KR20210130014A - Conjugated diene polymer composition, method for preparing the polymer composition and rubber composition comprising the polymer composition - Google Patents

Abstract

The present invention relates to a conjugated diene-based polymer composition, a method for preparing the same, and a rubber composition comprising the same. The conjugated diene-based polymer composition according to the present invention comprises a first conjugated diene-based polymer and a second conjugated diene-based polymer, wherein the first conjugated diene-based polymer includes a repeating unit derived from a conjugated diene-based monomer having a cis-1,4 bond content of 92 wt% or more, the second conjugated diene-based polymer includes an amine-based compound functional group at one terminal thereof, and the proportion of the second conjugated diene-based polymer is 0.1-10 wt% with respect to 100 wt% of the first conjugated diene-based polymer.

Description

Conjugated diene-based polymer composition, manufacturing method thereof, and rubber composition comprising the same

The present invention relates to a conjugated diene-based polymer composition excellent in low fuel consumption characteristics while maintaining tensile strength and viscoelastic properties, a method for preparing the same, and a rubber composition comprising the same.

Recently, as interest in energy saving and environmental issues increases, fuel efficiency reduction of automobiles is required. As one of the methods for realizing this, a method for reducing the exothermicity of a tire by using an inorganic filler such as silica or carbon black in a rubber composition for forming a tire has been proposed, but it is rather difficult to disperse the inorganic filler in the rubber composition. There was a problem in that the physical properties of the rubber composition, including abrasion resistance, crack resistance, or workability, etc., were deteriorated as a whole.

In order to solve this problem, as a method for increasing the dispersibility of inorganic fillers such as silica or carbon black in the rubber composition, the polymerization active site of the conjugated diene-based polymer obtained by anionic polymerization using organolithium can interact with the inorganic filler. A method of denaturation with a functional group has been developed. Specifically, a method of modifying the polymerization active terminal of a conjugated diene-based polymer with a tin-based compound, introducing an amino group, or modifying with an alkoxysilane derivative has been proposed. However, when preparing a rubber composition using the conjugated diene-based polymer modified by the above method, low heat generation can be ensured, but the effect of improving physical properties of the rubber composition, such as abrasion resistance and processability, was not sufficient.

As another method, in a living polymer obtained by coordination polymerization using a catalyst containing a lanthanum-based rare-earth element compound, a method has been developed to improve processability and physical properties by modifying the living active terminal with a specific coupling agent or modifier. . For example, in the method disclosed in U.S. Patent No. 5,557,784, in the literature, cis-1,4-polybutadiene is prepared in a non-polar solvent using a catalyst consisting of a combination of a neodymium carboxyl salt compound, an alkylaluminum compound, and a compound containing a halogen. After terminating the reaction with a reaction terminator and antioxidant, a method of introducing a branched structure by adding sulfur chloride is disclosed.

In particular, high cis polybutadiene having a high cis-1,4 bond content has higher abrasion resistance, crack resistance, and rebound elasticity than low cis polybutadiene, so it can be mainly applied to tire sidewalls. It is difficult to replace high-cis polybutadiene with low-cis polybutadiene for rubber applied to the back. Accordingly, even for high-cis polybutadiene, in order to improve the dispersibility of fillers such as carbon black or silica in the rubber composition, the high-cis polybutadiene is modified using a modifier containing a primary amine or a secondary amine. Efforts are ongoing. However, in the case of high cis polybutadiene, the modification of the living active end is not performed smoothly due to polymerization characteristics, and thus the modification rate is low, and thus there is a limit in improving processability and physical properties. In addition, in the case of a denaturant containing a primary amine or a secondary amine, a denaturant protected with trimethylsilane or the like is used to minimize polymerization stop due to protons, but in this case, there is a problem in that the manufacturing cost of the denaturant is increased.

US5557784A

The present invention has been devised to solve the problems of the prior art, and it is an object of the present invention to provide a conjugated diene-based polymer composition excellent in low fuel consumption while maintaining tensile properties and viscoelastic properties from a high-cis conjugated diene-based polymer in a rubber composition. do.

In addition, an object of the present invention is to provide a method for preparing a conjugated diene-based polymer composition comprising the high-cis conjugated diene-based polymer as described above.

In addition, by including the conjugated diene-based polymer composition, the present invention provides a rubber composition capable of preventing the problem of process oil from leaking while maintaining processability equivalent to or higher than that of including the process oil in high-cis polybutadiene. intended to provide

In order to solve the above problems, the present invention includes a first conjugated diene-based polymer and a second conjugated diene-based polymer, and the first conjugated diene-based polymer has a ratio of cis-1,4 bonds of the conjugated diene-based monomer unit. 92 wt% or more, wherein the second conjugated diene-based polymer includes an amine-based compound functional group at one end thereof, and the second conjugated diene-based polymer is 0.1 to 10 parts by weight based on 100 parts by weight of the first conjugated diene-based polymer. It provides a conjugated diene-based polymer composition included in parts by weight.

In addition, the present invention prepares a first conjugated diene-based polymer solution including a first conjugated diene-based polymer by polymerizing a conjugated diene-based monomer in the presence of a catalyst composition comprising a first organic solvent and a neodymium compound (S10) ); preparing a polymer solution including an unmodified conjugated diene-based polymer by polymerizing a conjugated diene-based monomer in the presence of a second organic solvent and an organolithium compound (S20); preparing a liquid second conjugated diene-based polymer by adding and reacting an amine-based compound to the polymer solution prepared in step (S20) (S30); and 0.1 parts by weight to 10 parts by weight of the liquid second conjugated diene-based polymer prepared in step (S30) to 100 parts by weight (based on solid content) of the first conjugated diene-based polymer solution prepared in step (S10) (based on solid content) ) and mixing (S40), wherein in the first conjugated diene-based polymer, the ratio of cis-1,4 bonds of the conjugated diene-based monomer unit is 92% by weight or more, and the second conjugated diene-based polymer provides a method for producing a conjugated diene-based polymer composition comprising an amine-based compound functional group at one end.

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

The conjugated diene-based polymer composition according to the present invention contains a high-cis conjugated diene-based polymer and a conjugated diene-based polymer including a functional group of an amine compound, thereby maintaining tensile properties and viscoelastic properties in the rubber composition, while maintaining excellent low fuel consumption properties. have.

In addition, the method for preparing a conjugated diene-based polymer composition according to the present invention includes the step of mixing a liquid conjugated diene-based polymer with a high-cis conjugated diene-based polymer solution, so that the conjugated diene-based polymer composition can be easily prepared. have.

In addition, by including the conjugated diene-based polymer composition, the rubber composition according to the present invention has excellent low fuel efficiency while maintaining tensile strength and viscoelastic properties, and processability equivalent to or higher than that of including process oil in high-cis polybutadiene. It has the effect of preventing the problem of process oil leaking while maintaining the

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 description and claims of the present invention should not be construed as being limited to their ordinary or dictionary meanings, and the inventor should properly understand the concept of the term in order to best describe his invention. Based on the principle that can be defined, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.

Terms and measurement methods used in the present invention may be defined as follows unless otherwise defined.

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

In the present invention, the term 'alkyl group' may refer to a monovalent aliphatic saturated hydrocarbon group, and may include linear alkyl groups such as methyl, ethyl, propyl and butyl; branched alkyl groups such as isopropyl, sec-butyl, tert-butyl and neo-pentyl; and a cyclic saturated hydrocarbon group, or a cyclic unsaturated hydrocarbon group including one or two or more unsaturated bonds.

In the present invention, the term 'alkylene group' may refer to a divalent aliphatic saturated hydrocarbon group such as methylene, ethylene, propylene, and butylene.

The term 'monomer unit' used in the present invention may refer to a repeating unit formed by a compound used as a monomer participating in a polymerization reaction, a structure resulting therefrom, or a material itself.

The term 'compound functional group' used in the present invention may mean a functional group formed by a compound participating in a denaturation reaction, a structure resulting therefrom, or the material itself.

As used herein, the term 'composition' includes reaction products and decomposition products formed from materials of the composition, as well as mixtures of materials comprising the composition.

The present invention provides a conjugated diene-based polymer composition. The conjugated diene-based polymer composition includes a first conjugated diene-based polymer and a second conjugated diene-based polymer, and in the first conjugated diene-based polymer, the ratio of cis-1,4 bonds of the conjugated diene-based monomer unit is 92% by weight. or more, wherein the second conjugated diene-based polymer includes an amine-based compound functional group at one end thereof, and the second conjugated diene-based polymer is included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the first conjugated diene-based polymer. it may be

According to an embodiment of the present invention, the first conjugated diene-based polymer may be a polymer in which a conjugated diene-based monomer is polymerized, and as a specific example, a neodymium-catalyzed conjugated diene-based polymer polymerized using a catalyst composition including a neodymium compound can That is, the first conjugated diene-based polymer may be a conjugated diene-based polymer including an organometallic moiety activated from a catalyst composition including a neodymium compound.

According to an embodiment of the present invention, the conjugated diene-based monomer forming the conjugated diene-based monomer unit of the first conjugated diene-based polymer includes 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, It may be at least one selected from the group consisting of 3-butyl-1,3-octadiene, isoprene and 2-phenyl-1,3-butadiene.

