RU2794173C2 - Modified polymer based on a conjuged diene and a rubber composition including it - Google Patents

Abstract

FIELD: chemical industry.

SUBSTANCE: invention relates to a modified conjugated diene based polymer as well as a rubber composition for tire or rubber products. The modified polymer based on a conjugated diene contains a functional group derived from the modified monomer of the formula

where R₂ represents an alkenyl group from 2 to 10 carbon atoms, and contains a functional group derived from the modifier based on aminoalkoxysilane at least one end. The aminoalkoxysilane-based modifier is a compound of the formula

wherein R_a1 and R_a4 are each independently a single bond or an alkylene group having 1 to 10 carbon atoms, R_a2 and R_a3 are each an independent alkyl group having 1 to 10 carbon atoms, R_a5 is an alkyl a group having 1 to 10 carbon atoms, or an alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, n1 is an integer from 1 to 3, and n2 is an integer from 0 to 2; or compound formula

wherein A₁ and A₂ are each an independent alkylene group having 1 to 20 carbon atoms, R_b1-R_b4 are each an independent alkyl group having 1 to 20 carbon atoms, and L₁-L₄ are each an independent alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms. The modified conjugated diene polymer has a unimodal molecular weight distribution curve and a molecular weight distribution of 1.0 or more to less than 1.7.

EFFECT: resulting polymer has a narrow and unimodal molecular weight distribution and exhibits excellent tensile properties and viscoelastic properties, while also having excellent processability.

13 cl, 4 dwg, 3 tbl, 3 ex

Description

Technical field

Cross-reference to related applications

[0001] This application claims the benefit of Korean Patent Application No. 10-2018-0052383 filed on May 8, 2018 with the Intellectual Property Office of the Republic of Korea, the disclosure of which is incorporated herein in its entirety by reference.

Technical field

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

State of the art

[0003] In accordance with the current demand for fuel-efficient vehicles, as a rubber material for a tire, a conjugated diene-based polymer having installation stability represented by wet road surface stability, as well as low rolling resistance and excellent abrasion resistance, and mechanical properties during stretching.

[0004] In order to reduce the rolling resistance of a tire, there is a method for reducing the hysteresis loss of the vulcanized rubber, and the rebound resilience at a temperature of 50 to 80°C, the tan δ value, or the Goodrich heat generation is used as an evaluation index of the vulcanized rubber. That is, it is desirable to use a rubber material having a high rebound resilience at the above temperature, or a low tan δ value or Goodrich heat generation.

[0005] Natural rubber, polyisoprene rubber, or polybutadiene rubber is known as a rubber material having low hysteresis loss, but such rubbers may have low wet resistance. As a result, recently, a conjugated diene-based polymer or copolymer such as styrene-butadiene rubber (hereinafter referred to as "SBR") or butadiene rubber (hereinafter referred to as "BR") has been obtained emulsion polymerization or solution polymerization to be used as tire rubber. Of such polymerization methods, the greatest advantage of solution polymerization over emulsion polymerization is that the vinyl structure content and styrene content, which determine the physical properties of rubber, can be arbitrarily adjusted, and its molecular weight and physical properties can be adjusted by bonding or modifications. Thus, the SBR obtained by solution polymerization is widely used as a rubber material for a tire, because it is easy to change the structure of the final SBR or BR, and the movement of the chain ends can be reduced, and the binding force to a filler such as silica or carbon black, can be increased by linking or modifying chain ends.

[0006] In the case where solution-polymerized SBR is used as a rubber material for a tire, since the glass transition temperature of rubber is increased by increasing the vinyl content of SBR, not only physical properties such as running resistance and braking force required can be controlled. for a tyre, but fuel consumption can also be reduced by appropriately controlling the glass transition temperature. Solution-polymerized BSC is obtained using an anionic polymerization initiator and is used when linking or modifying chain ends using various modifiers. For example, US Pat. No. 4,397,994 discloses a technique in which active anions at the chain ends of a polymer obtained by polymerization of styrene and butadiene in a non-polar solvent using an alkyl lithium as a monofunctional initiator are coupled using a binder such as a tin compound.

[0007] Polymerization of SBR or BR can be performed by batch or continuous polymerization, where relative to batch polymerization, there is an advantage in terms of improving physical properties due to the narrow molecular weight distribution of the resulting polymer, but productivity may be low and processability may be poor, and, with respect to continuous polymerization, productivity is excellent because polymerization is carried out continuously and there is an advantage in terms of improving processability, but the physical properties are poor due to the wide molecular weight distribution. Thus, there remains a need for research to simultaneously improve productivity, processability and physical properties during the production of SBR or BR.

Prior Art Document

Patent Document 1 - U.S. Patent No. 4,397,994 A.

Description of the invention

Technical task

[0008] The present invention provides a modified conjugated diene polymer having excellent physical properties such as tensile mechanical properties and viscoelastic properties as well as excellent processability, which is obtained by continuous polymerization, and a rubber composition containing the same.

Technical solution

[0009] In accordance with an aspect of the present invention, there is provided a modified conjugated diene polymer having a unimodal molecular weight distribution as indicated by a unimodal shape of a molecular weight distribution curve obtained by gel permeation chromatography (GPC) and a polydispersity index (PPD (PDI)) from 1.0 or more to less than 1.7, where the modified conjugated diene-based polymer includes a functional group derived from the modified monomer represented by formula 1, and includes a functional group derived from an aminoalkoxysilane-based modifier , at least at one end:

[0010] [Formula 1]

.

.

[0011] In formula 1

[0012] F ₁ is an amine-containing functional group, and R ₁ is an alkenyl group having 2 to 10 carbon atoms.

[0013] According to another aspect of the present invention, there is provided a rubber composition comprising a modified conjugated diene polymer and a filler.

Positive Effects

[0014] The modified conjugated diene polymer of the present invention may have a narrow molecular weight distribution defined by a polydispersity index of less than 1.7 while having a unimodal molecular weight distribution as indicated by a unimodal shape of the molecular weight distribution curve obtained by gel permeation chromatography, and can exhibit excellent tensile properties and viscoelastic properties while having excellent processability.

[0015] In addition, since the modified conjugated diene polymer according to the present invention includes a functional group derived from the modified monomer and includes a functional group derived from the modifier at at least one end thereof, tensile mechanical properties and viscoelastic properties can be further improved.

Brief description of the drawings

[0016] The following drawings, appended to the description, illustrate preferred examples of the present invention and serve to enable the technical concepts of the present invention to be better understood, along with the detailed description of the invention below, so the present invention should not be construed solely in view of the objects on such drawings.

[0017] FIG. 1 illustrates the molecular weight distribution curve of the modified conjugated diene based polymer of Example 1 according to an embodiment of the present invention by Gel Permeation Chromatography (GPC).

[0018] FIG. 2 illustrates the molecular weight distribution curve of the modified conjugated diene based polymer of Comparative Example 1 according to the Gel Permeation Chromatography (GPC) embodiment of the present invention.

[0019] FIG. 3 illustrates the molecular weight distribution curve of the modified conjugated diene based polymer of Reference Example 1 according to the Gel Permeation Chromatography (GPC) embodiment of the present invention.

[0020] FIG. 4 illustrates the molecular weight distribution curve of the modified conjugated diene based polymer of Reference Example 2 according to the Gel Permeation Chromatography (GPC) embodiment of the present invention.

Embodiment of the invention

[0021] Hereinafter, the present invention is described in more detail in order to provide a clearer understanding of the present invention.

[0022] It should be understood that words or terms used in the description and claims should not be interpreted as meaning defined in commonly used dictionaries. It should also be understood that words or terms should be construed as having a meaning that corresponds to their meaning in the context of the technical field in question and the technical idea of the invention, based on the principle that the inventor can correctly determine the meaning of words or terms in order to best explain the invention.

[0023] The term "substituted" in the present invention may mean that the hydrogen atom of a functional group, a group of atoms, or a compound is replaced by a specific substituent. If the hydrogen atom of the functional group, group of atoms, or compound is substituted with a specific substituent, one or more substituents, including two or more substituents, may be present depending on the number of hydrogen atoms present in the functional group, group of atoms, or compound, and if present a plurality of substituents, such substituents may be the same or different.

