KR20220013066A - Modified oligomer, modified conjugated diene-based polymer comprising functional group derived from thereof and method for preparing the polymer - Google Patents

Abstract

The present invention relates to a modified oligomer which can be applied as a rubber modifier to give a functional group, a modified conjugated diene-based polymer comprising the functional group derived therefrom, and a preparation method of the modified conjugated diene-based polymer. The present invention provides the modified oligomer which comprises: an aromatic vinyl-based monomer-derived unit substituted with an amine-containing substituent; a (meth) acrylate-based monomer-derived unit; and a unit derived from an aromatic vinyl-based monomer and satisfies conditions (i) to (iii), wherein (i) a number average molecular weight is 2,000 to 50,000 g/mol; (ii) a molecular weight distribution is 1.0 or more and 1.3 or less; and (iii) the number of N atoms in the oligomer is 2 or more.

Description

Modified oligomer, modified conjugated diene-based polymer including functional groups derived therefrom, and method for preparing the modified conjugated diene-based polymer

The present invention relates to a modified oligomer that can be applied as a rubber modifier to give a functional group, a modified conjugated diene-based polymer including a functional group derived therefrom, and a method for preparing the modified conjugated diene-based polymer.

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

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

As a rubber material having a small hysteresis loss, natural rubber, polyisoprene rubber, polybutadiene rubber, etc. are known, but these have a problem of low wet skid resistance. Accordingly, recently, conjugated diene-based (co)polymers such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) have been manufactured by emulsion polymerization or solution polymerization and are used as rubber for tires. . Among them, the greatest advantage of solution polymerization compared to emulsion polymerization is that the content of vinyl structure and styrene content defining rubber properties can be arbitrarily adjusted, and molecular weight and physical properties can be adjusted by coupling or modification. that it can be adjusted. Therefore, it is easy to change the structure of the finally manufactured SBR or BR rubber, and it is possible to reduce the movement of the chain ends by bonding or modifying the chain ends and to increase the binding force with fillers such as silica or carbon black, so SBR or BR by solution polymerization Rubber is widely used as a rubber material for tires.

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

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

In addition, when preparing a rubber composition by mixing SBR or BR with a filler such as silica or carbon black, a coupling agent having a functional group such as a silane group, an amine group, or an azo group is mixed together to increase the affinity between the SBR or BR and the filler. An attempt was made to improve the compounding properties and compounding processability by increasing the dispersibility of the filler, but the compounding property improvement effect was not obtained.

On the other hand, carbon black and silica are used as reinforcing fillers of tire treads. When silica is used as reinforcing fillers, there are advantages in that low hysteresis loss and wet skid resistance are improved. However, compared to carbon black on the hydrophobic surface, silica on the hydrophilic surface has a disadvantage in that it has poor dispersibility due to low affinity with rubber. It is necessary to use a ring agent.

Accordingly, a method has been made to introduce a functional group having affinity or reactivity with silica at the end of the rubber molecule, but the effect is not sufficient.

Therefore, there is a need to develop a rubber having high affinity with fillers including silica and carbon black.

JP 5172663 B2

The present invention has been devised to solve the problems of the prior art, and a modified oligomer capable of introducing a filler-affinity functional group into the polymer by acting as a polymer modifier comprising a controlled amount of a filler-affinity functional group in the molecule intended to provide

Another object of the present invention is to provide a modified conjugated diene-based polymer comprising a functional group derived from a modified oligomer.

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

In order to solve the above problems, the present invention is an aromatic vinyl-based monomer-derived unit substituted with an amine-containing substituent; (meth) acrylate-based monomer-derived units; and an aromatic vinylic monomer-derived unit, and provides a modified oligomer that satisfies the conditions of the following (i) to (iii):

(i) number average molecular weight: 2,000 g/mol to 50,000 g/mol;

(ii) molecular weight distribution: 1.0 or more and 1.3 or less, and

(iii) the number of N atoms in the oligomer: 2 or more.

In addition, the present invention is a repeating unit derived from a conjugated diene-based monomer; And it provides a modified conjugated diene-based polymer comprising a functional group derived from the modified oligomer.

In addition, the present invention comprises the steps of preparing an active polymer by polymerizing a conjugated diene-based monomer or an aromatic vinyl-based monomer and a conjugated diene-based monomer in a hydrocarbon solvent in the presence of a polymerization initiator (step 1); and 2) reacting the active polymer with the modified oligomer (step 2), wherein the modified oligomer is an aromatic vinyl-based monomer-derived unit substituted with an amine-containing substituent; (meth) acrylate-based monomer-derived units; and an aromatic vinyl-based monomer-derived unit, and provides a method for producing the modified conjugated diene-based polymer of claim 8, which satisfies the conditions of the following (i) to (iii):

(i) number average molecular weight: 2,000 g/mol to 50,000 g/mol;

(ii) molecular weight distribution: 1.0 or more and 1.3 or less, and

(iii) the number of N atoms in the oligomer: 2 or more.

The modified oligomer according to the present invention can smoothly react with the active site of the polymer by including a (meth)acrylate-based monomer-derived unit, and is applied as a polymer modifier so that the functional group derived from the modified oligomer having filler affinity is added to the polymer. can be easily introduced.

In addition, the modified conjugated diene-based polymer according to the present invention may include a functional group derived from the modified oligomer, for example, an amine group having filler affinity, and thus may have excellent affinity with the filler, and as a result, the modified conjugated diene-based polymer An article manufactured using the polymer (eg, a tire) may have excellent tensile strength, rolling resistance (fuel efficiency) and wet road resistance.

In addition, the manufacturing method according to the present invention can easily prepare a modified conjugated diene-based polymer having an excellent rate of modification by using the modified oligomer as a polymer modifier.

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

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

Terms

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

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

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

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

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

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

The term 'single bond' used in the present invention may mean a single covalent bond itself that does not include a separate atom or molecular group.

How to measure

In the present invention, 'weight average molecular weight (Mw)', 'number average molecular weight (Mn)' and 'molecular weight distribution (MWD)' are measured through gel permeation chromatohraph (GPC) analysis, and measured by checking the molecular weight distribution curve. will be. Molecular weight distribution (PDI, MWD, Mw/Mn) is calculated from each of the measured molecular weights. Specifically, the GPC uses a combination of two PLgel Olexis (Polymer Laboratories) columns and one PLgel mixed-C (Polymer Laboratories) column, and when calculating molecular weight, the GPC reference material (Standard material) is PS (polystyrene) The GPC measurement solvent is prepared by mixing 2 wt% of an amine compound with tetrahydrofuran.

