KR20220153928A - Rubber composition and method for preparing the composition - Google Patents

Abstract

The present invention relates to a rubber composition, and specifically, to a rubber composition, which comprises: hydrogenation-modified block copolymers including an aromatic vinyl-based polymer block, an olefin-based polymer block including an olefin-based monomer unit and a linking group derived from a modifier; and a random copolymer including at least one monomer unit selected from a group consisting of an aromatic vinyl monomer unit, an olefin monomer unit, and a conjugated diene monomer unit, and to a manufacturing method thereof. It is an object to provide the rubber composition having improved wear resistance.

Description

Rubber composition and its manufacturing method {RUBBER COMPOSITION AND METHOD FOR PREPARING THE COMPOSITION}

The present invention relates to a rubber composition that can further improve the abrasion resistance of a rubber composition that can be used in tires and the like, and a method for manufacturing the same.

In accordance with the recent demand for low fuel consumption for automobiles, conjugated diene-based polymers with low rolling resistance, excellent abrasion resistance and tensile properties, and control stability represented by wet road surface resistance are required as rubber materials for tires.

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

Natural rubber, polyisoprene rubber, polybutadiene rubber and the like are known as rubber materials with low hysteresis loss, but these have a problem of low wet road surface resistance. Recently, conjugated diene-based polymers or copolymers such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) are produced by emulsion polymerization or solution polymerization and are used as rubber for tires. . Among them, the greatest advantage of solution polymerization over emulsion polymerization is that the vinyl structure content and styrene content that define rubber properties can be arbitrarily controlled, and molecular weight and physical properties can be changed by coupling or modification. that it can be controlled. Therefore, it is easy to change the structure of the finally manufactured SBR or BR, reduce the movement of the chain ends by linking or modifying the chain ends, and increase the binding force with fillers such as silica or carbon black. It is widely used as a rubber material for

When such solution-polymerized SBR is used as a rubber material for tires, the glass transition temperature of rubber can be raised by increasing the vinyl content in the SBR, thereby controlling required physical properties of the tire, such as driving resistance and braking power, as well as increasing the glass transition temperature. Proper adjustment can reduce fuel consumption. The solution polymerization SBR is prepared using an anionic polymerization initiator, and a technique of combining or modifying the chain ends of the formed polymer using various denaturants to introduce functional groups into the ends is used. For example, U.S. Patent No. 4,397,994 suggests a technique in which active anions at the chain ends of a polymer obtained by polymerizing styrene-butadiene in a non-polar solvent using alkyllithium, a monofunctional initiator, are bonded using a binder such as a tin compound. did

However, there is a limit to improving the wear resistance of a tire only by adjusting or modifying the vinyl content of solution polymerized SBR, and since abrasion resistance is directly related to the lifespan of a tire, there is a continuous need for improvement in abrasion resistance.

US4397994A

The present invention has been made to solve the problems of the prior art, and an object of the present invention is to provide a rubber composition with improved wear resistance.

In addition, an object of the present invention is to provide a method for producing a rubber composition having improved wear resistance.

In order to solve the above problems, the present invention is an aromatic vinyl-based polymer block, an olefin-based polymer block containing an olefin-based monomer unit, and a hydrogenation-modified block copolymer containing a linking group derived from a modifier; and a random copolymer comprising an aromatic vinyl monomer unit and at least one monomer unit selected from the group consisting of an olefin monomer unit and a conjugated diene monomer unit.

In the present invention, in the presence of an organolithium compound, an aromatic vinyl-based monomer is introduced and polymerized to prepare an anionic active aromatic vinyl-based polymer (S10); preparing an anion-active diblock copolymer by adding and polymerizing a conjugated diene-based monomer in the presence of an anion-active aromatic vinyl-based polymer (S20); Preparing a modified block copolymer by adding and reacting a modifier in the presence of an anionic active diblock copolymer (S30); preparing a hydrogenated modified block copolymer by hydrogenating the modified block copolymer using hydrogen gas (S40); And a step (S50) of mixing a hydrogenated block copolymer and a random copolymer comprising one or more monomer units selected from the group consisting of an aromatic vinyl monomer unit and an olefin monomer unit and a conjugated diene monomer unit. A method for preparing a rubber composition is provided.

The rubber composition of the present invention has excellent wear resistance.

In particular, the rubber composition of the present invention has excellent abrasion resistance, low rolling resistance and excellent fuel efficiency, so it may be particularly suitable for tires.

Hereinafter, the present invention will be described in more detail to aid 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 ordinary or dictionary meanings, and the inventors use the concept of terms appropriately to describe their invention in the best way. Based on the principle that it can be defined, it should be interpreted as meaning and concept consistent with the technical spirit of the present invention.

In the present invention, the term 'alkyl group' may mean a monovalent aliphatic saturated hydrocarbon, and includes linear alkyl groups such as methyl, ethyl, propyl, and butyl, isopropyl, sec-butyl, and tert. It may mean including all branched alkyl groups such as sherry butyl (tert-butyl) and neo-pentyl (neo-pentyl).

In the present invention, the term 'alkenyl group' may refer to a monovalent aliphatic unsaturated hydrocarbon containing one or two or more double bonds.

In the present invention, the term 'alkynyl group' may refer to a monovalent aliphatic unsaturated hydrocarbon containing one or two or more triple bonds.

In the present invention, the term 'cycloalkyl group' may mean a monovalent aliphatic saturated or unsaturated cyclic hydrocarbon. Here, the unsaturated cyclic hydrocarbon may refer to a cyclic hydrocarbon that includes one or two or more unsaturated bonds in a cyclic structure formed from hydrocarbons, but is not an aromatic hydrocarbon.

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

In the present invention, the term 'heteroalkyl group' may mean one or two or more atoms other than carbon and hydrogen, that is, a heteroatom, in a monovalent aliphatic saturated or unsaturated hydrocarbon. Here, the hetero atoms may be oxygen (O), nitrogen (N), and sulfur (S) atoms. In addition, the heteroalkyl group may include an alkoxy group, an amino group, and a sulfide group.

In the present invention, the term 'heterocyclic group' may include all cycloalkyl groups or aryl groups in which a carbon atom in a cycloalkyl group or aryl group is substituted with one or more heteroatoms. Here, the hetero atoms may be oxygen (O), nitrogen (N), and sulfur (S) atoms. Also, the number of ring-forming atoms in the heterocyclic group may mean the number of atoms forming a ring including carbon and heteroatoms.

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

In the present invention, the term 'monomer unit' may represent a component, structure, or material itself derived from a monomer, and as a specific example, during polymerization of a polymer, the input monomer participates in the polymerization reaction to form a repeating unit in the polymer. it could mean

The term 'polymer' used in the present invention may include both a homopolymer formed by polymerization of one type of monomer and a copolymer formed by copolymerization of two types of monomers.

The term 'block' used in the present invention may refer to a repeating unit group composed of only repeating units derived from the same monomers in which only the same monomers participate in a polymerization reaction in the copolymer. As a specific example, an aromatic vinyl polymer block is an aromatic It may mean a block formed only of vinyl monomer units, and the conjugated diene-based polymer block may mean a block formed only of conjugated diene-based monomer units.

The term 'coupling agent linking group' used in the present invention is a part of a block copolymer and may mean a remaining part of a coupling agent formed by coupling a polymer block with a coupling agent.

The term 'anionic active polymer' used in the present invention is a polymer formed by anionic polymerization, and may refer to a polymer capable of further polymerization or reaction by maintaining an anionic state at one end of the polymer. Specific examples include living anionic polymers. can mean

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

The present invention provides a rubber composition with improved wear resistance.

According to one embodiment of the present invention, the rubber composition includes an aromatic vinyl-based polymer block, an olefin-based polymer block including an olefin-based monomer unit, and a hydrogenation-modified block copolymer including a linking group derived from a modifier; and a random copolymer comprising at least one monomer unit selected from the group consisting of an aromatic vinyl-based monomer unit, an olefin-based monomer unit, and a conjugated diene-based monomer unit.

According to one embodiment of the present invention, the hydrogenation-modified block copolymer and the random copolymer may each be a raw rubber component of a rubber composition. Here, the random copolymer may be the solution polymerized SBR described in the background technology of the present invention. As described in the background technology of the present invention, only adjusting or denaturing the vinyl content of the solution polymerized SBR can improve tire performance. There is a limit to improving abrasion resistance, and since abrasion resistance is directly related to the lifespan of a tire, the need for improvement in abrasion resistance is continuously demanded. Therefore, the rubber composition according to the present invention is characterized by including a hydrogenation-modified block copolymer as a raw rubber component in addition to the random copolymer.

According to one embodiment of the present invention, the weight ratio of the block copolymer and the random copolymer is 10:90 to 90:10, 20:80 to 80:20, 30:70 to 70:30, or 40:60 to It may be 60:40, and within this range, there is an effect of significantly improving wear resistance from the block copolymer while securing mechanical properties such as viscoelastic properties and tensile properties of the rubber composition by the random copolymer.

According to one embodiment of the present invention, the hydrogenation-modified block copolymer may include an aromatic vinyl-based polymer block, an olefin-based polymer block including an olefin-based monomer unit, and a linking group derived from a modifier. In this case, the hydrogenated modified block copolymer may be prepared by hydrogenating a modified block copolymer including a linking group derived from a modifier, as in the rubber composition manufacturing method described below.

According to one embodiment of the present invention, the aromatic vinyl-based polymer block may include an aromatic vinyl-based monomer unit, and the aromatic vinyl-based monomer for forming the aromatic vinyl-based polymer block may include styrene, α-methylstyrene, 1 species selected from the group consisting of 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, and 1-vinyl-5-hexylnaphthalene It may be more than one, and may be styrene as a specific example.

