BR112020008059B1 - MODIFIED CONJUGATED DIENE POLYMER AND RUBBER COMPOSITION INCLUDING THE SAME - Google Patents

Abstract

The present invention relates to a modified conjugated diene-based polymer, and more particularly to a modified conjugated diene-based polymer prepared by continuous polymerization and having a specific polymeric structure and degree and shape of molecular weight distribution, and therefore having extraordinary processability and strict molecular weight distribution and therefore having excellent physical properties, and a rubber composition including the same.

Description

TECHNICAL FIELD [Reference to related orders]

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

[Technical Field]

[002] The present invention relates to a polymer based on modified conjugated diene, with extraordinary processability and excellent tensile properties and viscoelastic properties, and a rubber composition including the same.

FUNDAMENTALS

[003] According to the current demand for vehicles with a low fuel consumption ratio, a conjugated diene-based polymer with modulational stability, represented by wet skid resistance, as well as a low resistance to bearing, and excellent traction properties and abrasion resistance, it is necessary as a tire rubber material.

[004] In order to reduce the rolling resistance of tires, there is a method of reducing the hysteresis loss of vulcanized rubber, and rebound resilience at 50°C to 80°C, tan δ, Goodrich heating , or similar is used as an evaluation index for vulcanized rubber. That is, it is desirable to use a rubber material with high rebound resilience at temperature above or a low tan δ value or Goodrich heating.

[005] Natural rubbers, polyisoprene rubbers or polybutadiene rubbers are known as rubber materials with low hysteresis loss, however, these rubbers have a limitation of low wet tensile strength. Thus, recently, polymers or copolymers based on conjugated diene, such as styrene-butadiene rubbers (hereinafter, referred to as “SBR”) and butadiene rubbers (hereinafter, referred to as “BR”), are prepared by emulsion polymerization or solution polymerization to be used as tire rubbers. Among these polymerization methods, the biggest advantage of solution polymerization over emulsion polymerization is that the vinyl structure content and styrene content, which specify the physical properties of rubber, can be adjusted arbitrarily, and its molecular weight and Physical properties can be controlled by coupling or modification. Thus, the SBR prepared by solution polymerization is widely used as a tire rubber material because it is easy to change a structure of the finally prepared SBR or BR, and the movement of the chain ends can be reduced and a coupling force with a material Fillers such as silica and carbon black can be increased by coupling or modifying the chain ends.

[006] If the polymerized SBR solution is used as the tire rubber material, since a glass transition temperature of the rubber is increased by increasing the vinyl content in the SBR, the physical properties such as resistance to movement (running resistance) and braking force, necessary for the tires to be controlled, and fuel consumption can be reduced as well, by properly adjusting the glass transition temperature. Solution-polymerized SBR is prepared using an anionic polymerization initiator and has been used by coupling or modifying the chain ends of the polymer thus formed through the use of various modifiers. For example, US Patent No. 4,397,994 describes a method of coupling active anions to the chain ends of a polymer obtained by polymerizing styrene-butadiene using alkyllithium, which is a monofunctional initiator in a non-polar solvent, with the use of a binder, such as a tin compound.

[007] Meanwhile, the polymerization of SBR or BR can be carried out by batch or continuous polymerization. In the case of batch polymerization, the molecular weight distribution of the polymer then produced is narrow, and batch polymerization is advantageous in view of the improvement of physical properties, but its productivity is low and the processability is inferior. In the case of continuous polymerization, the polymerization can be carried out continuously, and the productivity is excellent and the processability improvement is advantageous, but the molecular weight distribution is wide and the physical properties are inferior. Therefore, for the preparation of SBR or BR, studies to improve productivity, processability and physical properties concurrently are constantly needed. [State of the Art Documents] (Patent Document 1) US4397994 A (Patent Document 2) JP1994-271706 A

DISCLOSURE OF THE INVENTION TECHNICAL PROBLEM

[008] The present invention is developed to solve the problems of the conventional state of the art mentioned above, and an object of the present invention is to provide a polymer based on modified conjugated diene prepared by continuous polymerization and with extraordinary processability and excellent physical properties, such such as tensile properties and viscoelastic properties and a rubber composition including the same.

TECHNICAL SOLUTION

[009] To solve the tasks described above, according to an embodiment of the present invention, a modified conjugated diene-based polymer having a molecular weight distribution curve of unimodal shape by gel permeation chromatography ( GPC), and molecular weight distribution (PDI; MWD) of 1.0 to less than 1.7, and including a functional group derived from a modification initiator at one end and a functional group derived from a modifier represented by either selected from Formula 2 to Formula 4 below at the other end, wherein the modification initiator is a reaction product of a compound represented by the following Formula 1 and an organometallic compound: [Formula 1] in Formula 1, each R1 to R3 is independently hydrogen; an alkyl group of 1 to 30 carbon atoms; an alkenyl group of 2 to 30 carbon atoms; an alkynyl group of 2 to 30 carbon atoms; a heteroalkyl group of 1 to 30 carbon atoms, a heteroalkenyl group of 2 to 30 carbon atoms; a heteroalkynyl group of 2 to 30 carbon atoms; a cycloalkyl group of 5 to 30 carbon atoms; an aryl group of 6 to 30 carbon atoms; or a heterocyclic group of 3 to 30 carbon atoms, R4 is a single bond; a substituted or unsubstituted alkylene group of 1 to 20 carbon atoms by one substituent; a substituted or unsubstituted cycloalkylene group of 5 to 20 carbon atoms per substituent; or a substituted or unsubstituted arylene group of 6 to 20 carbon atoms by a substituent, wherein the substituent is an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms or an aryl group of 6 to 20 carbon atoms, R5 is an alkyl group of 1 to 30 carbon atoms; an alkenyl group of 2 to 30 carbon atoms; an alkynyl group of 2 to 30 carbon atoms; a heteroalkyl group of 1 to 30 carbon atoms; a heteroalkenyl group of 2 to 30 carbon atoms; a heteroalkynyl group of 2 to 30 carbon atoms; a cycloalkyl group of 5 to 30 carbon atoms; an aryl group of 6 to 30 carbon atoms; a heterocyclic group of 3 to 30 carbon atoms; or a functional group represented by the following Formula 1a or Formula 1b, n is an integer from 1 to 5, and at least one of the groups R5 is a functional group represented by the following Formula 1a or Formula 1b, in which case n is an integer from 2 to 5, a plurality of R5 groups can be the same or different:[Formula 1a] in Formula 1a, R6 is a substituted or unsubstituted alkylene group of 1 to 20 carbon atoms per one substituent; a substituted or unsubstituted cycloalkylene group of 5 to 20 carbon atoms per substituent; or a substituted or unsubstituted arylene group of 6 to 20 carbon atoms by a substituent, wherein the substituent is an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms or an aryl group of 6 to 20 carbon atoms, each of R7 and R8 is independently an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms, or a substituted or unsubstituted alkylene group of 1 to 20 carbon atoms. carbon by an aryl group of 6 to 20 carbon atoms, R9 is hydrogen; an alkyl group of 1 to 30 carbon atoms, an alkenyl group of 2 to 30 carbon atoms; an alkynyl group of 2 to 30 carbon atoms; a heteroalkyl group of 1 to 30 carbon atoms; a heteroalkenyl group of 2 to 30 carbon atoms; a heteroalkynyl group of 2 to 30 carbon atoms; a cycloalkyl group of 5 to 30 carbon atoms; an aryl group of 6 to 30 carbon atoms; or a heterocyclic group of 3 to 30 carbon atoms, and X is an atom of N, O or S, in the case where X is O or S, R9 is not present, [Formula 1b] in Formula 1b, R10 is a substituted or unsubstituted alkylene group of 1 to 20 carbon atoms per substituent; a substituted or unsubstituted cycloalkylene group of 5 to 20 carbon atoms per substituent; or a substituted or unsubstituted arylene group of 6 to 20 carbon atoms by a substituent, wherein the substituent is an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms or an aryl group of 6 to 20 carbon atoms and each R11 and R12 is independently an alkyl group of 1 to 30 carbon atoms; an alkenyl group of 2 to 30 carbon atoms; an alkynyl group of 2 to 30 carbon atoms; a heteroalkyl group of 1 to 30 carbon atoms; a heteroalkenyl group of 2 to 30 carbon atoms; a heteroalkynyl group of 2 to 30 carbon atoms; a cycloalkyl group of 5 to 30 carbon atoms; an aryl group of 6 to 30 carbon atoms; or a heterocyclic group of 3 to 30 carbon atoms, [Formula 2] in Formula 2, each of Ra1 and Ra4 is independently a single bond, or an alkylene group of 1 to 10 carbon atoms, each of Ra2 and Ra3 is independently an alkyl group of 1 to 10 carbon atoms, Ra5 is a five-membered heterocyclic group members having 2 to 4 carbon atoms, including one or more heteroatoms selected from the group consisting of N, O and S, n1 is an integer from 1 to 3 and n2 is an integer from 0 to 2, [Formula 3] in Formula 3, each A1 and A2 is independently an alkylene group of 1 to 20 carbon atoms, each Rb1 to Rb4 is independently an alkyl group of 1 to 20 carbon atoms, each of Rb5 and Rb6 is independently hydrogen or an alkyl group of 1 to 10 carbon atoms, and each A3 and A4 is independently that each Rb7 to Rb10 is independently hydrogen or an alkyl group of 1 to 10 carbon atoms, [Formula 4] in Formula 4, Rc1 is hydrogen or an alkyl group of 1 to 10 carbon atoms, each Rc2 to Rc4 is independently an alkylene group of 1 to 10 carbon atoms, each Rc5 to Rc8 is independently an alkyl group of 1 to 10 atoms of carbon, A5 is , where each Rc9 to Rci2 is independently hydrogen or an alkyl group of 1 to 10 carbon atoms, and each m1 and m2 is independently an integer from 0 to 3, where an equation of mi + m2 > 1 is met.

[010] Furthermore, the present invention provides a rubber composition including the modified conjugated diene-based polymer and a filler material.

ADVANTAGEOUS EFFECTS

[011] The polymer based on modified conjugated diene, according to the present invention, is prepared by continuous polymerization, in which a polymerization conversion rate is controlled, and has a molecular weight distribution curve of unimodal format by chromatography of gel permeation and strict distribution of molecular weight less than 1.7, and therefore it has excellent processability, tensile properties and viscoelasticity properties. Furthermore, the modified conjugated diene-based polymer according to the present invention includes a functional group derived from a modification initiator at one end and a functional group derived from a modifier at the other end, thereby showing viscoelastic properties. enhanced.

BRIEF DESCRIPTION OF THE DRAWINGS

[012] The drawings attached to the specification illustrate preferred examples of the present invention, for example, and serve to allow the technical concepts of the present invention to be better understood together with the detailed description of the invention presented below and, therefore, the present invention must should not be construed solely with the materials of such drawings.

[013] FIG. 1 illustrates a gel permeation chromatography (GPC) molecular weight distribution curve of a modified conjugated diene-based polymer of Example 1 in accordance with one embodiment of the present invention.

[014] FIG. 2 illustrates a gel permeation chromatography (GPC) molecular weight distribution curve of a modified conjugated diene-based polymer of Comparative Example 1 according to an embodiment of the present invention.

[015] FIG. 3 illustrates a gel permeation chromatography (GPC) molecular weight distribution curve of a modified conjugated diene-based polymer of Reference Example 1 according to an embodiment of the present invention.

[016] FIG. 4 illustrates a gel permeation chromatography (GPC) molecular weight distribution curve of a modified conjugated diene-based polymer of Reference Example 2 according to an embodiment of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

[017] The present invention will be described in detail below in order to assist the understanding of the present invention.

[018] It should be understood that words or terms used in the specification and claims of the present invention should not be interpreted with the meaning defined in commonly used dictionaries. It should further be understood that the words or terms are to be interpreted as having a meaning consistent with the meaning of the technical idea of the invention, based on the principle that an inventor can adequately define the meaning of the words or terms to better explain the invention.

[019] The term "alkyl group" used in the present invention may mean monovalent saturated aliphatic hydrocarbon and may include 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.

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

[021] The term "alkenyl group" used in the present invention may mean an alkyl group including one or two or more double bonds.

[022] The term "alkynyl group" used in the present invention may mean an alkyl group including one or two or more triple bonds.

[023] The term "cycloalkyl group" used in the present invention may mean saturated cyclic hydrocarbon or unsaturated cyclic hydrocarbon including one or two or more unsaturated bonds.

[024] The term "aryl group" used in the present invention may mean cyclic aromatic hydrocarbon and may include monocyclic aromatic hydrocarbon including one ring and polycyclic aromatic hydrocarbon including two or more bonded rings.

[025] The term "heteroalkyl group" used in the present invention can mean an alkyl group, in which a carbon atom (excluding a terminal carbon atom) in the alkyl group is replaced by one or more heteroatoms, in which the heteroatom can be selected from N, O and S.

[026] The term "heteroalkenyl group" used in the present invention may mean an alkenyl group, in which a carbon atom (excluding a terminal carbon atom) in the alkenyl group is replaced by one or more heteroatoms, in which the heteroatom may be selected from N, O and S.

