KR20210122580A - Modified conjugated diene polymer, method for preparing the polymer and rubber composition comprising the polymer - Google Patents

Abstract

The present invention relates to a modified conjugated diene-based polymer, comprising: a conjugated diene-based monomer unit; And it relates to a modified conjugated diene-based polymer comprising a functional group derived from a modifier represented by Formula 1, a method for preparing the same, and a rubber composition comprising the same.

Description

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

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

In 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 to reduce the hysteresis loss of the vulcanized rubber, and the 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, 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 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 a technique of introducing a functional group at the end by binding or modifying the chain end of the formed polymer using various modifiers is used. 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, as a modifier for introducing a functional group to the chain end of the polymer, a technique of applying an amino alkoxy silane modifier containing an alkoxy silane group and an amine group in a molecule simultaneously in order to maximize the dispersibility and reactivity of the filler is widely known. However, as the number of amine groups in the modifier increases, solubility in a hydrocarbon solvent used for preparing a polymer decreases, and thus, there is a problem in that it is difficult to easily perform a modification reaction.

US4397994A

The present invention has been devised to solve the problems of the prior art, and by including a functional group derived from a modifier represented by Formula 1, it has excellent affinity with a filler, and has excellent processability, tensile properties and viscoelastic properties. aims to provide

Another object of the present invention is to provide a method for producing the modified conjugated diene-based polymer using the modifier represented by Formula 1 above.

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

In order to solve the above problems, the present invention is a conjugated diene-based monomer unit; And it provides a modified conjugated diene-based polymer comprising a functional group derived from a modifier represented by the following formula (1).

[Formula 1]

In Formula 1, R ¹ to R ⁶ are each independently hydrogen, a monovalent hydrocarbon group having 1 to 30 carbon atoms, a substituent represented by the following Formula 2 or a substituent represented by the following Formula 2, R ¹ , R ³ and R ^{At least one of 5} is a substituent represented by the following formula (2),

[Formula 2]

In Formula 2, R ⁷ is a direct bond or a divalent hydrocarbon group having 1 to 30 carbon atoms, R ⁸ is a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ⁹ is hydrogen or a monovalent hydrocarbon group having 1 to 30 carbon atoms. , n is an integer from 1 to 10, and * is a bonding position in Formula 1.

In addition, the present invention comprises the steps of preparing an active polymer by adding and polymerizing a conjugated diene-based monomer in the presence of a polymerization initiator in a carbon-based solvent (S10); and reacting the active polymer with the modifier represented by Formula 1 (S20).

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

The modified conjugated diene-based polymer according to the present invention may have excellent affinity with the filler included in the rubber composition by including a modifier-derived functional group represented by Formula 1 at at least one end thereof.

In addition, the method for producing a modified conjugated diene-based polymer according to the present invention comprises the step of modifying the conjugated diene-based polymer with a modifier represented by Formula 1, thereby easily producing a modified conjugated diene-based polymer having excellent affinity with a filler. can

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

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

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

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

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

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

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

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

The term 'derived functional group' used in the present invention may refer to a functional group formed by participating in a denaturation reaction of a compound used as a modifier, a structure resulting therefrom, or a material itself.

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

The present invention provides a modified conjugated diene-based polymer. The modified conjugated diene-based polymer may include a conjugated diene-based monomer unit; and a functional group derived from a denaturant represented by Formula 1 below.

[Formula 1]

In Formula 1, R ¹ to R ⁶ are each independently hydrogen, a monovalent hydrocarbon group having 1 to 30 carbon atoms, a substituent represented by the following Formula 2 or a substituent represented by the following Formula 2, R ¹ , R ³ and R ^{At least one of 5} may be a substituent represented by the following formula (2),

[Formula 2]

In Formula 2, R ⁷ may be a direct bond or a divalent hydrocarbon group having 1 to 30 carbon atoms, R ⁸ may be a divalent hydrocarbon group having 1 to 10 carbon atoms, and R ⁹ is hydrogen or a monovalent hydrocarbon group having 1 to 30 carbon atoms. It may be a hydrocarbon group, n may be an integer of 1 to 10, and * is a bonding position in Chemical Formula 1.

