POLÍMERO CONJUGADO MODIFICADO COM BASE EM DIENO E COMPOSIÇÃO DE BORRACHA INCLUINDO O MESMO

Abstract

DIENE-BASED MODIFIED CONJUGATED POLYMER AND RUBBER COMPOSITION INCLUDING THE SAME. The present invention relates to a diene-based modified conjugated polymer and a rubber composition including the same, and provides a diene-based modified conjugated polymer including a first polymer chain and a second polymer chain, including a repeating unit derived from a conjugated diene-based monomer and a unit derived from a nitrogen-containing modification initiator, in each, wherein the first polymer chain includes a unit derived from an aminoalkoxysilane-based modifier at least at one terminus, the second polymer chain includes a unit derived from an aminoepoxy-based modifier at least at one terminus, and the aminoalkoxysilane-based modifier includes 6 or more alkoxy groups in one molecule.

Description

[001] This application claims the benefit of priority based on Korean Patent Application No. 10-2020-0098095, filed on August 5, 2020, the full content of which is incorporated herein by reference. TECHNICAL FIELD

[002] The present invention relates to a diene-based modified conjugated polymer with improved rotational strength, processability and abrasion resistance, and a rubber composition including the same. FUNDAMENTALS OF THE TECHNIQUE

[003] In accordance with the recent demand for cars with low fuel consumption ratios, a diene-based conjugated polymer with modulation stability represented by wet slip resistance, as well as low running resistance, and excellent abrasion resistance and traction properties is needed as a rubber material for tires.

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

[005] Natural rubbers, polyisoprene rubbers, or polybutadiene rubbers are known as rubber materials with low hysteresis loss, but these rubbers have a limitation of low wet slip resistance. Thus, recently, polymers or copolymers based on Petition 870220066288, dated 07 / 27 / 2022, page 11 / 68 2 / 48 Conjugated dienes, 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 for use as tire rubbers. Among these polymerization methods, the major advantage of solution polymerization compared to emulsion polymerization is that the vinyl structure content and styrene content, which specify the physical properties of the rubber, can be arbitrarily adjusted, and its molecular weight and physical properties can be adjusted, controlled by coupling or modification.Thus, SBR prepared by solution polymerization is widely used as a rubber material for tires, due to the fact that it is easy to alter the structure of the finally prepared SBR or BR, and the movement of the chain ends can be reduced and a coupling force with a filler, such as silica and carbon black, can be increased by coupling or modifying the chain ends.

[006] Solution-polymerized SBR is prepared using an anionic polymerization initiator, and a method that introduces a functional group at a terminal by coupling or modifying the chain terminal of the formed polymer using various modifiers is being used. For example, US Patent No. 4,397,994 discloses a method for coupling an active anion to the chain terminal of a polymer obtained by polymerizing styrene-butadiene using alkyl-lithium, which is a monofunctional initiator, in a nonpolar solvent using a coupling agent, such as a tin compound.

[007] Furthermore, in the case of using solution-polymerized SBR as a rubber material, the vinyl content in the SBR can increase and the physical properties required for tires, such as rolling resistance, can be controlled, but in the case where the vinyl content is high, the brake performance and abrasion resistance may become unfavorable in some aspects and, Petition 870220066288, dated 07 / 27 / 2022, p. 12 / 68 3 / 48 Therefore, the styrene content in SBR must be maintained at a certain level or higher; however, in this case, there are problems with not exhibiting effects due to the high vinyl content.

[008] Consequently, there have been attempts to improve running resistance, wet sliding resistance and abrasion resistance in equilibrium using an SBR block copolymer, including two block copolymer units with styrene and vinyl content gradients as the solution polymerized SBR, but the improvement was only negligible or there were no improvement effects. Prior Art Documents Patent Document 1 - Patent Open to the Public JP No Hei 8-193147 (07 / 30 / 1996) Patent Document 2 - US 4,397,994 A (09 / 08 / 1983) DISCLOSURE OF THE INVENTION TECHNICAL PROBLEM

[009] The present invention was conceived to solve the above-mentioned problems of the conventional art, and one objective is to provide a diene-based modified conjugated polymer having a high molecular weight and controlled molecular weight distribution and degree of branching and capable of improving abrasion resistance and processability during application to a rubber composition, including a first polymer chain and a second polymer chain, which include a unit derived from a modification initiator in each and include units derived from two different types of modifiers with different numbers of functional groups with reactive activity to an active polymer, respectively. Petition 870220066288, dated 07 / 27 / 2022, page 13 / 68 4 / 48

[010] Furthermore, an objective of the present invention is to provide a rubber composition, including the diene-based modified conjugated polymer and a filler, with excellent processability and abrasion resistance. SOLUTION OF THE TECHNIQUE

[011] To solve the tasks described above, according to one embodiment of the present invention, the present invention provides a diene-based modified conjugated polymer, including a first polymer chain and a second polymer chain, including a repeating unit derived from a monomer conjugated diene-based polymer and a unit derived from a nitrogen-containing modification initiator in each, wherein the first polymer chain includes a unit derived from an aminoalkoxysilane-based modifier at least one terminus, the second polymer chain includes a unit derived from an aminoepoxy-based modifier at least one terminus, and the aminoalkoxysilane-based modifier includes 6 or more alkoxy groups in one molecule.

[012] In addition, the present invention provides a rubber composition including the diene-based modified conjugated polymer and a filler. ADVANTAGEOUS EFFECTS

[013] The diene-based modified conjugated polymer according to the present invention includes a first polymer chain and a second polymer chain, with different degrees of branching including a functional group with affinity for a filler in each and being prepared using two types of modifiers with different numbers of functional groups with reaction activity with an active polymer, and has a high molecular weight, controlled molecular weight distribution and degree of branching, and excellent effects of mechanical properties, processability and rotational resistance in equilibrium. Petition 870220066288, dated 07 / 27 / 2022, page 14 / 68 5 / 48

[014] Furthermore, the rubber composition according to the present invention includes the diene-based modified conjugated polymer and, consequently, both abrasion resistance and processability can be excellent. BEST WAY TO CARRY OUT THE INVENTION

[015] Next, the present invention will be described in more detail to aid understanding of the present invention.

[016] It will be understood that words or terms used in the description and claims of the present invention should not be interpreted as having the meaning defined in commonly used dictionaries. It will further be understood that the words or terms should 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 words or terms to better explain the invention. DEFINITION

[017] In this disclosure, the term “polymer” refers to a polymer compound prepared by the polymerization of monomers independently of the same or different types of monomers. Similarly, the general term polymer refers to a polymer prepared from only one type of monomer and includes commonly used terms homopolymer and copolymer.

[018] In this disclosure, the term “1,2-vinyl linkage content” refers to the mass (or weight) percent of butadiene included in positions 1 and 2 in a polymer chain based on a conjugated diene monomer (butadiene, etc.) (based on the total weight of polymerized butadiene) in the polymer.

[019] In this disclosure, the term “alkyl group” may mean a monovalent aliphatic saturated hydrocarbon and may include both the alkyl group Petition 870220066288, dated 07 / 27 / 2022, page 15 / 68 6 / 48 linear, such as methyl, ethyl, propyl and butyl, and branched alkyl groups, such as isopropyl, sec-butyl, tert-butyl and neopentyl.

[020] In this disclosure, the term “alkenyl group” may mean a monovalent aliphatic unsaturated hydrocarbon including one or two or more double bonds.

[021] In this disclosure, the term “alkynyl group” may mean a monovalent aliphatic unsaturated hydrocarbon including one or two or more triple bonds.

[022] In this disclosure, the term “alkylene group” may mean a divalent aliphatic saturated hydrocarbon, such as methylene, ethylene, propylene and butylene.

[023] In this disclosure, the term “aryl group” may mean aromatic hydrocarbon and may include monocyclic aromatic hydrocarbon in which one ring is formed and polycyclic aromatic hydrocarbon in which two or more rings are combined.

[024] In the present disclosure, the term “heterocyclic group” is obtained by replacing carbon atoms in a cycloalkyl group or an aryl group with one or more heteroatoms and may mean, for example, either a heterocycloalkyl group or a heteroaryl group.

[025] In this disclosure, the terms “comprising” and “with” and their derivatives, whether particularly disclosed or not, are not intended to preclude the presence of optional additional components, steps or processes. In order to avoid any uncertainty, all compositions claimed using the term “comprising” may include optional additives, auxiliaries or additional compounds, including a polymer or any other materials, unless otherwise described. Conversely, the term “consisting essentially of ~” excludes those unnecessary for operation and excludes other components, steps or Petition 870220066288, dated 07 / 27 / 2022, p. 16 / 68 7 / 48 optional processes within the scope of the optional continuous description. The term “consisting of ~” excludes optional components, steps, or processes that are not specifically described or illustrated. METHOD AND MEASUREMENT CONDITIONS

[026] In the present disclosure, the “glass transition temperature (Tg)” is obtained as follows: a diene-based modified conjugated polymer is considered as a sample and based on ISO 22768:2006, a differential scanning calorimeter (product name “DSCQ100” manufactured by TA Co.), nitrogen is circulated at a rate of 50 mL / min, and a 70-6DSC curve is recorded while raising the temperature from -80 °C at a rate of 10 °C / min, and the top of the peak (inflection point) of a differential DSC curve is measured as the glass transition temperature.

[027] In this disclosure, a “weighted average molecular weight (Mw)”, a “number average molecular weight (Mn)” and “molecular weight distribution (MWD)” are measured by means of gel permeation chromatography (GPC) analysis and are measured by checking a molecular weight distribution curve. The molecular weight distribution (PDI, MWD, Mw / Mn) is calculated from each measured molecular weight. In particular, GPC uses two Olexis PLgel columns (Polymer Laboratory Co.) and one mixed-C PLgel column (Polymer Laboratories Co.) in combination, and polystyrene (PS) is used as the GPC standard material to calculate the molecular weights, and tetrahydrofuran mixed with 2 wt% of an amine compound is used as the GPC measurement solvent.