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

modified oligomers

The present invention provides modified oligomers that can be applied as polymer modifiers to introduce functional groups such as filler affinity functional groups into the polymer.

The modified oligomer according to an embodiment of the present invention includes an aromatic vinyl-based monomer-derived unit substituted with an amine-containing substituent; (meth) acrylate-based monomer-derived units; and a unit derived from an aromatic vinylic monomer, and conditions (i) number average molecular weight: 2,000 g/mol to 50,000 g/mol, (ii) molecular weight distribution: 1.0 or more and 1.3 or less, and (iii) the number of N atoms in the oligomer: It is characterized by satisfying two or more.

The modified oligomer according to an embodiment of the present invention may be applied as a modifier for modifying a polymer, and by including a unit derived from a (meth)acrylate-based monomer in the molecule, it reacts with the polymer active site to facilitate functional groups on the polymer can be introduced.

Specifically, the modified oligomer may include an aromatic vinyl-based monomer-derived unit substituted with an amine-containing substituent; (meth) acrylate-based monomer-derived units; and a unit derived from an aromatic vinylic monomer, wherein the number of each derived unit may be appropriately adjusted in a range such that the modified oligomer simultaneously satisfies the conditions (i) to (iii).

The modified oligomer must satisfy condition (i) a number average molecular weight of 2,000 g/mol to 50,000 g/mol, and specifically, a number average molecular weight of 2,000 g/mol to 30,000 g/mol, or 2,000 g/mol to 20,000 It may be g/mol, and the molecular weight distribution must satisfy 1.0 or more and 1.3 or less while satisfying the above condition (i).

In addition, the modified oligomer must satisfy the conditions (i) and (ii) while simultaneously containing two or more N atoms in the condition (iii) molecule, and may specifically contain 2 or more and 20 or less. In this case, it is applied as a polymer modifier to sufficiently introduce a functional group into the polymer, and as a result, the desired physical properties of the polymer can be sufficiently improved.

In addition, the number of (meth)acrylate-based monomer-derived units in the modified oligomer may be 1 or more and 12 or less, and when applied as a polymer modifier in this range, it reacts smoothly with the polymer active site while not causing excessive branching of the polymer. Functional groups can be easily introduced without degradation of physical properties due to branching.

The aromatic vinyl-based monomer substituted with the amine-containing substituent may be a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

R ₁ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,

R ₂ is a single bond or a substituted or unsubstituted C 1 to C 20 alkylene group,

R ₃ and R ₄ are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, which is substituted or unsubstituted with a substituent, and the substituent is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms.

More specifically, the aromatic vinyl-based monomer substituted with the amine-containing substituent may be at least one selected from compounds represented by the following Chemical Formulas 1-1 and 1-2.

[Formula 1-1]

[Formula 1-2]

In addition, the (meth) acrylate-based monomer may be a compound represented by the following formula (2).

[Formula 2]

In Formula 2,

R ₅ is a hydrogen atom or a methyl group,

R ₆ is an alkyl group having 1 to 20 carbon atoms or an alkoxyalkyl group having 1 to 20 carbon atoms.

More specifically, the (meth) acrylate-based monomer is methyl methacrylate, 2-methoxyethyl acrylate (2-methoxyethylacrylate) and 2-methoxyethyl methacrylate (2-methoxyethyl methacrylate). It may be at least one selected from the group consisting of.

The aromatic vinyl monomer is styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, 1- Vinyl-5-hexylnaphthalene, 3- (2-pyrrolidino ethyl) styrene (3- (2-pyrrolidino ethyl) styrene), 4- (2-pyrrolidino ethyl) styrene (4- (2-pyrrolidino ethyl) styrene) and 3-(2-pyrrolidino-1-methyl ethyl)-α-methylstyrene (3-(2-pyrrolidino-1-methyl ethyl)styrene) may be at least one selected from the group consisting of.

As another example, the modified oligomer according to an embodiment of the present invention may include an aromatic vinyl-based monomer-derived unit substituted with an amine-containing substituent; (meth) acrylate-based monomer-derived units; and a block polymer in which blocks composed of units derived from aromatic vinylic monomers are sequentially bonded; Each of the derived units may be a random polymer to which they are randomly bound, for example, the modified oligomer includes a structural unit represented by the following Chemical Formula 4, or a derived unit represented by the following Chemical Formulas 4a, 4b and 4c may include randomly connected constituent units.

[Formula 4]

[Formula 4a]

[Formula 4b]

[Formula 4c]

In Formulas 4 and 4a to 4c, R ₁ to R ₆ are as defined in Formula 1 or Formula 2.

On the other hand, n, m and o represent the composition ratio (molar ratio) of units derived from an aromatic vinyl-based monomer, a unit derived from a (meth)acrylate-based monomer, and a unit derived from an aromatic vinyl-based monomer, each substituted with an amine-containing substituent in the modified oligomer. , wherein n, m and o may have a value appropriately adjusted to satisfy the above-mentioned conditions (i) to (iii) of the modified oligomer, for example, n is an integer of 2 to 20, and m is 1 to It is an integer of 12, and o may be an integer of 1 to 200.

In addition, the modified oligomer may be prepared by, for example, living radical polymerization, such as reversible addition-fragmentation chain-transfer polymerization (RAFT).

Specifically, the modified oligomer is a living radical polymerization step in which an aromatic vinyl-based monomer substituted with an amine-containing substituent, a (meth)acrylate-based monomer, and an aromatic vinyl-based monomer are reacted collectively or sequentially in the presence of a radical initiator and a chain transfer agent ; And it can be prepared by a manufacturing method comprising a termination step of removing the unit derived from the chain transfer agent in the formed oligomer, for example, it can be prepared through the steps shown in Scheme 1 below.

[Scheme 1]

In Scheme 1, Formula 1 represents an aromatic vinyl monomer substituted with an amine-containing substituent, Formula 2 represents a (meth)acrylate monomer, RI represents a radical initiator, CTA represents a chain transfer agent, R ₁ to R ₆ is the same as described above.