The modified conjugated diene-based polymer according to an embodiment of the present invention is prepared by reacting an active polymer including a conjugated diene-based monomer unit with the modifier represented by Formula 1 as in the manufacturing method described below, so that the functional group derived from the modifier is It may be included in at least one end of the conjugated diene-based polymer. That is, the functional group derived from the modifier may be bonded to at least one terminal of the conjugated diene-based polymer. As such, the modified conjugated diene-based polymer contains at least one substituent selected from the group consisting of the modifier, such as a tertiary amine group and a polyalkylene glycol group, at at least one end of the conjugated diene-based polymer, so that the silica-based filler Excellent affinity to fillers such as, excellent processability of the rubber composition containing the modified conjugated diene-based polymer, and as a result, excellent tensile properties and viscoelastic properties of molded articles, such as tires, manufactured using the rubber composition It works.

According to an embodiment of the present invention, in Formula 1, R ¹ , R ³ and R ⁵ may each independently be a substituent represented by Formula 2, and R ² , R ⁴ and R ⁶ are each independently hydrogen or It may be a monovalent hydrocarbon group having 1 to 30 carbon atoms.

As a specific example, in Formula 1, R ¹ , R ³ and R ⁵ may each independently be a substituent represented by Formula 2, and R ² , R ⁴ and R ⁶ are each independently hydrogen or having 1 to 10 carbon atoms. may be an alkyl group, R ⁷ may be a direct bond or an alkylene group ^{having 1 to 10 carbon atoms, R 8} may be an alkylene group having 1 to 10 carbon atoms, R ⁹ may be hydrogen or an alkyl group having 1 to 10 carbon atoms, and , n may be an integer of 1 to 3.

As a more specific example, in Formula 1, R ¹ , R ³ and R ⁵ may each independently be a substituent represented by Formula 2, R ² , R ⁴ and R ⁶ may be hydrogen, R ⁷ is a carbon number It may be an alkylene group of 1 to 3, R ⁸ may be an alkylene group having 1 to 3 carbon atoms, R ⁹ may be hydrogen, and n may be an integer of 1 to 3. In this case, as the active polymer is substituted with a polyalkylene glycol group, the modifier represented by Formula 1 may be bonded to one terminal of the conjugated diene-based polymer, and an ether group of the polyalkylene glycol group together with a tertiary amine group There is an effect of improving the affinity for the filler from

According to an embodiment of the present invention, the denaturant represented by Chemical Formula 1 may be at least one selected from the group consisting of denaturants represented by the following Chemical Formulas 1-1 to 1-4.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In addition, according to an embodiment of the present invention, the modified conjugated diene-based polymer may include a conjugated diene-based monomer unit and a functional group derived from a modifier, wherein the conjugated diene-based monomer unit is a conjugated diene-based monomer in a polymerization reaction. It may mean a repeating unit formed, and the functional group derived from the modifier may mean a functional group derived from the modifier.

In addition, according to an embodiment of the present invention, the modified conjugated diene-based polymer may further include an aromatic vinyl-based monomer unit. In this case, the modified conjugated diene-based polymer includes a conjugated diene-based monomer unit and an aromatic vinyl-based monomer. It may be a copolymer comprising a unit and a functional group derived from a modifier.

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

In addition, according to an embodiment of the present invention, the aromatic vinyl-based monomer is, for example, styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexyl It may be at least one selected from the group consisting of styrene, 4-(p-methylphenyl)styrene, and 1-vinyl-5-hexylnaphthalene.