[028] Furthermore, a coupling number (CN) is obtained as follows: a portion of a polymer is collected before performing the first modification reaction by injecting an initial modifier to obtain the peak molecular weight (Mp1) of the polymer, the peak molecular weight (Mp2) of a conjugated polymer Petition 870220066288, dated 07 / 27 / 2022, page 17 / 68 8 / 48 modified based on finally modified and prepared diene is obtained, and the calculation is performed using Mathematical Equation 1 below. Mathematical Equation 1 Coupling number (CN) = Mp2 / Mp1

[029] In the present disclosure, the “1,2-vinyl linkage content” is measured and analyzed using Varian VNMRS 500 MHz NMR, and the 1,2-vinyl linkage content in the total polymer is calculated and measured using 1,1,2,2-tetrachloroethane as solvent during the NMR measurement and calculation of 6.0 ppm as solvent peak, 7.2 to 6.9 ppm as random styrene peaks, 6.9 to 6.2 ppm as block styrene peaks, 5.8 to 5.1 ppm as 1,4-vinyl and 1,2-vinyl peaks and 5.1 to 4.5 ppm as 1,2-vinyl peaks.

[030] In the present disclosure, to measure a “mooney viscosity (MV)” and a “mooney stress relaxation ratio (-S / R)”, the mooney viscosity (MV, (ML1+4, @100 °C MU)) is measured using MV-2000 (ALPHA Technologies Co.) using the large rotor at a rotor speed of 2±0.02 rpm at 100 °C. In this case, a sample is kept at room temperature (23±3 °C) for 30 minutes or more, and 27 ± 3 g of the sample are collected and placed in a die cavity, and then the cylinder is operated for 4 minutes for measurement. After measuring the mooney viscosity, the slope value of the mooney viscosity change is shown while the torque release is measured, and its absolute value is considered as the mooney stress relaxation ratio.

[031] In the present disclosure, the “N atom content” can be measured, for example, by means of an NSX analysis method and the NSX analysis method uses a quantitative analyzer of a trace amount of nitrogen (NSX-2100H). For example, in the case of using the quantitative analyzer of a trace amount of nitrogen, the quantitative analyzer of a trace amount of nitrogen (Auto sampler, horizontal furnace, PMT and nitrogen detector) is coupled, Petition 870220066288, dated 07 / 27 / 2022, page 18 / 68 9 / 48 The carrier gas flow rates are set to 250 mL / min for Ar, 350 mL / min for O2, and 300 mL / min for the ozonizer. A heater is set to 800 °C, and the analyzer is left to stand for approximately 3 hours to stabilize. After stabilizing the analyzer, a calibration curve is created using 5 ppm, 10 ppm, 50 ppm, 100 ppm, and 500 ppm intervals with a nitrogen standard (AccuStandard S-22750-01-5 mL), and an area corresponding to each concentration is obtained. Then, using the concentration-to-area ratios, a straight line is drawn. Next, a ceramic boat containing 20 mg of a sample is placed in the analyzer's autosampler, and a measurement is taken to obtain an area. Using the area of ​​the sample thus obtained and the calibration curve, the N content is calculated.In this case, the sample is a diene-based modified conjugated polymer from which solvents are removed by placing the sample in hot water heated by steam and stirring, and it may be a sample from which remaining monomers, remaining modifiers, and oil are removed.

[032] In this disclosure, the “Si atom content” is measured using inductively coupled plasma optical emission spectroscopy (ICP-OES; Optima 7300DV) as an ICP analysis method. Specifically, the measurement is performed by adding approximately 0.7 g of a sample to a platinum (Pt) crucible, adding approximately 1 mL of concentrated sulfuric acid (98 wt%, electronic grade) to it, heating at 300 °C for 3 hours, and incinerating the sample in an electric furnace (Thermo Scientific, Lindberg Blue M) following the program of steps 1 to 3: 1) Step 1: Initial temperature 0 °C, rate (temp. / h) 180 °C / h, temperature (holding time) 180 °C (1 h), 2) Step 2: Initial temperature 180 °C, rate (temp. / h) 85 °C / h, temperature (holding time) 370 °C (2 h), and Petition 870220066288, dated 07 / 27 / 2022, page 19 / 68 10 / 48 3) Step 3: Initial temp. 370 °C, rate (temp. / h) 47 °C / h, temp. (holding time) 510 °C (3 h), add 1 mL of concentrated nitric acid (48% by weight) and 20 mL of concentrated hydrofluoric acid (50% by weight) to a residue, seal the platinum crucible and shake for 30 minutes or more, add 1 mL of boric acid to the sample, store at 0 °C for 2 hours or more, dilute in 30 mL of ultrapure water and perform incineration.

[033] The present invention provides a diene-based modified conjugated polymer with excellent mechanical properties and equilibrium processability including a first polymer chain and a second polymer chain, with different degrees of branching, including a functional group with affinity for a filler in each, and being prepared using two types of modifiers with different numbers of functional groups with reactivity with an active polymer.

[034] The diene-based modified conjugated polymer, according to one embodiment of the present invention, is characterized by including a first polymer chain and a second polymer chain, including a repeating unit derived from a conjugated diene-based monomer and a unit derived from a modification initiator in each, wherein the first polymer chain includes a unit derived from an aminoalkoxysilane-based modifier at least one terminus, the second polymer chain includes a unit derived from an aminoepoxy-based modifier at least one terminus, and the aminoalkoxysilane-based modifier includes 6 or more alkoxy groups in one molecule.

[035] According to one embodiment of the present invention, the diene-based modified conjugated polymer is prepared by a preparation method that will be explained later and in which the modification reaction is Petition 870220066288, dated 07 / 27 / 2022, page 20 / 68 11 / 48 is carried out using two types of modifiers with different numbers of functional groups with reactive activity with an active polymer in order and may include a first polymer chain that is modified from a modifier with a relatively larger number of functional groups and has a higher degree of branching and a second polymer chain that is modified from a modifier with a relatively smaller number of functional groups and has a lower degree of branching. By including the first polymer chain and the second polymer chain, the diene-based modified conjugated polymer can achieve excellent mechanical properties and excellent processability.

[036] In particular, each of the first polymer chain and the second polymer chain may include a unit derived from a nitrogen-containing modification initiator and a repeating unit derived from a conjugated diene-based monomer, the first polymer chain may include a unit derived from an aminoepoxy-based aminoalkoxysilane modifier at at least one terminal and the second polymer chain may include a unit derived from an aminoepoxy-based modifier at at least one terminal.

[037] In this report, the repeating unit derived from the conjugated diene-based monomer may mean a repeating unit formed during the polymerization of a conjugated diene-based monomer and the unit derived from the modifier may mean a functional group derived from a modifier present at least one terminal of the active polymer through the reaction or coupling between the active polymer that is prepared by polymerization of the conjugated diene-based monomer and the modifier.

[038] 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, Petition 870220066288, dated 07 / 27 / 2022, page 21 / 68 12 / 48 3-butyl-1,3-octadiene, isoprene, 2-phenyl-1,3-butadiene, and 2-halo-1,3-butadiene (halo means a halogen atom).

[039] In addition, each of the first polymer chains and the second polymer chains may additionally include a repeating unit derived from an aromatic vinyl-based monomer and, in this case, may include the repeating unit derived from an aromatic vinyl monomer at 30% by weight or less, or 10% by weight to 25% by weight. Within this range, excellent balance effects between rolling resistance and wet slip resistance can be achieved.

[040] The aromatic vinyl monomer may be, 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 and 1-vinyl-5-hexylnaphthalene.

[041] In another embodiment, each link between the first polymer chain and the second polymer chain may additionally include a repeating unit derived from a diene-based monomer of 1 to 10 carbon atoms along with the repeating unit derived from 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 that is different from the conjugated diene-based monomer, and the diene-based monomer that is different from the conjugated diene-based monomer may be, for example, 1,2-butadiene.

[042] Furthermore, the diene-based modified conjugated polymer includes a first polymer chain and a second polymer chain and includes a first polymer chain with a relatively lower degree of branching and a second polymer chain with a relatively higher degree of branching, and since every degree of branching can be adequately controlled, Petition 870220066288, dated 07 / 27 / 2022, page 22 / 68 13 / 48 improving the effects of mechanical properties and processability in an optimized way.

[043] In particular, the first polymer chain includes a unit derived from a nitrogen-containing modification initiator, a repeating unit derived from a conjugated diene-based monomer and a unit derived from an aminoalkoxysilane-based modifier, it also includes a repeating unit derived from an aromatic vinyl-based monomer, as required, and is prepared by reacting an active polymer prepared by polymerizing a conjugated diene-based monomer, as by the preparation method described later, with the aminoalkoxysilane-based modifier including 6 or more alkoxy groups which are polymer-modifying functional groups, for a certain time, thereby obtaining a high degree of branching.

[044] In addition, the second polymer chain includes a unit derived from a nitrogen-containing modification initiator, a repeating unit derived from a conjugated diene-based monomer and a unit derived from an aminoepoxy-based modifier, it also includes a repeating unit derived from an aromatic vinyl-based monomer, as required, and is prepared by reacting an unmodified active polymer after the modification reaction with the aminoalkoxysilane-based modifier as in the preparation method described later, with an aminoepoxy-based modifier with 4 or fewer epoxy groups or epoxy and alkoxy groups, which are modification functional groups, in one molecule, thus obtaining a relatively lower degree of branching and high linearity.

