KR20210060107A - Copolymer, manufacturing method thereof and rubber composition comprising the same - Google Patents

Abstract

The present invention relates to a copolymer, a manufacturing method thereof and a rubber composition comprising the same, wherein the rubber composition comprising the copolymer according to the present invention has excellent processability, and a molded article (eg, a tire) manufactured by using the same has excellent fuel efficiency characteristics. The copolymer comprises a repeating unit derived from a conjugated diene-based monomer; and a repeating unit derived from an aromatic vinyl monomer.

Description

Copolymer, a manufacturing method thereof, and a rubber composition comprising the same TECHNICAL FIELD [0002] COPOLYMER, MANUFACTURING METHOD THEREOF AND RUBBER COMPOSITION COMPRISING THE SAME}

The present invention relates to a copolymer, a method for producing the same, and a rubber composition comprising the same. In more detail, the present invention is a repeating unit derived from a conjugated diene-based monomer having high binding efficiency with silica; And a repeating unit derived from an aromatic vinyl-based monomer, and a method for producing the same.

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

Carbon black and silica are used as reinforcing fillers for tire treads, and when silica is used as a reinforcing filler, low hysteresis loss and wet skid resistance are improved. However, silica on a hydrophilic surface compared to carbon black on a hydrophobic surface has a disadvantage of poor dispersibility due to low affinity with rubber. It is necessary to use a ring agent.

Accordingly, a method of introducing a functional group having affinity or reactivity with silica at the end of the rubber molecule has been made, but the effect is not sufficient. In addition, when the modified styrene-butadiene copolymerization is performed, the manufacturing efficiency is low and the effect of denaturation may be insufficient.

Korean Patent Publication No. 10-2016-0071337 discloses a styrene-butadiene copolymer terminally modified with a specific amino silane modifier. Although this compound exhibited an effect of improving fuel economy characteristics and grip power through terminal modification, it has a limitation in that the method of preparing a denaturant is very difficult.

An object of the present invention is to solve the above problems to provide a copolymer having a modified end of a copolymer having high efficiency with silica, and a method for producing the same. The copolymer according to the exemplary embodiment of the present invention can improve the physical properties of rubber by improving dispersibility and affinity when mixing silica.

An exemplary embodiment of the present invention is a repeating unit derived from a conjugated diene-based monomer; And

A copolymer containing a repeating unit derived from an aromatic vinyl monomer,

At least one of both ends of the copolymer provides a copolymer comprising a unit represented by the following formula (1).

[Formula 1]

In Formula 1,

n is an integer from 1 to 50,

E is an alkyl group having 1 to 10 carbon atoms,

R ₁ to R ₅ are each independently hydrogen; Hydroxy group; A hydrocarbon group having 1 to 20 carbon atoms; Or a hydrocarbon group having 1 to 20 carbon atoms in which at least one carbon atom is substituted with a hetero atom selected from the group consisting of O, S and N; or adjacent substituents are bonded to each other to form a hydrocarbon ring or a hetero ring,

Two or more of R ₁ to R _{5 are hydroxy groups;} Or a hydrocarbon group having 1 to 20 carbon atoms in which at least one carbon atom is substituted with a hetero atom selected from the group consisting of O, S, and N; Or, adjacent substituents are bonded to each other to form a heterocycle.

In addition, an exemplary embodiment of the present invention is a first step of polymerizing a conjugated diene-based monomer and an aromatic vinyl-based monomer in the presence of an organometallic compound in a hydrocarbon solvent; And

It provides a method for producing the above-described copolymer comprising; a second step of reacting the polymer with a compound represented by the following formula (2).

[Formula 2]

In Formula 2,

L ₁ is a halogen group; Or an alkenyl group,

R ₁ to R ₅ are each independently hydrogen; Hydroxy group; A hydrocarbon group having 1 to 20 carbon atoms; Or a hydrocarbon group having 1 to 20 carbon atoms in which at least one carbon atom is substituted with a hetero atom selected from the group consisting of O, S, and N; Or, adjacent substituents are bonded to each other to form a hydrocarbon ring or a hetero ring,

Two or more of R ₁ to R _{5 are hydroxy groups;} Or a hydrocarbon group having 1 to 20 carbon atoms in which at least one carbon atom is substituted with a hetero atom selected from the group consisting of O, S, and N; Or, adjacent substituents are bonded to each other to form a heterocycle.

Another embodiment of the present invention provides a rubber composition comprising the above-described copolymer.

Finally, an exemplary embodiment of the present invention provides a molded article formed using the rubber composition.

The copolymer according to the exemplary embodiment of the present invention includes a unit of a silica affinity group represented by Chemical Formula 1 at at least one of both ends, and has high binding efficiency with silica. Accordingly, when the rubber composition comprising the copolymer of the present invention is blended with an inorganic filler such as silica, it is possible to provide a rubber composition having excellent affinity with the filler, improved dispersibility, and high binding efficiency.

The rubber composition containing the copolymer is excellent in processability.

In addition, a molded article (eg, tire or tire tread) formed using the rubber composition may have excellent tensile strength, abrasion resistance, and fuel economy characteristics.

Hereinafter, the present specification will be described in detail.

In the present specification, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components unless specifically stated to the contrary.

In the present specification, "hydrocarbon group" refers to a monovalent organic radical formed by removing a hydrogen atom from a hydrocarbon as a hydrocarbon group consisting only of carbon and hydrogen regardless of the structure such as an alkyl group, an aryl group, an alkylaryl group, an arylalkyl group, and the like, It may be the same as the example of the organic groups described above, but is not limited thereto.

In addition, the term "alkyl group" described herein refers to a monovalent linear, branched or cyclic saturated hydrocarbon group composed of only carbon and hydrogen atoms, and is a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl Group, t-butyl group, pentyl group, hexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and the like, but are not limited thereto.

In addition, the term "aryl group" described herein refers to an organic group derived from an aromatic hydrocarbon by removal of one hydrogen, and includes a single or fused ring system. Specific examples of the aryl group include phenyl group, naphthyl group, biphenyl group, anthryl group, fluorenyl group, phenanthryl group, triphenylenyl group, pyrenyl group, perylenyl group, chrysenyl group, naphthacenyl group, fluorane Including, but not limited to, tenyl group and the like.

In addition, the term "alkylaryl group" described herein refers to an organic group in which at least one hydrogen of the aryl group is substituted by an alkyl group, and is methylphenyl group, ethylphenyl group, n-propylphenyl group, iso-propylphenyl group, n-butyl Phenyl group, iso-butylphenyl group, tert-butylphenyl group, and the like, but are not limited thereto.

In addition, the term "arylalkyl group" described herein refers to an organic group in which at least one hydrogen of an alkyl group is substituted by an aryl group, and includes, but is not limited to, a phenylpropyl group, a phenylhexyl group, and the like.

In the present specification, the term "substituted" means that a carbon atom included in the hydrocarbon group of the compound is substituted with a hetero atom selected from the group consisting of O, S, and N. For example, when a C1 hydrocarbon group is substituted with O, it may be a hydroxy group, and when two or more hydrocarbon groups are substituted with O, it may be an alkoxy group or an ether group.