According to an embodiment of the present invention, the first conjugated diene-based polymer may be a high-cis conjugated diene-based polymer, and specifically, the ratio of cis-1,4 bonds of the conjugated diene-based monomer unit is 92 wt% or more, 92 It may be from weight % to 100 weight %, from 92 weight % to 97 weight %, or from 95 weight % to 100 weight %, and when applied to a rubber composition for use as a tire within this range, abrasion resistance, crack resistance and repulsion resistance It has excellent elasticity. According to the present invention, the cis-1,4 bond of the conjugated diene-based monomer unit is a repeating unit through cis-1,4, trans-1,4 and vinyl-1,2 bonds as the conjugated diene-based monomer participates in a polymerization reaction. When forming, it may mean a formed cis-1,4 bond, and the ratio of cis-1,4 bonds is among the cis-1,4 bonds, trans-1,4 bonds and vinyl-1,2 bonds. It may mean a ratio based on weight for cis-1,4 bonds.

에서의 무니점도(mooney viscosity, MV)가 20 내지 100, 30 내지 80, 35 내지, 75, 40 내지 75, 또는 40 내지 50일 수 있고, 이 범위 내에서 가공성이 우수한 효과가 있다.According to an embodiment of the present invention, the first conjugated diene-based polymer is 100

The Mooney viscosity (MV) may be 20 to 100, 30 to 80, 35 to, 75, 40 to 75, or 40 to 50, in which processability is excellent.

According to an embodiment of the present invention, the second conjugated diene-based polymer may be a polymer in which a conjugated diene-based monomer is polymerized, and as a specific example, it may be a conjugated diene-based polymer polymerized using an organolithium compound.

According to an embodiment of the present invention, the conjugated diene-based monomer forming the conjugated diene-based monomer unit of the second conjugated diene-based polymer includes 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, It may be at least one selected from the group consisting of 3-butyl-1,3-octadiene, isoprene, and 2-phenyl-1,3-butadiene, and in this case, there is an effect of excellent compatibility with the first conjugated diene-based polymer.

In addition, according to an embodiment of the present invention, the second conjugated diene-based polymer may be a copolymer in which a conjugated diene-based monomer and an aromatic vinyl-based monomer are copolymerized, and as a specific example, a conjugated diene-based polymer polymerized using an organolithium compound It may be a copolymer.

According to an embodiment of the present invention, when the second conjugated diene-based polymer is a copolymer of a conjugated diene-based monomer and an aromatic vinyl-based monomer, the aromatic vinyl-based monomer forming the aromatic vinyl-based monomer unit is styrene, α-methylstyrene, One selected from the group consisting of 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, and 1-vinyl-5-hexylnaphthalene may be more than

According to an embodiment of the present invention, the second conjugated diene-based polymer is mixed with the first conjugated diene-based polymer solution in a liquid form to form a conjugated diene-based copolymer composition solution as in the manufacturing method to be described later. It can be obtained as a conjugated diene-based polymer composition according to the present invention. As such, when the second conjugated diene-based polymer is mixed with the first conjugated diene-based polymer in a liquid phase, the second conjugated diene-based polymer is present in a dispersed form in the first conjugated diene-based polymer, and accordingly, the rubber composition It has an effect of improving the dispersibility of carbon black and/or silica, which are fillers of

According to an embodiment of the present invention, the second conjugated diene-based polymer has a number average molecular weight (Mn) of 5,000 g/mol to 50,000 g/mol, 10,000 g/mol to 30,000 g/mol, or 19,000 g/mol to It may be 25,000 g/mol, and while improving the processability of the conjugated diene-based polymer composition within this range, at the same time, the first conjugated diene-based polymer and the second conjugated diene-based polymer are separated from each other by reducing the separation of the conjugated diene-based polymer. There is an effect of improving the dispersibility of the second conjugated diene-based polymer in the composition.

In addition, according to an embodiment of the present invention, the second conjugated diene-based polymer has a weight average molecular weight (Mw) of 5,000 g/mol to 100,000 g/mol, 10,000 g/mol to 50,000 g/mol, 20,000 g/mol to 40,000 g/mol, or 22,000 g/mol to 32,000 g/mol, while improving the processability of the conjugated diene-based polymer composition within this range, at the same time, the first conjugated diene-based polymer and the second conjugated diene-based polymer There is an effect of improving the dispersibility of the second conjugated diene-based polymer in the conjugated diene-based polymer composition by reducing the separation of the polymers from each other.

In addition, according to an embodiment of the present invention, the second conjugated diene-based polymer may have a molecular weight distribution (MWD, Mw/Mn) of 1.0 to 2.0, 1.0 to 1.5, or 1.2 to 1.3, within this range. While improving the processability of the conjugated diene-based polymer composition, at the same time reducing the separation of the first conjugated diene-based polymer and the second conjugated diene-based polymer from each other, the dispersibility of the second conjugated diene-based polymer in the conjugated diene-based polymer composition is improved. has an improving effect.

In addition, according to an embodiment of the present invention, the second conjugated diene-based polymer may have a vinyl content of 30% by weight or less, or 0.1% to 30% by weight of the conjugated diene-based monomer unit, and within this range, Separation of the first conjugated diene-based polymer and the second conjugated diene-based polymer is reduced, thereby improving the dispersibility of the second conjugated diene-based polymer in the conjugated diene-based polymer composition.

According to an embodiment of the present invention, the second conjugated diene-based polymer may include an amine-based compound functional group at one end. As a specific example, the functional group of the amine-based compound may be formed by a reaction between the amine-based compound and a conjugated diene-based polymer having one end in an anionic active state by polymerization using an organolithium compound. The reaction may be carried out by a substitution reaction between one terminal of the conjugated diene-based polymer in an anionic active state and a reaction site capable of a substitution reaction in the amine-based compound.

According to an embodiment of the present invention, the amine-based compound may include a primary amine or a secondary amine, and accordingly, the second conjugated diene-based polymer includes a primary amine or secondary amine functional group at one end. it could be In this case, there is an effect of improving the dispersibility of the inorganic filler such as silica or carbon black in the rubber composition from the amine group.

According to an embodiment of the present invention, the amine-based compound may be at least one selected from the group consisting of compounds represented by the following Chemical Formulas 1 to 4.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

In Formulas 1 to 4, X ¹ to X ⁵ are each independently -NH- or -CR ⁶ R ⁷ -, wherein at least one of ^{X 1} to X ^{5 may be -NH-, R 1} , R ⁴ and R ⁵ may each independently be an alkyl group having 1 to 30 carbon atoms, R ² and R ³ may each independently be an alkylene group having 1 to 30 carbon atoms, and R ⁶ and R ⁷ are each independently hydrogen or 1 carbon atom. to 30 may be an alkyl group, n may be 0, 1 or 2, m may be an integer selected from 1 to 3, and n+m may be 3.

As a specific example, in Formula 1, X ¹ to X ³ are each independently -NH- or -CR ⁶ R ⁷ -, ^{wherein at least one of X 1} to X ³ may be -NH-, and X ⁴ and X ⁵ may be -CR ⁶ R ⁷ -, R ¹ may be an alkyl group having 1 to 20 carbon atoms, and R ⁶ and R ⁷ may each independently be hydrogen or an alkyl group having 1 to 20 carbon atoms. As a more specific example, in Formula 1, X ¹ , X ² , X ⁴ and X ⁵ may each independently be -CR ⁶ R ⁷ -, X ³ may be -NH-, and R ¹ is C 1 to It may be an alkyl group of 10, and R ⁶ and R ⁷ may each independently be hydrogen or an alkyl group having 1 to 10 carbon atoms.

In addition, as a specific example, in Formula 2, R ¹ may be an alkyl group ^{having 1 to 20 carbon atoms, and R 2} may be an alkylene group having 1 to 20 carbon atoms. As a more specific example, in Formula 2, R ¹ may be an alkyl group ^{having 1 to 10 carbon atoms, and R 2} may be an alkylene group having 1 to 10 carbon atoms.

In addition, as a specific example, in Formula 4, R ³ may each independently be an alkylene group having 1 to 20 carbon atoms, R ⁴ and R ⁵ may each independently be an alkyl group having 1 to 20 carbon atoms, n is 0, It may be 1 or 2, m may be an integer selected from 1 to 3, and n+m may be 3. As a more specific example, in Formula 4, R ³ may each independently be an alkylene group having 1 to 10 carbon atoms, R ⁴ and R ⁵ may each independently be an alkyl group having 1 to 10 carbon atoms, and n is 0 or 1 , m may be 2 or 3, and n+m may be 3.

In addition, according to an embodiment of the present invention, the amine-based compound may be at least one selected from the group consisting of compounds represented by the following Chemical Formulas 1-1 to 4-1.

[Formula 1-1]

[Formula 2-1]

[Formula 3-1]

[Formula 4-1]

According to an embodiment of the present invention, when the second conjugated diene-based polymer includes an amine-based compound functional group represented by Chemical Formulas 1 to 4 at one end, each functional group is formed using an organolithium compound as described above. It may be formed by a reaction between a conjugated diene-based polymer and an amine-based compound having one end in an anionic active state by polymerization.

As a specific example, when the amine-based compound includes the compound represented by Formula 1 or 2, the reaction is performed at one end of the conjugated diene-based polymer in an anionic active state by reacting with the carbonyl group of the compound represented by Formula 1 or 2, ^{It may be substituted with R 1} -O- of the carboxyl group, and accordingly, the second conjugated diene-based polymer may include a primary amine or a secondary amine at one end.

In addition, when the amine-based compound includes the compound represented by Formula 3, the reaction is a reaction in which one terminal of the conjugated diene-based polymer in an anion-active state reacts with the carbonyl group of the compound represented by Formula 3, C=O double The bond may be opened while bonding, and accordingly, the second conjugated diene-based polymer may include a primary amine at one end thereof.