[045] Meanwhile, the nitrogen-containing modification initiator can be prepared by reacting a nitrogen-containing compound with an organometallic compound and may be particularly a styrene-based compound. Petition 870220066288, dated 07 / 27 / 2022, p. 23 / 68 14 / 48 including an amino group substituted by a substituent or unsubstituted, amide group, imino group, imidazole group, pyrimidine group or cyclic amino group in a molecule, where the substituent may be an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkylaryl group of 7 to 20 carbon atoms, an arylalkyl group of 7 to 20 carbon atoms or an alkoxysyl group of 1 to 10 carbon atoms.

[046] For example, the nitrogen-containing compound may be a compound represented by Formula 1 below. r2

[047] In Formula 1, Ri and Rs are 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 simple connection; an alkylene group substituted or unsubstituted with a substituent of 1 to 20 carbon atoms; a cycloalkylene group substituted or unsubstituted with a substituent of 5 to 20 carbon atoms; or an arylene group substituted or unsubstituted with a substituent of 5 to 20 carbon atoms, where the substituent is an alkyl group of 1 to 10 carbon atoms. Petition 870220066288, dated 07 / 27 / 2022, p. 24 / 68 15 / 48 cycloalkyl group of 5 to 10 carbon atoms or an aryl group of 5 to 20 carbon atoms, Rs 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 Formula 1a or Formula 1b below, n is an integer from 1 to 5, and at least one of the Rs groups is a functional group represented by Formula 1a or Formula 1b below, in the case where n is an integer from 2 to 5, several Rs groups may be the same or different from each other. Formula 1

[048] In Formula 1, Re is an alkylene group substituted or unsubstituted with 1 to 20 carbon atoms; a cycloalkylene group substituted or unsubstituted with 5 to 20 carbon atoms; or an arylene group substituted or unsubstituted with 5 to 20 carbon atoms, where 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 5 to 20 carbon atoms. R? and Rs are, independently, an alkylene group of 1 to 20 carbon atoms that is replaced by an alkyl group of 1 to 10 carbon atoms, a Petition 870220066288, dated 07 / 27 / 2022, p. 25 / 68 16 / 48 cycloalkyl group of 5 to 10 carbon atoms, or an aryl group of 5 to 20 carbon atoms with a substituent or unsubstituted, Rg 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 Z is an atom of N, O, or S; in the case where Z is O or S, Rg is not present. Formula 1b Rn River- R12

[049] In Formula 1b, Rw is an alkylene group substituted or unsubstituted with a substituent of 1 to 20 carbon atoms; a cycloalkylene group substituted or unsubstituted with a substituent of 5 to 20 carbon atoms; or an arylene group substituted or unsubstituted with a substituent of 5 to 20 carbon atoms, where 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 5 to 20 carbon atoms, and R1 and R12 are 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; a Petition 870220066288, dated 07 / 27 / 2022, p. 26 / 68 17 / 48 aryl group of 6 to 30 carbon atoms; or a heterocyclic group of 3 to 30 carbon atoms.

[050] In particular, the compound represented by Formula 1 may be the compound of Formula 1, where Ri to Rs are, 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, Rs 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 below, in Formula 1a, Re is an unsubstituted alkylene group of 1 to 10 carbon atoms, R7 and Rs are independently an unsubstituted alkylene group of 1 to 10 carbon atoms, R9 is an alkyl group of 1 to 10 carbon atoms; a cycloalkyl group of 5 to 20 carbon atoms; an aryl group of 5 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 Rn and R12 are independently an alkyl group of 1 to 10 carbon atoms; a cycloalkyl group of 5 to 20 carbon atoms; an aryl group of 5 to 20 carbon atoms; or a heterocyclic group of 3 to 20 carbon atoms.

[051] More specifically, the compound represented by Formula 1 may be a compound represented by Formula 1-1 to Formula 1-3 below. Formula 1-1 Formula 1-2 Petition 870220066288, dated 07 / 27 / 2022, p. 27 / 68 18 / 48

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

[053] In particular, the organometallic compound may be one or more selected from the group consisting of methyl-lithium, ethyl-lithium, isopropyl-lithium, n-butyl-lithium, sec-butyl-lithium, tert-butyl-lithium, n-decyl-lithium, tert-octyl-lithium, phenyl-lithium, 1-naphthyl-lithium, n-eicosyl-lithium, 4-butylphenyl-lithium, 4-tolyl-lithium, cyclohexyl-lithium, 3,5-di-n-heptylcyclohexyl-lithium and 4-cyclopentyl-lithium.

[054] In addition, the aminoalkoxysilane-based modifier may be a compound that includes 6 or more alkoxy groups in a molecule and, in particular, the aminoalkoxysilane-based modifier may be a compound that includes 6 to 12, more particularly, 6 to 9 alkoxy groups in a molecule, for example, one or more selected from the compounds represented by Formula 2 to Formula 4 below. Formula 2 [ R2s----R2d^N-|-R2a-Si(OR21))a(R2c)3.a|c

[055] In Formula 2, R2a and R2d are, independently, a single bond, an alkylene group substituted by a substituent or unsubstituted from 1 to 20 carbon atoms; a Petition 870220066288, dated 07 / 27 / 2022, p. 28 / 68 19 / 48 cycloalkylene group substituted or unsubstituted with a substituent of 5 to 20 carbon atoms; or an arylene group substituted or unsubstituted with a substituent of 6 to 20 carbon atoms, where 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, R2b and R2c are independently an alkyl group of 1 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, a heteroalkyl group of 1 to 20 carbon atoms, a heteroalkenyl group of 2 to 20 carbon atoms, a heteroalkynyl group of 2 to 20 carbon atoms, a cycloalkyl group of 5 to 20 carbon atoms, or an aryl group of 6 to 20 carbon atoms, and R2e is an alkyl group of 1 to 10 carbon atoms, an allyl group of 2 to 10 carbon atoms, an alkylsilyl group monosubstituted, disubstituted or trisubstituted by alkyl groups of 1 to 10 carbon atoms, a heterocyclic group of 2 to 10 carbon atoms, or -N-[R2f-Si(OR2g)d(R2h)3-d]2, where R2f is a single bond, an alkylene group substituted or unsubstituted with a substituent of 1 to 20 carbon atoms; a cycloalkylene group substituted or unsubstituted with a substituent of 5 to 20 carbon atoms; or an arylene group substituted or unsubstituted with a substituent of 6 to 20 carbon atoms, where 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. R2g and R2h are independently an alkyl group of 1 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, a heteroalkyl group of 1 to 20 carbon atoms, a heteroalkenyl group of 2 to 20 carbon atoms, a heteroalkynyl group of 2 to Petition 870220066288, dated 07 / 27 / 2022, p. 29 / 68 20 / 48 carbon atoms, a cycloalkyl group of 5 to 20 carbon atoms or an aryl group of 6 to 20 carbon atoms, d is an integer from 1 to 3, a is an integer from 1 to 3, b is 0 or 1, and c is 2 or 3, where in the case where b is 0, and in the case where b is 1, and R2e is not -N-[R2fSi(OR2g)d(R2h)sd]2, a + c is 5 or 6, and in the case where b is 1, and R2e is -N-[R2f-Si(OR2g)d(R2h)3-d]2, a + c is 4 or 5, Formula 3 (Rbw)3-m4x. (0Rb15URm (ORb17)m·! Rb2Rb3 (Rbie)3-m3Rb14Rb12 (Rb7Í3-m2 (Rbsh-ml (ORb6)m1(ORb8)m2

[056] In Formula 3, Rb2 to Rb4 are, independently, an alkylene group of 1 to 10 carbon atoms. Rbõ and Rbs are, independently, an alkyl group of 1 to 10 carbon atoms. Rbi2 to Rbi4 are, independently, an alkylene group of 1 to 10 carbon atoms. Rbis and Rbis are, independently, an alkyl group of 1 to 10 carbon atoms, and mi, m2, m3, and m4 are, independently, an integer from 1 to 3. Formula 4Rh1 / R \--Rh3

[057] In Formula 4, Petition 870220066288, dated 07 / 27 / 2022, p. 30 / 68 21 / 48 Rhi and Rh2 are, independently, either an alkyl group of 1 to 10 carbon atoms or an alkoxy group of 1 to 10 carbon atoms. Rh3 is a single bond or an alkylene group of 1 to 10 carbon atoms, and A3 is -N[Si(Rh4Rh5Rh6)]2, where Rh4 to Rh6 are independently an alkoxy group of 1 to 10 carbon atoms.

[058] In particular, in Formula 2, R2a and R2d can independently be a single bond or an alkylene group of 1 to 10 carbon atoms, R2b and R2c can independently be an alkyl group of 1 to 10 carbon atoms, a heteroalkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms or an aryl group of 6 to 10 carbon atoms, and R2e can be an alkyl group of 1 to 10 carbon atoms, an allyl group of 2 to 10 carbon atoms, a monosubstituted, disubstituted or trisubstituted alkyl group with 1 to 10 carbon atoms, a heterocyclic group of 2 to 10 carbon atoms, or -N-[R2f-Si(OR2g)d(R2h)3-d]2 , where R2f is a single bond, or an unsubstituted alkylene group of 1 to 10 carbon atoms, and R2g and R2h are independently an alkyl group of 1 to 10 carbon atoms, a heteroalkyl group of 1 to 10 carbon atoms,a cycloalkyl group of 5 to 10 carbon atoms or an aryl group of 6 to 10 carbon atoms.

