KR20210031263A - Modified conjugated diene polymer, preparing method thereof and rubber composition comprising the same - Google Patents

Abstract

The present invention relates to a modified conjugated diene-based polymer having excellent processability and remarkable tensile strength and viscoelastic properties, and a rubber composition comprising the same. The present invention provides the modified conjugated diene-based polymer, comprising a polymer chain including a repeating unit derived from a conjugated diene-based monomer and a functional group derived from a modifier bonded to at least one terminal of the polymer chain.

Description

Modified conjugated diene-based polymer, a method for producing the same, and a rubber composition containing the same TECHNICAL FIELD {MODIFIED CONJUGATED DIENE POLYMER, PREPARING METHOD THEREOF AND RUBBER COMPOSITION COMPRISING THE SAME}

The present invention relates to a modified conjugated diene-based polymer having excellent affinity with a filler and excellent processability, tensile strength, and viscoelastic properties, a method for preparing the same, and a rubber composition comprising the same.

In recent years, in accordance with the demand for low fuel consumption for automobiles, a conjugated diene-based polymer having low rolling resistance, excellent abrasion resistance, and tensile properties as a rubber material for tires, and also having adjustment stability typified by wet road surface resistance is required.

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

As a rubber material having a low hysteresis loss, natural rubber, polyisoprene rubber, polybutadiene rubber, and the like are known, but these have a problem of low resistance to wet road surfaces. Accordingly, recently, conjugated diene-based polymers or copolymers such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) are manufactured by emulsion polymerization or solution polymerization, and are used as rubber for tires. . Among them, the greatest advantage of solution polymerization compared to emulsion polymerization is that the vinyl structure content and styrene content that define rubber properties can be arbitrarily adjusted, and molecular weight and physical properties can be adjusted by coupling or modification. Is that it can be adjusted. Therefore, it is easy to change the structure of the final manufactured SBR or BR, reduce the movement of the chain ends by bonding or denaturation of the chain ends, and increase the bonding strength with fillers such as silica or carbon black. It is widely used as a rubber material.

When such a solution-polymerized SBR is used as a rubber material for a tire, the glass transition temperature of the rubber can be increased by increasing the vinyl content in the SBR, so that the required properties of the tire such as running resistance and braking force can be adjusted, as well as the glass transition temperature. Fuel consumption can be reduced by appropriate control. The solution polymerization SBR is prepared using an anionic polymerization initiator, and a technique of introducing a functional group at the terminal by bonding or denaturing the chain ends of the formed polymer using various modifiers is used. For example, U.S. Patent No. 4,397,994 proposes a technique in which the active anion at the chain end of a polymer obtained by polymerizing styrene-butadiene in a non-polar solvent using alkyllithium, a monofunctional initiator, is bound using a binder such as a tin compound. I did.

On the other hand, as a modifier for introducing a functional group at the end of the polymer chain, a technique of applying an aminoalkoxysilane group modifier including an alkoxysilane group and an amine group in the molecule at the same time in order to maximize the powdery properties and reactivity of the filler is widely known. However, as the number of amine groups in the modifier increases, the solubility in the hydrocarbon solvent used for polymer production decreases, and thus it is difficult to easily perform the modification reaction.

US 4397994 A

The present invention was devised to solve the problems of the prior art, and by including a functional group derived from a denaturant represented by Formula 1, it has excellent affinity with a filler, and thus, a modified conjugated diene system having excellent processability, tensile properties, and viscoelastic properties. It is an object to provide a polymer.

In addition, an object of the present invention is to provide a method for preparing the modified conjugated diene-based polymer using a modifier represented by Chemical Formula 1.

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

According to an embodiment of the present invention for solving the above problems, the present invention provides a polymer chain including a repeating unit derived from a conjugated diene-based monomer and a functional group derived from a denaturant represented by the following formula (1) bonded to at least one end of the polymer chain. It provides a modified conjugated diene-based polymer comprising:

[Formula 1]

In Formula 1,

n and m are each independently an integer of 1 to 3,

R ₁ and R ₂ are each independently a substituent represented by the following formula (i) or formula (ii), or -[CH ₂ CH ₂ O] _c R ₁₄ , wherein R ₁₄ is an alkyl group having 1 to 20 carbon atoms. , c is an integer from 1 to 10,

[Formula (i)]

In the above formula (i),

R ₃ is an alkylene group having 1 to 20 carbon atoms,

R ₄ and R ₅ are each independently an alkyl group having 1 to 20 carbon atoms,

a is an integer from 1 to 3,

[Formula (ii)]

In the above formula (ii),

R ₆ is an alkylene group having 1 to 20 carbon atoms,

R ₇ and R ₈ are each independently -R ₉ Si(OR ₁₀ ) _b (R ₁₁ ) _3-b or -R ₁₂ R ₁₃ , wherein R ₉ and R ₁₂ are independently of each other alkylene having 1 to 20 carbon atoms Is a group, R ₁₀ and R ₁₁ are each independently an alkyl group having 1 to 20 carbon atoms, R ₁₃ is an epoxy group, and b is an integer of 1 to 3.