In addition, when the amine-based compound includes the compound represented by Formula 4, the reaction is performed at one end of the conjugated diene-based polymer in an anionic active state reacts with the alkoxysilane group of the compound represented by Formula 4, and the R of the silane group ^{It may be substituted with any one of 5} -O-, and accordingly, the second conjugated diene-based polymer may include a primary amine at one end.

In addition, according to an embodiment of the present invention, the second conjugated diene-based polymer is 0.1 parts by weight to 10 parts by weight, 0.1 parts by weight to 5 parts by weight, 0.1 parts by weight based on 100 parts by weight of the first conjugated diene-based polymer. to 2 parts by weight, 2 parts by weight to 10 parts by weight, 2 parts by weight to 5 parts by weight, or 5 parts by weight to 10 parts by weight. there is Here, the content of the second conjugated diene-based polymer is a form in which the liquid second conjugated diene-based polymer is mixed with the first conjugated diene-based polymer solution, and then the second conjugated diene-based polymer is dispersed in the first conjugated diene-based polymer. Since it is obtained as , it may be the same as the input content (based on solid content) of the liquid second conjugated diene-based polymer described in the method for preparing a conjugated diene-based polymer composition to be described later.

In addition, according to an embodiment of the present invention, since the conjugated diene-based polymer composition includes the second conjugated diene-based polymer, a nitrogen atom derived from an amine-based compound functional group included in one end of the second conjugated diene-based polymer may contain, and therefrom, there is an effect of improving low fuel consumption characteristics in the rubber composition. As a specific example, the second conjugated diene-based polymer may have a nitrogen atom content of 10 ppm to 3,000 ppm, 100 ppm to 2,000 ppm, or 170 ppm to 1,500 ppm, while excellent processability within this range, tensile properties and viscoelastic properties This has an excellent effect.

In addition, according to an embodiment of the present invention, since the conjugated diene-based polymer composition includes the second conjugated diene-based polymer, It may contain a silicon atom derived therefrom, thereby having an effect of improving low fuel consumption properties in the rubber composition. As a specific example, the second conjugated diene-based polymer may have a silicon atom content of 10 ppm to 3,000 ppm, 100 ppm to 2,000 ppm, or 200 ppm to 500 ppm, while excellent processability within this range, tensile properties and viscoelastic properties This has an excellent effect.

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

According to an embodiment of the present invention, the method for preparing the conjugated diene-based polymer composition comprises a first conjugated diene-based polymer by polymerizing a conjugated diene-based monomer in the presence of a catalyst composition including a first organic solvent and a neodymium compound. 1 preparing a conjugated diene-based polymer solution (S10); preparing a polymer solution including an unmodified conjugated diene-based polymer by polymerizing a conjugated diene-based monomer in the presence of a second organic solvent and an organolithium compound (S20); preparing a liquid second conjugated diene-based polymer by adding and reacting an amine-based compound to the polymer solution prepared in step (S20) (S30); and 0.1 parts by weight to 10 parts by weight of the liquid second conjugated diene-based polymer prepared in step (S30) to 100 parts by weight (based on solid content) of the first conjugated diene-based polymer solution prepared in step (S10) (based on solid content) ) and mixing (S40), wherein in the first conjugated diene-based polymer, the ratio of cis-1,4 bonds of the conjugated diene-based monomer unit is 92% by weight or more, and the second conjugated diene-based polymer may include an amine-based compound functional group at one end.

According to an embodiment of the present invention, step (S10) is a step for preparing a first conjugated diene-based polymer solution including a first conjugated diene-based polymer, and in a first organic solvent, a catalyst containing a neodymium compound It may be a step for preparing an active polymer by polymerizing a conjugated diene-based monomer in the presence of the composition.

According to an embodiment of the present invention, the active polymer may be a conjugated diene-based polymer including an organometallic moiety, and the organometallic moiety of the active polymer including the organometallic moiety is an activated organometallic moiety at the end of the copolymer. (an activated organometallic moiety at the end of a molecular chain), an activated organometallic moiety in the main chain, or an activated organometallic moiety in a side chain (side chain). When obtaining a metal moiety, the organometallic moiety may represent an activated organometallic moiety at the end.

The polymerization may be carried out by radical polymerization, and may be carried out by various polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization or emulsion polymerization, and may be carried out by a batch method, a continuous method, or a semi-continuous method. could be As a specific example, the polymerization for preparing the active polymer may be carried out by reacting the catalyst composition by adding a conjugated diene-based monomer in an organic solvent.

In addition, according to an embodiment of the present invention, the polymerization may be elevated temperature polymerization, isothermal polymerization, or constant temperature polymerization (adiabatic polymerization). Here, the constant temperature polymerization refers to a polymerization method comprising a 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 to increase heat after the catalyst composition is added, or heat is taken away to maintain a constant temperature of a reactant.

According to an embodiment of the present invention, 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 60 °C to 90 °C It may be carried out for 15 minutes to 3 hours at a temperature range of °C, and within this range, it is possible to sufficiently control the polymerization reaction, prevent a decrease in the rate and efficiency of the polymerization reaction, and secure a high cis-1,4 bond content. can

In addition, according to an embodiment of the present invention, the polymerization may be carried out for 5 minutes to 1 hour within the above-described temperature range until a conversion of 100% of the conjugated diene-based polymer is reached, specifically, from 15 minutes to 1 hour. can be performed while

In addition, according to an embodiment of the present invention, the conjugated diene-based monomer input in step (S10) may be the same as the conjugated diene-based monomer forming the first conjugated diene-based polymer described above.

According to an embodiment of the present invention, the first organic solvent may be a hydrocarbon solvent, and specifically, may be a non-polar hydrocarbon solvent, and more specifically, an aliphatic hydrocarbon solvent such as pentane, hexane, isopentane, heptane, octane, isooctane, etc. ; cycloaliphatic hydrocarbon solvents such as cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane and the like; Or it may be at least one selected from the group consisting of aromatic hydrocarbon solvents such as benzene, toluene, ethylbenzene, and xylene. In addition, according to an embodiment of the present invention, during polymerization using the first organic solvent, the concentration of the monomer may be 3 wt% to 80 wt%, or 5 wt% to 30 wt%.

According to an embodiment of the present invention, the catalyst composition including the neodymium compound may include (a) a neodymium compound, (b) a first alkylating agent, (c) a second alkylating agent, and (d) a halogen compound, ( e) may further include a conjugated diene-based monomer.

According to an embodiment of the present invention, the catalyst composition may be used in an amount such that the neodymium compound is 0.10 to 0.50 mmol based on 100 g of the conjugated diene-based monomer, and specifically, the neodymium compound is the conjugated diene-based monomer It may be used in an amount such that it is 0.1 to 0.4 mmol, more specifically, 0.1 to 0.25 mmol based on 100 g. After the neodymium compound is activated by the first and second alkylating agents, it forms catalytically active species for polymerization of the conjugated diene.

According to an embodiment of the present invention, 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). acid salt, 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-diketonate (eg, neodymium acetylacetonate, neodymium trifluoroacetyl acetonate, neodymium hexafluoroacetyl acetonate or neodymium benzoyl acetonate, etc.); alkoxides or allyloxides (eg, neodymium methoxide, neodymium ethoxide, neodymium isopropoxide, neodymium phenoxide or neodymium nonyl phenoxide, etc.); halides or 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 organic neodymium containing compounds 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.

Specifically, the neodymium compound may be a compound represented by the following Chemical Formula 5.

[Formula 5]

In Formula 5, R _x to R _z are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms, but R _x to R _z may not all be hydrogen at the same time.

In addition, according to an embodiment of the present invention, 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 formulated with the above formula In 5, R _x is an alkyl group having 4 to 12 carbon atoms, and R _y and R _z are each independently hydrogen or an alkyl group having 2 to 8 carbon atoms, provided that R _y and R _z are not hydrogen at the same time. As a more specific example, in Formula 5, R _x is an alkyl group having 6 to 8 carbon atoms, R _y and R _z may each independently be hydrogen or an alkyl group having 2 to 6 carbon atoms, wherein R _y and R _z are At the same time, it may not be hydrogen. As a more specific example, in Formula 5, R _x may be an alkyl group having 6 to 8 carbon atoms, and R _y and R _z may each independently be an alkyl group having 2 to 6 carbon atoms. As such, the neodymium-based compound represented by Formula 5 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, has the 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.

According to an embodiment of the present invention, 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-di Octyl decanoate) ₃ , Nd(2-ethyl-2-propyl decanoate) ₃ , Nd(2-ethyl-2-butyl decanoate) ₃ , Nd(2-ethyl-2-hexyl decanoate) ₃ , Nd(2-propyl-2-butyl decanoate) ₃ , Nd(2-propyl-2-hexyl decanoate) ₃ , Nd(2-propyl-2-isopropyl decanoate) ₃ , Nd( 2-Butyl-2-hexyl decanoate) ₃ , Nd(2-hexyl-2-octyl decanoate) ₃ , Nd(2,2-diethyl octanoate) ₃ , Nd(2,2-dipropyl) Octanoate) ₃ , Nd(2,2-dibutyl octanoate) ₃ , Nd(2,2-dihexyl octanoate) ₃ , Nd(2-ethyl-2-propyl octanoate) ₃ , Nd (2-ethyl-2-hexyl octanoate) ₃ , Nd(2,2-diethyl nonanoate) ₃ , Nd(2,2-dipropyl nonanoate) ₃ , Nd(2,2-dibutyl nonanoate) ₃ , Nd(2,2-dihexyl nonanoate) ₃ , Nd(2-ethyl-2-propyl nonanoate) ₃ and Nd(2-ethyl-2-hexyl nonanoate) ₃ It may be at least one selected from the group consisting of.