According to one embodiment of the present invention, the content of the aromatic vinyl-based polymer block is 5% to 50% by weight, 10% to 40% by weight, or 20% to 40% by weight with respect to the hydrogenation-modified block copolymer. can be

According to one embodiment of the present invention, the olefin-based polymer block may include an olefin-based monomer unit formed by hydrogenation from a conjugated diene-based polymer block. That is, the olefin-based monomer unit may be formed by hydrogenation of a conjugated diene-based monomer unit. Conjugated diene-based monomers for forming the conjugated diene-based polymer block are 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, 2 It may be at least one selected from the group consisting of -phenyl-1,3-butadiene and 2-halo-1,3-butadiene (halo means a halogen atom), and as a specific example, it may be 1,3-butadiene. In addition, the olefin-based monomer unit may include two or more types of olefin-based monomer units that are different from each other according to the bonding form of the conjugated diene-based monomer unit to be hydrogenated. As a specific example, the conjugated diene-based monomer unit may be formed by 1,2-bonding or 1,4-bonding of the conjugated diene-based monomer during polymerization, and accordingly, the olefin-based monomer unit is formed by 1,2-bonding of the conjugated diene It may include an olefin-based monomer unit in which an olefin-based monomer unit is hydrogenated and a conjugated diene-based monomer unit formed by 1,4-bonding is hydrogenated. For example, when the conjugated diene monomer unit is 1,3-butadiene, the olefin monomer unit is a 1,2-linked conjugated diene monomer unit formed by hydrogenation of a 1-butene monomer unit, and a 1,4-butadiene monomer unit. The conjugated diene-based monomer unit formed by bonding may include a hydrogenated ethylene monomer unit. As such, the olefin-based monomer unit may be determined as two or more types of olefin-based monomer units in a substituted or unsubstituted form depending on the type and bonding form of the conjugated diene-based monomer unit to be hydrogenated.

According to one embodiment of the present invention, the olefin monomer unit is two or more monomers selected from the group consisting of a substituted or unsubstituted ethylene monomer unit and a substituted or unsubstituted alpha-olefin monomer unit having 3 to 10 carbon atoms unit, wherein the substituent of the substituted ethylene monomer unit and the substituted alpha-olefin monomer unit having 3 to 10 carbon atoms may be an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a halogen group. have. As a specific example, the olefin-based monomer unit may include an ethylene monomer unit and a 1-butene monomer unit.

According to one embodiment of the present invention, the content of the olefin-based polymer block is 50% to 95% by weight, 60% to 90% by weight, or 60% to 80% by weight relative to the hydrogenated block copolymer can

According to one embodiment of the present invention, the linking group derived from the modifier is formed by a coupling reaction of the anionic active diblock copolymer with the modifier during preparation of the modified block copolymer, and is derived from the modifier to form the diblock copolymer. It may be a connector that connects. That is, the denaturing agent may be a denaturing coupling agent.

According to one embodiment of the present invention, the modifier may be an alkoxy silane-based modifier. When the linking group derived from the modifier is formed from an alkoxysilane-based modifier, a modifier derived from the alkoxysilane-based modifier is attached to one end of the diblock copolymer by a substitution reaction between the anionic active diblock copolymer and the alkoxy group in the alkoxysilane-based modifier. A functional group may be formed, and at this time, when the alkoxy group remaining in the functional group derived from the modifier is substituted by another diblock copolymer, a linking group derived from the modifier may be formed. Therefore, from the viewpoint of inducing a coupling reaction by the denaturant, the alkoxy silane-based denaturant may be an alkoxy silane-based denaturant containing two or more alkoxy groups. In addition, when the linking group derived from the alkoxysilane-based modifier further includes one or more alkoxy groups, affinity to the filler may be improved.

According to one embodiment of the present invention, the alkoxy silane-based modifier may be an amino alkoxy silane-based modifier. When the denaturant further includes an amino group, that is, a functional group containing a nitrogen atom, affinity for the filler may be further improved.

According to one embodiment of the present invention, the modifier may include one or more compounds selected from the group consisting of compounds represented by Formulas 1 to 6 below.

[Formula 1]

In Formula 1, R ¹ may be a single bond or an alkylene group having 1 to 10 carbon atoms, R ² and R ³ may each independently be an alkyl group having 1 to 10 carbon atoms, and R ⁴ is hydrogen, or an alkylene group having 1 to 10 carbon atoms. It may be an alkyl group having 10 carbon atoms, a divalent, trivalent or tetravalent alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, or a heterocyclic group having 2 to 10 carbon atoms, and R ²¹ is a single bond, an alkylene group having 1 to 10 carbon atoms , or -[R ⁴² O] _j -, R ⁴² may be an alkylene group having 1 to 10 carbon atoms, a and m may each independently be an integer selected from 1 to 3, n is 0, 1, Alternatively, it may be an integer of 2, and j may be an integer selected from 1 to 30.

As a specific example, in Formula 1, R ¹ may be a single bond or an alkylene group having 1 to 5 carbon atoms, R ² and R ³ may each independently be hydrogen or an alkyl group having 1 to 5 carbon atoms, and R ⁴ is It may be a tetravalent alkylsilyl group substituted with hydrogen, an alkyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, or a heterocyclic group having 2 to 5 carbon atoms, and R ²¹ is a single bond or an alkylene group having 1 to 5 carbon atoms. , or -[R ⁴² O] _j -, R ⁴² may be an alkylene group having 1 to 5 carbon atoms, a may be an integer of 2 or 3, m may be an integer selected from 1 to 3, n may be an integer of 0, 1, or 2, where m+n=3, and j may be an integer selected from 1 to 10.

In Formula 1, when R ⁴ is a heterocyclic group, the heterocyclic group may be substituted or unsubstituted with a 3-substituted alkoxy silyl group, and when the hetero cyclic group is substituted with a 3-substituted alkoxy silyl group, the 3-substituted alkoxy silyl group It may be substituted by being connected to the heterocyclic group by an alkylene group having 1 to 10 carbon atoms, and the trisubstituted alkoxy silyl group may mean an alkoxy silyl group substituted with an alkoxy group having 1 to 10 carbon atoms.

As a more specific example, the compound represented by Formula 1 is N,N-bis(3-(dimethoxy(methyl)silyl)propyl)-methyl-1-amine (N,N-bis(3-(dimethoxy(methyl) silyl)propyl)-methyl-1-amine), N,N-bis(3-(diethoxy(methyl)silyl)propyl)-methyl-1-amine(N,N-bis(3-(diethoxy(methyl) silyl)propyl)-methyl-1-amine), N,N-bis(3-(trimethoxysilyl)propyl)-methyl-1-amine (N,N-bis(3-(trimethoxysilyl)propyl)-methyl -1-amine), N, N-bis (3- (triethoxysilyl) propyl) -methyl-1-amine (N, N-bis (3- (triethoxysilyl) propyl) -methyl-1-amine), N,N-diethyl-3-(trimethoxysilyl)propan-1-amine (N,N-diethyl-3-(trimethoxysilyl)propan-1-amine), N,N-diethyl-3-(trimethoxysilyl)propan-1-amine Ethoxysilyl) propan-1-amine (N, N-diethyl-3- (triethoxysilyl) propan-1-amine), tri (trimethoxysilyl) amine (tri (trimethoxysilyl) amine), tri (3- (tri Methoxysilyl) propyl) amine (tri- (3- (trimethoxysilyl) propyl) amine), N, N-bis (3- (diethoxy (methyl) silyl) propyl) -1,1,1-trimethylsilanamine ( N,N-bis(3-(diethoxy(methyl)silyl)propyl)-1,1,1-trimethlysilanamine), N,N-bis(3-(1H-imidazol-1-yl)propyl)-(trimethly) Ethoxysilyl)methan-1-amine (N,N-bis(3-(1H-imidazol-1-yl)propyl)-(triethoxysilyl)methan-1-amine), N-(3-(1H-1, 2,4-triazol-1-yl) propyl) -3- (trimethoxysilyl) -N- (3- (trimethoxysilyl) propyl) propan-1-amine (N- (3- (1H- 1,2,4-triazole-1-yl)propyl)-3-(trimethoxysilyl)-N-(trimethoxysi lyl)propyl)propan-1-amine), 3-(trimethoxysilyl)-N-(3-trimethoxysilyl)propyl)-N-(3-(1-(3-(trimethoxysilyl) Propyl)-1H-1,2,4-triazol-3-yl)propyl)propan-1-amine (3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)-N-(3-(1 -(3-(trimethoxysilyl)propyl)-1H-1,2,4-triazol-3-yl)propyl)propan-1-amine), N,N-bis(2-(2-methoxyethoxy)ethyl ) -3- (triethoxysilyl) propan-1-amine (N, N-bis (2- (2-methoxyethoxy) ethyl) -3- (triethoxysilyl) propna-1-amine), N, N-bis ( 3-(triethoxysilyl)propyl)-2,5,8,11,14-pentaoxahexadecane-16-amine (N,N-bis(3-(triethoxysilyl)propyl)-2,5,8, 11,14-pentaoxahexadecan-16-amine), N-(2,5,8,11,14-pentaoxahexadecane-16-yl)-N-(3-(triethoxysilyl)propyl)-2, 5,8,11,14-pentaoxahexadecane-16-amine (N-(2,5,8,11,14-pentaoxahexadecan-16-yl)-N-(3-(triethoxysilyl)propyl)-2, 5,8,11,14-pentaoxahexadecan-16-amine) and N-(3,6,9,12-tetraoxahexadecyl)-N-(3-(triethoxysilyl)propyl)-3,6, 9,12-tetraoxahexadecane-1-amine (N-(3,6,9,12-tetraoxahexadecyl)-N-(3-(triethoxysilyl)propyl)-3,6,9,12-tetraoxahexadecan-1- amine) may be one selected from the group consisting of.

