RU2790165C2 - Modified polymer based on conjugated diene and a rubber composition containing it - Google Patents

Abstract

FIELD: tire industry.

SUBSTANCE: invention relates to a group of inventions: a modified polymer based on conjugated diene and a rubber composition for the manufacture of tires. This modified polymer has a molecular mass distribution curve with a unimodal profile and a molecular mass distribution (CP; MMD) in the range of 1.0-1.7. The modified polymer contains a functional group derived from the initiator of modification in one end position and a functional group derived from the modifier in the other end position. The modification initiator is a reaction product between a compound

and an organometallic compound. The rubber composition contains a modified polymer based on conjugated diene and a filler.

EFFECT: creation of a modified polymer based on conjugated diene obtained as a result of continuous polymerization and characterized by remarkable recyclability and excellent physical properties, such as mechanical properties under tension, and viscoelasticity characteristics.

12 cl, 4 dwg, 6 tbl, 14 ex

Description

FIELD OF TECHNOLOGY TO WHICH THE INVENTION RELATES

[Cross-reference to related applications]

[0001] This application claims priority on the basis of Korean Patent Application Nos. 10-2017-0165575, filed on December 5, 2017, and 10-2018-0151386, filed on November 29, 2018, the entire contents of which are incorporated herein by reference. .

[Technical field to which the invention relates]

[0002] The present invention relates to a modified conjugated diene polymer having excellent processability and excellent viscoelastic properties, and a rubber composition containing the same.

BACKGROUND OF THE INVENTION

[0003] In accordance with the recent need for automobiles having low fuel consumption, a conjugated diene-based polymer is required as a rubber material for tires, which has modulation stability, represented by wet skid resistance, as well as low rolling resistance and excellent abrasion resistance. wear and tensile properties.

[0004] In order to reduce the rolling resistance of tires, there is a method to reduce the hysteresis loss for the vulcanized rubber, and as an estimate for the vulcanized rubber, rebound resilience in the range of 50°C to 80°C, tg δ, heating in the test according to Goodrich and the like. That is, it is desirable to use a rubber material having high rebound resilience at the aforementioned temperature or low tg δ or heat in the Goodrich test.

[0005] Natural rubbers, polyisoprene rubbers, or polybutadiene rubbers are known as rubber materials having low hysteresis loss, but these rubbers have the limitation of low wet skid resistance. Thus, for use as tire rubbers, conjugated diene-based polymers or copolymers such as styrene-butadiene rubbers (hereinafter referred to as "SBR") and butadiene rubbers (hereinafter referred to as term "BR") by carrying out emulsion polymerization or solution polymerization. Among these polymerization methods, the greatest advantage of solution polymerization compared to emulsion polymerization is that the level of vinyl structure and the level of styrene content, which determine the physical properties of rubber, can be arbitrarily adjusted, and the molecular weight and physical properties in this case can be controlled through combination or modification. Thus, the SBR polymer obtained by solution polymerization is widely used as a rubber material for tires, since the structure of the ultimately obtained SBR or BR polymers is easily changed, and as a result of combination or modification at the end positions of the chains, the movement at the end positions of the chains is reduced, and the adhesion force to filler such as silica and carbon black can be increased.

[0006] In the case of using an SBR resin obtained by solution polymerization as a tire rubber material, physical properties such as running resistance and braking force can be controlled under control due to the increase in the glass transition temperature of the rubber by increasing the vinyl content of the SBR resin. required for tires, and by properly adjusting the glass transition temperature, fuel consumption can also be reduced. The resulting solution polymerization of the SBR polymer is obtained using an anionic polymerization initiator and is used in coupling or modifying the chain ends of the thus obtained polymer using various modifiers. For example, U.S. Patent No. 4,397,994 discloses a coupling method for active anions at the chain ends of a polymer obtained by carrying out the polymerization of styrene-butadiene using an alkyl lithium, which is a monofunctional initiator, in a non-polar solvent using a binder such as a tin compound. .

[0007] Meanwhile, polymerization to obtain SBR or BR polymers can be carried out using batch or continuous polymerization. In the case of batch polymerization, the molecular weight distribution of the polymer thus obtained is narrow, and batch polymerization is advantageous in terms of improving physical properties, but productivity is low and processability is degraded. In the case of continuous polymerization, the polymerization can be carried out continuously and the productivity is excellent and the improvement in processability is advantageous, but the molecular weight distribution is wide and the physical properties are degraded. Accordingly, research is urgently required to simultaneously improve productivity, processability and physical properties to obtain SBR or BR polymers.

[0008] [Prior art documents]

[0009] (Patent document 1) US4397994

[0010] (Patent Document 2) JP1994-271706 A

DISCLOSURE OF THE INVENTION

TECHNICAL PROBLEM

[0011] The present invention has been developed to solve the aforementioned problems of the conventional technique, and the object of the present invention is to provide a modified conjugated diene based polymer obtained by carrying out continuous polymerization, which is characterized by excellent processability and excellent physical properties, such as mechanical properties at stretching, and viscoelasticity characteristics, and a rubber composition containing it.

TECHNICAL SOLUTION

[0012] In order to solve the problems described above, in accordance with one embodiment of the present invention, there is provided a modified conjugated diene polymer having a molecular weight distribution curve with a unimodal profile obtained using Gel Permeation Chromatography (GPC) and a molecular weight distribution (MWD) ; MMP) in the range from 1.0 to less than 1.7 and containing a functional group derived from the initiator of the modification in one end position and a functional group derived from the modifier represented by any formula selected from the following formulas from formula 2 to formula 4, in the other end position, where the modification initiator is the reaction product between the compound described by the following formula 1 and an organometallic compound:

[0013] [Formula 1]

,

,

[0014] where in formula 1

[0015] each of the groups from R ₁ to R ₃ independently represents a hydrogen atom; an alkyl group containing from 1 to 30 carbon atoms; an alkenyl group containing 2 to 30 carbon atoms; alkynyl group containing from 2 to 30 carbon atoms; a heteroalkyl group containing 1 to 30 carbon atoms; a heteroalkenyl group containing 2 to 30 carbon atoms; a heteroalkynyl group containing 2 to 30 carbon atoms; a cycloalkyl group containing 5 to 30 carbon atoms; an aryl group containing 6 to 30 carbon atoms; or a heterocyclic group containing from 3 to 30 carbon atoms,

[0016] R ₄ is a single bond; a substituted or unsubstituted alkylene group containing from 1 to 20 carbon atoms together with a substituent; a substituted or unsubstituted cycloalkylene group containing from 5 to 20 carbon atoms together with a substituent; or a substituted or unsubstituted arylene group containing from 6 to 20 carbon atoms together with a substituent, where the substituent is an alkyl group containing from 1 to 10 carbon atoms, a cycloalkyl group containing from 5 to 10 carbon atoms, or an aryl group containing from 6 to 20 carbons,

[0017] R ₅ is an alkyl group containing from 1 to 30 carbon atoms; an alkenyl group containing 2 to 30 carbon atoms; alkynyl group containing from 2 to 30 carbon atoms; a heteroalkyl group containing 1 to 30 carbon atoms; a heteroalkenyl group containing 2 to 30 carbon atoms; a heteroalkynyl group containing 2 to 30 carbon atoms; a cycloalkyl group containing 5 to 30 carbon atoms; an aryl group containing 6 to 30 carbon atoms; a heterocyclic group containing from 3 to 30 carbon atoms, or a functional group described by the following formula 1a or formula 1b, and

[0018] n is an integer in the range of 1 to 5, and at least one of the groups R ₅ is a functional group described by the following formula 1a or formula 1b, in the case where n is an integer in the range 2 to 5, the plurality of R ₅ groups may be identical or different:

[0019] [Formula 1a]

,

,

[0020] where in formula 1a

[0021] R ₆ is a substituted or unsubstituted alkylene group containing from 1 to 20 carbon atoms together with a substituent; a substituted or unsubstituted cycloalkylene group containing from 5 to 20 carbon atoms together with a substituent; or a substituted or unsubstituted arylene group containing from 6 to 20 carbon atoms together with a substituent, where the substituent is an alkyl group containing from 1 to 10 carbon atoms, a cycloalkyl group containing from 5 to 10 carbon atoms, or an aryl group containing from 6 to 20 carbons,

[0022] each of R ₇ and R ₈ independently represents an alkyl group containing from 1 to 10 carbon atoms, a cycloalkyl group containing from 5 to 10 carbon atoms, or a substituted or unsubstituted alkylene group containing from 1 to 20 carbon atoms together with an aryl group containing from 6 to 20 carbon atoms,

[0023] R ₉ is a hydrogen atom; an alkyl group containing from 1 to 30 carbon atoms; an alkenyl group containing 2 to 30 carbon atoms; alkynyl group containing from 2 to 30 carbon atoms; a heteroalkyl group containing 1 to 30 carbon atoms; a heteroalkenyl group containing 2 to 30 carbon atoms; a heteroalkynyl group containing 2 to 30 carbon atoms; a cycloalkyl group containing 5 to 30 carbon atoms; an aryl group containing 6 to 30 carbon atoms; or a heterocyclic group containing from 3 to 30 carbon atoms,

And

[0024] X represents an atom N, O or S, and in the case where X represents O or S, R ₉ is absent,

[0025] [Formula 1b]

[0026] in formula 1b

[0027] R ₁₀ is a substituted or unsubstituted alkylene group containing from 1 to 20 carbon atoms together with a substituent; a substituted or unsubstituted cycloalkylene group containing from 5 to 20 carbon atoms together with a substituent; or a substituted or unsubstituted arylene group containing from 6 to 20 carbon atoms together with a substituent, where the substituent is an alkyl group containing from 1 to 10 carbon atoms, a cycloalkyl group containing from 5 to 10 carbon atoms, or an aryl group containing from 6 to 20 carbons, and

[0028] each of R ₁₁ and R ₁₂ independently represents an alkyl group containing from 1 to 30 carbon atoms; an alkenyl group containing 2 to 30 carbon atoms; alkynyl group containing from 2 to 30 carbon atoms; a heteroalkyl group containing 1 to 30 carbon atoms; a heteroalkenyl group containing 2 to 30 carbon atoms; a heteroalkynyl group containing 2 to 30 carbon atoms; a cycloalkyl group containing 5 to 30 carbon atoms; an aryl group containing 6 to 30 carbon atoms; or a heterocyclic group containing from 3 to 30 carbon atoms,

[0024] [Formula 2]

,

,

[0030] where in formula 2

[0031] each of R _a1 and R _a4 independently represents a single bond or an alkylene group containing from 1 to 10 carbon atoms,

[0032] each of R _a2 and R _a3 independently represents an alkyl group containing from 1 to 10 carbon atoms,

[0033] R _a5 is a five-membered heterocyclic group containing from 2 to 4 carbon atoms and containing one or more heteroatoms selected from the group consisting of N, O and S,

[0034] n ₁ is an integer in the range 1 to 3, and

[0035] n ₂ is an integer in the range from 0 to 2,

[0036] [Formula 3]

,

,

[0037] where in formula 3

[0038] each of the groups A ₁ and A ₂ independently represents an alkylene group containing from 1 to 20 carbon atoms,

[0039] each of the groups from R _b1 to R _b4 independently represents an alkyl group containing from 1 to 20 carbon atoms,

[0040] each of R _b5 and R _b6 independently represents a hydrogen atom or an alkyl group containing from 1 to 10 carbon atoms, and

или

, где каждая из групп от R_b7 до R_b10 независимо представляет собой атом водорода или алкильную группу, содержащую от 1 до 10 атомов углерода,[0041] A ₃ and A ₄ are each independently

or

, where each of the groups from R _b7 to R _b10 independently represents a hydrogen atom or an alkyl group containing from 1 to 10 carbon atoms,

[0042] [Formula 4]

,

,

[0043] where in formula 4

[0044] R _c1 is a hydrogen atom or an alkyl group containing from 1 to 10 carbon atoms,

[0045] each of the groups from R _c2 to R _c4 independently represents an alkylene group containing from 1 to 10 carbon atoms,

[0046] each of the groups from R _c5 to R _c8 independently represents an alkyl group containing from 1 to 10 carbon atoms,

или

, где каждый из от R_с9 до R_с12 независимо представляет собой атом водорода или алкильную группу, содержащую от 1 до 10 атомов углерода, и[0047] A ₅ is

or

, where each of R _c9 to R _c12 independently represents a hydrogen atom or an alkyl group containing from 1 to 10 carbon atoms, and

[0048] each of m ₁ and m ₂ is independently an integer in the range from 0 to 3, whereby the equation m ₁ +m ₂ ≥1 is satisfied.

[0049] In addition, the present invention provides a rubber composition containing a modified conjugated diene-based polymer and a filler.

BENEFICIAL EFFECTS

[0050] The modified conjugated diene-based polymer of the present invention is obtained by carrying out continuous polymerization in which polymerization conversion is controlled in a controlled manner, and is characterized by a molecular weight distribution curve with a unimodal profile obtained using gel permeation chromatography and a narrow molecular weight distribution of less than 1.7, and thus exhibits excellent processability, tensile properties and viscoelastic properties. In addition, the modified conjugated diene-based polymer of the present invention contains a functional group derived from a modification initiator at one end position and a functional group derived from a modifier at the other end position, thereby providing a further demonstration improved viscoelastic properties.

BRIEF DESCRIPTION OF THE DRAWINGS

[0051]

The following drawings, which accompany the description of the invention, by way of example illustrate preferred examples of the present invention and, together with the following detailed description of the invention, are used to provide a further understanding of the concepts of the invention, and therefore the present invention should not be interpreted solely in connection with the material in such drawings.

[0052] FIGURE 1 shows a molecular weight distribution curve obtained using Gel Permeation Chromatography (GPC) for the modified conjugated diene-based polymer of Example 1, in accordance with one embodiment of the present invention.

[0053] FIGURE 2 shows the molecular weight distribution curve obtained using Gel Permeation Chromatography (GPC) for the modified conjugated diene-based polymer of Comparative Example 1, in accordance with one embodiment of the present invention.

[0054] FIGURE 3 shows a molecular weight distribution curve obtained using Gel Permeation Chromatography (GPC) for the modified conjugated diene-based polymer of Reference Example 1, in accordance with one embodiment of the present invention.

[0055] FIGURE 4 shows a molecular weight distribution curve obtained using Gel Permeation Chromatography (GPC) for the modified conjugated diene-based polymer of Reference Example 2, in accordance with one embodiment of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

[0056] Below in this document, the present invention will be described in more detail in order to facilitate understanding of the present invention.