In addition, the present invention comprises the steps of preparing an active polymer chain by polymerizing a conjugated diene-based monomer or a conjugated diene-based monomer and an aromatic vinyl-based monomer in a carbon solvent in the presence of a polymerization initiator (S1); And it provides a method for producing the modified conjugated diene-based polymer comprising the step (S2) of reacting the active polymer chain with the denaturant represented by the formula (1).

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

The modified conjugated diene-based polymer according to the present invention includes a functional group derived from a modifier represented by Formula 1 bonded to at least one end of the polymer chain, such as an amine group, an alkoxysilane group, an ethylene oxide group, an epoxy group, and thus a filler included in the rubber composition. And affinity can be excellent.

The method for preparing a modified conjugated diene-based polymer according to the present invention includes a step of reacting with a denaturing agent represented by Formula 1, so that a modified conjugated diene-based polymer having excellent affinity with a filler can be easily prepared.

In addition, the rubber composition according to the present invention has excellent processability, tensile properties and viscoelastic properties by including the modified conjugated diene-based polymer.

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

Terms and words used in the description and claims of the present invention should not be construed as being limited to their usual or dictionary meanings, and the inventors appropriately explain the concept of terms in order to explain their own invention in the best way. Based on the principle that it can be defined, it should be interpreted as a meaning and concept consistent with the technical idea of the present invention.

In the present invention, the term'polymer chain' may mean that units derived from monomers are repeatedly linked by polymerization of one or more monomers.

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

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

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

In the present invention, the term'cycloalkyl group' may mean a cyclic saturated hydrocarbon.

In the present invention, the term'aryl group' may mean a cyclic aromatic hydrocarbon, and also a monocyclic aromatic hydrocarbon having one ring formed, or a polycyclic aromatic hydrocarbon having two or more rings bonded thereto. hydrocarbon) may be included.

In the present invention, the terms "derived unit", "derived repeating unit" and "derived functional group" may refer to a component, structure, or the substance itself derived from a substance.

The present invention provides a modified conjugated diene polymer capable of providing a rubber composition having excellent affinity with a filler and, as a result, excellent processability, tensile properties, and viscoelastic properties.

The modified conjugated diene-based polymer according to an embodiment of the present invention comprises a polymer chain including a repeating unit derived from a conjugated diene-based monomer and a functional group derived from a modifier represented by the following Formula 1 bonded to at least one end of the polymer chain. It is done.

[Formula 1]

In Formula 1,

n and m are each independently an integer of 1 to 3,

R ₁ and R ₂ are each independently a substituent represented by the following formula (i) or formula (ii), or -[CH ₂ CH ₂ O] _c R ₁₄ , wherein R ₁₄ is an alkyl group having 1 to 20 carbon atoms. , c is an integer from 1 to 10,

[Formula (i)]

In the above formula (i),

R ₃ is an alkylene group having 1 to 20 carbon atoms,

R ₄ and R ₅ are each independently an alkyl group having 1 to 20 carbon atoms,

a is an integer from 1 to 3,

[Formula (ii)]

In the above formula (ii),

R ₆ is an alkylene group having 1 to 20 carbon atoms,

R ₇ and R ₈ are each independently -R ₉ Si(OR ₁₀ ) _b (R ₁₁ ) _3-b or -R ₁₂ R ₁₃ , wherein R ₉ and R ₁₂ are independently of each other alkylene having 1 to 20 carbon atoms Is a group, R ₁₀ and R ₁₁ are each independently an alkyl group having 1 to 20 carbon atoms, R ₁₃ is an epoxy group, and b is an integer of 1 to 3.

The modified conjugated diene-based polymer according to an embodiment of the present invention is prepared by the same method as in the manufacturing method described below, which includes reacting with a denaturant represented by Formula 1, and the functional group derived from the denaturant is included in the polymer. It may be bonded to at least one end of the polymer chain.

Specifically, the modified conjugated diene polymer is a functional group derived from the modifier, such as at least one functional group selected from an amine group, an alkoxysilane group, an ethylene oxide group and an epoxy group is bonded to at least one end of the polymer chain, such as a silica-based filler. It may have excellent affinity with a filler, and may have excellent processability of a rubber composition containing the modified conjugated diene polymer, and as a result, the tensile properties and viscoelastic properties of a molded article manufactured using the rubber composition, such as a tire, may be excellent. There is an improvement effect.

The modifying agent is a substituent represented for R ₁ and R ₂ in formula (I) by the following formula (i) independently from each other, and R ₃ is an alkylene group having 1 to 10 carbon atoms in the formula (i), R ₄ and R ₅ Are each independently an alkyl group having 1 to 10 carbon atoms, and a may be an integer of 2 or 3.

In addition, the modifier is a substituent represented by formula (ii) independently of each other _{in R 1} and R _{2 in Formula 1, R 6} in Formula (ii) is an alkylene group having 1 to 10 carbon atoms, R ₇ and R ₈ is independently of each other -R ₉ Si(OR ₁₀ ) _b (R ₁₁ ) _3-b or -R ₁₂ R ₁₃ , wherein R ₉ and R ₁₂ are each independently an alkylene group having 1 to 10 carbon atoms, R ₁₀ and R ₁₁ are each independently an alkyl group having 1 to 10 carbon atoms, R ₁₃ is an epoxy group, and b may be an integer of 2 or 3.