In the present specification, the hydrocarbon group or the hydrocarbon group in which at least one carbon atom is substituted with a hetero atom selected from the group consisting of O, S and N is a hydrocarbon group and at least one carbon atom is a hetero atom selected from the group consisting of O, S and N It may be further substituted with one or two or more substituents selected from the group consisting of substituted hydrocarbon groups. Here, the term substitution may mean that a hydrogen atom in the hydrocarbon group is replaced with another organic group.

In the present specification, the "adjacent" group means a substituent substituted on an atom directly connected to the atom where the corresponding substituent is substituted, a substituent located three-dimensionally closest to the corresponding substituent, or another substituent substituted on the atom where the corresponding substituent is substituted. I can. For example, two substituents substituted with an ortho position in a benzene ring and two substituents substituted with the same carbon in an aliphatic ring may be interpreted as "adjacent" to each other.

In the present specification, "adjacent substituents are bonded to each other to form a ring" means that a substituted or unsubstituted hydrocarbon group or at least one substituted or unsubstituted carbon atom is substituted with a hetero atom selected from the group consisting of O, S, and N. It may mean that hydrocarbon groups having 1 to 20 carbon atoms are bonded to each other to form a ring. In the present specification, the hydrocarbon ring may be an aliphatic, aromatic, or condensed ring of aliphatic and aromatic, and except for a monovalent group, a cyclo The heterocycle may be an aliphatic, aromatic, or condensed ring of an aliphatic and aromatic group, and may be selected from examples of a heterocyclic group except that it is not a monovalent group.

In the present specification, the'monomer-derived repeating unit' may represent a component, structure, or substance itself derived from a monomer, and during polymerization of the polymer, the introduced monomer participates in the polymerization reaction and refers to a repeating unit formed in the polymer. Can be.

In the present specification, the meaning of "including a unit" may mean that it is included in the main chain in the polymer.

An exemplary embodiment of the present specification is a repeating unit derived from a conjugated diene-based monomer; And a repeating unit derived from an aromatic vinyl-based monomer, wherein at least one of both ends of the copolymer comprises a unit represented by the following formula (1).

[Formula 1]

In Formula 1,

n is an integer from 1 to 50,

E is an alkyl group having 1 to 10 carbon atoms,

R ₁ to R ₅ are each independently hydrogen; Hydroxy group; A hydrocarbon group having 1 to 20 carbon atoms; Or a hydrocarbon group having 1 to 20 carbon atoms in which at least one carbon atom is substituted with a hetero atom selected from the group consisting of O, S and N; or adjacent substituents are bonded to each other to form a hydrocarbon ring or a hetero ring,

Two or more of R ₁ to R _{5 are hydroxy groups;} Or a hydrocarbon group having 1 to 20 carbon atoms in which at least one carbon atom is substituted with a hetero atom selected from the group consisting of O, S, and N; Or, adjacent substituents are bonded to each other to form a heterocycle.

In the present specification, E denotes the end of the formula, and in the formula 1, the portion facing E is the main chain of the polymer, that is, a repeating unit derived from a conjugated diene-based monomer constituting the polymer; Alternatively, it may be connected with a repeating unit derived from an aromatic vinyl monomer. In one exemplary embodiment, E may be a methyl group (-CH ₃ ) or an ethyl group (-CH ₂ CH ₃ ).

Since a number of hydroxyl groups are included on the silica surface, there is a problem in that dispersibility is deteriorated due to agglomeration between silicas having weak bonding strength with a copolymer composed of only non-polar hydrocarbons. The copolymer according to an exemplary embodiment of the present specification includes a hydroxyl group at the terminal; A hydrocarbon group substituted with two or more heteroatoms; Or, by including a hetero ring formed by bonding of adjacent substituents to each other, it is possible to improve dispersibility of an inorganic filler such as silica and improve affinity with the inorganic filler. Specifically, the copolymer according to an exemplary embodiment of the present invention includes a hydroxyl group at the terminal; Alternatively, a portion having a strong bond with the silica and the copolymer including two or more polar heteroatoms may be formed, thereby improving the dispersibility of the silica. Therefore, at least one of the both ends of the copolymer is a rubber composition comprising a copolymer including a unit represented by the following formula (1), it is possible to improve the dispersibility of the inorganic filler by preventing aggregation between the inorganic fillers in the rubber composition. . Accordingly, fuel economy characteristics and road gripping power of a tire formed by using a rubber composition including the same may be improved.

In the exemplary embodiment of the present specification, R ₃ and R ₄ are bonded to each other to form a hydrocarbon ring or a hetero ring.

In the exemplary embodiment of the present specification, R ₃ and R ₄ are bonded to each other to form a 5-membered hydrocarbon ring or a 5-membered hetero ring.

In an exemplary embodiment of the present specification, the unit represented by Formula 1 is represented by the following Formula 1-1 or 1-2.

[Formula 1-1]

[Formula 1-2]

In Formula 1-1 and Formula 1-2,

n and E are the same as defined in Formula 1,

A ₁ and A ₂ are each independently S, O or NR,

R is hydrogen; A hydrocarbon group having 1 to 20 carbon atoms; Or a hydrocarbon group having 1 to 20 carbon atoms in which at least one carbon atom is substituted with a hetero atom selected from the group consisting of O, S and N; and,

R ₆ and R ₇ are each independently hydrogen; Hydroxy group; A hydrocarbon group having 1 to 20 carbon atoms; Or a hydrocarbon group having 1 to 20 carbon atoms in which at least one carbon atom is substituted with a hetero atom selected from the group consisting of O, S and N; and,

R ₈ to R ₁₀ are each independently hydrogen; Hydroxy group; A hydrocarbon group having 1 to 20 carbon atoms; Or a hydrocarbon group having 1 to 20 carbon atoms in which at least one carbon atom is substituted with a hetero atom selected from the group consisting of O, S and N; and,

R ₁₁ to R ₁₅ are each independently hydrogen; Hydroxy group; A hydrocarbon group having 1 to 20 carbon atoms; Or a hydrocarbon group having 1 to 20 carbon atoms in which at least one carbon atom is substituted with a hetero atom selected from the group consisting of O, S and N; and,

Two or more of R ₁₁ to R _{15 are hydroxy groups;} Or at least one carbon atom is a hydrocarbon group having 1 to 20 carbon atoms substituted with a hetero atom selected from the group consisting of O, S and N.

In the present specification, R, R ₆ and R ₇ are a hydrocarbon group having 1 to 20 carbon atoms; Or, when at least one carbon atom is a hydrocarbon group having 1 to 20 carbon atoms substituted with a hetero atom selected from the group consisting of O, S, and N, the sum of carbon atoms of these is the sum of carbon atoms of R ₃ and R ₄ in Formula 1 above. It may be a value obtained by subtracting the number of carbon atoms used to form a ring or heterocycle.

In the exemplary embodiment of the present specification, A ₁ and A ₂ are O.

In the exemplary embodiment of the present specification, R ₆ and R ₇ are each a hydrocarbon group having 1 to 20 carbon atoms.

In one exemplary embodiment, R ₆ and R ₇ are methyl groups.

