KR20210156132A - Modified conjugated diene polymer comprising modified agent dreived functional group and rubber composition comprising the same - Google Patents

Abstract

The present invention relates to a modifier that is useful for the modification of a conjugated diene-based polymer, has excellent processability due to excellent affinity with a filler, and is capable of improving the abrasion and rolling resistance properties of a conjugated diene-based polymer, a modified conjugated diene-based polymer comprising a unit derived from the modifier, and a rubber composition comprising the polymer.

Description

Modified conjugated diene-based polymer comprising a functional group derived from a modifier, and a rubber composition comprising the same

The present invention relates to a modified conjugated diene-based polymer comprising a functional group derived from a modifier capable of improving processability and rolling resistance properties, and a rubber composition comprising the polymer.

In response to the recent demand for fuel economy reduction in automobiles, a conjugated diene-based polymer having low rolling resistance, excellent abrasion resistance and tensile properties, and adjustment stability typified by wet 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 Goodrich heat generation is preferable.

As a rubber material with a small hysteresis loss, natural rubber, polyisoprene rubber, polybutadiene rubber, etc. are known, but these have a problem of small wet road resistance. 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) 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 adjust the required physical properties of the tire such as running resistance and braking force, as well as lower the glass transition temperature. 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, carbon black and silica are used as reinforcing fillers for tire treads. When silica is used as reinforcing fillers, there are advantages in that low hysteresis loss and wet road resistance are improved. However, compared to carbon black on the hydrophobic surface, silica on the hydrophilic surface has a disadvantage in that it has poor dispersibility due to low affinity with rubber. It is necessary to use a ring agent. Accordingly, a method has been made to introduce a functional group having affinity or reactivity with silica at the end of the rubber molecule, but the effect is not sufficient.

US 4397994 A

The present invention has been devised to solve the problems of the prior art, and the number of functional groups is large to increase the coupling rate, and it is modified with a modifier capable of improving workability due to the presence of a functional group containing an oxygen atom, so that the workability is excellent, An object of the present invention is to provide a modified conjugated diene-based polymer having excellent wear resistance, rolling resistance and wet road resistance.

In order to solve the above problems, the present invention provides a modified conjugated diene-based polymer comprising a modifier-derived unit represented by the following formula (1):

[Formula 1]

In Formula 1, R ₁ and R ₂ are each independently an alkylene group having 1 to 30 carbon atoms, an alkenylene group having 2 to 30 carbon atoms, a cycloalkylene group having 5 to 30 carbon atoms, or an arylene group having 6 to 30 carbon atoms, R ₃ is a methylene group or ethylene group, R ₄ to R ₆ are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a monovalent heterocyclic group having 3 to 20 carbon atoms, n is 1, k is 2 or 3, wherein R ₁ to R ₁₃ are unsubstituted or substituted with a substituent, wherein the substituent is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms. , an aryl group having 6 to 20 carbon atoms, or a heterocyclic group having 3 to 20 carbon atoms.

In addition, in order to solve the above problems, the present invention provides a rubber composition comprising the modified conjugated diene-based polymer.

According to the present invention, the modifier represented by Chemical Formula 1 can improve processability during compounding due to the presence of a functional group including an oxygen atom, and can increase the coupling rate due to the presence of a plurality of modified functional groups. The conjugated diene-based polymer modified with a modifier may have excellent effects in abrasion resistance, rolling resistance and wet road resistance, and may have excellent processability during compounding.

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 must 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.

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

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

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

The term 'alkylsilyl group' used in the present invention may mean including all of monoalkylsilyl, dialkylsilyl, and trialkylsilyl.

The term 'alkenyl group' used in the present invention may refer to an alkyl group including one or two or more double bonds.

The term 'alkynyl group' used in the present invention may refer to an alkyl group including one or two or more triple bonds.

The term 'alkoxy group' used in the present invention may mean including all functional groups, atomic groups, or compounds in which hydrogen at the end of an alkyl group is substituted with an oxygen atom, such as methoxy, ethoxy, propoxy and butoxy. have.

