KR20210109946A - Modified conjugated diene polymer, preparation method thereof and rubber composition comprising the same - Google Patents

Abstract

The present invention relates to a highly branched high molecular weight modified conjugated diene-based polymer having excellent abrasion resistance, a method for manufacturing the same, and a rubber composition including the same. Provided are a modified conjugated diene-based polymer including a repeating unit derived from a conjugated diene-based monomer and a functional group derived from a modifying agent represented by chemical formula 1, a method for manufacturing the same, and a rubber composition including the same.

Description

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

The present invention relates to a highly branched, high molecular weight modified conjugated diene-based polymer having excellent wet road resistance and rolling resistance and improved abrasion resistance at the same time, a manufacturing method thereof, and a rubber composition comprising the same.

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 road 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 and Goodrich heat generation is preferable.

As a rubber material with a small 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 polymers or copolymers 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, 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. It is widely used as a rubber material for

When this solution-polymerized SBR is used as a rubber material for a tire, by increasing the vinyl content in the SBR, the glass transition temperature of the rubber can be increased to control the required physical properties of the tire such as running resistance and braking force, and the glass transition temperature can be lowered. By properly adjusting it, fuel consumption can be reduced. The solution polymerization SBR is prepared by using an anionic polymerization initiator, and is used by bonding or modifying the chain ends of the formed polymer using various modifiers. For example, U.S. Patent No. 4,397,994 discloses a technique in which an 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 combined using a binder such as a tin compound. did.

On the other hand, the polymerization of SBR or BR can be carried out by batch or continuous polymerization. In the case of batch polymerization, the molecular weight distribution of the prepared polymer is narrow, which has advantages in terms of improving physical properties, but productivity is low and , there is a problem of poor processability, and in the case of continuous polymerization, the polymerization is continuously performed and thus the productivity is excellent, and there are advantages in terms of processability improvement, but there is a problem in that the physical properties are poor because the molecular weight distribution is wide. Accordingly, there is a continuous demand for research to improve all of the productivity, processability and physical properties at the time of manufacturing SBR or BR.

US 4397994 A

The present invention has been devised to solve the problems of the prior art, and it is prepared by reacting an active polymer with a modifier represented by Formula 1, and has a high molecular weight of a highly branched structure, so that it can have excellent abrasion resistance, and functional groups derived from the modifier An object of the present invention is to provide a modified conjugated diene-based polymer having excellent filler affinity and excellent compounding processability by including.

Another object of the present invention is to provide a method for producing the modified conjugated diene-based polymer.

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

According to one embodiment of the present invention for solving the above problems, the present invention provides a modified conjugated diene-based polymer comprising a repeating unit derived from a conjugated diene-based monomer and a functional group derived from a modifier represented by the following formula (1):

[Formula 1]

In Formula 1,

R ₁ to R ₈ are independently of each other an alkylene group having 1 to 20 carbon atoms or an alkenylene group having 2 to 20 carbon atoms that is substituted or unsubstituted with a substituent, wherein the substituent is an alkyl group having 1 to 20 carbon atoms, 3 to 20 carbon atoms is a cycloalkyl group or an aryl group having 6 to 20 carbon atoms,

A ₁ to A ₄ are each independently a substituent represented by the following formula (a),

[Formula a]

In the above formula (a),

R ₉ to R ₁₁ are each independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, and at least one of _{R 9} to R _{11 is an alkoxy group having 1 to 20 carbon atoms.}

In addition, the present invention comprises the steps of preparing an active polymer by 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 (S1); and reacting the active polymer with the modifier represented by Formula 1 (S2).

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 is prepared by reacting an active polymer with a modifier represented by Formula 1 to have a highly branched structure and high molecular weight, thereby significantly improving abrasion resistance, and including functional groups derived from the modifier. By doing so, the affinity with the filler may be excellent, and the compounding processability may be excellent.

In addition, the method for producing a modified conjugated diene-based polymer according to the present invention comprises a step of reacting the active polymer with a modifier represented by Formula 1, thereby easily manufacturing a modified conjugated diene-based polymer having a highly branched structure and high molecular weight and excellent abrasion resistance. can do.

In addition, the rubber composition according to the present invention is excellent in abrasion resistance by including the modified conjugated diene-based polymer, and at the same time excellent in compounding processability, so there is an effect of excellent compounding properties such as tensile properties, wet road resistance and rolling resistance.