[Formula 2]

In Formula 2, R ⁵ , R ⁶ and R ⁹ may each independently be an alkylene group having 1 to 10 carbon atoms, and R ⁷ , R ⁸ , R ¹⁰ and R ¹¹ may each independently be an alkyl group having 1 to 10 carbon atoms. may be, R ¹² may be hydrogen or an alkyl group having 1 to 10 carbon atoms, b and c are each independently 0, 1, 2 or 3, may be b+c≥1, and A is represented by Formula 2-1 or a linking group represented by Formula 2-2, wherein R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ may each independently be hydrogen or an alkyl group having 1 to 10 carbon atoms.

[Formula 2-1]

[Formula 2-2]

As a specific example, the compound represented by Formula 2 is N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl ) Propan-1-amine (N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine) and 3-( 4,5-dihydro-1H-imidazol-1-yl)-N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine(3-(4,5-dihydro-1H- It may be one selected from the group consisting of imidazol-1-yl)-N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine).

[Formula 3]

In Chemical Formula 3, A ¹ and A ² may each independently be a divalent hydrocarbon group having 1 to 20 carbon atoms with or without an oxygen atom, and R ¹⁷ to R ²⁰ may each independently be a monovalent hydrocarbon group having 1 to 20 carbon atoms. It may be a hydrocarbon group, L ¹ to L ⁴ are each independently a divalent, trivalent or tetravalent alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or L ¹ and L ² , L ³ and L ⁴ may be connected to each other to form a ring having 1 to 5 carbon atoms, and when L ¹ and L ² and L ³ and L ⁴ are connected to each other to form a ring, the formed ring is 1 to 3 hetero atoms selected from the group consisting of N, O and S may be included.

As a specific example, in Formula 3, A ¹ and A ² may each independently be an alkylene group having 1 to 10, R ¹⁷ to R ²⁰ may each independently be an alkyl group having 1 to 10 carbon atoms, and L ¹ to L ⁴ is a tetravalent alkylsilyl group independently substituted with an alkyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or L ¹ and L ² and L ³ and L ⁴ are connected to each other to form a ring having 1 to 3 carbon atoms May form, and when L ¹ and L ² and L ³ and L ⁴ are connected to each other to form a ring, the formed ring includes one or more heteroatoms selected from the group consisting of N, O and S, Can contain 3.

As a more specific example, the compound represented by Formula 3 is 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine) (3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine), 3,3'-(1,1,3,3- Tetraethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine)(3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis( N,N-dimethylpropan-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine) (3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine), 3,3'-(1,1,3,3- Tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine)(3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis( N,N-diethylpropan-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine) (3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimpropylpropan-1-amine), 3,3'-(1,1,3,3- Tetraethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine)(3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis (N,N-diethylpropan-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1- amine)(3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine), 3,3'-(1,1,3, 3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine )(3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine), 3,3'-(1,1,3,3 -Tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine)(3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl) bis(N,N-dipropylpropan-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylmethane-1- amine)(3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1-amine), 3,3'-(1,1,3, 3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1-amine)(3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl )bis(N,N-diethylmethan-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diethylmethane- 1-amine)(3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1-amine), 3,3'-(1,1, 3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethan-1-amine)(3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl )bis(N,N-dimethylmethan-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethane-1 -amine)(3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethan-1-amine), 3,3'-(1,1,3 ,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethan-1-amine)(3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl )bis(N,N-dimethylmethan-1-amine), 3,3'-(1, 1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethan-1-amine)(3,3'-(1,1,3,3-tetrapropoxydisiloxane-1 ,3-diyl)bis(N,N-dipropylmethan-1-amine), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N- Dimethylmethan-1-amine)(3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethan-1-amine), 3,3'-(1 ,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethan-1-amine)(3,3'-(1,1,3,3-tetraethoxydisiloxane- 1,3-diyl)bis(N,N-dipropylmethan-1-amine), N,N'-((1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(propane-3 ,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine (N,N'-((1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis( propan-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine), N,N'-((1,1,3,3-tetraethoxydisiloxane-1, 3-diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silaneamine (N,N'-((1,1,3,3-tetraethoxydisiloxane -1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine), N,N'-((1,1,3,3 -Tetraprooxydisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine(N,N'-(( 1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine), N,N'- ((1,1,3,3-tetramethoxydisiloxane-1,3 -Diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilanamine(N,N'-((1,1,3,3-tetramethoxydisiloxane-1,3 -diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilanamine), N,N'-((1,1,3,3-tetraethoxydisiloxane- 1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilanamine(N,N'-((1,1,3,3-tetraethoxydisiloxane- 1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilanamine), N,N'-((1,1,3,3-tetrapropoxy Cidisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilanamine (N,N'-((1,1,3,3 -tetrapropoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilanamine), 1,3-bis(3-(1H-imidazole-1 -yl) propyl) 1,1,3,3-tetramethoxydisiloxane (1,3-bis (3- (1H-imidazol-1-yl) propyl) -1,1,3,3-tetramethoxydisiloxane), 1 ,3-bis(3-(1H-imidazol-1-yl)propyl)1,1,3,3-tetraethoxydisiloxane (1,3-bis(3-(1H-imidazol-1-yl) propyl) -1,1,3,3-tetraethoxydisiloxane), and 1,3-bis (3- (1H-imidazol-1-yl) propyl) 1,1,3,3-tetrapropoxydisiloxane (1 ,3-bis(3-(1H-imidazol-1-yl)propyl)-1,1,3,3-tetrapropoxydisiloxane).

[Formula 4]

In Formula 4, R ²² and R ²³ are each independently an alkylene group having 1 to 20 carbon atoms, or -R ²⁸ [OR ²⁹ ] _f -, and R ²⁴ to R ²⁷ are each independently an alkyl group having 1 to 20 carbon atoms, or It may be an aryl group having 6 to 20 carbon atoms, R ²⁸ and R ²⁹ may each independently be an alkylene group having 1 to 20 carbon atoms, R ⁴⁷ and R ⁴⁸ may each independently be a divalent hydrocarbon group having 1 to 6 carbon atoms, , d and e are each independently 0 or an integer selected from 1 to 3, d + e is an integer of 1 or more, and f may be an integer of 1 to 30.

Specifically, in Formula 4, R ²² and R ²³ may each independently be an alkylene group having 1 to 10 carbon atoms or -R ²⁸ [OR ²⁹ ] _f -, and R ²⁴ to R ²⁷ each independently have 1 carbon atom to 10 alkyl groups, R ²⁸ and R ²⁹ may each independently be an alkylene group having 1 to 10 carbon atoms, and d and e are each independently 0 or an integer selected from 1 to 3, but d+e is It may be an integer greater than or equal to 1, and f may be an integer selected from 1 to 30.

More specifically, the compound represented by Formula 4 may be a compound represented by Formula 4a, Formula 4b or Formula 4c.

[Formula 4a]

[Formula 4b]

[Formula 4c]

In Chemical Formulas 4a, 4b, and 4c, R ²² to R ²⁷ , d and e are as described above.

As a more specific example, the compound represented by Formula 4 is 1,4-bis (3- (3- (triethoxysilyl) propoxy) propyl) piperazine (1,4-bis (3- (3- (triethoxysilyl) )propoxy)propyl)piperazine, 1,4-bis(3-(triethoxysilyl)propyl)piperazine(1,4-bis(3-(triethoxysilyl)propyl)piperazine), 1,4-bis(3- (trimethoxysilyl) propyl) piperazine (1,4-bis (3- (trimethoxysilyl) propyl) piperazine), 1,4-bis (3- (dimethoxymethylsilyl) propyl) piperazine (1,4- bis(3-(dimethoxymethylsilyl)propyl)piperazine), 1-(3-(ethoxydimethylsilyl)propyl)-4-(3-(triethoxysilyl)propyl)piperazine(1-(3-(ethoxydimethylsilyl) propyl)-4-(3-(triethoxysilyl)propyl)piperazine), 1-(3-(ethoxydimethyl)propyl)-4-(3-(triethoxysilyl)methyl)piperazine(1-(3- (ethoxydimethyl)propyl)-4-(3-(triethoxysilyl)methyl)piperazine), 1-(3-(ethoxydimethyl)methyl)-4-(3-(triethoxysilyl)propyl)piperazine(1- (3-(ethoxydimethyl)methyl)-4-(3-(triethoxysilyl)propyl)piperazine), 1,3-bis(3-(triethoxysilyl)propyl)imidazolidine (1,3-bis(3 -(triethoxysilyl)propyl)imidazolidine), 1,3-bis(3-(dimethoxyethylsilyl)propyl)imidazolidine (1,3-bis(3-(dimethoxyethylsilyl)propyl)imidazolidine), 1,3- Bis (3- (trimethoxysilyl) propyl) hexahydropyrimidine (1,3-bis (3- (trimethoxysilyl) propyl) hexahydropyrimidine), 1,3-bis (3- (triethoxysilyl) propyl) hexa Hydropyrimidine (1,3-bis(3-(triethoxysilyl)prop yl)hexahydropyrimidine) and 1,3-bis(3-(tributoxysilyl)propyl)-1,2,3,4-tetrahydropyrimidine (1,3-bis(3-(tributoxysilyl)propyl)-1 ,2,3,4-tetrahydropyrimidine) may be one selected from the group consisting of.

