the reaction was terminated by adding a hexane solution containing 1.0 g of a polymerization terminator and 33 g of a solution in which the antioxidant WINGSTAY K (Eliokem SAS, France) was dissolved in hexane at 30% by weight, and the resulting heavy content was steamed. The solvent was removed by stirring in hot water heated to , and then roll-drying 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, CB24 (Lanxess) was used as a comparative polymer.

Comparative Example 2

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

Comparative Example 3

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 Nd (2,2-diethyl decanoate) ₃ 0.10 mmol hexane solution, diisobutylaluminum hydride (DIBAH) 0.89 mmol, diethylaluminum chloride (DEAC) 0.24 mmol and 1,3- It was prepared by mixing 3.3 mmol of butadiene. Thereafter, the reaction was terminated by adding a hexane solution containing 1.0 g of a polymerization terminator and a solution in which the antioxidant WINGSTAY K (Eliokem SAS, France) was dissolved in hexane at 30% by weight, and the resulting heavy content was heated with steam. The solvent was removed by stirring in hot water, and then roll-drying to remove the remaining amount of solvent and water to prepare an unmodified butadiene polymer.

Experimental Example 1

For the polymers of Examples 1 to 4 and Comparative Examples 1 to 3, each physical property was measured in the following manner, and the results are shown in Table 1 below.

1) Microstructure analysis

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

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

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

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

3) Mooney Viscosity (RP, Raw Polymer) and Mooney Stress Relief (-S/R)

For each polymer, Mooney viscosity (ML1+4, @100°C) (MU) was measured using a large rotor using Alpha Technologies' MV2000E at 100°C and a rotor speed of 2±0.02 rpm. At this time, the sample used was left at room temperature (23±3° C.) for more than 30 minutes, and then 27±3 g was collected, filled in the die cavity, and the Mooney viscosity was measured while applying a torque by operating the platen. In addition, the slope value of the change in Mooney viscosity appearing as the torque is released was measured, and the absolute value thereof was used as the Mooney Stress Relaxation Ratio.

division Example comparative example One 2 3 4 One 2 3 Cis-1,4 bond content (wt%) 98.3 98.2 98.4 98.3 96.3 96.7 97.1 GPC Results Mn (x10 ⁵ g/mol) 3.28 3.30 3.25 3.26 2.56 2.64 2.25 Mw (x10 ⁵ g/mol) 9.87 9.85 9.82 9.5 6.08 6.18 3.44 MWD (Mw/Mn) 3.01 2.98 3.02 3.02 2.37 2.37 1.53 Mooney Viscosity (RP) (ML1+4, @100℃)(MU) 47 44 45 44 45 44 39 Mooney stress relaxation rate (-S/R) 0.443 0.438 0.445 0.441 0.589 0.513 0.894

As shown in Table 1, it was confirmed that the modified butadiene polymers of Examples 1 to 4 had an increased molecular weight and reduced Mooney stress relaxation rate compared to Comparative Examples 1 to 3, which are unmodified butadiene polymers.

Here, the Mooney stress relaxation rate is used as an index of the branching structure of the polymer. In general, in a polymer having the same Mooney viscosity, the more branches there are, the less the Mooney stress relaxation rate.

Therefore, the Mooney stress relaxation rate of Examples 1 to 4 having the same level of Mooney viscosity as Comparative Examples 1 to 3 was decreased compared to Comparative Examples 1 to 3, and thus Examples 1 to 4 were It can be confirmed that it has branching, and through this, it can be confirmed that the diimine derivative compound represented by Chemical Formula 1 according to an embodiment of the present invention can react and combine with the polymer active site to modify the polymer properties.

In addition, it can be predicted that the modified conjugated diene-based polymer according to an embodiment of the present invention includes a functional group derived from the diimine derivative compound represented by Formula 1 above.

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, 300% modulus, and viscoelastic properties were measured as follows. The results are shown in Table 2 below.

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

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

Mooney viscosity (ML1+4, @100°C) (MU) was measured using each of the vulcanization formulations prepared above. Specifically, using a large rotor with Alpha Technologies' MV2000E, Mooney viscosity (MV) was measured at 100° C. under the conditions of a rotor speed of 2±0.02 rpm. At this time, after leaving the sample at room temperature (23±3℃) for more than 30 minutes, 27±3g is collected, filled in the die cavity, and the Mooney viscosity (FMB) is measured while applying torque by operating the platen. did

In addition, the Mooney viscosity of each polymer shown in Table 1 and the Mooney viscosity difference (ΔMV, FMB-RP) of the formulation were calculated. In this case, the smaller the Mooney viscosity difference, the better the processability.

2) 300% modulus (300% modulus)

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

3) Viscoelastic properties

For each rubber specimen, the most important property of tan δ for low fuel efficiency is the viscoelastic modulus (Tan δ) at -60°C to 80°C at a frequency of 10 Hz, prestrain 3%, and dynamic strain 3% using Gabo DMTS 500N from Germany. was measured. At this time, the Tanδ value at 60°C represents the rotational resistance characteristic (fuel efficiency).

division Example comparative example One 2 3 4 One 2 3 Mooney Viscosity (FMB) 55.0 55.2 54.8 55.1 63.8 68.8 71.8 △MV 8.0 11.2 9.8 11.1 18.8 24.8 32.8 M-300% (index(%)) 109 108 110 104 100 102 87 Tanδ @ 60℃(index(%)) 106 109 107 105 100 103 92

In Table 2, the 300% modulus of Examples 1 to 4, Comparative Examples 2 and 3 was calculated and indexed by Equation 1 below based on the measured value of Comparative Example 1, and was The Tanδ value was calculated and indexed by Equation 2 below.