[0057] As it should be understood, the words or terms used in the description of the invention and the claims of the present invention should not be interpreted as having the meaning defined in commonly used dictionaries. As it is further to be understood, words or terms are to be interpreted as having a meaning that is consistent with their meaning in light of the technical idea of the invention, on the principle that the inventor can properly determine the meaning of the words or terms for the best explanation of the invention.

[0058] The term "alkyl group" used in the present invention may refer to a monovalent aliphatic saturated hydrocarbon and may include both a linear alkyl group such as methyl, ethyl, propyl and butyl, and a branched alkyl group such as isopropyl, sec- butyl, tert-butyl and neopentyl.

[0059] The term "alkylene group" used in the present invention may refer to a divalent aliphatic saturated hydrocarbon such as methylene, ethylene, propylene and butylene.

[0060] The term "alkenyl group" used in the present invention may refer to an alkyl group containing one or two or more double bonds.

[0061] The term "alkynyl group" used in the present invention may refer to an alkyl group containing one or two or more triple bonds.

[0062] The term "cycloalkyl group" used in the present invention may refer to a cyclic saturated hydrocarbon or a cyclic unsaturated hydrocarbon containing one or two or more unsaturated bonds.

[0063] The term "aryl group" as used in the present invention may refer to a cyclic aromatic hydrocarbon and may include both a monocyclic aromatic hydrocarbon comprising one ring and a polycyclic aromatic hydrocarbon comprising two or more linked rings.

[0064] The term "heteroalkyl group" used in the present invention may refer to an alkyl group in which the carbon atom (excluding the carbon atom at the terminal position) in the alkyl group is substituted using one or more heteroatoms, where the heteroatom can be selected from N , O and S.

[0065] The term "heteroalkenyl group" used in the present invention may denote an alkenyl group in which the carbon atom (excluding the carbon atom at the terminal position) in the alkenyl group is substituted with one or more heteroatoms, where the heteroatom can be selected from N, O and S.

[0066] The term "heteroalkynyl group" used in the present invention may denote an alkynyl group in which the carbon atom (excluding the carbon atom at the terminal position) in the alkynyl group is substituted using one or more heteroatoms, where the heteroatom can be selected from N , O and S.

[0067] The term "heterocyclic group" used in the present invention may denote a cycloalkyl group in which the carbon atom in a cyclic saturated hydrocarbon or a cyclic unsaturated hydrocarbon containing one or more unsaturated bonds is substituted with one or more heteroatoms, where the heteroatom may be selected from N, O and S.

[0068] The terms "derived unit" and "derived functional group" used in the present invention may be a component or structure that arises from a particular substance, or the substance itself.

[0069] The term "single bond" used in the present invention may refer to the single covalent bond itself, not containing a separate atomic or molecular group.

[0070] A substituent or functional group in the present invention may be substituted or unsubstituted with identical or different substituent or functional group unless otherwise indicated.

[0071] The present invention provides a modified conjugated diene polymer obtained by carrying out continuous polymerization and is characterized by excellent processability, narrow molecular weight distribution, and excellent physical properties.

[0072] The modified conjugated diene polymer according to one embodiment of the present invention is characterized by having a molecular weight distribution curve with a unimodal profile obtained using gel permeation chromatography (GPC) and a molecular weight distribution (MW; MWD) ranging from 1.0 to less than 1.7, and contains a functional group derived from the initiator of the modification, in one terminal position and a functional group derived from the modifier and represented by any one fragment selected from the following formulas from formula 2 to formula 4, at the other end position, where the modification initiator is the product of the reaction between the compound represented by the following formula 1 and the organometallic compound:

[0073] [Formula 1]

[0074] in formula 1, each of the groups from R ₁ to R ₃ independently represents a hydrogen atom; an alkyl group containing from 1 to 30 carbon atoms; an alkenyl group containing 2 to 30 carbon atoms; alkynyl group containing from 2 to 30 carbon atoms; a heteroalkyl group containing 1 to 30 carbon atoms; a heteroalkenyl group containing 2 to 30 carbon atoms; a heteroalkynyl group containing 2 to 30 carbon atoms; a cycloalkyl group containing 5 to 30 carbon atoms; an aryl group containing 6 to 30 carbon atoms; or a heterocyclic group containing from 3 to 30 carbon atoms, R ₄ represents a single bond; a substituted or unsubstituted alkylene group containing from 1 to 20 carbon atoms together with a substituent; a substituted or unsubstituted cycloalkylene group containing from 5 to 20 carbon atoms together with a substituent; or a substituted or unsubstituted arylene group containing from 6 to 20 carbon atoms together with a substituent, where the substituent is an alkyl group containing from 1 to 10 carbon atoms, a cycloalkyl group containing from 5 to 10 carbon atoms, or an aryl group containing from 6 to 20 carbon atoms, R ₅ is an alkyl group containing 1 to 30 carbon atoms; an alkenyl group containing 2 to 30 carbon atoms; alkynyl group containing from 2 to 30 carbon atoms; a heteroalkyl group containing 1 to 30 carbon atoms; a heteroalkenyl group containing 2 to 30 carbon atoms; a heteroalkynyl group containing 2 to 30 carbon atoms; a cycloalkyl group containing 5 to 30 carbon atoms; an aryl group containing 6 to 30 carbon atoms; a heterocyclic group containing 3 to 30 carbon atoms; or a functional group described by the following formula 1a or formula 1b, n is an integer in the range from 1 to 5, and at least one of the R ₅ groups is a functional group described by the following formula 1a or formula 1b, in the case where n is an integer in the range of 2 to 5, the plurality of R ₅ groups may be identical or different:

[0075] [Formula 1a]

[0076] in formula 1a, R ₆ is a substituted or unsubstituted alkylene group containing from 1 to 20 carbon atoms together with a substituent; a substituted or unsubstituted cycloalkylene group containing from 5 to 20 carbon atoms together with a substituent; or a substituted or unsubstituted arylene group containing from 6 to 20 carbon atoms together with a substituent, where the substituent is an alkyl group containing from 1 to 10 carbon atoms, a cycloalkyl group containing from 5 to 10 carbon atoms, or an aryl group containing from 6 to 20 carbon atoms, each of R ₇ and R ₈ independently represents an alkyl group containing 1 to 10 carbon atoms, a cycloalkyl group containing 5 to 10 carbon atoms, or a substituted or unsubstituted alkylene group containing 1 to 20 carbon atoms together with an aryl group containing from 6 to 20 carbon atoms, R ₉ represents a hydrogen atom; an alkyl group containing from 1 to 30 carbon atoms; an alkenyl group containing 2 to 30 carbon atoms; alkynyl group containing from 2 to 30 carbon atoms; a heteroalkyl group containing 1 to 30 carbon atoms; a heteroalkenyl group containing 2 to 30 carbon atoms; a heteroalkynyl group containing 2 to 30 carbon atoms; a cycloalkyl group containing 5 to 30 carbon atoms; an aryl group containing 6 to 30 carbon atoms; or a heterocyclic group containing from 3 to 30 carbon atoms and X is an N, O or S atom, when X is O or S, R ₉ is absent,

[0077] [Formula 1b]

[0078] in formula 1b, R ₁₀ is a substituted or unsubstituted alkylene group containing from 1 to 20 carbon atoms together with a substituent; a substituted or unsubstituted cycloalkylene group containing from 5 to 20 carbon atoms together with a substituent; or a substituted or unsubstituted arylene group containing from 6 to 20 carbon atoms together with a substituent, where the substituent is an alkyl group containing from 1 to 10 carbon atoms, a cycloalkyl group containing from 5 to 10 carbon atoms, or an aryl group containing from 6 to 20 carbon atoms, and each of R ₁₁ and R ₁₂ independently represents an alkyl group containing from 1 to 30 carbon atoms; an alkenyl group containing 2 to 30 carbon atoms; alkynyl group containing from 2 to 30 carbon atoms; a heteroalkyl group containing 1 to 30 carbon atoms; a heteroalkenyl group containing 2 to 30 carbon atoms; a heteroalkynyl group containing 2 to 30 carbon atoms; a cycloalkyl group containing 5 to 30 carbon atoms; an aryl group containing 6 to 30 carbon atoms; or a heterocyclic group containing from 3 to 30 carbon atoms,

[0079] [Formula 2]

[0080] in Formula 2, R _a1 and R _a4 are each independently a single bond or an alkylene group having 1 to 10 carbon atoms, R _a2 and R _a3 are each independently an alkyl group having 1 to 10 carbon atoms , R _a5 is a five-membered heterocyclic group containing from 2 to 4 carbon atoms and containing one or more heteroatoms selected from the group consisting of N, O and S, n ₁ is an integer in the range from 1 to 3, and n ₂ is an integer in the range from 0 to 2,

[0081] [Formula 3]

или

, где каждый из от R_b7 до R_b10 независимо представляет собой атом водорода или алкильную группу, содержащую от 1 до 10 атомов углерода,[0082] in formula 3, each of A ₁ and A ₂ independently represents an alkylene group containing from 1 to 20 carbon atoms, each of R _b1 to R _b4 independently represents an alkyl group containing from 1 to 20 carbon atoms, each of R _b5 and R _b6 independently represents a hydrogen atom or an alkyl group containing from 1 to 10 carbon atoms, and each of A ₃ and A ₄ independently represents

or

, where each of R _b7 to R _b10 independently represents a hydrogen atom or an alkyl group containing from 1 to 10 carbon atoms,

[0083] [Formula 4]

или

, где каждый из от R_с9 до R_с12 независимо представляет собой атом водорода или алкильную группу, содержащую от 1 до 10 атомов углерода, и каждый из m₁ и m₂ независимо представляет собой целое число в диапазоне от 0 до 3, где удовлетворяется уравнение m₁+m₂≥1.[0084] in formula 4, R _c1 is a hydrogen atom or an alkyl group containing 1 to 10 carbon atoms, each of R _c2 to R _c4 independently represents an alkylene group containing 1 to 10 carbon atoms, each of R _c5 to R _c8 independently represents an alkyl group containing from 1 to 10 carbon atoms, A ₅ represents

or

, where each of R _c9 to R _c12 independently represents a hydrogen atom or an alkyl group containing from 1 to 10 carbon atoms, and each of m ₁ and m ₂ independently represents an integer in the range from 0 to 3, where the equation is satisfied m ₁ +m ₂ ≥1.

[0085] In accordance with one embodiment of the present invention, the modified conjugated diene polymer may contain a repeat unit derived from the conjugated diene monomer, a functional group derived from a modification initiator, and a functional group derived from a modifier. The term "conjugated diene monomer-derived repeating unit" may mean a repeating unit obtained by using a conjugated diene-based monomer during polymerization, and the terms "modification initiator-derived functional group" and "modification initiator-derived functional group" modifier" may denote functional groups derived from the initiator of the modification and the modifier, which are present, respectively, in the terminal positions of the polymer chain.

[0086] In addition, according to another embodiment of the present invention, the modified conjugated diene polymer may be a copolymer containing a repeat unit derived from a conjugated diene monomer, a repeat unit derived from an aromatic vinyl monomer , a functional group derived from the initiator of the modification, and a functional group derived from the modifier. In this case, the term "repeating elementary unit derived from aromatic vinyl monomer" may refer to a repeating elementary unit obtained by using an aromatic vinyl monomer during polymerization.

[0087] According to one embodiment of the present invention, the conjugated diene monomer may be one or more selected from the group consisting of 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 (the term "halogen" means a halogen atom).

[0088] The aromatic vinyl monomer may include, for example, one or more members selected from the group consisting of styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (p-methylphenyl)styrene, 1-vinyl-5-hexylnaphthalene, 3-(2-pyrrolidinoethyl)styrene, 4-(2-pyrrolidinoethyl)styrene and 3-(2-pyrrolidino-1-methylethyl)-α-methylstyrene.

[0089] In yet another embodiment, the modified conjugated diene-based polymer may be a copolymer further comprising a repeat unit derived from a diene-based monomer having 1 to 10 carbon atoms, together with a repeat unit derived from from a monomer based on a conjugated diene. The repeat unit derived from the diene-based monomer may be a repeat unit derived from the diene-based monomer which is different from the conjugated diene-based monomer, and the diene-based monomer which is different from the conjugated diene based monomer may represent is, for example, 1,2-butadiene. In the case of a modified conjugated diene based polymer which is a copolymer further including a diene based monomer, the modified conjugated diene based polymer may contain a repeat unit derived from the diene based monomer in an amount ranging from more than 0% (mass) to 1% (mass), more than 0% (mass) to 0.1% (mass), more than 0% (mass) to 0.01% ( mass.) or from more than 0% (mass.) to 0.001% (mass.), and within this range, you can achieve the effect of preventing gelation.

[0090] According to one embodiment of the present invention, the copolymer may be a random copolymer, and in this case, an excellent balance between each physical property can be achieved. The term "random copolymer" may refer to the arrangement of repeating unit units that form a copolymer when arranged randomly.

[0091] The modified conjugated diene polymer according to one embodiment of the present invention may have a number average molecular weight (Mn) in the range of 1,000 g/mol to 2,000,000 g/mol, 10,000 g/mol to 1,000,000 g/mol, or 100000 g/mol to 800000 g/mol, weight average molecular weight (Mw) ranging from 1000 g/mol to 3000000 g/mol, from 10000 g/mol to 2000000 g/mol or from 100000 g/mol to 2000000 g/mol and a peak molecular weight (Mp) ranging from 1000 g/mol to 3,000,000 g/mol, from 10,000 g/mol to 2,000,000 g/mol, or from 100,000 g/mol to 2,000,000 g/mol. Within these ranges, rolling resistance and wet slip resistance are excellent. In yet another embodiment, the modified conjugated diene polymer may have a molecular weight distribution (MW; MWD; Mw/Mn) ranging from 1.0 to less than 1.7, or from 1.1 to less than 1, 7, and within this range, the tensile mechanical properties and the viscoelasticity characteristics are excellent, and the balance between each physical property is excellent.

[0092] In yet another embodiment, the modified conjugated diene polymer may have a ratio between a weight average molecular weight (Mw) and a peak-top molecular weight (Mp) in the range of 0.7 to 1.4, and within this range the mechanical properties in tension, abrasion resistance and viscoelasticity characteristics are good, and the balance between each physical property is excellent.

[0093] At the same time, the modified conjugated diene-based polymer can be characterized by having a molecular weight distribution curve with a unimodal profile obtained using Gel Permeation Chromatography (GPC). This molecular weight distribution is shown by the polymer obtained by carrying out continuous polymerization, and this means that the modified conjugated diene-based polymer exhibits uniform properties. That is, the modified conjugated diene-based polymer according to one embodiment of the present invention is obtained by carrying out continuous polymerization, and can have a molecular weight distribution curve with a unimodal profile and a molecular weight distribution ranging from 1.0 to less than 1.7.