[Formula 5]

In Formula 5, R ³⁰ may be a monovalent hydrocarbon group having 1 to 30 carbon atoms, R ³¹ to R ³³ may each independently be an alkylene group having 1 to 10 carbon atoms, and R ³⁴ to R ³⁷ may each independently have a carbon number It may be an alkyl group of 1 to 10, and g and h are each independently an integer selected from 0 or 1 to 3, but g+h may be an integer of 1 or more.

[Formula 6]

In Formula 6, A ³ and A ⁴ may each independently be an alkylene group having 1 to 10, and R ³⁸ to R ⁴¹ may each independently be an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, , i may be an integer selected from 1 to 30.

According to one embodiment of the present invention, the modifier is 3,4-bis (2-methoxydeoxy) -N- (4- (triethoxysilyl) butyl) aniline (3,4-bis (2-methoxyethoxy )-N-(4-(trimethylsilyl)butyl)aniline), N,N-diethyl-3-(7-methyl-3,6,8,11-tetraoxa-7-silatridecan-7-yl) Propan-1-amine (N,N-diethyl-3-(7-methyl-3,6,8,11-tetraoxa-7-silatridecan-7-yl)propan-1-amine), 2,4-bis( 2-methoxydeoxy)-6-((trimethylsilyl)methyl)-1,3,5-triazine (2,4-bis(2-methoxyethoxy)-6-((trimethylsilyl)methyl)-1,3 ,5-triazine) and 3,14-dimethoxy-3,8,8,13-tetramethyl-2,14-dioxa-7,9-dithia-3,8,13-trisilapentadecane (3 ,13-dimethoxy-3,8,8,13-tetramethyl-2,14-dioxa-7,9-dithia-3,8,13-trisilapentadecane).

According to one embodiment of the present invention, the random copolymer may include one or more monomer units selected from the group consisting of an aromatic vinyl-based monomer unit, an olefin-based monomer unit, and a conjugated diene-based monomer unit. As a specific example, the random copolymer may be a random copolymer including an aromatic vinyl-based monomer unit and a conjugated diene-based monomer unit, or a random copolymer including the aromatic vinyl-based monomer unit and a conjugated diene-based monomer unit may be hydrogenated. The hydrogenated random copolymer may include an aromatic vinyl-based monomer unit and an olefin-based monomer unit.

According to one embodiment of the present invention, the aromatic vinyl monomer for forming the aromatic vinyl monomer unit of the random copolymer is styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, It may be at least one selected from the group consisting of 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, and 1-vinyl-5-hexylnaphthalene, and may be styrene as a specific example.

According to one embodiment of the present invention, the content of the aromatic vinyl-based monomer unit of the random copolymer is 5% to 50% by weight, 10% to 40% by weight, or 20% to 40% by weight with respect to the random copolymer. weight percent.

According to one embodiment of the present invention, the conjugated diene-based monomers for forming the conjugated diene-based monomer unit of the random copolymer are 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 a halogen atom) may be one or more selected from the group consisting of , As a specific example, it may be 1,3-butadiene. In addition, according to one embodiment of the present invention, the olefin-based monomer unit of the random copolymer may be formed by hydrogenation from a conjugated diene-based monomer unit. That is, the olefin-based monomer unit may be formed by hydrogenation of a conjugated diene-based monomer unit. In addition, the olefin-based monomer units of the random copolymer may include two or more types of olefin-based monomer units that are different from each other according to the bonding form of the conjugated diene-based monomer units to be hydrogenated. As a specific example, the conjugated diene-based monomer unit may be formed by 1,2-bonding or 1,4-bonding of the conjugated diene-based monomer during polymerization, and accordingly, the olefin-based monomer unit is formed by 1,2-bonding of the conjugated diene It may include an olefin-based monomer unit in which an olefin-based monomer unit is hydrogenated and a conjugated diene-based monomer unit formed by 1,4-bonding is hydrogenated. For example, when the conjugated diene monomer unit is 1,3-butadiene, the olefin monomer unit is a 1,2-linked conjugated diene monomer unit formed by hydrogenation of a 1-butene monomer unit, and a 1,4-butadiene monomer unit. The conjugated diene-based monomer unit formed by bonding may include a hydrogenated ethylene monomer unit. As such, the olefin-based monomer unit may be determined as two or more types of olefin-based monomer units in a substituted or unsubstituted form depending on the type and bonding form of the conjugated diene-based monomer unit to be hydrogenated.

According to one embodiment of the present invention, the olefin-based monomer unit of the random copolymer is selected from the group consisting of a substituted or unsubstituted ethylene monomer unit and a substituted or unsubstituted alpha-olefin monomer unit having 3 to 10 carbon atoms. It may include two or more types of monomer units, wherein the substituent of the substituted ethylene monomer unit and the substituted alpha-olefin monomer unit having 3 to 10 carbon atoms is an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms or a halogen group. As a specific example, the olefin-based monomer unit of the random copolymer may include an ethylene monomer unit and a 1-butene monomer unit.

According to one embodiment of the present invention, the content of the conjugated diene-based monomer unit or olefin-based monomer unit is 50% to 95% by weight, 60% to 90% by weight, or 60% to 60% by weight, based on the random copolymer. 80% by weight.

According to one embodiment of the present invention, the random copolymer may be a modified random copolymer including a functional group derived from an alkoxysilane-based modifier at at least one end thereof. The functional groups derived from the alkoxysilane-based modifier of the modified random copolymer may be formed by modification of the anionic active random copolymer with a modifier or coupling reaction during preparation of the random copolymer. The functional group derived from the alkoxysilane-based modifier of the modified random copolymer may be formed at one end of the anion-active random copolymer by a substitution reaction between the anion-active random copolymer and an alkoxy group in the alkoxysilane-based modifier. In addition, when the alkoxy group remaining in the alkoxysilane-based modifier-derived functional group is substituted with another random copolymer, a linking group derived from the modifier may be formed.

According to one embodiment of the present invention, the alkoxy silane-based modifier for forming the alkoxy silane-based modifier-derived functional group of the modified random copolymer may be an amino alkoxy silane-based modifier. When the denaturant further includes an amino group, that is, a functional group containing a nitrogen atom, affinity for the filler may be further improved.

According to an embodiment of the present invention, the alkoxy silane-based modifier for forming a functional group derived from the alkoxy silane-based modifier of the modified random copolymer is one or more compounds selected from the group consisting of compounds represented by Formulas 1 to 6 In this case, the alkoxysilane-based modifier for forming a functional group derived from the alkoxysilane-based modifier of the modified random copolymer may be the same as or different from the modifier for forming a linking group derived from the modifier of the hydrogenated block copolymer. have.

According to one embodiment of the present invention, the random copolymer is a random copolymer including an aromatic vinyl-based monomer unit and a conjugated diene-based monomer unit; hydrogenated random copolymers containing aromatic vinyl monomers and olefinic monomer units; A modified random copolymer including an aromatic vinyl-based monomer unit and a conjugated diene-based monomer unit, and including a functional group derived from an alkoxysilane-based modifier at at least one end thereof; and an aromatic vinyl-based monomer unit and an olefin-based monomer unit, and at least one selected from the group consisting of a hydrogenation-modified random copolymer including an alkoxysilane-based modifier-derived functional group at at least one end thereof.

According to one embodiment of the present invention, the rubber composition may further include other rubber components as needed in addition to the hydrogenation-modified block copolymer and the random copolymer, wherein the rubber component is based on the total weight of the rubber composition. It may be included in an amount of 90% by weight or less. As a specific example, the other rubber component may be included in an amount of 1 part by weight to 900 parts by weight based on 100 parts by weight of the hydrogenated block copolymer and the random copolymer.

According to one embodiment of the present invention, the rubber component may be natural rubber or synthetic rubber, and specific examples 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 obtained by modifying or refining the general natural rubber; Styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, polyisobutylene-co-isoprene, neoprene, poly(ethylene-co- propylene), poly(styrene-co-butadiene), poly(styrene-co-isoprene), poly(styrene-co-isoprene-co-butadiene), poly(isoprene-co-butadiene), poly(ethylene-co-propylene) -co-diene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, halogenated butyl rubber, and the like, and any one or a mixture of two or more of these may be used.

According to one embodiment of the present invention, the rubber composition may include a filler, and as a specific example, based on 100 parts by weight of the total of the hydrogenated block copolymer and the random copolymer, 0.1 part by weight to 200 parts by weight, Or 10 parts by weight to 120 parts by weight of the filler may be included.

According to one embodiment of the present invention, the filler may be at least one of a silica-based filler and a carbon black-based filler. As a specific example, the silica filler may be wet silica (hydrous silicic acid), dry silica (silicic anhydride), calcium silicate, aluminum silicate or colloidal silica. It may be wet silica that is most effective. In addition, the rubber composition may further include a carbon black-based filler, if necessary.

According to one embodiment of the present invention, when silica is used as the filler, a silane coupling agent for improving reinforcing properties and low heat generation properties may be used together. As a specific example, the silane coupling agent is bis(3-triethoxysilyl Propyl) 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-mercaptoethyl Trimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthio Carbamoyltetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilylpropylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzene Zolyltetrasulfide, 3-triethoxysilylpropylmethacrylate monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, bis(3-diethoxymethylsilylpropyl)tetrasulfide, 3-mer captopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide or dimethoxymethylsilylpropylbenzothiazolyltetrasulfide, etc., any one or a mixture of two or more of these may be can be used Preferably, considering the effect of improving reinforcing property, it may be bis(3-triethoxysilylpropyl) polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide.