The term 'heteroalkyl group' used in the present invention may refer to an alkyl group in which a carbon atom (excluding a carbon atom at the terminal) in the alkyl group is substituted with one or more hetero atoms.

The term 'cycloalkyl group' used in the present invention may include all cyclic saturated hydrocarbons or cyclic unsaturated hydrocarbons including one or two or more unsaturated bonds.

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

The term 'heterocyclic group' used in the present invention may mean including both a cycloalkyl group or an aryl group in which a carbon atom in a cycloalkyl group or an aryl group is substituted with one or more hetero atoms.

As used herein, the term 'aralkyl group' refers to an alkyl group in which one or more aryl groups are necessarily substituted.

In the present invention, the term 'single bond' may refer to a single covalent bond itself that does not include a separate atom or molecular group.

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

Modified conjugated diene-based polymer

The present invention is a modified conjugated diene-based polymer comprising a unit derived from a modifier represented by the following formula (1), and by using a modifier useful for modification, excellent abrasion resistance and rolling resistance while improving processability to provide a polymer.

[Formula 1]

In Formula 1, R ₁ and R ₂ are each independently an alkylene group having 1 to 30 carbon atoms, an alkenylene group having 2 to 30 carbon atoms, a cycloalkylene group having 5 to 30 carbon atoms, or an arylene group having 6 to 30 carbon atoms, R ₃ is a methylene group or ethylene group, R ₄ to R ₆ are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a monovalent heterocyclic group having 3 to 20 carbon atoms, n is 1, k is 2 or 3, wherein R ₁ to R ₁₃ are unsubstituted or substituted with a substituent, wherein the substituent is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms. , an aryl group having 6 to 20 carbon atoms, or a heterocyclic group having 3 to 20 carbon atoms.

Specifically, the modifier represented by Formula 1 may include a compound represented by Formula 2 below.

[Formula 2]

In Formula 2, R _1a to R _3a are each independently an alkylene group having 1 to 30 carbon atoms, an alkenylene group having 2 to 30 carbon atoms, a cycloalkylene group having 5 to 30 carbon atoms, or an arylene group having 6 to 30 carbon atoms, R _4a is a methylene group or ethylene group, R _5a to R _8a are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a monovalent heterocyclic group having 3 to 20 carbon atoms, l and m are each independently an integer of 1 to 3, and l+m is 4 to 6 may be an integer of .

In addition, R _1a to R _8a may be unsubstituted or substituted with a substituent, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a heteroalkyl group having 1 to 10 carbon atoms, and a carbon number It may be a cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heterocyclic group having 3 to 20 carbon atoms.

More specifically, R ₂₁ to R ₂₃ and R ₃₁ to R ₃₆ are each independently an alkylene group having 1 to 10 carbon atoms, or an alkenylene group having 2 to 10 carbon atoms, R ₂₄ to R ₂₉ and R ₃₇ to R ₄₀ may be each independently an alkyl group having 1 to 10 carbon atoms, a heteroalkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 5 to 20 carbon atoms.

In addition, R _4a may be a methylene group or an ethylene group, that is, a 3-membered epoxy group including an oxygen atom, or a 4-membered oxetanyl group. In this case, when a functional group is bonded to one end of the conjugated diene-based polymer as a modifier, affinity with a filler can be improved due to the presence of a functional group containing an oxygen atom, and dispersibility can be improved, so that processability is improved. can be improved The R _4a is more preferably a methylene group, and the functional group including an oxygen atom may be an epoxy group.

Furthermore, in the case of the compound represented by Formula 2, there may be four or more alkoxysilane groups. In this case, in that it has a plurality of sites capable of reacting with the active terminal of the conjugated diene-based polymer, a couple of modified conjugated diene-based polymers The ring rate can be increased. Accordingly, the degree of branching of the final polymer can be increased, which can have a great effect on improving abrasion resistance, and can increase the molecular weight of the modified conjugated diene-based polymer.