[027] The term "heteroalkynyl group" used in the present invention may mean an alkynyl group, in which a carbon atom (excluding a terminal carbon atom) in the alkynyl group is replaced by one or more heteroatoms, in which the heteroatom may be selected from N, O and S.

[028] The term "heterocyclic group" used in the present invention may mean a cycloalkyl group, in which a carbon atom in the saturated cyclic hydrocarbon or unsaturated cyclic hydrocarbon including one or more unsaturated bonds, is replaced by one or more heteroatoms, in which the heteroatom can be selected from N, O and S.

[029] The term "derived unit" and "derived functional group" used in the present invention may represent a component or structure from a particular material or the material itself.

[030] The term "single bond" used in the present invention may mean a covalent bond itself, not including a separate atomic or molecular group.

[031] The substituent or functional group in the present invention may be substituted or unsubstituted by the same or different functional group or substituent, unless otherwise indicated.

[032] The present invention provides a modified conjugated diene-based polymer prepared by continuous polymerization and with extraordinary processability, strict molecular weight distribution and excellent physical properties.

[033] The modified conjugated diene-based polymer, according to an embodiment of the present invention, has a molecular weight distribution curve of unimodal format by gel permeation chromatography (GPC) and molecular weight distribution (PDI ; MWD) of 1.0 to less than 1.7, and includes a functional group derived from a modification initiator at one end and a functional group derived from a modifier represented by any one selected from Formula 2 to Formula 4 below in the other terminal, where the modification initiator is a reaction product of a compound represented by the following Formula 1 and an organometallic compound: [Formula 1] in Formula 1, each R1 to R3 is independently hydrogen; an alkyl group of 1 to 30 carbon atoms; an alkenyl group of 2 to 30 carbon atoms; an alkynyl group of 2 to 30 carbon atoms; a heteroalkyl group of 1 to 30 carbon atoms, a heteroalkenyl group of 2 to 30 carbon atoms; a heteroalkynyl group of 2 to 30 carbon atoms; a cycloalkyl group of 5 to 30 carbon atoms; an aryl group of 6 to 30 carbon atoms; or a heterocyclic group of 3 to 30 carbon atoms, R4 is a single bond; a substituted or unsubstituted alkylene group of 1 to 20 carbon atoms by one substituent; a substituted or unsubstituted cycloalkylene group of 5 to 20 carbon atoms per substituent; or a substituted or unsubstituted arylene group of 6 to 20 carbon atoms by a substituent, wherein the substituent is an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms or an aryl group of 6 to 20 carbon atoms, R5 is an alkyl group of 1 to 30 carbon atoms; an alkenyl group of 2 to 30 carbon atoms; an alkynyl group of 2 to 30 carbon atoms; a heteroalkyl group of 1 to 30 carbon atoms; a heteroalkenyl group of 2 to 30 carbon atoms; a heteroalkynyl group of 2 to 30 carbon atoms; a cycloalkyl group of 5 to 30 carbon atoms; an aryl group of 6 to 30 carbon atoms; a heterocyclic group of 3 to 30 carbon atoms; or a functional group represented by the following Formula 1a or Formula 1b, n is an integer from 1 to 5, and at least one of the groups R5 is a functional group represented by the following Formula 1a or Formula 1b, in which case n is an integer from 2 to 5, a plurality of R5 groups can be the same or different:[Formula 1a] in Formula 1a, R6 is a substituted or unsubstituted alkylene group of 1 to 20 carbon atoms per one substituent; a substituted or unsubstituted cycloalkylene group of 5 to 20 carbon atoms per substituent; or a substituted or unsubstituted arylene group of 6 to 20 carbon atoms by a substituent, wherein the substituent is an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms or an aryl group of 6 to 20 carbon atoms, each of R7 and R8 is independently an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms, or a substituted or unsubstituted alkylene group of 1 to 20 carbon atoms. carbon by an aryl group of 6 to 20 carbon atoms, R9 is hydrogen; an alkyl group of 1 to 30 carbon atoms, an alkenyl group of 2 to 30 carbon atoms; an alkynyl group of 2 to 30 carbon atoms; a heteroalkyl group of 1 to 30 carbon atoms; a heteroalkenyl group of 2 to 30 carbon atoms; a heteroalkynyl group of 2 to 30 carbon atoms; a cycloalkyl group of 5 to 30 carbon atoms; an aryl group of 6 to 30 carbon atoms; or a heterocyclic group of 3 to 30 carbon atoms, and X is an atom of N, O or S, in the case where X is O or S, R9 is not present, [Formula 1b] in Formula 1b, R10 is a substituted or unsubstituted alkylene group of 1 to 20 carbon atoms per substituent; a substituted or unsubstituted cycloalkylene group of 5 to 20 carbon atoms per substituent; or a substituted or unsubstituted arylene group of 6 to 20 carbon atoms by a substituent, wherein the substituent is an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms or an aryl group of 6 to 20 carbon atoms, and each R11 and R12 is independently an alkyl group of 1 to 30 carbon atoms; an alkenyl group of 2 to 30 carbon atoms; an alkynyl group of 2 to 30 carbon atoms; a heteroalkyl group of 1 to 30 carbon atoms; a heteroalkenyl group of 2 to 30 carbon atoms; a heteroalkynyl group of 2 to 30 carbon atoms; a cycloalkyl group of 5 to 30 carbon atoms; an aryl group of 6 to 30 carbon atoms; or a heterocyclic group of 3 to 30 carbon atoms, [Formula 2] in Formula 2, each of Ra1 and Ra4 is independently a single bond, or an alkylene group of 1 to 10 carbon atoms, each of Ra2 and Ra3 is independently an alkyl group of 1 to 10 carbon atoms, Ra5 is a five-membered heterocyclic group members having 2 to 4 carbon atoms, including one or more heteroatoms selected from the group consisting of N, O and S, n1 is an integer from 1 to 3 and n2 is an integer from 0 to 2, [Formula 3] in Formula 3, each A1 and A2 is independently an alkylene group of 1 to 20 carbon atoms, each Rb1 to Rb4 is independently an alkyl group of 1 to 20 carbon atoms, each of Rb5 and Rb6 is independently hydrogen or an alkyl group of 1 to 10 carbon atoms, and each A3 and A4 is independently where each Rb7 to Rb10 is independently hydrogen or an alkyl group of 1 to 10 carbon atoms, [Formula 4] in Formula 4, Rc1 is hydrogen or an alkyl group of 1 to 10 carbon atoms, each Rc2 to Rc4 is independently an alkylene group of 1 to 10 carbon atoms, each Rc5 to Rc8 is independently an alkyl group of 1 to 10 atoms of carbon, A5 is where each Rc9 to Rc12 is independently hydrogen or an alkyl group of 1 to 10 carbon atoms, and each m1 and m2 is independently an integer from 0 to 3, where an equation of m1 + m2 > 1 is satisfied.

[034] According to one embodiment of the present invention, the modified conjugated diene-based polymer may include a repeating unit derived from a conjugated diene-based monomer, a functional group derived from a modification initiator, and a group functional derived from a modifier. The repeating unit derived from a conjugated diene-based monomer can mean a repeating unit formed by a conjugated diene-based monomer during polymerization, and the functional group derived from a modification initiator and the functional group derived from a modifier can mean functional groups derived from a modification initiator and a modifier, which are present at the termini of a polymeric chain, respectively.

[035] Furthermore, according to another embodiment of the present invention, the modified conjugated diene-based polymer may be a copolymer that includes a repeating unit derived from a conjugated diene-based monomer, a repeating unit derived of a vinyl aromatic monomer, a functional group derived from a modification initiator, and a functional group derived from a modifier. Here, the repeating unit derived from a vinyl aromatic monomer can mean a repeating unit formed by a vinyl aromatic monomer during polymerization.

[036] According to one embodiment of the present invention, the conjugated diene-based 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 (halo means a halogen atom).

[037] The vinyl aromatic monomer may include, for example, one or more 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.

[038] In another embodiment, the modified conjugated diene-based polymer may be a copolymer that further includes a repeating unit derived from a diene-based monomer of 1 to 10 carbon atoms together with the derived repeating unit of a conjugated diene-based monomer. The repeating unit derived from a diene-based monomer may be a repeating unit derived from a diene-based monomer other than the conjugated diene-based monomer, and the diene-based monomer other than the conjugated diene-based monomer it may be, for example, 1,2-butadiene. If the modified conjugated diene-based polymer is a copolymer that further includes a diene-based monomer, the modified conjugated diene-based polymer may include the repeating unit derived from the diene-based monomer in more than 0% by weight to 1% by weight, by more than 0% by weight to 0.1% by weight, by more than 0% by weight to 0.01% by weight, or by more than 0% by weight to 0.001% by weight, and with this strip, the effect of preventing gel formation can be achieved.

[039] According to an embodiment of the present invention, the copolymer can be a random copolymer, and in this case, an excellent balancing effect between each of the physical properties can be achieved. Random copolymer can mean that the repeating units that make up a copolymer are arranged in disorder.

[040] The modified conjugated diene-based polymer according to an embodiment of the present invention may have a number average molecular weight (Mn) of 1,000 g/mol to 2,000,000 g/mol, 10,000 g/mol to 1,000 .000 g/mol, or 100,000 g/mol to 800,000 g/mol, a weight average molecular weight (Mw) of 1,000 g/mol to 3,000,000 g/mol, 10,000 g/mol to 2,000,000 g/mol, or 100,000 g/mol to 2,000,000 g/mol, and a maximum peak molecular weight (Mp) of 1,000 g/mol to 3,000,000 g/mol, 10,000 g/mol to 2,000,000 g/mol, or 100,000 g /mol to 2,000,000 g/mol. Within these ranges, rolling resistance and wet tensile strength are excellent. In another embodiment, the modified conjugated diene-based polymer can have molecular weight distribution (PDI; MWD; Mw/Mn) of 1.0 to less than 1.7 or 1.1 to less than 1.7 and within this range, the tensile properties and viscoelastic properties are excellent, and the balance between physical properties is excellent.

[041] In another embodiment, the modified conjugated diene-based polymer may have a weight average molecular weight (Mw) to peak maximum molecular weight (Mp) ratio of 0.7 to 1.4, and within this range, tensile properties, abrasion resistance properties and viscoelasticity are good, and the balance between each of the physical properties is excellent.

[042] At the same time, the modified conjugated diene-based polymer can have a molecular weight distribution curve of unimodal shape by gel permeation chromatography (GPC). This molecular weight distribution is shown by a polymer polymerized by continuous polymerization and it means that the modified conjugated diene-based polymer has uniform properties. That is, the modified conjugated diene-based polymer according to an embodiment of the present invention is prepared by continuous polymerization and can have a molecular weight distribution curve of unimodal shape and molecular weight distribution of less than 1.0 that 1.7.

[043] Generally, the molecular weight distribution curve of a conjugated diene-based polymer prepared by preparing a conjugated diene-based polymer by a batch polymerization method and then carrying out the modification reaction is a multimodal molecular weight distribution curve, that is, bimodal or more. Particularly, in batch polymerization, the polymerization reaction is started after the injection of all the raw materials, and from a starting point, when the polymerization is carried out by a plurality of initiators, the propagation of the chains can occur simultaneously. . Therefore, the spread of each chain can be generally uniform, the molecular weight of the polymer chains so prepared can be constant, and the molecular weight distribution can be narrowed significantly to show a unimodal shape. However, in the case where a modifier is injected and the modification reaction is carried out, where two cases of an “unmodified case” and a “coupled modified case” can occur, two groups with large difference in molecular weight can be formed between the polymeric chains, and finally, a multimodal molecular weight distribution curve with two or more peaks of a molecular weight distribution curve can be formed. Meanwhile, in the continuous polymerization method, according to an embodiment of the present invention, different from the batch polymerization, an initiator and raw materials are continuously injected, the starting points are different when the polymerization is started and the Polymerization is initiated at several points, including the beginning of the reaction, the intermediate phase of the reaction, and the end of the reaction. Consequently, polymeric chains with diverse molecular weights are produced after the completion of the polymerization reaction. Consequently, in a curve showing the molecular weight distribution, no dominant peak is shown, but a broad molecular weight distribution curve is shown with a single peak. Furthermore, although the coupling of a chain, whose polymerization is initiated at the end of the reaction, is carried out, the molecular weight can be similar to a chain whose polymerization is initiated at the beginning of the reaction, and the diversity of molecular weight distribution can be kept the same and the unimodal distribution curve can still be kept in general.

[044] However, the modification conditions can be controlled to show a unimodal shape, although a polymer is polymerized by a batch polymerization method and then modified. However, in this case, it is necessary that the entire polymer is uncoupled or that the entire polymer is coupled. Otherwise, a unimodal molecular weight distribution curve may not be displayed.