In another exemplary embodiment, two or more of _{R 11} to R _{15 are hydroxy groups.}

In another exemplary embodiment _{, two of R 11} to R ₁₅ are hydroxy groups. Preferably, the two hydroxy groups are preferably in the ortho position.

In the exemplary embodiment of the present specification, R ₁₃ and R ₁₄ are hydroxy groups.

In an exemplary embodiment of the present specification, the conjugated diene-based monomer is 1,3-butadiene, isoprene, 1,3-pentadiene (piperylene), 2,3-dimethyl-1,3-butadiene, 1,3- Hexadiene, 2-methyl-1,3-pentadiene, 3,4-dimethyl-1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octa It is 1 type or 2 or more types selected from the group consisting of diene and 2-phenyl-1,3-butadiene. Specifically, the conjugated diene-based monomer may be 1,3-butadiene.

In another exemplary embodiment, the aromatic vinyl-based monomer is styrene, alphamethyl styrene, 3-methyl styrene, 4-methyl styrene, 4-propyl styrene, 1-vinyl naphthalene, 4-cyclohexyl styrene, 4-(para Methylphenyl) styrene and 1-vinyl-5-hexylnaphthalene. Specifically, the aromatic vinyl-based monomer may be styrene.

In an exemplary embodiment of the present specification, the repeating unit derived from the conjugated diene-based monomer is 60% by weight or more and 90% by weight or less based on the weight of the total polymer, and the repeating unit derived from the aromatic vinyl-based monomer is the weight of the entire polymer. Based on 10% by weight or more and 40% by weight or less.

In an exemplary embodiment of the present specification, the repeating unit derived from the conjugated diene-based monomer is 60% by weight or more and 90% by weight or less based on the weight of the total polymer. More specifically, the repeating unit derived from the conjugated diene-based monomer may be 60% by weight or more and 85% by weight or less based on the weight of the total polymer. In the case of the above content range, the elasticity of the copolymer may increase.

In the exemplary embodiment of the present specification, the repeating unit derived from the aromatic vinyl-based monomer is 10% by weight or more and 40% by weight or less based on the weight of the total polymer. Specifically, the repeating unit derived from the aromatic vinyl-based monomer may be 15% by weight or more and 40% by weight or less based on the weight of the entire polymer. In the case of the above content range, an effect of reinforcing mechanical properties of the copolymer can be expected.

In the exemplary embodiment of the present specification, other comonomers may be further included in addition to the conjugated diene-based monomer and the aromatic vinyl-based monomer. The comonomer is not limited as long as it can be copolymerized with a conjugated diene-based monomer or an aromatic vinyl-based monomer, but an acid anhydride-based monomer, an acrylonitrile-based monomer, and the like may be used.

In the exemplary embodiment of the present specification, the copolymer is a random copolymer. In the present specification, a random copolymer means that the units constituting the copolymer are arranged in an orderly manner.

In another exemplary embodiment, the weight average molecular weight (Mw) of the copolymer is 1,000 g/mol or more and 2,000,000 g/mol or less. Specifically, the weight average molecular weight (Mw) of the copolymer may be 10,000 g/mol or more, 2,000,000 g/mol or less, more specifically 100,000 g/mol or more, 2,000,000 g/mol or less. In the above range, a high molecular weight comonomer may contain a large amount of filler, and may have an effect of improving mechanical properties.

In the exemplary embodiment of the present specification, the polydispersity (Mw/Mn, PDI) of the copolymer is 1 or more and 10 or less. Specifically, the polydispersity of the copolymer may be 1 or more and 5 or less, and more specifically, the polydispersity of the copolymer may be 1 or more and 4 or less. The copolymer having a polydispersity within the above range can expect an effect of physical property stability due to a uniform molecular weight composition.

In the exemplary embodiment of the present specification, the Mooney viscosity (37.5phr, 1+4@100℃) of the copolymer may be 40 or more, specifically 40 or more, 90 or less, more specifically 50 or more, 80 or less. have. Since Mooney viscosity is proportional to the weight average molecular weight, there may be an effect of improving mechanical properties within the above range.

In one exemplary embodiment, the content of vinyl in the copolymer is 60% by weight or more. Specifically, the content of vinyl in the copolymer is 63% by weight or more, and more specifically, the content of vinyl in the copolymer is 63% by weight or more and 99% by weight or less. The copolymer containing vinyl in the above range can be used for tires and the like because the content of vinyl is high and fuel efficiency characteristics are improved. In the present specification, the "content of vinyl in the copolymer" refers to the content of 1,2-added conjugated diene-based monomers instead of 1,4-added to the aromatic vinyl-based monomer when the conjugated diene-based monomer and the aromatic vinyl-based monomer are copolymerized. Can mean

In addition, an exemplary embodiment of the present specification is a first step of polymerizing a conjugated diene-based monomer and an aromatic vinyl-based monomer in the presence of an organometallic compound in a hydrocarbon solvent; And a second step of reacting the polymer with a compound represented by the following formula (2).

[Formula 2]

In Formula 2,

L ₁ is a halogen group; Or an alkenyl group,

R ₁ to R ₅ are each independently hydrogen; Hydroxy group; A hydrocarbon group having 1 to 20 carbon atoms; Or a hydrocarbon group having 1 to 20 carbon atoms in which at least one carbon atom is substituted with a hetero atom selected from the group consisting of O, S, and N; Or, adjacent substituents are bonded to each other to form a hydrocarbon ring or a hetero ring,

Two or more of R ₁ to R _{5 are hydroxy groups;} Or a hydrocarbon group having 1 to 20 carbon atoms in which at least one carbon atom is substituted with a hetero atom selected from the group consisting of O, S, and N; Or, adjacent substituents are bonded to each other to form a heterocycle.

In the present specification, the conjugated diene-based monomer, the aromatic vinyl-based monomer, and the copolymer may include a repeating unit derived from the above-described conjugated diene-based monomer; And a repeating unit derived from an aromatic vinyl-based monomer, wherein at least one of both ends of the copolymer is the same as long as it does not contradict the matters mentioned in the copolymer containing the unit represented by Formula 1 Can be applied.

The manufacturing method according to an exemplary embodiment of the present specification is a copolymer of a conjugated diene-based monomer-aromatic vinyl-based monomer through a first step of polymerizing a conjugated diene-based monomer and an aromatic vinyl-based monomer in the presence of an organometallic compound in a hydrocarbon solvent. And an alkali metal is bonded to prepare an active copolymer. Through the second step of reacting the compound represented by Formula 2 with the prepared active copolymer, a copolymer polymerized in an oligomer form may be provided.

In the exemplary embodiment of the present specification, R ₃ and R ₄ are bonded to each other to form a hydrocarbon ring or a hetero ring.

In the exemplary embodiment of the present specification, R ₃ and R ₄ are bonded to each other to form a 5-membered hydrocarbon ring or a 5-membered hetero ring.

In the exemplary embodiment of the present specification, the compound represented by Formula 2 may be represented by the following Formula 2-1 or 2-2.