[059] In a more particular embodiment, the compound represented by Formula 2 may be selected from the group consisting of N,N-bis(3-(trimethoxysilyl)propyl)-methyl-1-amine, N,N-bis(3-(triethoxysilyl)propyl)-methyl-1-amine, tri(trimethoxysilyl)amine, tri(3-(trimethoxysilyl)propyl)amine, N-(3-(1H-1,2,4-triazol-1-yl)propyl)-3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine, 3(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)-N-(3-(1-(3)-(trimethoxysilyl)propyl)-1H-1,2,4-triazol-3-yl)propyl)propan-1-amine, N,N-bis(3-(triethoxysilyl)propyl)-2,5,8,11,14Petition 870220066288, of 07 / 27 / 2022, p. 31 / 68 22 / 48 pentaoxahexadecan-16-amine and Ni,Ni,N3,N3-tetrakis(3(trimethoxysilyl)propyl)propane-1,3-diamine.

[060] Furthermore, the compound represented by Formula 3 may be 3,3'piperazino-1,4-di-yl)bis(N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine.

[061] Furthermore, the compound represented by Formula 4 may be 3-(2,2-dimethoxy-1,2-azasilolidin-1-yl)-N,N-bis(3-(trimethoxysilyl)propyl)propan-1-amine.

[062] Furthermore, the aminoepoxy-based modifier may be a compound including four or fewer polymer-modifying functional groups in one molecule, and in this report, the polymer-modifying functional group may be an epoxy group or an epoxy group and an alkoxy group. In particular, the aminoepoxy-based modifier may be a compound including 1 to 4 polymer-modifying functional groups in one molecule, for example, one or more selected from the compounds represented by Formula 5 to Formula 7 below. Formula 5

[063] In Formula 5, Rsa and Rsb are independently an alkylene group of 1 to 10 carbon atoms, and Rsc and Rsf are, independently, hydrogen, an alkyl group of 1 to 10 carbon atoms, or -RsgRsh, where at least one of Rsc and Rsf is -RsgRsh, Rsg is a single bond or an alkylene group of 1 to 10 carbon atoms, which includes or excludes a heteroatom, and Rsh is an alkoxysyl group of 1 to 10 carbon atoms or an epoxy group. Formula 6 Petition 870220066288, dated 07 / 27 / 2022, p. 32 / 68 23 / 48

[064] In Formula 6, Rd1 to Rd3 are, independently, hydrogen, an alkyl group of 1 to 10 carbon atoms, or -Rd4 Rdõ, where at least one of Rd1 to Rd3 is -Rd4 Rd5, Rd4 is an alkylene group of 1 to 10 carbon atoms, which includes or excludes a heteroatom, and Rdõ is an epoxy group. Formula 7 %4χ / Λ1 RgZR«2

[065] In Formula 7, Rg1 to Rg4 are, independently, hydrogen, an alkyl group of 1 to 10 carbon atoms, an alkoxy group of 1 to 10 carbon atoms, an aryl group of 6 to 12 carbon atoms, or -Rgs ORg6, where at least one of Rg1 to Rg4 is Rg₂ ORg6, Rg5 is a single bond or an alkylene group of 1 to 10 carbon atoms, and Rg₅ is an epoxyalkyl group of 3 to 10 carbon atoms. Y is either C or N; in the case where Y is N, Rg4 is not present.

[066] In particular, in Formula 5, Rsa and Rsb are independently an alkylene group of 1 to 6 carbon atoms, and Rsc to Rst can independently be an alkyl group of 1 to 6 carbon atoms or -RsgRsh, where at least one of Rsc to Rst can be -RsgRsh, Rsg can be a single bond or an alkylene group of 1 to 6 carbon atoms, and Rsh can be an epoxy group.

[067] More specifically, the compound represented by Formula 5 may be a compound represented by Formula 5-1 below. Formula 5-1 Petition 870220066288, dated 07 / 27 / 2022, pp. 33 / 68 24 / 48

[068] In Formula 6, Rdi to Rd3 are independently an alkyl group of 1 to 6 carbon atoms or -Rd4Rd5, where at least one of Rdi to Rd3 may be Rd4Rd5, Rd4 may be an alkylene group of 1 to 6 carbon atoms, which includes or excludes a heteroatom, Rd5 may be an epoxy group and the heteroatom may be O (oxygen atom).

[069] More specifically, the compound represented by Formula 6 may be a compound represented by Formula 6-1 below.

[070] Furthermore, in Formula 7, Rg1 to Rg4 are independently an alkyl group of 1 to 6 carbon atoms, an alkoxy group of 1 to 6 carbon atoms, or -RgõRge, where at least one of Rg1 to Rg4 may be -RgsRge, Rg5 may be an alkylene group of 1 to 6 carbon atoms, which includes or excludes a heteroatom, Rg6 may be an epoxy group and the heteroatom may be O.

[071] More specifically, the compound represented by Formula 7 can be selected from the compounds represented by Formula 7-1 to Formula 7-4 below. Formula 7-1 Petition 870220066288, dated 07 / 27 / 2022, pp. 34 / 68 25 / 48 Formula 7-3 t----9

[072] Furthermore, the diene-based modified conjugated polymer can have a weighted average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 1,000,000 g / mol to 3,000,000 g / mol, particularly 1,200,000 g / mol to 2,000,000 g / mol. Within this range, excellent rolling resistance and abrasion resistance effects can be obtained.

[073] In addition, the diene-based modified conjugated polymer can have a molecular weight distribution (MWD; Mw / Mn) of 1.0 to 2.0, particularly, Petition 870220066288, dated 07 / 27 / 2022, pp. 35 / 68 26 / 48 Between 1.5 and 2.0, the tensile and viscoelastic properties are excellent, and an excellent balance between the physical properties can be achieved.

[074] Meanwhile, the diene-based modified conjugated polymer can have a number average molecular weight (Mn) of 500,000 g / mol to 3,000,000 g / mol, or 600,000 g / mol to 1,300,000 g / mol.

[075] In another embodiment, the diene-based modified conjugated polymer has a unimodal molecular weight distribution curve by gel permeation chromatography (GPC), and the unimodal curve shape can be determined in view of the continuous type polymerization method and in view of the modification reaction carried out by a modifier or a coupling agent.

[076] Furthermore, the diene-based modified conjugated polymer satisfies a glass transition temperature of -40 °C or less, particularly -70 °C to -40 °C, or -60 °C to -40 °C. The glass transition temperature can be altered depending on the amount of the aromatic vinyl-based monomer which is a comonomer, but it is not determined solely by the amount of the comonomer, but can be changeable according to the method and conditions of polymerization. That is, the diene-based modified conjugated polymer prepared to satisfy the range described above may have excellent affinity with a filler, such as silica and carbon black, during compounding with a prepared diene-based modified conjugated polymer and may have improved abrasion resistance, and within the range, the rotational resistance and abrasion resistance of a rubber compound including the same may be excellent in balance.

[077] In addition, the diene-based modified conjugated polymer can satisfy either a Si content or a N content of 70 ppm or more, particularly 70 ppm to 10,000 ppm, or 100 ppm to 5,000 ppm on a weight basis. Petition 870220066288, dated 07 / 27 / 2022, pp. 36 / 68 27 / 48 total polymer content, and within these ranges, a rubber composition including the diene-based modified conjugate polymer has effects that can exhibit excellent mechanical properties, such as tensile and viscoelastic properties. Si content and N content can signify the quantity of Si atoms and the quantity of N atoms, respectively, present in the diene-based modified conjugate polymer. Meanwhile, the Si atom can be derived from a functional group derived from a modifier, and the N atom can be derived from a functional group derived from a modification initiator and a modifier.

[078] In this report, the Si content and N content can be influenced by the degree of coupling by a modifier in the modification reaction and can be controlled by the amount of modifier injected, the amount of a polar additive and the reaction time during preparation, the mixing time and the degree of mixing of a modifier and an active polymer or similar.

[079] In addition, the diene-based modified conjugated polymer can satisfy coupling numbers greater than 2.5 and less than 5.0, particularly 2.8 or less and greater than 5.0, or 3.0 or less and greater than 4.5, and within this range, the Si content, the N content and the weighted average molecular weight can be easily controlled, as described above.

[080] Furthermore, the diene-based modified conjugated polymer can meet the Mooney viscosity measured under ASTM D1646 conditions of 90 or more, particularly 95 to 120. Within this range, processability can be significantly excellent.

[081] Furthermore, the diene-modified conjugated polymer satisfies a Mooney stress relaxation ratio (-S / R) measured at 100 °C of 0.40 or less. The Mooney stress relaxation ratio can be an index of the degree of branching and molecular weight of a diene-modified conjugated polymer. Petition 870220066288, dated 07 / 27 / 2022, pp. 37 / 68 28 / 48 base in the corresponding diene and, in particular, the Mooney strain relaxation ratio may be 0.35 or less. Furthermore, if the Mooney strain relaxation ratio decreases, the degree of branching may be high and the molecular weight may be large, and consequently, the lower limit is not specifically limited but may be 0.1 or more.

[082] The Mooney stress relaxation ratio measured at 100 °C can be an index of the degree of branching and molecular weight of the diene-based modified conjugate polymer as described above, and with a decrease in the Mooney stress relaxation ratio, the degree of branching and molecular weight of the diene-based modified conjugate polymer tends to increase. However, generally, the Mooney stress relaxation ratio can be related to the Mooney viscosity described above, and even with the same Mooney viscosity level according to the degree of branching of the polymer, the Mooney stress relaxation ratio can be quite different. For example, if the branching of the diene-based modified conjugate polymer increases, the Mooney stress relaxation ratio decreases, and consequently, the Mooney stress relaxation ratio may not be the same, even with the same Mooney viscosity, due to the difference in branching.

[083] Meanwhile, the diene-based modified conjugated polymer, according to one embodiment of the present invention, satisfies the aforementioned Mooney stress relaxation ratio at the aforementioned Mooney viscosity, and processability and the degree of branching can be controlled, and mechanical properties, such as tensile strength, can be even more excellent.