According to one embodiment of the present invention, the silane coupling agent may be used in an amount of 1 part by weight to 20 parts by weight, or 5 parts by weight to 15 parts by weight based on 100 parts by weight of silica, and within this range, the effect as a coupling agent is sufficiently There is an effect of preventing gelation of the rubber component while being exhibited.

The rubber composition according to an embodiment of the present invention may be sulfur crosslinkable and may further include a vulcanizing agent. The vulcanizing agent may be a sulfur powder, and may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the rubber component. 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, vulcanization accelerators, process oils, antioxidants, plasticizers, anti-aging agents, anti-scorch agents, zinc white), stearic acid, a thermosetting resin, or a thermoplastic resin may be further included.

According to one embodiment of the present invention, the vulcanization accelerator is M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazylsulfenamide), etc. A thiazole-based compound 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 one 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. Considering loss and low temperature characteristics, naphthenic or paraffinic process oils can be used. The processing 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 tensile strength and low heat generation (low fuel consumption) of vulcanized rubber.

According to one embodiment of the present invention, the antioxidant is 2,6-di-t-butyl paracresol, dibutylhydroxytoluenyl, 2,6-bis ((dodecylthio) methyl) -4-nonylphenol (2,6-bis((dodecylthio)methyl)-4-nonylphenol) or 2-methyl-4,6-bis((octylthio)methyl)phenol (2-methyl-4,6-bis((octylthio)methyl )phenol), 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 one embodiment of the present invention, the anti-aging agent is 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., in an amount of 0.1 to 6 parts by weight based on 100 parts by weight of the rubber component. can be used

According to one embodiment of the present invention, the rubber composition is a tire tread, under tread, side wall, carcass coated rubber, belt coated rubber, bead filler, wiper, or each member of a tire, such as a bead coated rubber, or anti-vibration It can be useful for manufacturing various industrial rubber products such as rubber, belt conveyors, and hoses.

The present invention provides a tire manufactured using the rubber composition. According to one embodiment of the present invention, the tire may include a tire or a tire tread.

The present invention provides a rubber composition manufacturing method for preparing the rubber composition.

According to one embodiment of the present invention, the method for preparing the rubber composition includes the steps of preparing an anion-active aromatic vinyl-based polymer by adding and polymerizing an aromatic vinyl-based monomer in the presence of an organolithium compound (S10); preparing an anion-active diblock copolymer by adding and polymerizing a conjugated diene-based monomer in the presence of an anion-active aromatic vinyl-based polymer (S20); Preparing a modified block copolymer by adding and reacting a modifier in the presence of an anionic active diblock copolymer (S30); preparing a hydrogenated modified block copolymer by hydrogenating the modified block copolymer using hydrogen gas (S40); And a step (S50) of mixing a hydrogenated block copolymer and a random copolymer comprising one or more monomer units selected from the group consisting of an aromatic vinyl monomer unit and an olefin monomer unit and a conjugated diene monomer unit. it could be

According to one embodiment of the present invention, the step (S10) may be a step for preparing an aromatic vinyl-based polymer forming an aromatic vinyl-based polymer block. As a specific example, the step (S10) may be performed by anionic polymerization by introducing an aromatic vinyl-based monomer in a hydrocarbon-based solvent in the presence of an organolithium compound.

According to one embodiment of the present invention, the aromatic vinyl-based monomer for forming the aromatic vinyl-based polymer block is styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene , 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, and 1-vinyl-5-hexylnaphthalene, and may be at least one selected from the group consisting of, and may be styrene as a specific example.

According to one embodiment of the present invention, the input amount of the aromatic vinyl-based monomer in the step (S10) is the total amount of the aromatic vinyl-based monomer added in the step (S10) and the conjugated diene-based monomer added in the step (S20). 5% to 50% by weight, 10% to 40% by weight, or 20% to 40% by weight.

According to one embodiment of the present invention, the hydrocarbon-based solvent does not react with organolithium compounds, and can be used as long as it is usually used for anionic polymerization, and specific examples include butane, n-pentane, n-hexane, n-heptane or linear or branched aliphatic hydrocarbon compounds such as iso-octane; cyclic aliphatic hydrocarbon compounds unsubstituted or substituted with an alkyl group such as cyclopentane, cyclohexane, cycloheptane, methyl cyclohexane or methyl cycloheptane; and an aromatic hydrocarbon compound unsubstituted or substituted with an alkyl group such as benzene, toluene, xylene, or naphthalene, and any one or a mixture of two or more thereof may be used.

In addition, according to one embodiment of the present invention, the organolithium compound is a polymerization initiator for initiating an anionic polymerization reaction, and n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, ethyllithium, isopropyl It may be at least one selected from the group consisting of lithium, cyclohexyllithium, allyllithium, vinyllithium, phenyllithium, and benzyllithium.

According to one embodiment of the present invention, since the step (S10) is carried out by anionic polymerization, the aromatic vinyl polymer prepared in step (S10) may be an anionic active aromatic vinyl polymer, specifically, an anion. It can be obtained in a solution phase containing an active aromatic vinyl polymer.

According to one embodiment of the present invention, the step (S20) may be a step for preparing a diblock copolymer in which a conjugated diene-based polymer block is formed in addition to the aromatic vinyl-based polymer block. As a specific example, in the step (S20), a conjugated diene-based monomer is added to a solution containing the anion-active aromatic vinyl-based polymer obtained in the step (S10), in the presence of the anion-active aromatic vinyl-based polymer, by anionic polymerization. can be carried out. Here, the anion polymerization reaction for the conjugated diene-based monomer may be initiated from an anion-active aromatic vinyl-based polymer.

According to one embodiment of the present invention, the conjugated diene-based monomers for forming the conjugated diene-based polymer block are 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 a halogen atom) may be at least one selected from the group consisting of, and specific examples, It may be 1,3-butadiene.

According to an embodiment of the present invention, the input amount of the conjugated diene-based monomer in the step (S20) is the total amount of the aromatic vinyl monomer added in the step (S10) and the conjugated diene-based monomer added in the step (S20). , 50 wt% to 95 wt%, 60 wt% to 90 wt%, or 60 wt% to 80 wt%.

According to one embodiment of the present invention, since step (S20) is carried out by anionic polymerization, the diblock copolymer prepared in step (S20) may be an anionic active diblock copolymer, specifically, an anionic It can be obtained as a solution phase containing the active diblock copolymer.

According to one embodiment of the present invention, in the step (S30), a denaturant is introduced and reacted in the presence of the anion-active diblock copolymer in a solution containing the anion-active diblock copolymer obtained in the step (S20). This can be done by a coupling reaction. Here, the coupling reaction with the denaturant may be carried out from the anion active site of the anion active diblock copolymer.

According to one embodiment of the present invention, the modifier may be used in an amount of 0.01 mmol to 10 mmol based on 100 g of the total monomer. As another example, the modifier may be used in a molar ratio of 1:0.1 to 10, 1:0.1 to 5, or 1:0.1 to 1:3 based on 1 mole of the organic lithium compound in step (S10).

According to one embodiment of the present invention, since the step (S30) is performed by a coupling reaction, the modified block copolymer prepared in step (S30) includes an aromatic vinyl polymer block and a conjugated diene polymer block. The diblock copolymer may be a triblock copolymer connected by a modifier, and specifically, the triblock copolymer is added to the coupling agent in the solution containing the anionic active diblock copolymer obtained in step (S20). Since it is carried out by a coupling reaction by , it can be obtained in a solution phase containing a triblock copolymer.

According to one embodiment of the present invention, the modified block copolymer prepared in step (S30) has a number average molecular weight (Mn) of 100,000 g/mol to 150,000 g/mol, 105,000 g/mol to 140,000 g/mol, or It may be 110,000 g/mol to 132,000 g/mol.

According to an embodiment of the present invention, when the modified block copolymer prepared in step (S30) is reacted with a modifier in the presence of the anionic active diblock copolymer in step (S30), A diblock copolymer in which no coupling reaction has been performed may be included in the form of a composition. That is, in the conjugated diene-based polymer prepared in step (S30), the diblock copolymer including the aromatic vinyl-based polymer block and the conjugated diene-based polymer block in step (S20) is connected by a modifier to the triblock copolymer and the modifier. It may be a conjugated diene-based polymer composition comprising a diblock copolymer not connected by At this time, the content of the diblock copolymer may be 10% to 50% by weight, 20% to 45% by weight, or 30% to 43% by weight, and the content of the diblock copolymer is During the coupling reaction of the step, it may be adjusted according to the reaction environment and coupling efficiency.

According to one embodiment of the present invention, the step (S40) is a step of performing a hydrogenation reaction on the modified block copolymer prepared in the step (S30) using hydrogen gas, the hydrogenation reaction is represented by the following formula It may be carried out in the presence of a catalyst containing the compound represented by 7. In this case, during the hydrogenation reaction, decomposition of the modified block copolymer is prevented, and at the same time, hydrogenation is possible at a high hydrogenation rate.

[Formula 7]

In Formula 7, Cp is each independently a substituted or unsubstituted cyclopentadienyl group.

According to one embodiment of the present invention, the substituted cyclopentadienyl group may mean a cyclopentadienyl group substituted with a substituent other than hydrogen, and the unsubstituted cyclopentadienyl group is not substituted with a substituent other than hydrogen. It may mean a cyclopentadienyl group that is not.

According to one embodiment of the present invention, the compound represented by Chemical Formula 7 may be a compound represented by Chemical Formula 8 below.