[Equation 1]

Index(%)=(measured value/reference value)×100

[Equation 2]

Index(%)=(reference value/measurement value)×100

As shown in Table 2, Examples 1 to 4 exhibited improved effects of tensile properties and viscoelastic properties while exhibiting excellent workability at the same level as Comparative Examples 1 to 3.

Specifically, Examples 1 to 4 exhibited an effect of significantly improving 300% modulus and rotational resistance compared to commercially available Comparative Examples 1 and 2, and at the same time, remarkably improved processability characteristics to about 170% to 300%. In addition, Examples 1 to 4 exhibited remarkably improved effects in all of the 300% modulus, rotation resistance, and workability characteristics compared to Comparative Example 3.

Through the results of Tables 1 and 3, the modified conjugated diene-based polymer according to the present invention includes a functional group derived from the diimine derivative compound represented by Formula 1, and thus has excellent filler affinity and dispersibility, and tensile properties. , it can be seen that the viscoelastic properties and the processability properties have a well-balanced effect.

Claims (15)

A diimine derivative compound represented by the following formula (1):
[Formula 1]

In Formula 1,
R ₁ to R ₃ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms substituted or unsubstituted with a substituent,
R ₄ and R ₅ are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms, or a divalent heterohydrocarbon group having 1 to 20 carbon atoms including at least one hetero element selected from N, O and S,
R ₆ to R ₉ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms substituted or unsubstituted with a substituent, or R ₆ and R ₇ and R ₈ and R ₉ are each connected to each other and saturated with 3 to 20 carbon atoms Or to form an unsaturated ring group,
The substituents are an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 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, an alkylaryl group having 7 to 20 carbon atoms. , a C 1 to C 20 heteroalkyl group, or a C 2 to C 20 heterocyclic group.
According to claim 1,
In Formula 1,
R ₁ to R ₃ are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with a substituent, an alkenyl group having 2 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;
R ₄ and R ₅ are each independently an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, or a heteroalkylene group having 1 to 20 carbon atoms including at least one hetero element selected from N, O and S,
R ₆ to R ₉ are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, or R ₆ and R ₇ and R ₈ and R ₉ are each linked to each other to form a saturated cyclic group having 6 to 20 carbon atoms or an unsaturated ring group having 6 to 20 carbon atoms.
According to claim 1,
In Formula 1,
R ₁ to R ₃ are each independently a hydrogen atom or an unsubstituted C 1 to C 10 alkyl group, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms,
R ₄ and R ₅ are each independently an alkylene group having 1 to 10 carbon atoms, or a heteroalkylene group having 1 to 10 carbon atoms including at least one hetero element selected from N, O and S,
R ₆ to R ₉ are each independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, or R ₆ and R ₇ and R ₈ and R ₉ each are connected to each other to form a saturated cyclic group having 6 to 10 carbon atoms or an unsaturated ring group having 6 to 12 carbon atoms.
The method of claim 1,
The diimine derivative compound represented by Formula 1 is at least one diimine derivative compound selected from compounds represented by Formula 1-1 to Formula 1-4:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

.
According to claim 1,
A diimine derivative compound that is a denaturing agent for polymers.
6. The method of claim 5,
The polymer is a diimine derivative compound comprising a repeating unit derived from a conjugated diene-based monomer.
a repeating unit derived from a conjugated diene-based monomer; and
A modified conjugated diene-based polymer comprising a functional group derived from the diimine derivative compound represented by Formula 1 of claim 1.
8. The method of claim 7,
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.
8. The method of claim 7,
The diimine derivative compound represented by Formula 1 is a modified conjugated diene-based polymer that is at least one selected from compounds represented by Formula 1-1 to Formula 1-4:
[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 the presence of a catalyst composition including a neodymium compound in a hydrocarbon solvent; and
2) A method for producing the modified conjugated diene-based polymer of claim 7, comprising reacting the active polymer with a diimine derivative compound represented by the following formula (1):
[Formula 1]

In Formula 1,
R ₁ to R ₃ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms substituted or unsubstituted with a substituent,
R ₄ and R ₅ are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms, or a divalent heterohydrocarbon group having 1 to 20 carbon atoms including at least one hetero element selected from N, O and S,
R ₆ to R ₉ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms substituted or unsubstituted with a substituent, or R ₆ and R ₇ and R ₈ and R ₉ are each connected to each other and saturated with 3 to 20 carbon atoms Or to form an unsaturated ring group,
The substituents are an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 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, an alkylaryl group having 7 to 20 carbon atoms. , a C 1 to C 20 heteroalkyl group, or a C 2 to C 20 heterocyclic group.
11. The method of claim 10,
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.
11. The method of claim 10,
The neodymium compound is a method for producing a modified conjugated diene-based polymer that is a compound represented by the following formula 2:
[Formula 2]

In Formula 2,
R _a to R _c are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms,
However, R _a to R _c are not all hydrogen atoms at the same time.
11. The method of claim 10,
The diimine derivative compound represented by Formula 1 is used in a ratio of 0.5 to 20 moles based on 1 mole of the neodymium compound. Method for producing a modified conjugated diene-based polymer.
A rubber composition comprising the modified conjugated diene-based polymer according to claim 7 and a filler.
15. The method of claim 14,
The rubber composition is that the filler is carbon black.