[0024] The term "alkyl group" in the present invention may mean a monovalent aliphatic saturated hydrocarbon, and may include a linear alkyl group such as methyl, ethyl, propyl, and butyl; a branched alkyl group such as isopropyl, sec-butyl, t-butyl and neopentyl; and cyclic saturated hydrocarbons or cyclic unsaturated hydrocarbons containing one or two or more unsaturated bonds.

[0025] The term "alkylene group" in the present invention may mean a divalent aliphatic saturated hydrocarbon such as methylene, ethylene, propylene and butylene.

[0026] The term "cycloalkyl group" in the present invention may mean a cyclic saturated hydrocarbon.

[0027] The term "aryl group" in the present invention may mean a cyclic aromatic hydrocarbon, and may include both a monocyclic aromatic hydrocarbon in which one ring is formed and a polycyclic aromatic hydrocarbon in which two or more rings are combined.

[0028] The term "heterocyclic group" in the present invention means a cyclic saturated hydrocarbon or a cyclic unsaturated hydrocarbon containing at least one unsaturated bond, in which the carbon atom in the hydrocarbon may be replaced by one or more heteroatoms, where the heteroatom may be selected from nitrogen (N), oxygen (O) and sulfur (S) atoms.

[0029] The term "monovalent hydrocarbon group" in the present invention means a monovalent substituent derived from a hydrocarbon group, where, for example, a monovalent hydrocarbon group may denote a monovalent group of atoms in which carbon and hydrogen atoms are bonded, such as an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkyl group containing at least one unsaturated bond, and an aryl group, and a monovalent group of atoms may have a linear or branched structure depending on its bonding structure.

[0030] The term "divalent hydrocarbon group" in the present invention means a divalent substituent derived from a hydrocarbon group, where, for example, a divalent hydrocarbon group may mean a divalent group of atoms in which carbon and hydrogen atoms are bonded, such as an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, a cycloalkylene group containing at least one unsaturated bond, and an arylene group, and a divalent group of atoms may have a linear or branched structure depending on its bonding structure.

[0031] the Term "single bond" in the present invention may mean a simple covalent bond in itself, which does not include a separate atomic or molecular group.

[0032] The terms "derived unit" and "derived functional group" in the present invention may mean a component or structure formed from some material, or may mean the material itself.

[0033] The present invention provides a modified conjugated diene polymer having excellent tensile properties and viscoelastic properties while simultaneously having excellent processability.

[0034] The modified conjugated diene polymer according to an embodiment of the present invention has a unimodal molecular weight distribution as indicated by a unimodal shape of the molecular weight distribution curve obtained using gel permeation chromatography (GPC) and a polydispersity index (PPD) of 1.0 or more and up to less than 1.7, where the modified conjugated diene-based polymer includes a functional group derived from the modified monomer represented by formula 1, and includes a functional group derived from an aminoalkoxysilane-based modifier on at least one its end.

[0035] [Formula 1]

.

.

[0036] In formula 1

[0037] F ₁ is an amine-containing functional group, and R ₁ is an alkenyl group having 2 to 10 carbon atoms.

[0038] According to an embodiment of the present invention, the modified conjugated diene polymer may include a repeat unit derived from the conjugated diene monomer, a functional group derived from the modified monomer, and a functional group derived from the modifier. A repeating unit derived from a conjugated diene based monomer may mean a repeating unit formed by polymerization of a conjugated diene based monomer, and a functional group derived from a modified monomer and a functional group derived from a modifier may mean a functional group derived from a modified monomer present in the polymer chain, and a functional group derived from the modifier, respectively.

[0039] In addition, the functional group derived from the modified monomer may be present in the polymer chain or may be located at least one end of the polymer chain, and, in the case where the functional group derived from the modified monomer is present at one end of the polymer chain, the functional group derived from the modified monomer may be at one end of the polymer chain, and the functional group derived from the modifier may be present at the other end of the polymer chain. That is, in this case, the modified conjugated diene based polymer according to the embodiment of the present invention may be a conjugated diene based polymer modified at both ends.

[0040] Further, according to another embodiment of the present invention, the modified conjugated diene polymer may be a copolymer comprising a repeat unit derived from a conjugated diene monomer, a repeat unit derived from an aromatic vinyl monomer, derived from a functional group derived from the modified monomer; and a functional group derived from the modifier. In this case, the repeat unit derived from the aromatic vinyl monomer may mean a repeat unit formed by polymerization of the aromatic vinyl monomer.

[0041] According to an embodiment of the present invention, a conjugated diene monomer may mean at least a monomer selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3 -butyl-1,3-octadiene, isoprene, 2-phenyl-1,3-butadiene and 2-halo-1,3-butadiene (the term "halogen" means a halogen atom).

[0042] An aromatic vinyl monomer, for example, may mean at least a monomer selected from the group consisting of styrene, b-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene , 4-(p-methylphenyl)styrene, 1-vinyl-5-hexylnaphthalene, 3-(2-pyrrolidino-ethyl)styrene), 4-(2-pyrrolidinoethyl)styrene), and 3-(2-pyrrolidino-1-methylethyl) ) styrene.

[0043] As another example, the modified conjugated diene-based polymer may be a copolymer further comprising a repeating unit derived from a diene-based monomer having 1 to 10 carbon atoms in addition to a repeating unit derived from a conjugated diene-based monomer. The repeat unit derived from a diene-based monomer may be a repeat unit derived from a diene-based monomer other than a conjugated diene-based monomer and a diene-based monomer other than a conjugated diene based monomer, for example, may be 1 ,2-butadiene. In the case where the modified conjugated diene-based polymer is a copolymer further comprising a diene-based monomer, the modified conjugated diene-based polymer may include a repeating unit derived from the diene-based monomer in an amount of more than 0 to 1% by mass. , from more than 0 to 0.1% wt., from more than 0 to 0.01% wt. or from more than 0 to 0.001% by mass, and within this range, the effect of preventing gelation occurs.

[0044] In accordance with an embodiment of the present invention, the copolymer may be a random copolymer, in which case there is an excellent balance between physical properties. A random copolymer may mean that the repeat units that make up the copolymer are randomly distributed.

[0045] The modified conjugated diene polymer according to an embodiment of the present invention may have a number average molecular weight (Mn) of 1,000 to 2,000,000 g/mol, 10,000 to 1,000,000 g/mol, or 100,000 to 800,000 g/mol, may have weight average molecular weight (Mw) from 1000 to 3000000 g/mol, from 10000 to 2000000 g/mol or from 100000 to 2000000 g/mol, and may have a maximum average molecular weight (Mp) from 1000 to 3000000 g/mol, from 10000 to 2000000 g/mol or from 100000 to 2000000 g/mol. Within this range, rolling resistance and wet handling are excellent. In another example, the modified conjugated diene polymer may have a polydispersity index (PPD; Mw/Mn) of 1.0 or more and less than 1.7, or 1.1 or more and less than 1.7, where within this range, tensile properties and viscoelastic properties are excellent and there is an excellent balance between physical properties. Here, the modified conjugated diene-based polymer has a unimodal molecular weight distribution, as indicated by the unimodal shape of the molecular weight distribution curve obtained by gel permeation chromatography (GPC), where this is the molecular weight distribution that appears in the polymer polymerized with using continuous polymerization, and may mean that the modified conjugated diene polymer has uniform properties. That is, since the modified conjugated diene polymer according to the embodiment of the present invention is obtained by continuous polymerization, the modified conjugated diene based polymer can have a polydispersity index of 1.0 or more and less than 1.7 while having a unimodal molecular -mass distribution.