[0094] In general, the molecular weight distribution curve for a conjugated diene-based polymer obtained during the preparation of a conjugated diene-based polymer using a batch polymerization method, and after that carrying out the modification reaction, is a molecular weight distribution curve related to multimodal , that is, bimodal and more polymodal, variant. In particular, when carrying out batch polymerization, the polymerization reaction is initiated after injection of all raw materials, and from the point of initiation, when the polymerization is carried out using a plurality of initiators, chain growth can also take place simultaneously. Accordingly, the growth of each chain may be generally uniform, the molecular weight of the polymer chains thus obtained may be constant, and the molecular weight distribution may be sufficiently narrow to exhibit a unimodal profile. However, in the case of injecting the modifier and carrying out the modification reaction, there may be two cases - "the case without modification" and "the case of modification and combination", two groups can be formed in the number of polymer chains, showing a large difference in molecular weights, and at least , at least a multimodal molecular weight distribution curve having two or more peaks of the molecular weight distribution curve can be formed. Meanwhile, in the continuous polymerization method according to one embodiment of the present invention, unlike batch polymerization, the initiator and raw materials are injected continuously, the initiation timings when polymerization is initiated are different, and the polymerization is initiated at various timings, including reaction initiation, intermediate the state of the reaction and the end of the reaction. Accordingly, after completion of the polymerization reaction, polymer chains having different molecular weights are produced. Accordingly, in the molecular weight distribution curve, not the absence of a dominant peak is shown, but the broad molecular weight distribution curve is shown as a single peak. In addition, although coupling is carried out for the chain to which polymerization is initiated at the end of the reaction, the molecular weight may be similar to that of the chain to which polymerization is initiated at the beginning of the reaction, and the peculiarity of the molecular weight distribution may be kept identical, and in general the unimodal distribution curve can still be kept.

[0095] However, the conditions for carrying out the modification can be controlled to show a unimodal profile despite the polymer being obtained by carrying out polymerization using a batch polymerization method and then modifying it. However, in this case, the coupling is not required to be carried out for the entire polymer, or it is not required to have the entire polymer coupled. Otherwise, a unimodal molecular weight distribution curve may not be shown.

[0096] In addition, in accordance with the above description of the invention, in the case of showing a molecular weight distribution curve for a modified polymer based on a conjugated diene of a unimodal distribution, despite being obtained using a batch polymerization method and performing a coupling, polymers will be present for the entire polymer, having an equivalent molecular weight level, and thus processability may be impaired, and functional groups that may interact with filler such as silica and carbon black are reduced in number due to the passage of the coupling, and compounding performance may be impaired. Conversely, in the case of coupling not all of the polymer, the functional groups at the end position of the polymer, which must interact with the filler, such as silica and carbon black, during processing, predominantly lead to the interaction between the end functional groups of the polymer, and not with the filler. , and interaction with the filler can be prevented. Accordingly, the processability may be significantly degraded, and at least in the case of controlled exposure to the polymer exhibiting a unimodal molecular weight distribution curve while being produced using a batch polymerization process, the processability and compounding characteristics of the modified conjugated diene-based polymer obtained thus, may be impaired, and in particular, processability may be noticeably impaired.

[0097] Meanwhile, the coupling progress status of the modified conjugated diene-based polymer can be checked by the coupling number (CN), where the coupling number is a value dependent on the number of functional groups that are able to bind to the polymer present in the modifier after modification. polymer. That is, the coupling number is the ratio between a polymer obtained by modifying an end group without coupling between polymer chains and a polymer in which a plurality of polymer chains are coupled using a single modifier, and may be in the range of 1≦C≦F, where F denotes the number of functional groups in the modifier, which are able to react with the end group of the active polymer. In other words, the term "modified conjugated diene based polymer having a coupling number of 1" means non-coupling for all polymer chains, and the term "modified conjugated diene based polymer having a coupling number F" means coupling for all polymer chains.

[0098] Accordingly, the modified conjugated diene polymer according to one embodiment of the present invention may have a molecular weight distribution curve with a unimodal profile and a combination number greater than 1 and less than the number of functional groups in the used modifier, (1 < CHS < F).

[0099] In yet another embodiment, the modified conjugated diene polymer may have a Si content of 50 ppm. and more, 100 ppm and more, being in the range from 100 hours/million. up to 10,000 ppm or from 100 ppm up to 5000 ppm on a weight basis, and within this range, mechanical properties such as tensile properties and viscoelasticity characteristics of the rubber composition containing the modified conjugated diene polymer are excellent. The term "Si level" may refer to the number of Si atoms present in the modified conjugated diene based polymer. Meanwhile, the Si atom may be derived from the modifier.

[00100] The Si level can be measured using, for example, an ICP analysis method, and can be measured using an ICP analysis method using inductively coupled plasma optical emission spectroscopy (ICP-OES; Optima 7300DV). In the case of inductively coupled plasma optical emission spectroscopy, measurement can be made by adding approximately 0.7 g of sample to a platinum (Pt) crucible, adding approximately 1 ml of concentrated sulfuric acid (98% (wt.), electron purity), heating at 300°C for 3 hours, calcining the sample in an electric oven (Thermo Scientific, Lindberg Blue M) using the following program, including steps 1 to 3:

[00101] 1) stage 1: initial temperature 0°C, rate (temperature/hour) 180°C/hour, temperature (hold time) 180°C (1 hour),

[00102] 2) stage 2: initial temperature 180°C, rate (temperature/hour) 85°C/hour, temperature (hold time) 370°C (2 hours), and

[00103] 3) stage 3: initial temperature 370°C, rate (temperature/hour) 47°C/hour, temperature (hold time) 510°C (3 hours),

[00104] adding 1 ml of concentrated nitric acid (48% (wt.)) and 20 μl of concentrated hydrofluoric acid (50% (wt.)) to the residue, sealing the platinum crucible and shaking it for 30 minutes or more, adding to the sample 1 ml of boric acid, storage at 0°C for 2 hours or more, dilution in 30 ml of highly pure water and calcination.

[00105] In this case, the sample used in the ICP analysis method is a modified conjugated diene-based polymer sample obtained by placing it in hot water heated using steam and subjecting it to agitation to remove solvents and remove remaining monomer from it. and modifier. In addition, in the case of adding oil to a sample, the sample may be the sample after the oil has been extracted (removed) from it.

[00106] In yet another embodiment, the modified conjugated diene polymer may have a N content of 50 ppm. and more, 100 ppm and more, being in the range from 100 hours/million. up to 10,000 ppm or from 100 ppm up to 5000 ppm on a total weight basis, and within this range, mechanical properties such as tensile mechanical properties and viscoelastic properties are excellent for a rubber composition containing a modified conjugated diene-based polymer. The term "N level" may refer to the number of N atoms present in the modified conjugated diene-based polymer, and in this case, the N atom may be derived from a functional group derived from the modifier.

[00107] The level of N content can be measured using, for example, the NSX analysis method (nitrogen, sulfur, halogen), and can be measured using the NSX analysis method using a trace nitrogen quantitative analyzer (NSX-2100H).

[00108] For example, in the case of using a quantitative trace nitrogen analyzer, the quantitative trace nitrogen analyzer (autosampler, horizontal oven, PMT and nitrogen detector) was turned on, the flowing quantities of the carrier gas were set such that Ar would take place 250 ml / min, for O ₂ there would be 350 ml/min and for the ozonator there would be 300 ml/min, the heater was set to 800° C. and the analyzer was allowed to stand for approximately 3 hours to stabilize. After stabilizing the analyzer using a nitrogen standard (AccuStandard S-22750-01-5 ml), a calibration curve was obtained in the calibration ranges 5 ppm, 10 ppm, 50 ppm, 100 ppm . and 500 ppm, an area corresponding to each concentration was obtained, and a straight line was obtained using the ratio between concentration and area. Thereafter, a ceramic boat containing 20 mg of sample was placed on the autosampler of the analyzer and measured to obtain an area. The N content was calculated using the sample area thus obtained and the calibration curve.

[00109] In this case, the sample used in the NSX analysis method is a modified conjugated diene based polymer sample obtained by placing it in hot water heated using steam, and subjecting it to agitation to remove solvents and remove remaining monomer from it and modifier. In addition, in the case of adding oil to a sample, the sample may be the sample after the oil has been extracted (removed) from it.

[00110] In yet another embodiment, the modified conjugated diene polymer may have a Mooney stress relaxation ratio of 0.7 or greater as measured at 100°C, ranging from 0.7 to 3.0, from 0, 7 to 2.5 or 0.7 to 2.0.

[00111] Here, the Mooney stress relaxation ratio is the change in stress exhibited in response to the same amount of strain, and can be measured using a Mooney viscometer. In particular, the Mooney stress relaxation ratio was obtained as an absolute value by measuring the Mooney viscosity using a large rotor for the MV-2000E device from Monsanto Co. at a rotor speed of 2 ± 0.02 rpm at 100°C, when the polymer is kept at room temperature (23 ± 3°C) for 30 minutes or more, collecting 27 ± 3 g of the polymer and placing it in the matrix cavity, and after that actuating the platen while simultaneously applying torque, and after that measuring the magnitude of the level of the demonstrated change in Mooney viscosity while bleeding off the torque.

[00112] Meanwhile, the Mooney stress relaxation ratio can be used as an indicator of the presence of a branched structure in the corresponding polymer. For example, in the case of comparing polymers having an equivalent Mooney viscosity, the Mooney stress relaxation ratio may decrease as the degree of branching increases, and thus can be used as an indicator of the degree of branching.

[00113] In addition, the modified conjugated diene polymer may have a Mooney viscosity of 30 or more at 100° C., ranging from 40 to 150 or 40 to 140, and within this range, processability and productivity may be excellent.

[00114] In yet another embodiment, the modified conjugated diene polymer may have a shrinkage factor (g'), which is measured using a gel permeation chromatography-light scattering method equipped with a viscometer, and which is 0.8 or more, in particular is in the range from 0.8 to 3.0, more specifically, from 0.8 to 1.3, more specifically, from 1.0 to 1.3.

[00115] In this case, the shrinkage coefficient (g') obtained from the measurement using the GPC-Light Scattering method is the ratio between the intrinsic viscosity of a polymer having branching and the intrinsic viscosity of a linear polymer having the same absolute molecular weight, and can be used as an indicator of the presence of a branched structure in a polymer characterized by the presence of branching, that is, an indicator of the proportion occupied by branching. For example, as the shrinkage ratio decreases, the degree of branching for the respective polymer tends to increase. Accordingly, in the case of comparing polymers having an equivalent absolute molecular weight, the shrinkage ratio will decrease as branching increases, and the shrinkage ratio can be used as an indicator of the degree of branching.

[00116] In addition, the shrinkage coefficient is obtained by measuring the chromatogram using a gel permeation chromatography-light scattering apparatus equipped with a viscometer and performing a computer calculation based on the viscosity of the solution and the light scattering method. In particular, when using a GPC light scattering apparatus equipped with a light scattering detector, in which two columns filled as a filler with a polystyrene-based gel and a viscometer are connected, the absolute molecular weight and intrinsic viscosity corresponding to each absolute molecular weight are obtained, computer calculating the intrinsic viscosity for the linear polymer corresponding to the absolute molecular weight, and obtaining the shrinkage ratio as a ratio for the intrinsic viscosity corresponding to each absolute molecular weight. For example, the shrinkage ratio was obtained as follows. The sample was injected into a GPC light scattering apparatus (Viscotek TDAmax, Malvern Co.) equipped with a light scattering detector in which two columns packed with a polystyrene-based gel as a filler and a viscometer were connected, and the absolute molecular weight was obtained from the light scattering detector, intrinsic viscosity [η] relative to absolute molecular weight from the light scattering detector and viscometer, using the following mathematical formula 3, a computer calculation of the intrinsic viscosity [η] ₀ for a linear polymer with respect to absolute molecular weight was carried out, and the average value was presented as the shrinkage coefficient ratios for intrinsic viscosity ([η]/[η] ₀ ) corresponding to each absolute molecular weight. In this case, the measurement was carried out using a mixture solution of tetrahydrofuran and N,N,N',N'-tetramethylethylenediamine (corrected by mixing 20 ml of N,N,N',N'-tetramethylethylenediamine with 1 liter of tetrahydrofuran) as eluent and a PL Olexix device (Agilent Co.) as a column under conditions of an oven temperature of 40° C. and a THF flow rate of 1.0 ml/min. The sample was obtained by dissolving 15 mg of polymer in 10 ml of THF.

[00117] [Mathematical formula 3]

[η] ₀ =10 ^{- 3.883} M ^0.771

[00118] In the mathematical formula, 3 M is the absolute molecular weight.

[00119] In addition, the modified conjugated diene polymer may have a vinyl content of 5% (wt.) or more, 10% (wt.) or more, or ranging from 10% (wt.) to 60% (wt.). In this case, the term "vinyl level" may refer to the amount of conjugated diene-based monomer attached not by 1,4-addition mechanism, but by 1,2-addition mechanism, relative to 100% (wt.) of the conjugated diene-based copolymer a diene formed from a monomer containing a vinyl group and an aromatic vinyl monomer.

[00120] In yet another embodiment, the modified conjugated diene polymer may be characterized by having a unimodal molecular weight distribution curve obtained using gel permeation chromatography (GPC), weight average molecular weight (Mw) when expressed in terms of molecular weight in terms of polystyrene standard as defined using gel permeation chromatography in the range of 1000 g/mol to 3000000 g/mol, the ratio (Mw/Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the range of 1.0 to less than 1.7, the ratio (Mw/Mp) between the weight average molecular weight (Mw) and the molecular weight of the top of the peak (Mp) in the range of 0.7 to 1.4, the level of Si content and the level of N content, respectively, 50 parts. /mln. and more in terms of weight, and the ratio of stress relaxation according to Mooney, which, according to the measurement at 100°C, is 0.7 or more. Also, the modified conjugated diene-based polymer contains a polymer component characterized by a molecular weight of 100,000 g/mol or more when expressed in terms of molecular weight in terms of a polystyrene standard as determined using gel permeation chromatography (GPC), and the presence of a unimodal profile. In addition, the modified conjugated diene-based polymer may have a shrinkage ratio measured using a gel permeation chromatography-light scattering method equipped with a viscometer of 0.8 or more.