More specifically, in the compound represented by Formula 2, R _1a to R _3a are each independently an alkylene group having 1 to 5 carbon atoms, and R _4a may be a methylene group, in which case optimization of the above effect may be possible. have.

According to an embodiment of the present invention, in Formula 2, the sum of l and m, that is, the number of alkoxysilane groups in Formula 2 may be 5 or 6. As such, when a modifier having a large number of alkoxysilanes is used, not only affinity with the filler can be improved, but also a coupling rate between polymers can be increased, and thus, abrasion resistance and viscoelastic properties can be further improved.

The conjugated diene-based monomer-derived repeating unit may mean a repeating unit formed during polymerization of the conjugated diene-based monomer, and the conjugated diene-based monomer is, for example, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene. , piperylene, 3-butyl-1,3-octadiene, isoprene, 2-phenyl-1,3-butadiene and 2-halo-1,3-butadiene (halo means halogen atom) There may be more than one type.

On the other hand, the modified conjugated diene-based copolymer may be, for example, a copolymer further comprising a repeating unit derived from an aromatic vinyl monomer together with the repeating unit derived from the conjugated diene-based monomer.

The repeating unit derived from the aromatic vinyl monomer may mean a repeating unit formed during polymerization of the aromatic vinyl monomer, and the aromatic vinyl monomer may include, for example, styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, and 4-propyl It may be at least one selected from the group consisting of styrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, and 1-vinyl-5-hexylnaphthalene.

When the modified conjugated diene-based polymer is a copolymer including a repeating unit derived from an aromatic vinyl monomer, the modified conjugated diene-based polymer contains at least 20 wt%, 30 wt%, 40 wt%, 50 wt% of the conjugated diene-based monomer-derived repeating unit %, 55% by weight or 60% by weight, up to 95% by weight, 90% by weight, or 80% by weight, at least 5% by weight, 10% by weight of a repeating unit derived from an aromatic vinyl monomer; or 20% by weight, up to 80% by weight, 70% by weight, 60% by weight, 55% by weight, 50% by weight, 45% by weight, or 40% by weight, within this range cloud It has excellent effects on resistance, wet road resistance and abrasion resistance.

According to an embodiment of the present invention, the copolymer may be a random copolymer, and in this case, an excellent balance between physical properties is obtained. In the random copolymer, repeating units constituting the copolymer may be disorderly arranged, and a weight ratio of these two repeating units may be 90:10 to 10:90.

The modified conjugated diene-based polymer according to an embodiment of the present invention has a number average molecular weight (Mn) of 50,000 g/mol to 2,000,000 g/mol, 100,000 g/mol to 1,800,000 g/mol, or 120,000 g/mol to 1,500,000 g /mol, preferably 200,000 g/mol to 800,000 g/mol. In addition, the weight average molecular weight (Mw) may be 50,000 g / mol to 5,000,000 g / mol, 100,000 g / mol to 3,500,000 g / mol, or 120,000 g / mol to 2,000,000 g / mol, preferably 300,000 g / mol to 1,500,000 g/mol. Within this range, there is an excellent effect of rolling resistance and wet road resistance. As another example, the modified conjugated diene-based polymer may have a molecular weight distribution (Mw/Mn) of 1.0 to 8.0, 1.0 to 4.0, or 1.0 to 3.5, and within this range, the physical property balance between properties is excellent.

Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are polystyrene equivalent molecular weights analyzed by gel permeation chromatography (GPC), respectively, and the molecular weight distribution (Mw / Mn) is also called polydispersity, It was calculated as the ratio (Mw/Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn).

As another example, the modified conjugated diene-based polymer may have a Mooney viscosity of 20 to 150 at 100° C. and 20 to 150 at 140° C., and within this range, processability and productivity are excellent. .

Here, the Mooney viscosity was measured using a Mooney viscometer, for example, a large rotor of MV2000E (ALPHA Technologies) at 100°C and 140°C, and a rotor speed of 2±0.02 rpm. Specifically, after leaving the polymer at room temperature (23±5° C.) for more than 30 minutes, 27±3 g was collected, filled in the die cavity, and measured while applying a torque by operating a platen.