[0046] Generally, in the case where a conjugated diene based polymer is produced by batch polymerization and subjected to a modification reaction, the resulting conjugated diene based polymer has a multimodal (bimodal or more) molecular weight distribution curve. More specifically, with regard to batch polymerization, since the polymerization reaction is initiated after the introduction of all raw materials, so that the development of chains can occur simultaneously from the initiation point generated by a plurality of initiators, the development of each chain can be approximately uniform, and accordingly, the molecular weights of the resulting polymer chains are constant, so that the molecular weight distribution curve can have a unimodal shape with a very narrow molecular weight distribution. However, in the case where the modifier is added to carry out the modification reaction, there may be two possible cases, the case of no modification and the case of modification and coupling, respectively, two groups with a large molecular weight difference between the polymer chains can be formed, and as a result, a curve is formed multimodal molecular weight distribution, which presents two or more peaks of the molecular weight distribution curve. With regard to the continuous polymerization method according to the embodiment of the present invention, since the reaction initiation and the introduction of raw materials are carried out continuously in contrast to batch polymerization, and the time at which the initiation point is generated from which the reaction is initiated is different, the polymerization initiation is changed, for example , polymerization initiation starts from the start of the reaction, starts in the middle of the reaction, and starts at the end of the reaction, and therefore, polymer chains having different molecular weights are obtained when the polymerization reaction is completed. Accordingly, the specific peak does not appear dominant in the curve showing the molecular weight distribution, so that the molecular weight distribution curve as a single peak is wide, and since the molecular weight can be similar to the molecular weight of the chain in which polymerization is initiated at the beginning of the reaction, even if the chain in which polymerization is initiated at the end of the reaction is linked, the diversity of the molecular weight distribution can be kept the same, and therefore, as a rule, the unimodal distribution curve is still maintained.

[0047] However, even in the case where the polymer is obtained by batch polymerization and modified, the modification conditions can be adjusted to obtain a unimodal form, but in this case, the entire polymer must be unbound or must be bound, and in other cases, the unimodal molecular- mass distribution cannot be obtained.

[0048] In addition, when the entire polymer is bonded, as in the case where the molecular weight distribution curve of the modified conjugated diene based polymer has a unimodal distribution, despite the fact that the modified conjugated diene based polymer is obtained by the batch polymerization described above, processability may be poor since only polymers having the same molecular weight level are present, and miscibility characteristics may be poor since the amount of functional groups capable of interacting with a filler such as silica or carbon black is reduced due to binding. On the other hand, in the case where the entire polymer is not bonded, since the functional groups at the end of the polymer that can interact with the filler such as silica or carbon black are more likely to interact with each other during processing than with the filler, a phenomenon may occur that interferes with the interaction with the filler, and accordingly the processability may be very poor. As a result, in the case where the polymer is controlled to have a unimodal molecular weight distribution curve, although the polymer is obtained by batch polymerization, there may be limitations that the processability and miscibility characteristics of the resulting conjugated diene-based modified polymer deteriorate, and especially processability may be impaired.

[0049] Whether or not a modified conjugated diene based polymer is bound can be confirmed by the binding number (C.N), where the binding number is a number that depends on the number of functional groups with which the polymer present in the modifier can be associated after polymer modifications. That is, the bond number indicates the ratio of a polymer with only one modified end and no bond between polymer chains to a polymer with multiple polymer chains associated with a single modifier, where the bond number can be in the range 1≤C.N≤F, with F being the number of functional groups capable of reacting with the end of the active polymer in the modifier. In other words, a modified conjugated diene based polymer with a binding number of 1 means that all polymer chains are unlinked, and a modified conjugated diene based polymer with a binding number of F means that all polymer chains are linked.

[0050] Thus, with respect to the modified conjugated diene polymer according to an embodiment of the present invention, the binding number may be greater than 1 and less than the number of functional groups of the modifier used (1<C.N<F), while the molecular curve -mass distribution has a unimodal form.

[0051] As another example, the content of silicon (Si) in the modified conjugated diene polymer may be in the range of 50 ppm or more, 100 ppm or more, 100 to 10,000 ppm, or 100 to 5000 ppm based on the weight of the modified conjugated diene based polymer, and the mechanical properties such as tensile mechanical properties and viscoelastic properties of the rubber composition comprising the modified conjugated diene based polymer are excellent within this range . The Si content may indicate the number of Si atoms present in the modified conjugated diene based polymer. The Si atom may be introduced from a functional group derived from the modifier.

[0052] As another example, the content of nitrogen (N) in the modified conjugated diene polymer may be in the range of 50 ppm or more, 100 ppm or more, 100 to 10,000 ppm, or 100 to 5000 ppm based on the total weight of the modified conjugated diene based polymer, and the mechanical properties such as tensile mechanical properties and viscoelastic properties of the rubber composition comprising the modified conjugated diene based polymer within this range are beautiful. The N content may refer to the number of N atoms present in the modified conjugated diene polymer, where the N atom may be introduced from a functional group derived from the modifier.

[0053] Si content, for example, can be measured using inductively coupled plasma (ICP) analysis, and ICP analysis can be performed using an inductively coupled plasma optical emission spectrometer (ICP-OES; Optima 7300DV) . Using an inductively coupled plasma optical emission spectrometer, the Si content can be measured as follows. Approximately 0.7 g of the sample is placed in a platinum (Pt) crucible, 1 ml of concentrated sulfuric acid (98% wt., electronic purity) is added and heated at 300°C for 3 hours, the sample is burned in an electric furnace (Thermo Scientific, Lindberg Blue M) with a program that includes the following steps 1 to 3:

[0054] 1) step 1: start temperature 0°C, speed (temperature/hour) 180°C/hour, temperature (hold time) 180°C (1 hour)

[0055] 2) step 2: start temperature 180°C, speed (temperature/hour) 85°C/hour, temperature (hold time) 370°C (2 hour)

[0056] 3) step 3: start temperature 370°C, rate (temperature/hour) 47°C/hour, temperature (hold time) 510°C (3 hours);

[0057] 1 ml of concentrated nitric acid (48 wt. %) and 20 μl of concentrated hydrofluoric acid (50 wt. %) are added to the residue, the platinum crucible is sealed and shaken for 30 minutes or more to obtain a sample, 1 ml of boric acid is added to the sample. acid, the mixture is stored at 0°C for 2 hours or more, and then diluted with 30 ml of ultrapure water to measure the Si content.

[0058] In this case, the sample is a modified conjugated diene based polymer from which the solvent has been removed by placing and stirring the sample in steam-heated hot water, with residual monomer, residual modifier and oil removed.

[0059] In addition, the content of N, for example, can be measured using NSX analysis, and NSX analysis can be performed using a nitrogen trace analyzer (NSX-2100H).

[0060] When using, for example, a trace nitrogen analyzer, the trace nitrogen analyzer (autosampler, horizontal oven, PMT detector and nitrogen detector) is turned on, the carrier gas flow rates are set to 250 ml/min for Ar, 350 ml/ min for O ₂ and 300 ml/min for the ozonator, the heater is set to 800°C, and the analyzer is stabilized, waiting for approximately 3 hours. After the analyzer is stabilized, a calibration curve is generated at 5 ppm, 10 ppm, 50 ppm, 100 ppm, and 500 ppm using a nitrogen standard (AccuStandard S-22750-01-5 ml), get the area corresponding to each concentration, and then get a straight line using the ratio of concentration to area. After that, a ceramic boat containing 20 mg of the sample is placed in the autosampler of the analyzer and the area is measured. The N content is calculated using the obtained sample area and the calibration curve.

[0061] In this case, the sample used in the NSX analysis is a modified conjugated diene based polymer sample from which the solvent is removed by placing and stirring the sample in hot steam heated water, which may be a sample from which residual monomer has been removed and a residual modifier. In addition, if oil is added to the sample described above, it may be the sample after the oil has been extracted (removed).

[0062] As another example, the modified conjugated diene polymer may have a Mooney stress relaxation rate, measured at 100°C, of 0.7 or more, 0.7 or more, and 3.0 or less, of 0 .7 or more and up to 2.5 or less, or 0.7 or more and up to 2.0 or less.

[0063] In this case, the Mooney stress relaxation rate means the change in stress in response to the same amount of strain, and it can be measured using a Mooney viscometer. More specifically, the Mooney stress relaxation rate is measured using a large rotor at a rotor speed of 2 ± 0.02 rpm at 100° C. using an MV2000E instrument (Monsanto Company), and after holding the polymer at rest for 30 minutes or more at room temperature (23±5°C), take 27±3 g of polymer and fill into the cavity of the die, measure the Mooney viscosity by applying a torque due to the work of the plate, and the Mooney stress relaxation rate is obtained by measuring the slope of the change in Mooney viscosity obtained when the torque is released.