[Formula 2-1]

[Formula 2-2]

In Formula 2-1 and Formula 2-2,

L ₁ is the same as defined in Formula 2,

A ₁ and A ₂ are each independently S, O or NR,

R is hydrogen; A hydrocarbon group having 1 to 20 carbon atoms; Or a hydrocarbon group having 1 to 20 carbon atoms in which at least one carbon atom is substituted with a hetero atom selected from the group consisting of O, S and N; and,

R ₆ and R ₇ are each independently hydrogen; Hydroxy group; A hydrocarbon group having 1 to 20 carbon atoms; Or a hydrocarbon group having 1 to 20 carbon atoms in which at least one carbon atom is substituted with a hetero atom selected from the group consisting of O, S and N; and,

R ₈ to R ₁₀ are each independently hydrogen; Hydroxy group; A hydrocarbon group having 1 to 20 carbon atoms; Or a hydrocarbon group having 1 to 20 carbon atoms in which at least one carbon atom is substituted with a hetero atom selected from the group consisting of O, S and N; and,

R ₁₁ to R ₁₅ are each independently hydrogen; Hydroxy group; A hydrocarbon group having 1 to 20 carbon atoms; Or a hydrocarbon group having 1 to 20 carbon atoms in which at least one carbon atom is substituted with a hetero atom selected from the group consisting of O, S and N; and,

Two or more of R ₁₁ to R _{15 are hydroxy groups;} Or at least one carbon atom is a hydrocarbon group having 1 to 20 carbon atoms substituted with a hetero atom selected from the group consisting of O, S and N.

In the exemplary embodiment of the present specification, the number n of units represented by Formula 1 may be adjusted by adjusting the number of Formula 2 above.

In the exemplary embodiment of the present specification, when n is 1, L ₁ is a halogen group. More specifically, when n is 1, L ₁ may be bromine.

In the exemplary embodiment of the present specification, when n is 2 or more, L ₁ is an alkenyl group. More specifically, when n is 2 or more, L ₁ may be an ethylene group.

In the exemplary embodiment of the present specification, A ₁ and A ₂ are O.

In the present specification, the hydrocarbon solvent may include one or more of n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene, and xylene, but is not limited thereto. Although a hydrocarbon solvent may be used as it is, it is preferable to use it after passing through a molecular sieve and/or activated alumina to remove moisture, oxygen, or catalytic toxic substances.

In the present specification, in the first step of polymerizing the conjugated diene-based monomer and the aromatic vinyl-based monomer in the presence of an organometallic compound in the hydrocarbon solvent, a polar additive may be further added. In this case, it is possible to induce a random copolymer to be easily formed by compensating for a difference in reaction rate when the conjugated diene-based monomer and the aromatic vinyl-based monomer are copolymerized. Specifically, when the polar additive is added, a random copolymer may be induced by increasing the reaction rate of the aromatic vinyl-based monomer having a slow reaction rate.

The step polymerization may be performed by adding a polar additive as necessary, and the polar additive is 0.005% by weight or more, 10% by weight or less, specifically 0.007% by weight or more, 7% by weight or less based on the total monomers. , More specifically, it may be added in an amount of 0.009% by weight or more and 4% by weight or less.

In the present specification, the polar additive may be a salt, ether, amine, or a mixture thereof, specifically tetrahydrofuran, ditetrahydrofurylpropane, diethyl ether, cycloamal ether, dipropyl ether, ethylene dimethyl ether, ethylene dimethyl Ether, diethylene glycol, dimethyl ether, tertiary butoxyethoxyethane bis(3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, ethyl tetrafurfuryl ether, trimethylamine, triethylamine, tripropylamine And it may be one or more selected from the group consisting of tetramethylethylenediamine. More specifically, it may be ethyl tetrahydrofurfuryl ether, ditetrahydrofuryl propane, ethyl tetrafurfuryl ether, or tetramethylethylenediamine.

In the exemplary embodiment of the present specification, in the first step of polymerizing a conjugated diene-based monomer and an aromatic vinyl-based monomer in the presence of an organometallic compound in the hydrocarbon solvent, the organometallic compound acts as an anionic polymerization initiator, Polymerization can be carried out. Specifically, it may be a polymerization reaction in which an active site is obtained by a growth reaction by an anion, but the polymerization step is not limited thereto.

In the present specification, the organometallic compound may include at least one selected from the group consisting of an organic alkali metal compound such as an organic lithium compound, an organic sodium compound, an organic potassium compound, an organic rubidium compound, and an organic cesium compound. Preferably, it may contain an organolithium compound useful for polymerization of 1,3-diene monomers as an anionic polymerization initiator.

Specifically, the organic lithium compound includes a compound composed of a lithium cation and an anion of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. The aliphatic group is a linear or branched alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, sec-butyl, n-amine, sec-amyl, n -Hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, etc., and the alicyclic hydrocarbon group is an alicyclic hydrocarbon group having 5 to 10 carbon atoms such as cyclohexyl group, methylcyclohexyl group, ethylcyclohexyl group , A cycloheptyl group, a cyclopentylmethyl group, a methylcyclopentylethyl group, and the like, and the aromatic hydrocarbon group is an aryl group having 6 to 10 carbon atoms, such as a phenyl group, a tolyl group, a phenylethyl group, a benzyl group, a naphthyl group, or a phenylcyclohexyl group.

Preferably, the organometallic compound is methyllithium, ethyllithium, propyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octyllithium, phenyllithium, 1- Naphthyllithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naphthyl sodium, naphthyl Potassium and the like may be included.

The organometallic compound may be included in an amount of 0.0001 parts by weight to 0.64 parts by weight, for example, 0.00012 parts by weight to 0.32 parts by weight, 0.0002 parts by weight to 0.13 parts by weight, and 0.0003 parts by weight to 0.064 parts by weight, based on 100 parts by weight of the total monomer mixture. In the above range, it may be possible to prepare a high molecular weight copolymer.

In the present specification, the first step of polymerizing the conjugated diene-based monomer and the aromatic vinyl-based monomer in the presence of an organometallic compound in a hydrocarbon solvent may be elevated temperature polymerization, isothermal polymerization, or adiabatic polymerization.

Adiabatic polymerization refers to a method of adding an organometallic compound and then performing polymerization with its own heat of reaction without arbitrarily inputting heat. Temperature-raising polymerization refers to a method of polymerizing while increasing the temperature by optionally applying heat after adding an organometallic compound. Isothermal polymerization refers to a method of polymerization while maintaining a constant polymerization temperature by adding an organometallic compound and then increasing it by applying heat or removing heat.

The polymerization temperature in the first step of polymerizing the conjugated diene-based monomer and the aromatic vinyl-based monomer in the presence of an organometallic compound in a hydrocarbon solvent is -20°C or higher, 200°C or lower, specifically 0°C or higher, 150°C or lower, more specifically It may be performed at 10° C. or more and 120° C. or less. In the above range, the copolymerization of each monomer in the monomer mixture may be sufficiently completed.

In the exemplary embodiment of the present specification, the first step of polymerizing the conjugated diene-based monomer and the aromatic vinyl-based monomer in the presence of an organometallic compound in the hydrocarbon solvent is a batch type (batch type) or a continuous polymerization method including one or more reactors. Can be done by

In addition, after the above step, if necessary, at least one step of recovering and drying the solvent and the unreacted monomer may be further included.