In addition, according to an embodiment of the present invention, the solubility of the neodymium compound may be about 4 g or more per 6 g of the non-polar solvent at room temperature (23 ± 5 °C). 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, according to an embodiment of the present invention, the neodymium compound may be used in the form of a reactant with a Lewis base. This reactant has the effect of improving the solubility of the neodymium compound in a solvent by 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 mole to 10 moles relative to 1 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.

According to an embodiment of the present invention The first alkylating agent may be aluminoxane, and the aluminoxane may be prepared by reacting a trihydrocarbyl aluminum-based compound with water. Specifically, the aluminoxane may be a straight-chain aluminoxane of Formula 6 or a cyclic aluminoxane of Formula 7 below.

[Formula 6]

[Formula 7]

In Formulas 6 and 7, R is a monovalent organic group bonded to an aluminum atom through a carbon atom, and may be a hydrocarbyl group, and a and b are each independently an integer of 1 or more, 1 to 100, or 2 to 50 may be an integer of .

According to an embodiment of the present invention, 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, phenylaluminoxane or 2, 6-dimethylphenyl aluminoxane and the like, and any one or a mixture of two or more thereof may be used.

In addition, according to an embodiment of the present invention, the modified methylaluminoxane is a methyl group of methylaluminoxane is substituted with a modifying group (R), specifically, a hydrocarbon group having 2 to 20 carbon atoms, specifically represented by the following formula (8) It may be the indicated compound.

[Formula 8]

In Formula 8, R is as defined above, c and d may be each independently an integer of 2 or more, and Me represents a methyl group.

Specifically, in Formula 8, 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.

As a more specific example, 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, 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 alkylaluminum may be triisobutylaluminum, triethylaluminum, trihexylaluminum or trioctylaluminum, and any one or a mixture of two or more thereof may be used.

In addition, according to an embodiment of the present invention, it is possible to form a narrow molecular weight distribution of the modified conjugated diene-based polymer to be prepared, and thus, preferably in terms of improving the physical properties of the polymer, the first alkylating agent is methylaluminoxane or modified methylalumin It may be rust.

The second alkylating agent according to an embodiment of the present invention may be hydrocarbyl aluminum dihydride, and specifically, the second alkylating agent is diethyl aluminum hydride, di-n-propyl aluminum hydride, diisopropyl aluminum Hydride, di-n-butylaluminum hydride, diisobutylaluminum hydride (DIBAH), di-n-octylaluminum hydride, diphenylaluminum hydride, di-p-tolylaluminum hydride, dibenzylaluminum hydride Ride, phenylethylaluminum hydride, phenyl-n-propylaluminum hydride, phenylisopropylaluminum hydride, phenyl-n-butylaluminum hydride, 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-n-butylaluminum hydride, benzylisobutylaluminum hydride or benzyl-n- dihydrocarbyl aluminum hydride such as octylaluminum hydride; One selected from the group consisting of ethylaluminum dihydride, n-propylaluminum dihydride, isopropylaluminum dihydride, n-butylaluminum dihydride, isobutylaluminum dihydride and n-octylaluminum dihydride It may be more than

According to an embodiment of the present invention, in the catalyst composition, the alkylating agent is an organometallic compound capable of transferring a hydrocarbyl group to another metal, and may serve as a co-catalyst.

In addition, if necessary, the catalyst composition of the present invention may further include an alkylating agent used as an alkylating agent in the preparation of the conjugated diene-based polymer in addition to the first and second alkylating agents, such alkylating agents include trimethylaluminum, triethylaluminum, Alkyl such as tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, and trioctylaluminum aluminum; and alkyl magnesium compounds such as diethyl magnesium, di-n-propyl magnesium, diisopropyl magnesium, dibutyl magnesium, dihexyl magnesium, diphenyl magnesium, and dibenzyl magnesium. and alkyl lithium compounds such as n-butyllithium.

According to an embodiment of the present invention, the halogen compound may include a halogen simple substance, an interhalogen compound, a hydrogen halide, an organic halide, a non-metal halide, a metal halide, or an organometallic halide. , any one of them 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 halogen compound in consideration of the excellent effect of improving catalytic activity and thus improving reactivity.

According to an embodiment of the present invention, the halogen simple substance may be fluorine, chlorine, bromine or iodine.

In addition, according to an embodiment of the present invention, the interhalogen compound may be iodine monochloride, iodine monobromide, iodine trichloride, iodine pentafluoride, iodine monofluoride or iodine trifluoride.

In addition, according to an embodiment of the present invention, the hydrogen halide may be hydrogen fluoride, hydrogen chloride, hydrogen bromide or hydrogen iodide.

In addition, according to an embodiment of the present invention, as the organic halide, t-butyl chloride (t-BuCl), t-butyl bromide, allyl chloride, allyl bromide, benzyl chloride, benzyl bromide, chloro-di-phenylmethane, bromine Mo-di-phenylmethane, triphenylmethyl chloride, triphenylmethyl bromide, benzylidene chloride, benzylidene bromide, methyltrichlorosilane, phenyltrichlorosilane, dimethyldichlorosilane, diphenyldichlorosilane, trimethylchlorosilane (TMSC1) , benzoyl chloride, benzoyl bromide, propionyl chloride, propionyl bromide, methyl chloroformate, methyl bromoformate, iodomethane, diiodomethane, triiodomethane (also called iodoform), tetraio Domethane, 1-iodopropane, 2-iodopropane, 1,3-diiodopropane, t-butyl iodide, 2,2-dimethyl-1-iodopropane ('neopentyl iodide') rho), allyl iodide, iodobenzene, benzyl iodide, diphenylmethyl iodide, triphenylmethyl iodide, benzylidene iodide (also called 'benzal iodide'), trimethylsilyl Iodide, triethylsilyl iodide, triphenylsilyl iodide, dimethyldiiodosilane, diethyldiiodosilane, diphenyldiiodosilane, methyltriiodosilane, ethyltriiodosilane, phenyltriiodosilane, benzoyl iodide, propionyl iodide, or methyl iodoformate.

In addition, according to an embodiment of the present invention, the non-metal halide is 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, oxyiodide It may be phosphorus iodide or selenium tetraiodide.

In addition, according to an embodiment of the present invention, the metal halide is tin tetrachloride, tin tetrabromide, aluminum trichloride, aluminum tribromide, antimony trichloride, antimony pentachloride, antimony tribromide, aluminum trifluoride, gallium trichloride, gallium tribromide, Gallium trifluoride, indium trichloride, indium tribromide, indium trifluoride, titanium tetrachloride, titanium tetrabromide, zinc dichloride, zinc dibromide, zinc difluoride, aluminum triiodide, gallium triiodide, indium triiodide, titanium tetraiodide, Zinc iodide, germanium tetraiodide, tin tetraiodide, tin iodide, antimony triiodide, or magnesium iodide may be used.

In addition, according to an embodiment of the present invention, the organometallic halide is specifically dimethylaluminum chloride, diethylaluminum chloride, dimethylaluminum bromide, diethylaluminum bromide, dimethylaluminum fluoride, diethylaluminum fluoride, methylaluminum dichloride , ethylaluminum dichloride, methylaluminum dibromide, ethylaluminum dibromide, methylaluminum difluoride, ethylaluminum difluoride, methylaluminum sesquichloride, ethylaluminum sesquichloride (EASC), isobutylaluminum sesquichloride, Methylmagnesium chloride, methylmagnesium bromide, ethylmagnesium chloride, ethylmagnesium bromide, n-butylmagnesium chloride, n-butylmagnesium bromide, phenylmagnesium chloride, phenylmagnesium bromide, benzylmagnesium chloride, trimethyltin chloride, trimethyltin bromide, triethyl Tin 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, isobutyl Aluminum sesquiiodide, ethylmagnesium iodide, n-butylmagnesium iodide, isobutylmagnesium iodide, phenylmagnesium iodide, benzylmagnesium iodide, trimethyltin iodide, triethyltin iodide id, tri-n-butyltin iodide, di-n-butyltin diiodide, or di-t-butyltin diiodide.

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

As a specific example, 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. As a more specific example, 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, according to an embodiment of the present invention, the non-coordinating anion precursor is a compound capable of forming a non-coordinating anion under reaction conditions, and a triaryl boron compound (BR ₃ , where R is a pentafluorophenyl group or 3,5-bis (trifluoromethyl) a strong electron-withdrawing aryl group such as a phenyl group).

In addition, according to an embodiment of the present invention, the catalyst composition may further include a conjugated diene-based monomer, and a part of the conjugated diene-based monomer used in the polymerization is mixed with the catalyst composition for polymerization in advance to pre-polymerize. By using it in the form of one preforming or premix catalyst composition, it is possible not only to improve the catalyst composition activity but also to stabilize the active polymer to be prepared. Here, the “preforming” refers to a catalyst composition including a neodymium compound, an alkylating agent and a halide, i.e., diisobutylaluminum hydride (DIBAH) in the catalyst system. A small amount of a conjugated diene-based monomer such as 1,3-butadiene is added to reduce the possibility of species generation, and it may mean that pre-polymerization is performed in the catalyst composition system together with the addition of 1,3-butadiene. 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 reaction, for example, with respect to 1 mole of the neodymium compound. 1 mole to 100 moles, 1 mole to 50 moles, or 1 mole to 30 moles may be included.