As shown in Scheme 1, the oligomer is an aromatic vinyl-based monomer substituted with an amine-containing substituent in the presence of a radical initiator (RI) and a chain transfer agent (CTA), a (meth)acrylate-based monomer and an aromatic vinyl-based monomer polymerization reaction It can be carried out to obtain a modified oligomer intermediate in which a chain transfer agent-derived unit is bonded to the terminal, and can be prepared by removing the chain transfer agent-derived unit.

Here, the radical initiator is not particularly limited, for example, 2,2-azobis (isobutyronitrile) (2,2-azobis (isobutyronitrile), AIBN), dicumyl peroxide (dicumyl peroxide, DCPO), Di-t-butyl peroxide (DTBT), benzoyl peroxide (BPO), lauroyl peroxide (LPO), potassium persulfate (porassium persulfate) or mixtures thereof can be

In addition, the chain transfer agent can be used by appropriately selecting a conventional chain transfer agent of dithioester series, trithiocarbonate series, dithiocarbamate series, and xanthan series, for example, 4-cyano-4-[(dodecylsulfa Nylthiocarbonyl)sulfanyl]pentanoic acid (4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoic acid, CPDA), S-dodecyl-S'-(α,α'-dimethyl-α''- Acetic acid) trithiocarbonate (S-Dodecyl-S'-(α,α'-dimethyl -α''-acetic acid)trithiocarbonate, DDMAT), 2-cyano-2-propyl benzodithioate (2- cyano-2-propyl benzodithioate, CPDB) or a mixture thereof.

On the other hand, the termination step is to remove the chain transfer agent-derived unit present at the terminal from the modified oligomer intermediate, and is appropriately selected according to the chain transfer agent used during the reaction using a known radical initiator, thermal decomposition reaction, and amination reaction. can be done

Illustratively, the termination step may be performed by an aminolysis reaction using an amine material. In this case, the aminolysis reaction can remove the chain transfer agent-derived unit from the oligomer precursor only by using a small amount of an amine material, and can be applied regardless of the type of the chain transfer agent used.

In addition, the modified oligomer may further include a unit derived from a conjugated diene-based monomer, wherein the conjugated diene-based monomer is 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3- It may be at least one selected from the group consisting of butyl-1,3-octadiene, isoprene, 2-phenyl-1,3-butadiene and 2-halo-1,3-butadiene (halo means a halogen atom).

Modified conjugated diene-based polymer

The present invention provides a modified conjugated diene-based polymer having excellent compounding properties by including the modified oligomer-derived functional group and having excellent filler affinity.

The modified conjugated diene-based polymer according to an embodiment of the present invention includes a repeating unit derived from a conjugated diene-based monomer; and a functional group derived from the modified oligomer.

Specifically, the modified conjugated diene-based polymer may have an N atom content of 50 ppm to 20,000 ppm, 100 ppm to 20,000 ppm, or 100 ppm to 5,000 ppm based on the total weight of the polymer.

The modified conjugated diene-based polymer may have excellent affinity with a filler since an amine group, which is a functional group derived from a modified oligomer, is bound to a polymer chain. Accordingly, the compounding properties with the filler may be excellent, and the processability of the rubber composition including the modified conjugated diene-based polymer may be excellent, and as a result, the tensile strength of a molded article manufactured using the rubber composition, such as a tire, Wet road resistance and rolling resistance can be improved.

In addition, the modified conjugated diene-based polymer may have a number average molecular weight (Mn) of 1,000 g/mol to 2,000,000 g/mol, 10,000 g/mol to 1,000,000 g/mol, or 100,000 g/mol to 800,000 g/mol, The weight average molecular weight (Mw) may be 1,000 g / mol to 3,000,000 g / mol, 10,000 g / mol to 2,000,000 g / mol, or 100,000 g / mol to 2,000,000 g / mol, the peak average molecular weight (Mp) is 1,000 g /mol to 3,000,000 g/mol, 10,000 g/mol to 2,000,000 g/mol, or 100,000 g/mol to 2,000,000 g/mol. Within this range, there is an excellent effect of rolling resistance and wet road resistance. As another example, the modified conjugated diene-based polymer may have a molecular weight distribution (PDI; MWD; Mw/Mn) of 1.0 or more and 10.0 or less, or 1.1 or more and 5.0 or less, or 1.1 or more and 3.0 or less, and tensile properties within this range and excellent viscoelastic properties, and excellent balance between physical properties.

In addition, the modified conjugated diene polymer may have a Mooney viscosity of 20 to 150, or 30 to 120 at 100° C., and has excellent processability and productivity within this range.

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

In addition, in the present invention, the modified conjugated diene-based polymer may be a butadiene homopolymer such as polybutadiene, or a diene-based copolymer such as a butadiene-isoprene copolymer, as another example, the modified conjugated diene-based polymer is derived from an aromatic vinylic monomer. It may be a copolymer further comprising a repeating unit.

As a specific example, the modified conjugated diene-based polymer may be a butadiene homopolymer or a diene-based copolymer, and in this case, the modified conjugated diene-based polymer is 80 to 100% by weight of a unit derived from a 1,3-budiene-based monomer, and optionally It may contain 20 wt% or less of units derived from other conjugated diene-based monomers copolymerizable with 1,3-butadiene, and within the above range, the 1,4-cis bond content in the polymer is not reduced. In this case, the 1,3-butadiene monomer includes 1,3-butadiene or derivatives thereof, such as 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, or 2-ethyl-1,3-butadiene. and other conjugated diene-based monomers copolymerizable with 1,3-butadiene include 2-methyl-1,3-pentadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 4 -methyl-1,3-pentadiene, 1,3-hexadiene, or 2,4-hexadiene may be mentioned, and any one or two or more compounds of these may be used.

As another example, when the modified conjugated diene-based polymer is a copolymer further comprising a repeating unit derived from an aromatic vinyl-based monomer, the modified conjugated diene-based polymer contains an aromatic vinyl-based monomer-derived repeating unit in an amount of 40 wt% or less, specifically 5 wt% % or more and 40 wt% or less, or 10 wt% or more and 30 wt% or less, in this case, the driving resistance may be further improved while excellent in abrasion resistance and wet road resistance.