[045] Furthermore, as described above, in the case where the molecular weight distribution curve of the conjugated polymer based on modified diene shows a unimodal distribution, although it is prepared by a batch polymerization method and the entire polymer is coupled , polymers with equivalent level of molecular weights are present and therefore the processability may be lower, and the functional groups that can interact with a filler material such as silica and carbon black, decrease due to coupling, and the properties of composition may be lower. In contrast, in the case where the entire polymer is not coupled, the functional groups at the end of the polymer, which are required to interact with a filler material such as silica and carbon black, during processing predominantly produce carbon ions. interaction between the terminal functional groups of the polymer instead of the filler, and the interaction with the filler can be prevented. Therefore, the processability can deteriorate significantly, and finally, in the case where a polymer is controlled to show a unimodal molecular weight distribution curve while being prepared by the batch polymerization method, the processability and compositional properties of the polymer based on modified conjugated diene then prepared can be degraded and, in particular, the processability can be notoriously degraded.

[046] However, the coupling state of the polymer based on modified conjugated diene can be verified by the coupling number (C.N.), where the coupling number is a value dependent on the number of the functional group that is able to bind to a polymer present in a modifier after polymer modification. That is, the coupling number represents the ratio between a polymer obtained by terminal modification without coupling between the polymeric chains and a polymer in which a plurality of polymeric chains are coupled to a modifier and can have a range of 1<C.N.<F, where F means the functional group number in a modifier, which is capable of reacting with the terminal of an active polymer. In other words, a modified conjugated diene-based polymer with a coupling number of 1 means that all polymer chains are uncoupled, and a modified conjugated diene-based polymer with a coupling number of F means that all chains are uncoupled. polymers are coupled.

[047] Therefore, the modified conjugated diene-based polymer, according to an embodiment of the present invention, may have a unimodal shape molecular weight distribution curve and a coupling number greater than 1 and less than the number of functional groups of the used modifier (1<C.N.<F).

[048] In another embodiment, the modified conjugated diene-based polymer may have a Si content of 50 ppm or more, 100 ppm or more, 100 ppm to 10,000 ppm, or 100 ppm to 5,000 ppm based on the weight, and within this range, the mechanical properties such as tensile properties and viscoelastic properties of a rubber composition including the modified conjugated diene-based polymer are excellent. The Si content can mean the amount of Si atoms present in the modified conjugated diene-based polymer. Meanwhile, the Si atom can be derived from the functional group derived from the modifier.

[049] The Si content can be measured, for example, by an ICP analysis method, and the ICP analysis method can be measured using an inductively coupled plasma optical emission spectroscopy (ICP-OES; Optima 7300DV). If inductively coupled plasma optical emission spectroscopy is used, the measurement can be performed by adding about 0.7 g of a sample to a platinum (Pt) crucible, adding about 1 mL of concentrated sulfuric acid (98% by weight, electronic grade), heating at 300°C for 3 hours, incinerating the sample in an electric oven (Thermo Scientific, Lindberg Blue M) by the following program of steps 1 to 3: 1) step 1: initial temperature of 0°C, rate (temp/hour) of 180°C/h, temperature (hold time) of 180°C (1 h), 2) step 2: initial temperature of 180°C, rate (temp/hour ) of 85°C/h, temperature (holding time) of 370°C (2 h), and 3) step 3: initial temperature of 370°C, rate (temp/hour) of 47°C/h, temperature (holding time) of 510°C (3 h),

[050] adding 1 mL of concentrated nitric acid (48% by weight) and 20 μL of concentrated hydrofluoric acid (50% by weight) to a residue, sealing the platinum crucible and stirring for 30 minutes or more, adding 1 mL of boric acid to the sample, storing at 0°C for 2 hours or more, diluting in 30 mL of ultrapure water and incinerating.

[051] 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 with steam and stirring to remove solvents, and removing the remaining monomer and modifier of the same. Also, if an oil is added to the sample, the sample may be a sample after extracting (removing) the oil from the sample.

[052] In another embodiment, the modified conjugated diene-based polymer may have a N content of 50 ppm or more, 100 ppm or more, 100 ppm to 10,000 ppm or 100 ppm to 5,000 ppm based on total weight , and within this range, the mechanical properties such as tensile properties and viscoelastic properties of a rubber composition including the modified conjugated diene-based polymer are excellent. The N content can mean the amount of N atoms present in the modified conjugated diene-based polymer and, in this case, the N atom can be derived from the functional group derived from the modifier.

[053] The N content can be measured, for example, by an NSX analysis method, and the measurement by the NSX analysis method can be performed using a quantitative analyzer of a trace amount of nitrogen (NSX-2100H).

[054] For example, in the case where the quantitative analyzer of a trace amount of nitrogen was used, the quantitative analyzer of a trace amount of nitrogen (autosampler, horizontal oven, PMT and nitrogen detector) was turned on, the amounts of Carrier gas flows were adjusted so that Ar was 250 mL/min, O2 was 350 mL/min, and the ozonator was 300 mL/min, the heater was set to 800°C, and the analyzer was held for about 3 hours for stabilization. After analyzer stabilization, a calibration curve in the calibration ranges of 5 ppm, 10 ppm, 50 ppm, 100 ppm and 500 ppm was made using the nitrogen standard (AccuStandard S-22750-01-5 mL), an area corresponding to each concentration was obtained and a straight line was obtained using the ratio of concentration versus area. Next, a ceramic boat containing 20 mg of a sample was placed in the analyzer's autosampler and measurement was performed to obtain an area. The N content was calculated using the area of the sample then obtained and the calibration curve.

[055] 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 with steam and stirring to remove solvents, and removing the remaining monomer and modifier of the same. Also, if an oil is added to the sample, the sample may be a sample after extracting (removing) the oil from the sample.

[056] In another embodiment, the modified conjugated diene-based polymer may have a Mooney stress-relaxation ratio measured at 100°C of 0.7 or more, 0.7 to 3.0, 0.7 to 2.5 or 0.7 to 2.0.

[057] Here, the Mooney stress-relaxation ratio represents the change in stress shown as a 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 a Mooney viscosity using a Monsanto Co. MV-2000E large rotor at a rotor speed of 2 ± 0.02 rpm at 100°C. , leaving a polymer at room temperature (23 ± 3°C) for 30 minutes or more, collecting 27 ± 3 g of the polymer and placing it in a die cavity, then operating the Platen while torque is applied and , then measuring the grade value of the Mooney viscosity change shown upon releasing the torque.

[058] Meanwhile, the Mooney stress-relaxation ratio can be used as the index of the branch structure of a corresponding polymer. For example, if polymers with an equivalent Mooney viscosity are compared, the Mooney stress-relaxation ratio can decrease with increasing degree of branching, and therefore can be used as the index of degree of branching.

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

[060] In another embodiment, the modified conjugated diene-based polymer may have a shrinkage factor (g'), which is obtained by measuring it by a light scattering-gel permeation chromatography method endowed with a viscometer of 0.8 or more, particularly 0.8 to 3.0, more particularly 0.8 to 1.3, more particularly 1.0 to 1.3.

[061] Here, the shrinkage factor (g') obtained by measuring the method of light scattering-gel permeation chromatography is a ratio of the intrinsic viscosity of a polymer that has a branch in relation to the intrinsic viscosity of the linear polymer with the same absolute molecular weight and can be used as an index of the branch structure of a polymer having a branch, i.e., an index of a ratio occupied by branch. For example, with decreasing shrinkage factor, the degree of branching of a corresponding polymer tends to increase. Therefore, if polymers of equivalent absolute molecular weight are compared, the shrinkage factor decreases with increasing branching, and the shrinkage factor can be used as an index of the degree of branching.

[062] In addition, the shrinkage factor is obtained by measuring a chromatogram using a light scattering-gel permeation chromatography measuring device equipped with a viscometer, and the calculation based on a viscosity of the solution and a method of light dispersion. Particularly, using a light scattering measuring apparatus-GPC equipped with a light scattering detector, in which two columns filled with a polystyrene-based gel as a filling material are connected, and a viscometer, an absolute molecular weight and the intrinsic viscosity corresponding to each absolute molecular weight are obtained, the intrinsic viscosity of a linear polymer corresponding to the absolute molecular weight is calculated, and a shrinkage factor is obtained as a ratio between the corresponding intrinsic viscosity and each absolute molecular weight. For example, the shrinkage factor was obtained as follows. A sample was injected into a GPC-light scattering measuring apparatus (Viscotek TDAmax, Malvern Co.) equipped with a light scattering detector, in which two columns filled with a polystyrene-based gel as a packing material were connected, and a viscometer, and an absolute molecular weight was obtained from the light scattering detector, intrinsic viscosity [n] in relation to the absolute molecular weight was obtained from the light scattering detector and the viscometer, intrinsic viscosity [n]0 of a linear polymer in relation to the absolute molecular weight was calculated using Mathematical Formula 3 below and an average value between the corresponding intrinsic viscosity ratio ([n]/[n]0) and each absolute molecular weight was represented as the shrinkage factor . In this case, the measurement was performed using a mixture solution of tetrahydrofuran and N,N,N',N'-tetramethylethylenediamine (adjusted by mixing 20 mL of N,N,N',N'-tetramethylethylenediamine with 1 L of tetrahydrofuran) as an eluent, and PL Olexix (Agilent Co.) as a column, under the conditions of an oven temperature of 40°C and a THF flow rate of 1.0 mL/min. A sample was prepared by dissolving 15 mg of a polymer in 10 mL of THF.[Mathematical Formula 3] [n]0 = 10-3.883M0.771

[063] In mathematical formula 3, M is an absolute molecular weight.

[064] In addition, the modified conjugated diene-based polymer may have the vinyl content of 5% by weight or more, 10% by weight or more, or 10% by weight to 60% by weight. Here, vinyl content may mean the amount of conjugated diene-based monomer not 1,4-added but 1,2-added relative to 100% by weight of a conjugated diene-based copolymer composed of a monomer having a vinyl group and a vinyl aromatic monomer.

[065] In another embodiment, the modified conjugated diene-based polymer may have a molecular weight distribution curve of unimodal shape by gel permeation chromatography (GPC), a weighted average molecular weight (Mw) in a weight Molecular conversion standard of polystyrene by gel permeation chromatography from 1,000 g/mol to 3,000,000 g/mol, a ratio (Mw/Mn) of a weight average molecular weight (Mw) and a number average molecular weight (Mn) from 1.0 to less than 1.7, a ratio (Mw/Mp) of a weight average molecular weight (Mw) and a maximum peak molecular weight (Mp) of 0.7 to 1.4, the content of Si and N content of 50 ppm or more on a weight basis, respectively, and a Mooney stress-relaxation ratio measured at 100°C of 0.7 or more. Furthermore, the modified conjugated diene-based polymer has a polymeric component with a molecular weight of 100,000 g/mol or more in a gel permeation chromatography (GPC) conversion standard molecular weight of polystyrene with a unimodal format. Furthermore, the modified conjugated diene-based polymer may have a shrinkage factor measured by a light scattering-gel permeation chromatography method having a viscometer of 0.8 or greater.

[066] Meanwhile, the modification initiator, according to an embodiment of the present invention, is produced by the reaction of a compound represented by Formula 1 with an organometallic compound, where a functional group can be introduced at one end of the chain polymeric then polymerized at the same time that polymerization is initiated.[Formula 1] in Formula 1, each R1 to R3 is independently hydrogen; an alkyl group of 1 to 30 carbon atoms; an alkenyl group of 2 to 30 carbon atoms; an alkynyl group of 2 to 30 carbon atoms; a heteroalkyl group of 1 to 30 carbon atoms, a heteroalkenyl group of 2 to 30 carbon atoms; a heteroalkynyl group of 2 to 30 carbon atoms; a cycloalkyl group of 5 to 30 carbon atoms; an aryl group of 6 to 30 carbon atoms; or a heterocyclic group of 3 to 30 carbon atoms, R4 is a single bond; a substituted or unsubstituted alkylene group of 1 to 20 carbon atoms by one substituent; a substituted or unsubstituted cycloalkylene group of 5 to 20 carbon atoms per substituent; or a substituted or unsubstituted arylene group of 6 to 20 carbon atoms by a substituent, wherein the substituent is an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms or an aryl group of 6 to 20 carbon atoms, R5 is an alkyl group of 1 to 30 carbon atoms; an alkenyl group of 2 to 30 carbon atoms; an alkynyl group of 2 to 30 carbon atoms; a heteroalkyl group of 1 to 30 carbon atoms; a heteroalkenyl group of 2 to 30 carbon atoms; a heteroalkynyl group of 2 to 30 carbon atoms; a cycloalkyl group of 5 to 30 carbon atoms; an aryl group of 6 to 30 carbon atoms; a heterocyclic group of 3 to 30 carbon atoms; or a functional group represented by the following Formula 1a or Formula 1b, the symbol n represents an integer from 1 to 5, and at least one of the groups R5 is a functional group represented by the following Formula 1a or Formula 1b, in which case since n is an integer from 2 to 5, a plurality of R5 groups can be the same or different: [Formula 1a] in Formula 1a, R6 is a substituted or unsubstituted alkylene group of 1 to 20 carbon atoms per one substituent; a substituted or unsubstituted cycloalkylene group of 5 to 20 carbon atoms per substituent; or a substituted or unsubstituted arylene group of 6 to 20 carbon atoms by a substituent, wherein the substituent is an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms or an aryl group of 6 to 20 carbon atoms, each of R7 and R8 is independently an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms, or a substituted or unsubstituted alkylene group of 1 to 20 carbon atoms for an aryl group of 6 to 20 carbon atoms, R9 is hydrogen; an alkyl group of 1 to 30 carbon atoms; an alkenyl group of 2 to 30 carbon atoms; an alkynyl group of 2 to 30 carbon atoms; a heteroalkyl group of 1 to 30 carbon atoms; a heteroalkenyl group of 2 to 30 carbon atoms; a heteroalkynyl group of 2 to 30 carbon atoms; a cycloalkyl group of 5 to 30 carbon atoms; an aryl group of 6 to 30 carbon atoms; or a heterocyclic group of 3 to 30 carbon atoms, and X is an atom of N, O or S, in the case where X is O or S, R9 is not present, [Formula 1b] in Formula 1b, R10 is a substituted or unsubstituted alkylene group of 1 to 20 carbon atoms per substituent; a substituted or unsubstituted cycloalkylene group of 5 to 20 carbon atoms per substituent; or a substituted or unsubstituted arylene group of 6 to 20 carbon atoms by a substituent, wherein the substituent is an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms or an aryl group of 6 to 20 carbon atoms, and each R11 and R12 is independently an alkyl group of 1 to 30 carbon atoms; an alkenyl group of 2 to 30 carbon atoms; an alkynyl group of 2 to 30 carbon atoms; a heteroalkyl group of 1 to 30 carbon atoms; a heteroalkenyl group of 2 to 30 carbon atoms; a heteroalkynyl group of 2 to 30 carbon atoms; a cycloalkyl group of 5 to 30 carbon atoms; an aryl group of 6 to 30 carbon atoms; or a heterocyclic group of 3 to 30 carbon atoms.