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

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

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

In the present invention, the term 'alkyl group' may refer to a monovalent aliphatic saturated hydrocarbon, 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 cyclic saturated hydrocarbons, or cyclic unsaturated hydrocarbons including one or two or more unsaturated bonds.

In the present invention, the term 'alkylene group' may mean a divalent aliphatic saturated 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 in which one ring is formed, or a polycyclic aromatic hydrocarbon in which two or more rings are bonded. It may mean including all hydrocarbons.

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

The present invention provides a modified conjugated diene-based polymer having a highly branched structure and a high molecular weight and having excellent abrasion resistance.

The modified conjugated diene-based polymer according to an embodiment of the present invention is characterized in that it includes a repeating unit derived from a conjugated diene-based monomer and a functional group derived from a modifier represented by Formula 1 below.

[Formula 1]

In Formula 1,

R ₁ to R ₈ are independently of each other an alkylene group having 1 to 20 carbon atoms or an alkenylene group having 2 to 20 carbon atoms that is substituted or unsubstituted with a substituent, wherein the substituent is an alkyl group having 1 to 20 carbon atoms, 3 to 20 carbon atoms is a cycloalkyl group or an aryl group having 6 to 20 carbon atoms,

A ₁ to A ₄ are each independently a substituent represented by the following formula (a),

[Formula a]

In the above formula (a),

R ₉ to R ₁₁ are each independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, and at least one of _{R 9} to R _{11 is an alkoxy group having 1 to 20 carbon atoms.}

According to an embodiment of the present invention, the modified conjugated diene-based polymer may include a repeating unit derived from a conjugated diene-based monomer and a functional group derived from a modifier represented by Formula 1, wherein the repeating unit derived from the conjugated diene-based monomer is It may mean a repeating unit formed during polymerization of the conjugated diene-based monomer, and the functional group derived from the modifier represented by Formula 1 is derived from the modifier represented by Formula 1 present in the polymer chain including the repeating unit derived from the conjugated diene-based monomer. The functional group may be a functional group, and the functional group derived from the modifier represented by Formula 1 may be present at at least one end of the polymer chain.

In addition, according to another embodiment of the present invention, the modified conjugated diene-based polymer may further include a repeating unit derived from an aromatic vinyl-based monomer, and in this case, the modified conjugated diene-based polymer is a repeating unit derived from a conjugated diene-based monomer; It may be a copolymer including a repeating unit derived from an aromatic vinyl-based monomer and a functional group derived from a modifier represented by Formula 1. Here, the repeating unit derived from the aromatic vinyl-based monomer may mean a repeating unit formed during polymerization of the aromatic vinyl-based monomer.

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, 2 It may be at least one member selected from the group consisting of -phenyl-1,3-butadiene and 2-halo-1,3-butadiene (halo means a halogen atom).

The aromatic vinyl monomer is, for example, 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 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 the repeating unit derived from the conjugated diene-based monomer. The repeating unit derived from the diene-based monomer 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 more than 0% by weight to 1% by weight of the repeating unit derived from the diene-based monomer, more than 0% by weight to 0.1% by weight, It may contain more than 0 wt% to 0.01 wt%, or more than 0 wt% to 0.001 wt%, and has the effect of preventing gel formation within this range.

According to an embodiment of the present invention, when the modified conjugated diene-based polymer is a copolymer, the copolymer may be a random copolymer, and in this case, a good balance between physical properties is obtained. The random copolymer may mean that repeating units constituting the copolymer are disorderly arranged.

The modified conjugated diene-based polymer according to an embodiment of the present invention is prepared by a manufacturing method comprising reacting an active polymer to be described later with a modifier represented by Formula 1, wherein the modifier represented by Formula 1 is an active polymer A plurality of polymer chains composed of a repeating unit derived from a conjugated diene-based monomer of an active polymer or a repeating unit derived from a conjugated diene-based monomer and a repeating unit derived from an aromatic vinyl-based monomer of the active polymer by having a plurality of reactive active sites capable of reacting with the modifier By binding to and coupling to each other, it may have a highly branched structure and high molecular weight, and thus may have remarkably excellent abrasion resistance.