In addition, the modifier, in Formula 1, R ₁ and R ₂ independently of each other -[CH ₂ CH ₂ O] _c R ₁₄ , wherein R ₁₄ is an alkyl group having 1 to 10 carbon atoms, and c is 2 to 4 It may be an integer of.

More specifically, the modifier may be one or more selected from the group consisting of compounds represented by the following Formulas 1-1 to 1-6.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

In Formulas 1-1 to 1-6, n and m are integers of 1 or 2, respectively.

In addition, according to an embodiment of the present invention, the modified conjugated diene-based polymer includes a polymer chain containing a repeating unit derived from a conjugated diene-based monomer and a functional group derived from a modifier bonded to the polymer chain, wherein the conjugated diene-based polymer The monomer-derived repeating unit may mean a repeating unit formed when the conjugated diene-based monomer is polymerized, and the functional group derived from the denaturant may mean a functional group derived from the denaturing agent.

In addition, according to another embodiment of the present invention, the polymer chain may include a repeating unit derived from an aromatic vinyl monomer. In this case, the modified conjugated diene-based polymer is a repeating unit derived from a conjugated diene-based monomer and an aromatic vinyl-based monomer. It may be a copolymer containing a derived repeating unit and a functional group derived from a denaturant.

According to an embodiment of the present invention, the conjugated diene-based monomer is 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, and 2 -It may be one or more selected from the group consisting of phenyl-1,3-butadiene.

The aromatic vinyl monomer is, for example, styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, and It may be one or more selected from the group consisting of 1-vinyl-5-hexylnaphthalene.

As another example, the modified conjugated diene-based polymer may be a copolymer further comprising a repeating unit derived from a diene-based monomer having 1 to 10 carbon atoms together with a repeating unit derived from the conjugated diene-based monomer. The diene-based monomer-derived repeating unit may be a repeating unit derived from a diene-based monomer different from the conjugated diene-based monomer, and the diene-based monomer different from the conjugated diene-based monomer may be, for example, 1,2-butadiene. . When the modified conjugated diene-based polymer is a copolymer further comprising a diene-based monomer, the modified conjugated diene-based polymer contains a diene-based monomer-derived repeating unit in excess of 0% to 1% by weight, more than 0% to 0.1% by weight, It may be included in an amount exceeding 0% by weight to 0.01% by weight, or exceeding 0% by weight to 0.001% by weight, and there is an effect of preventing gel formation within this range.

According to an embodiment of the present invention, the polymer chain constituting the skeleton of the modified conjugated diene-based polymer may be a random copolymer chain, and in this case, there is an effect of having an excellent balance between physical properties. The random copolymer may mean that the repeating units constituting the copolymer are randomly arranged.

The modified conjugated diene-based polymer according to an embodiment of the present invention has 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, and a weight average molecular weight (Mw) of 10,000 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, and a peak average molecular weight (Mp) 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. Within this range, there are excellent effects of rolling resistance and wet road surface resistance. In another example, the modified conjugated diene-based polymer may have a molecular weight distribution (PDI; MWD; Mw/Mn) of 1.0 or more and 3.0 or less, or 1.1 or more and 2.5 or less, or 1.1 or more and 2.0 or less, and tensile properties within this range And viscoelastic properties are excellent, and there is an effect of excellent balance between physical properties.

In addition, the modified conjugated diene-based polymer may have a Mooney viscosity at 100° C., 30 or more, 40 to 150, or 40 to 140, and has excellent processability and productivity within this range.

Here, the Mooney viscosity may be measured using a Mooney viscometer. Specifically, using a large rotor of Monsanto's MV2000E, under the conditions of 100°C and a rotor speed of 2±0.02 rpm, leave the polymer at room temperature (23±5°C) for 30 minutes or more, and then collect 27±3 g to the inside of the die cavity. It was measured while filling in and applying torque by operating a platen.

In addition, the modified conjugated diene-based polymer may have a 1,2-vinyl bond content of 5% by weight or more, 10% by weight or more, or 10% by weight to 60% by weight. Here, the 1,2-vinyl bond content is a 1,2-added conjugated diene monomer, not 1,4-added, based on 100% by weight of the conjugated diene-based copolymer composed of a vinyl group-containing monomer and an aromatic vinyl-based monomer It can mean the content of.

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

The method for preparing the modified conjugated diene-based polymer according to an embodiment of the present invention comprises the steps of polymerizing a conjugated diene-based monomer or a conjugated diene-based monomer and an aromatic vinyl-based monomer in a hydrocarbon solvent in the presence of a polymerization initiator to prepare an active polymer chain. (S1); It characterized in that it comprises a step (S2) of reacting the active polymer chain with a denaturant represented by the following formula (1).

[Formula 1]

In Formula 1, R ₁ and R ₂ , n and m are as defined above, and the modifier is as described above.

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

The polymerization initiator is not particularly limited, for example, methyllithium, ethyllithium, propyllithium, isopropyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octyl Lithium, phenyllithium, 1-naphthyllithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium , Naphthyl sodium, naphthyl potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide and lithium isopropylamide It can be more than that.