An exemplary embodiment of the present specification, the repeating unit derived from the conjugated diene-based monomer; And a repeating unit derived from an aromatic vinyl-based monomer, wherein at least one of both ends of the copolymer is provided with a rubber composition comprising a copolymer including a unit represented by Formula 1.

In the present specification, the copolymer contained in the rubber composition may include a repeating unit derived from the conjugated diene-based monomer; And a repeating unit derived from an aromatic vinyl-based monomer, and at least one of both ends may be equally applied as long as they do not contradict each other with the matters mentioned in the copolymer including the unit represented by Formula 1 above.

In one embodiment of the present specification, the rubber composition may further include a filler.

The copolymer according to the exemplary embodiment of the present specification has excellent affinity with a filler, and a molded article formed by using a rubber composition containing the same has excellent abrasion resistance, low rolling resistance, and high wet skid resistance, thus excellent adjustment stability. Do.

In an exemplary embodiment of the present specification, the content of the filler includes 10 parts by weight or more and 200 parts by weight or less, and specifically, the content of the filler is 50 parts by weight or more and 200 parts by weight, based on 100 parts by weight of the copolymer. Below. When the content of the filler in the rubber composition is within the above range, a molded article having excellent wear resistance and durability improving effect can be provided.

In the present specification, the filler may include at least one of organic fillers and inorganic fillers commonly used in rubber compositions. For example, the organic filler may include one or more of carbon black and starch. The inorganic filler may include one or more of silica, aluminum hydroxide, magnesium hydroxide, and clay (hydrated aluminum silicate). Preferably, it may contain at least one of silica and carbon black as a filler.

More specifically, in the rubber composition according to an exemplary embodiment of the present specification, as the tanδ measured at 0°C increases, the wetting resistance and roughness resistance are improved, thereby improving braking performance, and the lower tanδ measured at 60°C By improving rolling resistance and rolling resistance, there may be an effect of improving fuel economy performance.

In the characteristics of the viscoelasticity of the copolymer according to the exemplary embodiment of the present specification, when measured at 10 Hz through a dynamic mechanical analysis (DMA) after mixing silica, the Tan δ value at 0°C (loss at 0°C) The modulus of elasticity) is, for example, 0.1 or more, 1 or less, specifically 0.3 or more, and 0.8 or less. There is an effect of greatly improving road surface resistance or wetting resistance within the above range. In addition, the Tan δ value at 60° C. may be, for example, 0.03 or more, 0.30 or less, specifically 0.04 or more, and 0.20 or less, and within this range, rolling resistance or rolling resistance (RR) is greatly improved.

In an exemplary embodiment of the present specification, the rubber composition includes a repeating unit derived from the conjugated diene-based monomer; And a repeating unit derived from an aromatic vinyl-based monomer, and at least one of both ends may further include a conjugated diene-based copolymer other than the copolymer including the unit represented by Formula 1 above. The conjugated diene-based copolymer may be a homo-type copolymer of the above-described conjugated diene-based monomer.

In the exemplary embodiment of the present specification, the repeating unit derived from the conjugated diene-based monomer; And a repeating unit derived from an aromatic vinyl-based monomer, wherein at least one of both ends includes a repeating unit derived from the conjugated diene-based monomer; And a repeating unit derived from an aromatic vinyl-based monomer; and at least one of both ends may include 10 parts by weight or more and 60 parts by weight or less based on 100 parts by weight of the copolymer including the unit represented by Formula 1 above. have. Specifically, it may include 10 parts by weight or more, 50 parts by weight or less, and more specifically 10 parts by weight or more and 30 parts by weight or less. A repeating unit derived from the conjugated diene-based monomer; And a repeating unit derived from an aromatic vinyl-based monomer; wherein at least one of both ends of the range is a rubber composition in which a conjugated diene-based copolymer other than the copolymer including the unit represented by Formula 1 is included in the above range. Physical properties can be improved.

In the exemplary embodiment of the present specification, the rubber composition may further include oil. The oils include vegetable oils such as paraffinic oil, aromatic oil, castor oil, mild extracted solvate (MES) oil, treated distillate aromatic extracted (TDAE) oil, low PCA oil including SRAE, heavy naphthenic oil, and black oil. It may include one or two or more selected from the group consisting of.

In the exemplary embodiment of the present specification, the content of the oil in the rubber composition is a repeating unit derived from the conjugated diene-based monomer; And a repeating unit derived from an aromatic vinyl-based monomer; and at least one of both ends of the range is 1 part by weight or more, 100 parts by weight or less, specifically It may be included in an amount of 10 parts by weight or more, 100 parts by weight or less, and more specifically 20 parts by weight or more and 80 parts by weight or less. When the oil in the above content range is included, the physical properties of the rubber composition may be well expressed, and the rubber composition may be appropriately softened to provide excellent processability.

In one embodiment of the present specification, the rubber composition may further include an additive. The additive may be one or two or more from the group consisting of accelerators, waxes, fatty acids, processing aids, antioxidants, anti-aging agents, crosslinking agents, softeners, accelerators, and zinc oxide.

The content of the additive is a repeating unit derived from the conjugated diene-based monomer; And a repeating unit derived from an aromatic vinyl-based monomer; and at least one of both ends of the range is 1 part by weight or more, 50 parts by weight or less, specifically It may be 1 part by weight or more, 30 parts by weight or less, more specifically 1 part by weight or more and 10 parts by weight or less. In the above range, it may serve as an additive without affecting the effect of the rubber composition.

In one embodiment of the present specification, the rubber composition may be a vulcanized rubber composition further containing sulfur. Sulfur is included in the rubber composition and forms a network of rubber through a crosslinking reaction, so that additive filling and durability can be improved.

In an exemplary embodiment of the present specification, the content of sulfur is a repeating unit derived from the conjugated diene-based monomer; And a repeating unit derived from an aromatic vinyl-based monomer; and at least one of both ends of the range is 0.1 parts by weight or more, 50 parts by weight or less, specifically, based on 100 parts by weight of the copolymer including the unit represented by Formula 1 It may be 0.1 parts by weight or more, 30 parts by weight or less, more specifically 0.1 parts by weight or more and 10 parts by weight or less. In the above range, it is possible to achieve an effect without affecting the effect of the rubber composition.

Another exemplary embodiment of the present specification provides a molded article formed by using the rubber composition.

The molded article formed using the rubber composition according to an exemplary embodiment of the present specification is a tire, such as a tire, a tire tread, an under tread, a side wall, a carcass coated rubber, a belt coated rubber, a bead filler, a pancreas, or a bead coated rubber. And various industrial rubber products such as anti-vibration rubber, belt conveyor, and hose. The molded article formed by using the rubber composition may specifically be a tire or a tire tread, and may have excellent fuel economy characteristics.

Hereinafter, examples will be described in detail in order to describe the present invention in detail. However, the embodiments according to the present invention may be modified in various forms, and the scope of the present invention is not construed as being limited to the embodiments described below. The embodiments of the present specification are provided to more completely describe the present invention to those of ordinary skill in the art. Unless otherwise specified, all percentages (%) are based on weight.

The physical properties of the copolymer prepared according to the examples described later in the present specification were analyzed according to the following method.