[084] Furthermore, the diene-modified conjugated polymer, according to one embodiment of the present invention, can satisfy a 1,2-vinyl linkage content of 30% by weight relative to the total weight of the polymer. The content Petition 870220066288, dated 07 / 27 / 2022, pages 38 / 68 29 / 48 of vinyl may mean the % by weight of conjugated diene-based monomer not 1,4 added, but 1,2 added relative to a conjugated diene-based copolymer composed of a monomer with a vinyl group and an aromatic vinyl-based monomer, and may be affected by the polymerization reaction termination point during polymerization, reaction environments at the polymerization reaction termination point or similar.

[085] In particular, the 1,2-vinyl linkage content can be from 5 to 30 wt%, preferably from 10 to 2.5 wt%, and, depending on the 1,2-vinyl linkage content, the abrasion resistance and rotational resistance can be influenced. If the 1,2-vinyl linkage content is greater than 30 wt%, the glass transition temperature can also be influenced, and it is believed that the rotational resistance and wet slip resistance may be deteriorated. Thus, the reaction conditions need to be carefully considered so that the 1,2-vinyl linkage content satisfies the range described above during the preparation of the diene-based modified conjugated polymer.

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

[087] The preparation method is characterized by including a polymerization step of a conjugated diene-based monomer, or a conjugated diene-based monomer and an aromatic vinyl-based monomer in the presence of a nitrogen-containing modification initiator in a hydrocarbon solvent to prepare an active polymer (S1); a first modification reaction step of the active polymer with an aminoalkoxysilane-based modifier (S2); and a second modification reaction step of the aminoepoxy-based modifier after the first modification reaction. Petition 870220066288, dated 07 / 27 / 2022, pp. 39 / 68 30 / 48

[088] Next, the characteristics of the prepared diene-based modified conjugate polymer and the amine-containing modification initiator, monomer, aminoalkoxysilane-based modifier and aminoepoxy-based monomer used in the reaction are superimposed with the description above, and the explanation will be omitted.

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

[090] According to one embodiment of the present invention, the nitrogen-containing modification initiator can be used at 0.01 mmol to 10 mmol, 0.05 mmol to 5 mmol, 0.1 mmol to 2 mmol, 0.1 mmol to 1 mmol or 0.15 to 0.8 mmol based on a total of 100 g of monomer.

[091] The (S1) step polymerization can be, for example, an anionic polymerization and, particularly, a living anionic polymerization whereby an anionic active moiety is formed at the polymer terminal via an anion propagation reaction. Furthermore, the (S1) step polymerization can be a heating polymerization, an isothermal polymerization, or a constant-temperature polymerization (adiabatic polymerization). Constant-temperature polymerization can mean a polymerization method including a polymerization step using self-generated reaction heat without optionally applying heat after the addition of an initiator, and heating polymerization can mean a polymerization method including injecting the initiator and then increasing the temperature by optionally applying heat. Isothermal polymerization can mean a polymerization method whereby the temperature of a polymer is kept constant. Petition 870220066288, dated 07 / 27 / 2022, pp. 40 / 68 31 / 48 increasing the heat by applying heat or receiving heat after the addition of the initiator.

[092] Furthermore, according to one embodiment of the present invention, the polymerization of step (S1) can be carried out by including a compound based on a diene of 1 to 10 carbon atoms in addition to the conjugated diene-based monomer and, in this case, effects of preventing gel formation on the reactor wall during long-term operation can be obtained. The diene-based compound can be, for example, 1,2-butadiene.

[093] The polymerization of step (S1) can be carried out in a temperature range of 100 °C or less, 50 °C to 100 °C or 50 °C to 80 °C. Within the range, the conversion ratio of the polymerization reaction can increase and the weighted average molecular weight of the polymer can be satisfied while controlling the molecular weight distribution and the effects of improving physical properties can be excellent.

[094] The active polymer prepared by step (S1) may mean a polymer in which a polymer anion and an organometallic cation are combined.

[095] According to one embodiment of the present invention, the active polymer prepared by the polymerization of step (S1) can be a random copolymer and, in this case, excellent balance effects can be obtained between each of the physical properties. The random copolymer can mean the arrangement of repeating units forming a disordered copolymer.

[096] Meanwhile, the polymerization of step (S1) can be carried out by including a polar additive and the polar additive can be added at a ratio of 0.001 g 50 g, or 0.002 g 0.1 g based on the total 100 g of monomer. In another embodiment, the polar additive can be added at a ratio greater than 0 g 1 g, 0.01 g 1 g or 0.1 g 0.9 g based on the total 100 g of the organometallic compound. In the case of injecting the polar additive in the range described above, Petition 870220066288, dated 07 / 27 / 2022, pp. 41 / 68 32 / 48 the glass transition temperature, mooney viscosity and 1,2-vinyl bond content in the ranges described above can be satisfied.

[097] The polar additive may be, for example, one or more selected from the group consisting of tetrahydrofuran, ditetrahydrofurylpropane, diethyl ether, cyclopentyl ether, dipropyl ether, ethylene methyl ether, ethylene dimethyl ether, diethyl glycol, dimethyl ether, tert-butoxyethoxyethane, bis(2-dimethylaminoethyl)ether, (dimethylaminoethyl)ethyl ether, trimethylamine, triethylamine, tripropilamine and tetramethylethylenediamine, and may preferably be triethylamine or tetramethylethylenediamine. If the polar additive is included and if a conjugated diene-based monomer and an aromatic vinyl-based monomer are copolymerized, the difference in reaction rates between them can be compensated for and the effects of easy formation of a random copolymer can be obtained.

[098] Furthermore, step (S2) is a first modification reaction step to form a first polymer chain by reacting an active polymer with an aminoalkoxysilane-based modifier and first modifying the active polymer, and can be carried out by reacting the active polymer with the aminoalkoxysilane-based modifier.

[099] In addition, the first modification reaction step can be carried out to modify 10% by weight to 90% by weight of the total weight of the active polymer.

[0100] In this report, the degree of modification of the active polymer can be controlled by the ratio of the aminoalkoxysilane-based modifier to the active polymer and by the temperature and reaction time during the first modification reaction, and particularly by using the aminoalkoxysilane-based modifier at 0.05 mmol to 0.20 mmol, or 0.10 mmol to 0.15 mmol based on Petition 870220066288, dated 07 / 27 / 2022, pp. 42 / 68 33 / 48 of a total of 100 g of the active polymer, 10% by weight to 90% by weight of the active polymer can be modified by the first modification reaction.

[0101] Furthermore, step (S3) is a second modification reaction step to form a second polymer chain by reacting an unmodified active polymer that is not modified by the first modification reaction with an aminoepoxy-based modifier and can be carried out by reacting the first modified active polymer with an aminoepoxy-based modifier. In this case, the aminoepoxy-based modifier can be used so that the aminoalkoxy-based modifier and the aminoepoxy-based modifier have a weight ratio of 8:2 to 5:5.

[0102] The preparation method, according to one embodiment of the present invention, includes steps to perform the first modification reaction using a modifier with a relatively larger number of functional groups and to perform the second modification reaction using a modifier with a relatively smaller number of functional groups and can produce a diene-based modified conjugated polymer including a first polymer chain with a high degree of branching and a second polymer chain with a relatively lower degree of branching simultaneously. The polymer includes the first polymer chain and the second polymer chain and exhibits excellent mechanical properties and excellent processability.

[0103] According to the present invention, a rubber composition is provided including the diene-based modified conjugated polymer.

[0104] The rubber composition may include diene-based modified conjugated 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 this range, mechanical properties such as tensile strength and abrasion resistance are Petition 870220066288, dated 07 / 27 / 2022, pp. 43 / 68 34 / 48 excellent, and effects of excellent balance between physical properties can be obtained.

[0105] Furthermore, the rubber composition may also include other rubber components, as required, in addition to the diene-based modified conjugate polymer, and in this case, the rubber component may be included in an amount of 90% by weight or less based on the total weight of the 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 diene-based modified conjugate polymer.

[0106] The rubber component may be, for example, natural rubber or synthetic rubber, and may be, in particular, natural rubber (NR) including cis-1,4-polyisoprene; modified natural rubber which is obtained by modifying or purifying ordinary natural rubber, such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR) and hydrogenated natural rubber;and synthetic rubber, such as styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene propylene copolymer, polyisobutylene-co-isoprene, neoprene, poly(ethylene-co-propylene), poly(styrene-co-butadiene), poly(styrene-co-isoprene), poly(styrene-co-isoprene-cobutadiene), poly(isoprene-co-butadiene), poly(ethylene-co-propylene-co-diene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, butyl rubber and halogenated butyl rubber, and any one or a mixture of two or more of these may be used.

[0107] The rubber composition may include a filler of 0.1 parts by weight to 200 parts by weight, or 10 parts by weight to 120 parts by weight based on 100 parts by weight of the diene-modified conjugated polymer of the present invention. The filler may be, for example, a filler with Petition 870220066288, dated 07 / 27 / 2022, pp. 44 / 68 35 / 48 silica-based, particularly wet silica (hydrated silicate), dry silica (anhydrous silicate), calcium silicate, aluminum silicate, or colloidal silica. Preferably, the filler may be wet silica, which has the most significant effect of improving the destruction characteristics and compatible wet adhesion effect. In addition, the rubber composition may also include a carbon-based filler, if necessary.