In addition, the modified conjugated diene-based polymer may have a vinyl content of 5 wt% or more, specifically 10 wt% or more, more specifically 10 wt% to 50 wt%, and when the vinyl content is within the above range, the glass transition temperature can be adjusted in an appropriate range, so that when applied to tires, the properties required for tires such as running resistance and braking force are excellent, and fuel consumption is reduced.

In this case, the vinyl content represents the content of the 1,2-added conjugated diene-based monomer, not the 1,4-added, based on 100% by weight of the conjugated diene-based polymer composed of a monomer having a vinyl group or a conjugated diene-based monomer.

As another example, the modified conjugated diene-based polymer according to an embodiment of the present invention may be a neodymium-catalyzed modified conjugated diene-based polymer, specifically, a neodymium-catalyzed butadiene homopolymer, or a diene-based copolymer. Here, the neodymium-catalyzed modified conjugated diene-based polymer refers to a polymer prepared by polymerization of a monomer in the presence of a catalyst composition including a neodymium compound.

In addition, the neodymium-catalyzed modified conjugated diene-based polymer has a cis-1,4 bond content of the conjugated diene part measured by Fourier transform infrared spectroscopy (FT-IR) of 95% by weight or more, more specifically 98% by weight or more. and the vinyl content may be 5 wt% or less, more specifically 2 wt% or less. Accordingly, when applied to the rubber composition, the abrasion resistance, crack resistance and ozone resistance of the rubber composition may be improved.

Method for producing a modified conjugated diene-based polymer

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

The manufacturing method according to an embodiment of the present invention comprises the steps of preparing an active polymer by polymerizing a conjugated diene-based monomer or an aromatic vinyl-based monomer and a conjugated diene-based monomer in a hydrocarbon solvent in the presence of a polymerization initiator (step 1); and reacting the active polymer with the modified oligomer (step 2).

Here, the conjugated diene-based polymer, the aromatic vinyl-based monomer, and the modified oligomer are the same as described above.

Step 1 is a step for preparing an active polymer containing an organometallic moiety by polymerizing a monomer, and is performed by polymerizing a conjugated diene-based monomer or an aromatic vinyl-based monomer and a conjugated diene-based monomer in the presence of a polymerization initiator in a hydrocarbon solvent. can

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

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

The polymerization initiator may be a catalyst composition including an organolithium compound or a neodymium compound, and the polymerization initiator may be used in an amount of 0.01 mmol to 10 mmol based on 100 g of the total monomer, wherein the polymerization initiator is a catalyst composition In the case of , the polymerization initiator may be used in an amount such that the neodymium compound in the catalyst composition is 0.01 to 10 mmol based on 100 g of the total monomer.

The organolithium compound is methyllithium, ethyllithium, propyllithium, isopropyllithium, n-butyllithium, s-butyllithium, 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 It may be at least one selected from the group consisting of tyl potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide and lithium isopropylamide.

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

Specifically, the neodymium compound may be a compound represented by the following formula (3).

[Formula 3]

In Formula 3, R _a to R _c are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms, with the proviso that R _a to R _c are not all hydrogen at the same time.

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

In addition, as another example, considering the excellent solubility in solvents, conversion to catalytically active species, and thus the catalytic activity improvement effect without concerns about oligomerization, the neodymium compound is more specifically, R _a in Formula 3 an alkyl group having 4 to 12 carbon atoms, and R _b and R _c are each independently hydrogen or an alkyl group having 2 to 8 carbon atoms, provided that R _b and R _c are not hydrogen at the same time.

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

More specifically, in Formula 3, R _a may be an alkyl group having 6 to 8 carbon atoms, and R _b and R _c may each independently be an alkyl group having 2 to 6 carbon atoms.

As such, the neodymium-based compound represented by Formula 3 includes a carboxylate ligand including an alkyl group having various lengths of 2 or more carbon atoms as a substituent at the α (alpha) position, thereby inducing a steric change around the neodymium central metal compound It is possible to block the clumping phenomenon of the liver, and thus, there is an effect that can suppress oligomerization. In addition, such a neodymium-based compound has a high solubility in a solvent, and a ratio of neodymium located in a central portion having difficulty in conversion to a catalytically active species is reduced, thereby increasing the conversion rate to a catalytically active species.

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

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

In addition, the neodymium compound according to an embodiment of the present invention may be used in the form of a reactant with a Lewis base. This reactant has the effect of improving the solubility of the neodymium compound in 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 to 10 moles per mole of neodymium element. The Lewis base may be, for example, acetylacetone, tetrahydrofuran, pyridine, N,N-dimethylformamide, thiophene, diphenyl ether, triethylamine, an organophosphorus compound, or monovalent or divalent alcohol.

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

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

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

(a) alkylating agent

The alkylating agent is an organometallic compound capable of transferring a hydrocarbyl group to another metal, and may serve as a co-catalyst. The alkylating agent may be used without particular limitation as long as it is used as an alkylating agent in the production of a diene-based polymer, for example, it is soluble in a polymerization solvent, such as an organoaluminum compound, an organomagnesium compound, or an organolithium compound, and forms a metal-carbon bond. It may be an organometallic compound containing.

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

In addition, the organoaluminum compound may be aluminoxane.

The aluminoxane may be prepared by reacting a trihydrocarbyl aluminum-based compound with water, and specifically may be a linear aluminoxane of the following Chemical Formula 5a or a cyclic aluminoxane of the following Chemical Formula 5b.

[Formula 5a]

[Formula 5b]

In Formulas 5a and 5b, R is a monovalent organic group bonded to an aluminum atom through a carbon atom, and may be a hydrocarbyl group, and x and y are each independently an integer of 1 or more, specifically 1 to 100 , more specifically, may be an integer of 2 to 50.

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

In addition, the modified methylaluminoxane is a compound in which the methyl group of methylaluminoxane is substituted with a modifying group (R), specifically, a hydrocarbon group having 2 to 20 carbon atoms, and specifically, it may be a compound represented by the following formula (6).

[Formula 6]

In Formula 6, R is as defined above, and m and n may be each independently an integer of 2 or more. In addition, in Formula 6, Me represents a methyl group.

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

More specifically, the modified methylaluminoxane may be obtained by substituting about 50 mol% 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, it is possible to promote alkylation to increase catalytic activity.