In Formula 1, R ₁ to R ₈ are each independently an unsubstituted C 1 to C 10 alkylene group, A ₁ to A ₄ are each independently a substituent represented by the following Formula (a), and in Formula (a), R ₉ to R ₁₁ are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and at least one of _{R 9} to R _{11 may be an alkoxy group having 1 to 10 carbon atoms.}

Also, as another example, the modifier represented by Formula 1 may include 8 to 12 alkoxy groups in a molecule.

Specifically, the modifier represented by Formula 1 may be at least one selected from compounds represented by Formulas 1-1 to 1-6 below.

[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, Me is a methyl group, Et is an ethyl group.

In addition, the modified conjugated diene-based polymer according to an embodiment of the present invention has a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 800,000 g/mol to 3,000,000 g/mol, 1 It may be ,00,000 g/mol to 3,000,000 g/mol or 1,200,000 to 3,000,000 g/mol, and within this range, the abrasion resistance of the modified conjugated diene-based polymer may be excellent.

On the other hand, the modified conjugated diene-based polymer may have a number average molecular weight (Mn) of 500,000 g/mol to 2,000,000 g/mol, 800,000 g/mol to 2,000,000 g/mol, or 800,000 g/mol to 1,700,000 g/mol, The molecular weight distribution (PDI; MWD; Mw/Mn) may be 1.0 or more and 5.0 or less, or 1.0 or more and 3.0 or less, while having a number average molecular weight and a weight average molecular weight in the above range, and in this case, the balance between each physical property is excellent. .

In addition, the modified conjugated diene-based polymer may have a Mooney stress relaxation rate measured at 140° C. of 0.050 to 0.300, and specifically, the Mooney stress relaxation rate may be 0.050 to 0.200 or 0.050 to 0.150. Here, the Mooney stress relaxation rate may be an indicator of the degree of branching and molecular weight of the polymer. For example, when the Mooney stress relaxation rate decreases, the degree of branching and molecular weight of the polymer tends to increase.

On the other hand, it is generally thought that the Mooney stress relaxation rate is related to the Mooney viscosity, but the higher the branching of the modified conjugated diene-based polymer, the smaller the Mooney stress relaxation rate. can be different.

As another example, the modified conjugated diene-based polymer may have a Mooney viscosity at 140° C. of 80 or more, 80 to 150, or 80 to 140.

When having a Mooney stress relaxation rate in the above range while having a weight average molecular weight in the above range, the balance between physical properties may be excellent and abrasion resistance may be greatly improved.

Here, the Mooney viscosity was measured using a Monsanto MV2000E Large Rotor at 140° C. and a rotor speed of 2±0.02 rpm, and after leaving the polymer at room temperature (23±5° C.) for 30 minutes or more, 27±3 g It may be taken and measured while filling the inside of the die cavity and applying a torque by operating a platen. In addition, the Mooney stress relaxation rate was measured by measuring the slope value of the Mooney viscosity change appearing when the torque was released after measuring the Mooney viscosity, and an absolute value thereof was used as the Mooney stress relaxation ratio.

In addition, the modified conjugated diene-based polymer may have a vinyl content of 5 wt% or more, 10 wt% or more, or 10 wt% to 80 wt%. Here, the vinyl content means 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 copolymer consisting of a monomer having a vinyl group and an aromatic vinyl-based monomer. can

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

The method for producing the modified conjugated diene-based polymer according to an embodiment of the present invention comprises the steps of preparing an active polymer by 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 ( S1); and reacting the active polymer with a modifier represented by Formula 1 below (S2).

[Formula 1]

In Formula 1, R ₁ to R ₈ and A ₁ to A ₄ are the same as described above, and the conjugated diene-based monomer and the aromatic vinyl-based monomer are also the same as described above.

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.

In addition, according to an embodiment of the present invention, the polymerization initiator may be an organometallic compound, and the organometallic compound is not particularly limited, for example, methyllithium, itellithium, propyllithium, isopropyllithium, n- Butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octyllithium, phenyllithium, 1-naphthyllithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolyl Lithium, cyclohexyl lithium, 3,5-di-n-heptylcyclohexyl lithium, 4-cyclopentyl lithium, naphthyl sodium, naphthyl potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, It may be at least one selected from the group consisting of potassium sulfonate, lithium amide, sodium amide, potassium amide and lithium isopropylamide.