[00121] Meanwhile, the modification initiator according to one embodiment of the present invention is produced by carrying out the reaction between the compound of formula 1 and an organometallic compound, and can introduce a functional group at one end position of the polymer chain obtained by carrying out the polymerization, in the same time as polymerization initiation.

[00122] [Formula 1]

[00123] in formula 1, each of R ₁ to R ₃ independently represents a hydrogen atom; an alkyl group containing from 1 to 30 carbon atoms; an alkenyl group containing 2 to 30 carbon atoms; alkynyl group containing from 2 to 30 carbon atoms; a heteroalkyl group containing 1 to 30 carbon atoms; a heteroalkenyl group containing 2 to 30 carbon atoms; a heteroalkynyl group containing 2 to 30 carbon atoms; a cycloalkyl group containing 5 to 30 carbon atoms; an aryl group containing 6 to 30 carbon atoms; or a heterocyclic group containing from 3 to 30 carbon atoms, R ₄ represents a single bond; a substituted or unsubstituted alkylene group containing from 1 to 20 carbon atoms together with a substituent; a substituted or unsubstituted cycloalkylene group containing from 5 to 20 carbon atoms together with a substituent; or a substituted or unsubstituted arylene group containing from 6 to 20 carbon atoms together with a substituent, where the substituent is an alkyl group containing from 1 to 10 carbon atoms, a cycloalkyl group containing from 5 to 10 carbon atoms, or an aryl group containing from 6 to 20 carbon atoms, R ₅ is an alkyl group containing 1 to 30 carbon atoms; an alkenyl group containing 2 to 30 carbon atoms; alkynyl group containing from 2 to 30 carbon atoms; a heteroalkyl group containing 1 to 30 carbon atoms; a heteroalkenyl group containing 2 to 30 carbon atoms; a heteroalkynyl group containing 2 to 30 carbon atoms; a cycloalkyl group containing 5 to 30 carbon atoms; an aryl group containing 6 to 30 carbon atoms; a heterocyclic group containing 3 to 30 carbon atoms; or a functional group described by the following formula 1a or formula 1b, n is an integer in the range from 1 to 5, and at least one of the R ₅ groups is a functional group described by the following formula 1a or formula 1b, in the case where n is an integer in the range of 2 to 5, the plurality of R ₅ groups may be identical or different:

[00124] [Formula 1a]

[00125] in formula 1a, R ₆ is a substituted or unsubstituted alkylene group containing from 1 to 20 carbon atoms together with a substituent; a substituted or unsubstituted cycloalkylene group containing from 5 to 20 carbon atoms together with a substituent; or a substituted or unsubstituted arylene group containing from 6 to 20 carbon atoms together with a substituent, where the substituent is an alkyl group containing from 1 to 10 carbon atoms, a cycloalkyl group containing from 5 to 10 carbon atoms, or an aryl group containing from 6 to 20 carbon atoms, each of R ₇ and R ₈ independently represents an alkyl group containing 1 to 10 carbon atoms, a cycloalkyl group containing 5 to 10 carbon atoms, or a substituted or unsubstituted alkylene group containing 1 to 20 carbon atoms together with an aryl group containing from 6 to 20 carbon atoms, R ₉ represents a hydrogen atom; an alkyl group containing from 1 to 30 carbon atoms; an alkenyl group containing 2 to 30 carbon atoms; alkynyl group containing from 2 to 30 carbon atoms; a heteroalkyl group containing 1 to 30 carbon atoms; a heteroalkenyl group containing 2 to 30 carbon atoms; a heteroalkynyl group containing 2 to 30 carbon atoms; a cycloalkyl group containing 5 to 30 carbon atoms; an aryl group containing 6 to 30 carbon atoms; or a heterocyclic group containing from 3 to 30 carbon atoms and X is an N, O or S atom, when X is O or S, R ₉ is absent,

[00126] [Formula 1b]

[00127] in formula 1b, R ₁₀ is a substituted or unsubstituted alkylene group containing from 1 to 20 carbon atoms together with a substituent; a substituted or unsubstituted cycloalkylene group containing from 5 to 20 carbon atoms together with a substituent; or a substituted or unsubstituted arylene group containing from 6 to 20 carbon atoms together with a substituent, where the substituent is an alkyl group containing from 1 to 10 carbon atoms, a cycloalkyl group containing from 5 to 10 carbon atoms, or an aryl group containing from 6 to 20 carbon atoms, and each of R ₁₁ and R ₁₂ independently represents an alkyl group containing from 1 to 30 carbon atoms; an alkenyl group containing 2 to 30 carbon atoms; alkynyl group containing from 2 to 30 carbon atoms; a heteroalkyl group containing 1 to 30 carbon atoms; a heteroalkenyl group containing 2 to 30 carbon atoms; a heteroalkynyl group containing 2 to 30 carbon atoms; a cycloalkyl group containing 5 to 30 carbon atoms; an aryl group containing 6 to 30 carbon atoms; or a heterocyclic group containing 3 to 30 carbon atoms.

[00128] In particular, the compound described by formula 1 may correspond to formula 1, where each of R ₁ to R ₃ independently represents a hydrogen atom; an alkyl group containing from 1 to 10 carbon atoms; an alkenyl group containing 2 to 10 carbon atoms; or an alkynyl group containing 2 to 10 carbon atoms, R ₄ is a single bond; or an unsubstituted alkylene group containing 1 to 10 carbon atoms, R ₅ is an alkyl group containing 1 to 10 carbon atoms; an alkenyl group containing 2 to 10 carbon atoms; an alkynyl group containing 2 to 10 carbon atoms; or a functional group described by the following formula 1a or formula 1b, in formula 1a R ₆ is an unsubstituted alkylene group containing 1 to 10 carbon atoms, each of R ₇ and R ₈ independently represents an unsubstituted alkylene group containing 1 to 10 carbon atoms, R ₉ is an alkyl group containing 1 to 10 carbon atoms; a cycloalkyl group containing 5 to 20 carbon atoms; an aryl group containing 6 to 20 carbon atoms; or a heterocyclic group containing from 3 to 20 carbon atoms, and in the formula 1b R ₁₀ represents an unsubstituted alkylene group containing from 1 to 10 carbon atoms, and each of R ₁₁ and R ₁₂ independently represents an alkyl group containing from 1 to 10 carbon atoms; a cycloalkyl group containing 5 to 20 carbon atoms; an aryl group containing 6 to 20 carbon atoms; or a heterocyclic group containing 3 to 20 carbon atoms.

[00129] More specifically, the compound described by formula 1 may be a compound described by the following formulas from formula 1-1 to formula 1-3:

[00130] [Formula 1-1]

[00131] [Formula 1-2]

[00132] [Formula 1-3]

[00133] In addition, the organometallic compound may be an organic alkali metal compound, for example, one or more selected from an organolithium compound, an organosodium compound, an organopotassium compound, an organorubidium compound, and an organocesium compound.

[00134] In particular, the organometallic compound may be one or more selected from the group consisting of methyl lithium, ethyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, t-butyl lithium, n-decyl lithium, t-octyl lithium, phenyl lithium, 1 -naphthyllithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium and 4-cyclopentyllithium.

[00135] In addition, the modifier of the present invention may be a modifier designed to modify the remaining one end group of the conjugated diene polymer, and in one particular embodiment may be a modifier having an affinity for silica. The term "modifier having affinity for silica" may refer to a modifier having a functional group having affinity for silica in the compound used as a modifier, and the term "functional group having affinity for silicon dioxide" may refer to a functional group which has an excellent affinity for a filler, in particular a silica filler, and it is capable of obtaining an interaction between the silica filler and the modifier-derived functional group.

[00136] In particular, in accordance with one embodiment of the present invention, the modifier may be a compound described by formula 2, and in formula 2, each of R _a1 and R _a4 independently represents a single bond or an alkylene group containing from 1 to 5 atoms carbon, each of R _a2 and R _a3 independently represents an alkyl group containing from 1 to 5 carbon atoms, R _a5 represents a five-membered heterocyclic group containing from 2 to 4 carbon atoms and containing one or more heteroatoms selected from the group consisting of of N, O and S, where the heterocyclic group may be substituted or unsubstituted using a (trialkoxysilyl)alkyl group, and the alkyl group in the (trialkoxysilyl)alkyl group may be an alkyl group containing from 1 to 5 carbon atoms, and the alkoxy group may be an alkoxy group containing from 1 to 5 carbon atoms. In addition, the five-membered heterocyclic group may be a five-membered heterocyclic group containing N.

[00137] In one more specific embodiment, the compound of formula 2 may be one member selected from the group consisting of N-(3-(1H-imidazol-1-yl)propyl)-3-(1H-imidazol- 1-yl)-N-((triethoxysilyl)methyl)propan-1-amine, N-(3-(1H-1,2,4-triazol-1-yl)propyl)-3-(trimethoxysilyl)-N- ((trimethoxysilyl)propyl)propan-1-amine, N-(3-(1H-1,2,4-triazol-1-yl)propyl)-3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl )propan-1-amine and 3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)-N-(3-(1-(3-(trimethoxysilyl)propyl)-1H-1,2,4-triazole -3-yl)propyl)propan-1-amine.

или

, где каждый из от R_b7 до R_b10 независимо представляет собой атом водорода или алкильную группу, содержащую от 1 до 10 атомов углерода.[00138] In addition, in particular, in accordance with another embodiment of the present invention, the modifier may be a compound described by formula 3, and in formula 3, each of A ₁ and A ₂ independently represents an alkylene group containing from 1 up to 10 carbon atoms, each of R _b1 to R _b4 independently represents an alkyl group containing from 1 to 10 carbon atoms, each of R _b5 and R _b6 independently represents a hydrogen atom or an alkyl group containing from 1 to 10 carbon atoms , and each of A ₃ and A ₄ independently represents

or

, where each of R _b7 to R _b10 independently represents a hydrogen atom or an alkyl group containing from 1 to 10 carbon atoms.

[00139] More specifically, the compound described by formula 3 may be the compound described by the following formula 3-1 or formula 3-2:

[00140] [Formula 3-1]

[00141] [Formula 3-2]

[00142] In formula 3-1 and formula 3-2, each of A ₁ and A ₂ independently represents an alkylene group containing from 1 to 10 carbon atoms, and each of R _b1 to R _b4 independently represents an alkyl group containing from 1 to 10 carbon atoms.

[00143] In one more specific embodiment, the compound of Formula 3 may be one member selected from the group consisting of 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 and 1,3-bis(3-(1H-imidazol-1 -yl)propyl)-1,1,3,3-tetrapropoxydisiloxane.

или

, где каждый из от R_с9 до R_с12 независимо представляет собой атом водорода или алкильную группу, содержащую от 1 до 10 атомов углерода.[00144] In addition, in particular, in accordance with another embodiment of the present invention, the modifier may be a compound described by formula 4, and in formula 4 R _c1 represents a hydrogen atom or an alkyl group containing from 1 to 5 atoms carbon, each of R _c2 to R _c4 independently represents an alkylene group containing from 1 to 5 carbon atoms, each of R _c5 to R _c8 independently represents an alkyl group containing from 1 to 5 carbon atoms, A ₅ represents

or

, where each of R _c9 to R _c12 independently represents a hydrogen atom or an alkyl group containing from 1 to 10 carbon atoms.

[00145] In one more specific embodiment, the compound of Formula 4 may be one member selected from the group consisting of 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.

[00146] As described above, in the modified conjugated diene polymer according to one embodiment of the present invention, the polymer has a specific structure and may have a specific degree and profile of molecular weight distribution. Such a polymer structure can be expressed in terms of physical properties such as shrinkage ratio, Mooney stress relaxation ratio, and combination number. The degree and profile of its molecular weight distribution can be expressed in terms of the CP value, the profile of the molecular weight distribution curve and the number of combinations, and modification at both end positions using a modifier and a modification initiator can affect its structure and the degree and profile of molecular mass distribution. The parameters expressing the structure of such a polymer and the characteristics related to the molecular weight distribution can be satisfied using the method of preparation, which will be described below. In addition, the above-mentioned characteristics can preferably be satisfied using this production method, but the effects intended to be carried out in the present invention can only be achieved if all of the above-mentioned characteristics are satisfied.

[00147] In addition, the present invention provides a method for producing a modified polymer based on a conjugated diene.

[00148] A method for producing a modified conjugated diene based polymer according to one embodiment of the present invention may include the step of polymerizing a conjugated diene based monomer or a conjugated diene based monomer and an aromatic vinyl monomer in the presence of a modification initiator in a hydrocarbon solvent to obtain an active polymer, containing a functional group derived from the modification initiator, (S1); and a step of carrying out a reaction or coupling between the active polymer obtained in step (S1) and the modifier having any one formula selected from Formula 2 to Formula 4 below, (S2), wherein step (S1) is continuously carried out in two and more polymerization reactors, and the degree of polymerization conversion in the first reactor among the polymerization reactors may be 50% or less, and the modification initiator is a reaction product obtained by carrying out the reaction between the compound described by the following formula 1 and an organometallic compound.

[00149] [Formula 1]

[00150] [Formula 2]

[00151] [Formula 3]

[00152] [Formula 4]

[00153] In formulas 1 to formula 4, R ₁ to R ₅ , R _a1 to R _a5 , R _b1 to R _b6 , R _c1 to R _c8 , A ₁ to A ₅ , n, from n ₁ to n ₂ , m ₁ and m ₂ are the same as the corresponding parameters defined above.

[00154] The hydrocarbon solvent is not particularly limited and may be, for example, one or more selected from the group consisting of n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene, and xylene .

[00155] In addition, the conjugated diene monomer and the aromatic vinyl monomer are the same as the corresponding parameters defined above.

[00156] In accordance with one embodiment of the present invention, the modification initiator can be used in an amount in the range from 0.01 mmol to 10 mmol, from 0.05 mmol to 5 mmol, from 0.1 mmol to 2 mmol, from 0, 1 mmol to 1 mmol or from 0.15 mmol to 0.8 mmol when calculated on a total of 100 g of monomers.

[00157] The polymerization of step (S1) may be, for example, an anionic polymerization, and in particular a "living" anionic polymerization, in which an anionic active moiety is formed at the end position of the polymerization by a chain propagation reaction using anions. In addition, the polymerization of step (S1) may be carried out as a heating polymerization, an isothermal polymerization, or a constant temperature polymerization (adiabatic polymerization). The term "constant temperature polymerization" refers to a polymerization method comprising a polymerization step using a self-generated heat of reaction without optional heat input after adding a polymerization initiator, and the term "heat polymerization" refers to a polymerization method including injecting a polymerization initiator and increasing the temperature by optionally supplying heat. The term "isothermal polymerization" means a polymerization process in which the temperature of the polymer is kept constant by heat input or heat removal after the addition of a polymerization initiator.