[067] In particular, the compound represented by Formula 1 can be represented by Formula 1, in which each R1 to R3 is independently hydrogen; an alkyl group of 1 to 10 carbon atoms; an alkenyl group of 2 to 10 carbon atoms; or an alkynyl group of 2 to 10 carbon atoms, R4 is a single bond; or an unsubstituted alkylene group of 1 to 10 carbon atoms, R5 is an alkyl group of 1 to 10 carbon atoms; an alkenyl group of 2 to 10 carbon atoms; an alkynyl group of 2 to 10 carbon atoms; or a functional group represented by Formula 1a or Formula 1b, in Formula 1a, R6 is an unsubstituted alkylene group of 1 to 10 carbon atoms, each of R7 and R8 is independently an unsubstituted alkylene group of 1 to 10 carbon atoms, R9 is an alkyl group having 1 to 10 carbon atoms; a cycloalkyl group of 5 to 20 carbon atoms; an aryl group of 6 to 20 carbon atoms; or a heterocyclic group of 3 to 20 carbon atoms, and in Formula 1b, R10 is an unsubstituted alkylene group of 1 to 10 carbon atoms, and each R11 and R12 is independently an alkyl group of 1 to 10 carbon atoms; a cycloalkyl group of 5 to 20 carbon atoms; an aryl group of 6 to 20 carbon atoms; or a heterocyclic group of 3 to 20 carbon atoms.

[068] More particularly, the compound represented by Formula 1 may be a compound represented by the following Formula 1-1 to Formula 1-3:[Formula 1-1] [Formula 1-2] [Formula 1-3]

[069] 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 organocaesium compound.

[070] In particular, the organometallic compound may be one or more selected from methyl lithium, ethyl lithium, isopropyl lithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-decyl- lithium, tert-octyl lithium, phenyl lithium, 1-naphthyl lithium, n-eicolithium 4-butylphenyl lithium, 4-tolylyllithium, cyclohexyl lithium, 3,5-di-n-heptylcyclohexyl -lithium and 4-cyclopentyl lithium.

[071] Furthermore, the modifier, according to the present invention, may be a modifier for modifying a remaining terminal of the conjugated diene-based polymer, and, in a specific embodiment, may be a modifier with affinity for silica. Silica-affinity modifier can mean a modifier including a silica-affinity functional group in a compound used as the modifier, and silica-affinity functional group can mean a functional group that has excellent affinity for a filler material, particularly a silica-based filler and is capable of performing the interaction between a silica-based filler and a functional group derived from a modifier.

[072] In particular, according to an embodiment of the present invention, the modifier may be a compound represented by Formula 2 and in Formula 2, each Ra1 and Ra4 is independently a single bond, or an alkylene group of 1 to 5 carbon atoms, each of Ra2 and Ra3 is independently an alkyl group of 1 to 5 carbon atoms, Ra5 is a five-membered heterocyclic group of 2 to 4 carbon atoms, including one or more heteroatoms selected from the group consisting of N, O and S, where the heterocyclic group may be substituted or unsubstituted by a (trialkoxysilyl)alkyl group, and the alkyl group in the (trialkoxysilyl)alkyl group may be an alkyl group of 1 to 5 carbon atoms, and the alkoxy group may be an alkoxy group of 1 to 5 carbon atoms. Furthermore, the five-membered heterocyclic group may be a five-membered heterocyclic group including N.

[073] In a more particular embodiment, the compound represented by Formula 2 may be one 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.

[074] Furthermore, particularly, according to another embodiment of the present invention, the modifier may be a compound represented by Formula 3, and in Formula 3, each A1 and A2 is independently an alkylene group of 1 to 10 carbon atoms carbon, each Rb1 through Rb4 is independently an alkyl group of 1 to 10 carbon atoms, each of Rb5 and Rb6 is independently hydrogen or an alkyl group of 1 to 10 carbon atoms, and each A3 and A4 is independently wherein each Rb7 to Rbw is independently hydrogen or an alkyl group of 1 to 10 carbon atoms.

[075] More particularly, the compound represented by Formula 3 may be a compound represented by the following Formula 3-1 or Formula 3-2:[Formula 3-1] [Formula 3-2]

[076] In Formula 3-1 and Formula 3-2, each A1 and A2 is independently an alkylene group of 1 to 10 carbon atoms, and each Rb1 to Rb4 is independently an alkyl group of 1 to 10 carbon atoms.

[077] In a more specific embodiment, the compound represented by Formula 3 can be one selected from 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.

[078] Furthermore, particularly, according to another embodiment of the present invention, the modifier may be a compound represented by Formula 4, and, in Formula 4, Rc1 is hydrogen or an alkyl group of 1 to 5 carbon atoms , each Rc2 to Rc4 is independently an alkylene group of 1 to 5 carbon atoms, each Rc5 to Rc8 is independently an alkyl group of 1 to 5 carbon atoms, A5 is , where each Rc9 to Rci2 is independently hydrogen or an alkyl group of 1 to 10 carbon atoms.

[079] In a more specific embodiment, the compound represented by Formula 4 may be one selected from 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.

[080] As described above, in the modified conjugated diene-based polymer according to an embodiment of the present invention, the polymer has a specific structure and may have a specific degree and shape of molecular weight distribution. Such a polymeric structure can be expressed by physical properties such as the shrinkage factor, a Mooney stress-relaxation ratio, and a coupling number. The degree and shape of molecular weight distribution thereof can be expressed by a PDI value, the shape of a molecular weight distribution curve, and the coupling number and modification of both ends by a modifier and a primer. modification can influence the structure, and the degree and form of molecular weight distribution thereof. Parameters that express the structure of such a polymer and characteristics related to molecular weight distribution can be met by a preparation method, which will be described later. Furthermore, the above-mentioned characteristics can be met preferentially through the preparation method, but the effects for carrying out the present invention can only be achieved if all the above-mentioned characteristics are met.

[081] Furthermore, the present invention provides a method for preparing polymer based on modified conjugated diene.

[082] The method for preparing the modified conjugated diene-based polymer, according to an embodiment of the present invention, may include a polymerization step of a conjugated diene-based monomer, or a diene-based monomer conjugate and a vinyl aromatic monomer in the presence of a modification initiator in a hydrocarbon solvent to prepare an active polymer including a functional group derived from the modification initiator (S1); and a step of reacting or coupling the active polymer prepared in step (S1) with a modifier represented by any one selected from Formula 2 to Formula 4 below (S2), wherein step (S1) is carried out continuously in two or more reactors of polymerization, a polymerization conversion rate in a first reactor among the polymerization reactors is 50% or less, and the modification initiator is a reaction product prepared by reacting a compound represented by Formula 1 below and a compound organometallic. [Formula 1] [Formula 2] [Formula 3] [Formula 4]

[083] In Formula 1, Formula 4, R1 to R5, Ra1 to Ra5, Rb1 to Rb6, Rc1 to Rc8, A1 to A5, n, n1 to n2, m1 and m2 are the same as those defined above.

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

[085] In addition, the conjugated diene-based monomer and the vinyl aromatic monomer are the same as those defined above.

[086] According to one embodiment of the present invention, the modification initiator can be used in 0.01 mmol to 10 mmol, 0.05 mmol to 5 mmol, 0.1 mmol to 2 mmol, 0.1 mmol to 1 mmol or 0.15 mmol to 0.8 mmol based on 100 g total of the monomers.

[087] The polymerization of step (S1) can be, for example, an anionic polymerization, and particularly a live anionic polymerization by which an active anionic moiety is formed at the polymerization terminal through an anion propagation reaction. Furthermore, the polymerization of step (S1) can be carried out by a polymerization with heating, an isothermal polymerization or a polymerization at a constant temperature (adiabatic polymerization). Polymerization at constant temperature means a polymerization method including a polymerization step utilizing the self-generated heat of reaction without optionally applying heat after adding a polymerization initiator, and polymerization with heating means a polymerization method comprising injecting the polymerization initiator and raise the temperature by optionally applying heat. Isothermal polymerization means a polymerization method whereby the temperature of a polymer is maintained constant by applying heat or absorbing heat after addition of the polymerization initiator.

[088] Furthermore, according to an embodiment of the present invention, the polymerization of step (S1) can be carried out including a diene-based compound of 1 to 10 carbon atoms, in addition to the diene-based monomer conjugated, and in this case, the effect of preventing gel formation can be achieved on the wall side of a reactor after operating for a long time. The diene-based compound may be, for example, 1,2-butadiene.

[089] The polymerization of step (S1) can be carried out in a temperature range of 80°C or less, -20°C to 80°C, 0°C to 80°C, 0°C to 70°C, or 10°C to 70°C, and in this range, a polymer having a high linearity can be easily prepared, the Mooney stress-relaxation ratio and the shrinkage factor of the polymer can be improved, and furthermore, the weight distribution molecular weight of a polymer is strictly controlled, and the effect of excellent improvement of physical properties can be achieved.

[090] The active polymer prepared by step (S1) can mean a polymer in which a polymeric anion and an organometallic cation are coupled.

[091] According to one embodiment of the present invention, the method for preparing a modified conjugated diene-based polymer can be carried out in a plurality of reactors including two or more polymerization reactors and a modification reactor per one continuous polymerization method. In a specific embodiment, step (S1) can be carried out continuously in two or more polymerization reactors, including a first reactor, and the polymerization reactor number can be flexibly determined according to the reaction conditions and of the environment. The continuous polymerization method can mean reaction processes of continuously supplying reagents to a reactor and continuously discharging the reaction products then produced. By the continuous polymerization method, effects of excellent productivity and processability, and excellent uniformity of the polymer thus prepared can be achieved.

[092] Furthermore, according to an embodiment of the present invention, in the case where the active polymer is continuously prepared in the polymerization reactor, a polymerization conversion rate in the first reactor can be 50% or less, 10 % to 50%, or from 20% to 50%, and within this range, the side reactions generated during the formation of a polymer after the initiation of the polymerization reaction can be restrained and a polymer with a linear structure can be induced during the polymerization. In this case, since the degree of branching of the polymer with a linear structure is low, if the polymer is prepared by controlling the polymerization conversion rate in the first reactor to 50% or less as described above, the strain ratio -Mooney relaxation and the shrinkage factor of the polymer can be increased, and in addition, the molecular weight distribution of the polymer can be controlled strictly, and the effect of excellent improvement of physical properties can be achieved.

[093] In this case, the polymerization conversion rate can be controlled according to the reaction temperature, the retention time in the reactor, etc.

[094] The polymerization conversion rate can be determined, for example, by measuring a solid concentration in a polymer solution phase including the polymer during the polymerization of a polymer. In a particular embodiment, in order to contain the polymeric solution, a cylindrical container is installed at the outlet of each polymerization reactor to fill a certain amount of the polymeric solution in the cylindrical container. Then the cylindrical vessel is separated from the reactor, the weight (A) of the cylinder filled with the polymeric solution is measured, the polymeric solution filled in the cylindrical vessel is transported into an aluminum vessel, for example an aluminum dish, the weight (B) of the cylindrical container from which the polymer solution was removed is measured, the aluminum container containing the polymer solution is dried in an oven at 140°C for 30 minutes, the weight (C) of a dry polymer is measured and the calculation is performed according to the following Mathematical Equation 1:

[095] Meanwhile, the polymer polymerized in the first reactor can be transported to a polymerization reactor in front of an order modification reactor, and polymerization can be carried out until the final polymerization conversion rate is 95% or more. After carrying out polymerization in the first reactor, the polymerization conversion rate of the second reactor, or of each reactor from the second reactor to the polymerization reactor in front of the modification reactor, can be controlled appropriately to control the weight distribution molecular.