According to one 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 100 g of the total monomer. Can be used. Here, the monomer may represent the content of the conjugated diene-based monomer or the total amount of the conjugated diene-based monomer and the aromatic vinyl-based monomer.

The polymerization in step (S1) may be, for example, anionic polymerization, and as a specific example, living anionic polymerization having an anionic active site at the polymerization end by an anion-based growth polymerization reaction. In addition, the polymerization in step (S1) may be an elevated temperature polymerization, isothermal polymerization, or constant temperature polymerization (adiabatic polymerization), and the constant temperature polymerization includes the step of polymerizing with the heat of its own reaction without optionally applying heat after adding a denaturation initiator may mean a polymerization method, and the temperature-rising polymerization may refer to a polymerization method in which the temperature is increased by arbitrarily applying heat after the addition of the modification initiator, and the isothermal polymerization is heat by adding heat after adding the modification initiator It may refer to a polymerization method in which the temperature of the polymer is maintained constant by increasing the temperature or taking heat away.

In addition, the polymerization of step (S1) may be performed through a batch reaction, a continuous reaction, or a reaction combining them appropriately.

In addition, according to an embodiment of the present invention, the polymerization in step (S1) may be carried out by further including a diene-based compound having 1 to 10 carbon atoms in addition to the conjugated diene-based monomer, and in this case, a gel is formed on the reactor wall during long-term operation. This has the effect of preventing its formation. An example of the diene-based compound 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. There is an effect of increasing the polymerization conversion rate of the polymerization reaction within.

The active polymer prepared by the step (S1) may refer to a polymer in which a polymer anion and an organometallic cation are bound.

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

The polar additive is, for example, tetrahydrofuran, 2,2-di(2-tetrahydrofuryl)propane, diethyl ether, cycloamyl ether, dipropyl ether, ethylene methyl ether, ethylene dimethyl ether, diethylene glycol, dimethyl ether. , tertiary butoxyethoxyethane, bis (3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine, N,N,N',N'-tetramethyl It may be at least one selected from the group consisting of ethylenediamine, sodium mentholate, and 2-ethyl tetrahydrofurfuryl ether, preferably 2,2-di (2-tetrahydro It may be furyl) propane, triethylamine, tetramethylethylenediamine, sodium mentholate, or 2-ethyl tetrahydrofurfuryl ether, and when the polar additive is included, a conjugated diene-based In the case of copolymerizing a monomer or a conjugated diene-based monomer and an aromatic vinyl-based monomer, there is an effect of inducing a random copolymer to be easily formed by compensating for a difference in their reaction rate.

According to an embodiment of the present invention, the reaction in step (S2) may be a denaturation reaction or a coupling reaction using a denaturant, wherein the denaturant is used in an amount of 0.01 mmol to 10 mmol based on 100 g of the total monomer. can As another example, the modifier may be used in an amount of 0.1 mol to 10 mol, 0.1 mol to 5 mol, or 0.1 mol to 3 mol based on 1 mol 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 include the modified conjugated diene-based polymer in an amount of 10 wt% or more, 10 wt% to 100 wt%, or 20 wt% to 90 wt%, within this range, tensile strength, abrasion resistance, etc. It has excellent mechanical properties and an excellent balance between the physical properties.

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. 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 thereof include natural rubber (NR) including cis-1,4-polyisoprene; Modified natural rubbers such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber, which are modified or refined of the general natural rubber; Styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, polyisobutylene-co-isoprene, neoprene, poly(ethylene-co-) propylene), poly(styrene-co-butadiene), poly(styrene-co-isoprene), poly(styrene-co-isoprene-co-butadiene), poly(isoprene-co-butadiene), poly(ethylene-co-propylene) -co-diene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, or a synthetic rubber such as halogenated butyl rubber, and any one or a mixture of two or more thereof 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, for example, a silica-based filler, and specific examples thereof include wet silica (hydrous silicic acid), dry silica (silicic anhydride), calcium silicate, aluminum silicate or colloidal silica, and preferably, the effect of improving the breaking properties and wet Wet silica may be the most excellent in compatibility with 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 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 It may be silane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide or dimethoxymethylsilylpropylbenzothiazolyltetrasulfide, and any one or a mixture of two or more thereof may be used. Preferably, in consideration of the reinforcing improvement effect, it may be bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide.