In addition, the modified conjugated diene-based polymer may have a vinyl content of 5% by weight or more, 10% by weight or more, or 10% to 60% by weight, and the glass transition temperature can be adjusted within this range to an appropriate range. It has excellent resistance, wet road resistance and low fuel efficiency. 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

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

Method for producing a modified conjugated diene-based polymer

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

In the method for producing the modified conjugated diene-based polymer according to an embodiment of the present invention, in a hydrocarbon solvent containing an organometallic compound, a conjugated diene-based monomer or an aromatic vinyl-based monomer and a conjugated diene-based monomer are polymerized to bind an organic metal. preparing an active polymer (step 1); and reacting with a denaturant comprising the active polymer and the compound represented by Formula 1 (step 2).

Step 1 is a step for preparing an active polymer to which an organometallic compound is bound, and may be performed by polymerizing a conjugated diene-based monomer, or an aromatic vinylic monomer and a conjugated diene-based monomer in a hydrocarbon solvent containing an organometallic compound. have.

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

The conjugated diene-based monomer and the aromatic vinyl-based monomer are as defined above.

According to an embodiment of the present invention, the organometallic compound may be used in an amount of 0.01 mmol to 10 mmol, 0.05 mmol to 5 mmol, 0.1 mmol to 2 mmol, or 0.1 mmol to 1 mmol based on 100 g of the total monomer.

The organometallic compound is, for example, methyllithium, ethyllithium, propyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octyllithium, phenyllithium, 1-naph tyllithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolylylithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naphthyl sodium, naphthyl potassium , lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide, and may be at least one selected from the group consisting of lithium isopropylamide.

Meanwhile, the polymerization of step 1 may be carried out by including a polar additive, and the polar additive may be added in an amount 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. In addition, the polar additive is tetrahydrofuran, ditetrahydrofuryl propane, diethyl ether, cycloamal ether, dipropyl ether, ethylene dimethyl ether, ethylene dimethyl ether, diethyl glycol, dimethyl ether, tertiary butoxyethoxyethane , bis(3-dimethylaminoethyl)ether, (dimethylaminoethyl)ethylether, trimethylamine, triethylamine, tripropylamine, and tetramethylethylenediamine may be at least one selected from the group consisting of, specifically, triethyl It may be an amine or tetramethylethylenediamine, and when the polar additive is included, a conjugated diene-based monomer, or a conjugated diene-based monomer and an aromatic vinyl-based monomer are copolymerized by compensating for a difference in their reaction rate to facilitate random copolymerization It has the effect of inducing it to be formed.

The polymerization in step 1 may be, for example, anionic polymerization, and as a specific example, living anionic polymerization having an anionic active site at the polymerization end by growth polymerization reaction by anion. In addition, the polymerization in step 1 may be an elevated temperature polymerization, isothermal polymerization, or constant temperature polymerization (adiabatic polymerization), wherein the constant temperature polymerization comprises the step of polymerizing by its own heat of reaction without optionally applying heat after adding an organometallic compound. It may mean a method, wherein the elevated temperature polymerization may refer to a polymerization method in which the temperature is increased by optionally applying heat after the organometallic compound is added, and the isothermal polymerization is performed by adding heat after adding the organometallic compound It may refer to a polymerization method that maintains a constant temperature of the polymer by increasing heat or taking heat.

In addition, the polymerization of step 1 is, for example, the polymerization may be carried out in a temperature range of -20 ℃ to 200 ℃, 0 ℃ to 150 ℃, or 10 ℃ to 120 ℃.

The active polymer prepared by step 1 may refer to a polymer in which a polymer anion and an organometallic cation are bound.

Step 2 is a step of reacting the active polymer with the modifier represented by Formula 1 in order to prepare a modified conjugated diene-based polymer.

In the manufacturing method according to an embodiment of the present invention, the denaturant represented by Chemical Formula 1 may be prepared, for example, by a mechanism as shown in Scheme 1 below.