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

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

The modified conjugated diene-based polymer according to an embodiment of the present invention has a number average molecular weight (Mn) of 1,000 g/mol to 2,000,000 g/mol, 10,000 g/mol to 1,000,000 g/mol, or 10,000 g/mol to 500,000 g /mol, the weight average molecular weight (Mw) may be 10,000 g / mol to 3,000,000 g / mol, 10,000 g / mol to 2,000,000 g / mol, or 10,000 g / mol to 1,000,000 g / mol, the peak molecular weight ( Mp) may be from 1,000 g/mol to 3,000,000 g/mol, from 10,000 g/mol to 2,000,000 g/mol, or from 10,000 g/mol to 2,000,000 g/mol. Within this range, there is an excellent effect of rolling resistance and wet road resistance.

The modified conjugated diene-based polymer according to an embodiment of the present invention may have a molecular weight distribution (PDI; MWD; Mw/Mn) of 1.0 to 5.0, or 1.1 to 3.0, 1.1 to 2.5, or 1.3 to 1.4, within this range. It has excellent tensile properties and viscoelastic properties, and excellent balance between physical properties.

In addition, the modified conjugated diene-based polymer according to an embodiment of the present invention may have a Mooney viscosity of 30 or more, 40 to 150, 40 to 140, or 70 to 75 at 100° C., within this range It has excellent processability and productivity. Here, the Mooney viscosity may be measured using a Mooney viscometer. Specifically, using Monsanto's MV2000E Large Rotor, under the conditions of 100 ℃ and Rotor Speed 2±0.02 rpm, the polymer was left at room temperature (23±5 ℃ for 30 minutes or more, and then 27±3 g was collected and placed inside the die cavity. It was measured while filling and applying a torque by operating a platen.

In addition, the modified conjugated diene-based polymer may have a 1,2-vinyl bond content of 5 wt% or more, 10 wt% or more, or 10 wt% to 60 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 a modified conjugated diene-based polymer. The method for producing the modified conjugated diene-based polymer comprises the steps of preparing an active polymer by adding a conjugated diene-based monomer in a hydrocarbon solvent in the presence of a polymerization initiator and polymerization (S10); and reacting the active polymer with a modifier represented by the following Chemical Formula 1 (S20).

[Formula 1]

Here, the modifier represented by Chemical Formula 1 is the same as described above.

According to an embodiment of the present invention, the hydrocarbon solvent may be 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 is methyllithium, ethyllithium, propyllithium, isopropyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium , t-octyllithium, phenyllithium, 1-naphthyllithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolylithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4 -cyclopentyl lithium, naphthyl sodium, naphthyl potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide and lithium isopropylamide It may be at least one selected from

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

According to an embodiment of the present invention, the polymerization in step (S10) may be, for example, anionic polymerization, and as a specific example, living anionic polymerization having an anionic active site at the polymerization end by a growth polymerization reaction by an anion. In addition, the polymerization in step (S10) may be an elevated temperature polymerization, isothermal polymerization, or constant temperature polymerization (adiabatic polymerization), and the constant temperature polymerization includes a step of polymerizing by its own heat of reaction without optionally applying heat after the polymerization initiator is added. may refer to a polymerization method, and the temperature-rising polymerization may refer to a polymerization method in which the temperature is increased by optionally applying heat after the polymerization initiator is added, and the isothermal polymerization is heat by adding heat after the polymerization initiator is added 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, according to an embodiment of the present invention, the polymerization in step (S10) may be carried out by further including an aromatic vinyl-based monomer.

In addition, according to an embodiment of the present invention, the polymerization in step (S10) may be carried out by further including a diene-based monomer having 1 to 10 carbon atoms in addition to the conjugated diene-based monomer. It has the effect of preventing the formation of a gel. As a specific example, the diene-based monomer may be 1,2-butadiene.

According to an embodiment of the present invention, the polymerization of step (S10) is, for example, 80 ℃ or less, -20 ℃ to 80 ℃, 0 ℃ to 80 ℃, 0 ℃ to 70 ℃ or 10 ℃ to 70 ℃ in a temperature range It can be carried out, and by adjusting the molecular weight distribution of the polymer narrowly within this range, there is an excellent effect of improving physical properties.