In addition, in the rubber composition according to an embodiment of the present invention, as a rubber component, a modified conjugated diene-based polymer in which a functional group with high affinity for silica is introduced is used as a rubber component, so the compounding amount of the silane coupling agent is a common may be reduced 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 within this range, the effect as a coupling agent is not significant. It has the effect of preventing the gelation of the rubber component while being sufficiently exhibited.

The rubber composition according to an embodiment of the present invention may be crosslinkable with sulfur, and 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. It has an excellent effect.

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, a process oil, an antioxidant, a plasticizer, an anti-aging agent, an anti-scorch agent, a zinc (zinc) white), stearic acid, a thermosetting resin, or a thermoplastic resin may be further included.

The vulcanization accelerator is, for example, a thiazole-based compound such as M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazyl sulfenamide), 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. Naphthenic or paraffinic process oils 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, for example, and has an effect of preventing deterioration of the tensile strength and low heat generation (low fuel efficiency) of the vulcanized rubber within this range.

The antioxidant is, for example, 2,6-di-t-butylparacresol, dibutylhydroxytoluenyl, 2,6-bis((dodecylthio)methyl)-4-nonylphenol (2,6-bis(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 antioxidant 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 condensate of diphenylamine and acetone, etc., 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, an internal mixer, etc. according to the compounding prescription, and has low heat generation and wear resistance by a vulcanization process after molding processing. This excellent rubber composition can be obtained.

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

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 given to describe 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 explain the present invention to those of ordinary skill in the art.

In addition, the materials used in the following Examples and Comparative Examples were prepared and used with reference to a conventionally known manufacturing method, or purchased and used materials in circulation, except for those mentioned in particular.

Preparation Example 1

After removing water completely under reduced pressure in a 5 L round bottom flask connected to a shrink line, 1000 ml of acetonitrile was added under an Irgon atmosphere, and 4 mol of (3-chloropropyl) triethoxysilane (963.2 g) ) and 10.12 g of triethylamine were added and cooled to 0 °C. Then, 1 mol (172.27 g) of 1,4,7,10-tetraazacyclododecane (1,4,7,10-tetraazacyclododecane) was added through a dropping funnel over 1 hour, and after completion of the addition, the temperature was heated to 40°C. The reaction was carried out by raising the temperature and stirring for 4 hours. Thereafter, the solvent and triethylamine were removed using a rotary concentrator to prepare a compound represented by the following Chemical Formula 1-1.

[Formula 1-1]

Preparation 2

The following Chemical Formula 1- The compound represented by 2 was prepared.

[Formula 1-2]

Preparation 3

The following Chemical Formula 1- The compound represented by 3 was prepared.

[Formula 1-3]

Preparation 4

1 mol (200.32 g) of 1,4,8,11-tetraazacyclotetradecane (1,4,8,11-tetraazacyclotetradecane) was used instead of 1,4,7,10-tetraazacyclododecane in Preparation Example 1 A compound represented by the following Chemical Formula 1-4 was prepared in the same manner as in Preparation Example 1, except that it was used.

[Formula 1-4]

Preparation 5

In the same manner as in Preparation Example 4, the following formula 1- The compound represented by 5 was prepared.

[Formula 1-5]

Preparation 6

The following Chemical Formula 1- The compound represented by 6 was prepared.

[Formula 1-6]

Example 1

In a 20 L autoclave reactor, 100 g of styrene, 880 g of 1,3-butadiene, 5000 g of n-hexane and 0.70 g of 2,2-di(2-tetrahydrofuryl)propane as a polar additive were put into the reactor, and the internal temperature of the reactor was lowered to 50. The temperature was raised to °C. When the internal temperature of the reactor reached 50° C., 3.0 mmol of n-butyllithium was added as a polymerization initiator to conduct an adiabatic temperature rise reaction. After about 20 minutes, 20 g of 1,3-butadiene was added to cap the end of the polymer chain with butadiene. After 5 minutes, 1.2 mmol of the compound represented by Formula 1-1 prepared in Preparation Example 1 was added as a denaturant and reacted for 15 minutes. Thereafter, the polymerization reaction was stopped using ethanol, and 45 ml of a solution in which an antioxidant IR1520 (BASF) was dissolved in n-hexane at 0.3 wt% was added. The resulting polymer was put into hot water heated with steam and stirred to remove the solvent to prepare a modified conjugated diene-based polymer.