[00158] In addition, according to one embodiment of the present invention, the polymerization of step (S1) can be carried out by further incorporating a diene-based compound having 1 to 10 carbon atoms in addition to the conjugated diene-based monomer, and in this case, it is possible to achieve the effect of preventing the formation of gel on the side wall of the reactor during the operation for a long time. The diene-based compound may be, for example, 1,2-butadiene.

[00159] The polymerization of stage (S1) can be carried out in a temperature range of 80°C or less, concluded in the range from -20°C to 80°C, from 0°C to 80°C, from 0°C to 70 °C or 10°C to 70°C, and in this range, a highly linear polymer can be easily obtained, the Mooney stress relaxation ratio and the shrinkage ratio of the polymer can be improved, and moreover, the narrow molecular weight can be controlled in a controlled manner. mass distribution for the polymer, and the effect of excellent improvement in physical properties can be achieved.

[00160] The term "active polymer obtained from step (S1)" may refer to a polymer in which a polymer anion and an organometallic cation are combined.

[00161] In accordance with one embodiment of the present invention, a process for producing a modified conjugated diene polymer can be carried out in a plurality of reactors, including two or more polymerization reactors and a modification reactor, as a result of the continuous polymerization process. In one particular embodiment, step (S1) can be carried out continuously in two or more polymerization reactors including the first reactor, and the number of polymerization reactors can be flexibly determined according to the reaction conditions and the reaction medium. The term "continuous polymerization process" may refer to reaction processes in which reactants are continuously fed into the reactor and the reaction products thus obtained are continuously discharged. By using the continuous polymerization method, the effect of excellent productivity and processability and excellent uniformity can be achieved for the polymer thus obtained.

[00162] In addition, according to one embodiment of the present invention, in the case of continuous production of active polymer in the polymerization reactor, the polymerization conversion in the first reactor may be 50% or less, may be in the range of 10% to 50%, or 20% to 50%, and within this range, side reactions generated during polymer production after initiation of the polymerization reaction can be suppressed, and during polymerization, formation of a polymer having a linear structure can be induced. In this case, due to the low degree of branching for a polymer having a linear structure, when the polymer is produced by controlling the polymerization conversion in the first reactor at 50% or less, according to the above description of the invention, the stress relaxation ratio can be increased and the shrinkage ratio of the polymer, and moreover, the narrow molecular weight distribution of the polymer can be controlled in a controlled manner, and the effect of excellent improvement in physical properties can be achieved.

[00163] Here, the polymerization conversion rate can be controlled in accordance with the reaction temperature, the residence time in the reactor, and the like.

[00164] The degree of conversion during polymerization can be determined, for example, by measuring the concentration of solids in the phase of the polymer solution containing the polymer during polymerization to obtain a polymer. In one particular embodiment, in order to ensure that a polymer solution is obtained, a cylindrical type container is installed at the outlet from each polymerization reactor in order to fill the cylindrical type container with a certain amount of polymer solution. After that, the cylindrical type container is separated from the reactor, the mass (A) of the cylinder filled with polymer solution is measured, the polymer solution filling the cylindrical type container is transported into an aluminum container, such as an aluminum tray, the mass (B) is measured. of the cylindrical type container from which the polymer solution has been removed, the aluminum container containing the polymer solution is dried in an oven at 140° C. for 30 minutes, the mass (C) of the dried polymer is measured, and the calculation is carried out according to the following mathematical equation 1 :

[00165] [Math Equation 1]

[00166] Meanwhile, the polymer obtained by polymerization in the first reactor can be transported to the polymerization reactor in the order before the modification reactor, and polymerization can be carried out up to a final polymerization conversion of 95% or more. After polymerization in the first reactor, the polymerization conversion in the second reactor or in each reactor from the second reactor to the polymerization reactor before the modification reactor can be properly controlled to control the molecular weight distribution.

[00167] Meanwhile, in step (S1), during the preparation of the active polymer, the residence time of the polymer in the first reactor may be in the range of 1 minute to 40 minutes, 1 minute to 30 minutes, or 5 minutes to 30 minutes, and within within this range, it is favorable to controllably maintain the polymerization conversion rate, and thus, it is possible to controllably maintain a narrow molecular weight distribution for the polymer, and the effect of improving physical properties can be excellent.

[00168] The term "polymer" as used in the present invention may refer to an intermediate relating to the type of polymer that is in a state of polymerization in each reactor during step (S1), after completion of step (S1) or step (S2) , to obtain an active polymer or a modified conjugated diene-based polymer, or may refer to a polymer having a polymerization conversion rate of less than 95%, which is in a state of polymerization in a reactor.

[00169] In accordance with one embodiment of the present invention, the molecular weight distribution (PC, polydispersity index; MWD, molecular weight distribution; Mw/Mn) for the active polymer obtained in step (S1) may be less than 1, 5 may range from 1.0 to less than 1.5, or from 1.1 to less than 1.5, and within this range, the molecular weight distribution for the modified conjugated diene-based polymer that is produced in the result of carrying out the modification or coupling reaction using the modifier is narrow, and the effect of improving the physical properties can be excellent.

[00170] Meanwhile, the polymerization of step (S1) can be carried out by including a polar additive, and the polar additive can be added at a ratio in the range of 0.001 g to 50 g, 0.001 g to 10 g, or 0.005 g to 0. 1 g based on a total of 100 g of monomers. In yet another embodiment, the polar additive may be added at a ratio ranging from 0.001 g to 10 g, 0.005 g to 5 g, or 0.005 g to 4 g, based on a total of 1 mmol of modification initiator.

[00171] The polar additive may be, for example, one or more selected from the group consisting of tetrahydrofuran, 2,2-di(2-tetrahydrofuryl)propane, diethyl ether, cycloamyl ether, dipropyl ether, ethylene methyl ether , ethylenedimethyl ether, diethyl glycol, dimethyl ether, tert-butoxyethoxyethane, bis(3-dimethylaminoethyl) ether, (dimethylaminoethyl)ethyl ether, trimethylamine, triethylamine, tripropylamine, N,N,N',N'-tetramethylethylenediamine, methylate sodium and 2-ethyltetrahydrofurfuryl ether, and may preferably be 2,2-di(2-tetrahydrofuryl)propane, triethylamine, tetramethylethylenediamine, sodium methoxide or 2-ethyltetrahydrofurfuryl ether. In the case of including a polar additive and in the case of copolymerization of the conjugated diene-based monomer or the conjugated diene-based monomer and the vinyl aromatic-based monomer, the difference in their reaction rates can be compensated, and the effect of inducing easy production of a random copolymer can be achieved.

[00172] In accordance with one embodiment of the present invention, the reaction or combination of step (S2) can be carried out in a modification reactor, in which case the modifier can be used in an amount in the range from 0.01 mmol to 10 mmol, based on a set of 100 g of monomers. In yet another embodiment, the modifier can be used at 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 initiator of the stage modification (S1 ).

[00173] In addition, according to one embodiment of the present invention, the modifier may be injected into the modification reactor, and step (S2) may be carried out in the modification reactor. In yet another embodiment, the modifier may be injected into the transport portion to transport the active polymer obtained in step (S1) to the modification reactor for step (S2) and the reaction or combination may be carried out by mixing the active polymer and the modifier in the transport portion. .

[00174] A method for producing a modified conjugated diene based polymer according to one embodiment of the present invention is a method that satisfies the above-mentioned properties of the modified conjugated diene based polymer. In accordance with the above description of the invention, if the above properties are satisfied, the effects intended to be achieved in the present invention can be realized, but in this production method, it is required to satisfy at least the polymerization conversion during transportation from the first reactor to the second reactor in continuous process conditions, while other polymerization conditions are controlled in a variety of ways. Accordingly, the physical properties of the modified conjugated diene-based polymer of the present invention can be realized.

[00175] The present invention also provides a rubber composition containing a modified conjugated diene based polymer.

[00176] The rubber composition may contain a modified conjugated diene-based polymer in an amount of 10% (wt.) or more, in the range from 10% (wt.) to 100% (wt.) or from 20% (wt. ) up to 90% (mass), and within this range, mechanical properties such as tensile strength and abrasion resistance are excellent, and an excellent balance between each physical property can be achieved.

[00177] The rubber composition containing the modified conjugated diene polymer of the present invention can have a Mooney viscosity at 100°C (ML 1+4, 100°C) in the range of 50 to 80, and this feature can be used as an indicator expressing the processing characteristics.

[00178] In addition, the processability characteristics can be evaluated better when the Mooney viscosity is reduced and, in addition, can be evaluated better if the "difference" between the Mooney viscosity of the rubber composition, i.e., blend composition, is reduced. and Mooney viscosity for the modified conjugated diene based polymer. It may be preferable to change the Mooney viscosity, that is, the difference, depending on its increase or decrease, of 20 or less.

[00179] In addition, the rubber composition may also contain, as needed, another rubber component in addition to the modified conjugated diene polymer, in which case the rubber component may be included in an amount of 90% ( wt.) and less when calculating the total amount of the rubber composition. In one particular embodiment, the rubber component may be included in an amount ranging from 1 mass part to 900 mass parts based on 100 mass parts of the modified conjugated diene copolymer.

[00180] The rubber component may be, for example, natural rubber or synthetic rubber, and in particular may be natural rubber (NR) comprising cis-1,4-polyisoprene; modified natural rubber, which is obtained by modifying or refining conventional natural rubber such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber; and synthetic rubber such as styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, copoly(isobutylene-isoprene), neoprene, copoly(ethylene-propylene), copoly(styrene-butadiene), copoly(styrene-isoprene), copoly(styrene-isoprene-butadiene), copoly(isoprene-butadiene), copoly(ethylene-propylene-diene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber , epichlorohydrin rubber, butyl rubber and halogenated butyl rubber, and any one or a mixture of two or more of them can be used.

[00181] The rubber composition may contain, for example, from 0.1 mass parts to 200 mass parts or from 10 mass parts to 120 mass parts of a filler based on 100 mass parts of the modified conjugated diene based polymer of the present invention. The filler can be, for example, a silica-based filler, in particular wet silica (hydrosilicate), dry silica (anhydrous silicate), calcium silicate, aluminum silicate or fumed silica. Preferably, the filler may be wet silica, which has the most significant effect of improving degradation characteristics and a compatible effect of wet grip. In addition, the rubber composition may further contain a carbon-based filler as needed.

[00182] In yet another embodiment, if silica filler is used to improve reinforcement and low heat generation characteristics, a silane coupling agent can be used together. Specific examples of the silane coupling agent may include bis(3-triethoxysilylpropyl)tetrasulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2- триметоксисилилэтил)тетрасульфид, 3-меркаптопропилтриметоксисилан, 3-меркаптопропилтриэтоксисилан, 2-меркаптоэтилтриметоксисилан, 2-меркаптоэтилтриэтоксисилан, 3-триметоксисилилпропил-N, N-диметилтиокарбамоилтетрасульфид, 3-триэтоксисилилпропил-N, N-диметилтиокарбамоилтетрасульфид, 2-триэтоксисилилэтил-N, N-диметилтиокарбамоилтетрасульфид, 3-триметоксисилилпропилбензотиазолилтетрасульфид, 3-триэтоксисилилпропилбензолилтетрасульфид, 3-триэтоксисилилпропилметакрилатмоносульфид, 3-триметоксисилилпропилметакрилатмоносульфид, бис(3-диэтоксиметилсилилпропил)тетрасульфид, 3-меркаптопропилдиметоксиметилсилан, диметоксиметилсилилпропил-N, N-диметилтиокарбамоилтетрасульфид или диметоксиметилсилилпропилбензотиазолилтетрасульфид, и могут быть и any one or a mixture of two or more of their representatives are used. Preferably, in view of the reinforcing effect, bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide may be used.

[00183] In addition, in the rubber composition according to one embodiment of the present invention, due to the use of a modified conjugated diene-based polymer in which a functional group having a high affinity for silica has been introduced into the active portion, the admixture amount silane coupling may be less than in the usual case. Thus, the silane coupling agent can be used in an amount ranging from 1 mass part to 20 mass parts, or from 5 mass parts to 15 mass parts, based on 100 mass parts of silicon dioxide. By having the amount used in the above-mentioned range, an effect as a sizing can be sufficiently exhibited, and an effect of preventing gelation in the rubber component can be achieved.

[00184] The rubber composition according to one embodiment of the present invention may be crosslinkable using sulfur and thus may further comprise a vulcanizing agent. The vulcanizing agent may in particular be powdered sulfur and may be included in an amount ranging from 0.1 parts by mass to 10 parts by mass, based on 100 parts by mass of the rubber component. By having the amount used in the above-mentioned range, the elasticity and strength required for the vulcanized rubber composition can be obtained, and at the same time, excellent low fuel consumption can be achieved.

[00185] The rubber composition according to one embodiment of the present invention may further contain various additives used in the conventional rubber industry in addition to the above components, such as a vulcanization accelerator, process oil, an antioxidant, a plasticizer, an antioxidant, a preservative. scorch, zinc white, stearic acid, thermoset resin or thermoplastic resin.

[00186] The vulcanization accelerator may include, for example, thiazole-based compounds such as 2-mercaptobenzothiazole (M), dibenzothiazyl disulfide (DM), and N-cyclohexyl-2-benzothiazylsulfenamide (CZ), or guanidine-based compounds such as diphenylguanidine ( DPG), in an amount ranging from 0.1 mass parts to 5 mass parts, based on 100 mass parts of the rubber component.

[00187] The process oil functions as an emollient in the rubber composition and may include, for example, a paraffin-based compound, a naphthenic-based compound, or an aromatic compound. Considering tensile strength and abrasion resistance, an aromatic process oil may be used, and considering hysteresis loss and low temperature properties, a naphthenic-based or paraffin-based process oil may be used. Process oil may be included in an amount of 100 parts by mass or less based on 100 parts by mass of the rubber component. Within the above-described range for the vulcanized rubber, deterioration in tensile strength and low heat generation characteristics (low fuel consumption) can be prevented.

[00188] The antioxidant may include, for example, 2,6-di-tert-butyl-para-cresol, dibutylhydroxytoluene, 2,6-bis((dodecylthio)methyl)-4-nonylphenyl, or 2-methyl-4,6-bis ((octylthio)methyl)phenol) and can be used in an amount ranging from 0.1 mass parts to 6 mass parts based on 100 mass parts of the rubber component.