According to an embodiment of the present invention, the polymerization initiator is 0.01 mmol to 10 mmol, 0.05 mmol to 5 mmol, 0.1 mmol to 2 mmol, 0.1 mmol to 1 mmol, or 0.15 to 0.8 mmol based on a total of 100 g of monomers. Can be used. Here, the total of 100 g of the monomers may represent the total amount of a conjugated diene-based monomer or a conjugated diene-based monomer and an aromatic vinyl-based monomer.

The polymerization in step (S1) may be an anionic polymerization as an example, and a specific example may be a living anionic polymerization having an anionic active site at the polymerization end by a growth polymerization reaction by an anion. In addition, the polymerization in step (S1) may be elevated temperature polymerization, isothermal polymerization, or constant temperature polymerization (insulation polymerization), and the constant temperature polymerization includes polymerization by self-reaction heat without optionally applying heat after the polymerization initiator is added. It may mean a polymerization method, and the elevated-temperature polymerization may mean a polymerization method in which heat is arbitrarily applied after the polymerization initiator is added to increase the temperature, and the isothermal polymerization is heated by applying heat after the polymerization initiator is added. It may mean a polymerization method in which the temperature of the polymerized product is kept constant by increasing or taking away heat.

In addition, according to an embodiment of the present invention, the polymerization in step (S1) may further include a diene-based compound having 1 to 10 carbon atoms in addition to the conjugated diene-based monomer. There is an effect of preventing this formation. As an example of the diene-based compound, it may be 1,2-butadiene.

The polymerization of step (S1) may be carried out in a temperature range of 80° C. or less, -20° C. to 80° C., 0° C. to 80° C., 0° C. to 70° C., or 10° C. to 70° C., for example, and this range By narrowly controlling the molecular weight distribution of the polymer within, there is an excellent effect of improving physical properties.

The active polymer chain prepared by the step (S1) may mean a polymer in which a polymer anion and an organic metal cation are bonded.

Meanwhile, the polymerization of step (S1) may be carried out including a polar additive, and the polar additive is added in a ratio of 0.001 g to 50 g, 0.001 g to 10 g, or 0.005 g to 0.1 g based on a total of 100 g of monomers. can do. As another example, the polar additive may be added in a ratio of 0.001g to 10g, 0.005g to 5g, and 0.005g to 4g based on a total of 1 mmol of the polymerization initiator.

The polar additives include, for example, tetrahydrofuran, 2,2-di (2-tetrahydrofuryl) propane, diethyl ether, cyclopentyl ether, dipropyl ether, ethylene methyl ether, ethylene dimethyl ether, diethyl glycol, dimethyl ether. , Tertiary butoxyethoxyethane, bis(3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine, N,N,N',N'-tetramethyl It may be one or more selected from the group consisting of ethylenediamine, sodium mentholate, and 2-ethyl tetrahydrofurfuryl ether, preferably 2,2-di(2-tetrahydro Furyl) propane, triethylamine, tetramethylethylenediamine, sodium mentholate, or 2-ethyl tetrahydrofurfuryl ether, and when the polar additive is included, a conjugated diene-based When a monomer and an aromatic vinyl-based monomer are copolymerized, there is an effect of inducing a random copolymer to be easily formed by compensating for a difference in reaction rate thereof.

The step (S2) is a step for preparing a modified conjugated diene-based polymer by reacting an active polymer chain with a denaturant, wherein the reaction may be a denaturation or a coupling reaction, wherein the denaturant is based on a total of 100 g of monomers. It can be used in an amount of 0.01 mmol to 10 mmol. As another example, the modifier may be used in a molar ratio of 1:0.1 to 10, 1: 0.1 to 5, or 1:0.1 to 1:3, based on 1 mole of the polymerization initiator in step (S1).

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

The rubber composition may contain the modified conjugated diene-based polymer in an amount of 10% by weight or more, 10% by weight to 100% by weight, or 20% by weight to 90% by weight, and within this range, tensile strength, abrasion resistance, etc. It has excellent mechanical properties and excellent balance between properties.

In addition, the rubber composition may further include other rubber components as necessary in addition to the modified conjugated diene-based polymer, and in this case, the rubber component may be included in an amount of 90% by weight or less based on the total weight of the rubber composition. As a specific example, the other rubber component 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 polymer.

The rubber component may be, for example, natural rubber or synthetic rubber, and specific examples include natural rubber (NR) including cis-1,4-polyisoprene; Modified natural rubber such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), hydrogenated natural rubber, etc. obtained by modifying or purifying the general natural rubber; Styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, polyisobutylene-co-isoprene, neoprene, poly(ethylene-co- Propylene), poly(styrene-co-butadiene), poly(styrene-co-isoprene), poly(styrene-co-isoprene-co-butadiene), poly(isoprene-co-butadiene), poly(ethylene-co-propylene -Co-diene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, halogenated butyl rubber, and the like, and any one or a mixture of two or more of them may be used.

The rubber composition may include, for example, 0.1 parts by weight to 200 parts by weight, or 10 parts by weight to 120 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene-based polymer of the present invention. The filler may be a silica-based filler as an example, and a specific example may be wet silica (hydrous silicic acid), dry silica (silicic anhydride), calcium silicate, aluminum silicate, or colloidal silica, and preferably, the effect of improving fracture properties and wet It may be wet-type silica that has the best effect of both wet grip. In addition, the rubber composition may further include a carbon black-based filler if necessary.