[0064] The Mooney stress relaxation rate can be used as an indicator of the branched structure of a polymer, and for example, when polymers having the same Mooney viscosity are compared, since the greater the number of branches, the lower the Mooney stress relaxation rate, the stress relaxation rate is Mooney can be used as an indicator of the degree of branching.

[0065] In addition, the modified conjugated diene polymer can have a Mooney viscosity of 30 or more, 40 to 150, or 40 to 140 at 100°C, and within this range, processability and productivity are excellent.

[0066] As another example, the modified conjugated diene polymer may have a shrinkage coefficient (g'), which is obtained by measuring (gel permeation chromatography)-light scattering with a viscosity detector, 0.8 or more, especially from 0.8 or more and up to 3.0 or less, and more preferably 0.8 or more and 1.3 or less.

[0067] In this case, the shrinkage ratio (g') obtained by (gel permeation chromatography)-light scattering measurement is the ratio of the intrinsic viscosity of a polymer having branching to the intrinsic viscosity of a linear polymer having the same absolute molecular weight, and it can be used as an indicator of the branched structure of the polymer having branches, that is, as an indicator of the percentage of branches. For example, the number of branches of the corresponding polymer increases as the shrinkage ratio decreases, and therefore, when comparing polymers having the same absolute molecular weight, since the shrinkage ratio becomes smaller as the number of branches increases, the shrinkage ratio can be used as an indicator of the degree ramifications.

[0068] In addition, a chromatogram is obtained using a measuring instrument (gel permeation chromatography)-light scattering equipped with a viscosity detector, and the shrinkage coefficient is calculated based on the viscosity of the solution and the light scattering method, more specifically, the absolute molecular weight and intrinsic viscosity corresponding to each absolute molecular weight, is obtained using a measuring instrument (gel permeation chromatography)-light scattering, equipped with a viscosity detector and a light scattering detector, to which two columns are attached, in which a polystyrene-based gel is used as a filler, the intrinsic viscosity of a linear polymer corresponding to the absolute molecular weight, and the shrinkage factor can then be determined as the ratio of intrinsic viscosities corresponding to each absolute molecular weight. For example, after injecting a sample into a light scattering (GPC)-light scattering instrument (Viscotek TDAmax, Malvern Panalytical Ltd.) equipped with a light scattering detector and a viscosity detector, to obtain the absolute molecular weight from the light scattering detector and obtain the intrinsic viscosity [ƞ] relative to the absolute molecular weight from the light scattering detector and the viscosity detector, the intrinsic viscosity [ƞ] ₀ of the linear polymer relative to the absolute molecular weight is calculated using Equation 2 below, and the average value of the ratios ([ƞ]/[ƞ] ₀ ) of the intrinsic viscosities corresponding to each absolute molecular weight, expressed as a shrinkage factor. In this case, a mixed solution of tetrahydrofuran and N,N,N',N'-tetramethylethylenediamine (adjusted by mixing 20 ml of N,N,N',N'-tetramethylethylenediamine with 1 liter of tetrahydrofuran) is used as eluent, PL is used as column Olexis (Agilent Technologies, Inc.), measurements are made at an oven temperature of 40° C. and a THF flow rate of 1.0 ml/min, and a sample is prepared by dissolving 15 mg of polymer in 10 ml of THF.

[0069] [Equation 2]

[ƞ] ₀ = 10 ^-3.883 M ^0.771 .

[0070] In Equation 2, M is the absolute molecular weight.

[0071] In addition, the modified conjugated diene polymer may have a vinyl content of 5 wt%. or more, 10% of the mass. or more, or from 10 to 60% of the mass. In this case, the vinyl content means the content of 1,2-attached conjugated diene-based monomer, but not 1,4-attached conjugated diene-based monomer, based on 100 wt%. a conjugated diene based copolymer consisting of a monomer having a vinyl group and an aromatic vinyl based monomer.

[0072] The modified monomer represented by formula 1 according to an embodiment of the present invention can introduce a functional group into a polymer chain when it is polymerized with another monomer to form a polymer chain.

[0073] Specifically, in formula 1, the F ₁ group may be a 5-membered heterocyclic group having 2 to 4 carbon atoms, which contains at least one heteroatom selected from the group consisting of nitrogen (N), sulfur (S) and oxygen (O).

[0074] More specifically, the modified monomer represented by formula 1 may be the compound shown by formula 2 below.

[0075] [Formula 2]

.

.

[0076] In Formula 2, R ₂ is an alkenyl group having 2 to 10 carbon atoms.

[0077] More specifically, the modified monomer represented by formula 1 may be the compound shown by formula 3 below, that is, 1-vinylimidazole (1-vinyl-1H-imidazole).

[0078] [Formula 3]

.

.

[0079] In addition, the modifier according to the present invention may be a modifier for modifying at least one end of the conjugated diene-based polymer, and as a specific example, may be a modifier having an affinity for silicon dioxide. A silica-affinity modifier may mean a modifier having a silica-affinity functional group, and a silica-affinity functional group may mean a functional group in which interaction between the silica-based filler and the functional group derived from the modifier is possible due to excellent affinity for the filler, in particular the silica-based filler.

[0080] More specifically, in accordance with an embodiment of the present invention, the aminoalkoxysilane-based modifier may include at least a modifier selected from the compounds represented by Formulas 4 and 5 below.

[0081] [Formula 4]

.

.

[0082] In formula 4

[0083] R _a1 and R _a4 are each independently a single bond or an alkylene group having 1 to 10 carbon atoms,

[0084] R _a2 and R _a3 are each independently an alkyl group having 1 to 10 carbon atoms,

[0085] R _a5 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a divalent, trivalent or tetravalent alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms,

[0086] n1 means an integer from 1 to 3, and

[0087] n2 means an integer from 0 to 2,

[0088] [Formula 5]

.

.

[0089] In formula 5

[0090] the A ₁ and A ₂ groups are each independently an alkylene group having 1 to 20 carbon atoms,

[0091] The R _b1 -R _b4 substituents are each independently an alkyl group having 1 to 20 carbon atoms, and

[0092] The L ₁ -L ₄ substituents are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a divalent, trivalent, or tetravalent alkylsilyl group substituted with an alkyl group having from 1 to 10 carbons.

[0093] More specifically, the aminoalkoxysilane-based modifier according to an embodiment of the present invention may be a compound indicated by formula 4, wherein in formula 4, the substituents R _a1 and R _a4 each independently may be a single bond or an alkylene group having from 1 to 5 carbon atoms, the substituents R _a2 and R _a3 can each independently be an alkyl group having 1 to 5 carbon atoms, the substituent R _a5 can be a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a tetravalent an alkylsilyl group substituted with an alkyl group having 1 to 5 carbon atoms, n1 may be an integer of 2 or 3, and n2 may be an integer of 0 to 2.

[0094] More specifically, the compound represented by formula 4 may include at least a compound selected from the group consisting of N,N-bis(3-(dimethoxy(methyl)silyl)propyl)-methyl-1-amine, N, N-bis(3-(diethoxy(methyl)silyl)propyl)-methyl-1-amine, N,N-bis(3-(trimethoxysilyl)propylmethyl-1-amine, N,N-bis(3-( triethoxysilyl)propyl)-methyl-1-amine, N,N-diethyl-3-(trimethoxysilyl)propan-1-amine, N,N-diethyl-3-(triethoxysilyl)propan-1-amine, 3-( dimethoxy(methyl)silyl)-N,N-diethylpropan-1-amine, tri(trimethoxysilyl)amine, tri-(3-(trimethoxysilyl)propyl)amine and N,N-bis(3-(diethoxy(methyl)silyl) propyl)-1,1,1-trimethylsilanamine.