[00189] The antioxidant may include, for example, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 6-ethoxy-2,2,4 -trimethyl-1,2-dihydroquinoline or a condensate of diphenylamine and acetone at high temperature in an amount in the range from 0.1 mass parts to 6 mass parts based on 100 mass parts of the rubber component.

[00190] The rubber composition according to one embodiment of the present invention can be obtained by kneading using kneading equipment such as a Banbury mixer, rollers, and an internal mixer, in accordance with mixing regulations. A rubber composition exhibiting low heat generation characteristics and good abrasion characteristics can be obtained by using a vulcanization process after a molding process.

[00191] Therefore, the rubber composition may be suitable for use in the manufacture of each element of the tire, such as tire tread, undertread, sidewall, carcass cover rubber, breaker cover rubber, bead filler cord, bead tape, and bead cover rubber, or in the manufacture of rubber products in various industries such as vibration resistant rubber, conveyor belt and hose.

[00192] The present invention also provides a tire made using a rubber composition.

[00193] The tire may be a tire or a tire including a tire tread.

[00194] Hereinafter, the present invention will be explained in more detail with reference to embodiments. The embodiments of the present invention may be modified to various other types, and the scope of the present invention should not be limited to the embodiments described below. Embodiments of the present invention are provided to fully explain the present invention to a person of ordinary skill in the relevant art.

[00195] Obtaining Example 1

[00196] Two of the 4 L stainless steel pressure vessels subjected to vacuum drying were prepared. Into the first pressure vessel, 6922 g of cyclohexane, 85 g of the compound having the following formula 1-3, and 60 g of tetramethylethylenediamine were injected to obtain a first reaction solution. At the same time, 180 g of liquid-phase n-butyl lithium at 2.0 mol/L and 6926 g of cyclohexane were injected into the second pressure vessel to obtain a second reaction solution. In this case, the molar ratio of the compound of formula 1-3 to n-butyl lithium and tetramethylethylenediamine was 1:1:1. While maintaining the pressure in each pressure vessel at 7 bar, respectively, the first reaction solution was injected at an injection rate of 1.0 g/min through the first continuous-type channel, and the second reaction solution was injected at an injection rate of 1.0 g/min through the second continuous-type channel into the continuous-type reactor , when using a mass flow meter. In this case, the temperature in the reactor of the continuous type was kept at −10° C., the internal pressure was kept at 3 bar using a backpressure regulator, and the residence time in the reactor was controlled within 10 minutes. The reaction was terminated upon receipt of the modification initiator.

[00197] [Formula 1-3]

[00198] Obtaining Example 2

[00199] Two of the 4 L stainless steel pressure vessels subjected to vacuum drying were prepared. Into the first pressure vessel, 6922 g of cyclohexane, 120 g of the compound having the following formula 1-1, and 60 g of tetramethylethylenediamine were injected to obtain a first reaction solution. At the same time, 180 g of liquid-phase n-butyl lithium at 2.0 mol/L and 6926 g of cyclohexane were injected into the second pressure vessel to obtain a second reaction solution. In this case, the molar ratio of the compound of formula 1-1 to n-butyllithium and tetramethylethylenediamine was 1:1:1. While maintaining the pressure in each pressure vessel at 7 bar, respectively, the first reaction solution was injected at an injection rate of 1.0 g/min through the first continuous-type channel, and the second reaction solution was injected at an injection rate of 1.0 g/min through the second continuous-type channel into the continuous-type reactor , when using a mass flow meter. In this case, the temperature in the reactor of the continuous type was kept at −10° C., the internal pressure was kept at 3 bar using a backpressure regulator, and the residence time in the reactor was controlled within 10 minutes. The reaction was terminated upon receipt of the modification initiator.

[00200] [Formula 1-1]

[00201] Obtaining Example 3

[00202] Two of the 4 L stainless steel pressure vessels subjected to vacuum drying were prepared. Into the first pressure vessel, 6922 g of cyclohexane, 145 g of the compound having the following formula 1-2, and 60 g of tetramethylethylenediamine were injected to obtain a first reaction solution. At the same time, 180 g of liquid-phase n-butyl lithium at 2.0 mol/L and 6926 g of cyclohexane were injected into the second pressure vessel to obtain a second reaction solution. In this case, the molar ratio of the compound of formula 1-2 to n-butyllithium and tetramethylethylenediamine was 1:1:1. While maintaining the pressure in each pressure vessel at 7 bar, respectively, the first reaction solution was injected at an injection rate of 1.0 g/min through the first continuous-type channel, and the second reaction solution was injected at an injection rate of 1.0 g/min through the second continuous-type channel into the continuous-type reactor , when using a mass flow meter. In this case, the temperature in the reactor of the continuous type was kept at −10° C., the internal pressure was kept at 3 bar using a backpressure regulator, and the residence time in the reactor was controlled within 10 minutes. The reaction was terminated upon receipt of the modification initiator.

[00203] [Formula 1-2]

[00204] Example 1

[00205] In the first reactor, among the continuous reactors of the three reactors that were connected in series, a styrene solution was injected with a flow rate of 3.3 kg / h, in which 60% (wt.) of styrene was dissolved in n-hexane, with a flow rate of 12 .5 kg/h 1,3-butadiene solution, in which 60% (mass.) of 1,3-butadiene was dissolved in n-hexane, with a flow rate of 47.4 kg/h n-hexane, with a flow rate of 40 g/h 1 ,2-butadiene solution, in which 2.0% (wt.) 1,2-butadiene was dissolved in n-hexane, with a flow rate of 25.0 g / h, a solution of 2,2-di (2-tetrahydrofuryl) propane (DTP) , in which 10% (wt.) 2,2-di(2-tetrahydrofuryl)propane was dissolved in n-hexane as a polar additive, and the modification initiator obtained in Preparation Example 1 was dissolved at a rate of 300.0 g/h. In this case, the temperature in the first reactor was maintained at 50° C., and when the polymerization conversion reached 43%, the polymer was transported from the first reactor to the second reactor through a transport pipe.

[00206] After that, a 1,3-butadiene solution was injected into the second reactor at a flow rate of 0.7 kg/h, in which 60% (wt.) of 1,3-butadiene was dissolved in n-hexane. In this case, the temperature in the second reactor was maintained at 65° C., and when the polymerization conversion reached 95% or more, the polymer was transported from the second reactor to the third reactor through a transfer pipe.

[00207] The polymer was transported from the second reactor to the third reactor, and a solution was continuously injected into the third reactor as a modifier, in which N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilyl)-N- (3-(triethoxysilyl) propyl) propane-1-amine (solvent: n-hexane), [modifier: act. Li=1 : 1 (mol.)]. The temperature in the third reactor was maintained at 65°C.

[00208] Following this, a solution of IR1520 product (BASF Co.) was injected into the polymerization solution discharged from the third reactor at a flow rate of 170 g/hour, in which 30% (mass.) was dissolved as an antioxidant, and stirring was performed. The polymer thus obtained was injected into hot water heated using steam, and agitation was carried out to remove solvents to obtain a modified conjugated diene-based polymer.

[00209] Example 2

[00210] The modified conjugated diene based polymer was obtained in Example 1 by carrying out the same procedure as the procedure described in Example 1, except for continuous feeding to the first reactor at a rate of 350.0 g/hour as the initiator modification initiator of the modification obtained in Production Example 2 instead of the modification initiator obtained in Production Example 1, transporting the polymer from the first reactor to the second reactor through a conveying pipe while reaching a polymerization conversion of 40%, and continuously supplying a solution in which 1,3-bis was dissolved (3-(1H-imidazol-1-yl)propyl)-1,1,3,3-tetraethoxydisiloxane (solvent: n-hexane), instead of the solution in which N-(3-(1H-imidazole-1- yl) propyl) -3- (triethoxysilyl) -N- (3- (triethoxysilyl) propyl) propane-1-amine as a modifier [modifier: act. Li=1 : 1 (mol.)].

[00211] Example 3

[00212] In the first reactor, among the continuous reactors of the three reactors that were connected in series, a styrene solution was injected with a flow rate of 6.5 kg/h, in which 60% (wt.) of styrene was dissolved in n-hexane, with a flow rate of 7 .7 kg/h 1,3-butadiene solution, in which 60% (wt.) 1,3-butadiene was dissolved in n-hexane, with a flow rate of 47.0 kg/h n-hexane, with a flow rate of 40 g/h 1 ,2-butadiene solution, in which 2.0% (wt.) of 1,2-butadiene was dissolved in n-hexane, with a flow rate of 50.0 g/h, a solution in which 10% (wt.) N, N, N', N'-tetramethylethylenediamine (TMEDA), and at a rate of 400.0 g/h, the modification initiator obtained in Production Example 3.

[00213] In this case, the temperature in the first reactor was maintained at 55° C., and upon reaching a polymerization conversion of 41%, the polymer was transported from the first reactor to the second reactor through a transfer pipe.

[00214] After that, a 1,3-butadiene solution was injected into the second reactor at a flow rate of 2.3 kg/h, in which 60% (wt.) of 1,3-butadiene was dissolved in n-hexane. In this case, the temperature in the second reactor was maintained at 65° C., and when the polymerization conversion reached 95%, the polymer was transported from the second reactor to the third reactor through a transfer pipe.

[00215] The polymer was transported from the second reactor to the third reactor, and a solution was injected into the third reactor as a modifier, in which N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilyl)-N-( 3-(triethoxysilyl) propyl) propane-1-amine (solvent: n-hexane), [modifier: act. Li=1 : 1 (mol.)]. The temperature in the third reactor was maintained at 65°C.

[00216] Following this, a solution of the product IR1520 (BASF Co.) was injected into the polymerization solution discharged from the third reactor at a flow rate of 170 g/hour, in which 30% (mass.) was dissolved as an antioxidant, and stirring was performed. The polymer thus obtained was injected into hot water heated using steam, and agitation was carried out to remove solvents to obtain a modified conjugated diene-based polymer.

[00217] Example 4

[00218] The modified conjugated diene based polymer was prepared in Example 3 by carrying out the same procedure as the procedure described in Example 3, except for continuous feeding to the first reactor at a flow rate of 350.0 g/hour as the initiator polymerization initiator modification obtained in Production Example 2 instead of the modification initiator obtained in Production Example 3, transporting the polymer from the first reactor to the second reactor through a conveying pipe while reaching a polymerization conversion of 42%, and continuously supplying a solution in which 1,3-bis was dissolved (3-(1H-imidazol-1-yl)propyl)-1,1,3,3-tetraethoxydisiloxane (solvent: n-hexane), instead of the solution in which N-(3-(1H-imidazole-1- yl) propyl) -3- (triethoxysilyl) -N- (3- (triethoxysilyl) propyl) propane-1-amine as a modifier [modifier: act. Li=1 : 1 (mol.)].

[00219] Example 5

[00220] The modified conjugated diene polymer was prepared in Example 3 by carrying out the same procedure as the procedure described in Example 3, except for continuous feeding to the first reactor at a flow rate of 300.0 g/hour as the polymerization initiator of the initiator of the modification obtained in Production Example 1 instead of the modification initiator obtained in Production Example 3, transporting the polymer from the first reactor to the second reactor through a conveying pipe while reaching a polymerization conversion rate of 43%, and continuously supplying a solution in which N-(3- (1H-1,2,4-triazol-1-yl)propyl)-3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine (solvent: n-hexane), instead of solution, in which N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine was dissolved as a modifier [modifier: act. Li=1 : 1 (mol.)].

[00221] Comparative Example 1

[00222] A 20 L autoclave reactor was injected with 180 g of styrene, 880 g of 1,3-butadiene, 5000 g of n-hexane and 1.2 g of 2,2-di(2-tetrahydrofuryl)propane as a polar additive and an internal temperature in the reactor was increased to 50°C. After reaching an internal temperature in the reactor of 50° C., 4.7 mmol of the modification initiator obtained in Production Example 1 was injected, and an adiabatic reaction was carried out with heating. After approximately 20 minutes, 20 g of 1,3-butadiene was injected to introduce the butadiene polymer at the chain ends. After 5 minutes, 4.7 mmol of N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine was injected and the reaction was carried out for 15 minutes. Thereafter, the polymerization reaction was quenched using ethanol, and 45 ml of a solution in which 0.3% (wt.) of the antioxidant IR1520 (BASF Co.) was dissolved in n-hexane was added thereto. Thereafter, the polymer thus obtained was injected into hot steam-heated water, and agitation was carried out to remove solvents to obtain a modified conjugated diene-based polymer.

[00223] Comparative Example 2

[00224] In the first reactor, among the continuous reactors of the three reactors that were connected in series, a styrene solution was injected with a flow rate of 3.3 kg / h, in which 60% (wt.) of styrene was dissolved in n-hexane, with a flow rate of 12 .5 kg/h 1,3-butadiene solution, in which 60% (mass.) of 1,3-butadiene was dissolved in n-hexane, with a flow rate of 47.4 kg/h n-hexane, with a flow rate of 40 g/h 1 ,2-butadiene solution, in which 2.0% (wt.) of 1,2-butadiene was dissolved in n-hexane, with a flow rate of 25.0 g/h, a solution in which 10% (wt.) 2,2-(di-(2-tetrahydrofuryl)propane (DTP), and with a flow rate of 30.0 g/h as a polymerization initiator, a solution of n-butyllithium, in which 5% (wt. .) n-butyllithium In this case, the temperature in the first reactor was maintained at 50° C., and upon reaching a polymerization conversion of 43%, the polymer was transported from the first reactor to the second reactor through a transport pipe.

[00225] After that, a 1,3-butadiene solution was injected into the second reactor at a flow rate of 0.7 kg/h, in which 60% (wt.) of 1,3-butadiene was dissolved in n-hexane. In this case, the temperature in the second reactor was maintained at 65° C., and when the polymerization conversion reached 95% or more, the polymer was transported from the second reactor to the third reactor through a transfer pipe.

[00226] The polymer was transported from the second reactor to the third reactor, and a solution was injected into the third reactor as a coupling agent in which dichlorodimethylsilane (solvent: n-hexane) was dissolved [coupling agent: act. Li=1 : 1 (mol.)]. The temperature in the third reactor was maintained at 65°C.

[00227] Following this, a solution of IR1520 product (BASF Co.) was injected into the polymerization solution discharged from the third reactor at a flow rate of 170 g/hour, in which 30% (mass.) was dissolved as an antioxidant, and stirring was performed. The polymer thus obtained was injected into hot water heated using steam, and agitation was carried out to remove solvents to obtain a modified conjugated diene-based polymer.