[0108] In another embodiment, if silica is used as filler, a silane coupling agent may be used in conjunction to improve the reinforcing and low exothermic properties. Particular examples of the silane coupling agent may include bis(3-triethoxysilylpropyl)tetrasulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis(2triethoxysilylpropyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2trimethoxysilylethyl)tetrasulfide, 3-mercaptopropyltrimethoxysilane,3mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane,2mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 2-triethoxysilylpropyl-N,Ndimethylthiocarbamoyltetrasulfide, 2-triethoxysilylpropyl-N,Ndimethylthiocarbamoyltetrasulfide -dimethylthiocarbamoyltetrasulfide,3trimethoxysilylpropylbenzothiazolyltetrasulfide,3-triethoxysilylpropylbenzoyltetrasulfide, 3-triethoxysilylpropylmethacrylatemonosulfide, 3-trimethoxysilylpropylmethacrylatemonosulfide, bis(3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide or dimethoxymethylsilylpropylbenzothiazolyltetrasulfide, and any one or a mixture of two or more of these may be used. Preferably, bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazolyltetrasulfide may be used, taking into account the effects of improving reinforcing properties. Petition 870220066288, dated 07 / 27 / 2022, pp. 45 / 68 36 / 48

[0109] Furthermore, in the rubber composition, according to one embodiment of the present invention, since a diene-based modified conjugated polymer in which a functional group with high affinity for silica is brought into an active part is used as a rubber component, the amount of silane coupling agent can be less than in a 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. Within the above amount range, the effects as a coupling agent can be sufficiently exhibited and the gelation prevention effects of a rubber component can be obtained.

[0110] The rubber composition, according to one embodiment of the present invention, may be crosslinkable with sulfur and therefore may additionally include a vulcanizing agent. The vulcanizing agent may particularly be a sulfur powder and may be included in an amount of 0.1 parts by weight to 10 parts by weight based on 100 parts by weight of a rubber component. With the above quantity 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 obtained.

[0111] The rubber composition, according to one embodiment of the present invention, may additionally include various additives used in a common rubber industry in addition to the above components, particularly, a vulcanization accelerator, a process oil, a plasticizer, an anti-aging agent, a burn prevention agent, a zinc white, stearic acid, a thermosetting resin or a thermoplastic resin. Petition 870220066288, dated 07 / 27 / 2022, pp. 46 / 68 37 / 48

[0112] The vulcanization accelerator may include, for example, thiazole-based compounds such as 2-mercaptobenzothiazole (M), dibenzothiazyl disulfide (DM) and N-cyclohexyl-2-benzothiazylsulfenamide (CZ), or guanidine-based compounds such as diphenylguanidine (DPG), in an amount of 0.1 parts by weight to 5 parts by weight based on 100 parts by weight of the rubber component.

[0113] Process oil acts as a softener in a rubber compound and may include, for example, a paraffin-based, naphthene-based, or aromatic compound. An aromatic process oil may be used in consideration of tensile strength and abrasion resistance, and a naphthene-based or paraffin-based process oil may be used in consideration of hysteresis loss and low-temperature properties. 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 rate) of the vulcanized rubber can be avoided.

[0114] 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 under high temperature, in an amount of 0.1 parts by weight to 6 parts by weight based on 100 parts by weight of the rubber component.

[0115] The rubber composition according to one embodiment of the present invention can be obtained by mixing using a mixing apparatus, 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. Petition 870220066288, dated 07 / 27 / 2022, pp. 47 / 68 38 / 48

[0116] Therefore, rubber compounds can be useful for manufacturing each component of a tire, such as a tread, a sidewall, a carcass lining rubber, a belt lining rubber, a bead filler, a liner and a bead lining rubber, or for manufacturing rubber products in various industries, such as vibration-proof rubber, a belt carrier and a hose.

[0117] Furthermore, the present invention provides a tire manufactured using a rubber compound.

[0118] The tire may include a tire or a tread. EXAMPLES

[0119] Next, the present invention will be explained in more detail with reference to embodiments. The embodiments according to the present invention may be modified into various other types, and the scope of the present invention should not be limited to the embodiments described below. The embodiments of the present invention are provided to fully explain the present invention to a person skilled in the art. EXAMPLE 1

[0120] For a first reactor among continuous reactors of three reactors connected in series, a styrene solution was injected in which 60 wt% styrene was dissolved in n-hexane at a rate of 2.58 kg / h, a 1,3-butadiene solution in which 60 wt% 1,3-butadiene was dissolved in n-hexane at a rate of 12.68 kg / h, n-hexane at a rate of 46.94 kg / h, a 1,2-butadiene solution in which 2.0 wt% 1,2-butadiene was dissolved in n-hexane at a rate of 40 g / h, a solution in which 10 wt% 2,2-(di-2(tetrahydrofuryl)propane was dissolved in n-hexane as a polar additive at a rate of 50.0 g / h, and an n-initiator solution in which 10 wt% of 1-methyl-4-(4-vinylbenzyl)piperazine was dissolved in n-hexane as a modification initiator. Petition 870220066288, dated 07 / 27 / 2022, pages 48 / 68 39 / 48 at a rate of 50.0 g / h. At this point, the temperature of the first reactor was controlled at 60 °C and maintained. At a point where a polymerization conversion rate reached 45%, a polymer was transported from the first reactor to a second reactor via a transport tube.

[0121] Next, a 1,3-butadiene solution in which 60% by weight of 1,3-butadiene was dissolved in n-hexane was injected into the second reactor at a rate of 1.41 kg / h, the temperature of the second reactor was maintained at 70 °C and polymerization continued. At a point where a polymerization conversion rate reached 9.5% or more, the polymer was transported from the second reactor to a third reactor via a transport tube.

[0122] During the transport of the polymer from the second reactor to the third reactor, a first modifying solution in which 10 wt% of N1,N1,N3,N3tetrakis(3-(trimethoxysilyl)propyl)propane-1,3-diamine was dissolved in n-hexane as a first modifier was injected into a transport portion at a rate of 135.0 g / h, and a second modifying solution in which 5 wt% of 1,3,5tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione was dissolved in n-hexane as a second modifier was injected into the third reactor at a rate of 56 μm, 1 g / h. The temperature of the third reactor was maintained at 75 °C.

[0123] Next, for the polymerization solution discharged from the third reactor, a solution in which 30 wt% of IR1520 (BASF Co.) was dissolved when an antioxidant was injected at a rate of 16.7 g / h stirred. The polymer thus obtained was placed in hot water heated with steam and stirred to remove solvents to obtain a diene-based modified conjugated polymer. EXAMPLE 2

[0124] A diene-based modified conjugated polymer was prepared using the same method as in Example 1, except by injecting a solution of Petition 870220066288, dated 07 / 27 / 2022, pp. 49 / 68 40 / 48 initiator in which 10 wt% of 1-phenyl-4-(4-vinylbenzyl)piperazine was dissolved in n-hexane at a rate of 60 g / h instead of 1-methyl-4-(4-vinylbenzyl)piperazine as the modification initiator, as in Example 1. EXAMPLE 3

[0125] A diene-based modified conjugated polymer was prepared by performing the same method as in Example 1, except for the injection of a first modifying solution in which 10 wt% of 3-(2,2-dimethoxy-1,2-azasilolidin-1-yl)N,N-bis(3-(trimethoxysilyl)propyl)propan-1-amine were dissolved in n-hexane at a rate of 99.8 g / h reacting, instead of N1,N1,N3,N3-tetrakis(3(trimethoxysilyl)propyl)propan-1,3-amine as the first modifier, in Example 1. EXAMPLE 4

[0126] A diene-based modified conjugated polymer was prepared by performing the same method as in Example 1, except for the injection of a first modifying solution in which 10 wt% of 3,3'-piperazino-1,4-di-yl)bis(N,Nbis(3-(triethoxysilyl)propyl)propan-1-amine were dissolved in n-hexane at a rate of 187.5 g / h reacting, instead of N1,N1,N3,N3-tetrakis(3(trimethoxysilyl)propyl)propan-1,3-amine as the first modifier, in Example 1. EXAMPLE 5

[0127] A diene-based modified conjugated polymer was prepared by performing the same method as in Example 1, except by injecting a second modifying solution in which 5 wt% of N,N'-(1,3-phenylenebis(methylene))bis(1-(oxiran-2-yl)-N-(oxiran-2-ylmethyl)methanamine were dissolved in n-hexane at a rate of 67.5 g / h reacting, instead of 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinan-2,4,6-trion as the second modifier in Example 1. EXAMPLE 6

[0128] A diene-based modified conjugated polymer was prepared by performing the same method as in Example 1, except by injecting a second Petition 870220066288, dated 07 / 27 / 2022, pages 50 / 68 41 / 48 modifying solution in which 5 wt% of 2-(oxiran-2-yl)-N,N-bis((oxiran-2-ylmethoxy)methyl)ethanamine was dissolved in n-hexane at a rate of 54 g / h reacting, instead of 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinan-2,4,6-trion as the second modifier, in Example 1. COMPARATIVE EXAMPLE 1

[0129] A diene-based modified conjugated polymer was prepared by performing the same method as in Example 1, except that the second modifying solution was not injected in Example 1. COMPARATIVE EXAMPLE 2

[0130] A diene-based modified conjugated polymer was prepared by performing the same method as in Example 1, except that the first modifying solution was not injected in Example 1. COMPARATIVE EXAMPLE 3

[0131] A diene-based modified conjugated polymer was prepared by performing the same method as in Example 1, except by injecting a solution in which 10 wt% of N1,N1,N3,N3-tetrakis(3-(trimethoxysilyl)propyl)propane-1,3amine were dissolved in n-hexane at a rate of 56.1 g / h as each of the first modifying solution and the second modifying solution in Example 1. COMPARATIVE EXAMPLE 4

[0132] A diene-based modified conjugated polymer was prepared by performing the same method as in Example 1, except by injecting a solution in which 5 wt% of 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinan-2,4,6-trion were dissolved in n-hexane at a rate of 67.8 g / h as each of the first modifying solution and the second modifying solution in Example 1. COMPARATIVE EXAMPLE 5