[Scheme 1]

In Scheme 1, R1 to R8 are as defined in Formula 1, Lv is a leaving group that can be easily released with a halogen atom, and Base may be a basic compound. At this time, the basic compound may act as a catalyst in the reaction, and the basic compound is 0.05 to 1.00 moles, specifically 0.1 to 0.8 moles, preferably based on 1 mole of the secondary amino alkoxysilane compound in the reaction scheme. It may be added in an amount of 0.1 to 0.5 mol.

In addition, the basic compound is, for example, trimethylamine (trimethylamine), tetramethylethylenediamine (tetramethylethylenediamine), lithium diisopropylamide (lithium diisopropylamide), 1,8-diazabicyclounde-7-cene (1,8-diazabicycloundes- 7-ene), 2,6-di-tert-butylpyridine, and lithium tetramethylpiperidine may be at least one selected from the group consisting of.

As the peroxide, a peroxide generally used in the epoxidation reaction may be applied, for example, meta-chloroperoxybenzoic acid (m-CPBA), magnesium monoperoxyphthalate (MMPP), dimethyldioxirane (DMDO) One or more selected from the group may be utilized.

According to an embodiment of the present invention, the modifier represented by Formula 1 may be used in an amount of 0.01 mmol to 10 mmol, 0.01 mmol to 5 mmol, or 0.02 mmol to 3 mmol based on 100 g of the total monomer.

In addition, according to an embodiment of the present invention, the modifier represented by Formula 1 and the organometallic compound have a molar ratio of 1:0.1 to 1:10, a molar ratio of 1:0.1 to 1:5, or 1:0.2 to 1: It can be used in a molar ratio of 3, and it is possible to perform a denaturation reaction of optimal performance within this range, thereby obtaining a conjugated diene-based polymer having a high denaturation rate.

The reaction in step 2 is a modification reaction for introducing a functional group derived from the modifier into the active polymer, and may be performed at 0° C. to 90° C. for 1 minute to 5 hours.

Further, according to an embodiment of the present invention, the method for producing the modified conjugated diene-based polymer may be performed by a batch method (batch type) or a continuous polymerization method including one or more types of reactors.

The method for preparing the modified conjugated diene-based polymer may further include at least one of the steps of recovering and drying the solvent and unreacted monomers, if necessary, following step 2 of the present invention.

Rubber composition and tire

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

The rubber composition according to an embodiment of the present invention 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 the range, mechanical properties such as tensile strength and abrasion resistance are excellent, and there is an effect of 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 that are modified or refined of the general natural rubber; Styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, polyisobutylene-co-isoprene, neoprene, poly(ethylene-co-) propylene), poly(styrene-co-butadiene), poly(styrene-co-isoprene), poly(styrene-co-isoprene-co-butadiene), poly(isoprene-co-butadiene), poly(ethylene-co-propylene) -co-diene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, butyl rubber, halogenated butyl rubber, etc. may be synthetic rubbers, and any one or mixture of two or more thereof may be used. have.

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 It may be wet silica that has the best effect of 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 conventional. 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 the effect as a coupling agent within this range is 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, and within this range, the vulcanized rubber composition has a low fuel efficiency while securing the required elasticity modulus and strength. It has an excellent effect.

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

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, 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, cheffer, or bead coated rubber, vibration proof rubber, belt conveyor, hose, etc. It may be useful in the manufacture of various industrial rubber products of

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

The tire may include a tire or a tire tread.