1. Content of conjugated diene-based monomer and content of aromatic vinyl-based monomer in the conjugated diene-based monomer-aromatic vinyl-based monomer copolymer (unit: wt%): Conjugated diene-based monomer-aromatic vinyl-based monomer obtained in Examples and Comparative Examples A small amount of the copolymer was taken and redissolved in a _{CDCl 3 solvent for NMR.} Take a small amount and measure the content of styrene and vinyl group in the copolymer through ^{400MHz 1 H NMR (Avance DRX400, Bruker).}

2. Weight average molecular weight (Mw, unit: g/mol), polydispersity (Mw/Mn): GPC (gel filtration chromatography) for the conjugated diene-based monomer-aromatic vinyl-based monomer copolymer obtained in Examples and Comparative Examples. , PL-GPC220, Agilent).

3. Glass transition temperature (Tg): The conjugated diene-based monomer-aromatic vinyl-based monomer copolymer obtained in Examples and Comparative Examples was measured by differential scanning calorimetry (Differential Scanning Calorimetry, device name: Q200, TA Instruments). .

4. Mooney Viscosity: Using a Mooney viscometer (MV2000, Alpha Technology) for the sample impregnated with 37.5 parts by weight of TDAE oil in 100 parts by weight of the conjugated diene-based monomer-aromatic vinyl-based monomer copolymer obtained in Examples and Comparative Examples. After passing through a preheating time of 1 minute at 100° C., it was measured and analyzed for 4 minutes.

5. Pyrolyzer GC/MS: Pyrolysis gas chromatography mass spectrometry (pyrolyzer: JCI-55, JAI, GC) for the conjugated diene-based monomer-aromatic vinyl-based monomer copolymer obtained in Examples and Comparative Examples. /MS: Clarus 690T, Perkinelmer, Column: DB-5MS 30m, Perkin-elmer).

6. Tanδ of the formulation (@60°C, @0°C): The copolymer obtained in Examples and Comparative Examples was added to an internal type mixer in the amount of Table 1 below to prepare a formulation. The mixture was pressed against the prepared formulation to obtain a specimen capable of measuring the tan δ of the formulation. For the obtained specimens, tanδ of 0°C and 60°C were measured using a dynamic mechanical analyzer (DMA; Dynamic Mechanical Analyzer, TA Instrument Co., Ltd.) as a temperature sweep test under conditions of 10Hz and 0.2% strain, respectively.

Preparation Example 1. Synthesis of 4-Methylcatechol acetonide

4-Methyl catechol (30.0 g, 241.5 mmol), 2,2-Dimethoxypropane (87.36 g, 102.9 mL, 840 mmol), para-toluenesulfonic acid mono Hydrate (p-Toluenesulfonic acid monohydrate) (0.4 g, 2.0 mmol) and benzene (262.2 g, 300 mL) were added to a 1 L, two necked round bottom flask to make a homogeneous solution. After the sucsillet extraction device was mounted, it was reacted for 8 hours at a temperature of 120°C. After removing all of the solvent, the remaining material was ^{purified by distillation under reduced pressure at 65° C. and 1×10 −3} mbar to synthesize 4-methylcatechol acetonide in a pale yellow liquid state. (yield = 89%)

Preparation Example 2. Synthesis of 4-Bromomethylcatechol acetonide

4-Methyl catechol acetonide (20.0 g, 121.8 mmol), N-Bromosuccinimide (21.6 g, 121.2 mmol), 2,2'-azobisiso Butyronitrile (2,2'-Azobisiso butyronitrile) (0.8 g, 4.88 mmol) and cyclohexane (262.2 g, 300 mL) were placed in a 1 L, two necked round bottom flask. After mounting a reflux cooler, it was reacted for 6 hours at a temperature of 100°C. Then, the precipitated succinimide was removed by filtration, and all solvents of the remaining liquid substance were removed to synthesize 4-Bromomethyl catechol acetonide in a yellow liquid state. (yield = 98%)

¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) = 6.84 (dd, 1H, Ar-C5H, 7.8 Hz, 1.8 Hz), 6.81 (d, 1H, ArC3H, 1.8 Hz), 6.68 (d, 1H , ArC6H, 7.8 Hz), 4.48 (s, 2H, CH ₂ Br), 1.70 (s, 6H, C(CH ₃ ) ₂ ).

Preparation Example 3. Synthesis of (4-methylcatechol) triphenylphosphonium bromide ((4-Methylcatechol) triphenylphosphonium bromide)

4-Bromomethyl catechol acetonide (10.0 g, 60.7 mmol), triphenylphosphine (15.0 g, 57.1 mmol), distilled acetone (156.9 g, 200 mL) was placed in a 500 mL, two necked round bottom flask. After mounting a reflux cooler, it was reacted for 4 hours at a temperature of 90°C. Then, the precipitated product was separated by filtering, washed with acetone, and synthesized in the form of a white powder (4-methylcatechol) triphenylphosphonium bromide ((4-Methylcatechol) triphenylphosphonium bromide). (yield = 57%)

Preparation Example 4. Synthesis of 4-Vinylcatechol acetonide

Formaldehyde solution (37 wt%, 109 g, 100 mL) solution in which (4-methylcatechol) triphenylphosphonium bromide ((4-Methylcatechol) triphenylphosphonium bromide) (10.0 g, 121.8 mmol) is dispersed To this 500 mL 1-neck round bottom flask, a 70 ml aqueous solution in which 5.5 g of sodium hydroxide was dissolved was added dropwise and reacted at room temperature for 12 hours. After the reaction solution was extracted with 12.5 mL of dichloronmethane, water remaining as magnesium sulfate was removed, and then all remaining organic solvents were removed through distillation. Subsequently, 4-Vinylcatechol acetonide, a pale yellow liquid form, was purified through column chromatography using a dichloromethane solvent as a mobile phase and silica as a stationary phase. Was synthesized. (yield = 91%)

¹ H NMR (400 MHz, CDCl ₃ ): δ (ppm) = 6.94 (d, 1H, Ar-C3H, 1.7 Hz), 6.84 (dd, 1H, ArC5H, 8.0, 1.7 Hz), 6.72 (d, 1H, ArC6H, 8.0 Hz), 6.67 (dd, 1H, CH=CH ₂ , 17.5, 10.8 Hz), 5.61 (dd, 1H, cis-CH=CH ₂ , 17.5, 1.0 Hz), 5.15 (dd, 1H, trans- CH=CH ₂ , 10.9, 0.9 Hz), 1.72 (s, 6H,C(CH ₃ ) ₂ ).