Example 2

In Example 1, the same as in Example 1, except that 1.2 mmol of the compound represented by Formula 1-2 prepared in Preparation Example 2 was added instead of the compound represented by Formula 1-1 to conduct the denaturation reaction. to prepare a modified conjugated diene-based polymer.

Example 3

In Example 1, the same as in Example 1, except that 1.2 mmol of the compound represented by Formula 1-3 prepared in Preparation Example 3 was added instead of the compound represented by Formula 1-1 to conduct the denaturation reaction. to prepare a modified conjugated diene-based polymer.

Example 4

In Example 1, the same as in Example 1, except that 1.2 mmol of the compound represented by Formula 1-4 prepared in Preparation Example 4 was added instead of the compound represented by Formula 1-1 to conduct the denaturation reaction. to prepare a modified conjugated diene-based polymer.

Example 5

In Example 1, the same as in Example 1, except that 1.2 mmol of the compound represented by Formula 1-5 prepared in Preparation Example 5 was added instead of the compound represented by Formula 1-1 to conduct the denaturation reaction. to prepare a modified conjugated diene-based polymer.

Example 6

In Example 1, the same as in Example 1, except that 1.2 mmol of the compound represented by Formula 1-6 prepared in Preparation Example 6 was added instead of the compound represented by Formula 1-1 to conduct the denaturation reaction. to prepare a modified conjugated diene-based polymer.

Comparative Example 1

In a 20 L autoclave reactor, 100 g of styrene, 880 g of 1,3-butadiene, 5000 g of n-hexane and 0.70 g of 2,2-di(2-tetrahydrofuryl)propane as a polar additive were put into the reactor, and the internal temperature of the reactor was lowered to 50. The temperature was raised to °C. When the internal temperature of the reactor reached 50° C., 3.0 mmol of n-butyllithium was added as a polymerization initiator to conduct an adiabatic temperature rise reaction. After about 20 minutes, 20 g of 1,3-butadiene was added to cap the end of the polymer chain with butadiene. After 5 minutes, _{0.8 mmol of SiCl 4} was added as a coupling agent and reacted for 15 minutes. Thereafter, the polymerization reaction was stopped using ethanol, and 45 ml of a solution in which an antioxidant IR1520 (BASF) was dissolved in n-hexane at 0.3 wt% was added. The resulting polymer was put into hot water heated with steam and stirred to remove the solvent to prepare an unmodified conjugated diene-based polymer.

Comparative Example 2

In Example 1, as a modifier N ¹ ,N ¹ ,N ³ ,N ³ -tetrakis(3-(trimethoxysilyl)propyl)propane-1,3-diamine (N ¹ ,N ¹ ,N ³ , A modified conjugated diene-based polymer was prepared in the same manner as in Example 1 except that ^{N 3 -tetrakis(3-(trimethoxysilyl)propyl)propan-1,3-diamine) was used.} Here, the N ¹ ,N ¹ ,N ³ ,N ³ -tetrakis(3-(trimethoxysilyl)propyl)propane-1,3-diamine is JP 2019-14014 B2 (2019. 11. 15.) It was prepared and used with reference to the description.

Experimental Example 1

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

1) Styrene units and vinyl content (wt%)

Styrene unit (SM) and vinyl (Vinyl) contents in each polymer were measured and analyzed using Varian VNMRS 500 MHz NMR.

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

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

The weight average molecular weight (Mw) and number average molecular weight (Mn) were measured through gel permeation chromatography (GPC) analysis, and molecular weight distributions (PDI, MWD, Mw/Mn) were 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 standard material is PS (polystyrene). was used. The GPC measurement solvent was prepared by mixing 2 wt% of an amine compound in tetrahydrofuran.