As another example, when silica is used as the filler, a silane coupling agent for improving reinforcing properties and low heat generation properties may be used together, and as a specific example, the silane coupling agent is bis(3-triethoxysilylpropyl)tetrasulfide. , Bis(3-triethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilyl) Propyl) tetrasulfide, bis(2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide Feed, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilylpropylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzolyltetrasulfide, 3-triethoxysilylpropylmethacrylate monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, bis(3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethyl Silane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, dimethoxymethylsilylpropylbenzothiazolyltetrasulfide, and the like, and any one or a mixture of two or more of them may be used. Preferably, when considering the effect of improving reinforcing properties, it may be bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide.

In addition, in the rubber composition according to an embodiment of the present invention, since a modified conjugated diene-based polymer in which a functional group having high affinity with silica is introduced as a rubber component is used, the amount of the silane coupling agent is usually It may be less than the case, and accordingly, the silane coupling agent may be used in an amount of 1 to 20 parts by weight, or 5 to 15 parts by weight based on 100 parts by weight of silica, and the effect as a coupling agent within this range is While sufficiently exerted, there is an effect of preventing the gelation of the rubber component.

The rubber composition according to an embodiment of the present invention may be sulfur crosslinkable, and may further include a vulcanizing agent. The vulcanizing agent may specifically be a 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, within this range, while securing the required elastic modulus and strength of the vulcanized rubber composition, and at the same time having low fuel economy. It has an excellent effect.

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

The vulcanization accelerator is, for example, a thiazole compound such as M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazylsulfenamide), or DPG A guanidine-based compound such as (diphenylguanidine) may be used, and may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the rubber component.

The process oil acts as a softener in the rubber composition, and may be, for example, a paraffinic, naphthenic, or aromatic compound, and when considering tensile strength and abrasion resistance, when considering aromatic process oil price, hysteresis loss, and low-temperature characteristics Naphthenic or paraffinic process oil may be used. For example, 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, and within this range, there is an effect of preventing a decrease in tensile strength and low heat generation (low fuel economy) of the vulcanized rubber.

The antioxidant is, for example, 2,6-di-t-butylparacresol, dibutylhydroxytoluenyl, 2,6-bis((dodecylthio)methyl)-4-nonylphenol (2,6-bis( (dodecylthio)methyl)-4-nonylphenol) or 2-methyl-4,6-bis((octylthio)methyl)phenol (2-methyl-4,6-bis((octylthio)methyl)phenol), It 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 anti-aging agent is, for example, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 6-ethoxy-2 ,2,4-trimethyl-1,2-dihydroquinoline, or a high-temperature condensation product of diphenylamine and acetone, and the like, and 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 formulation, and has low heat generation and abrasion resistance by a vulcanization process after molding processing. This excellent rubber composition can be obtained.

Accordingly, the rubber composition is a tire tread, under tread, side wall, carcass coated rubber, belt coated rubber, bead filler, pancreas, or bead coated rubber, and other tire members, anti-vibration rubber, belt conveyor, hose, etc. It may be useful in the manufacture of various industrial rubber products.

In addition, the present invention provides a tire manufactured using the rubber composition.

The tire may include a tire or a tire tread.

Hereinafter, examples will be described in detail to illustrate the present invention in detail. However, the embodiments according to the present invention may be modified in various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to more completely describe the present invention to those of ordinary skill in the art.

Meanwhile, the compounds represented by Chemical Formula 1-1, Chemical Formula 1-3, Chemical Formula 1-5, and Chemical Formula 1-6 used in the following Examples are “RUSSIAN JOURNAL OF GENERAL CHEMISTRY (2005), Vol. 75, No. It was synthesized and used by referring to the method described in “4, page 1”.

Example 1

In a 20 L autoclave reactor, 3 kg of n-hexane, 270 g of styrene, 710 g of 1,3-butadiene, and 1.29 g of 2,2-bis(2-oxoranyl)propane as a polar additive were added to the reactor. The temperature was adjusted to ℃ and the adiabatic heating reaction was performed. After 30 minutes elapsed, 1,3-butadiene 20 g was added to cap the polymer end with butadiene, and after 10 minutes elapsed, 4,10-bis(3-(trie) represented by the following formula 1-1 as a denaturant. Oxysilyl)propyl)-1,7-dioxa-4,10-diazacyclododecane (4,10-bis(3-(triethoxysilyl)propyl)-1,7-dioxa-4,10-diazacyclododecane) It was added and reacted for 15 minutes ([DTP]/[act. Li]=1.5:1 molar ratio, [modifier]/[act. Li]=1:1 molar ratio). Thereafter, the reaction was stopped using ethanol, and 33 g of a solution in which 30% by weight of the antioxidant Wingstay K was dissolved in hexane was added. The resulting polymer was put in hot water heated with steam and stirred to remove the solvent, and then roll-dried to remove the remaining amount of solvent and water, thereby preparing a modified styrene-butadiene copolymer.