In addition, according to an embodiment of the present invention, the catalyst composition is at least one of the above-mentioned neodymium compound and alkylating agent, halide and conjugated diene-based monomer in an organic solvent, specifically, a neodymium compound, an alkylating agent and a halide, and optionally conjugated. It can be prepared by mixing a diene-based monomer. In this case, the organic solvent may be a non-polar solvent that is not reactive with the components of the catalyst composition.

According to an embodiment of the present invention, the non-polar solvent is n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, isopentane, isohexane, isopentane, isooctane, 2,2 - a linear, branched or cyclic aliphatic hydrocarbon having 5 to 20 carbon atoms, such as dimethylbutane, cyclopentane, cyclohexane, methylcyclopentane or methylcyclohexane; a mixed solvent of aliphatic hydrocarbons having 5 to 20 carbon atoms, such as petroleum ether or petroleum spirits, or kerosene; Or it may be an aromatic hydrocarbon-based solvent such as benzene, toluene, ethylbenzene, xylene, etc., and may be any one or a mixture of two or more thereof. As a specific example, the non-polar solvent may be a linear, branched or cyclic aliphatic hydrocarbon having 5 to 20 carbon atoms or a mixed solvent of an aliphatic hydrocarbon, and more specifically, it may be n-hexane, cyclohexane, or a mixture thereof.

In addition, according to an embodiment of the present invention, in the polymerization reaction, in order not to inactivate the catalyst composition and the polymer, for example, it is preferable to prevent the incorporation of a compound having an inactivating action such as oxygen, water, carbon dioxide gas, etc. in the polymerization reaction system. can do. As a result of the polymerization reaction as described above, an active polymer including an organometallic moiety activated from the catalyst composition including the neodymium compound, more specifically, a neodymium-catalyzed conjugated diene-based polymer including a 1,3-butadiene monomer unit is produced, and the prepared conjugated diene-based polymer may have pseudo-living properties.

In addition, according to an embodiment of the present invention, after preparing the active polymer by the polymerization reaction, alcohol such as methanol, ethanol, propanol or isopropanol, a reaction terminator for completing the polymerization reaction such as polyoxyethylene glycol phosphate Alternatively, the step (S11) of terminating the polymerization by further using an additive such as an antioxidant such as 2,6-di-t-butylparacresol may be included. 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 adjuster, an oxygen scavenger or an oxygen scavenger may be optionally further used.

According to an embodiment of the present invention, the first conjugated diene-based polymer prepared by the step (S10) may be a high-cis conjugated diene-based polymer, and specifically, the cis-1,4 bond of the conjugated diene-based monomer unit. The proportion may be 92 wt% or more, 92 wt% to 100 wt%, 92 wt% to 97 wt%, or 95 wt% to 100 wt%.

According to an embodiment of the present invention, the step (S20) is a step for preparing an unmodified conjugated diene-based polymer for preparing a liquid modified conjugated diene-based polymer, and in the second organic solvent, the presence of an organolithium compound It may be a step for preparing an unmodified conjugated diene-based polymer having an anionic activity at one end by polymerizing a conjugated diene-based monomer under

According to an embodiment of the present invention, the second organic solvent may be at least one selected from the group consisting of -pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene, and xylene.

In addition, according to an embodiment of the present invention, the organolithium compound is a polymerization initiator for conducting an anionic polymerization reaction, including methyl lithium, ethyl lithium, propyl lithium, isopropyl lithium, n-butyl lithium, s-butyl lithium, t-butyllithium, hexyllithium, n-decyllithium, t-octyllithium, phenyllithium, 1-naphthyllithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolylylithium, cyclohexyllithium, 3, 5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naphthyl sodium, naphthyl potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium It may be at least one selected from the group consisting of amide, potassium amide, and lithium isopropylamide.

According to an embodiment of the present invention, the organolithium compound is 0.01 mmol to 10 mmol, 0.05 mmol to 5 mmol, 0.1 mmol to 2 mmol, 0.1 mmol to 1 based on 100 g of the total monomer of the second conjugated diene-based polymer. mmol, or 0.15-0.8 mmol.

According to an embodiment of the present invention, the polymerization in step (S20) may be, for example, anionic polymerization, and as a specific example, living anionic polymerization having an anionic active site at the polymerization end by an anion-based growth polymerization reaction. In addition, the polymerization in step (S20) may be an elevated temperature polymerization, isothermal polymerization, or constant temperature polymerization (adiabatic polymerization).

According to an embodiment of the present invention, the unmodified conjugated diene-based polymer prepared by the step (S20), that is, the active polymer may refer to a polymer in which a polymer anion and an organometallic cation are combined.

According to an embodiment of the present invention, the polymerization in step (S20) may be carried out including a polar additive, and the polar additive is 0.001 g to 50 g, 0.001 g based on 100 g of the monomer input in step (S20). to 10 g, or 0.005 g to 0.500 g. According to another embodiment of the present invention, the polar additive may be added in a proportion of 0.001 g to 10 g, 0.005 g to 5 g, 0.005 g to 4 g based on 1 mmol of the total organolithium compound.

According to an embodiment of the present invention, the polar additive is tetrahydrofuran, 2,2-di(2-tetrahydrofuryl)propane, diethyl ether, cyclopentyl ether, dipropyl ether, ethylene methyl ether, ethylene dimethyl ether , diethyl glycol, dimethyl ether, tertiary butoxyethoxyethane, bis (3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine, N,N,N It may be at least one selected from the group consisting of ',N'-tetramethylethylenediamine, sodium mentholate, and 2-ethyl tetrahydrofurfuryl ether, and a specific example of 2,2- di(2-tetrahydrofuryl)propane, triethylamine, tetramethylethylenediamine, sodium mentholate or 2-ethyl tetrahydrofurfuryl ether.

According to an embodiment of the present invention, the step (S30) is a step for preparing a second conjugated diene-based polymer by reacting the unmodified conjugated diene-based polymer prepared in the step (S20) with an amine-based compound, wherein The reaction may be a denaturation or coupling reaction, and in this case, the amine-based compound may be used in an amount of 0.01 mmol to 10 mmol based on 100 g of the total monomer. According to another embodiment of the present invention, the amine-based compound is 1:0.1 to 10, 1:0.1 to 5, or 1:0.1 to 1:3 based on 1 mole of the organolithium compound in step (S20). It can be used in molar ratio.

According to an embodiment of the present invention, the second conjugated diene-based polymer prepared in step (S30) may include an amine-based compound functional group at one end thereof.

According to an embodiment of the present invention, the first conjugated diene-based polymer solution containing the first conjugated diene-based polymer prepared in step (S10), and the liquid phase prepared in steps (S20) and (S30) Each of the second conjugated diene-based polymers may be individually implemented. As a specific example, after step (S10), steps (S20) and (S30) may be performed, and steps (S20) and (S30) may be performed simultaneously with step (S10), and step (S20) and (S30) may be performed after the step (S10).

According to an embodiment of the present invention, the step (S40) is a step for preparing a solution of the conjugated diene-based polymer composition, and without recovering the second conjugated diene-based polymer prepared in the step (S30), the solution, that is, It is characterized in that it is added to the first conjugated diene-based polymer solution prepared in step (S10) in a liquid state and mixed. As a specific example, in step (S40), 0.1 weight of the liquid second conjugated diene-based polymer prepared in step (S30) is added to 100 parts by weight (based on solid content) of the first conjugated diene-based polymer solution prepared in step (S10). It can be carried out by adding parts to 10 parts by weight (based on solid content) and mixing.

Further, according to an embodiment of the present invention, the method for preparing the conjugated diene-based polymer composition may include a step (S50) of drying the conjugated diene-based polymer composition solution prepared in the step (S40). As a specific example, the drying may be carried out through solvent removal treatment such as steam stripping and vacuum drying treatment to lower the partial pressure of the solvent through supply of water vapor, and thus the first conjugated diene-based polymer solution and the liquid second conjugated diene A conjugated diene-based polymer composition may be obtained from a solution of the conjugated diene-based polymer composition in which the polymer is mixed.

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

According to an embodiment of the present invention, the rubber composition may include 0.1 to 100% by weight of the conjugated diene-based polymer composition, specifically 10 to 100% by weight, or 20 to 90% by weight, within this range It has an excellent effect in abrasion resistance and crack resistance.

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

According to an embodiment of the present invention, 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, which 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.

In addition, according to an embodiment of the present invention, the rubber composition may include 0.1 to 150 parts by weight of a filler based on 100 parts by weight of the conjugated diene-based polymer composition, and the filler may be silica-based, carbon black, or a combination thereof. and carbon black as a specific example.

According to an embodiment of the present invention, the carbon black 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, , the dibutyl phthalate oil absorption (DBP) may be 80 cc/100g to 200 cc/100g, and within this range, the processability of the rubber composition is not reduced and the reinforcing performance by the filler is excellent.

In addition, according to an embodiment of the present invention, the silica 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 effect of wet grip. In addition, the silica has a nitrogen adsorption specific surface area (nitrogen 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 /g may be, and within this range, the workability of the rubber composition is not reduced, and the reinforcement performance by the filler is excellent.

Meanwhile, according to an embodiment of the present invention, when silica is used as the filler, a silane coupling agent may be used together to improve reinforcing properties and low heat generation. 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-dimethylthiocarbamoyltetrasulfide, 3 -triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilylpropylbenzothia Zolyltetrasulfide, 3-triethoxysilylpropylbenzolyltetrasulfide, 3-triethoxysilylpropylmethacrylate monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, bis(3- diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide or dimethoxymethylsilylpropylbenzothiazolyltetrasulfide 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 obtain low fuel economy.