Example

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

Example 1

In a 20L autoclave reactor, 270 g of styrene, 710 g of 1,3-butadiene, 5,000 g of n-hexane, and 0.9 g of ditetrahydrofuryl propane as a polar additive were added, and then the temperature inside the reactor was raised to 40°C. When the internal temperature of the reactor reached 40° C., 4.3 mmol of active n-butyllithium was added to the reactor to proceed with an adiabatic temperature rise reaction. After 20 minutes after the adiabatic temperature rise reaction was completed, 20 g of 1,3-butadiene was added, and the end of the polymer was capped with butadiene. After 5 min, N-(oxiran-2-ylmethyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine (N-(oxiran- 4.3 mmol of 2-ylmethyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine) was added, and the mixture was reacted for 15 minutes. Thereafter, the polymerization reaction was stopped using ethanol, and 45 ml of a solution in which 0.3 wt% of an antioxidant BHT (butylated hydroxytoluene) was dissolved in hexane was added. The resulting polymer was put into hot water heated with steam, stirred to remove the solvent, and then roll-dried to remove the remaining solvent and water to prepare a modified conjugated diene-based polymer.

Example 2

In Example 1, the modifier N-(oxiran-2-ylmethyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine (N- N-(oxiran-2-ylmethyl)-3-(trimethoxysilyl) instead of (oxiran-2-ylmethyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine) )-N-(3-(trimethoxysilyl)propyl)propan-1-amine(N-(oxiran-2-ylmethyl)-3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1 -amine), except that 4.3 mmol was added, and a modified conjugated diene-based polymer was prepared in the same manner as in Example 1.

Example 3

In Example 1, the modifier N-(oxiran-2-ylmethyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine (N- (oxiran-2-ylmethyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine) instead of N-(2-(oxiran-2-yl)ethyl)-3-( Trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine(N-(2-(oxiran-2-yl)ethyl)-3-(trimethoxysilyl)-N-(3 -(trimethoxysilyl)propyl)propan-1-amine) was added, and a modified conjugated diene-based polymer was prepared in the same manner as in Example 1, except that 4.3 mmol was added.

Comparative Example 1

In a 20L autoclave reactor, 270 g of styrene, 710 g of 1,3-butadiene, 5,000 g of n-hexane, and 0.9 g of ditetrahydrofuryl propane as a polar additive were added, and then the temperature inside the reactor was raised to 40°C. When the internal temperature of the reactor reached 40° C., 4.3 mmol of active n-butyllithium was added to the reactor to proceed with an adiabatic temperature rise reaction. After 20 minutes after the adiabatic temperature rise reaction was completed, 20 g of 1,3-butadiene was added, and the end of the polymer was capped with butadiene. Thereafter, the polymerization reaction was stopped using ethanol, and 45 ml of a solution in which an antioxidant BHT (butylated hydroxytoluene) was dissolved in hexane at 0.3 wt% was added. The resulting polymer was put into hot water heated with steam, stirred to remove the solvent, and then roll-dried to remove the remaining solvent and water to prepare a conjugated diene-based polymer.

Comparative Example 2

In Example 1, the modifier N-(oxiran-2-ylmethyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine (N- (oxiran-2-ylmethyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine) instead of tris(3-(trimethoxysilyl)propyl)amine (tris(3-( A modified conjugated diene-based polymer was prepared in the same manner as in Example 1, except that 4.3 mmol (trimethoxysilyl)propyl)amine) was added.

Comparative Example 3

In Example 1, the modifier N-(oxiran-2-ylmethyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine (N- (oxiran-2-ylmethyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine) instead of N,N-bis(oxiran-2-ylmethyl)-3-(tri The same as in Example 1, except that 4.3 mmol of methoxysilyl) propan-1-amine (N,N-bis(oxiran-2-ylmethyl)-3-(trimethoxysilyl)propan-1-amine) was added. A modified conjugated diene-based polymer was prepared by the method.

Comparative Example 4

In Example 1, the modifier N-(oxiran-2-ylmethyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine (N- 3-(dimethoxy(methyl)silyl)-N-(3-(methoxyl group) instead of (oxiran-2-ylmethyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine) Dimethylsilyl)propyl)-N-(oxiran-2-ylmethyl)propan-1-amine(3-(dimethoxy(methyl)silyl)-N-(3-(methoxydimethylsilyl)propyl)-N-(oxiran-2 -ylmethyl)propan-1-amine), except that 4.3 mmol) was added, and a modified conjugated diene-based polymer was prepared in the same manner as in Example 1.