3) Mooney stress relaxation rate

Using Monsanto's MV2000E's Large Rotor, at 140°C and Rotor Speed 2±0.02 rpm, the polymer was left at room temperature (23±5℃) for more than 30 minutes, then 27±3 g was collected and filled inside the die cavity. Place and operate a platen to measure the Mooney viscosity while applying a torque, measure the slope value of the Mooney viscosity change that appears as the torque is released, and convert the absolute value to the Mooney stress relaxation ratio was done with

division Example comparative example One 2 3 4 5 6 One 2 NMR
(weight%) SM 10 10 10 10 10 10 10 10 Vinyl 38 38 38 38 38 38 38 38 GPC Mw (X10 ³ g/mol) 2108 2284 2146 2284 1601 1643 1547 1577 Mn (X10 ³ g/mol) 1301 1377 1328 1369 979 998 967 997 PDI 1.62 1.66 1.62 1.67 1.64 1.65 1.60 1.58 Mooney stress relaxation rate 0.1214 0.1077 0.1196 0.1026 0.1476 0.1397 0.1607 0.1555

As shown in Table 1, the modified conjugated diene-based polymers of Examples 1 to 6 prepared using the modifier represented by Chemical Formula 1 presented in the present invention are unmodified conjugated diene-based polymers of Comparative Example 1 and amines. Compared to the modified conjugated diene-based polymer of Comparative Example 2 prepared using a modifier having a structure different from that of the modifier represented by Formula 1, including a group and an alkoxysilane group, the molecular weight increased and the Mooney stress relaxation rate decreased, and the Mooney stress relaxation From the reduced rate, it was confirmed that the modified conjugated diene-based polymers of Examples 1 to 6 had a highly branched structure compared to Comparative Examples 1 and 2.

The above result means that the modified conjugated diene-based polymer according to the present invention can have a high molecular weight and a highly branched structure by being prepared using the modifier represented by Chemical Formula 1.

Experimental Example 2

In order to comparatively analyze the physical properties of the rubber composition containing each modified or unmodified conjugated diene-based polymer prepared in Examples and Comparative Examples and molded articles prepared therefrom, tensile properties and viscoelastic properties were measured respectively and the results are shown below. Table 3 shows.

1) Preparation of rubber specimens

Each modified or unmodified conjugated diene-based polymer of Examples and Comparative Examples was compounded under the compounding conditions shown in Table 2 below as raw rubber. The content of the raw material 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 Zincizing 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 oxide (ZnO), stearic acid using a Banbari mixer with a temperature control device is used. , antioxidant (TMQ(RD) (2,2,4-trimethyl-1,2-dihydroquinoline polymer), antioxidant (6PPD ((dimethylbutyl)-N-phenyl-phenylenediamine) and wax (Microcrystaline Wax) ) was kneaded. At this time, the initial temperature of the kneader was controlled to 70° C., and after the mixing was completed, a first formulation was obtained at a discharge temperature of 145° C. to 155° C. In the second stage of kneading, the first formulation was cooled to room temperature. After mixing, the primary compound, sulfur, rubber accelerator (DPD (diphenylguanine)) and vulcanization accelerator (CZ (N-cytlohexyl-2-benzothiazylsulfenamide)) are added to the kneader, and the temperature is not higher than 100°C. A secondary formulation was obtained by mixing in. Then, a rubber specimen was prepared through a curing process at 160° C. for 20 minutes.

2) 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 room temperature at a speed of 50 cm/min using a Universal Test Machin 4204 (Instron Co., Ltd.) tensile tester. In Table 3, the result value is shown as an index based on Comparative Example 1, and the higher the numerical value, the better.

3) Viscoelastic properties

For the 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°C to 60°C) 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 resistance, and the lower the high temperature 60℃ tan δ value, the less the hysteresis loss and the better the rolling resistance characteristics (fuel efficiency). Since the result value is expressed as an index based on Comparative Example 1, the higher the numerical value, the better.

4) Wear resistance (DIN wear test)

For each rubber specimen, a DIN wear test was performed according to ASTM D5963, and it was expressed as DIN wt loss index (loss volume index): ARIA (Abration resistance index, Method A). The higher the number, the better. indicates.

division Example comparative example One 2 3 4 5 6 One 2 Tensile properties
(Index, %) tensile strength 109 108 110 114 114 112 100 107 300% modulus 114 117 120 120 117 119 100 114 Viscoelastic properties
(Index, %) tan δ
(at 0°C) 102 101 107 106 103 107 100 101 tan δ
(at 60℃) 122 123 129 131 121 124 100 114 wear resistance 119 119 124 122 116 114 100 108

As shown in Table 3, Examples 1 to 6 according to an embodiment of the present invention were superior in tensile properties, viscoelastic properties, and abrasion resistance compared to Comparative Examples 1 and 2 in a well-balanced manner.