[0095] In addition, the aminoalkoxysilane modifier according to another embodiment of the present invention may be a compound shown in Formula 5, wherein in Formula 5, groups A ₁ and A ₂ each independently may be an alkylene group having 1 to 10 carbon atoms, substituents R _b1 to R _b4 each independently can be an alkyl group having 1 to 10 carbon atoms, and substituents L ₁ to L ₄ can each independently be an alkyl group having 1 to 10 carbon atoms, aryl a group having 6 to 12 carbon atoms, or a tetravalent alkylsilyl group substituted with an alkyl group having 1 to 5 carbon atoms.

[0096] More specifically, the compound represented by formula 5 may include at least a compound selected from the group consisting of 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis( N, N-dimethylpropan-1-amine), 3,3'-(1,1,3,3-tetraethoxy-disiloxane-1,3-diyl)bis(N, N-dimethylpropan-1-amine), 3, 3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N, N-dimethylpropan-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1 ,3-diyl)bis(N,N-diethylpropan-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1- amine), 3,3'-(1,1,3,3-tetraethoxy-disiloxane-1,3-diyl)bis(N, N-diethylpropan-1-amine), 3,3'-(1,1, 3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N, N-diethylpropan-1-amine), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N , N-dipropyl-propan-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)-bis(N, N-dipropylpropan-1-amine), 3, 3'-(1,1,3,3-tetramethoxy-disiloxane-1,3-diyl)bis(N, N-diethylmethane-1-amine), 3,3'-(1,1,3,3-tetraethoxydisiloxane -1,3-diyl)bis(N, N-diethylmethane-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N, N-diethyl- methane-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)-bis(N, N-dimethylmethane-1-amine), 3,3'-(1 ,1,3,3-tetramethoxy-disiloxane-1,3-diyl)bis(N, N-dipropylmethane-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3- diyl)bis(N, N-dimethylmethane-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)-bis(N, N-dipropylmethane-1-amine) , 3,3'-(1,1,3,3-tetraethoxy-disiloxane-1,3-diyl)bis(N, N-dimethylmethane-1-amine), 3,3'-(1,1,3, 3-tetraethoxydisiloxane-1,3-diyl)bis(N, N-dipropylmethane-1-amine), N, N'-((1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(propane- 3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine)), N, N'-((1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis (propan-3,1-diyl))-bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine)), N, N'-((1,1,3,3-tetrapropoxydisiloxane-1,3 -diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine)), N, N'-((1,1,3,3-tetramethoxydisiloxane- 1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilanamine)), N, N'-((1,1,3,3-tetraethoxy- disiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilanamine)) and N, N'-((1,1,3,3- tetrapropoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilanamine)).

[0097] As described above, with respect to the modified conjugated diene polymer according to the embodiment of the present invention, the polymer may have a specific structure and may have a specific molecular weight distribution and shape thereof. The structure of a polymer can be expressed by physical properties such as shrinkage ratio, Mooney stress relaxation rate and binding number, molecular weight distribution and its shape can be expressed in terms of the magnitude of molecular weight distribution, shape of the molecular weight distribution curve, and binding number and modification of both ends with a modifier and a modified monomer can affect the structure and molecular weight distribution and its shape. The parameters expressing the structure of the polymer and the characteristics related to the molecular weight distribution can be satisfied by the method of obtaining, which is described later.

[0098] In addition, the production of a polymer by the above method is desirable in order to provide the characteristics described above, and when all of the characteristics described above are satisfied, the effects to be realized in the present invention can be achieved.

[0099] Moreover, the present invention provides a method for producing a modified conjugated diene-based polymer. Since the modified conjugated diene based polymer according to the embodiment of the present invention is produced by the method described below, the molecular weight distribution may be narrow and have a polydispersity index from 1.0 or more to less than 1.7, while the molecular weight -weight distribution is unimodal, as indicated by the molecular weight distribution curve obtained using gel permeation chromatography, having a unimodal shape. Therefore, with respect to the modified conjugated diene-based polymer, both the tensile properties and the viscoelastic properties are well balanced and excellent, and the processability is also excellent.

[00100] The method for producing a modified conjugated diene polymer according to an embodiment of the present invention includes the step (S1) of obtaining an active polymer having a functional group derived from the modified monomer introduced therein by polymerizing the modified monomer represented by the following formula 1 with the monomer based on a conjugated diene or with a conjugated diene based monomer and an aromatic vinyl based monomer in the presence of a polymerization initiator in a hydrocarbon solvent; and a step (S2) of reacting or binding the active polymer obtained in step (S1) with an aminoalkoxysilane-based modifier, where step (S1) can be carried out continuously in two or more polymerization reactors, and the degree of polymerization conversion in the first reactor of the reactors polymerization may be 50% or less.

[00101] [Formula 1]

.

.

[00102] In formula 1, F ₁ and R ₁ have the same meanings as defined above, and the aminoalkoxysilane-based modifier is the same as described above.

[00103] In addition, more specifically, the modified monomer shown by formula 1 may be a compound represented by formula 2 or a compound represented by formula 3 as described above.

[00104] The hydrocarbon solvent is not particularly limited, and, for example, may be at least a solvent selected from the group consisting of n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene, and xylene.

[00105] The polymerization initiator is not particularly limited, and, for example, may be at least one selected from the group consisting of methyllithium, ethyllithium, propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, tert-octyllithium, phenyllithium, 1-naphthyllithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naphthylsodium, naphthyllithium, lithium alkoxide, alkoxide sodium, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide and lithium isopropylamide.

[00106] According to an embodiment of the present invention, the polymerization initiator may be used in an amount of 0.01 to 10 mmol, 0.05 to 5 mmol, 0.1 to 2 mmol, 0.1 to 1 mmol, or 0.15 to 0.8 mmol based on total 100 g of monomer. In this case, the total 100 g of monomer may mean the total amount of modified monomer and conjugated diene based monomer, or the total amount of modified monomer, conjugated diene based monomer and aromatic vinyl based monomer.

[00107] In addition, according to an embodiment of the present invention, the modified monomer can be used in an amount of 0.001 to 10 g, preferably 0.01 to 10 g, and more preferably 0.1 to 10 g, based on 100 g of monomer based on a conjugated diene.

[00108] The polymerization in step (S1), for example, may be an anionic polymerization, and more specifically, it may be a living anionic polymerization in which an anionic active site at the end of the polymerization is obtained by advancing the polymerization reaction with anions. In addition, the polymerization of the step (S1) may be a temperature increase polymerization, an isothermal polymerization, or a constant temperature polymerization (adiabatic polymerization), wherein the constant temperature polymerization may mean a polymerization method including the step of carrying out the polymerization by not randomly applying heat, and by the heat of reaction itself after the addition of the polymerization initiator, the temperature rise polymerization may mean a polymerization method in which the temperature is increased by random application of heat after the addition of the polymerization initiator, and isothermal polymerization may mean a polymerization method in which the temperature of the polymer is kept constant by heat removal or by applying heat after adding the polymerization initiator.

[00109] Moreover, according to an embodiment of the present invention, the polymerization in step (S1) can be carried out by further including a diene-based compound having 1 to 10 carbon atoms, in addition to the conjugated diene-based monomer, and in this case has place the effect of preventing gel formation on the reactor wall during long-term operation. An example of a diene-based compound may be 1,2-butadiene.

[00110] The polymerization in step (S1), for example, can be carried out in a temperature range of 80°C or less, -20 to 80°C, 0 to 80°C, 0 to 70°C, or 10 to 70 °C, and since the molecular weight distribution of the polymer is controlled to be narrow within this range, an excellent improvement in physical properties takes place.

[00111] The active polymer obtained in step (S1) may mean a polymer in which a polymeric anion is combined with an organometallic cation.

[00112] According to an embodiment of the present invention, the process for producing a modified conjugated diene polymer can be carried out in a plurality of polymerization reactors, including two or more polymerization reactors, and in a modification reactor by a continuous polymerization process. As a specific example, step (S1) can be carried out continuously in two or more polymerization reactors including the first reactor, and the number of polymerization reactors can be freely determined depending on the reaction conditions and environment. A continuous polymerization process may mean a reaction process in which reactants are continuously fed into the reactor and the resulting reaction product is continuously discharged. In the case where a continuous polymerization method is used, the productivity and processability are excellent, and the uniformity of the resulting polymer is excellent.