In addition, the rubber composition according to an embodiment of the present invention includes, in addition to the above components, various additives commonly used in the rubber industry, specifically, a vulcanization accelerator, a plasticizer, an anti-aging agent, an anti-scorch agent, zinc white, stear. An 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 antioxidant is specifically N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 6- oxy-2,2,4-trimethyl-1,2-dihydroquinoline, or a high-temperature condensate of diphenylamine and acetone; and the like. 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.

On the other hand, the rubber composition generally includes a process oil that acts as a softener in the rubber composition during compounding and processing of rubber. Accordingly, the rubber composition according to an embodiment of the present invention may also include a paraffinic, naphthenic, or aromatic compound, if necessary, as a process oil. The paraffinic process oil may be included in an amount of 100 parts by weight or less based on 100 parts by weight of the rubber component, and in this case, it is possible to prevent deterioration of the tensile strength and low heat generation (low fuel consumption) of the vulcanized rubber. However, the process oil has a problem in that the process oil flows out of the rubber composition over time after mixing the rubber. On the other hand, since the rubber composition according to an embodiment of the present invention includes the conjugated diene-based polymer composition including the second conjugated diene-based polymer, the amount of the process oil is reduced or the process oil is not included. It can maintain processability equivalent to or higher than that containing As such, the rubber composition according to an embodiment of the present invention does not contain process oil, or is 30 parts by weight or less, 25 parts by weight or less, or 15 parts by weight or less, or more than 0 parts by weight based on 100 parts by weight of the rubber component. It may be included in an amount of 15 parts by weight or less, and thus there is an effect of preventing the problem of the process oil leaking from the rubber composition.

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, an internal mixer, etc. 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, chaff, 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, a tire sidewall, or a tire tread.

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in many different forms and is not limited to the embodiments described herein.

How to measure

For the conjugated diene-based polymers prepared in Examples and Comparative Examples, the microstructure, molecular weight, Mooney viscosity, content of the second conjugated diene-based polymer, nitrogen atom (N) content, and silicon atom (Si) content were measured as follows. .

* Microstructure analysis: Fourier transform infrared spectroscopy (FT-IR) was used to measure the content of cis-1,4 bonds, trans-1,4 bonds and vinyl-1,2 bonds in the conjugated diene-based polymer. Specifically, after measuring the FT-IR transmittance spectrum of the carbon disulfide solution of the modified butadiene polymer prepared at a concentration of 5 mg/mL using carbon disulfide as a blank, the maximum peak value in the vicinity of ^{1130 cm -1 of the measurement spectrum (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-1,2 bonds (c) and cis-1 ,4 The content of each was measured using the minimum peak value (d) near ^{736 cm -1 indicating binding.}

* Weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (MWD, Mw/Mn): Each polymer was dissolved in tetrahydrofuran (THF) at 40 ° C for 30 minutes, followed by gel permeation chromatography ( GPC, Gel Permeation Chromatography) was loaded and flowed. In this case, the column was used by combining two PLgel Olexis columns under the trade name of Polymer Laboratories and one PLgel mixed-C column. 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).

* Mooney viscosity (MV, (ML1+4, @100 ℃)) (MU): For each polymer, using a large rotor with Monsanto's MV2000E, Mooney viscosity was measured at 100 ℃ under the conditions of a rotor speed of 2±0.02 rpm. . At this time, after leaving the sample used at room temperature (23±3 ℃) for more than 30 minutes, collect 27±3 g, fill it in the die cavity, and operate the platen to measure Mooney viscosity while applying torque. did.

* Second conjugated diene-based polymer content: 1 g of the conjugated diene-based polymer composition is formed into a thin film using a roll mill, put into a 500 ml Erlenmeyer flask, and a solution obtained by mixing ethanol and toluene in a weight ratio of 7:3 is 200 g, and after heating at a temperature of 200 ° C. for 20 minutes, the rubber was recovered and dried at a temperature of 140 ° C. for 10 minutes, and the content of the second conjugated diene-based polymer was calculated using the difference in weight before and after the process.

* Nitrogen atom (N) content: The nitrogen atom content was measured using a trace nitrogen quantitative analyzer (NSX-2100H) by the NSX analysis method. Specifically, turn on the trace nitrogen quantitative analyzer (Auto sampler, Horizontal furnace, PMT & Nitrogen detector) _{and set the carrier gas flow rate to 250 ml/min for Ar, 350 ml/min for O 2} , and 300 ml/min for the ozonizer, After setting the heater to 800 °C, the analyzer was stabilized by waiting for about 3 hours. After the analyzer is stabilized, use the Nitrogen standard (AccuStandard S-22750-01-5 ml) to draw a calibration curve in the range of 5 ppm, 10 ppm, 50 ppm, 100 ppm and 500 ppm, and draw the area corresponding to each concentration. After obtaining, a straight line was drawn using the ratio of concentration to area. Thereafter, a ceramic boat containing 20 mg of the sample was placed on the auto sampler of the analyzer and measured to obtain an area. The nitrogen atom content was calculated using the area of the obtained sample and the calibration curve.

At this time, the sample is mixed with 40 g of methanol and 10 g of a liquid second conjugated diene-based polymer in a 100 ml media bottle and left to separate the solution layer, then the second conjugated diene-based polymer solution layer is separated, After repeating the process twice, it was collected by drying in an oven at 100° C. for 20 minutes.

* Silicon atom (Si) content: Silicon atom content was measured using an inductively coupled plasma emission analyzer (ICP-OES, Optima 7300DV) as an ICP analysis method. Specifically, about 0.7 g of the sample is placed in a platinum crucible (Pt crucible), and about 1 ml of concentrated sulfuric acid (98 wt%, Electronic grade) is added, heated at 300 ° C. for 3 hours, and the sample is heated in an electric furnace (Thermo Scientific, Lindberg Blue M), after incineration with the program of steps 1 to 3 below, 1 ml of concentrated nitric acid (48 wt%) and 20 μl of concentrated hydrofluoric acid (50 wt%) were added to the residue, followed by a platinum crucible After sealing and shaking for more than 30 minutes, 1 ml of boric acid was added to the sample, stored at 0 ° C. for 2 hours or more, diluted in 30 ml of ultrapure water, and incinerated to measure. .

1) step 1: initial temp 0 ℃, rate(temp/hr) 180 ℃/hr, temp(holdtime) 180 ℃(1hr)

2) step 2: initial temp 180 ℃, rate(temp/hr) 85 ℃/hr, temp(holdtime) 370 ℃(2hr)

3) step 3: initial temp 370 ℃, rate(temp/hr) 47 ℃/hr, temp(holdtime) 510 ℃(3hr)

At this time, the sample is mixed with 40 g of methanol and 10 g of a liquid second conjugated diene-based polymer in a 100 ml media bottle and left to separate the solution layer, then the second conjugated diene-based polymer solution layer is separated, After repeating the process twice, it was collected by drying in an oven at 100° C. for 20 minutes.

Example

Example 1

<Preparation of catalyst composition>

In a 2 L stainless steel pressure reactor, 280 g of a hexane solution containing 20 wt% of neodymium versatate (NdV) was added, and diisobutylaluminum hydride (DIBAH) and diethylaluminum chloride (DEAC) were added to the neodymium versatate (DEAC). With respect to tate, the molar ratio of neodymium versatate:DIBAH:DEAC was added sequentially so that the molar ratio was 1.0:12.0:2.4, mixed at a temperature of 20°C for 10 minutes, and 1,3-butadiene was added to 1 mole of neodymium versatate by 10 After pre-polymerization was carried out by adding the molar mixture, the catalyst composition was prepared by aging at a temperature of -10 °C for 4 hours.

<Preparation of first conjugated diene-based polymer solution>

Under nitrogen condition, 500 g of 1,3-butadiene and 4,500 g of n-hexane were added to a 15 L stainless steel pressure reactor, and the temperature was raised to 70 ° C. Then, 0.38 mmol of the prepared catalyst composition was added and polymerization was carried out for 1 hour. did. The polymerization conversion was 98%. Thereafter, 0.2 parts by weight of HPSS and 0.3 parts by weight of Wingstay-K were added as a polymerization terminator relative to 100 parts by weight of 1,3-butadiene, and the reaction was terminated by stirring for 30 minutes, and then stored in a 20 L container. A sample for measuring the microstructure (cis-1,4 bond ratio) and Mooney viscosity (MV) from the prepared first conjugated diene-based polymer solution was recovered by steam stripping, and as a result of analysis, Mooney viscosity (MV, (ML1+) 4, @100 °C)) was 45, and the cis-1,4 bond content was 97 wt%.

<Preparation of second conjugated diene-based polymer in liquid phase>

960 g of n-hexane, 36 mg of tetramethylethylenediamine, and 36 g of an n-hexane solution containing 2% by weight of n-butyllithium were added to a 5 L stainless steel pressure reactor, and then, the internal temperature of the reactor was adjusted to 50°C. Then, 240 g of an n-hexane solution in which 1,3-butadiene was diluted to 50% by weight was put into the reactor, and an adiabatic temperature rising reaction was performed. After the reactor internal temperature reached the maximum temperature, the reaction was additionally carried out for 30 minutes, and 0.4 g of a compound represented by the following Chemical Formula 1-1 was added and reacted for 30 minutes. Thereafter, 5 g of ethanol and 0.5 g of Irgacure 1520 were added and mixed for 10 minutes to terminate the reaction and stored in a 10 L container. A sample for measuring molecular weight and nitrogen atom content was recovered from the prepared liquid second conjugated diene-based polymer by steam stripping, and as a result of analysis, number average molecular weight (Mn) 23,000 g/mol, weight average molecular weight (Mw) 27,000, The molecular weight distribution (MWD, Mw/Mn) was 1.2, and the nitrogen atom content was 260 ppm.