[096] Meanwhile, in step (S1), during the preparation of an active polymer, the retention time of a polymer in the first reactor can be from 1 minute to 40 minutes, from 1 minute to 30 minutes or from 5 minutes to 30 minutes, and within this range, control of a polymerization conversion rate is favorable, and therefore, strict control of the molecular weight distribution of a polymer is possible, and the effect of improving physical properties can be excellent.

[097] The term "polymer" used in the present invention may mean an intermediate of a type of polymer, which is under polymerization in each reactor during the realization step (S1), after the termination step (S1) or step (S2 ), before obtaining an active polymer or a modified conjugated diene-based polymer or it can mean a polymer with a polymerization conversion rate of less than 95%, which is under polymerization in a reactor.

[098] According to an embodiment of the present invention, the molecular weight distribution (PDI, polydisperse index; MWD, molecular weight distribution; Mw/Mn) of the active polymer prepared in step (S1) may be less than 1 .5, from 1.0 to less than 1.5, or from 1.1 to less than 1.5, and within that range, the molecular weight distribution of a modified conjugated diene-based polymer, which is prepared by means of a modification reaction or coupling to a modifier, it is strict and the effect of improving physical properties can be excellent.

[099] Meanwhile, the polymerization of step (S1) can be carried out including a polar additive, and the polar additive can be added in a proportion of 0.001 g to 50 g, 0.001 g to 10 g or 0.005 g to 0.1 g based in total 100 g of the monomers. In another embodiment, the polar additive can be added in a ratio of 0.001 g to 10 g, 0.005 g to 5 g, or 0.005 g to 4 g based on 1 mmol total of a modification initiator.

[0100] 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 , ethylene dimethyl ether, diethyl glycol, dimethyl ether, tert-butoxy ethoxyethane, bis(3-dimethylaminoethyl)ether, (dimethylaminoethyl)ethyl ether, trimethylamine, triethylamine, tripropylamine, N,N,N',N'-tetramethylethylenediamine, mentholate sodium, and 2-ethyl tetrahydrofurfuryl ether, and may preferably be 2,2-di(2-tetrahydrofuryl)propane, triethylamine, tetramethylethylenediamine, sodium mentholate, or 2-ethyl tetrahydrofurfuryl ether. If the polar additive is included, and if the conjugated diene based monomer or a conjugated diene based monomer and a vinyl aromatic based monomer are copolymerized, the difference in their reaction rates can be compensated and the effect of inducing the easy formation of a random copolymer can be achieved.

[0101] According to an embodiment of the present invention, the reaction or coupling of step (S2) can be carried out in a modification reactor and, in this case, the modifier can be used in an amount of 0.01 mmol to 10 mmol based on 100 g total of the monomers. In another embodiment, the modifier can be used in a molar ratio of 1:0.1 to 10.1:0.1 to 5 or 1:0.1 to 1:3 based on 1 mol of the modification initiator of step (S1).

[0102] Furthermore, according to an embodiment of the present invention, the modifier can be injected into a modification reactor and step (S2) can be performed in the modification reactor. In another embodiment, the modifier can be injected into a transport part to transport the active polymer prepared in step (S1) to a modification reactor to carry out step (S2), and in the transport part, the reaction or the coupling by mixing the active polymer and the modifier can be performed.

[0103] The method for preparing the modified conjugated diene-based polymer according to an embodiment of the present invention is a method satisfying the above-mentioned properties of the modified conjugated diene-based polymer. As described above, the effects for carrying out the present invention can be achieved if the above-mentioned properties are met, but in the preparation method, at least the polymerization conversion rate during transportation from the first reactor to the second reactor in process continuous flow needs to be met, while other polymerization conditions are differently controlled. Therefore, the physical properties of the modified conjugated diene-based polymer according to the present invention can be achieved.

[0104] Furthermore, the present invention provides a rubber composition that includes the modified conjugated diene-based polymer.

[0105] The rubber composition may include the modified conjugated diene-based polymer in an amount of 10% by weight or more, 10% by weight to 100% by weight or 20% by weight to 90% by weight and, within From this range, mechanical properties such as tensile strength and abrasion resistance are excellent, and the effect of an excellent balance between each of the physical properties can be achieved.

[0106] The rubber composition including the modified conjugated diene-based polymer according to the present invention may have a Mooney viscosity at 100°C (ML 1+4, 100°C) of 50 to 80, and this feature can be used as an index expressing processability properties.

[0107] In addition, processability properties can be better evaluated with decreasing Mooney viscosity and, additionally, can be better evaluated if the “difference” between the Mooney viscosity of the rubber composition, that is, a rubber compound mixture and the Mooney viscosity of the modified conjugated diene-based polymer decreases. It may be preferable that the amount of change in Mooney viscosity, i.e., the difference depending on whether it increases or decreases, be 20 or less.

[0108] In addition, the rubber composition may include yet another rubber component, if necessary, in addition to the modified conjugated diene-based polymer, and in this case, the rubber component may be included in an amount of 90% by weight or less based on the total amount of rubber composition. In a particular embodiment, the rubber component may be included in an amount of 1 part by weight to 900 parts by weight based on 100 parts by weight of the modified conjugated diene-based copolymer.

[0109] The rubber component may be, for example, a natural rubber or a synthetic rubber, and may particularly be a natural rubber (NR) including cis-1,4-polyisoprene; a modified natural rubber which is obtained by modifying or purifying a common natural rubber, such as an epoxidized natural rubber (ENR), a deproteinized natural rubber (DPNR) and a hydrogenated natural rubber; and a synthetic rubber, such as a styrene-butadiene copolymer (SBR), a polybutadiene (BR), a polyisoprene (IR), a butyl rubber (IIR), an ethylene-propylene copolymer, a polyisobutylene-co -isoprene, a neoprene, a poly(ethylene-co-propylene), a poly(styrene-co-butadiene), a poly(styrene-co-isoprene), a poly(styrene-co-isoprene-co-butadiene), a poly(isoprene-co-butadiene), a poly(ethylene-co-propylene-co-diene), a polysulfide rubber, an acrylic rubber, a urethane rubber, a silicone rubber, an epichlorohydrin rubber and a rubber halogenated butyl and any one or a mixture of two or more of these can be used.

[0110] The rubber composition may, for example, include 0.1 part by weight to 200 parts by weight or 10 parts by weight to 120 parts by weight of a filler material relative to 100 parts by weight of the base polymer of modified conjugated diene of the present invention. The filler material may be, for example, a silica-based filler material, particularly wet silica (hydrated silicate), dry silica (anhydrous silicate), calcium silicate, aluminum silicate or colloidal silica. Preferably, the filler material may be wet silica which has the most significant improvement effect on the destruction characteristics and compatible wet adhesion effect. Furthermore, the rubber composition can further include a carbon-based filler material, if necessary.

[0111] In another embodiment, if silica is used as a filler material, a silane coupling agent can be used together to improve the low exothermic and reinforcing properties. Particular 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-trimethoxysilylethyl)tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide , 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilylpropylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzolyltetrasulfide, 3-triethoxysilylpropylmethacrylatemonosulfide, 3-trimethoxysilylpropylmethacrylatomonosulfide, bis(3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilyl propyl-N,N-dimethylthiocarbamoyltetrasulfide or dimethoxymethylsilylpropylbenzothiazolyltetrasulfide and any one or a mixture of two or more of these can be used. Preferably, bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide can be used in connection with the effect of improving the reinforcing properties.

[0112] Furthermore, in the rubber composition, according to an embodiment of the present invention, since a modified conjugated diene-based polymer in which a functional group with high affinity for silica is brought into an active part is used as a rubber component, the mixing amount of silane coupling agent may be less than common case. Thus, the silane coupling agent can be used in an amount of 1 part by weight to 20 parts by weight, or 5 parts by weight to 15 parts by weight based on 100 parts by weight of silica. With the amount used in the above range, the effect of a coupling agent can be sufficiently displayed, and the effect of preventing gelling of a rubber component can be achieved.

[0113] The rubber composition, according to an embodiment of the present invention, may be crosslinkable with sulfur and therefore may further include a vulcanizing agent. The vulcanizing agent may particularly be a sulfur powder and may be included in an amount of 0.1 part by weight to 10 parts by weight based on 100 parts by weight of a rubber component. With the amount used in the above range, the elasticity and strength required for a vulcanized rubber composition can be ensured, and at the same time an excellent low fuel consumption ratio can be achieved.

[0114] The rubber composition according to an embodiment of the present invention may further include various additives used in a common rubber industry, in addition to the above components, particularly, a vulcanization accelerator, a process oil, an antioxidant, a plasticizer, an anti-aging agent, a premature vulcanization prevention agent, a zinc white, stearic acid, a thermosetting resin or a thermoplastic resin.

[0115] The vulcanization accelerator may include, for example, thiazole-based compounds such as 2-mercaptobenzothiazole (M), dibenzothiazyldisulfide (DM) and N-cyclohexyl-2-benzothiazylsulfenamide (CZ), or compounds based on guanidine, such as diphenylguanidine (DPG), in an amount of 0.1 part by weight to 5 parts by weight based on 100 parts by weight of the rubber component.

[0116] The process oil acts as a softener in a rubber composition and may include, for example, a paraffin-based, nathphene-based or aromatic compound. An aromatic process oil can be used in view of tensile strength and abrasion resistance, and a naphthene or paraffin based process oil can be used in view of loss of hysteresis and properties at low temperature. The process oil may be included in an amount of 100 parts by weight or less based on 100 parts by weight of the rubber component. Within the range described above, deterioration of tensile strength and low exothermic properties (low fuel consumption ratio) of a vulcanized rubber can be avoided.

[0117] The antioxidant may include, for example, 2,6-di-t-butyl paracresol, dibutylhydroxytoluene, 2,6-bis((dodecylthio)methyl)-4-nonylphenol or 2-methyl-4,6- bis((octylthio)methyl)phenol, and can be used in an amount of 0.1 part by weight to 6 parts by weight based on 100 parts by weight of a rubber component.

[0118] The anti-aging agent 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 a high temperature, in an amount of 0.1 part by weight to 6 parts by weight based on 100 parts by weight of the component rubber.

[0119] The rubber composition according to an embodiment of the present invention can be obtained by mixing (mulling) using a mixer such as a banbury mixer, a roller and an internal mixer according to a mixing prescription. A rubber composition with low exothermic properties and good abrasion properties can be obtained by a vulcanization process after a molding process.

[0120] Therefore, the rubber composition can be useful for the manufacture of each member of a tire, such as a tire tread, a lower tread, a sidewall, a carcass coating rubber, a tire belt lining, a bead filler material, a chafer and a bead lining rubber or for manufacturing rubber products in various industries such as a vibration proof rubber, conveyor belt and hose.

[0121] Furthermore, the present invention provides a tire manufactured using the rubber composition.

[0122] The tire may be a tire or a tire including a tread.

[0123] In the following, the present invention will be explained in more detail with reference to embodiments. Embodiments according to the present invention can be modified into 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 art.