[00113] In addition, according to an embodiment of the present invention, during continuous production of active polymer in the polymerization reactor, the polymerization conversion rate in the first reactor may be in the range of 50% or less, 10 to 50%, or 20 to 50%. , and a polymer having a linear structure can be formed during polymerization by suppressing a side reaction occurring when a polymer is formed within this range after polymerization is initiated. Accordingly, since the molecular weight distribution of the polymer can be controlled within a narrow range, an excellent improvement in physical properties takes place.

[00114] In this case, the degree of polymerization conversion can be controlled depending on the reaction temperature and residence time in the reactor.

[00115] The degree of conversion during polymerization, for example, can be determined by measuring the concentration of solids in the polymer solution containing the polymer during polymerization of the polymer. As a specific example, to withdraw a polymer solution, a cylindrical vessel is placed at the outlet of each polymerization reactor to fill the cylindrical vessel with a predetermined amount of polymer solution; the cylindrical vessel is separated from the reactor to measure the mass (A) of the cylinder filled with the polymer solution; the polymer solution filling the cylindrical vessel is transferred to an aluminum container, such as an aluminum cup, to measure the mass (B) of the cylindrical vessel from which the polymer solution is removed; the aluminum container containing the polymer solution is dried in an oven at 140° C. for 30 minutes; determine the mass (C) of the dried polymer; and then the polymerization conversion rate is calculated according to Equation 1 below.

[00116] [Equation 1]

[00117] The polymer polymerized in the first reactor is sequentially transferred to the polymerization reactor before the modification reactor, so that the polymerization can proceed to achieve a polymerization conversion rate of 95% or more, and after polymerization in the first reactor, the polymerization conversion rate for each reactor, for example , for the second reactor, or from the second reactor to the polymerization reactor before the modification reactor can be adjusted accordingly to control the molecular weight distribution.

[00118] In step (S1), in the preparation of the active polymer, the residence time of the polymer in the first reactor may be in the range of 1 to 40 minutes, 1 to 30 minutes, or 5 to 30 minutes, and control of the polymerization conversion within this range is simple. Accordingly, the molecular weight distribution of the polymer can be controlled within a narrow range, and therefore, excellent improvement in physical properties takes place.

[00119] The definition of "polymer" in the present invention may mean an intermediate compound in the form of a polymer, which undergoes polymerization in each reactor during step (S1) before step (S2), or step (S2) is completed to obtain an active polymer or a modified polymer on based on a conjugated diene, or may mean a polymer having a polymerization conversion rate of less than 95%, which is polymerized in a reactor.

[00120] According to an embodiment of the present invention, the active polymer obtained in step (S1) may have a molecular weight distribution indicated by a polydispersity index (PPD Mw/Mn) of less than 1.5, from 1.0 or more and up to less than 1.5, or from 1.1 or more and up to less than 1.5, and since the modified conjugated diene-based polymer obtained by the modification or coupling reaction with the modifier within this range has a narrow molecular weight distribution, observe a fine improvement in physical properties.

[00121] The polymerization in step (S1) can be carried out by including a polar additive, and the polar additive can be added in an amount of 0.001 to 50 g, 0.001 to 10 g, or 0.005 to 0.1 g, based on a total of 100 g of monomer. As another example, the polar additive may be added in an amount of 0.001 to 10 g, 0.005 to 5 g, or 0.005 to 4 g, based on a total of 1 mmol of polymerization initiator.

[00122] The polar additive, for example, may be at least one selected from the group consisting of tetrahydrofuran, 2,2-di(2-tetrahydrofuryl)propane, diethyl ether, cycloamyl ether, dipropyl ethyl, ethylene methyl ether , ethylene dimethyl ether, diethyl glycol, dimethyl ether, tert-butoxyethoxyethane, bis(3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine, N, N, N', N'-tetramethylethylenediamine, menthol sodium and 2-ethyltetrahydrofurfuryl ether, and may preferably be 2,2-di(2-tetrahydrofuryl)propane, triethylamine, tetramethylethylenediamine, sodium menthol or 2-ethyltetrahydrofurfuryl ether, and in the case where the conjugated diene-based monomer and the aromatic vinyl are copolymerized by the inclusion of a polar additive, since the polar additive compensates for the differences in the reaction rates of such monomers, this contributes to the easy formation of a random copolymer.

[00123] In accordance with an embodiment of the present invention, the reaction or coupling in step (S2) may be carried out in a modification reactor, in which case the modifier may be used in an amount of 0.01 to 10 mmol based on a total of 100 g of monomer. As another example, the modifier can be used in a mole ratio of 1:0.1 to 1:10, 1:0.1 to 1:5, or 1:0.1 to 1:3, based on 1 mole of polymerization initiator. in step (S1).

[00124] In addition, according to an embodiment of the present invention, the modifier may be added to the modification reactor, and step (S2) may be carried out in the modification reactor. As another example, a modifier may be introduced into the transfer station to transfer the active polymer obtained in step (S1) to the modification reactor for step (S2) and the reaction or binding may proceed by mixing the active polymer and the modifier in the transfer station.

[00125] The method for producing a modified conjugated diene based polymer according to an embodiment of the present invention is a method capable of satisfying the characteristics of the above described modified conjugated diene based polymer, and the effect to be achieved in the present invention can be achieved when the above characteristics satisfy those described above, but it is necessary that at least the degree of polymerization conversion from the first reactor to the second reactor under the process conditions in the above production method be satisfied, and the physical properties of the modified conjugated diene-based polymer according to with the present invention can be implemented by adjusting other polymerization conditions in various ways.

[00126] In addition, the present invention provides a rubber composition comprising the modified conjugated diene-based polymer described above.

[00127] The rubber composition may include a modified conjugated diene-based polymer in an amount of 10% by weight. or more, from 10 to 100% of the mass. or 20 to 90% by mass, and mechanical properties such as tensile strength and abrasion resistance are excellent, and within this range there is an excellent balance between physical properties.

[00128] In addition, the rubber composition may further include another rubber component, if necessary, in addition to the modified conjugated diene-based polymer, in which case the rubber component may be included in the amount of 90% of the mass. or less based on the total weight of the rubber composition. More specifically, the other rubber component may be included in an amount of 1 to 900 parts by mass. based on 100 mass.h. modified polymer based on conjugated diene.

[00129] The rubber component, for example, may be natural rubber or synthetic rubber, and specific examples of the rubber component may be natural rubber (NR), including cis-1,4-polyisoprene, modified natural rubber such as epoxidized natural rubber (ENR ), deproteinized natural rubber (DPNR) and hydrogenated natural rubber in which the base natural rubber is modified or purified; and synthetic rubber such as styrene-butadiene rubber (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, polyisobutylene-co-isoprene, neoprene, poly(ethylene-co-propylene) , poly(styrene-co-butadiene), poly(styrene-co-isoprene), poly(styrene-co-isoprene-co-butadiene), poly(isoprene-co-butadiene), poly(ethylene-co-propylene-co -diene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, butyl rubber, and halogenated butyl rubber. One of these, or a mixture of two or more of them, may be used.

[00130] The rubber composition, for example, may include from 0.1 to 200 wt.h. or from 10 to 120 mass.h. filler based on 100 mass.h. modified conjugated diene based polymer of the present invention. The filler, for example, may be a silica-based filler, and specific examples of the silica-based filler may be wet silica (water-containing silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, or colloidal dioxide. silicon, and the filler may preferably be wet silica, in which the effect of improving both the breaking characteristics and the wet grip of the tire is most significant. In addition, the rubber composition may further include a carbon black filler, if necessary.

[00131] As another example, in the case where silica is used as a filler, a silane coupling agent may be used along with it to improve the reinforcing and low heat generation properties. Specific examples of the silane coupling agent may be 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-dimethylthiocarbamoyl-tetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyl -tetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyl-tetrasulfide, 3-trimethoxysilylpropylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzoyltetrasulfide, 3-triethoxysilylpropylmethacrylate monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, bis(3-diethoxymethylsilylpropyl)tetrapropylsilanemethylpto, -N ,N-dimethylthiocarbamoyltetrasulfide or dimethoxymethylsilylpropylbenzothiazolyltetrasulfide, and any one of these, or a mixture of two or more of them, may be used. In view of the reinforcement improvement effect of the silane coupling agent, bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazolyltetrasulfide may be preferred.