[0133] A diene-based modified conjugated polymer was prepared by performing the same method as in Example 1, except for the injection of a first Petition 870220066288, dated 07 / 27 / 2022, pp. 51 / 68 42 / 48 modifying solution in which 10 wt% of N,N-diethyl-3-(trimethoxysilyl)propan-1,3-amine was dissolved in n-hexane at a rate of 105.0 g / h reacting, instead of N1,N1,N3,N3-tetrakis(3-(trimethoxysilyl)propyl)propane-1,3-amine as the first modifier, in Example 1. COMPARATIVE EXAMPLE 6

[0134] A diene-based modified conjugated polymer was prepared by performing the same method as in Example 1, except by injecting a second modifying solution in which 10 wt% of N,N-diethyl-3-(trimethoxysilyl)propan-1-amine was dissolved in n-hexane at a rate of 105 g / h instead of 1,3,5tris(oxiran-2-ylmethyl)-1,3,5-triazinan-2,4,6-trion as the second modifier in Example 1. EXPERIMENTAL EXAMPLE 1

[0135] With respect to each of the diene-based modified conjugated polymers prepared in the Examples and Comparative Examples, a weighted average molecular weight (Mw, x103g / mol), a number average molecular weight (Mn, x103g / mol), molecular weight distribution (MWD), mooney viscosity (MV), a coupling number and a mooney strain relaxation ratio were measured, respectively, and the results are shown in Table 1 below. 1) Weighted average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (MWD)

[0136] By gel permeation chromatography (GPC) analysis, the weighted average molecular weight (Mw) and the number-average molecular weight (Mn) were measured and the molecular weight distribution (PDI, MWD, Mw / Mn) was calculated from each measured molecular weight. Specifically, GPC was performed using two Olexis PLgel columns (Polymer Laboratories Co.) and one mixed-C PLgel column (Polymer Laboratories Co.) in combination and polystyrene (PS) as the GPC standard material to calculate the molecular weights. A solvent for Petition 870220066288, dated 07 / 27 / 2022, pages 52 / 68 43 / 48 measuring GPC was prepared by mixing tetrahydrofuran with 2% by weight of an amine compound. 2) Mooney viscosity (MV) and Mooney stress relaxation ratio (-S / R)

[0137] Mooney viscosity (MV, (ML1+4, @ 100 °C MU)) was measured using MV-2000 (A LPHA Technologies Co.) using a Large Rotor at a rotor speed of 2±0.02 rpm at 100 °C. In this case, a sample was kept at room temperature (23±3 °C) for 30 minutes or more, and 27±3 g of the sample were collected and placed in a mold cavity, and then the Platen was operated for 4 minutes for measurement.

[0138] Furthermore, after measuring the mooney viscosity, the slope of the mooney viscosity change shown during torque release was measured and, from its absolute value, the mooney relaxation ratio was obtained. Table 1 Division Example Example Comparative 1 2 3 4 5 6 1 2 3 4 5 6 GPC Mw (χ103 g / mol) 138 4 138 8 135 0 139 4 137 2 136 4 141 2 108 9 154 5 123 5 856 1377 Mn (χ103 g / mol) 753 767 741 705 758 739 756 622 813 667 479 740 PDI 1.8 3 1.8 1 1.8 2 1.8 3 1.8 1 1.8 5 1.8 7 1.7 4 1.9 0 1.8 5 1.7 9 1.86 Mooney's viscosity 103 103 100 106 101 100 112 89 118 97 72 98 -S / R 0.3 189 0.3 234 0.3 486 0.3 044 0.3 200 0.3 049 0.2 852 0.4 796 0.2 657 0.4 576 0.7 490 0.37 66

[0139] As shown in Table 1 above, it was confirmed that Examples 1 to 6 have high molecular weights and a narrow molecular weight distribution and show controlled Mooney strain relaxation ratios (degrees of branching) to an average level when compared to Comparative Examples 1 to 6. EXPERIMENTAL EXAMPLE 2 Petition 870220066288, dated 07 / 27 / 2022, pages 53 / 68 44 / 48

[0140] In order to compare and analyze the physical properties of rubber compositions, including diene-based modified conjugated copolymers prepared in Examples and Comparative Examples and molded products manufactured from them, processability and abrasion resistance properties were measured, respectively, and the results are shown in Table 3 below. 1) Preparation of the rubber sample

[0141] The composition was carried out using each of the diene-based modified conjugated polymers from the Examples and Comparative Examples as a rubber feedstock under the composition conditions shown in Table 2 below. The feedstocks in Table 2 are represented by parts by weight based on 100 parts by weight of the rubber feedstock. Table 2 Raw Material Division Quantity (parts by weight) First-stage mixture Rubber 100 Silica 70 Coupling agent (X50S) 11.2 Process oil 37.5 Zinc white 3 Stearic acid 2 Antioxidant 2 Anti-aging agent 2 Wax 1 Second-stage mixture Sulfur 1.5 Rubber accelerator 1.75 Petition 870220066288, dated 07 / 27 / 2022, pages 54 / 68 45 / 48 Vulcanization accelerator 2

[0142] Specifically, the rubber sample was mixed by means of a first-stage mixing and a second-stage mixing. In the first mixing stage, a rubber raw material, silica (filler), an organic silane coupling agent (X50S, Evonik), a process oil (TDAE oil), zinc oxide (ZnO), stearic acid, an antioxidant (TMQ (RD )) (2,2,4-trimethyl-1,2-dihydroquinoline polymer), an anti-aging agent (6PPD ((dimethylbutyl)-N-phenyl-phenylenediamine)) and wax (Microcrystalline Wax) were mixed using a Banbury mixer equipped with a temperature control apparatus. In this case, the initial temperature of the mixing apparatus was controlled at 70 °C and, after the completion of the composition, a first mixture of compounds was obtained at a discharge temperature of 145 °C.In the second mixing stage, the first compound mixture was cooled to room temperature, and the first compound mixture, sulfur, a rubber accelerator (DPD (diphenylguanine)), and a vulcanization accelerator (CZ (N-cyclohexyl-2-benzothiazylsulfenamide)) were added to the mixing apparatus and mixed at a temperature of 100 °C or less to obtain a second compound mixture. Then, through a curing process at 160 °C for 20 minutes, a rubber test specimen was formed. 2) Processability properties

[0143] By measuring the Mooney viscosity (MV, ML 1+4, @ 100 °C MU) of the second compound mixture obtained during 1) preparation of the rubber sample, the processability properties of each polymer were compared and analyzed. The resulting values ​​in Table 3 below are index values ​​based on the resulting value measured for Comparative Example 1, and the lower the value, the better the properties. Petition 870220066288, dated 07 / 27 / 2022, pages 55 / 68 46 / 48

[0144] Specifically, using MV-2000 (Alpha Technologies Co.) using Large Rotor at a rotor speed of 2±0.02 rpm at 100 °C, each second mixture of compound was kept at room temperature (23± 3 °C) for 30 minutes or more, and 27±3 g were collected and placed in a mold cavity and then the Platen was operated for 4 minutes for measurement. 3) Abrasion resistance (DIN abrasion test)

[0145] For each rubber sample, the DIN abrasion test was performed based on ASTM D5963, and the DIN loss index (loss volume index: abrasion resistance index (ARIA), Method A) is shown. The resulting values ​​in Table 3 are index values ​​based on the measured result for Comparative Example 1, and the higher the value, the better the abrasion resistance. 4) Resistance to rotation

[0146] The viscoelastic properties were ensured by measuring the viscoelastic behavior 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 stress mode and fixing a tan δ value. In this case, if the tan δ value at a high temperature of 60 °C increases, the hysteresis loss decreases and the resistance to rotation (fuel consumption ratio) is excellent. Meanwhile, the resulting values ​​in Table 3 are indexed based on the resulting value from Comparative Example 1. Table 3 Division Example Comparative Example 1 2 3 4 5 6 1 2 3 4 5 6 Processability (Index) 92 92 90 93 90 90 100 80 110 86 82 109 Petition 870220066288, dated 07 / 27 / 2022, pages 56 / 68 47 / 48 Abrasion resistance (Index) 100 100 98 101 99 100 100 89 103 97 81 101 Rotation resistance (Index) 101 102 98 103 101 99 100 82 98 86 89 97

[0147] As shown in Table 3 above, it was confirmed that Examples 1 to 6 showed excellent rotational resistance, processability and abrasion resistance in balance, unlike Comparative Examples 1 to 6.

[0148] In particular, Examples 1 to 6 showed uniformly excellent processability, abrasion resistance, and rotational resistance properties at equivalent levels; conversely, Comparative Examples 1, 3, and 6 showed processability largely degraded by 10% or more, unlike Examples 1 to 6, and Comparative Examples 2, 4, and 5 showed rotational resistance and abrasion resistance markedly degraded by 10% or more, unlike Examples 1 to 6. In this case, Comparative Examples 1 to 6 correspond to polymers prepared by not performing the modification reaction using an aminoalkoxysilane-based modifier or an aminoepoxy-based modifier, or performing the modification reaction with both modifiers but using a compound including less than 6 alkoxy groups in a molecule as the aminoalkoxysilane-based modifier.

[0149] From the results, it can be confirmed that the diene-based modified conjugated polymer, according to the present invention, includes a first polymer chain and a second polymer chain, which have different degrees of branching, including a functional group with affinity for a filler in each and being prepared using two types of modifiers with different numbers of functional groups with activity of Petition 870220066288, dated 07 / 27 / 2022, pages 57 / 68 48 / 48 reaction with an active polymer, and with a high molecular weight and controlled distribution of molecular weight and degree of branching, thus showing excellent effects of mechanical properties, processability and rotational resistance in equilibrium (see Table 1 and Table 3).