Preparation Example 1

[0124] Two of the 4 L vacuum-dried stainless steel pressure vessels were prepared. Into a first pressure vessel, 6922 g of cyclohexane, 85 g of a compound represented by Formula 1-3 below and 60 g of tetramethylethylenediamine were injected to prepare a first reaction solution. At the same time, in a second pressure vessel, 180 g of a 2.0 M n-butyllithium in liquid phase and 6926 g of cyclohexane were injected to prepare a second reaction solution. In this case, the molar ratio between the compound represented by Formula 13, n-butyllithium and tetramethylethylenediamine was 1:1:1. While the pressure in each pressure vessel was maintained at 7 bar, the first reaction solution was injected at an injection rate of 1.0 g/min through a first continuous-type channel and the second reaction solution was injected at a injection rate of 1.0 g/min through a second continuous-type channel, respectively, in a continuous-type reactor using a mass flowmeter. In this case, the temperature of the continuous-type reactor was maintained at -10°C, the internal pressure was maintained at 3 bar using a backpressure regulator, and the retention time in the reactor was controlled to be within 10 minutes. The reaction was terminated to obtain a modification primer.[Formula 1-3]

Preparation Example 2

[0125] Two of the 4 L vacuum-dried stainless steel pressure vessels were prepared. Into a first pressure vessel, 6922 g of cyclohexane, 120 g of a compound represented by Formula 1-1 below and 60 g of tetramethylethylenediamine were injected to prepare a first reaction solution. At the same time, in a second pressure vessel, 180 g of a 2.0 M n-butyllithium in liquid phase and 6926 g of cyclohexane were injected to prepare a second reaction solution. In this case, the molar ratio between the compound represented by Formula 1-1, n-butyllithium and tetramethylethylenediamine was 1:1:1. While the pressure in each pressure vessel was maintained at 7 bar, the first reaction solution was injected at an injection rate of 1.0 g/min through a first continuous-type channel and the second reaction solution was injected at a injection rate of 1.0 g/min through a second continuous-type channel, respectively, in a continuous-type reactor using a mass flowmeter. In this case, the temperature of the continuous-type reactor was maintained at -10°C, the internal pressure was maintained at 3 bar using a backpressure regulator, and the retention time in the reactor was controlled to be within 10 minutes. The reaction was terminated to obtain a modification primer.[Formula 1-1]

Preparation Example 3

[0126] Two of the 4 L vacuum-dried stainless steel pressure vessels were prepared. Into a first pressure vessel, 6922 g of cyclohexane, 145 g of a compound represented by Formula 1-2 below and 60 g of tetramethylethylenediamine were injected to prepare a first reaction solution. At the same time, in a second pressure vessel, 180 g of a 2.0 M n-butyllithium in liquid phase and 6926 g of cyclohexane were injected to prepare a second reaction solution. In this case, the molar ratio between the compound represented by Formula 1-2, n-butyllithium and tetramethylethylenediamine was 1:1:1. While the pressure in each pressure vessel was maintained at 7 bar, the first reaction solution was injected at an injection rate of 1.0 g/min through a first continuous-type channel and the second reaction solution was injected at a injection rate of 1.0 g/min through a second continuous-type channel, respectively, in a continuous-type reactor using a mass flowmeter. In this case, the temperature of the continuous-type reactor was maintained at -10°C, the internal pressure was maintained at 3 bar using a backpressure regulator, and the retention time in the reactor was controlled to be within 10 minutes. The reaction was terminated to obtain a modification primer.[Formula 1-2]

Example 1

[0127] In a first reactor among the continuous reactors, in which three reactors were connected in series, a styrene solution was injected, in which 60% by weight of styrene was dissolved in n-hexane at a rate of 3.3 kg /h, a solution of 1,3-butadiene, in which 60% by weight of 1,3-butadiene was dissolved in n-hexane at a rate of 12.5 kg/h, n-hexane at a rate of 47, 4 kg/h, a 1,2-butadiene solution, in which 2.0% by weight of 1,2-butadiene was dissolved in n-hexane at a rate of 40 g/h, a 2,2- di(2-tetrahydrofuryl)propane (DTP), in which 10% by weight of 2,2-di(2-tetrahydrofuryl)propane was dissolved in n-hexane as a polar additive at a rate of 25.0 g/h, and the modification initiator prepared in Preparation Example 1 at a rate of 300.0 g/h. In this case, the temperature of the first reactor was maintained at 50°C, and when a polymerization conversion rate reached 43%, a polymer was transported from the first reactor to a second reactor through a transport pipe.

[0128] Then, in the second reactor, a solution of 1,3-butadiene, in which 60% by weight of 1,3-butadiene was dissolved in n-hexane, was injected at a rate of 0.7 kg/h . In this case, the temperature of the second reactor was maintained at 65°C, and when a polymerization conversion rate reached 95% or more, a polymer was conveyed from the second reactor to a third reactor through a transport pipe.

[0129] The polymer was transported from the second reactor to the third reactor and a solution, in which N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl) )propyl)propan-1-amine was dissolved (solvent: n-hexane), it was continuously injected into the third reactor as a modifier [modifier: act. Li = 1:1 mol]. The temperature of the third reactor was maintained at 65°C.

[0130] Thereafter, into a polymerization solution discharged from the third reactor, a solution of IR1520 (BASF Co.), in which 30% by weight was dissolved as an antioxidant, was injected at a rate of 170 g/h and stirred. The polymer thus obtained was injected into hot water heated with steam and stirred to remove solvents to prepare a modified conjugated diene-based polymer.

Example 2

[0131] A modified conjugated diene-based polymer was prepared by performing the same procedure described in Example 1, except for the continuous supply of the modification initiator prepared in Preparation Example 2 instead of the modification initiator prepared in Preparation Example 1 as a modification initiator at a rate of 350.0 g/h to the first reactor, transporting the polymer from the first to the second reactor through the transport tube when a polymerization conversion rate reached 40%, and continuously supplying a solution in which 1.3 -bis(3-(1H-imidazol-1-yl)propyl)-1,1,3,3-tetraethoxydisiloxane was dissolved (solvent: n-hexane) instead of the solution in which N-(3-(1H-imidazole -1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine was dissolved as a modifier [modifier: Liato = 1:1 mol] in Example 1.

Example 3

[0132] In a first reactor among the continuous reactors, in which three reactors were connected in series, a styrene solution was injected, in which 60% by weight of styrene was dissolved in n-hexane at a rate of 6.5 kg /h, a solution of 1,3-butadiene, in which 60% by weight of 1,3-butadiene was dissolved in n-hexane at a rate of 7.7 kg/h, n-hexane at a rate of 47, 0 kg/h, a solution of 1,2-butadiene, in which 2.0% by weight of 1,2-butadiene was dissolved in n-hexane at a rate of 40.0 g/h, a solution in which 10 % by weight of N,N,N',N'-tetramethylethylenediamine (TMEDA) was dissolved in n-hexane as a polar additive at a rate of 50.0 g/h, and the modification initiator prepared in Preparation Example 3 at a rate of 400.0 g/h.

[0133] In this case, the temperature of the first reactor was maintained at 55°C, and when a polymerization conversion ratio reached 41%, a polymer was transported from the first reactor to a second reactor through a transport tube .

[0134] Then, in the second reactor, a solution of 1,3-butadiene, in which 60% by weight of 1,3-butadiene was dissolved in n-hexane, was injected at a rate of 2.3 kg/h . In this case, the temperature of the second reactor was maintained at 65°C, and when a polymerization conversion rate reached 95%, a polymer was transported from the second reactor to a third reactor through a transport tube.

[0135] The polymer was transported from the second reactor to the third reactor and a solution, in which N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl) )propyl)propan-1-amine was dissolved (solvent: n-hexane), it was injected into the third reactor as a modifier [modifier: act. Li = 1:1 mol]. The temperature of the third reactor was maintained at 65°C.

[0136] Thereafter, into a polymerization solution discharged from the third reactor, a solution of IR1520 (BASF Co.), in which 30% by weight was dissolved as an antioxidant, was injected at a rate of 170 g/h and stirred. The polymer thus obtained was injected into hot water heated with steam and stirred to remove solvents to prepare a modified conjugated diene-based polymer.

Example 4

[0137] A modified conjugated diene-based conjugated polymer was prepared by performing the same procedure described in Example 3, except for the continuous supply of the modification initiator prepared in Preparation Example 2 instead of the modification initiator prepared in Preparation Example 3 as a polymerization initiator at a rate of 350.0 g/h to the first reactor, transporting the polymer from the first to the second reactor through the transport tube when a polymerization conversion rate reached 42%, and continuously supplying a solution in which 1 ,3-bis(3-(1H-imidazol-1-yl)propyl)-1,1,3,3-tetraethoxydisiloxane was dissolved (solvent: n-hexane) instead of the 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: Liato = 1: 1 mol], in the Example 3.

Example 5

[0138] A modified conjugated diene-based polymer was prepared by performing the same procedure described in Example 3, except for the continuous supply of the modification initiator prepared in Preparation Example 1 instead of the modification initiator prepared in Preparation Example 3 as a polymerization initiator at a rate of 300.0 g/h to the first reactor, transporting the polymer from the first reactor to the second reactor through the transport pipe when a polymerization conversion rate reached 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 was dissolved (solvent: n-hexane ) instead of the solution in which N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine was dissolved as modifier [ modifier: ato Li = 1: 1 mol], in Example 3.

Comparative Example 1

[0139] In a 20 L autoclave reactor, 180 g of styrene, 800 g of 1,3-butadiene, 5,000 g of n-hexane and 1.2 g of 2,2-di(2-tetrahydrofuryl) propane as a polar additive were injected, and the internal temperature of the reactor was raised to 50°C. After the internal temperature of the reactor reached 50°C, 4.7 mmol of the modification initiator prepared in Preparation Example 1 was injected and an adiabatic reaction with heating was carried out. After about 20 minutes, 20 g of 1,3-butadiene were injected to cover the ends of a polymeric chain with butadiene. After 5 minutes, 4.7 mmol of N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine were injected and reacted for 15 minutes. Then, the polymerization reaction was stopped using ethanol, and 45 ml of a solution were added to it in which 0.3% by weight of antioxidant IR1520 (BASF Co.) was dissolved in n-hexane. Then, the polymer thus obtained was injected into hot water heated with steam and stirred to remove the solvents to prepare a modified conjugated diene-based polymer.

Comparative Example 2

[0140] In a first reactor among the continuous reactors, in which three reactors were connected in series, a styrene solution was injected, in which 60% by weight of styrene was dissolved in n-hexane at a rate of 3.3 kg /h, a solution of 1,3-butadiene, in which 60% by weight of 1,3-butadiene was dissolved in n-hexane at a rate of 12.5 kg/h, n-hexane at a rate of 47, 4 kg/h, a solution of 1,2-butadiene, in which 2.0% by weight of 1,2-butadiene was dissolved in n-hexane at a rate of 40.0 g/h, a solution in which 10 % by weight of 2,2-(di-(2-tetrahydrofuryl)propane (DTP) was dissolved in n-hexane as a polar additive at a rate of 25.0 g/h, and a solution of n-butyl -lithium, in which 5% by weight of n-butyllithium was dissolved in n-hexane as a polymerization initiator at a rate of 30.0 g/h. In this case, the temperature of the first reactor was maintained at 50° C, and when a polymerization conversion rate reached 43%, a polymer was conveyed from the first reactor to a second reactor through a transport tube.

[0141] Then, in the second reactor, a solution of 1,3-butadiene, in which 60% by weight of 1,3-butadiene was dissolved in n-hexane, was injected at a rate of 0.7 kg/h . In this case, the temperature of the second reactor was maintained at 65°C, and when a polymerization conversion rate reached 95% or more, a polymer was conveyed from the second reactor to a third reactor through a transport tube.

[0142] The polymer was transported from the second reactor to the third reactor and a solution in which dichlorodimethylsilane was dissolved (solvent: n-hexane) was injected into the third reactor as a coupling agent [coupling agent: act. Li = 1: 1 mol]. The temperature of the third reactor was maintained at 65°C.

[0143] Thereafter, into a polymerization solution discharged from the third reactor, a solution of IR1520 (BASF Co.), in which 30% by weight was dissolved as an antioxidant, was injected at a rate of 170 g/h and stirred. The polymer thus obtained was injected into hot water heated with steam and stirred to remove solvents to prepare a modified conjugated diene-based polymer.

Comparative Example 3

[0144] A modified conjugated diene-based polymer was prepared by performing the same procedure described in Example 1, except for maintaining the temperature of the first reactor at 75°C and transporting a polymer from the first reactor to the second reactor through the tube of transport when a polymerization conversion rate reached 78%, in Example 1.

Comparative Example 4

[0145] A terminal-modified conjugated diene-based polymer was prepared by performing the same procedure described in Example 1, except for transporting a polymer from the first reactor to the second reactor through the transport tube when a polymerization conversion rate reached 42% and for carrying out the reaction without injecting the modifier in the third reactor, in Example 1.

Comparative Example 5

[0146] A terminal-modified conjugated diene-based polymer was prepared by performing the same procedure described in Example 1, except for the continuous injection of a solution of n-butyllithium, in which 5% by weight of n-butyllithium lithium were dissolved in n-hexane instead of the modification initiator prepared in Preparation Example 1 as a polymerization initiator at a rate of 30.0 g/h in the first reactor in Example 1.

Comparative Example 6

[0147] A modified conjugated diene-based polymer was prepared by performing the same procedure described in Example 3, except for the continuous injection of a solution of n-butyllithium, in which 5% by weight of n-butyllithium was dissolved in n-hexane instead of the modification initiator prepared in Preparation Example 1 as a polymerization initiator at a rate of 30.0 g/h, and a solution in which dimethyldichlorosilane was dissolved in n-hexane (solvent: n- hexane) as a coupling agent instead of the modifier in the third reactor, in Example 3 [coupling agent: act. Li = 1:1 mol].

Reference Example 1

[0148] A two-terminal modified conjugated diene-based polymer was prepared by performing the same procedure described in Comparative Example 1, except for the injection of 14.1 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)propan-1-amine as a modifier, in Comparative Example 1.

Reference Example 2

[0149] A two-terminal modified conjugated diene-based polymer was prepared by performing the same procedure described in Comparative Example 1, except for the injection of 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)propan-1-amine as a modifier, in Comparative Example 1.