[00132] In addition, in the rubber composition according to the embodiment of the present invention, since a modified conjugated diene-based polymer in which a functional group having a high affinity for silica is introduced into the active site is used as a rubber component, a miscible the amount of silane coupling agent can be reduced compared to the usual case. Accordingly, silane coupling agent can be used from 1 to 20 wt.h. or from 5 to 15 wt.h. at the rate of 100 mass.h. silicon dioxide. Within this range, the silane coupling agent can prevent the rubber component from gelling while still having an effect as a coupling agent sufficiently.

[00133] The rubber composition according to an embodiment of the present invention may be cross-linked with sulfur and may further include a vulcanizing agent. The vulcanizing agent, as a rule, can be a powder of sulfur and can be included in an amount of from 0.1 to 10 wt.h. based on 100 mass.h. rubber component, and within this range, the low fuel consumption property is excellent while maintaining the elastic modulus and strength required for the vulcanized rubber composition.

[00134] The rubber composition according to an embodiment of the present invention, in addition to the components described above, may further include various additives such as a vulcanization accelerator, process oil, an antioxidant, a plasticizer, an antioxidant, a scorch inhibitor, zinc white, stearic acid, a thermosetting resin, or a thermoplastic resin. used in the main rubber industry.

[00135] For example, a thiazole-based compound such as 2-mercaptobenzothiazole (M), dibenzothiazyl disulfide (DM), and N-cyclohexylbenzothiazole-2-sulfenamide (CZ), or a guanidine-based compound such as diphenylguanidine (DPG) can be used as a vulcanization accelerator, and the vulcanization accelerator can be included in an amount of from 0.1 to 5 wt.h. based on 100 mass.h. rubber component.

[00136] The process oil in the rubber composition acts as a softener, while examples of the process oil can be a paraffin-based compound, a naphthene-based compound, or an aromatic compound, and the process oil based on an aromatic compound can be used taking into account tensile strength and stability to abrasion and a naphthenic or paraffinic process oil can be used considering hysteresis loss and low temperature performance. Process oil, for example, can be included in the amount of 100 wt.h. or less based on 100 mass.h. rubber component, and within this range, the reduction in tensile strength and low heat generation properties (low fuel consumption property) of the vulcanized rubber can be prevented.

[00137] Examples of an antioxidant can be 2,6-di-tert-butyl-p-cresol, dibutylhydroxytoluene, 2,6-bis((dodecylthio)-methyl)-4-nonylphenol, or 2-methyl-4,6-bis( (octylthio)methyl)phenol, and the antioxidant can be used in an amount of from 0.1 to 6 mass.h. based on 100 mass.h. rubber component.

[00138] Examples of an antioxidant can be H-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl -1,2-dihydroquinoline or high-temperature condensate of diphenylamine and acetone, and the antioxidant can be used in an amount of from 0.1 to 6 mass.h. based on 100 mass.h. rubber component.

[00139] The rubber composition according to the embodiment of the present invention can be obtained by kneading the above formulation for mixing using a kneading machine such as a Banbury mixer, roller and internal mixer, and a rubber composition having excellent abrasion resistance can also be obtained. , as well as the property of low heat generation, due to the vulcanization process after molding.

[00140] Thus, the rubber composition may be suitable for making any element of a tire, such as a tire tread, undertread, sidewall, carcass cover rubber, belt cover rubber, bead filler, bead tape or bead cover rubber, or for various industrial rubber products such as anti-vibration rubber, conveyor belt and hose.

[00141] In addition, the present invention provides a tire made using a rubber composition.

[00142] The tire may include a tire or tire tread.

[00143] Hereinafter, the present invention is described in more detail based on examples. However, the invention may be embodied in many different forms and should not be construed as being limited to the embodiments presented herein. Rather, these exemplary embodiments are provided so that the description is complete and complete, and fully conveys the scope of the present invention to a person skilled in the art.

[00144] Preparation Example 1: Preparation of 3-(dimethoxy(methyl)-silyl)-N,N-diethylpropan-1-amine

[00145] (3-Chloropropyl)dimethoxymethylsilane (CAS No. 18171-19-2, Sigma-Aldrich, 1.83 g, 10 mmol) and diethylamine (0.8 g, 11 mmol) are completely dissolved by stirring in 100 ml of toluene at room temperature (23±3°C), then the mixture is refluxed and stirred at 110°C for 2 hours, get 3-(dimethoxy(methyl)silyl)-N,N-diethylpropan-1-amine (yield 2 .5 g, >98%).

[00146] Preparation Example 2: Preparation of N,N-bis(3-(diethoxy-(methyl)silyl)propyl)-1,1,1-trimethylsilanamine

[00147] Add 33.9 g (0.2 mol) of diallyltrimethylsilylamine and 0.26 g of a toluene solution (platinum content 3% wt.) of the platinum-1,3-divinyl-1,1,3,3-tetramethyl complex -disiloxane and heated to 70°C. After stabilization of the reactor temperature, 53.7 g (0.4 mol) of methyldiethoxysilane are added dropwise over 4 hours, the reaction is carried out at the above temperature for 1 hour, 58.1 g of N,N-bis(3-(diethoxy(methyl) -silyl)propyl)-1,1,1-trimethylsilanamine.

[00148 ] Preparation Example 3: Preparation of N,N'-((1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1- trimethyl-N-(trimethylsilyl)silanamine)

[00149] Completely dissolve 3,3'-(1,1,3,3-tetramethoxysiloxane-1,3-diyl)bis(propan-1-amine) (CAS No. 76712-65-7, LookChem, 3, 13 g, 10 mmol) by stirring in 100 ml of toluene at room temperature (23±3°C), then the mixture is reacted with trimethylsilyl chloride (1.14 g, 10.5 mmol) in the presence of triethylamine (1.11 g, 11 mmol) as a base at 40°C for 2 hours, as in the reaction scheme below, N,N'-((1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(propane- 3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine) (yield 5.6 g, >98%).

[00150]

[00151] Example 1

[00152] A solution of styrene, in which 60% of the mass. styrene dissolved in n-hexane, a solution of 1,3-butadiene, in which 60% of the mass. 1,3-butadiene is dissolved in n-hexane, a solution of the modified monomer, in which 15% of the mass. 1-vinylimidazole (Sigma-Aldrich, CAS No. 1072-63-5) dissolved in n-hexane, n-hexane, 1,2-butadiene solution, in which 2.0% wt. 1,2-butadiene is dissolved in n-hexane, a solution in which 10% of the mass. 2,2-di(2-tetrahydrofuryl)propane is dissolved in n-hexane, as a polar additive, and a solution of n-butyllithium, in which 6.6% of the mass. n-butyllithium dissolved in n-hexane is injected into the first reactor from continuous reactors, where three reactors are connected in series, at rates of 1.85 kg/h (styrene solution), 11.9 kg/h (1,3-butadiene solution ), 30 g/h (modified monomer solution), 48.0 kg/h (n-hexane), 40.0 g/h (1,2-butadiene solution), 61.0 g/h (polar additive solution) and 106.1 g/h (n-butyllithium solution), respectively. In this case, the temperature of the first reactor is maintained at 50° C., and the polymer is transferred from the first reactor to the second reactor via a transfer line when the polymerization conversion reaches 40%.

[00153] Then a solution of 1,3-butadiene, in which 60% of the mass. 1,3-butadiene dissolved in n-hexane is injected into the second reactor at a rate of 2.96 kg/hour. In this case, the temperature of the second reactor is maintained at 65°C, and the polymer is transferred from the second reactor to the third reactor through the transfer line when the polymerization conversion reaches 95% or more.