[00228] Comparative Example 3

[00229] The modified conjugated diene polymer was prepared in Example 1 by following the same procedure as described in Example 1, except for maintaining the temperature in the first reactor at 75°C and transporting the polymer from the first reactor to the second reactor through a transfer tube when a polymerization conversion of 78% is reached.

[00230] Comparative Example 4

[00231] The one-terminally modified conjugated diene-based polymer was obtained in Example 1 by carrying out the same procedure as the procedure described in Example 1, except for transporting the polymer from the first reactor to the second reactor through a transport pipe when the degree conversion during polymerization of 42% and carrying out the reaction without injection of the modifier into the third reactor.

[00232] Comparative Example 5

[00233] The one-terminally modified conjugated diene polymer was prepared in Example 1 by following the same procedure as described in Example 1, except for continuous injection at a rate of 30.0 g/hour into the first reactor in as a polymerization initiator of the n-butyllithium solution in which 5% (mass) of n-butyllithium was dissolved in n-hexane instead of the modification initiator obtained in Production Example 1.

[00234] Comparative Example 6

[00235] The modified conjugated diene polymer was prepared in Example 3 by carrying out the same procedure as the procedure described in Example 3, except for continuous injection into the third reactor at a rate of 30.0 g/hour as the solution polymerization initiator n-butyllithium in which 5% (mass) of n-butyllithium was dissolved in n-hexane instead of the modification initiator obtained in Production Example 1, and as a coupling agent of the solution in which dimethyldichlorosilane (solvent: n -hexane), instead of the modifier [combination agent: act. Li=1 : 1 (mol.)].

[00236] Reference Example 1

[00237] A conjugated diene-based polymer modified at both ends was obtained in Comparative Example 1 by following the same procedure as that described in Comparative Example 1, except for injecting 14.1 mmol of 3-(dimethoxy) as a modifier (methyl)silyl)-N, N-diethylpropan-1-amine instead of N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propane -1-amine.

[00238] Reference Example 2

[00239] A conjugated diene-based polymer modified at both ends was obtained in Comparative Example 1 by following the same procedure as that described in Comparative Example 1, except for injecting 2.3 mmol of 3-(dimethoxy (methyl)silyl)-N, N-diethylpropan-1-amine instead of N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propane -1-amine.

[00240] Experimental Example 1

[00241] For each of the modified or unmodified conjugated diene-based polymers obtained in the Examples and Comparative Examples, the levels of styrenic unit and vinyl in each polymer, weight average molecular weight (Mw, × 10 ³ g/mol ), number average molecular weight (Mn, x 10 ³ g/mol), molecular weight distribution (CP, MWD), Mooney viscosity (MV), and Si level. The results are shown in Table 1 and Table 2 below.

[00242] 1) Styrene unit and vinyl levels (% (wt.))

[00243] Styrene unit (SM) and vinyl levels in each polymer were measured and analyzed using a Varian VNMRS 500 MHz NMR instrument.

[00244] When measuring using the NMR method, 1,1,2,2-tetrachloroethanol was used as a solvent, and the levels of the styrene elementary unit and vinyl were calculated by calculating the solvent peak in the region of 5.97 ppm and assigning the peaks in the region of 7.2-6.9 ppm to the peaks of styrene with its random arrangement in the chain, peaks in the region of 6.9-6.2 ppm to the peaks of styrene with its block arrangement in the chain, peaks in the region 5.8-5.1 ppm to the peaks of 1,4-vinyl and peaks in the region of 5.1-4.5 ppm to the peaks of 1,2-vinyl.

[00245] 2) Weight average molecular weight (Mw, × 10 ³ g/mol), number average molecular weight (Mn, × 10 ³ g/mol), peak molecular weight (Mp, × 10 ³ g/mol), molecular mass distribution (CP, MWD) and combination number (NC)

[00246] As a result of the analysis using Gel Permeation Chromatography (GPC), the weight average molecular weight (Mw), the number average molecular weight (Mn) and the peak molecular weight (Mp) were measured at 40°C and a molecular weight distribution curve was obtained. In addition, from each weight average molecular weight and number average molecular weight thus measured, the molecular weight distribution (CP, MWD, Mw/Mn) was calculated. In particular, the GPC method was carried out using two PLgel Olexis columns (Polymer Laboratories Co.) and one PLgel mixed-C column (Polymer Laboratories Co.) in combination and polystyrene (PS) as the standard material of the GPC method for calculating molecular weights. The solvent for carrying out the measurement using the GPC method was obtained by mixing tetrahydrofuran with 2% (wt.) amine compounds. In this case, the molecular weight distribution curves thus obtained are shown in FIGS. 1 to FIG. 4.

[00247] In addition, the coupling number was calculated by collecting a portion of the polymer before injecting the modifier or coupling agent in each of the examples and comparative examples and obtaining the peak molecular weight (Mp ₁ ) for the polymer, thereafter obtaining the peak molecular weight (Mp ₂ ) for each modified conjugated diene based polymer and calculate according to the following mathematical formula 2:

[00248] [Mathematical formula 2]

Combination number (NC) = MP ₂ / MP ₁

[00249] 3) Mooney Viscosity and Mooney Stress Relaxation Relationship

[00250] Mooney viscosity (MV, (ML1+4, at 100°C) MU (Mooney viscosity units)) was measured using an MV-2000 instrument (Alpha Technologies Co.) using a large rotor at a rotor speed of 2 ± 0 .02 rpm at 100°C. In this case, the used sample was kept at room temperature (23±3°C) for 30 minutes or more, and 27±3 g of the sample was taken, which was placed in the cavity of the matrix, and then the plate was activated to take measurements for 4 minutes in order to obtain the Mooney viscosity.

[00251] After measuring the Mooney viscosity, the magnitude of the gradient (absolute value) for changing the Mooney viscosity while releasing the torque was measured, and based on its absolute value, the Mooney stress relaxation ratio was obtained.

[00252] 4) Si level

[00253] The Si level was measured by performing an ICP analysis method using inductively coupled plasma optical emission spectroscopy (ICP-OES; Optima 7300DV). In particular, the measurement was carried out by adding approximately 0.7 g of the sample to a platinum (Pt) crucible and adding approximately 1 ml of concentrated sulfuric acid (98% (wt.), electronic purity) thereto, heating at 300° C. for for 3 hours, calcining the sample in an electric oven (Thermo Scientific, Lindberg Blue M) using the following program, including steps 1 to 3:

[00254] 1) stage 1: initial temperature 0°C, rate (temperature/hour) 180°C/hour, temperature (hold time) 180°C (1 hour),

[00255] 2) stage 2: initial temperature 180°C, rate (temperature/hour) 85°C/hour, temperature (hold time) 370°C (2 hours),

[00256] 3) stage 3: initial temperature 370°C, rate (temperature/hour) 47°C/hour, temperature (hold time) 510°C (3 hours),

[00257] adding 1 ml of concentrated nitric acid (48% (wt.)) and 20 μl of concentrated hydrofluoric acid (50% (wt.)) to the residue, sealing the platinum crucible and shaking it for 30 minutes or more, adding to the sample 1 ml of boric acid, storage at 0°C for 2 hours or more, dilution in 30 ml of highly pure water and calcination.

[00258] 5) N level

[00259] The N content was measured using, for example, the NSX analysis method using a quantitative trace nitrogen analyzer (NSX-2100H). Specifically, a quantitative trace nitrogen analyzer (autosampler, horizontal oven, PMT and nitrogen detector) was turned on, the flowing amounts of carrier gas were set such that 250 ml/min would occur for Ar, 350 ml/min would occur for O ₂ , and for the ozonizer would be 300 ml/min, the heater was set to 800°C and the analyzer stood for approximately 3 hours to stabilize. After stabilizing the analyzer using a nitrogen standard (AccuStandard S-22750-01-5 ml), a calibration curve was obtained in the calibration ranges 5 ppm, 10 ppm, 50 ppm, 100 ppm . and 500 ppm, an area corresponding to each concentration was obtained, and a straight line was obtained using the ratio between concentration and area. Thereafter, a ceramic boat containing 20 mg of sample was placed on the autosampler of the analyzer and measured to obtain an area. The N content was calculated using the sample area thus obtained and the calibration curve.

[00260] 6) Shrink ratio (g')

[00261] The shrinkage ratio was obtained as follows. The sample was injected into a GPC light scattering apparatus (Viscotek TDAmax, Malvern Co.) equipped with a light scattering detector in which two columns packed with a polystyrene-based gel as a filler and a viscometer were connected, and the absolute molecular weight was obtained from the light scattering detector, intrinsic viscosity [η] relative to absolute molecular weight from the light scattering detector and viscometer, using the following mathematical formula 3, a computer calculation of the intrinsic viscosity [η] ₀ for a linear polymer with respect to absolute molecular weight was carried out, and the average value was presented as the shrinkage coefficient ratios for intrinsic viscosity ([η]/[η] ₀ ) corresponding to each absolute molecular weight. In this case, the measurement was carried out using a mixture solution of tetrahydrofuran and N,N,N',N'-tetramethylethylenediamine (corrected by mixing 20 ml of N,N,N',N'-tetramethylethylenediamine with 1 liter of tetrahydrofuran) as eluent and a PL Olexix device (Agilent Co.) as a column under conditions of an oven temperature of 40° C. and a THF flow rate of 1.0 ml/min. The sample was obtained by dissolving 15 mg of polymer in 10 ml of THF.

[00262] [Mathematical formula 3]

[η] ₀ =10 ^{- 3.883} M ^0.771

[00263] In the mathematical formula, 3 M is the absolute molecular weight.

[00264] [Table 1]

Chapter Example Comparative Example Reference Example 1 2 1 2 3 4 5 1 2 Reaction Conditions Initiator a b a d a a d a a Modifier or combination agent A B A E A - A D D Polar supplement DTP DTP DTP DTP DTP DTP DTP DTP DTP Temperature in the first reactor (°C) 50 50 50→80 50 75 50 50 50→80 50→80 Polymerization conversion rate in the first reactor (%) 43 40 Periodic mode 43 78 42 43 Periodic mode Periodic mode NMR (% (wt.)) SM 18 18 18 18 18 18 18 18 18 Vinyl 47 47 47 47 47 47 47 47 47 Mw (× 10 ³ g/mol) 512 507 538 484 756 542 492 369 594 Mn (× 10 ³ g/mol) 310 321 332 310 360 352 301 260 440 Mp (× 10 ³ g/mol) 473 371 225(70)/432(30) 378 439 360 452 226 440 Mw/Mp 1.08 1.37 1.87 1.28 1.72 1.51 1.09 1.63 1.35 KP 1.65 1.58 1.62 1.56 2.1 1.54 1.63 1.42 1.35 emergency 2.1 1.65 1.92 1.50 1.95 - 2.15 1.0 2.0 Molecular weight distribution curve Unimodal Unimodal Unimodal Unimodal Unimodal Unimodal Unimodal Unimodal Unimodal Mooney Viscosity (MV) 60 59 60 58 76 61 56 51 63 Mooney stress relaxation ratio 0.83 0.82 0.82 0.85 0.57 0.69 1.1 1.03 0.84 Shrinkage ratio 0.86 1.08 0.87 0.92 0.68 0.89 0.84 1.07 1.00 Si level (ppm) 245 223 241 thirty 185 - 250 251 130 N level (ppm) 190 285 211 - 156 42 180 185 91

[00265] [Table 2]

Chapter Example Comparative Example 3 4 5 6 Reaction Conditions Initiator c b a d Modifier or combination agent A B C E Polar supplement TMEDA TMEDA TMEDA TMEDA Temperature in the first reactor (°C) 55 55 55 55 Polymerization conversion rate in the first reactor (%) 41 42 43 42 NMR (% (wt.))
GPC SM 39 39 39 39 Vinyl 25 25 25 25 Mw (× 10 ³ g/mol) 551 498 578 503 Mn (× 10 ³ g/mol) 340 315 350 305 Mp (× 10 ³ g/mol) 504 403 554 378 Mw/Mp 1.09 1.24 1.04 1.33 KP 1.62 1.58 1.65 1.65 emergency 2.0 1.6 2.2 1.5 Molecular weight distribution curve Unimodal Unimodal Unimodal Unimodal Mooney Viscosity (MV) 62 60 67 60 Mooney stress relaxation ratio 0.80 0.98 0.70 0.91 Shrinkage ratio 1.10 1.09 0.81 0.89 Si level (ppm) 245 232 255 thirty N level (ppm) 210 302 205 -

[00266] In Table 1 and Table 2 above, the specific substances used as initiator, modifier, and coupling agent are shown in Table 3 below.

[00267] [Table 3]

Initiator a Modification Initiator Obtained in Obtaining Example 1 b Modification Initiator Obtained in Obtaining Example 2 c Modification Initiator Obtained in Obtaining Example 3 d n-butyllithium Modifier A N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine B 1,3-bis(3-(1H-imidazol-1-yl)propyl)-1,1,3,3-tetraethoxydisiloxane C N-(3-(1H-1,2,4-triazol-1-yl)propyl)-3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine D 3-(dimethoxy(methyl)silyl)-N, N-diethylpropan-1-amine Combination agent E dichlorodimethylsilane

[00268] As established by referring to Tables 1 and 2, the modified conjugated diene based polymers of Examples 1 to 5 prepared in accordance with embodiments of the present invention satisfy all required ranges of physical properties. In particular, the molecular weight distribution curve obtained by using Gel Permeation Chromatography has a unimodal profile, and at the same time, the CP value is in the range of 1.0 to less than 1.7, and the processability is predicted to be largely excellent, and the compounding characteristics are also excellent. For all options, the Mooney stress relaxation ratio is 0.7 or more, and linearity is predicted to be excellent. The shrinkage ratio is 0.8 or more, and the balance between physical properties is predicted to be excellent.

[00269] In contrast, Comparative Example 3, in which the polymerization conversion during transport from the first reactor to the second reactor was not controlled, showed a high CP value, and the Mooney stress relaxation ratio and the shrinkage ratio were evaluated as having a certain or more smaller value, and thus the balance between physical properties and linearity, showed unsatisfactory results.

[00270] Also in the case where batch polymerization is used, the conventional modified conjugated diene polymer has a CP value of less than 1.7 as in Comparative Example 1, but exhibits a molecular weight distribution curve with a bimodal profile, and according to the prediction, the processability is degraded. As a result of performing batch polymerization, a molecular weight distribution curve with a unimodal profile can be demonstrated as in Reference Examples 1 and 2, but the Reference Examples correspond to limiting cases where the combination number is the minimum or maximum value for the number of functional groups of the modifier, i.e., a case in which not all polymers are coupled with a modifier (Reference Example 1); or a case in which all polymers are coupled with a modifier (Reference Example 2). Such a modified conjugated diene-based polymer obtained by batch polymerization causes deterioration in mixing characteristics, as is known from the above explanation and evaluation results to be described below.