According to an embodiment of the present invention, the active polymer prepared by the step (S10) may refer to a polymer in which a polymer anion and an organometallic cation are combined.

On the other hand, according to an embodiment of the present invention, the polymerization in step (S10) may be carried out including a polar additive, the polar additive is 0.001 g to 50 g, 0.001 g to 10 g, based on 100 g of the total monomer, or 0.005 g to 0.500 g. According to another embodiment of the present invention, the polar additive may be added in a ratio 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.

According to an embodiment of the present invention, the polar additive is tetrahydrofuran, 2,2-di(2-tetrahydrofuryl)propane, diethyl ether, cyclopentyl ether, dipropyl ether, ethylene methyl ether, ethylene dimethyl ether , diethyl glycol, dimethyl ether, tertiary butoxyethoxyethane, bis (3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine, N,N,N It may be at least one selected from the group consisting of ',N'-tetramethylethylenediamine, sodium mentholate, and 2-ethyl tetrahydrofurfuryl ether, and a specific example of 2,2- di(2-tetrahydrofuryl)propane, triethylamine, tetramethylethylenediamine, sodium mentholate or 2-ethyl tetrahydrofurfuryl ether. In the polymerization of step (S10), in the case of including the polar additive, when copolymerizing the conjugated diene-based monomer and the aromatic vinyl-based monomer, the difference in reaction rate between them is compensated to facilitate the formation of a random copolymer. has the effect of

According to an embodiment of the present invention, step (S20) is a step for preparing a modified conjugated diene-based polymer by reacting an active polymer with a modifier, wherein the reaction may be a modification or a coupling reaction, and in this case, the The denaturant may be used in an amount of 0.01 mmol to 10 mmol based on 100 g of the total monomer. According to another embodiment of the present invention, the modifier may be used in a molar ratio of 1:0.1 to 10, 1:0.1 to 5, or 1:0.1 to 1:3 based on 1 mole of the polymerization initiator in step (S10). can

The present invention also provides a rubber composition. The rubber composition may include the modified conjugated diene-based polymer.

According to an embodiment of the present invention, 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 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, according to an embodiment of the present invention, the rubber composition may further include other rubber components as necessary in addition to the modified conjugated diene-based polymer, wherein the rubber component is 90% by weight or less based on the total weight of the rubber composition. may be included in the amount of 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.

According to an embodiment of the present invention, 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.

Further, according to an embodiment of the present invention, the rubber composition may include 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. 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.

According to an embodiment of the present invention, when silica is used as the filler, a silane coupling agent for improving reinforcing properties and low heat generation may be used together, and in 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- Trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltri Methoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarb Bamoyltetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilylpropylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzolyl Tetrasulfide, 3-triethoxysilylpropylmethacrylate monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, bis(3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercapto It may be propyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide or dimethoxymethylsilylpropylbenzothiazolyltetrasulfide, and any one or a mixture of two or more thereof may be used. can 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 usually It can be further reduced, and thus, 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 sufficient. It has the effect of preventing the gelation of the rubber component while being exerted.

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.

According to an embodiment of the present invention, the vulcanization accelerator is, for example, M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazylsulfenamide) A thiazole-based compound such as, or a guanidine-based compound such as DPG (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.

According to an embodiment of the present invention, the process oil acts as a softener in the rubber composition, and may be a paraffinic, naphthenic, or aromatic compound. And in consideration of low-temperature characteristics, a naphthenic or paraffin-based process oil may be used. The process oil may be included in an amount of 100 parts by weight or less based on 100 parts by weight of the rubber component, and within this range, there is an effect of preventing deterioration of the tensile strength and low heat generation (low fuel efficiency) of the vulcanized rubber.