[Formula 8]

In Formula 8, R ⁵¹ to R ⁶⁰ are each independently hydrogen, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, and a carbon atom group having 6 to 30 carbon atoms. It may be an aryl group having 30 carbon atoms, a heteroalkyl group having 1 to 30 carbon atoms, or a heterocyclic group having 5 to 30 ring atoms, or two adjacent ones of R ⁵¹ to R ⁶⁰ may be connected to each other to form a ring.

In specific examples, R ⁵¹ to R ⁶⁰ are each independently selected from hydrogen, 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 cycloalkyl group having 5 to 20 carbon atoms, and a cycloalkyl group having 6 to 20 carbon atoms. It may be an aryl group, a heteroalkyl group having 1 to 20 carbon atoms, or a heterocyclic group having 5 to 20 ring-forming atoms, or two adjacent ones of R ⁵¹ to R ⁶⁰ may be connected to each other to form a ring.

In more specific examples, R ⁵¹ to R ⁶⁰ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, and a carbon atom having 6 to 10 carbon atoms. It may be an aryl group having 10 carbon atoms, a heteroalkyl group having 1 to 10 carbon atoms, or a heterocyclic group having 5 to 10 ring atoms, or two adjacent ones of R ⁵¹ to R ⁶⁰ may be connected to each other to form a ring.

According to one embodiment of the present invention, the compound represented by Chemical Formula 7 may be an unsubstituted cyclopentadienyl group, and more specifically, the compound represented by Chemical Formula 7 may be a Tebbe reagent.

According to one embodiment of the present invention, the subject of the hydrogenation reaction in step (S40) is the conjugated diene-based monomer unit of the modified block copolymer prepared in step (S30) or the conjugated diene-based monomer of the conjugated diene-based polymer block. It may be a carbon-carbon double bond included in the unit. As a specific example, the hydrogenation reaction in step (S40) is performed on the unsaturated double bond included in the conjugated diene-based monomer unit of the modified block copolymer prepared in step (S30) or the conjugated diene-based monomer unit of the conjugated diene-based polymer block. It may be a reaction in which an unsaturated double bond becomes a saturated single bond by adding hydrogen. As a more specific example, in the hydrogenation reaction, an active catalyst is formed by electron distribution in the catalyst system, a π-complex is formed between the catalyst and the polymer, and hydrogen is added to the double bond. is carried out as

According to one embodiment of the present invention, the hydrogenation reaction in step (S40) includes: pressurizing a modified block copolymer using hydrogen gas to a reactor in which hydrogen gas is substituted (S41); Injecting the catalyst into the reactor into which the modified block copolymer is pressurized (S42); and increasing the pressure of the hydrogen gas inside the reactor into which the catalyst is introduced (S43).

According to one embodiment of the present invention, the catalyst introduced in the step (S42) may be dissolved in an organic solvent and introduced. The organic solvent may be a hydrocarbon-based solvent, and may be cyclohexane as a specific example.

According to one embodiment of the present invention, during the hydrogenation reaction, the pressure of the hydrogen gas may be 5 bar to 20 bar, 8 bar to 15 bar, or 9 bar to 12 bar, and safety during the hydrogenation reaction within this range While ensuring, there is an effect capable of conducting a hydrogenation reaction at a high hydrogenation rate.

According to one embodiment of the present invention, the catalyst has a Ti atom content of the compound represented by Formula 7 relative to the content of the modified block copolymer of 1 ppm to 10 ppm, 2 ppm to 8 ppm, or 4 ppm to 6 ppm It may be introduced so that it becomes, and there is an effect of securing a high hydrogenation rate during the hydrogenation reaction of the modified block copolymer within this range.

According to one embodiment of the present invention, the step (S50) includes at least one monomer unit selected from the group consisting of a hydrogenation-modified block copolymer, an aromatic vinyl monomer unit, an olefin monomer unit, and a conjugated diene monomer unit It may be a step for preparing a rubber composition by mixing a random copolymer.

According to one embodiment of the present invention, the mixing in step (S50) may be carried out by including the formulation described above in the rubber composition, and kneaded using a kneading machine such as a Banbury mixer, a roll, an internal mixer, etc. And, a rubber composition having excellent wear resistance can be obtained by a vulcanization process after molding.

According to one embodiment of the present invention, the random copolymer comprising the aromatic vinyl monomer unit of the step (S50) and at least one monomer unit selected from the group consisting of an olefin monomer unit and a conjugated diene monomer unit. It may be produced through a step separate from the hydrogenation-modified block copolymer prepared from steps (S10) to (S40). As a specific example, the random copolymer comprising the aromatic vinyl monomer unit and at least one monomer unit selected from the group consisting of an olefin monomer unit and a conjugated diene monomer unit may be the same as the random copolymer described above in the rubber composition. can

According to an embodiment of the present invention, the random copolymer is prepared by introducing an aromatic vinyl monomer and a conjugated diene monomer in the presence of an organolithium compound and polymerizing to prepare an anionic active random copolymer (S100) may be manufactured.

According to an embodiment of the present invention, the step (S100) may be performed by anionic polymerization by introducing an aromatic vinyl monomer and a conjugated diene monomer in the presence of an organolithium compound in a hydrocarbon solvent.

According to one embodiment of the present invention, the aromatic vinyl monomers introduced in the step (S100) are styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4 It may be at least one selected from the group consisting of -cyclohexyl styrene, 4-(p-methylphenyl)styrene, and 1-vinyl-5-hexylnaphthalene, and may be styrene as a specific example.

According to one embodiment of the present invention, the input content of the aromatic vinyl-based monomer in the step (S100) is 5% to 50% by weight based on the total content of the aromatic vinyl-based monomer and the conjugated diene-based monomer added in the step (S100). wt%, 10 wt% to 40 wt%, or 20 wt% to 40 wt%.

According to an embodiment of the present invention, the conjugated diene-based monomers introduced in the step (S100) are 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3 -It may be at least one selected from the group consisting of octadiene, isoprene, 2-phenyl-1,3-butadiene and 2-halo-1,3-butadiene (halo means a halogen atom), and specific examples include 1, It may be 3-butadiene.

According to one embodiment of the present invention, the input content of the conjugated diene-based monomer in the step (S100) is 50% to 95% by weight based on the total content of the aromatic vinyl monomer and the conjugated diene-based monomer added in the step (S100). wt%, 60 wt% to 90 wt%, or 60 wt% to 80 wt%.

According to an embodiment of the present invention, in the step (S100), the hydrocarbon-based solvent does not react with the organolithium compound and can be used as long as it is normally used for anionic polymerization, and specific examples include butane, n-pentane, and n-hexane. , linear or branched aliphatic hydrocarbon compounds such as n-heptane or iso-octane; cyclic aliphatic hydrocarbon compounds unsubstituted or substituted with an alkyl group such as cyclopentane, cyclohexane, cycloheptane, methyl cyclohexane or methyl cycloheptane; and an aromatic hydrocarbon compound unsubstituted or substituted with an alkyl group such as benzene, toluene, xylene, or naphthalene, and any one or a mixture of two or more thereof may be used.

According to an embodiment of the present invention, in the step (S100), the organolithium compound is a polymerization initiator for initiating an anionic polymerization reaction, and n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, ethyllithium , isopropyllithium, cyclohexyllithium, allyllithium, vinyllithium, phenyllithium, and benzyllithium.

According to one embodiment of the present invention, since the step (S100) is carried out by anionic polymerization, the random copolymer prepared in step (S100) may be an anionic active random copolymer, specifically, an anionic active random copolymer. It can be obtained in a solution phase containing a copolymer.

According to an embodiment of the present invention, the random copolymer prepared in the step (S100) is a random copolymer comprising an aromatic vinyl monomer unit and a conjugated diene monomer unit by removing anionic activity by adding alcohol or the like. can be obtained

According to one embodiment of the present invention, the random copolymer is prepared by adding an alkoxysilane-based modifier and reacting in the presence of the anionic active random copolymer prepared in step (S100) to prepare a modified random copolymer ( S200) may be prepared.

According to an embodiment of the present invention, in the step (S200), in the presence of the anionic active random copolymer, an alkoxy silane-based modifier is added to the solution containing the anionic active random copolymer obtained in the step (S100) It may be carried out by a denaturation reaction or a coupling reaction. Here, the denaturation or coupling reaction with the alkoxy silane-based modifier may be carried out from the anion active site of the anion active random copolymer.

According to one embodiment of the present invention, the alkoxysilane-based modifier added in step (S200) may be used in an amount of 0.01 mmol to 10 mmol based on 100 g of the total monomer. As another example, the alkoxysilane-based 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 organolithium compound in step (S100). have.

According to an embodiment of the present invention, the random copolymer prepared in step (S200) includes an aromatic vinyl monomer unit and a conjugated diene monomer unit by removing anionic activity by adding alcohol or the like, and at least one end thereof. It can be obtained as a modified random copolymer containing a functional group derived from an alkoxysilane-based modifier.

According to an embodiment of the present invention, the random copolymer is obtained by hydrogenating the random copolymer obtained in the step (S100) or the modified random copolymer obtained in the step (S200) using hydrogen gas. It may be prepared by including the step of preparing a hydrogenated random copolymer or a hydrogenated modified random copolymer (S300).

According to one embodiment of the present invention, in the step (S300), the random copolymer obtained in the step (S100) or the modified random copolymer obtained in the step (S200) is hydrogenated using hydrogen gas. As a step of carrying out the reaction, the hydrogenation reaction may be carried out in the presence of a catalyst containing the compound represented by Chemical Formula 7. In this case, during the hydrogenation reaction, the random copolymer or the modified random copolymer is prevented from being decomposed, and at the same time, hydrogenation is possible at a high hydrogenation rate.