<Example 1> Preparation of catechol acetonide oligomer (n=10) modified styrene-butadiene copolymer using 4-vinylcatechol acetonide

After replacing the inside of the high-pressure reactor (internal capacity: 3 L, stainless steel) with nitrogen at room temperature, 2 L of cyclohexane, 56 mL of styrene, 178 g of 1,3-butadiene and 3 mL of ethyl tetrafurfuryl ether (monomer A mixture of styrene and 1,3-butadiene was added in an amount of 0.014 parts by weight based on 100 parts by weight of the total amount. After that, the reactor temperature was preheated to 50°C, and 0.21 mmol of n-butyllithium (0.00058 parts by weight based on 100 parts by weight of styrene and 1,3-butadiene as a monomer mixture) was injected into the reactor, followed by an adiabatic elevated temperature polymerization reaction. I did. After the reaction was reached for 30 minutes after reaching the maximum temperature, 2.1 mmol of 4-Vinylcatechol acetonide (0.0016 parts by weight based on 100 parts by weight of the total amount of styrene and 1,3-butadiene as a monomer mixture) was added. It was allowed to react for 60 minutes. Ethanol was added to stop the reaction, the temperature was lowered to room temperature, and then a solution in which 1 phr of Songnox 1076 antioxidant was dissolved in 20 mL of hexane was added. Subsequently, the copolymer polymerization solution dispersed in the solvent was transferred to a container, and then dried for 15 hours or more while heating at 80° C. in a vacuum oven to obtain a modified styrene-butadiene copolymer.

Pyrolyzer GC/MS (386℃, 15s, m/z=163&178, split 1:20): 12.744s (5-Formyl-2,2-Dimethyl-1,3-Benzodioxole)

<Example 2> Preparation of catechol acetonide modified styrene-butadiene copolymer using 4-Bromomethylcatechol acetonide

After replacing the inside of the high-pressure reactor (internal capacity: 3 L, stainless steel) with nitrogen at room temperature, 2 L of cyclohexane, 56 mL of styrene, 178 g of 1,3-butadiene and 3 mL of ethyl tetrafurfuryl ether (monomer A mixture of styrene and 1,3-butadiene was added in an amount of 0.014 parts by weight based on 100 parts by weight of the total amount. After that, the reactor temperature was preheated to 50°C, and 0.21 mmol of n-butyllithium (0.00058 parts by weight based on 100 parts by weight of styrene and 1,3-butadiene as a monomer mixture) was injected into the reactor, followed by an adiabatic elevated temperature polymerization reaction. I did. After reaching the maximum temperature for 30 minutes, 4-Bromomethylcatechol acetonide 0.21 mmol (0.00022 parts by weight based on 100 parts by weight of the total amount of styrene and 1,3-butadiene as a monomer mixture) was added. It was added and reacted for 60 minutes. Ethanol was added to stop the reaction, the temperature was lowered to room temperature, and then a solution in which 1 phr of Songnox 1076 antioxidant was dissolved in 20 mL of hexane was added. Subsequently, the copolymer polymerization solution dispersed in the solvent was transferred to a container and dried for 15 hours or more while heating at 80° C. in a vacuum oven to obtain a modified styrene-butadiene copolymer.

Pyrolyzer GC/MS (386℃, 15s, m/z=163&178, split 1:20): 12.739s (5-Formyl-2,2-Dimethyl-1,3-Benzodioxole)

<Example 3> Preparation of catechol oligomer (n=10) modified styrene-butadiene copolymer using catechol acetonide

After dissolving 200 g of 4-Vinylcatechol acetonide modified styrene-butadiene copolymer prepared according to the method of Example 1 in 4 L of cyclohexane, 1 L of trichloroacetic acid was added and stirred at room temperature for 6 hours. Made it. Trichloroacetic acid was removed using water and ethanol, and 10 mL of 28% aqueous ammonia was added to neutralize the remaining acid, and then the copolymer polymerization solution was transferred to a container and heated to 80° C. in a vacuum oven for 15 hours or longer. It was dried to obtain a modified styrene-butadiene copolymer.

<Example 4> Preparation of catechol-modified styrene-butadiene copolymer using catechol acetonide

After dissolving 200 g of 4-bromomethylcatechol acetonide modified styrene-butadiene copolymer prepared according to the method of Example 2 in 4 L of cyclohexane, 1 L of trichloroacetic acid was added to room temperature for 6 hours. Stirred at. Trichloroacetic acid was removed using water and ethanol, and 10 mL of 28% aqueous ammonia was added to neutralize the remaining acid, and then the copolymer polymerization solution was transferred to a container and heated to 80° C. in a vacuum oven for 15 hours or longer. It was dried to obtain a modified styrene-butadiene copolymer.

<Comparative Example 1>

Styrene-butadiene copolymerization was obtained in the same manner as in Example 1, except that 4-vinylcatechol acetonide was not used in Example 1.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Terminal denatured structure Catechol acetonide oligomer
(n=10) Catechol acetonide Catechol
oligomer
(n=10) Catechol
- Styrene content (% by weight) 25.2 24.9 25.0 24.8 25.1 Vinyl content (% by weight) 65.0 65.0 64.6 64.8 64.9 Weight average molecular weight (Mw) 1,743,547 1,500,065 1,685,365 1,392,232 1,389,268 Molecular weight distribution (MwD; g/mol) 1.26 1.42 1.33 1.30 1.02 Tg (℃) -19.8 -20.1 -19.7 -19.6 -20 Mooney viscosity (37.5phr)
(ML1+4, 100℃) 61.4 61.0 61.3 60.7 60.6

As in Examples 1 to 4, it was confirmed that the molecular weight was slightly increased compared to Comparative Example 1, which did not include the unit represented by Formula 1, when preparing a modified SSBR having a terminal having a unit represented by Formula 1 above. In Examples 1 and 2, 5-formyl-2,2-dimethyl-1,3-benzodioxole, a catechol acetonide derivative, at 12.744 and 12.739 seconds through Pyrolyzer GC/MS. ,2-Dimethyl-1,3-Benzodioxole) structure was confirmed to be added to the end of the polymer. Examples 3 and 4 were prepared by using the polymers of Examples 1 and 2 through a deprotection process. As a result, the structure of the acetonide derivative was not detected in Pyrolyzer GC/MS, and all acetonide ( It was confirmed that the acetonide) group was converted to a catechol group.

<Experimental Example: Preparation of rubber composition>

The polymers obtained in the above Examples and Comparative Examples were blended and kneaded in the composition shown in Table 2 below to prepare a rubber composition. In detail, the styrene-butadiene copolymer (SSBR) prepared in Examples 1 to 4 and Comparative Examples was added to a Banbari or internal type mixer, and silica, carbon black, anti-aging agent, softener, crosslinking aid, and A crosslinking agent or the like was added and blended to obtain a tire tread composition.

Substance name Content (phr; parts by weight) SSBR 80.0 Butadiene Rubber 20.0 Silica 80.0 TDAE Oil 37.5 ZnO 3.0 Stearic acid 1.0 Coupling agent X50S 12.8 Roadside 6PPD 2.0 Roadside RD 1.0 Roadside WAX 2.0 Accelerated CZ (CBS) 1.7 Promotion D (DPG) 2.0 Sulfur 1.9

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Terminal denatured structure Catechol acetonide oligomer(n=10) Catechol acetonide Catechol
oligomer
(n=10) Catechol
- tan δ 60℃ 0.114 0.127 0.136 0.130 0.147 tan δ 0℃ 0.433 0.430 0.430 0.429 0.376

Looking at the results of Table 3, the repeating unit derived from the conjugated diene-based monomer according to an exemplary embodiment of the present specification; And a repeating unit derived from an aromatic vinyl-based monomer, wherein at least one of both ends of the copolymer comprises a unit represented by Chemical Formula 1, wherein the copolymer does not contain a unit represented by Chemical Formula 1 Compared to Example 1, it can be seen that tan δ at 60° C. is lower. It can be seen that rolling resistance and rotational resistance are improved, thereby providing a molded article having excellent fuel economy performance.