Experimental Example 1

[0150] With respect to each of the modified or unmodified conjugated diene-based polymers prepared in the Examples and Comparative Examples, a unit of styrene and vinyl content in each polymer, a weight average molecular weight (Mw, x103 g/ mol), a number average molecular weight (Mn, x103 g/mol), molecular weight distribution (PDI, MWD), a Mooney viscosity (MV) and Si content were measured, respectively. The results are shown in Table 1 and Table 2 below.

1) Unit of styrene and vinyl content (% by weight)

[0151] The styrene unit (SM) and vinyl content in each polymer were measured and analyzed using Varian VNMRS 500 MHz NMR.

[0152] When measuring NMR, 1,1,2,2-tetrachloroethanol was used as a solvent, and the styrene unit and vinyl content were calculated by calculating a solvent peak as 5.97 ppm, and in relative to 7.2-6.9 ppm as a random styrene peak, 6.9-6.2 ppm as a block styrene peak, 5.8-5.1 ppm as a 1,4-vinyl peak , and 5.1-4.5 ppm as a 1,2-vinyl peak.

[0153] 2) Weight average molecular weight (Mw, x 103 g/mol), number average molecular weight (Mn, x103 g/mol), peak maximum molecular weight (Mp, x103 g/mol), weight distribution molecular (PDI, MWD) and coupling number (C.N.)

[0154] By gel permeation chromatography (GPC) analysis, the weight average molecular weight (Mw), the number average molecular weight (Mn) and the peak maximum molecular weight (Mp) were measured at 40°C and a molecular weight distribution curve was obtained. Furthermore, molecular weight distribution (PDI, MWD, Mw/Mn) was calculated from each weight average molecular weight and number average molecular weight then measured. Particularly, GPC was conducted using two Olexis PLgel columns (Polymer Laboratories Co.) and one C-mixed PLgel column (Polymer Laboratories Co.) in combination, and polystyrene (PS) as a standard GPC material for the calculation. of the molecular weight. A solvent for measuring GPC was prepared by mixing tetrahydrofuran with 2% by weight of an amine compound. In this case, the molecular weight distribution curves thus obtained are shown in FIG. 1 to FIG. 4.

[0155] In addition, the coupling number was calculated by collecting a portion of a polymer before injecting a modifier or a coupling agent into each of the Examples and Comparative Examples and obtaining a peak molecular weight ( Mp1) of the polymer, then obtaining the peak molecular weight (Mp2) of each polymer based on modified conjugated diene, and calculating it according to the following Mathematical Formula 2:[Mathematical Formula 2] Coupling Number (C.N. ) = Mp2/Mp1

3) Mooney viscosity and Mooney stress-relaxation ratio

[0156] The Mooney viscosity (MV, (ML 1+4, at 100°C) MU) was measured using an MV-2000 (Alpha Technologies Co.) with a large rotor at a rotor speed of 2 ± 0 .02 rpm at 100°C. In this case, the used sample was left at room temperature (23 ± 3°C) for 30 minutes or more, and 27 ± 3 g of the sample was collected and placed in a cavity of the matrix, and then Platen was operated for 4 minutes for measurement to obtain the Mooney viscosity.

[0157] After measuring the Mooney viscosity, a gradient value (absolute value) of change in the Mooney viscosity shown during torque release was measured, and the Mooney stress-relaxation ratio was obtained from the absolute value of the same.

4) Si content

[0158] Si content was measured by an ICP analysis method, which used inductively coupled plasma optical emission spectroscopy (ICP-OES; Optima 7300DV). Particularly, the measurement was carried out by adding about 0.7 g of a sample to a platinum (Pt) crucible and adding about 1 mL of concentrated sulfuric acid (98% by weight, electronic grade) to it, heating the 300°C for 3 hours, incinerating the sample in an electric oven (Thermo Scientific, Lindberg Blue M) by the following program of steps 1 to 3: 1) step 1: initial temperature of 0°C, rate (temp/hour) of 180°C/h, temperature (holding time) 180°C (1 h), 2) step 2: initial temperature 180°C, rate (temp/hour) 85°C/h, temperature (setting time) hold) of 370°C (2 h), and 3) step 3: initial temperature of 370°C, rate (temp/hour) of 47°C/h, temperature (holding time) of 510°C (3 h ),

[0159] adding 1 mL of concentrated nitric acid (48% by weight) and 20 μL of concentrated hydrofluoric acid (50% by weight) to a residue, sealing the platinum crucible and stirring for 30 minutes or more, adding 1 mL of boric acid to the sample, storing at 0°C for 2 hours or more, diluting in 30 mL of ultrapure water and incinerating.

5) N content

[0160] The N content was measured through an NSX analysis method, using a quantitative analyzer of a trace amount of nitrogen (SX-2100H). In particular, the quantitative analyzer of a trace amount of nitrogen (autosampler, horizontal oven, PMT and nitrogen detector) was turned on, the carrier gas flow rates were adjusted so that the Ar was 250 mL/min, the O2 was 350 mL/min and the ozonator was 300 mL/min, the heater was set to 800°C and the analyzer was held for about 3 hours for stabilization. After analyzer stabilization, a calibration curve in the calibration ranges of 5 ppm, 10 ppm, 50 ppm, 100 ppm and 500 ppm was made using the nitrogen standard (AccuStandard S-22750-01-5 mL), an area corresponding to each concentration was obtained and a straight line was obtained using a ratio of concentration versus area. Next, a ceramic boat containing 20 mg of a sample was placed in the analyzer's autosampler and measurement was performed to obtain an area. The N content was calculated using the area of the sample then obtained and the calibration curve.

6) Shrinkage Factor (g')

[0161] The shrinkage factor was obtained as follows. A sample was injected into a light scattering-GPC measuring apparatus (Viscotek TDAmax, Malvern Co.) equipped with a light scattering detector, in which two columns filled with a polystyrene-based gel as a packing material were connected, and a viscometer, and an absolute molecular weight was obtained from the light scattering detector, intrinsic viscosity [n] in relation to the absolute molecular weight was obtained from the light scattering detector and the viscometer, intrinsic viscosity [n]0 of a linear polymer in relation to the absolute molecular weight was calculated using Mathematical Formula 3 below and an average value between the corresponding intrinsic viscosity ratio ([n]/[n]0) and each absolute molecular weight was represented as the shrinkage factor . In this case, the measurement was performed using a mixture solution of tetrahydrofuran and N,N,N',N'-tetramethylethylenediamine (adjusted by mixing 20 mL of N,N,N',N'-tetramethylethylenediamine with 1 L of tetrahydrofuran) as an eluent, and PL Olexix (Agilent Co.) as a column, under the conditions of an oven temperature of 40°C and a THF flow rate of 1.0 mL/min. A sample was prepared by dissolving 15 mg of a polymer in 10 mL of THF. [Mathematical Formula 3] [n]0= 1O-3,883Mo,771 In Mathematical Formula 3, M is an absolute molecular weight. [Table 1] [Table 2]

[0162] In Table 1 and Table 2 above, specific materials used as initiator, modifier and coupling agent are shown in Table 3 below.[Table 3]

[0163] With reference to Tables 1 and 2, it was found that the modified conjugated diene-based polymers of Examples 1 to 5, prepared according to the embodiments of the present invention, meet all the necessary ranges of physical properties. Particularly, the molecular weight distribution curve by gel permeation chromatography has a unimodal shape and at the same time a PDI value of 1.0 to less than 1.7, and the processability is expected to be significantly excellent and the composition properties are also excellent. Mooney's stress-relaxation ratio is 0.7 or better for all, and linearity is expected to be excellent. The shrinkage factor is 0.8 or more, and the balance between physical properties is expected to be superior.

[0164] On the other hand, Comparative Example 3, in which the polymerization conversion rate during transport from the first reactor to the second reactor was controlled, did not show a high PDI value, and the Mooney stress-relaxation ratio and shrinkage factor were evaluated as a certain value or less, and therefore the balance between physical properties and linearity gave unsatisfactory results.

[0165] Furthermore, in the case where batch polymerization is applied, an ordinary modified conjugated diene-based polymer has a small PDI value of less than 1.7 as in Comparative Example 1, but a molecular weight distribution curve of bimodal format is shown and processability is expected to be lower. As a result of batch polymerization, a molecular weight distribution curve of unimodal shape can be shown as in Reference Examples 1 and 2, but the Reference Examples correspond to extreme cases where the coupling number is the minimum or maximum value of the number of functional groups of the modifier, i.e. a case where all polymers are not coupled by the modifier (Reference Example 1) or a case where all polymers are coupled by the modifier (Reference Example 2). Such polymer based on conjugated diene modified by batch polymerization causes deterioration of the properties of the mixture as explained in the above explanation and the results of the evaluation, which will be described later.

[0166] FIGS. 1 to 4 show the molecular weight distribution curves of Example 1, Comparative Example 1 and Reference Examples 1 and 2, and it was observed that the shape of each molecular weight distribution curve has the shape described above.

Experimental Example 2

[0167] In order to comparatively analyze the physical properties of rubber compositions, including modified or unmodified copolymers, prepared in the Examples, Comparative Examples and Reference Examples, respectively, and the molded articles manufactured from them, the tensile properties and viscoelastic properties were measured, and the results are shown in Table 5 and Table 6 below.

1) Preparation of the rubber sample

[0168] The mixing was carried out using each of the modified or unmodified conjugated diene-based polymers of the Examples, Comparative Examples and Reference Examples as the rubber raw material under the mixing conditions listed in Table 4 below. Raw materials in Table 4 are represented by parts by weight, based on 100 parts by weight of rubber raw material. [Table 4]

[0169] Particularly, the rubber sample was mixed (mulled) by means of a first mixing step (mulling) and a second mixing step. In the first step, a raw material of rubber, silica (filler), an organic silane coupling agent, a process oil, zinc white, stearic acid, an antioxidant, an anti-aging agent and wax were mixed using if a banbury mixer equipped with temperature control apparatus. In this case, the initial temperature of a mixing apparatus was controlled at 70°C and, after completion of mixing, a first mixture of compounds was obtained at a discharge temperature of 145°C to 155°C. In the second mixing step, the first compound mixture was cooled to room temperature and the first compound mixture, sulfur, a rubber accelerator and a vulcanization accelerator were added to the mixing apparatus and mixed at a temperature of 100°C or less to obtain a second mixture of compounds. Then, through a curing/hardening process at 160°C for 20 minutes, a rubber sample was formed.

2) Traction properties

[0170] Tensile properties were measured by manufacturing each sample and measuring tensile strength by tensile stress and rupture when elongated by 300% (300% modulus) of each sample, according to a tensile test method ASTM 412. In particular, tensile properties were measured using a Universal Test Machin 4204 tensile tester (Instron Co.) at a rate of 50 cm/min at room temperature.

3) Viscoelastic properties

[0171] The viscoelastic properties were ensured by measuring the behavior of viscoelasticity in thermodynamic deformation at each measurement temperature (-60°C to 60°C) with a frequency of 10 Hz, using a dynamic mechanical analyzer (GABO Co .) in a film tension mode and setting a tan δ value. In the measurement values, if the tan δ value at a low temperature of 0°C increases, the wet tensile strength becomes better, and if the tan δ value at a high temperature of 60°C decreases, the hysteresis loss decreases, and the low resistance to movement (fuel consumption ratio) improves. In Table 5 and Table 6 below, viscoelastic properties have been indexed (%) by defining a reference value. The higher the value, the better the properties.

4) Processability properties

[0172] By measuring the Mooney viscosity (MV, (ML 1+4, at 100°C) MU) of the second mixture of compounds obtained during the preparation of the 1) rubber sample, the processability properties of each polymer were analyzed comparatively, and in this case, the lower the measured Mooney viscosity value, the better the processability properties.

[0173] In particular, using an MV-2000 (Alpha Technologies Co.) with a large rotor at a rotor speed of 2 ± 0.02 rpm at 100°C, every second mixture of compounds was maintained at room temperature ( 23 ± 3°C) for 30 minutes or more, and 27 ± 3 g were collected and placed in a well of the matrix, and then the Platen was operated for 4 minutes for measurement.[Table 5]

[0174] In Table 5, the values resulting from Examples 1 and 2, Comparative Examples 1 and 3 to 5, and Reference Examples 1 and 2 were indexed based on the measurement value of Comparative Example 2 to 100. The greater the value, the better the properties.

[0175] Referring to Table 5 above, as predicted from the measured properties of the polymers in Experimental Example 1, it was found that Examples 1 and 2 show equivalent or better levels of tensile strength and significantly better modulus in the properties of traction when compared with those of the Comparative Examples. In the viscoelastic properties, the tan δ value at a low temperature was maintained at equivalent or better level, and the tan δ value at a high temperature was markedly improved, and it could be found that the fuel consumption ratio was greatly improved. without loss of surface resistance.

[0176] In addition, as in Reference Examples 1 and 2, in the case where a polymer prepared by batch polymerization presented a unimodal shape molecular weight distribution curve, it was found that the intrinsic lower processability of batch polymerization was maintained, while excellent compounding properties, which could be achieved as an advantage in batch polymerization, were not achieved. Meanwhile, the lower intrinsic processability of batch polymerization can be confirmed in Comparative Example 1, in which the same initiator and the same modifier were applied and the equivalent range of coupling number was applied as in Example 1.