According to an embodiment of the present invention, the object of the hydrogenation reaction in the step (S300) is the conjugated diene-based monomer of the random copolymer obtained in the step (S100) or the modified random copolymer obtained in the step (S200). It may be a carbon-carbon double bond included in the unit. As a specific example, the hydrogenation reaction in step (S300) is performed on the unsaturated double bonds included in the conjugated diene-based monomer units of the random copolymer obtained in step (S100) or the modified random copolymer obtained in step (S200). It may be a reaction in which an unsaturated double bond becomes a saturated single bond by adding hydrogen. As a more specific example, in the hydrogenation reaction, an active catalyst is formed by electron distribution in the catalyst system, a π-complex is formed between the catalyst and the polymer, and hydrogen is added to the double bond. is carried out as

According to an embodiment of the present invention, the hydrogenation reaction in the step (S300) includes the steps of pressurizing a random copolymer or a modified random copolymer using hydrogen gas to a hydrogen gas-substituted reactor (S310); Injecting the catalyst into the reactor in which the random copolymer or the modified random copolymer is pumped (S320); and increasing the pressure of the hydrogen gas inside the reactor into which the catalyst is introduced (S330).

According to one embodiment of the present invention, the catalyst introduced in the step (S320) may be dissolved in an organic solvent and introduced. The organic solvent may be a hydrocarbon-based solvent, and may be cyclohexane as a specific example.

According to one embodiment of the present invention, during the hydrogenation reaction, the pressure of the hydrogen gas may be 5 bar to 20 bar, 8 bar to 15 bar, or 9 bar to 12 bar, and safety during the hydrogenation reaction within this range While ensuring, there is an effect capable of conducting a hydrogenation reaction at a high hydrogenation rate.

According to one embodiment of the present invention, the catalyst has a Ti atom content of the compound represented by Formula 7 relative to the amount of the random copolymer or the modified random copolymer of 1 ppm to 10 ppm, 2 ppm to 8 ppm, or It may be added so as to be 4 ppm to 6 ppm, and there is an effect of securing a high hydrogenation rate during hydrogenation of a random copolymer or a modified random copolymer within this range.

According to one embodiment of the present invention, the random copolymer may be prepared by including the steps (S100) and (S300), in this case, as a hydrogenated random copolymer containing an aromatic vinyl monomer and an olefin monomer unit can be obtained In addition, the random copolymer may be prepared by including steps (S100), (S200) and (S300), and in this case, it includes an aromatic vinyl monomer unit and an olefin monomer unit, and at least one end thereof has an alkoxy group. It can be obtained as a hydrogenation-modified random copolymer containing a functional group derived from a silane-based modifier.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement 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

<Hydrogenated Modified Block Copolymer>

After purging the inside of the 10 L autoclave reactor with nitrogen gas, 4,500 g of cyclohexane, 65 g of styrene, and 0.6 g of tetramethylethylenediamine were introduced, and the temperature inside the reactor was raised to 50°C. Subsequently, 0.79 g of n-butyllithium was added and polymerization was performed for 30 minutes. Subsequently, 435 g of 1,3-butadiene was added and a polymerization reaction was performed for 30 minutes. Then, 0.52 g of 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine) was added and stirred for 10 minutes. A modified styrene-butadiene-styrene block copolymer (M-SBS) was prepared by liver reaction. At this time, the number average molecular weight of the prepared modified block copolymer was 125,000 g / mol, and the content of the diblock copolymer was 36% by weight.

Then, after replacing the inside of the 2 L autoclave reactor with hydrogen gas, 1,000 g of the prepared modified styrene-butadiene-styrene block copolymer (M-SBS) was pumped using hydrogen gas at 1 bar. After the pumping is complete, the internal temperature of the reactor is stabilized at 70 ° C., and Tebbe reagent (CAS No. 67719-69-1) is dissolved in 2 g of cyclohexane so that the content of Ti atoms relative to the copolymer is 5 ppm. , was put into the reactor. Thereafter, the hydrogen gas pressure inside the reactor was increased to 10 bar, and then the reaction was performed for 2 hours. After completion of the reaction, methanol was added to precipitate and recover modified styrene-ethylene-butylene-styrene block copolymer (M-SEBS), which is a hydrogenation-modified styrene-butadiene-styrene block copolymer.

<Random Copolymer>

After replacing the inside of the 10 L autoclave reactor with nitrogen gas, 4,500 g of cyclohexane, 65 g of styrene, 435 g of 1,3-butadiene, and 0.6 g of tetramethylethylenediamine were introduced, and the temperature inside the reactor was raised to 50 ° C. The temperature was raised. Subsequently, 0.64 g of n-butyllithium was added and a polymerization reaction was performed for 30 minutes to prepare a styrene-butadiene random copolymer (SSBR). At this time, the number average molecular weight of the prepared random copolymer was 127,000 g/mol.

<Rubber composition>

The above-prepared hydrogenation-modified block copolymer and random copolymer were mixed under the compounding conditions shown in Table 1 below as raw material rubber. The content of raw materials in Table 1 is each part by weight based on 100 parts by weight of raw rubber.

division Raw material Content (parts by weight) 1st stage kneading Hydrogenated Modified Block Copolymer 50 random copolymer 50 silica 770 Coupling agent (X50S) 11.2 fair oil 37.5 zincating agent 3 stearic acid 2 antioxidant 2 anti aging 2 wax One 2nd stage kneading sulfur 1.5 rubber accelerator 1.75 Vulcanization accelerator 2

Specifically, the rubber composition was kneaded through first stage kneading and second stage kneading. In the first stage kneading, raw material rubber (hydrogenated block copolymer and random copolymer), silica (filler), organosilane coupling agent (X50S, Evonik), process oil (TDAE) are mixed using a Banbari mixer equipped with a temperature controller. oil), zincating agent (ZnO), stearic acid, antioxidant (TMQ(RD) (2,2,4-trimethyl-1,2-dihydroquinoline polymer), antioxidant (6PPD ((dimethylbutyl)-N- Phenyl-phenylenediamine) and wax (Microcrystaline Wax) were kneaded.At this time, the initial temperature of the kneader was controlled to 70 ° C, and after mixing was completed, a first mixture was obtained at a discharge temperature of 145 ° C to 155 ° C. However, in kneading, after cooling the primary compound to room temperature, the primary compound, sulfur, rubber accelerator (DPD (diphenylguanine)) and vulcanization accelerator (CZ (N-citlohexyl-2-benzothiazylsulfene) amide)) was added and mixed at a temperature of 100° C. or lower to obtain a secondary compound, and then, a rubber composition was prepared through a curing process at 160° C. for 20 minutes.

Example 2

In Example 1, when preparing the rubber composition, the same as in Example 1 except that the modified random copolymer (M-SSBR) prepared as follows was used instead of the styrene-butadiene random copolymer (SSBR) as the random copolymer. method was carried out.

<Modified random copolymer>

After replacing the inside of the 10 L autoclave reactor with nitrogen gas, 4,500 g of cyclohexane, 65 g of styrene, 435 g of 1,3-butadiene, and 0.6 g of tetramethylethylenediamine were introduced, and the temperature inside the reactor was raised to 50 ° C. The temperature was raised. Subsequently, 0.79 g of n-butyllithium was added and polymerization was performed for 30 minutes. Then, 0.52 g of 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine) was added and stirred for 10 minutes. A modified styrene-butadiene random copolymer (M-SSBR) was prepared by liver reaction. At this time, the number average molecular weight of the modified random copolymer prepared was 126,000 g/mol.

Example 3

In Example 1, in the preparation of the rubber composition, in the same manner as in Example 1 except for using a hydrogenated random copolymer (HSSBR) prepared as follows instead of a styrene-butadiene random copolymer (SSBR) as a random copolymer. conducted.

<Hydrogenated random copolymer>

After replacing the inside of the 10 L autoclave reactor with nitrogen gas, 4,500 g of cyclohexane, 65 g of styrene, 435 g of 1,3-butadiene, and 0.6 g of tetramethylethylenediamine were introduced, and the temperature inside the reactor was raised to 50 ° C. The temperature was raised. Subsequently, 0.64 g of n-butyllithium was added and a polymerization reaction was performed for 30 minutes to prepare a styrene-butadiene random copolymer (SSBR). At this time, the number average molecular weight of the prepared random copolymer was 127,000 g/mol.

Then, after replacing the inside of the 2 L autoclave reactor with hydrogen gas, 1,000 g of the prepared styrene-butadiene random copolymer (SSBR) was pumped using hydrogen gas at 1 bar. After completion of pumping, the internal temperature of the reactor was stabilized at 70 ° C., and Tebbe reagent (CAS No. 67719-69-1) was dissolved in 2 g of cyclohexane so that the content of Ti atoms compared to the copolymer was 5 ppm. , was put into the reactor. Thereafter, the hydrogen gas pressure inside the reactor was increased to 10 bar, and then the reaction was performed for 2 hours. After completion of the reaction, methanol was added to precipitate and recover a styrene-ethylene-butylene random copolymer, which is a hydrogenated styrene-butadiene random copolymer (HSSBR).

Example 4

In Example 1, except for using a hydrogenated modified random copolymer (M-HSSBR) prepared as follows instead of a styrene-butadiene random copolymer (SSBR) as a random copolymer when preparing the rubber composition, the same as in Example 1 It was carried out in the same way.

<Hydrogenation Modified Random Copolymer>

After replacing the inside of the 10 L autoclave reactor with nitrogen gas, 4,500 g of cyclohexane, 65 g of styrene, 435 g of 1,3-butadiene, and 0.6 g of tetramethylethylenediamine were introduced, and the temperature inside the reactor was raised to 50 ° C. The temperature was raised. Subsequently, 0.79 g of n-butyllithium was added and polymerization was performed for 30 minutes. Then, 0.52 g of 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine) was added and stirred for 10 minutes. A modified styrene-butadiene random copolymer (M-SSBR) was prepared by liver reaction. At this time, the number average molecular weight of the modified random copolymer prepared was 126,000 g/mol.