[00271] FIGURES 1 to 4 show the molecular weight distribution curves from Example 1, Comparative Example 1, and Reference Examples 1 and 2, and the profile of each molecular weight distribution curve was found to exhibit the profile described above.

[00272] Experimental Example 2

[00273] In order to perform a comparative analysis of the physical properties of the rubber compositions containing, respectively, modified or unmodified copolymers obtained in the examples, comparative examples and reference examples, and molded articles made therefrom, the tensile mechanical properties and viscoelasticity characteristics were measured, and the results are shown in Table 5 and Table 6 below.

[00274] 1) Obtaining a rubber sample

[00275] When using each of the modified or unmodified conjugated diene-based polymers from Examples, Comparative Examples, and Reference Examples as the raw material rubber, mixing was carried out under the mixing conditions listed in Table 4 below. mass parts when calculating 100 mass parts of the rubber material of the feedstock.

[00276] [Table 4]

Chapter Raw Material Quantity (mass parts) Mixing the first stage Rubber 100 Silica 70 Combination Agent (X50S) 11.2 Process oil 37.5 Zinc white 3 Stearic acid 2 Antioxidant 2 Antioxidant 2 Wax 1 Second stage kneading Sulfur 1.5 rubber accelerator 1.75 Vulcanization accelerator 2

[00277] In particular, the rubber sample was kneaded using the first stage kneading and the second stage kneading. In the first stage kneading, raw material rubber, silica (filler), organic silane coupling agent, process oil, zinc white, stearic acid, antioxidant, anti-oxidant and wax were kneaded using a Banbury mixer equipped with temperature controlled apparatus. In this case, the initial temperature in the kneader was controlled at 70°C and after mixing was complete, the first blend was obtained at an outlet temperature in the range of 145°C to 155°C. In the second stage kneading, the first mixture was cooled to room temperature, and the first mixture, sulfur, rubber accelerator, and vulcanization accelerator were added to the kneading apparatus and mixed at a temperature of 100° C. or less to obtain a second mixture. After that, as a result of the implementation of the technological process of curing at 160°C for 20 minutes, a rubber sample was obtained.

[00278] 2) Tensile properties

[00279] Tensile properties were measured by manufacturing each sample and measuring the tensile strength at break and tensile stress when stretched by 300% (300% modulus) for each sample in accordance with the tensile test method from of ASTM 412. Specifically, tensile properties were measured using a Universal Test Machine 4204 (Instron Co.) tensile tester at a speed of 50 cm/min at room temperature.

[00280] 3) Viscoelastic characteristics

[00281] Viscoelastic characterization was achieved by measuring the viscoelastic behavior with respect to thermodynamic deformation at each measurement temperature (-60°C~60°C) at a frequency of 10 Hz using a torque analyzer (GABO Co.) in film tension mode and providing values tg δ. Among the measurement values, if the tg δ value is increased at a low temperature of 0°C, the wet slip resistance will become better, and if the tg δ value is reduced at a high temperature of 60°C, the hysteresis loss will decrease, and the low running resistance will become better (consumption level fuel). In Table 5 and Table 6 below, the viscoelastic properties were recalculated to the given values (%) by setting the reference value. The larger this value, the better these properties will be.

[00282] 4) Processability characteristics

[00283] As a result of measuring the Mooney viscosity (MV, (ML 1+4, at 100°C) MU) for the second compound composition obtained during the preparation of 1) rubber sample, a comparative analysis of the processing characteristics of each polymer was carried out, and in In this case, the lower the measured Mooney viscosity, the better the processability characteristics.

[00284] In particular, when using the MV-2000 (Alpha Technologies Co.), using a large rotor at a rotor speed of 2 ± 0.02 rpm at 100 ° C, every second mixture composition was kept at room temperature (23 ± 3°C) for 30 minutes or more and took 27±3 g, which was placed in the cavity of the matrix, and then for 4 minutes the plate was activated for measurement.

[00285] [Table 5]

Chapter Example Comparative Example Reference Example 1 2 1 2 3 4 5 1 2 Tensile properties Tensile strength (kgf/cm ² ) (kPa) 190 (18630) 188 (18440) 188 (18440) 172 (16870) 183 (17950) 184 (18040) 186 (18240) 170 (16670) 181 (17750) 300% modulus (kgf/cm ² ) (kPa) 101 (9900) 98 (9610) 97 (9510) 70 (6860) 84 (8240) 80 (7850) 83 (8140) 78 (7650) 76 (7450) Viscoelastic characteristics Reduced value tg δ (at 0°C) 103 100 99 100 101 99 101 97 100 Reduced value tg δ (at 60°C) 134 130 120 100 119 111 121 105 107 Processability characteristics 85 90 105 70 85 80 82 112 107

[00286] In Table 5, the resulting values from Examples 1 and 2, Comparative Examples 1 and 3 to 5, and Reference Examples 1 and 2 were recalculated to the reported values by assigning a measurement value from Comparative Example 2 to be 100. The larger this value is , the better these properties will be.

[00287] In particular, with reference to Table 5 above, as predicted from the measured properties of the polymers in Experimental Example 1, Examples 1 and 2 were found to exhibit equivalent or better levels of tensile properties and significantly better modulus in terms of tensile mechanical properties compared to those of the Comparative Examples. With respect to the viscoelasticity characteristics, the tg δ value at low temperature was maintained at an equivalent or better level, and the tg δ value at high temperature was markedly improved, and it could be found that the fuel consumption level was greatly improved without loss of surface resistance.

[00288] In addition, as is the case in Reference Examples 1 and 2, in the case in which the polymer obtained by carrying out batch polymerization was characterized by the presence of a molecular weight distribution curve with a unimodal profile, it was found to be maintained by itself own reduced processability for batch polymerization while not achieving the excellent compounding characteristics that could be achieved as an advantage in batch polymerization. Meanwhile, the inherent inferior processability for batch polymerization could be confirmed in Comparative Example 1, which used the same initiator and the same modifier, and used an equivalent range of the combination number as in Example 1.

[00289] In addition, in Comparative Example 3, results not consistent with the production method of the present invention were obtained, the ranges of CP value, shrinkage ratio and Mooney stress relaxation ratio were unsatisfactory in accordance with the above description of the invention. Also, as it was found, the tensile properties and viscoelastic properties were degraded in comparison with what was the case in the examples. In addition, in Comparative Examples 2, 4 and 5, in which the modifier and modification initiator of the present invention were not used, the tensile mechanical properties and viscoelastic properties were also found to be degraded.

[00290] [Table 6]

Chapter Example Comparative Example 3 4 5 6 Tensile properties Tensile strength (kgf/cm ² ) (kPa) 187 (18340) 188 (18440) 190 (18630) 185 (18140) 300% modulus (kgf/cm ² ) (kPa) 97 (9510) 95 (9320) 99 (9710) 85 (8340) Viscoelastic characteristics Reduced value tg δ (at 0°C) 102 103 105 100 Reduced value tg δ (at 60°C) 131 130 137 100 Processability characteristics 79 78 79 68

[00291] In the above Table 6, the resulting values of the viscoelasticity characteristics from Examples 3 to Example 5 were converted to the given values (%) and demonstrated when assigning the measurement value of Comparative Example 6 to be 100, and the larger this value is, the these properties will be the best.

[00292] Table 6 shows the resulting sets for which the amounts of comonomers differed from the sets from Table 5. As it could be established, the effects did not change despite changing the amounts of monomers from Table 6, and the same results were demonstrated as and improved results in physical properties, confirmed in Table 5.

Claims (85)

1. A modified conjugated diene polymer having a molecular weight distribution curve with a unimodal profile obtained using gel permeation chromatography (GPC), and molecular weight distribution (MD; MWD) in the range from 1.0 to less than 1.7 and containing a functional group derived from the initiator of the modification, in one end position and a functional group derived from the modifier represented by any formula selected from the following formulas from formula 2 to formula 4, in the other end position, where the modification initiator is the product of the reaction between the compound described by the following formula 1 and the organometallic compound: [Formula 1]

where in formula 1 each of the groups from R ₁ to R ₃ independently represents a hydrogen atom, R ₄ is a single bond, R ₅ represents a functional group described by the following formula 1a or formula 1b, and n is an integer in the range of 1 to 5, and when n is an integer in the range of 2 to 5, the plurality of R ₅ groups may be identical or different: [Formula 1a]

where in formula 1a R ₆ is an unsubstituted alkylene group containing from 1 to 20 atoms, each of R ₇ and R ₈ independently represents an unsubstituted alkylene group containing from 1 to 20 carbon atoms, R ₉ is an alkyl group containing from 1 to 30 carbon atoms; or an aryl group containing 6 to 30 carbon atoms, and X is an N atom, [Formula 1b]

where in formula 1b R ₁₀ is an unsubstituted alkylene group containing from 1 to 20 carbon atoms, and each of R ₁₁ and R ₁₂ independently represents an alkyl group containing from 1 to 30 carbon atoms, [Formula 2]

where in formula 2 each of R _a1 and R _a4 independently represents an alkylene group containing from 1 to 10 carbon atoms, each of R _a2 and R _a3 independently represents an alkyl group containing from 1 to 10 carbon atoms, R _a5 is a five-membered heterocyclic group containing from 2 to 4 carbon atoms and containing one or more heteroatoms selected from the group consisting of N, n ₁ is an integer in the range from 1 to 3 and n ₂ is an integer in the range from 0 to 2, [Formula 3]

where in formula 3 each of the groups A ₁ and A ₂ independently represents an alkylene group containing from 1 to 20 carbon atoms, each of the groups from R _b1 to R _b4 independently represents an alkyl group containing from 1 to 20 carbon atoms, each of R _b5 and R _b6 independently represents a hydrogen atom and each of A ₃ and A ₄ independently represents

, where each of the groups R _b9 and R _b10 independently represents a hydrogen atom, [Formula 4]

where in formula 4 R _c1 is a hydrogen atom, each of the groups from R _c2 to R _c4 independently represents an alkylene group containing from 1 to 10 carbon atoms, each of the groups from R _c5 to R _c8 independently represents an alkyl group containing from 1 to 10 carbon atoms, And ₅ represents

, where each of the groups R _c11 and R _c12 independently represents a hydrogen atom, and each of m ₁ and m ₂ is independently an integer in the range from 0 to 3, whereby the equation m ₁ +m ₂ ≥ 1 is satisfied. 2. A modified polymer based on a conjugated diene according to claim 1, where in formula 1 each of the groups from R ₁ to R ₃ independently represents a hydrogen atom, R ₄ is a single bond and R ₅ is a functional group described by formula 1a or formula 1b, in formula 1a, R ₆ is an unsubstituted alkylene group containing 1 to 10 carbon atoms, each of R ₇ and R ₈ independently represents an unsubstituted alkylene group containing 1 to 10 carbon atoms, and R ₉ is an alkyl group containing from 1 to 10 carbon atoms; or an aryl group containing 6 to 20 carbon atoms, and in formula 1b, R ₁₀ is an unsubstituted alkylene group containing 1 to 10 carbon atoms, and each of R ₁₁ and R ₁₂ independently represents an alkyl group containing 1 to 10 carbon atoms. 3. A modified polymer based on a conjugated diene according to claim 1, where in formula 2 each of R _a1 and R _a4 independently represents an alkylene group containing from 1 to 5 carbon atoms, each of R _a2 and R _a3 independently represents an alkyl group containing from 1 to 5 carbon atoms, R _a5 is a five-membered heterocyclic group containing 2 to 4 carbon atoms, wherein the five-membered heterocyclic group contains one or more heteroatoms selected from the group consisting of N atoms, n ₁ is an integer from 1 to 3 and n ₂ is an integer from 0 to 2. 4. Modified polymer based on a conjugated diene according to claim 1, where in formula 3 each of A ₁ and A ₂ independently represents an alkylene group containing from 1 to 10 carbon atoms, each of R _b1 to R _b4 independently represents an alkyl group containing from 1 to 10 carbon atoms, each of R _b5 and R _b6 independently represents a hydrogen atom and each of A ₃ and A ₄ independently represents

, where each of the groups R _b9 and R _b10 independently represents a hydrogen atom. 5. The modified conjugated diene polymer according to claim 1, wherein the compound of formula 3 is a compound represented by the following formula 3-1: [Formula 3-1]

where in formula 3-1 each of A ₁ and A ₂ independently represents an alkylene group containing from 1 to 10 carbon atoms, and each of the groups from R _b1 to R _b4 independently represents an alkyl group containing from 1 to 10 carbon atoms. 6. Modified polymer based on a conjugated diene according to claim 1, where in formula 4 R _c1 is a hydrogen atom, each of the groups from R _c2 to R _c4 independently represents an alkylene group containing from 1 to 5 carbon atoms, each of the groups from R _c5 to R _c8 independently represents an alkyl group containing from 1 to 5 carbon atoms, And ₅ represents

, where each of the groups R _c11 and R _c12 independently represents a hydrogen atom or an alkyl group containing from 1 to 5 carbon atoms, and each of m ₁ and m ₂ is independently an integer in the range from 0 to 3, whereby the equation m ₁ +m ₂ ≥ 1 is satisfied. 7. The modified conjugated diene based polymer according to claim 1, wherein the modified conjugated diene based polymer has a number average molecular weight (Mn) in the range of 1,000 to 2,000,000 g/mol and a weight average molecular weight (Mw) in the range of 1,000 to 3,000,000 g /mol. 8. The modified conjugated diene based polymer according to claim 1, wherein the modified conjugated diene based polymer has a Si content and a N content of 50 ppm or more, respectively, by weight. 9. The modified conjugated diene polymer according to claim 1, wherein the modified conjugated diene polymer has a Mooney stress relaxation ratio, measured at 100° C., ranging from 0.7 to 3.0. 10. The modified conjugated diene based polymer according to claim 1, wherein the modified conjugated diene based polymer has a shrinkage ratio measured using a gel permeation chromatography-light scattering method equipped with a viscometer in the range of 0.8 to 3.0. 11. The modified conjugated diene based polymer according to claim 1, wherein the modified conjugated diene based polymer has a combination number (CN) of 1 < CN < F, where F is the number of functional groups in the modifier. 12. A rubber composition for making tires containing a modified conjugated diene-based polymer according to claim 1 and a filler.

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