According to an embodiment of the present invention, the antioxidant is, for example, 2,6-di-t-butylparacresol, dibutylhydroxytoluenyl, 2,6-bis((dodecylthio)methyl)-4-nonyl Phenol (2,6-bis((dodecylthio)methyl)-4-nonylphenol) or 2-methyl-4,6-bis((octylthio)methyl)phenol (2-methyl-4,6-bis((octylthio) methyl) phenol), and may be used in an amount of 0.1 to 6 parts by weight based on 100 parts by weight of the rubber component.

According to an embodiment of the present invention, the antioxidant is, for example, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylene It may be diamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, or a high-temperature condensate of diphenylamine and acetone, and 0.1 to 6 parts by weight based on 100 parts by weight of the rubber component. can be used as wealth.

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.

According to an embodiment of the present invention, the tire may include a tire wall or a tire tread.

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

Example

Example 1

In a 20 L autoclave reactor, 3,000 g of n-hexane, 270 g of styrene, 710 g of 1,3-butadiene and 1.29 g of 2,2-di(2-tetrahydrofuryl)propane (DTP) as a polar additive were put into the reactor, After adjusting the internal temperature to 60 ℃, an adiabatic temperature increase reaction was carried out. After 30 excess, 20 g of 1,3-butadiene was added to cap the polymer end with butadiene, and after 10 excess, 1,3,5-tris(2-to) represented by the following Chemical Formula 1-1 as a denaturant Toxyethyl)-1,3,5-triazinane (1,3,5-tris(2-ethoxylethyl)-1,3,5-triazinane) (CAS Number: 52183-63-8) was added for 15 minutes reacted ([DTP]/[act. Li]=1.5:1 molar ratio, [denaturant]/[act. Li]=1:1 molar ratio). Then, the reaction was stopped using ethanol, and 33 g of a solution in which 30 wt% of an antioxidant, Wingstay K, 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, thereby preparing a modified styrene-butadiene copolymer.

[Formula 1-1]

Example 2

In Example 1, 1,3,5-tris(2-(methoxymethoxy)ethyl)-1,3,5-triazinane (1,3,5- A modified styrene-butadiene copolymer was prepared in the same manner as in Example 1, except that tris(2-(methoxymethoxy)ethyl)-1,3,5-triazinane) was used in the same molar ratio.

[Formula 1-2]

Example 3

In Example 1, 1,3,5-tris(3-ethoxypropyl)-1,3,5-triazinane (1,3,5-tris(3- A modified styrene-butadiene copolymer was prepared in the same manner as in Example 1, except that ethoxypropyl)-1,3,5-triazinane) was used in the same molar ratio.

[Formula 1-3]

Example 4

In Example 1, 1,3,5-tris(2-((methoxymethoxy)methoxy)ethyl)-1,3,5-triazinane (1, 3,5-tris(2-((methoxymethoxy)methoxy)ethyl)-1,3,5-triazinane) was used in the same molar ratio as in Example 1, but modified styrene-butadiene copolymer was prepared.

[Formula 1-4]

Comparative Example 1

In a 20 L autoclave reactor, 3,000 g of n-hexane, 270 g of styrene, 710 g of 1,3-butadiene and 1.29 g of 2,2-di(2-tetrahydrofuryl)propane (DTP) as a polar additive were introduced into the reactor, After adjusting the internal temperature to 60 ℃, an adiabatic temperature increase reaction was performed. After 30 lapses, 20 g of 1,3-butadiene was added to cap the end of the polymer with butadiene, and after 10 lapses, the reaction was stopped using ethanol, and 30 wt% of Wingstay K, an antioxidant, was dissolved in hexane. 33 g of the solution 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, thereby preparing a styrene-butadiene copolymer.