[0177] In addition, in Comparative Example 3, the results were obtained not according to the preparation method of the present invention, the ranges of the PDI value, the shrinkage factor and the Mooney stress-relaxation ratio were unsatisfactory, as described above. Furthermore, the tensile properties and viscoelastic properties were found to be inferior to the Examples. Furthermore, in Comparative Examples 2, 4 and 5, in which the modifier and modification initiator according to the present invention were not applied, the tensile properties and viscoelastic properties were also found to be inferior.[Table 6]

[0178] In Table 6 above, the resulting values of viscoelasticity properties from Example 3 to Example 5 have been indexed (%) and shown based on the measured value of Comparative Example 6, and the higher the value, the better the properties.

[0179] Table 6 shows the resulting sets, whose amounts of comonomers were different from the sets in Table 5. It can be seen that the effects are not changed although the amounts of monomers in Table 6 have been changed, and results identical to the results of improvement of physical properties confirmed in Table 5 were shown.

Claims (15)

1. Modified conjugated diene-based polymer CHARACTERIZED by the fact that it has a gel permeation chromatography (GPC) unimodal shaped molecular weight distribution curve, and molecular weight distribution (PDI; MWD) from 1.0 to less than 1.7, and comprising a functional group derived from a modification initiator at one end and a functional group derived from a modifier represented by any one selected from the following Formula 2 to Formula 4 at the other end, wherein the initiator of modification modification is a reaction product of a compound represented by the following Formula 1 and an organometallic compound: [Formula 1] in Formula 1, each R1 to R3 is independently hydrogen; an alkyl group of 1 to 30 carbon atoms; an alkenyl group of 2 to 30 carbon atoms; an alkynyl group of 2 to 30 carbon atoms; a heteroalkyl group of 1 to 30 carbon atoms, a heteroalkenyl group of 2 to 30 carbon atoms; a heteroalkynyl group of 2 to 30 carbon atoms; a cycloalkyl group of 5 to 30 carbon atoms; an aryl group of 6 to 30 carbon atoms; or a heterocyclic group of 3 to 30 carbon atoms, R4 is a single bond; a substituted or unsubstituted alkylene group of 1 to 20 carbon atoms by one substituent; a substituted or unsubstituted cycloalkylene group of 5 to 20 carbon atoms per substituent; or a substituted or unsubstituted arylene group of 6 to 20 carbon atoms by a substituent, wherein the substituent is an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms or an aryl group of 6 to 20 carbon atoms, R5 is an alkyl group of 1 to 30 carbon atoms; an alkenyl group of 2 to 30 carbon atoms; an alkynyl group of 2 to 30 carbon atoms; a heteroalkyl group of 1 to 30 carbon atoms; a heteroalkenyl group of 2 to 30 carbon atoms; a heteroalkynyl group of 2 to 30 carbon atoms; a cycloalkyl group of 5 to 30 carbon atoms; an aryl group of 6 to 30 carbon atoms; a heterocyclic group of 3 to 30 carbon atoms; or a functional group represented by the following Formula 1a or Formula 1b, n is an integer from 1 to 5, at least one of the groups R5 is a functional group represented by the following Formula 1a or Formula 1b, in which case n is a integer from 2 to 5, a plurality of R5 groups can be the same or different: [Formula 1a] in Formula 1a, R6 is a substituted or unsubstituted alkylene group of 1 to 20 carbon atoms per one substituent; a substituted or unsubstituted cycloalkylene group of 5 to 20 carbon atoms per substituent; or a substituted or unsubstituted arylene group of 6 to 20 carbon atoms by a substituent, wherein the substituent is an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms or an aryl group of 6 to 20 carbon atoms, each of R7 and R8 is independently an alkyl group of 1 to 10 carbon atoms; a cycloalkyl group of 5 to 10 carbon atoms or a substituted or unsubstituted alkylene group of 1 to 20 carbon atoms by an aryl group of 6 to 20 carbon atoms, R9 is hydrogen; an alkyl group of 1 to 30 carbon atoms; an alkenyl group of 2 to 30 carbon atoms; an alkynyl group of 2 to 30 carbon atoms; a heteroalkyl group of 1 to 30 carbon atoms; a heteroalkenyl group of 2 to 30 carbon atoms; a heteroalkynyl group of 2 to 30 carbon atoms; a cycloalkyl group of 5 to 30 carbon atoms; an aryl group of 6 to 30 carbon atoms; or a heterocyclic group of 3 to 30 carbon atoms, and X is an atom of N, O or S, in the case where X is O or S, R9 is not present, [Formula 1b] in Formula 1b, R10 is a substituted or unsubstituted alkylene group of 1 to 20 carbon atoms per substituent; a substituted or unsubstituted cycloalkylene group of 5 to 20 carbon atoms per substituent; or a substituted or unsubstituted arylene group of 6 to 20 carbon atoms by a substituent, wherein the substituent is an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms or an aryl group of 6 to 20 carbon atoms and each R11 and R12 is independently an alkyl group of 1 to 30 carbon atoms; an alkenyl group of 2 to 30 carbon atoms; an alkynyl group of 2 to 30 carbon atoms; a heteroalkyl group of 1 to 30 carbon atoms; a heteroalkenyl group of 2 to 30 carbon atoms; a heteroalkynyl group of 2 to 30 carbon atoms; a cycloalkyl group of 5 to 30 carbon atoms; an aryl group of 6 to 30 carbon atoms; or a heterocyclic group of 3 to 30 carbon atoms, [Formula 2] in Formula 2, each of Ra1 and Ra4 is independently a single bond, or an alkylene group of 1 to 10 carbon atoms, each of Ra2 and Ra3 is independently an alkyl group of 1 to 10 carbon atoms, Ra5 is a five-membered heterocyclic group members having 2 to 4 carbon atoms comprising one or more heteroatoms selected from the group consisting of N, O and S, n1 is an integer from 1 to 3 and n2 is an integer from 0 to 2, [Formula 3 ] in Formula 3, each A1 and A2 is independently an alkylene group of 1 to 20 carbon atoms, each Rb1 to Rb4 is independently an alkyl group of 1 to 20 carbon atoms, each of Rb5 and Rb6 is independently hydrogen or an alkyl group of 1 to 10 carbon atoms, and each A3 and A4 is independently that each Rb7 to Rb10 is independently hydrogen or an alkyl group of 1 to 10 carbon atoms, [Formula 4] in Formula 4, Rc1 is hydrogen or an alkyl group of 1 to 10 carbon atoms, each Rc2 to Rc4 is independently an alkylene group of 1 to 10 carbon atoms, each Rc5 to Rc8 is independently an alkyl group of 1 to 10 atoms of carbon, A5 is where each Rc9 to Rc12 is independently hydrogen or an alkyl group of 1 to 10 carbon atoms, and each m1 and m2 is independently an integer from 0 to 3, where an equation of mi + m2 > 1 is met. 2. Polymer based on modified conjugated diene, according to claim 1, CHARACTERIZED by the fact that in Formula 1, each R1 to R3 is independently hydrogen; an alkyl group of 1 to 10 carbon atoms; an alkenyl group of 2 to 10 carbon atoms; or an alkynyl group of 2 to 10 carbon atoms, R4 is a single bond; or an unsubstituted alkylene group of 1 to 10 carbon atoms, and R5 is an alkyl group of 1 to 10 carbon atoms; an alkenyl group of 2 to 10 carbon atoms; an alkynyl group of 2 to 10 carbon atoms; or a functional group represented by the following Formula 1a or Formula 1b, in Formula 1a, R6 is an unsubstituted alkylene group of 1 to 10 carbon atoms, each of R7 and R8 is independently an unsubstituted alkylene group of 1 to 10 carbon atoms , and R9 is an alkyl group of 1 to 10 carbon atoms; a cycloalkyl group of 5 to 20 carbon atoms; an aryl group of 6 to 20 carbon atoms; or a heterocyclic group of 3 to 20 carbon atoms, and in Formula 1b, R10 is an unsubstituted alkylene group of 1 to 10 carbon atoms, each of R11 and R12 is independently an alkyl group of 1 to 10 carbon atoms; a cycloalkyl group of 5 to 20 carbon atoms; an aryl group of 6 to 20 carbon atoms; or a heterocyclic group of 3 to 20 carbon atoms. 3. Polymer based on modified conjugated diene, according to claim 1, CHARACTERIZED by the fact that in Formula 2, each Ra1 and Ra4 is independently a single bond, or an alkylene group of 1 to 5 carbon atoms, each Ra2 and Ra3 is independently an alkyl group of 1 to 5 carbon atoms, Ra5 is a five-membered heterocyclic group of 2 to 4 carbon atoms, the five-membered heterocyclic group being substituted or unsubstituted by a (trialkoxysilyl)alkyl group, and comprising one or more heteroatoms selected from the group consisting of N, O and S, the alkyl group of the (trialkoxysilyl)alkyl group is an alkyl group of 1 to 5 carbon atoms and the alkoxy group of the (trialkoxysilyl)alkyl group is a group alkoxy of 1 to 5 carbon atoms, n1 is an integer from 1 to 3 and n2 is an integer from 0 to 2. 4. Polymer based on modified conjugated diene, according to claim 1, CHARACTERIZED by the fact that in Formula 3, each A1 and A2 is independently an alkylene group of 1 to 10 carbon atoms, each Rb1 to Rb4 is independently a alkyl group of 1 to 10 carbon atoms, each Rb5 and Rb6 is independently hydrogen or an alkyl group of 1 to 10 carbon atoms, and each A3 and A4 is independently wherein each Rb7 to Rb10 is independently hydrogen or an alkyl group of 1 to 10 carbon atoms. 5. Polymer based on modified conjugated diene, according to claim 1, CHARACTERIZED by the fact that Formula 3 is a compound represented by the following Formula 3-1 or 3-2: [Formula 3-1] [Formula 3-2] in Formula 3-1 and Formula 3-2, each A1 and A2 is independently an alkylene group of 1 to 10 carbon atoms, and each Rb1 to Rb4 is independently an alkyl group of 1 to 10 carbon atoms. 6. Polymer based on modified conjugated diene, according to claim 1, CHARACTERIZED by the fact that in Formula 4, Rc1 is hydrogen or an alkyl group of 1 to 5 carbon atoms, each Rc2 to Rc4 is independently an alkylene group of 1 to 5 carbon atoms, each Rc5 to Rc8 is independently an alkyl group of 1 to 5 carbon atoms, A5 is where each Rc9 to Rci2 is independently hydrogen or an alkyl group of 1 to 5 carbon atoms, and each m1 and m2 is independently an integer from 0 to 3, where an equation of m1 + m2 > 1 is satisfied. 7. Polymer based on modified conjugated diene, according to claim 1, CHARACTERIZED by the fact that the polymer based on modified conjugated diene has a number average molecular weight (Mn) of 1,000 g/mol to 2,000,000 g/ mol and a weight average molecular weight (Mw) of 1,000 g/mol to 3,000,000 g/mol. 8. Polymer based on modified conjugated diene, according to claim 1, CHARACTERIZED by the fact that the polymer based on modified conjugated diene has a Si content and a N content of 50 ppm or more based on a weight , respectively. 9. Modified conjugated diene-based polymer, according to claim 1, CHARACTERIZED by the fact that the modified conjugated diene-based polymer has a Mooney stress-relaxation ratio measured at 100°C from 0.7 to 3 ,0. 10. Polymer based on modified conjugated diene, according to claim 1, CHARACTERIZED by the fact that the polymer based on modified conjugated diene has a shrinkage factor obtained by measurement using a method of light scattering-permeation chromatography in gel supplied by a viscometer from 0.8 to 3.0. 11. Polymer based on modified conjugated diene, according to claim 1, CHARACTERIZED by the fact that the polymer based on modified conjugated diene has a coupling number (C.N.) of 1<C.N.<F, where F is a number modifier functional groups. 12. Polymer based on modified conjugated diene, according to claim 1, CHARACTERIZED by the fact that it has a weighted average molecular weight (Mw) in the standard molecular weight of polystyrene conversion by gel permeation chromatography of 1,000 g/mol to 3,000,000 g/mol, a ratio (Mw/Mp) of a weight average molecular weight (Mw) and a maximum peak molecular weight (Mp) of 0.7 to 1.4, a Si content and a of N of 50 ppm or more based on a weight, respectively, a Mooney stress-relaxation ratio measured at 100°C of 0.7 or more, and a shrinkage factor obtained by measurement using a light scattering method - gel permeation chromatography provided by a viscometer of 0.8 or more. 13. Rubber composition CHARACTERIZED by the fact that it comprises the modified conjugated diene-based polymer, as defined in claim 1, and a filler material. 14. Rubber composition, according to claim 13, characterized by the fact that the rubber composition comprises 0.1 part by weight to 200 parts by weight of filler material based on 100 parts by weight of polymer based on modified conjugated diene. 15. Rubber composition, according to claim 13, CHARACTERIZED by the fact that the filler material is a silica-based filler material or a carbon-based filler material.