[Formula 1-1]

(CAS No. 1126-09-6)

<Preparation of conjugated diene-based polymer composition>

With respect to the prepared first conjugated diene-based polymer solution, based on 100 parts by weight of the first conjugated diene-based polymer solid content, 2 parts by weight of the prepared liquid second conjugated diene-based polymer based on the solid content is added, and for 1 hour mixed. Thereafter, the solvent was removed by steam stripping, and then the remaining solvent and water were removed by roll drying, thereby preparing a conjugated diene-based polymer composition. The Mooney viscosity (MV, (ML1+4, @100° C.)) of the conjugated diene-based polymer composition was 43, and the content of the second conjugated diene-based polymer in the dried conjugated diene-based polymer composition was 100 solids of the first conjugated diene-based polymer. It was 2 parts by weight based on parts by weight.

Example 2

In Example 1, it was carried out in the same manner as in Example 1, except that 0.22 g of the compound represented by the following formula 2-1 was added instead of the compound represented by the formula 1-1.

The prepared liquid second conjugated diene-based polymer had a number average molecular weight (Mn) of 19,000 g/mol, a weight average molecular weight (Mw) of 22,000, and a molecular weight distribution (MWD, Mw/Mn) of 1.2, and the nitrogen atom content was 170 ppm. In addition, the Mooney viscosity (MV, (ML1+4, @100° C.)) of the prepared conjugated diene-based polymer composition was 43, and the content of the second conjugated diene-based polymer in the dried conjugated diene-based polymer composition was the first conjugated diene. It was 2 parts by weight based on 100 parts by weight of the solid content of the polymer.

[Formula 2-1]

(CAS No. 4244-84-2)

Example 3

In Example 1, it was carried out in the same manner as in Example 1, except that 2.3 g of the compound represented by the following formula 3-1 was added instead of the compound represented by the formula 1-1.

The prepared liquid second conjugated diene-based polymer had a number average molecular weight (Mn) of 20,000 g/mol, a weight average molecular weight (Mw) of 24,000, and a molecular weight distribution (MWD, Mw/Mn) of 1.2, and the nitrogen atom content was 190 ppm. In addition, the Mooney viscosity (MV, (ML1+4, @100° C.)) of the prepared conjugated diene-based polymer composition was 43, and the content of the second conjugated diene-based polymer in the dried conjugated diene-based polymer composition was the first conjugated diene. It was 2 parts by weight based on 100 parts by weight of the solid content of the polymer.

[Formula 3-1]

(CAS No. 611-98-3)

Example 4

In Example 1, it was carried out in the same manner as in Example 1, except that 0.31 g of the compound represented by the following formula 4-1 was added instead of the compound represented by the formula 1-1.

The number average molecular weight (Mn) of the prepared liquid second conjugated diene-based polymer was 25,000 g/mol, the weight average molecular weight (Mw) 32,000, and the molecular weight distribution (MWD, Mw/Mn) was 1.3, and the nitrogen atom content was 1,500 ppm, The silicon atom content was 320 ppm. In addition, the Mooney viscosity (MV, (ML1+4, @100° C.)) of the prepared conjugated diene-based polymer composition was 43, and the content of the second conjugated diene-based polymer in the dried conjugated diene-based polymer composition was the first conjugated diene. It was 2 parts by weight based on 100 parts by weight of the solid content of the polymer.

[Formula 4-1]

(CAS No. 13822-56-5)

Example 5

In Example 1, it was carried out in the same manner as in Example 1, except that 0.1 parts by weight of the second conjugated diene-based polymer was added in an amount of 0.1 parts by weight instead of 2 parts by weight based on the solid content.

The Mooney viscosity (MV, (ML1+4, @100 °C)) of the prepared conjugated diene-based polymer composition was 45.

Example 6

In Example 1, it was carried out in the same manner as in Example 1, except that 5 parts by weight of the second conjugated diene-based polymer was added in an amount of 5 parts by weight instead of 2 parts by weight based on the solid content.

The Mooney viscosity (MV, (ML1+4, @100° C.)) of the prepared conjugated diene-based polymer composition was 41, and the content of the second conjugated diene-based polymer in the dried conjugated diene-based polymer composition was the first conjugated diene-based polymer. It was 5 parts by weight based on 100 parts by weight of the solid content.

Example 7

In Example 1, it was carried out in the same manner as in Example 1, except that 10 parts by weight of the second conjugated diene-based polymer was added in an amount of 10 parts by weight instead of 2 parts by weight based on the solid content.

The Mooney viscosity (MV, (ML1+4, @100° C.)) of the prepared conjugated diene-based polymer composition was 37, and the content of the second conjugated diene-based polymer in the dried conjugated diene-based polymer composition was the first conjugated diene-based polymer. It was 10 parts by weight based on 100 parts by weight of the solid content.

Comparative Example 1

The solvent was removed from the first conjugated diene-based polymer solution prepared in Example 1 by steam stripping, and then the remaining solvent and water were removed by roll-drying to prepare a conjugated diene-based polymer.

Comparative Example 2

Under nitrogen condition, 500 g of 1,3-butadiene and 4,500 g of n-hexane were added to a 15 L stainless steel pressure reactor, and the temperature was raised to 70 ° C., 0.48 mmol of the catalyst composition prepared in Example 1 was added and 30 minutes Polymerization was carried out during the The polymerization conversion was 96%. Then, 0.3 g of a compound represented by the following Chemical Formula 9 was added and stirred for an additional 30 minutes. Thereafter, 0.2 parts by weight of HPSS and 0.3 parts by weight of Wingstay-K were added as a polymerization terminator relative to 100 parts by weight of 1,3-butadiene, and the reaction was terminated by stirring for 30 minutes. Then, the solvent was removed by steam stripping, and then the remaining solvent and water were removed by roll drying, thereby preparing a conjugated diene-based polymer. The prepared conjugated diene-based polymer had a Mooney viscosity (MV, (ML1+4, @100° C.)) of 50, a cis-1,4 bond content of 95 wt%, and a nitrogen atom content of 110 ppm.

[Formula 9]

(CAS No. 183994-40-3)

Comparative Example 3

In Example 1, it was carried out in the same manner as in Example 1, except that 0.05 parts by weight of the second conjugated diene-based polymer was added in an amount of 0.05 parts by weight instead of 2 parts by weight based on the solid content.

The Mooney viscosity (MV, (ML1+4, @100 °C)) of the prepared conjugated diene-based polymer composition was 45.

Comparative Example 4

In Example 1, it was carried out in the same manner as in Example 1, except that 15 parts by weight of the second conjugated diene-based polymer was added in an amount of 15 parts by weight instead of 2 parts by weight based on the solid content.

The Mooney viscosity (MV, (ML1+4, @100° C.)) of the prepared conjugated diene-based polymer composition was 33, and the content of the second conjugated diene-based polymer in the dried conjugated diene-based polymer composition was the first conjugated diene-based polymer. It was 15 parts by weight based on 100 parts by weight of the solid content.

Experimental example

Experimental Example 1

Each of the conjugated diene-based polymer compositions or conjugated diene-based polymers prepared in Examples 1 to 3, 5 to 7 and Comparative Examples 1 to 4 was used as a raw rubber, and the following Tables 1 and 2 were used using a Banbary mixer. It was blended under the compounding conditions shown in and a rubber specimen was prepared. The content of each raw material in Tables 1 and 2 is each part by weight based on 100 parts by weight of the raw rubber. Using each prepared rubber specimen, Mooney viscosity, tensile strength, 300% modulus, and viscoelastic properties (rolling resistance properties) were measured, respectively, and the results are shown in Tables 3 and 4, respectively.

division
Content (parts by weight) Example One 2 3 5 6 7 raw rubber Conjugated diene-based polymer composition
or
Conjugated diene-based polymer 50 50 50 50 50 50 natural rubber 50 50 50 50 50 50 carbon black 50 50 50 50 50 50 fair oil 14.0 14.0 14.0 15.0 12.5 10.0 anti-aging agent 2 2 2 2 2 2 zinc oxide 3 3 3 3 3 3 stearic acid 2 2 2 2 2 2 sulfur 2 2 2 2 2 2 Vulcanization accelerator (CZ) 2 2 2 2 2 2 Vulcanization accelerator (DPG) 0.5 0.5 0.5 0.5 0.5 0.5

division
Content (parts by weight) comparative example One 2 3 4 raw rubber Conjugated diene-based polymer composition
or
Conjugated diene-based polymer 50 50 50 50 natural rubber 50 50 50 50 carbon black 50 50 50 50 fair oil 15.0 15.0 15.0 7.5 anti-aging agent 2 2 2 2 zinc oxide 3 3 3 3 stearic acid 2 2 2 2 sulfur 2 2 2 2 Vulcanization accelerator (CZ) 2 2 2 2 Vulcanization accelerator (DPG) 0.5 0.5 0.5 0.5

Specifically, conjugated diene-based polymer composition or conjugated diene-based polymer, natural rubber, carbon black (X-50S), process oil (TDAE oil), antioxidant (6PPD ((dimethylbutyl)-N-phenyl-phenylenediamine), A first composition in which zinc oxide (ZnO) and stearic acid are mixed is formed, and then sulfur, a vulcanization accelerator (CZ (N-cytlohexyl-2-benzothiazylsulfenamide)) and a vulcanization accelerator ( DPG (diphenylguanine)) was added and mixed at 50 rpm for 1 minute and 30 seconds at 50° C., and then a vulcanized formulation in the form of a sheet was obtained using a roll at 50° C. The obtained vulcanized formulation was heated at 160° C. A rubber specimen was prepared by vulcanization for 25 minutes.