Comparative Example 2

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

Experimental example

Experimental Example 1

For each of the modified or unmodified conjugated diene-based polymers prepared in Examples 1 to 4 and Comparative Examples 1 and 2, the styrene unit content and vinyl content and weight average molecular weight (Mw, X10 ³ g/mol), number in the polymer, respectively Average molecular weight (Mn, X10 ³ g/mol), molecular weight distribution (PDI, MWD) and Mooney viscosity (MV) were measured, respectively. The results are shown in Table 1 below.

1) Styrene 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), number average molecular weight (Mn, X10 ³ g/mol), molecular weight distribution (PDI, MWD)

The weight average molecular weight (Mw) and number average molecular weight (Mn) were measured through gel permeation chromatography (GPC) analysis, and a molecular weight distribution curve was obtained. In addition, molecular weight distributions (PDI, MWD, Mw/Mn) were calculated and obtained 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 viscosity

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

division Example comparative example One 2 3 4 One 2 NMR (wt%) SM 27 27 27 27 27 27 Vinyl 43 43 43 43 43 43 GPC Mw (X10 ³ g/mol) 41 40 42 41 50 69 Mn (X10 ³ g/mol) 31 32 30 32 42 38 PDI 1.3 1.3 1.4 1.3 1.2 1.8 Mooney viscosity (MV) 71 70 72 71 64 80

Experimental Example 2

In order to compare and analyze the physical properties of the rubber compositions comprising each modified or unmodified conjugated diene-based copolymer prepared in Examples 1 to 4 and Comparative Examples 1 and 2 and molded articles prepared therefrom, tensile properties and viscoelastic properties were measured Each was measured and the results are shown in Table 3 below.

(1) Preparation of rubber specimens

1) Examples 1 to 4 and Comparative Examples 1 to 2

Each of the modified or unmodified conjugated diene-based polymers of Examples 1 to 4 and Comparative Examples 1 to 2 was used as a raw rubber and blended under the compounding conditions shown in Table 2 below. 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 blend was obtained at a discharge temperature of 145 ° C to 155 ° C. In the second stage kneading, the first blend was cooled to room temperature. After mixing, the primary compound, sulfur, rubber accelerator (DPD (diphenylguanine)) and vulcanization accelerator (CZ (N-cytlohexyl-2-benzothiazylsulfenamide)) were added to the kneader, and the temperature was 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.

3) Viscoelastic properties

For viscoelastic properties, the tan δ value was confirmed by measuring the viscoelastic behavior against dynamic deformation at a frequency of 10 Hz and each measurement temperature (-60 ℃ ~ 60 ℃) in film tension mode using a dynamic mechanical analyzer (GABO). Measurement Results The higher the low temperature (0 ℃) tan δ 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 low running resistance (fuel efficiency). In Table 3, the result value is expressed in Index (%) based on the result value of Comparative Example 2, so the higher the numerical value, the better.

4) Machinability characteristics

1) Each polymer by measuring the Mooney viscosity (CMV, (ML1+4, @100 ℃) of the primary compound obtained during the preparation of the rubber specimen and the Mooney viscosity (FMV, (ML1+4, @100 ℃ MU) of the secondary compound) was comparatively analyzed, and in this case, the smaller the difference between the Mooney viscosity of the primary formulation and the Mooney viscosity of the secondary formulation, the better the processability characteristics.

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

division Example comparative example One 2 3 4 One 2 Tensile properties Tensile strength (kgf/cm ² ) 182 184 183 184 168 167 300% modulus (kgf/cm ² ) 120 124 123 121 104 98 Viscoelastic properties tan δ(at 0 ℃, Index) 102 103 103 104 98 100 tan δ(at 60 ℃, Index) 132 132 132 131 105 100 Machinability characteristics CMV 87 88 87 89 87 85 FMV 70 72 72 71 71 62 △FMV-CMV (absolute value) 17 16 15 18 16 23

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

From these results, it was confirmed that the modified conjugated diene-based polymer according to the present invention has excellent affinity with the filler included in the rubber composition, and thus has excellent processability, tensile properties and viscoelastic properties of the rubber composition.