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

(b) halides

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

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

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

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

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

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

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

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

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

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

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

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

(c) conjugated diene-based monomers

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

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

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

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

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

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

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

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

In addition, the polymerization in step 1 may be performed by further adding a polar additive as necessary, and the polar additive may be added in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the total monomer. Specifically, it may be added in an amount of 0.001 parts by weight to 1 part by weight, more specifically 0.003 parts by weight to 0.5 parts by weight, based on 100 parts by weight of the total monomer.

The polar additive is tetrahydrofuran, ditetrahydrofuryl propane, diethyl ether, cyclopentyl ether, dipropyl ether, ethylene dimethyl ether, ethylene dimethyl ether, diethyl glycol, dimethyl ether, tertiary butoxyethoxyethane, bis It may be at least one selected from the group consisting of (3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine, and tetramethylethylenediamine.

In the manufacturing method according to an embodiment of the present invention, when copolymerizing a conjugated diene-based monomer and an aromatic vinyl-based monomer by using the polar additive, a random copolymer can be easily formed by compensating for a difference in their reaction rate. can induce

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

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

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

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

The polymerization may be carried out in a temperature range of -20 °C to 200 °C, specifically 50 °C to 150 °C, more specifically 10 °C to 120 °C or 60 °C to 90 °C for 15 minutes to It may be performed for 3 hours. If the polymerization temperature exceeds 200° C., it is difficult to sufficiently control the polymerization reaction, and when the temperature is less than -20° C., there is a fear that the polymerization reaction rate and efficiency may be lowered.

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

Step 2 is a step of preparing a modified conjugated diene-based polymer including a functional group by modifying or coupling the active polymer, and may be performed by reacting the active polymer with a modified oligomer.

The modified oligomer may be used in a ratio of 0.1 to 5 moles relative to 1 mole of the polymerization initiator, and when the polymerization initiator is a catalyst composition, the modified oligomer is used in a ratio of 0.1 to 5 moles relative to 1 mole of the neodymium compound it could be

The reaction of step 2 according to an embodiment of the present invention may be performed at a temperature range of 10°C to 120°C for 10 minutes to 5 hours.

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

In the manufacturing method according to an embodiment of the present invention, after step 2, a modified conjugated diene-based polymer can be obtained through a solvent removal treatment such as steam stripping or vacuum drying treatment to lower the partial pressure of the solvent through supply of water vapor. . In addition, an unmodified active polymer may be included in the reaction product obtained as a result of the above-mentioned reaction together with the above-mentioned modified conjugated diene polymer.

rubber composition

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Preparation Example 1

In a 500 ml round-bottom flask, add 3.0 g of 2-cyano-2-propyl benzodithioate (CPDB) and 47.1 g (0.45 mol) of styrene (SM), 2-methoxy Ethyl acrylate (MEA) 14.7 g (0.11 mol) and N,N-dimethylvinylbenzylamine (N,N-dimethylvinylbenzylamine, DMVBA 18.2 g (0.11 mol) and 120 g of toluene were added and mixed, followed by mixing in 20 g of toluene. A solution of 0.11 g of 2,2-azobis(isobutyronitrile) (AIBN) was added and reacted for 20 hours at 80° C. Yiwu, after precipitation in a mixed solvent of ethanol and acetone, 6 in an oven at 50° C. After drying for an hour, 62 g of solid were recovered.

Then, 62 g of the solid was dissolved in 120 g of toluene in a 500 ml round-bottom flask, 47 g of 2,2-azobis(isobutyronitrile) was added thereto, and the mixture was stirred at 80° C. for 7 hours. After precipitating this in a mixed solvent of ethanol and acetone, it was dried again in an oven at 50° C. for 6 hours to prepare a modified oligomer including a structural unit represented by the following Chemical Formula 1-1. It was confirmed that the oligomer was synthesized through ¹ H-NMR.

[Formula 1-1]

In Formula 1-1, n is 2, m is 2, and o is 7 (n:m:o=2:2:7 molar ratio).

Preparation 2

In Preparation Example 1, 2.8 g of 2-cyano-2-propyl benzodithioate, 36.1 g (0.35 mol) of styrene, 11.3 g (0.087 mol) of 2-methoxyethyl acrylate, N,N- 32.6 g (0.20 mol) of dimethylvinylbenzylamine, and 0.10 g of 2,2-azobis(isobutyronitrile) in the same manner as in Preparation Example 1, except that the composition represented by the following Chemical Formula 1-2 A modified oligomer including a unit was prepared, and it was confirmed that the oligomer was synthesized through ¹ H-NMR.

[Formula 1-2]

In Formula 1-2, n is 3, m is 1, and o is 5 (n:m:o=3:1:5 molar ratio).

Preparation 3

In Preparation Example 1, 2.9 g of 2-cyano-2-propyl benzodithioate, 37.8 g (0.36 mol) of styrene, 27.6 g (0.21 mol) of 2-methoxyethyl acrylate, N,N- 14.6 g (0.091 mol) of dimethylvinylbenzylamine, and 0.11 g of 2,2-azobis (isobutyronitrile) in the same manner as in Preparation Example 1, except that the composition represented by the following formula 1-3 A modified oligomer including a unit was prepared, and it was confirmed that the oligomer was synthesized through ¹ H-NMR.

[Formula 1-3]

In Formula 1-3, n is 1, m is 3, and o is 5 (n:m:o=1:3:5 molar ratio).

In addition, it was confirmed that the denaturants A to C, each of the modified oligomers prepared in Preparation Examples 1 to 3, were synthesized through molecular weight analysis, and the results are shown in Table 1 below.

Specifically, molecular weight analysis was measured by GPC analysis under 40°C conditions. At this time, as a column, two PLgel Olexis columns from Polymer Laboratories and one PLgel mixed-C column were combined, and all of the newly replaced columns used a mixed bed type column. In addition, PS (Polystyrene) was used as a GPC standard material when calculating molecular weight.

As shown in Table 1, the modifiers A to C, which are the modified oligomers according to the present invention, have conditions (i) number average molecular weight: 2,000 g/mol to 50,000 g/mol, (ii) molecular weight distribution: 1.0 or more and 1.3 or less, And (iii) the number of N atoms in the oligomer: it was confirmed that two or more were simultaneously satisfied.