In the case of a copolymer containing a unit represented by Formula 1-1, compared to Example 2 in which n is 1, the oligomer-type copolymer with n is 10 has lower tanδ at 60°C and the higher the modified, the better the fuel economy performance. Can be expected.

In addition, in the case of the copolymer including the unit represented by Formula 1-2 after deprotection, the tan δ value at 60°C was overall higher than that of the copolymer including the unit represented by Formula 1-1, The higher the denaturation, the higher the value. This does not seem to have a significant effect on the dispersibility of silica in the formulation due to reaggregation between molecules due to the strong electrophilic properties of the catechol structure. However, compared to Comparative Example 1 which does not contain the unit represented by Formula 1, it can be seen that the value of tanδ at 60° C. is lower, which seems to be due to a catechol group bonded to some silica.

Further, looking at Examples 1 to 4, in the case of Example 1, which is a copolymer containing a unit represented by Chemical Formula 1-1, tan δ at 0°C is high, so that wetting resistance and rough surface resistance are improved, and thus high braking Performance can be expected. In addition, Examples 1 to 4, which are copolymers including at the end a unit represented by Formula 1 according to an exemplary embodiment of the present specification, have a higher tanδ at 0°C than Comparative Example 1 not including the unit represented by Formula 1 You can see it has a value

Accordingly, it can be confirmed that a molded article (eg, tire or tire tread) formed using the rubber composition containing the copolymer according to an exemplary embodiment of the present invention has high fuel efficiency and/or braking performance.

Simple modifications or changes of the present invention can be easily implemented by those of ordinary skill in the art, and all such modifications or changes can be considered to be included in the scope of the present invention.

Claims (11)

Repeating units derived from conjugated diene-based monomers; And
A copolymer containing a repeating unit derived from an aromatic vinyl monomer,
At least one of both ends of the copolymer comprises a unit represented by the following formula (1):
[Formula 1]

In Formula 1,
n is an integer from 1 to 50,
E is an alkyl group having 1 to 10 carbon atoms,
R ₁ to R ₅ are each independently hydrogen; Hydroxy group; A hydrocarbon group having 1 to 20 carbon atoms; Or a hydrocarbon group having 1 to 20 carbon atoms in which at least one carbon atom is substituted with a hetero atom selected from the group consisting of O, S and N; or adjacent substituents are bonded to each other to form a hydrocarbon ring or a hetero ring,
Two or more of R ₁ to R _{5 are hydroxy groups;} Or a hydrocarbon group having 1 to 20 carbon atoms in which at least one carbon atom is substituted with a hetero atom selected from the group consisting of O, S, and N; Or, adjacent substituents are bonded to each other to form a heterocycle. The method according to claim 1,
The unit represented by Formula 1 is a copolymer represented by the following Formula 1-1 or 1-2:
[Formula 1-1]

[Formula 1-2]

In Formula 1-1 and Formula 1-2,
n and E are the same as defined in Formula 1,
A ₁ and A ₂ are each independently S, O or NR,
R is hydrogen; A hydrocarbon group having 1 to 20 carbon atoms; Or a hydrocarbon group having 1 to 20 carbon atoms in which at least one carbon atom is substituted with a hetero atom selected from the group consisting of O, S and N; and,
R ₆ and R ₇ are each independently hydrogen; Hydroxy group; A hydrocarbon group having 1 to 20 carbon atoms; Or a hydrocarbon group having 1 to 20 carbon atoms in which at least one carbon atom is substituted with a hetero atom selected from the group consisting of O, S and N; and,
R ₈ to R ₁₀ are each independently hydrogen; Hydroxy group; A hydrocarbon group having 1 to 20 carbon atoms; Or a hydrocarbon group having 1 to 20 carbon atoms in which at least one carbon atom is substituted with a hetero atom selected from the group consisting of O, S and N; and,
R ₁₁ to R ₁₅ are each independently hydrogen; Hydroxy group; A hydrocarbon group having 1 to 20 carbon atoms; Or a hydrocarbon group having 1 to 20 carbon atoms in which at least one carbon atom is substituted with a hetero atom selected from the group consisting of O, S and N; and,
Two or more of R ₁₁ to R _{15 are hydroxy groups;} Or at least one carbon atom is a hydrocarbon group having 1 to 20 carbon atoms substituted with a hetero atom selected from the group consisting of O, S and N. The method according to claim 1,
The conjugated diene-based monomer is 1,3-butadiene, isoprene, 1,3-pentadiene (piperylene), 2,3-dimethyl-1,3-butadiene, 1,3-hexadiene, 2-methyl-1, 3-pentadiene, 3,4-dimethyl-1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene and 2-phenyl-1,3 -A copolymer that is one or two or more selected from the group consisting of butadiene. The method according to claim 1,
The aromatic vinyl monomers are styrene, alphamethyl styrene, 3-methyl styrene, 4-methyl styrene, 4-propyl styrene, 1-vinyl naphthalene, 4-cyclohexyl styrene, 4-(paramethylphenyl) styrene and 1-vinyl- One or more copolymers selected from the group consisting of 5-hexyl naphthalene. The method according to claim 1,
The repeating unit derived from the conjugated diene-based monomer is 60% by weight or more and 90% by weight or less based on the weight of the total polymer, and the repeating unit derived from the aromatic vinyl-based monomer is 10% by weight or more and 40% by weight based on the weight of the total polymer. % Or less. The method according to claim 1,
The copolymer is a copolymer that is a random copolymer. The method according to claim 1,
The copolymer has a weight average molecular weight (Mw) of 1,000 g/mol or more and 2,000,000 g/mol or less. The method according to claim 2,
A ₁ and A ₂ is a copolymer that will be O. A first step of polymerizing a conjugated diene-based monomer and an aromatic vinyl-based monomer in the presence of an organometallic compound in a hydrocarbon solvent; And
A method for preparing a copolymer according to any one of claims 1 to 8, including a second step of reacting the polymer with a compound represented by the following formula (2):
[Formula 2]

In Formula 2,
L ₁ is a halogen group; Or an alkenyl group,
R ₁ to R ₅ are each independently hydrogen; Hydroxy group; A hydrocarbon group having 1 to 20 carbon atoms; Or a hydrocarbon group having 1 to 20 carbon atoms in which at least one carbon atom is substituted with a hetero atom selected from the group consisting of O, S, and N; Or, adjacent substituents are bonded to each other to form a hydrocarbon ring or a hetero ring,
Two or more of R ₁ to R _{5 are hydroxy groups;} Or a hydrocarbon group having 1 to 20 carbon atoms in which at least one carbon atom is substituted with a hetero atom selected from the group consisting of O, S, and N; Or, adjacent substituents are bonded to each other to form a heterocycle. A rubber composition comprising the copolymer according to any one of claims 1 to 8. A molded article formed using the rubber composition according to claim 10.