Claims

1. Diene-based modified conjugated polymer CHARACTERIZED in that it comprises a first polymer chain and a second polymer chain, each comprising a repeating unit derived from a conjugated diene-based monomer and a unit derived from a nitrogen-containing modification initiator, wherein the first polymer chain comprises a unit derived from an aminoalkoxysilane-based modifier at least one terminus, the second polymer chain comprises a unit derived from an aminoepoxy-based modifier at least one terminus, and the aminoalkoxysilane-based modifier comprises 6 or more alkoxy groups in a molecule.

2. Modified diene-based conjugated polymer according to claim 1, CHARACTERIZED in that each link between the first polymer chain and the second polymer chain additionally comprises a repeating unit derived from an aromatic vinyl-based monomer.

3. A diene-based modified conjugated polymer according to claim 1, CHARACTERIZED in that the aminoepoxy-based modifier comprises 4 or fewer polymer-modifying functional groups in a molecule, and the polymer-modifying functional group comprises an epoxy group, or an alkoxy group and an epoxy group.

4. Modified diene-based conjugated polymer according to claim 1, CHARACTERIZED in that the nitrogen-containing modification initiator is a reaction product of a nitrogen-containing compound and an organometallic compound, and the nitrogen-containing compound is a styrene-based compound comprising a substituent-substituted or unsubstituted amino group, amide group, imino group, imidazole group, Petition 870240100480, dated 11 / 26 / 2024, page 1. 9 / 26 2 / 9 pyrimidine or cyclic amino group in a molecule, where the substituent is an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkylaryl group of 7 to 20 carbon atoms, an arylalkyl group of 7 to 20 carbon atoms, or an alkoxysyl group of 1 to 10 carbon atoms.

5. Modified diene-based conjugated polymer according to claim 4, CHARACTERIZED in that the nitrogen-containing compound is a compound represented by the following Formula 1: r2 in Formula 1, each Ri to Rs 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; an alkylene group substituted with a substituent or unsubstituted with 1 to 20 carbon atoms; a cycloalkylene group substituted with a substituent or unsubstituted with 5 to 20 carbon atoms;or an arylene group substituted or unsubstituted with a substituent of 5 to 20 carbon atoms, 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 5 to 20 carbon atoms, Petition 870240100480, dated 11 / 26 / 2024, p. 10 / 26 3 / 9 Rs 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, where n is an integer from 1 to 5, at least one of the Rs groups is a functional group represented by the following Formula 1a or Formula 1b, where n is an integer from 2 to 5, several Rs groups may be the same or different from each other: Formula 1a in Formula 1a, Re is an alkylene group substituted or unsubstituted with 1 to 20 carbon atoms; a cycloalkylene group substituted or unsubstituted with 5 to 20 carbon atoms;or an arylene group substituted by a substituent or unsubstituted of 5 to 20 carbon atoms, where 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 5 to 20 carbon atoms. Each R? and Rs is independently an alkyl group of 1 to 20 carbon atoms substituted by an alkyl group of 1 to 10 carbon atoms, a cycloalkyl group of 5 to 20 carbon atoms or an aryl group of 5 to 20 carbon atoms or unsubstituted. Petition 870240100480, 11 / 26 / 2024, p. 11 / 26 4 / 9 Rg 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 Z is an N, O, or S atom, in the case where Z is O or S, Rg is not present, Formula 1b Rn Rio — R12 in Formula 1b, Rw is an alkylene group substituted or unsubstituted with 1 to 20 carbon atoms; a cycloalkylene group substituted or unsubstituted with 5 to 20 carbon atoms; or an arylene group substituted or unsubstituted with 5 to 20 carbon atoms, where 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 5 to 20 carbon atoms, and each Ri 1 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. Petition 870240100480, dated 11 / 26 / 2024, p. 12 / 26 5 / 9; 6. Modified conjugated polymer based on diene, according to claim 1, CHARACTERIZED in that the aminoalkoxysilane-based modifier is one or more selected from the compounds represented by the following Formula 2 to Formula 4: Formula 2 [ R2e----R2d}^N R2a — Si(OR2b)a(R2c)3-a ]c in Formula 2, each R2a and R2d is independently a single bond, an alkylene group substituted or unsubstituted with 1 to 20 carbon atoms; a cycloalkylene group substituted or unsubstituted with 5 to 20 carbon atoms; or an arylene group substituted by a substituent or unsubstituted of 6 to 20 carbon atoms, where 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 R2b and R2c is independently an alkyl group of 1 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms,an alkynyl group of 2 to 20 carbon atoms, a heteroalkyl group of 1 to 20 carbon atoms, a heteroalkenyl group of 2 to 20 carbon atoms, a heteroalkynyl group of 2 to 20 carbon atoms, a cycloalkyl group of 5 to 20 carbon atoms, or an aryl group of 6 to 20 carbon atoms, and R2e is an alkyl group of 1 to 10 carbon atoms, an allyl group of 2 to 10 carbon atoms, a monosubstituted, disubstituted, or trisubstituted alkylsilyl group with 1 to 10 carbon atoms, a heterocyclic group of 2 to 10 carbon atoms, or -N-[R2f-Si(OR2g)d(R2h)3-d]2, where R2f is a single bond, an alkylene group substituted or unsubstituted with a substituent. 1 to 20 carbon atoms; a cycloalkylene group substituted or unsubstituted with a substituent of 5 to 20 carbon atoms; or an arylene group substituted or unsubstituted with a substituent of 6 to 20 carbon atoms.where 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 Rzg and R2h is independently an alkyl group of 1 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, a heteroalkyl group of 1 to 20 carbon atoms, a heteroalkenyl group of 2 to 20 carbon atoms, a heteroalkynyl group of 2 to 20 carbon atoms, a cycloalkyl group of 5 to 20 carbon atoms, or an aryl group of 6 to 20 carbon atoms, d is an integer from 1 to 3, a is an integer from 1 to 3, b is 0 or 1, and c is 2 or 3, where in the case where b is 0, and in the case where b is 1, and R2e is not -N-[R2fSi(OR2g)d(R2h)sd]2, a + c is 5 or 6, and in the case where b is 1, and R2e is -N-[R2f-Si(OR2g)d(R2h)3-d]2, a + c is 4 or 5,(Rbie)3-m4 Si' (ORbi5)m3 Rbn (ORbs)m2 Rb2 Rb3 Formula 3 (URb17Ím4 ^Si^ / (Rb16)3-m3 Rb14 Rb12 (Rb7)s-m2 (Rb5)3-m1 (ORbe)m1 in Formula 3, each Rb2 to Rb4 is independently an alkylene group of 1 to 10 carbon atoms, each Rbõ to Rbs is independently an alkyl group of 1 to 10 carbon atoms, each Rbi2 to Rbi4 is independently an alkylene group of 1 to 10 carbon atoms, Petition 870240100480, of 11 / 26 / 2024, p. carbon atoms, and each m1, m2, m3 and m4 is independently an integer from 1 to 3, Formula 4 Rh1 / In Formula 4, each Rh1 and Rh2 is independently an alkyl group of 1 to 10 carbon atoms or an alkoxy group of 1 to 10 carbon atoms, Rh3 is a single bond or an alkylene group of 1 to 10 carbon atoms, and A3 is -N[Si(Rh4Rh5Rh6)]2, where each Rh4 to Rh6 is independently an alkoxy group of 1 to 10 carbon atoms.

7. Modified conjugated polymer based on diene, according to claim 1, CHARACTERIZED in that the aminoepoxy-based modifier is a compound represented by the following Formula 5 to Formula 7: In Formula 5, each Rsa and Rsb is independently an alkylene group of 1 to 10 carbon atoms, and each Rsc to Rst is independently hydrogen, an alkyl group of 1 to 10 carbon atoms or -RsgRsh, wherein at least one of Rsc to Rst is -RsgRsh, Rsg is a single bond or an alkylene group of 1 to 10 carbon atoms, which includes or excludes a heteroatom, and Rsh is an epoxy group. (Petition 870240100480, 26 / 11 / 2024, p. 7)15 / 26 8 / 9 in Formula 6, each Rd1 to Rd3 is independently hydrogen, an alkyl group of 1 to 10 carbon atoms, or -Rd4Rd5, where at least one of Rd1 to Rd3 is -Rd4Rd5, Rd4 is an alkylene group of 1 to 10 carbon atoms, which includes or excludes a heteroatom, and Rd6 is an epoxy group. Formula 7 %4χ / Λ1 RgZ R«2 in Formula 7, each Rg1 to Rg4 is independently hydrogen, an alkyl group of 1 to 10 carbon atoms, an alkoxy group of 1 to 10 carbon atoms, an aryl group of 6 to 12 carbon atoms, or -Rg6ORge, where at least one of Rg1 to Rg4 is Rg5ORg6, Rg5 is a single bond or an alkylene group of 1 to 10 carbon atoms. carbon atoms and Rg is an epoxyalkyl group of 3 to 10 carbon atoms, and Y is C or N, in the case where Y is N, Rg4 is not present.

8. Modified diene-based conjugated polymer according to claim 1, CHARACTERIZED in that the weighted average molecular weight is from 1,000,000 g / mol to 3,000,000 g / mol and the molecular weight distribution is from 1.0 to 2.

0.

9. Modified diene-based conjugated polymer according to claim 1, CHARACTERIZED in that each Si content and N content is 70 ppm or more based on the total weight of the polymer. Petition 870240100480, dated 11 / 26 / 2024, page 16 / 26 9 / 9 10. Rubber composition CHARACTERIZED in that it comprises a diene-based modified conjugated polymer, as defined in claim 1, and a filler.

11. Rubber composition, according to claim 10, CHARACTERIZED in that it comprises 100 parts by weight of the diene-based modified conjugated polymer and 0.1 part by weight to 200 parts by weight of the filler.