1) Mooney viscosity (MV, (ML1+4, @100 °C)) (MU): Measured using each prepared vulcanization formulation. Specifically, using a large rotor with Monsanto's MV2000E, Mooney viscosity was measured at 100 °C and at a rotor speed of 2±0.02 rpm. At this time, after leaving the sample used at room temperature (23±3 ℃) for more than 30 minutes, collect 27±3 g, fill it in the die cavity, and operate the platen to measure Mooney viscosity while applying torque. did. Here, the Mooney viscosity indicates a workability characteristic, and the lower the Mooney viscosity, the better the workability.

2) Tensile strength (tensile strength, kgf/cm ² ) and 300 % modulus (300 % modulus, kgf/cm ² ): After vulcanizing each rubber composition at 150 ° C for t90 minutes, according to the tensile test method of ASTM D412, Tensile strength, modulus at 300% elongation, and elongation at break were measured. In the table below, the results are expressed as Index (%) based on the results of Comparative Example 1, so a higher value means better.

3) Viscoelastic properties (Tan δ @60 ℃): Viscoelastic properties were measured using a dynamic mechanical analyzer DMTS 500N of GABO, Germany, at a frequency of 10 Hz, Prestrain 3 %, Dynamic Strain 3 %, viscoelastic modulus (Tan δ) at 60 ℃ was measured. At this time, the value of the viscoelastic coefficient (Tan δ) at 60 ℃ shows low fuel efficiency as a rolling resistance characteristic. In the table below, the results are expressed as Index (%) based on the results of Comparative Example 1, so a higher value means better.

division Example One 2 3 5 6 7 Mooney viscosity 38 38 37 37 39 41 Tensile strength (Index) 104 103 101 101 104 103 300 % modulus (Index) 106 104 103 103 108 110 Viscoelastic properties (Tan δ @60 ℃, Index) 108 106 105 101 110 113

division comparative example One 2 3 4 Mooney viscosity 37 45 37 44 Tensile strength (Index) 100 105 100 104 300 % modulus (Index) 100 110 100 111 Viscoelastic properties (Tan δ @60 ℃, Index) 100 115 100 114

As shown in Tables 3 and 4, in the case of a rubber composition using the conjugated diene-based polymer composition according to the present invention as a raw rubber, processability is equivalent or It was confirmed that the tensile properties and viscoelastic properties were excellent while maintaining the above level.

In particular, referring to Examples 1 and 5 to 7, it was confirmed that by including the second conjugated diene-based polymer in the conjugated diene-based polymer composition, it was possible to control the content of the process oil input during the manufacture of the rubber composition, in particular, Example 6 and 7, it was confirmed that the tensile properties and viscoelastic properties were excellent while reducing the content of the process oil to the extent that the second conjugated diene-based polymer was included and exhibiting the same level of processability.

On the other hand, in the case of Comparative Example 2, in which the modified gocis conjugated diene-based polymer was used as the raw rubber, although the tensile properties and viscoelastic properties were increased, it was confirmed that the Mooney viscosity was rapidly increased and the workability was poor.

In addition, even when a conjugated diene-based polymer composition including the second conjugated diene-based polymer is used, in Comparative Example 3 in which the content of the second conjugated diene-based polymer is included in a small amount, processability as well as tensile properties and viscoelastic properties compared to Comparative Example 1 It can be confirmed that no improvement of could

Experimental Example 2

Each of the conjugated diene-based polymer compositions or conjugated diene-based polymers prepared in Example 4 and Comparative Example 1 was used as a raw rubber and blended under the mixing conditions shown in Table 5 below using a banbary mixer, and a rubber specimen was prepared. produced. The content of each raw material in Table 5 is each part by weight based on 100 parts by weight of the raw rubber. Using each prepared rubber specimen, Mooney viscosity, tensile strength, 300% modulus, and viscoelastic properties (rolling resistance properties) were measured in the same manner as in Experimental Example 1, respectively, and the results are shown in Table 6 below.

division
Content (parts by weight) Example comparative example 4 One raw rubber Conjugated diene-based polymer composition
or
Conjugated diene-based polymer 40 40 Modified SSBR 60 60 Silica (7000 gr) 70 70 fair oil 23 25 anti-aging agent 2 2 zinc oxide 3 3 stearic acid 2 2 sulfur 2 2 Vulcanization accelerator (CZ) 2 2 Vulcanization accelerator (DPG) 0.5 0.5

Specifically, conjugated diene-based polymer composition or conjugated diene-based polymer, modified SSBR, silica (7000 GR), process oil (TDAE oil), antioxidant (6PPD ((dimethylbutyl)-N-phenyl-phenylenediamine), zinc oxide (ZnO) and stearic acid to form a first composition, after which sulfur, a vulcanization accelerator (CZ (N-cytlohexyl-2-benzothiazylsulfenamide)) and a vulcanization accelerator (DPG ( diphenylguanine)) was added and mixed at 50 rpm for 1 minute and 30 seconds at 50° C., and then a vulcanized formulation in the form of a sheet was obtained using a roll at 50° C. The obtained vulcanized formulation was heated at 160° C. for 25 minutes During vulcanization, a rubber specimen was prepared.

division Example comparative example 4 One Mooney viscosity 59 58 Tensile strength (Index) 104 100 300 % modulus (Index) 103 100 Viscoelastic properties (Tan δ @60 ℃, Index) 105 100

As shown in Table 6, in the case of a rubber composition using the conjugated diene-based polymer composition according to the present invention as a raw rubber, processability is maintained at the same level as compared to Comparative Example 1 using a high-cis conjugated diene-based polymer as a raw rubber. It was confirmed that the tensile properties and viscoelastic properties were excellent.

From these results, the rubber composition containing the conjugated diene-based polymer composition according to the present invention as a raw rubber has excellent tensile strength and viscoelastic properties, and furthermore, it is equivalent to or higher than that containing the process oil in high-cis polybutadiene. It was confirmed that there is an effect of preventing the problem of process oil from leaking while maintaining processability.

Claims (10)

A first conjugated diene-based polymer and a second conjugated diene-based polymer,
The first conjugated diene-based polymer has a ratio of cis-1,4 bonds of the conjugated diene-based monomer unit of 92% by weight or more,
The second conjugated diene-based polymer includes an amine-based compound functional group at one end,
The second conjugated diene-based polymer is a conjugated diene-based polymer composition that is included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the first conjugated diene-based polymer. According to claim 1,
The second conjugated diene-based polymer has a number average molecular weight of 5,000 g/mol to 50,000 g/mol of a conjugated diene-based polymer composition. According to claim 1,
The second conjugated diene-based polymer is a conjugated diene-based polymer composition having a vinyl content of 30% by weight or less of the conjugated diene-based monomer unit. According to claim 1,
The amine-based compound is a conjugated diene-based polymer composition comprising a primary amine or a secondary amine. According to claim 1,
The amine-based compound is a conjugated diene-based polymer composition of at least one selected from the group consisting of compounds represented by the following Chemical Formulas 1 to 4:
[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

In Formulas 1 to 4,
X ¹ to X ⁵ are each independently -NH- or -CR ⁶ R ⁷ -, wherein at least one of ^{X 1} to X ^{5 is -NH-,}
R ¹ , R ⁴ and R ⁵ are each independently an alkyl group having 1 to 30 carbon atoms,
R ² and R ³ are each independently an alkylene group having 1 to 30 carbon atoms,
R ⁶ and R ⁷ are each independently hydrogen or an alkyl group having 1 to 30 carbon atoms,
n is 0, 1 or 2, m is an integer selected from 1 to 3, and n+m is 3. According to claim 1,
The amine-based compound is a conjugated diene-based polymer composition of at least one selected from the group consisting of compounds represented by the following Chemical Formulas 1-1 to 4-1:
[Formula 1-1]

[Formula 2-1]

[Formula 3-1]

[Formula 4-1]

. According to claim 1,
The second conjugated diene-based polymer is a conjugated diene-based polymer composition having a nitrogen atom content of 10 ppm to 3,000 ppm. preparing a first conjugated diene-based polymer solution including a first conjugated diene-based polymer by polymerizing a conjugated diene-based monomer in the presence of a catalyst composition including a first organic solvent and a neodymium compound (S10);
preparing a polymer solution including an unmodified conjugated diene-based polymer by polymerizing a conjugated diene-based monomer in the presence of a second organic solvent and an organolithium compound (S20);
preparing a liquid second conjugated diene-based polymer by adding and reacting an amine-based compound to the polymer solution prepared in step (S20) (S30); and
0.1 parts by weight to 10 parts by weight of the liquid second conjugated diene-based polymer prepared in step (S30) to 100 parts by weight (based on solid content) of the first conjugated diene-based polymer solution prepared in step (S10) (based on solid content) Including the step of adding and mixing (S40),
The first conjugated diene-based polymer has a ratio of cis-1,4 bonds of the conjugated diene-based monomer unit of 92% by weight or more,
The second conjugated diene-based polymer is a method for producing a conjugated diene-based polymer composition comprising an amine-based compound functional group at one end. 9. The method of claim 8,
Method for producing a conjugated diene-based polymer composition comprising the step (S50) of drying the conjugated diene-based polymer composition solution prepared in the step (S40). A rubber composition comprising the conjugated diene-based polymer composition according to any one of claims 1 to 7.