In this case, Examples 1 to 6 are prepared by modifying the reaction with a modifier represented by Formula 1, Comparative Examples 1 and 2 are unmodified or have an amine group and an alkoxysilane group, but are represented by Formula 1 presented in the present invention It is prepared by denaturing the denaturant with a denaturant having a different structure from that of the denaturant.

As a result of Table 1 and Table 3 above, the modified conjugated diene-based copolymer of the present invention can have a highly branched structure and high molecular weight by being prepared by using the modifier represented by Formula 1, thereby significantly improving abrasion resistance. , at the same time, by including a functional group derived from a modifier, excellent affinity with the filler can improve compounding processability, which means that tensile properties and viscoelastic properties can be balanced and excellent.

Claims (14)

A modified conjugated diene-based polymer comprising a repeating unit derived from a conjugated diene-based monomer and a functional group derived from a modifier represented by the following formula (1):
[Formula 1]

In Formula 1,
R ₁ to R ₈ are independently of each other an alkylene group having 1 to 20 carbon atoms or an alkenylene group having 2 to 20 carbon atoms that is substituted or unsubstituted with a substituent, wherein the substituent is an alkyl group having 1 to 20 carbon atoms, 3 to 20 carbon atoms is a cycloalkyl group or an aryl group having 6 to 20 carbon atoms,
A ₁ to A ₄ are each independently a substituent represented by the following formula (a),
[Formula a]

In the above formula (a),
R ₉ to R ₁₁ are each independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, and at least one of _{R 9} to R _{11 is an alkoxy group having 1 to 20 carbon atoms.}
According to claim 1,
In Formula 1, R ₁ to R ₈ are each independently an unsubstituted C 1 to C 10 alkylene group, A ₁ to A ₄ are each independently a substituent represented by the following Formula (a),
In Formula (a), R ₉ to R ₁₁ are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, at least one of which is an alkoxy group.
According to claim 1,
The modifier represented by Formula 1 is a modified conjugated diene-based polymer comprising 8 to 12 alkoxy groups in the molecule.
According to claim 1,
The modifier represented by Formula 1 is a modified conjugated diene-based polymer that is at least one selected from compounds represented by Formulas 1-1 to 1-6 below:
[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,
Me is a methyl group, Et is an ethyl group.
According to claim 1,
A modified conjugated diene-based polymer having a weight average molecular weight of 1,200,000 g/mol to 3,000,000 g/mol.
According to claim 1,
A modified conjugated diene-based polymer having a Mooney stress relaxation rate of 0.050 to 0.150 measured at 140°C.
According to claim 1,
A modified conjugated diene-based polymer further comprising a repeating unit derived from an aromatic vinyl-based monomer.
Preparing an active polymer by 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 (S1); and
A method for producing the modified conjugated diene-based polymer of claim 1, comprising the step (S2) of reacting the active polymer with a modifier represented by the following formula (1):
[Formula 1]

In Formula 1,
R ₁ to R ₈ are independently of each other an alkylene group having 1 to 20 carbon atoms or an alkenylene group having 2 to 20 carbon atoms that is substituted or unsubstituted with a substituent, wherein the substituent is an alkyl group having 1 to 20 carbon atoms, 3 to 20 carbon atoms is a cycloalkyl group or an aryl group having 6 to 20 carbon atoms,
A ₁ to A ₄ are each independently a substituent represented by the following formula (a),
[Formula a]

In the above formula (a),
R ₉ to R ₁₁ are each independently an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, and at least one of _{R 9} to R _{11 is an alkoxy group having 1 to 20 carbon atoms.}
9. The method of claim 8,
A method for producing a modified conjugated diene-based polymer wherein the modifier represented by Formula 1 is at least one selected from compounds represented by 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,
Me is a methyl group, Et is an ethyl group.
9. The method of claim 8,
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 conjugated diene-based monomer.
9. The method of claim 8,
The method for producing a modified conjugated diene-based polymer that the modifier is used in an amount of 0.1 mol to 10 mol based on 1 mol of the polymerization initiator.
9. The method of claim 8,
The polymerization of the step (S1) is a method for producing a modified conjugated diene-based polymer that is performed by further using a polar additive.
A rubber composition comprising the modified conjugated diene-based polymer of claim 1 and a filler.
14. The method of claim 13,
A rubber composition comprising 0.1 parts by weight to 200 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene-based polymer.