Example 1

After putting 800 g of 1,3-butadiene and 7,200 g of n-hexane in a 20L autoclave reactor, the temperature inside the reactor was raised to 70°C. After the catalyst composition was added in an amount of 0.61 mol of neodymium versatate, polymerization was performed for 60 minutes. In this case, the catalyst composition is obtained by adding neodymium versatate (Nd (2-ethylhexanoate) ₃ ), Solvay Corporation) in an n-hexane solvent, and diisobutylaluminum hydride (DIBAH), diethylaluminum Chloride (DEAC) was sequentially added so that the molar ratio of neodymium versatate:DIBAH:DEAC=1:12:2.4 was mixed at 20°C for 10 minutes, and 1,3-butadiene was added in an amount of 10 mol relative to 1 mol of neodymium versatate. pre-polymerized, and aged at -10°C for 4 hours before use. After the addition of the denaturant A prepared in Preparation Example 1, the denaturation reaction was performed at 70° C. for 30 minutes (denaturant: Nd=1:2 molar ratio). Thereafter, the reaction was terminated by adding a hexane solution containing 1.0 g of a polymerization terminator and a solution in which the antioxidant WINGSTAY (Eliokem SAS, France) was dissolved in hexane at 30% by weight, and the resulting heavy content was heated with steam. The solvent was removed by putting it in hot water and stirring, and then roll drying was performed to remove the remaining amount of solvent and water to prepare a modified butadiene polymer.

On the other hand, after the polymerization reaction, before adding the modifier, 300 g of the polymer is aliquoted from the reactor, put into hot water heated with steam, stirred to remove the solvent, and then roll-dried to remove the remaining solvent and water to recover it, and then recover it before modification. It was used to measure the Mooney viscosity of the polymer.

Example 2

In Example 1, a modified butadiene polymer was prepared in the same manner as in Example 1, except that the modifier B prepared in Preparation Example 2 was used instead of the modifier A prepared in Preparation Example 1.

In addition, after the polymerization reaction as in Example 1, before adding the modifier, 300 g of the polymer is aliquoted from the reactor, put into steam heated hot water, stirred to remove the solvent, and then roll-dried to remove the residual amount of solvent and water to recover Then, it was used to measure the Mooney viscosity of the polymer before modification.

Example 3

In Example 1, a modified butadiene polymer was prepared in the same manner as in Example 1, except that the modifier C prepared in Preparation Example 3 was used instead of the modifier A prepared in Preparation Example 1.

In addition, after the polymerization reaction as in Example 1, before adding the modifier, 300 g of the polymer is aliquoted from the reactor, put into steam heated hot water, stirred to remove the solvent, and then roll-dried to remove the residual amount of solvent and water to recover Then, it was used to measure the Mooney viscosity of the polymer before modification.

Example 4

In a 20 L autoclave reactor, 224 g of styrene, 576 g of 1,3-butadiene and 5.6 kg of n-hexane, and 0.8 g of ditetrahydrofuryl propane as a polar additive were added, and then the temperature inside the reactor was raised to 60°C. When the temperature inside the reactor reached 60° C., 21.6 g of a 2.0 wt% n-hexane solution of n-butyllithium was added to the reactor to proceed with adiabatic temperature increase. Thereafter, 16.0 g of the modifier A prepared in Preparation Example 1 was dissolved in 144 g of anhydrous tetrahydrofuran, put into a reactor, and the reaction was allowed to proceed for 30 minutes. Thereafter, the reaction was stopped using isopropyl alcohol, and 45 ml of a solution in which 0.3 wt% of an antioxidant BHT (butylated hydroxytoluene) was dissolved in hexane was added. The resulting polymer was put into hot water heated with steam, stirred to remove the solvent, and then roll-dried to remove the remaining solvent and water to prepare a modified styrene-butadiene copolymer.

On the other hand, after 40 minutes after the adiabatic temperature rise reaction is over, 30 g of the polymer is aliquoted from the reactor and added to 100 g of isopropyl alcohol before the addition of the modifier, precipitated and roll-dried to remove the remaining amount of solvent and water and recover, then denaturation It was used to measure the Mooney viscosity of the whole polymer.

Comparative Example 1

After putting 800 g of 1,3-butadiene and 7,200 g of n-hexane in a 20L autoclave reactor, the temperature inside the reactor was raised to 70°C. A catalyst composition was added thereto in an amount of 0.52 mmol of neodymium versatate, followed by polymerization for 60 minutes. In this case, the catalyst composition is obtained by adding neodymium versatate (Nd (2-ethylhexanoate) ₃ ), Solvay Corporation) in an n-hexane solvent, and diisobutylaluminum hydride (DIBAH), diethylaluminum Chloride (DEAC) was sequentially added so that the molar ratio of neodymium versatate:DIBAH:DEAC=1:12:2.4 was mixed at 20°C for 10 minutes, and 1,3-butadiene was added in an amount of 10 mol relative to 1 mol of neodymium versatate. pre-polymerized, and aged at -10°C for 4 hours before use. Thereafter, the reaction was terminated by adding a hexane solution containing 1.0 g of a polymerization terminator and a solution in which the antioxidant WINGSTAY (Eliokem SAS, France) was dissolved in hexane at 30% by weight, and the resulting heavy content was heated with steam. The solvent was removed by stirring in hot water, and then roll-drying to remove the remaining amount of solvent and water to prepare an unmodified butadiene polymer.

Comparative Example 2

In a 20 L autoclave reactor, 224 g of styrene, 576 g of 1,3-butadiene and 5.6 kg of n-hexane, and 0.8 g of ditetrahydrofuryl propane as a polar additive were added, and then the temperature inside the reactor was raised to 60°C. When the internal temperature of the reactor reached 60° C., 12.0 g of a 2.0 wt% n-hexane solution of n-butyllithium was added to the reactor to proceed with an adiabatic temperature rise reaction. Thereafter, the reaction was stopped using isopropyl alcohol, and 45 ml of a solution in which 0.3 wt% of an antioxidant BHT (butylated hydroxytoluene) was dissolved in hexane was added. The resulting polymer was put into hot water heated by steam, stirred to remove the solvent, and then roll-dried to remove the remaining amount of solvent and water to prepare an unmodified styrene-butadiene copolymer.

Comparative Example 3

A butadiene polymer was prepared in the same manner as in Example 1, except that 4.0 g of a 10 wt% n-hexane solution of tetrachlorosilane was used as a coupling agent instead of the modifier A.