Subsequently, after purging the inside of the 2 L autoclave reactor with hydrogen gas, 1,000 g of the prepared modified styrene-butadiene random copolymer (M-SSBR) was pumped using hydrogen gas at 1 bar. After the pumping is complete, the internal temperature of the reactor is stabilized at 70 ° C., and Tebbe reagent (CAS No. 67719-69-1) is dissolved in 2 g of cyclohexane so that the content of Ti atoms relative to the copolymer is 5 ppm. , was put into the reactor. Thereafter, the hydrogen gas pressure inside the reactor was increased to 10 bar, and then the reaction was performed for 2 hours. After completion of the reaction, methanol was added to precipitate and recover a modified styrene-ethylene-butylene random copolymer, which is a hydrogenated modified styrene-butadiene random copolymer (M-HSSBR).

Comparative Example 1

In Example 1, the rubber composition was prepared in the same manner as in Example 1, except that only 100 parts by weight of the random copolymer was used without containing the hydrogenation-modified block copolymer as the raw rubber.

Comparative Example 2

In Example 2, the rubber composition was prepared in the same manner as in Example 1, except that only 100 parts by weight of the modified random copolymer was used without containing the hydrogenation-modified block copolymer as the raw material rubber.

Comparative Example 3

In Example 1 above, When preparing the rubber composition, the same method as in Example 1 was performed except that only 100 parts by weight of the hydrogenation-modified block copolymer was used without including the random copolymer as the raw rubber, but the processability was extremely poor, so the measurement of physical properties was difficult. It was not possible to prepare a rubber composition for

Experimental example

In order to compare and analyze the physical properties of the rubber compositions prepared in Examples 1 to 4 and Comparative Examples 1 and 2 and molded articles prepared therefrom, viscoelastic properties and wear resistance were measured, respectively, and the results are shown in Table 2 below.

* Viscoelastic properties: For the viscoelastic properties, the tan δ value was measured by measuring the viscoelastic behavior for dynamic deformation at a frequency of 10 Hz and each measurement temperature (-60 ℃ ~ 60 ℃) in Film Tension mode using a dynamic mechanical analyzer (GABO). Confirmed. In the measurement results, the lower the high temperature 60 ℃ tanδ value, the lower the hysteresis loss and the better the low running resistance (fuel economy). As shown, the higher the number, the better.

* Abrasion resistance: Abrasion resistance is a comparative example of the amount of abrasion after moving a rubber specimen in a direction perpendicular to the direction of drum rotation by applying a load of 10 N to a rotating drum with a safety walk attached using a DIN abrasion tester. It is expressed as Index (%) based on the wear amount of 1. The rotational speed of the drum is 40 rpm, and the total moving distance of the specimen upon completion of the test is 40 m.

division Example comparative example One 2 3 4 One 2 60 °C tan δ 113 121 111 122 100 121 wear resistance 115 117 123 121 100 99

As shown in Table 2, in the case of the rubber composition of Comparative Example 2 including the modified random copolymer obtained by modifying the random copolymer, the viscoelastic properties are improved compared to Comparative Example 1 including the random copolymer, but the wear resistance is rather deteriorated. can confirm that it is. On the other hand, the rubber compositions of Examples 1 to 4 including the hydrogenation-modified block copolymer according to the present invention have not only improved viscoelastic properties compared to Comparative Example 1 containing only a random copolymer as a raw material rubber component, but also significantly improved abrasion resistance. improvement could be observed.

From these results, it was confirmed that the rubber composition of the present invention has excellent fuel consumption performance due to low rolling resistance and particularly excellent abrasion resistance.

Claims (13)

hydrogenation-modified block copolymers comprising an aromatic vinyl-based polymer block, an olefin-based polymer block comprising an olefin-based monomer unit, and a linking group derived from a modifier; and
A rubber composition comprising a random copolymer comprising an aromatic vinyl monomer unit and at least one monomer unit selected from the group consisting of an olefin monomer unit and a conjugated diene monomer unit. According to claim 1,
The rubber composition wherein the weight ratio of the hydrogenation-modified block copolymer and the random copolymer is 10:90 to 90:10. According to claim 1,
The rubber composition wherein the weight ratio of the hydrogenation-modified block copolymer and the random copolymer is 40:60 to 60:40. According to claim 1,
The rubber composition wherein the modifier is an alkoxy silane-based modifier. According to claim 1,
The rubber composition comprising the modifier comprising at least one compound selected from the group consisting of compounds represented by Formulas 1 to 6 below:
[Formula 1]

In Formula 1,
R ¹ is a single bond or an alkylene group having 1 to 10 carbon atoms;
R ² and R ³ are each independently an alkyl group having 1 to 10 carbon atoms;
R ⁴ is hydrogen, an alkyl group having 1 to 10 carbon atoms, a divalent, trivalent or tetravalent alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, or a heterocyclic group having 2 to 10 carbon atoms;
R ²¹ is a single bond, an alkylene group having 1 to 10 carbon atoms, or -[R ⁴² O] _j -, R ⁴² is an alkylene group having 1 to 10 carbon atoms,
a and m are each independently an integer selected from 1 to 3, n is an integer of 0, 1, or 2, j is an integer selected from 1 to 30,
[Formula 2]

In Formula 2,
R ⁵ , R ⁶ and R ⁹ are each independently an alkylene group having 1 to 10 carbon atoms;
R ⁷ , R ⁸ , R ¹⁰ and R ¹¹ are each independently an alkyl group having 1 to 10 carbon atoms;
R ¹² is hydrogen or an alkyl group having 1 to 10 carbon atoms;
b and c are each independently 0, 1, 2 or 3, b+c≥1,
A is a linking group represented by Formula 2-1 or Formula 2-2, wherein R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms;
[Formula 2-1]

[Formula 2-2]

[Formula 3]

In Formula 3,
A ¹ and A ² are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms with or without an oxygen atom;
R ¹⁷ to R ²⁰ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms;
L ¹ to L ⁴ are each independently a divalent, trivalent or tetravalent alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or L ¹ and L ² and L ³ and L ⁴ may be connected to each other to form a ring having 1 to 5 carbon atoms, and when L ¹ and L ² and L ³ and L ⁴ are connected to each other to form a ring, the formed ring is N, O and S Contains 1 to 3 at least one heteroatom selected from the group consisting of
[Formula 4]

In Formula 4,
R ²² and R ²³ are each independently an alkylene group having 1 to 20 carbon atoms or -R ²⁸ [OR ²⁹ ] _f -;
R ²⁴ to R ²⁷ are each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms;
R ²⁸ and R ²⁹ are each independently an alkylene group having 1 to 20 carbon atoms;
R ⁴⁷ and R ⁴⁸ are each independently a divalent hydrocarbon group having 1 to 6 carbon atoms;
d and e are each independently 0 or an integer selected from 1 to 3, d + e is an integer greater than or equal to 1, f is an integer from 1 to 30,
[Formula 5]

In Formula 5,
R ³⁰ is a monovalent hydrocarbon group having 1 to 30 carbon atoms;
R ³¹ to R ³³ are each independently an alkylene group having 1 to 10 carbon atoms;
R ³⁴ to R ³⁷ are each independently an alkyl group having 1 to 10 carbon atoms;
g and h are each independently 0 or an integer selected from 1 to 3, but g + h is an integer of 1 or more;
[Formula 6]

In Formula 6,
A ³ and A ⁴ are each independently an alkylene group of 1 to 10;
R ³⁸ to R ⁴¹ are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and i is an integer selected from 1 to 30. According to claim 1,
The random copolymer is a rubber composition comprising an aromatic vinyl-based monomer unit and a conjugated diene-based monomer unit. According to claim 1,
The random copolymer is a rubber composition comprising an aromatic vinyl-based monomer unit and an olefin-based monomer unit. According to claim 1,
The random copolymer is a rubber composition that is a modified random copolymer including a functional group derived from an alkoxysilane-based modifier at at least one end. According to claim 1,
The rubber composition of the rubber composition comprising a filler. According to claim 9,
The rubber composition comprises 0.1 part by weight to 200 parts by weight of a filler based on 100 parts by weight of the total of the hydrogenation-modified block copolymer and the random copolymer. According to claim 9,
The rubber composition of claim 1, wherein the filler is at least one of a silica-based filler and a carbon black-based filler. In the presence of an organolithium compound, an aromatic vinyl-based monomer is introduced and polymerized to prepare an anionic active aromatic vinyl-based polymer (S10);
preparing an anion-active diblock copolymer by adding and polymerizing a conjugated diene-based monomer in the presence of an anion-active aromatic vinyl-based polymer (S20);
Preparing a modified block copolymer by adding and reacting a modifier in the presence of an anionic active diblock copolymer (S30);
preparing a hydrogenated modified block copolymer by hydrogenating the modified block copolymer using hydrogen gas (S40); and
A step (S50) of mixing a hydrogenated block copolymer, an aromatic vinyl monomer unit, and a random copolymer comprising at least one monomer unit selected from the group consisting of an olefin monomer unit and a conjugated diene monomer unit. Method for preparing the composition. According to claim 12,
The hydrogenation reaction in step (S40) is carried out in the presence of a catalyst containing a compound represented by Formula 7 below:
[Formula 7]

In Formula 7,
Cp is each independently a substituted or unsubstituted cyclopentadienyl group.