[Formula 1-1]

Example 2

In Example 1, as a denaturing agent, N,N'-((1,7-dioxa-4,10-diazacyclododecane-4,10-diyl)bis(ethane- 2,1-diyl)bis(3-(diethoxy(methic)silyl)-N-(3-(diethoxy(methyl)silyl)propyl)propan-1-amine)(N,N'-((1, 7-dioxa-4,10-diazacyclododecane-4,10-diyl)bis(ethane-2,1-diyl)bis(3-(diethoxy(methyl)silyl)-N-(3-(diethoxy(methyl)silyl) Except for using propyl) propan-1-amine), a modified styrene-butadiene copolymer was prepared in the same manner as in Example 1 above.

[Formula 1-3]

Example 3

In Example 1, 2,2'-((1,7-dioxa-4,10-diazacyclododecane-4,10-diyl)bis(N,N -Bis(oxiran-2-ylmethyl)ethan-1-amine (2,2'-((1,7-dioxa-4,10-diazacyclododecane-4,10-diyl)bis(N,N-bis( Except for using oxiran-2-ylmethyl)ethan-1-amine), a modified styrene-butadiene copolymer was prepared in the same manner as in Example 1 above.

[Formula 1-5]

Example 4

In Example 1, 4,10-bis(2-(2-methoxyethoxy)ethyl)-1,7-dioxa-4,10-diazacyclodo represented by the following formula 1-6 as a denaturing agent Except for using decane (4,10-bis(2-(2-methoxyethoxy)ethyl)-1,7-dioxa-4,10-diazacyclododecane), it was carried out in the same manner as in Example 1, and modified styrene-butadiene A copolymer was prepared.

[Formula 1-6]

Comparative Example 1

In a 20 L autoclave reactor, 3 kg of n-hexane, 270 g of styrene, 710 g of 1,3-butadiene, and 1.29 g of 2,2-bis(2-oxoranyl)propane as a polar additive were added to the reactor. The temperature was adjusted to ℃ and the adiabatic heating reaction was performed. After about 30 minutes, 20 g of 1,3-butadiene is added to cap the polymer end with butadiene, and after 10 minutes have elapsed, the reaction is stopped using ethanol, and the antioxidant Wingstay K is dissolved in 30% by weight in hexane. 33 g of the present solution were added. The resulting polymer was put in hot water heated with steam and stirred to remove the solvent, and then roll-dried to remove the remaining amount of solvent and water, thereby preparing a styrene-butadiene copolymer.

Comparative Example 2

A commercially available conventional styrene-butadiene copolymer (5025-2HM grade, LANXESS Co.) was used as a comparison object.

Experimental Example 1

For each modified or unmodified conjugated diene-based polymer prepared in the above Examples and Comparative Examples, the styrene unit content, 1,2-vinyl bond content, and weight average molecular weight (Mw, X10 ³ g/mol), number average in the polymer, respectively Molecular weight (Mn, X10 ³ g/mol), molecular weight distribution (PDI, MWD), and Mooney viscosity (MV) were measured, respectively. The results are shown in Table 1 below.

1) Styrene unit and 1,2-vinyl bond content (% by weight)

The content of styrene units (SM) and 1,2-vinyl bonds in each polymer was measured and analyzed using Varian VNMRS 500 MHz NMR.

In the NMR measurement, 1,1,2,2-tetrachloroethane was used as the solvent, and the solvent peak was calculated as 5.97 ppm, 7.2 to 6.9 ppm was random styrene, 6.9 to 6.2 ppm was block styrene, and 5.8 to 5.1 ppm was 1,4-vinyl, 5.1 to 4.5 ppm was calculated as the peak of 1,2-vinyl, and the content of styrene units and 1,2-vinyl bonds were calculated.

2) Weight average molecular weight (Mw, X10 ³ g/mol), number average molecular weight (Mn, X10 ³ g/mol), molecular weight distribution (PDI, MWD)

The weight average molecular weight (Mw) and number average molecular weight (Mn) were measured through GPC (Gel permeation Chromatography) analysis, and a molecular weight distribution curve was obtained. In addition, the molecular weight distribution (PDI, MWD, Mw/Mn) was obtained by calculating from the measured molecular weights. Specifically, the GPC is used by combining two columns of PLgel Olexis (Polymer Laboratories) and one column of PLgel mixed-C (Polymer Laboratories), and when calculating the molecular weight, the GPC standard material is PS (polystyrene). It was carried out using. The GPC measurement solvent was prepared by mixing 2% by weight of an amine compound in tetrahydrofuran.

3) Mooney viscosity

The Mooney viscosity (MV, (ML1+4, @100°C) MU) was measured using a Rotor Speed 2±0.02 rpm, Large Rotor at 100°C using MV-2000 (ALPHA Technologies). Samples were left at room temperature (23±3°C) for at least 30 minutes, and then 27±3 g was collected, filled in the die cavity, and platen was operated to measure for 4 minutes.

division Example Comparative example One 2 3 4 One 2 NMR
(weight%) SM 27 27 27 27 27 27 Vinyl 43 43 43 43 43 43 GPC Mw(X10 ³ g/mol) 41 40 42 41 50 69 Mn(X10 ³ g/mol) 30 31 32 30 42 320 PDI 14 1.3 1.3 1.4 1.2 1.8 Mooney viscosity (MV) 70 72 71 71 64 61

Experimental Example 2

In order to compare and analyze the physical properties of the rubber compositions containing the modified or unmodified conjugated diene-based copolymers prepared in the above Examples and Comparative Examples and the molded articles prepared therefrom, tensile properties and viscoelastic properties were measured, respectively, and the results were obtained. It is shown in Table 3 below.