Claims (10)

conjugated diene-based monomer units; And a modified conjugated diene-based polymer comprising a functional group derived from a modifier represented by the following formula (1):
[Formula 1]

In Formula 1,
R ¹ to R ⁶ are each independently hydrogen, a monovalent hydrocarbon group having 1 to 30 carbon atoms, a substituent represented by the following Formula 2 or a substituent represented by the following Formula 2, R ¹ , R ³ and R ⁵ At least one or more of R 1 , R 3 and R 5 is a substituent represented by the following formula (2),
[Formula 2]

In Formula 2,
R ⁷ is a direct bond or a divalent hydrocarbon group having 1 to 30 carbon atoms,
R ⁸ is a divalent hydrocarbon group having 1 to 10 carbon atoms,
R ⁹ is hydrogen or a monovalent hydrocarbon group having 1 to 30 carbon atoms,
n is an integer from 1 to 10,
* is a bonding position in formula (1). According to claim 1,
R ¹ , R ³ and R ⁵ are each independently a substituent represented by Formula 2,
R ² , R ⁴ and R ⁶ are each independently hydrogen or a monovalent hydrocarbon group having 1 to 30 carbon atoms. According to claim 1,
R ¹ , R ³ and R ⁵ are each independently a substituent represented by Formula 2, R ² , R ⁴ and R ⁶ are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms, R ⁷ is a direct bond or a carbon number ^{A modified conjugated diene-based polymer wherein R 8} is an alkylene group having 1 to 10 carbon atoms, R ^{8 is an alkylene group having 1 to 10 carbon atoms, R 9} is hydrogen or an alkyl group having 1 to 10 carbon atoms, and n is an integer of 1 to 3. According to claim 1,
R ¹ , R ³ and R ⁵ are each independently a substituent represented by Formula 2 above, R ² , R ⁴ and R ⁶ are hydrogen, R ⁷ is an alkylene group having 1 to 3 carbon atoms, and R ⁸ is a carbon number 1 to 3 alkylene group, R ⁹ is hydrogen, and n is an integer of 1 to 3, a modified conjugated diene-based polymer. According to claim 1,
The modified conjugated diene-based polymer of which the modifier represented by Formula 1 is at least one selected from the group consisting of modifiers represented by the following Formulas 1-1 to 1-4:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

. According to claim 1,
The modified conjugated diene-based polymer is a modified conjugated diene-based polymer comprising an aromatic vinyl-based monomer unit. According to claim 1,
The modified conjugated diene-based polymer of which the functional group derived from the modifier represented by Formula 1 is included in at least one terminal of the conjugated diene-based polymer. Preparing an active polymer by adding a conjugated diene-based monomer in the presence of a polymerization initiator in a hydrocarbon solvent and polymerization (S10); and
A method for producing a modified conjugated diene-based polymer comprising the step (S20) of reacting the active polymer with a modifier represented by the following formula (1):
[Formula 1]

In Formula 1,
R ¹ to R ⁶ are each independently hydrogen, a monovalent hydrocarbon group having 1 to 30 carbon atoms, a substituent represented by the following Formula 2 or a substituent represented by the following Formula 2, R ¹ , R ³ and R ⁵ At least one or more of R 1 , R 3 and R 5 is a substituent represented by the following formula (2),
[Formula 2]

In Formula 2,
R ⁷ is a direct bond or a divalent hydrocarbon group having 1 to 30 carbon atoms,
R ⁸ is a divalent hydrocarbon group having 1 to 10 carbon atoms,
R ⁹ is hydrogen or a monovalent hydrocarbon group having 1 to 30 carbon atoms,
n is an integer from 1 to 10,
* is a bonding position in formula (1). A rubber composition comprising the modified conjugated diene-based polymer according to any one of claims 1 to 7. 10. The method of claim 9,
The rubber composition is 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.