Also, after the polymerization reaction as in Example 1, before adding the coupling agent, 300 g of the polymer was aliquoted from the reactor, put into steam heated hot water, stirred to remove the solvent, and then roll-dried to remove the remaining amount of solvent and water. After recovery, it was used to measure the Mooney viscosity of the polymer before coupling.

Comparative Example 4

20 wt of ethyl 1- (trimethylsilyl) piperidine-4-carboxylate (CAS No. 183994-40-3, NC CHEM) instead of denaturant A % In the same manner as in Example 1, except that 4.0 g of n-hexane solution was used, a modified butadiene copolymer was prepared.

In addition, after the polymerization reaction as in Example 1, before adding the modifier, 300 g of the polymer is aliquoted from the reactor, put into steam heated hot water, stirred to remove the solvent, and then roll-dried to remove the residual amount of solvent and water to recover Then, it was used to measure the Mooney viscosity of the polymer before modification.

Experimental Example 1

For each of the copolymers prepared in Examples 1 to 4 and Comparative Examples 1 to 4, a weight average molecular weight (Mw), a number average molecular weight (Mn), a maximum peak molecular weight (Mp), and a molecular weight distribution (MWD) , Mw/Mn) and Mooney viscosity (MV) were measured, respectively. The results are shown in Table 2 below.

1) Molecular weight analysis

The weight average molecular weight (Mw, g/mol) and number average molecular weight (Mn, g/mol) were measured through GPC analysis under the condition of 40°C, and the molecular weight distribution (Mw/Mn) was the measured weight average molecular weight and number average molecular weight. was calculated as the ratio of At this time, as a column, two PLgel Olexis columns from Polymer Laboratories and one PLgel mixed-C column were combined, and all of the newly replaced columns used a mixed bed type column. In addition, PS (Polystyrene) was used as a GPC standard material when calculating molecular weight.

2) Mooney viscosity analysis

Mooney viscosity (MV, (ML1+4, @100℃)) of each copolymer was measured using ALPHA Technologies' MV-2000, Rotor Speed 2±0.02 rpm, and Large Rotor. After standing at room temperature (23±3℃) for more than 30 minutes, 27±3 g was collected, filled in the die cavity, operated the platen, preheated at 100℃ for 1 minute, and then measured for 4 minutes.

3) N atom content (ppm)

The N 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), 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, and heater was set to 800°C and then waited for about 3 hours to stabilize the analyzer. After the analyzer is stabilized, a calibration curve in the range of 5 ppm, 10 ppm, 50 ppm, 100 ppm and 500 ppm was prepared using Nitrogen standard (AccuStandard S-22750-01-5 ml), and the area corresponding to each concentration was obtained. Afterwards, 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 N content was calculated using the area of the obtained sample and the calibration curve.

Through Table 2, the modified oligomer through the presence of an N atom content of 100 ppm or more in the polymers of Examples 1 to 4, and an increase in the Mooney viscosity of the final polymer compared to the Mooney viscosity before modification or coupling It can be predicted that the functional group derived from the is included in the prepared polymer.

Experimental Example 2

The physical properties of the rubber compositions including the polymers prepared in Examples 1 to 4 and Comparative Examples 1 to 4 and molded articles prepared therefrom were comparatively analyzed, and the results are shown in Table 3 below.

1) Preparation of rubber composition

Each rubber composition was prepared through the first stage kneading, the second stage kneading and the third stage kneading process. In this case, the amount of the material other than the modified conjugated diene-based copolymer is shown based on 100 parts by weight of the modified conjugated diene-based copolymer. In the first stage kneading, 100 parts by weight of each modified conjugated diene-based copolymer, 60 parts by weight of carbon black, 15 parts by weight of process oil (TDAE), 15 parts by weight of anti-aging agent ( TMDQ) 2 parts by weight, antioxidant 2 parts by weight, zinc oxide (ZnO) 3 parts by weight, stearic acid 2 parts by weight, and wax 1 part by weight were mixed and kneaded. At this time, the temperature of the kneader was controlled and the first formulation was obtained at a discharge temperature of 140°C to 150°C. In the second stage kneading, after cooling the first mixture to room temperature, 2.0 parts by weight of the first vulcanization accelerator (CZ), 2.0 parts by weight of sulfur powder, and 0.5 parts by weight of the second vulcanization accelerator are added to the kneader and mixed at 45 to 60° C. Thus, a secondary formulation was obtained. After that, in the third stage kneading, the secondary compound was molded in a roll mill at 50° C., and vulcanized at 160° C. for t90+10 minutes with a vulcanizing press to prepare each vulcanized rubber.

2) Mooney viscosity

The Mooney viscosity (MV, (ML1+4, @100℃)) of each rubber composition was measured using ALPHA Technologies' MV-2000, Rotor Speed 2±0.02 rpm, and Large Rotor. After standing at room temperature (23±3℃) for more than 30 minutes, 27±3 g was collected, filled in the die cavity, operated the platen, preheated at 100℃ for 1 minute, and then measured for 4 minutes.

3) Payne effect

Using RPA 2000 of ALPHA Technologies, a specimen weight of 7 g or more was measured at 60° C. at a rate of 1 Hz with 0.04 - 40.0% strain swips. On the other hand, the Payne effect is an evaluation of the amount of bond breakage between the filler and the filler by measuring the storage elastic modulus of the rubber in a small deformation of the rubber composition containing the filler. Indirectly, it indicates that the smaller the value, the less the bond breakage between the filler and the filler and the mutual attraction between the rubber and the filler increases.

4) Tensile properties

For tensile properties, each test piece was prepared according to the tensile test method of ASTM 412, and the tensile strength at the time of cutting the test piece and the tensile stress (300% modulus) at 300% elongation were measured. Specifically, the tensile properties were measured at a speed of 50 cm/min at room temperature using a Universal Test Machin 4204 (Instron Co., Ltd.) tensile tester, and the measured value of the rubber composition containing the polymer of Comparative Example 1 was used as an index based on 100. It was compared numerically, and the higher the index value, the better.

5) Viscoelastic properties (rolling resistance (RR) and braking performance (wet grip))

Viscoelastic properties were measured using DMTS (Dynamic mechanical thermal spectrometry; GABO, EPLEXOR 500N) in torsional mode, with a frequency of 10 Hz, strain (static strain: 3%, dynamic strain: 0.25%), and each measurement temperature (-60℃~70℃). ) to measure Tan δ by changing the strain. The higher the low temperature 0°C Tan δ, the better the braking performance, and the lower the high temperature 60°C Tan δ, the less the hysteresis loss and the better the low rolling resistance (fuel efficiency). The result value was compared as an Index value based on the measured value of the rubber composition containing the polymer of Comparative Example 1 as 100, and it means that the index value increases as the value increases.