1) Preparation of rubber specimen

Each modified or unmodified conjugated diene-based polymer of Examples, Comparative Examples and Reference Examples was used as a raw material rubber and was blended under the blending conditions shown in Table 2 below. The content of the raw materials in Table 2 is each part by weight based on 100 parts by weight of the raw rubber.

division Raw material Content (parts by weight) 1st stage kneading Rubber 100 Silica 70 Coupling agent (X50S) 11.2 Fair oil 37.5 Zinc agent 3 Stearic acid 2 Antioxidant 2 Anti-aging agent 2 Wax One 2nd stage kneading sulfur 1.5 Rubber accelerator 1.75 Vulcanization accelerator 2

Specifically, the rubber specimen is kneaded through the first stage kneading and the second stage kneading. In the first-stage kneading, raw rubber, silica (filler), organosilane coupling agent (X50S, Evonik), process oil (TDAE oil), zinc agent (ZnO), stearic acid are used by using a Banbari mixer attached with a temperature control device. , Antioxidant (TMQ(RD) (2,2,4-trimethyl-1,2-dihydroquinoline polymer), anti-aging agent (6PPD ((dimethylbutyl)-N-phenyl-phenylenediamine) and wax (Microcrystaline Wax) At this time, the initial temperature of the kneader was controlled at 70° C., and after completion of the blending, a first blend was obtained at a discharge temperature of 145° C. to 155° C. In the second stage kneading, the first blend was cooled to room temperature. After that, the first blend, sulfur, a rubber accelerator (DPD (diphenylguanine)) and a vulcanization accelerator (CZ (N-cyclohexyl-2-benzothiazylsulfenamide)) were added to the kneader, and a temperature of 100°C or less. The mixture was mixed at, to obtain a secondary compound, and then subjected to a curing process at 160° C. for 20 minutes to prepare a rubber specimen.

2) Tensile characteristics

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 and the tensile stress at the time of 300% elongation (300% modulus) were measured. Specifically, tensile properties were measured at a rate of 50 cm/min at room temperature using a Universal Test Machin 4204 (Instron) tensile tester.

3) Viscoelastic properties

For viscoelastic properties, the tan δ value was confirmed by measuring the viscoelastic behavior against dynamic deformation at a frequency of 10 Hz and each measurement temperature (-60℃~60℃) in Film Tension mode using a dynamic mechanical analyzer (GABO). In the measurement result, the higher the low-temperature 0℃ tan value, the better the wet road surface resistance, and the lower the high-temperature 60℃ tan δ value, the lower the hysteresis loss and the better low-driving resistance (fuel economy). The result value is expressed in Index (%) based on the result value of Comparative Example 2, so the higher the value, the better.

4) Processability characteristics

By measuring the Mooney viscosity (CMV, (ML1+4, @100°C) and Mooney viscosity of the second compound (FMV, (ML1+4, @100°C) MU) of the 1) rubber specimen obtained in the manufacture of the above. The processability characteristics of each polymer were compared and analyzed, and at this time, the smaller the difference between the Mooney viscosity and the Mooney point focus of the second mixture, the better the processability characteristics.

Specifically, MV-2000 (ALPHA Technologies, Inc.) was used at 100°C with a Rotor Speed of 2±0.02 rpm, and a Large Rotor was used, and each secondary compound was left at room temperature (23±3°C) for 30 minutes or more, and then 27 ±3 g was collected, filled inside the die cavity, and measured for 4 minutes by operating the platen.

division Example Comparative example One 2 3 4 One 2 Tensile properties Tensile strength (kgf/cm ² ) 184 185 187 185 168 167 300% modulus (kgf/cm ² ) 120 121 124 122 104 98 Viscoelastic properties tan δ(at 0℃, Index) 103 102 104 101 98 100 tan δ(at 60℃, Index) 132 138 135 134 105 100 Processability characteristics CMV 87 86 88 85 87 85 FMV 70 71 72 69 71 62 △FMV-CMV (absolute value) 17 15 16 16 16 23

As shown in Table 3, the modified styrene-butadiene copolymers of Examples 1 to 4 prepared by the manufacturing method of a denaturing reaction using a denaturing agent represented by Formula 1 were compared to the copolymers of Comparative Examples 1 and 2 in tensile properties. , It was confirmed that the viscoelastic properties and processability properties were excellent.