Comparative Example 5

In Example 1, the modifier N-(oxiran-2-ylmethyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine (N- (oxiran-2-ylmethyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine) instead of N,N-diethyl-3-(trimethoxysilyl)propane-1- A modified conjugated diene-based polymer was prepared in the same manner as in Example 1, except that 4.3 mmol of amine (N,N-diethyl-3-(trimethoxysilyl)propan-1-amine) was added.

Experimental example

Experimental Example 1

For each modified or unmodified conjugated diene-based polymer prepared in Examples and Comparative Examples, the weight average molecular weight (Mw, X10 ⁴ g/mol), the number average molecular weight (Mn, X10 ⁴ g/mol), the molecular weight distribution ( MWD) and Mooney viscosity (MV) were measured, respectively. The results are shown in Table 1 below.

The weight average molecular weight (Mw) and number average molecular weight (Mn) were measured through gel permeation chromatohraph (GPC) analysis, and molecular weight distribution (MWD, Mw/Mn) was obtained by calculating from each of the measured molecular weights. Specifically, the GPC used a combination of two PLgel Olexis (Polymer Laboratories) columns and one PLgel mixed-C (Polymer Laboratories) column, and all newly replaced columns were mixed bed type columns, When calculating molecular weight, the GPC standard material was performed using PS (polystyrene).

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

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Mw (X10 ⁴ g/mol) 52 53 55 24 78 42 46 39 Mn (X10 ⁴ g/mol) 36 36 37 23 44 32 35 32 Mw/Mn 1.45 1.48 1.48 1.05 1.78 1.30 1.32 1.22 MV 67 68 71 41 80 65 69 64

Experimental Example 2

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

1) Preparation of rubber specimens

Each of the modified or unmodified styrene-butadiene copolymers of Examples and Comparative Examples was compounded under the compounding conditions shown in Table 2 below as raw rubber. Raw materials in Table 2 are each part by weight based on 100 parts by weight of rubber.

division Raw material Content (parts by weight) 1st stage kneading rubber 100 silica 70 coupling agent 11.2 fair oil 25 Zincizing agent 3 stearic acid 2 antioxidant 2 anti-aging agent 2 wax One rubber accelerator 1.75 2nd stage kneading sulfur 1.5 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), zincating agent (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 below 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.

1) Compound Mooney Viscosity

The sheet produced after working 3 times or more with a roll mill at 50° C. using the first compound was used as a specimen. Mooney viscosity (MV, (ML1+4, @100℃) MU) was measured using MV-2000 (ALPHA Technologies) at 100℃ at 100℃ using a Rotor Speed 2±0.02 rpm, Large Rotor, and the sample used at this time was left at room temperature (23±3℃) for more than 30 minutes, and then collected 27±3 g, filled it in the die cavity, and operated the platen to measure for 4 minutes. The compound MV indicates that the higher the value, the more disadvantageous the processability is.

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.

3) Wear resistance

The abrasion resistance of the prepared rubber specimen was obtained by applying a load of 10 N to the rotating drum to which the abrasion paper was attached using a DIN abrasion tester, and moving the rubber specimen in a direction perpendicular to the rotating direction of the drum, and then abrasion loss The weight was measured, and it was expressed as an index based on the weight loss of Comparative Example 1. The rotational speed of the drum is 40 rpm, and the total moving distance of the specimen at the completion of the test is 40 m. The smaller the loss weight, the greater the index value of the loss weight, indicating that the wear resistance is excellent.