6) Wear resistance

Measurements were made using a DIN wear meter. The result value was compared as an Index value based on the measured value of the rubber composition containing the polymer of Comparative Example 1 as 100, and it means that the index value increases as the value increases.

As shown in Table 3, Examples 1 to 4 were superior in tensile properties, viscoelastic properties, and abrasion resistance compared to Comparative Examples 1 to 4, and it was confirmed that the filler affinity was excellent.

Specifically, Examples 1 to 3 exhibited a Payne effect reduced to about 70% compared to the butadiene polymer of Comparative Examples 1 and 3, and Example 4 exhibited a Payne effect reduced to a level of 75% compared to Comparative Example 2 Through this, in the case of the modified polymers of Examples 1 to 4 prepared by modification with the modified oligomer according to the present invention, the affinity with the filler is significantly excellent compared to the unmodified polymer or the polymer modified with other modifying agents. confirmed that there is.

In addition, this excellent filler affinity was also confirmed through the remarkable improvement effect of tensile properties, viscoelastic properties and abrasion resistance, which are compound properties.

Specifically, Examples 1 to 3 showed excellent wear resistance and improved tensile properties of about 10% or more compared to Comparative Example 1, and at the same time, low-rolling resistance (fuel efficiency, 60℃ Tan δ) was significantly improved by 20% or more. Confirmed. In addition, it was confirmed that Example 4 showed a tensile property increased by 10% or more in Comparative Example 2, and remarkably improved abrasion resistance by about 20% and low rolling resistance by 30% or more.

Through the above results, the modified oligomer according to the present invention can be applied as a polymer modifier to remarkably improve the filler affinity of the polymer, and after modification, the modified oligomer-derived functional group is included in the prepared modified polymer to form a polymer blending property It can also be confirmed that there is an effect of remarkably improving.

Claims (16)

a unit derived from an aromatic vinyl-based monomer substituted with an amine-containing substituent;
(meth) acrylate-based monomer-derived units; and
comprising a unit derived from an aromatic vinylic monomer;
A modified oligomer that satisfies the conditions of (i) to (iii) below:
(i) number average molecular weight: 2,000 g/mol to 50,000 g/mol;
(ii) molecular weight distribution: 1.0 or more and 1.3 or less, and
(iii) the number of N atoms in the oligomer: 2 or more.
According to claim 1,
A modified oligomer further comprising a repeating unit derived from a conjugated diene-based monomer.
According to claim 1,
The condition (i) a modified oligomer having a number average molecular weight of 2,000 g/mol to 30,000 g/mol.
According to claim 1,
The condition (iii) a modified oligomer wherein the number of N atoms in the oligomer is 2 or more and 20 or less.
According to claim 1,
A modified oligomer wherein the number of units derived from the (meth)acrylate-based monomer is 1 or more and 12 or less.
According to claim 1,
A modified oligomer wherein the aromatic vinyl-based monomer substituted with the amine-containing substituent is a compound represented by the following formula (1):
[Formula 1]

In Formula 1,
R ₁ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
R ₂ is a single bond or a substituted or unsubstituted C 1 to C 20 alkylene group,
R ₃ and R ₄ are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, which is substituted or unsubstituted with a substituent, and the substituent is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms.
According to claim 1,
The (meth) acrylate-based monomer is a modified oligomer that is a compound represented by the following formula 2:
[Formula 2]

In Formula 2,
R ₅ is a hydrogen atom or a methyl group,
R ₆ is an alkyl group having 1 to 20 carbon atoms or an alkoxyalkyl group having 1 to 20 carbon atoms.
a repeating unit derived from a conjugated diene-based monomer; And a modified conjugated diene-based polymer comprising the functional group derived from the modified oligomer of claim 1.
9. The method of claim 8,
A modified conjugated diene-based polymer further comprising a repeating unit derived from an aromatic vinyl-based monomer.
9. The method of claim 8,
A modified conjugated diene-based polymer having a cis 1,4-bond content of 95% by weight or more.
9. The method of claim 8,
A modified conjugated diene-based polymer having an N atom content of 100 ppm to 20,000 ppm based on the total weight of the polymer.
1) preparing an active polymer by polymerizing a conjugated diene-based monomer or an aromatic vinyl-based monomer and a conjugated diene-based monomer in a hydrocarbon solvent in the presence of a polymerization initiator; and
2) reacting the active polymer with a modified oligomer,
The modified oligomer may include an aromatic vinyl-based monomer-derived unit substituted with an amine-containing substituent; (meth) acrylate-based monomer-derived units; and an aromatic vinyl-based monomer-derived unit, and the method for producing the modified conjugated diene-based polymer of claim 8, which satisfies the conditions of (i) to (iii):
(i) number average molecular weight: 2,000 g/mol to 50,000 g/mol;
(ii) molecular weight distribution: 1.0 or more and 1.3 or less, and
(iii) the number of N atoms in the oligomer: 2 or more.
13. The method of claim 12,
The polymerization initiator is methyllithium, ethyllithium, propyllithium, isopropyllithium, n-butyllithium, s-butyllithium, 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 A modified conjugate which is at least one organolithium compound selected from the group consisting of potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassiumamide and lithium isopropylamide Method for producing a diene-based polymer.
13. The method of claim 12,
The polymerization initiator is a method for producing a modified conjugated diene-based polymer that is a catalyst composition comprising a neodymium compound represented by the following Chemical Formula 3:
[Formula 3]

In Formula 3,
R _a to R _c are each independently hydrogen or an alkyl group having 1 to 12 carbon atoms,
However, R _a to R _c are not all hydrogen at the same time.
13. The method of claim 12,
The polymerization initiator is a method for producing a modified conjugated diene-based polymer to be used in an amount of 0.01 mmol to 10 mmol based on 100 g of the total monomer.
13. The method of claim 12,
The modified oligomer is a method for producing a modified conjugated diene-based polymer is used in an amount of 0.1 to 5.0 moles relative to 1 mole of the polymerization initiator.