Claims (15)

A modified conjugated diene-based polymer comprising a polymer chain containing a repeating unit derived from a conjugated diene-based monomer and a functional group derived from a modifier represented by the following formula (1) bonded to at least one end of the polymer chain:
[Formula 1]

In Chemical Formula 1,
n and m are each independently an integer of 1 to 3,
R ₁ and R ₂ are each independently a substituent represented by the following formula (i) or formula (ii), or -[CH ₂ CH ₂ O] _c R ₁₄ , wherein R ₁₄ is an alkyl group having 1 to 20 carbon atoms. , c is an integer from 1 to 10,
[Formula (i)]

In the above formula (i),
R ₃ is an alkylene group having 1 to 20 carbon atoms,
R ₄ and R ₅ are each independently an alkyl group having 1 to 20 carbon atoms,
a is an integer from 1 to 3,
[Formula (ii)]

In the above formula (ii),
R ₆ is an alkylene group having 1 to 20 carbon atoms,
R ₇ and R ₈ are each independently -R ₉ Si(OR ₁₀ ) _b (R ₁₁ ) _3-b or -R ₁₂ R ₁₃ , wherein R ₉ and R ₁₂ are independently of each other alkylene having 1 to 20 carbon atoms Is a group, R ₁₀ and R ₁₁ are each independently an alkyl group having 1 to 20 carbon atoms, R ₁₃ is an epoxy group, and b is an integer of 1 to 3.
The method according to claim 1,
_{R 1} and R ₂ in Formula 1 are each independently a substituent represented by Formula (i),
In the formula (i), R ₃ is an alkylene group having 1 to 10 carbon atoms, R ₄ and R ₅ are each independently an alkyl group having 1 to 10 carbon atoms, and a is a modified conjugated diene-based polymer that is an integer of 2 or 3.
The method according to claim 1,
_{R 1} and R ₂ in Formula 1 are each independently a substituent represented by Formula (ii),
In the above formula (ii), R ₆ is an alkylene group having 1 to 10 carbon atoms, and R ₇ and R ₈ are independently of each other -R ₉ Si(OR ₁₀ ) _b (R ₁₁ ) _3-b or -R ₁₂ R ₁₃ , Wherein R ₉ and R ₁₂ are each independently an alkylene _{group having 1 to 10 carbon atoms, R 10} and R ₁₁ are each independently an alkyl group having 1 to 10 carbon atoms, R ₁₃ is an epoxy group, and b is 2 or 3 Modified conjugated diene polymer that is an integer.
The method according to claim 1,
In Formula 1, R ₁ and R ₂ are independently of each other -[CH ₂ CH ₂ O] _c R ₁₄ , wherein R ₁₄ is an alkyl group having 1 to 10 carbon atoms, and c is a modified conjugated diene that is an integer of 2 to 4 Based polymer.
The method according to claim 1,
The modified conjugated diene polymer represented by Formula 1 is one or more selected from the group consisting of compounds represented by the following Formulas 1-1 to 1-6:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

In Formulas 1-1 to 1-6, n and m are integers of 1 or 2, respectively.
The method according to claim 1,
The polymer chain is a modified conjugated diene-based polymer further comprising a repeating unit derived from an aromatic vinyl monomer.
The method according to claim 1,
The number average molecular weight (Mn) is 1,000 g/mol to 2,000,000 g/mol, the weight average molecular weight (Mw) is 1,000 g/mol to 3,000,000 g/mol, and the peak average molecular weight (Mp) is 1,000 g/mol to 3,000,000 g /mol of modified conjugated diene-based polymer.
The method according to claim 1,
Modified conjugated diene polymer having a molecular weight distribution of 1 to 5.
The method according to claim 1,
The modified conjugated diene polymer having a 1,2-vinyl bond content of 5% by weight or more.
Preparing an active polymer chain by polymerizing a conjugated diene-based monomer or a conjugated diene-based monomer and an aromatic vinyl-based monomer in a carbon solvent in the presence of a polymerization initiator (S1); And
A method for producing a modified conjugated diene-based polymer of claim 1 comprising the step (S2) of reacting the active polymer chain with a denaturant represented by the following formula (1):
[Formula 1]

In Chemical Formula 1,
n and m are each independently an integer of 1 to 3,
R ₁ and R ₂ are each independently a substituent represented by the following formula (i) or formula (ii), or -[CH ₂ CH ₂ O] _c R ₁₄ , wherein R ₁₄ is an alkyl group having 1 to 20 carbon atoms. , c is an integer from 1 to 10,
[Formula (i)]

In the above formula (i),
R ₃ is an alkylene group having 1 to 20 carbon atoms,
R ₄ and R ₅ are each independently an alkyl group having 1 to 20 carbon atoms,
a is an integer from 1 to 3,
[Formula (ii)]

In the above formula (ii),
R ₆ is an alkylene group having 1 to 20 carbon atoms,
R ₇ and R ₈ are each independently -R ₉ Si (OR ₁₀ ) _b (R ₁₁ ) _3-b or -R ₁₂ R ₁₃ , wherein R ₉ and R ₁₂ are independently of each other alkylene having 1 to 20 carbon atoms Is a group, R ₁₀ and R ₁₁ are each independently an alkyl group having 1 to 20 carbon atoms, R ₁₃ is an epoxy group, and b is an integer of 1 to 3.
The method of claim 10,
The method for producing a modified conjugated diene-based polymer to be used in an amount of 0.1 to 10 mol relative to 1 mol of the polymerization initiator.
The method of claim 10,
The polymerization of step (S1) is a method of producing a modified conjugated diene-based polymer to be performed by further adding a polar additive.
The method of claim 10,
The polar additive is a method for producing a modified conjugated diene-based polymer to be added in an amount of 0.001 g to 10 g based on 1 mmol of a polymerization initiator.
A rubber composition comprising the modified conjugated diene polymer and a filler according to claim 1.
The method of claim 14,
The rubber composition is a rubber composition containing 0.1 to 200 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene-based polymer.