4) Viscoelastic properties

Viscoelastic properties were measured using a dynamic mechanical analyzer (TA) by changing the strain at a frequency of 10 Hz and each measurement temperature (-60°C to 60°C) in torsion mode, measuring tan δ, and indexing it based on Comparative Example 1. As the index of high temperature 60℃ tan δ is higher, hysteresis loss is small and low running resistance (fuel efficiency) is excellent.

division Example comparative example One 2 3 One 2 3 4 5 Compound Mooney Viscosity 85 82 80 91 112 92 96 96 Tensile properties
(kgf/cm ² ) 300% modulus 123 125 120 87 123 107 115 105 The tensile strength 198 197 196 162 190 197 192 185 wear resistance Index 125 129 126 100 128 117 115 111 viscoelastic
characteristic tan δ@60℃ 124 126 125 100 125 115 120 112

As shown in Table 3, the modified conjugated diene-based polymers of Examples 1 to 3 modified with the modifier according to the present invention had tensile properties and compared to the unmodified or modified conjugated diene-based polymers of Comparative Examples 1 to 5. It can be seen that the abrasion resistance and viscoelastic properties are excellent.

Claims (10)

A modified conjugated diene-based polymer comprising a repeating unit derived from a conjugated diene-based monomer and comprising a functional group derived from a modifier represented by the following Chemical Formula 1 at at least one end:
[Formula 1]

In Formula 1,
R ₁ and R ₂ are an alkylene group having 1 to 30 carbon atoms, an alkenylene group having 2 to 30 carbon atoms, a cycloalkylene group having 5 to 30 carbon atoms, or an arylene group having 6 to 30 carbon atoms,
R ₃ is a methylene group or an ethylene group,
R ₄ and R ₅ are each independently of each other an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkyl group having 6 carbon atoms to 20 aryl group, a monovalent heterocyclic group having 3 to 20 carbon atoms,
n is 1, k is 2 or 3,
Wherein R ₁ to R ₅ are unsubstituted or substituted with a substituent, wherein the substituent is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, and 1 to 20 carbon atoms. a heteroalkyl group, a cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heterocyclic group having 3 to 20 carbon atoms.
The method according to claim 1,
The modifier represented by the formula (1) is a modified conjugated diene-based polymer comprising a compound represented by the following formula (2):
[Formula 2]

In Formula 2,
R _1a to R _3a are each independently an alkylene group having 1 to 30 carbon atoms, an alkenylene group having 2 to 30 carbon atoms, a cycloalkylene group having 5 to 30 carbon atoms, or an arylene group having 6 to 30 carbon atoms,
R _4a is a methylene group or an ethylene group,
R _5a to R _8a are independently of each other an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkyl group having 6 carbon atoms to 20 aryl group, or a monovalent heterocyclic group having 3 to 20 carbon atoms,
l and m are each independently an integer of 1 to 3, and l+m is an integer of 4 to 6,
Wherein R _1a to R _8a are unsubstituted or substituted with a substituent, wherein the substituent is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or an alkynyl group having 1 to 20 carbon atoms. a heteroalkyl group, a cycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heterocyclic group having 3 to 20 carbon atoms.
3. The method according to claim 2,
In Formula 2,
R _1a to R _3a are each independently an alkylene group having 1 to 10 carbon atoms, or an alkenylene group having 2 to 10 carbon atoms,
R _5a to R _8a are each independently an alkyl group having 1 to 10 carbon atoms, a heteroalkyl group having 1 to 10 carbon atoms, or a cycloalkyl group having 5 to 20 carbon atoms.
3. The method according to claim 2,
In Formula 2, l + m is 5 or 6 of the modified conjugated diene-based polymer.
3. The method according to claim 2,
In Formula 2, R _4a is a methylene group modified conjugated diene-based polymer.
3. The method according to claim 2,
In Formula 2,
R _1a to R _3a are each independently an alkylene group having 1 to 5 carbon atoms,
R _4a is a methylene group,
R _5a to R _8a are each independently an alkyl group having 1 to 5 carbon atoms.
The method according to claim 1,
The modified conjugated diene-based polymer further comprises a repeating unit derived from an aromatic vinyl monomer.
The method according to claim 1,
The modified conjugated diene-based polymer has a molecular weight distribution (Mw/Mn) of 1.0 to 5.0.
A rubber composition comprising the modified conjugated diene-based polymer according to claim 1 .
10. The method of claim 9,
The rubber composition further comprises 0.1 parts by weight to 150 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene-based polymer.