[00154] The polymer is transferred from the second reactor to the third reactor, and the solution in which 20% of the mass is dissolved. 3-(dimethoxy-(methyl)silyl)-N,N-diethylpropan-1-amine from Preparation 1 was added as a modifier to the third reactor at a rate of 64.0 g/hr. The temperature of the third reactor is maintained at 65°C.

[00155] Then a solution of IR1520 (BASF SE), in which 30% of the mass is dissolved. IR1520, as an antioxidant, is injected into the polymerization solution discharged from the third reactor at a rate of 167 g/hour and mixed. The resulting polymer is placed in hot steam-heated water, stirred to remove the solvent, and a modified polymer based on a conjugated diene is obtained.

[00156] Example 2

[00157] A modified conjugated diene based polymer is prepared in the same manner as in Example 1, except that in Example 1, the polymer is transferred from the first reactor to the second reactor through a transfer line when the polymerization conversion reaches 43%, and the solution , in which 20% of the mass is dissolved. N,N-bis(3-(diethoxy-(methyl)silyl)propyl)-1,1,1-trimethylsilanamine from Preparation 2 instead of 3-(dimethoxy(methyl)silyl)-N,N-diethylpropan-1- amine, continuously served as a modifier in the third reactor at a rate of 116.0 g/hour.

[00158] Example 3

[00159] A modified conjugated diene based polymer is prepared in the same manner as in Example 1, except that in Example 1, the polymer is transferred from the first reactor to the second reactor through a transfer line when the polymerization conversion reaches 41%, and the solution , in which 20% of the mass is dissolved. N, N'-((1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)- silanamine) from preparation example 3, instead of 3-(dimethoxy(methyl)-silyl)-N,N-diethylpropan-1-amine, is continuously fed as a modifier into the third reactor at a rate of 103.5 g/hour.

[00160] Comparative Example 1

[00161] 110 g of styrene, 870 g of 1,3-butadiene, 0.54 g of 1-vinylimidazole, 5000 g of n-hexane and 1.13 g of 2,2-di(2-tetrahydrofuryl) are added to a 20 L autoclave reactor. propane as a polar additive, then the internal temperature of the reactor is raised to 50°C. When the internal temperature of the reactor reaches 50°C, 5.5 mmol of n-butyllithium is added to the reactor to carry out the reaction with adiabatic heating. Approximately 20 minutes later, 20 g of 1,3-butadiene are added to cap the polymer end groups with butadiene. After 5 minutes, 5.5 mmol of 3-(dimethoxy(methyl)-silyl)-N,N-diethylpropan-1-amine from Preparation 1 was added as a modifier and the reaction was carried out for 15 minutes. After that, the polymerization reaction is stopped using ethanol and add 45 ml of a solution in which 0.3% of the mass. IR1520 (BASF SE) dissolved in n-hexane as an antioxidant. The polymer thus obtained is placed in steam-heated hot water and stirred to remove the solvent, and a modified conjugated diene-based polymer is obtained.

[00162] Comparative Example 2

[00163] A solution of styrene, in which 60% of the mass. styrene dissolved in n-hexane, a solution of 1,3-butadiene, in which 60% of the mass. 1,3-butadiene dissolved in n-hexane, n-hexane, a solution of 1,2-butadiene, in which 2.0% of the mass. 1,2-butadiene is dissolved in n-hexane, a solution in which 10% of the mass. 2,2-di(2-tetrahydro-furyl)propane is dissolved in n-hexane, as a polar additive, and a solution of n-butyllithium, in which 6.6% of the mass. n-butyl lithium dissolved in n-hexane is injected into the first reactor from continuous reactors, where two reactors are connected in series, at rates of 1.85 kg/h (styrene solution), 11.9 kg/h (1.3 -butadiene), 48.0 kg/h (n-hexane), 40.0 g/h (1,2-butadiene solution), 61.0 g/h (polar additive) and 106.1 g/h (solution n-butyllithium), respectively. In this case, the temperature of the first reactor is maintained at 55° C., and the polymer is transferred from the first reactor to the second reactor via a transfer line when the polymerization conversion reaches 48%.

[00164] Then a solution of 1,3-butadiene, in which 60% of the mass. 1,3-butadiene dissolved in n-hexane is injected into the second reactor at a rate of 2.96 kg/h. In this case, the temperature of the second reactor is maintained at 65°C, and the reaction is stopped when the polymerization conversion reaches 95% or more.

[00165] After that, a solution of IR1520 (BASF SE), in which 30% of the mass is dissolved. IR1520 as an antioxidant is injected into the polymerization solution discharged from the second reactor at a rate of 167 g/hour and mixed. The resulting polymer is placed in hot steam-heated water and stirred to remove the solvent to obtain an unmodified conjugated diene-based polymer.

[00166] Comparative Example 3

[00167] A solution of styrene, in which 60% of the mass. styrene dissolved in n-hexane, a solution of 1,3-butadiene, in which 60% of the mass. 1,3-butadiene dissolved in n-hexane, n-hexane, a solution of 1,2-butadiene, in which 2.0% of the mass. 1,2-butadiene is dissolved in n-hexane, a solution in which 10% of the mass. 2,2-di(2-tetrahydro-furyl)propane is dissolved in n-hexane, as a polar additive, and a solution of n-butyllithium, in which 6.6% of the mass. n-butyl lithium dissolved in n-hexane is injected into the first reactor from continuous reactors, where three reactors are connected in series, at rates of 1.85 kg/h (styrene solution), 11.9 kg/h (1.3 -butadiene), 48.0 kg/h (n-hexane), 40.0 g/h (1,2-butadiene solution), 61.0 g/h (polar additive) and 106.1 g/h (solution n-butyllithium), respectively. In this case, the temperature of the first reactor is maintained at 50° C., and the polymer is transferred from the first reactor to the second reactor via a transfer line when the polymerization conversion reaches 41%.

[00168] Then a solution of 1,3-butadiene, in which 60% of the mass. 1,3-butadiene dissolved in n-hexane is injected into the second reactor at a rate of 2.96 kg/h. In this case, the temperature of the second reactor is maintained at 65°C, and the polymer is transferred from the second reactor to the third reactor through the transfer line when the polymerization conversion reaches 95% or more.

[00169] The polymer is transferred from the second reactor to the third reactor, and the solution in which 20% of the mass is dissolved. 3-(dimethoxy-(methyl)silyl)-N,N-diethylpropan-1-amine is added as a modifier to the third reactor at a rate of 64.0 g/hour. The temperature of the third reactor is maintained at 65°C.

[00170] After that, a solution of IR1520 (BASF SE), in which 30% of the mass is dissolved. IR1520 as an antioxidant is injected into the polymerization solution discharged from the third reactor at a rate of 167 g/h and stirred. The resulting polymer is placed in hot steam-heated water and stirred to remove the solvent to obtain a modified conjugated diene-based polymer.

[00171] Comparative Example 4

[00172] A modified conjugated diene based polymer is prepared in the same manner as in Example 1, except that in Example 1, the polymer is transferred from the first reactor to the second reactor through a transfer line when the polymerization conversion reaches 47%, and the solution , in which 2.0% of the mass. dichlorodimethylsilane instead of 3-(dimethoxy(methyl)silyl)-N,N-diethylpropan-1-amine dissolved in n-hexane, added as a modifier to the third reactor at a rate of 40.0 g/hour.

[00173] Comparative Example 5

[00174] A modified conjugated diene polymer is prepared in the same manner as in Example 1, except that in Example 1, the reactor temperature is maintained at 75°C in the first reactor, at 80°C in the second reactor, and at 80°C in the third reactor, respectively, and the polymer is transferred from the first reactor to the second reactor through a transfer line when the degree of polymerization conversion reaches 70%.

[00175] Reference Example 1

[00176] A modified conjugated diene polymer was prepared in the same manner as in Comparative Example 1, except that in Comparative Example 1, 16.5 mmol of 3-(dimethoxy(methyl)silyl)-N,N-diethylpropane- 1-amine.

[00177] Reference Example 2

[00178] A modified conjugated diene polymer was prepared in the same manner as in Comparative Example 1, except that in Comparative Example 1, 2.5 mmol of 3-(dimethoxy(methyl)silyl)-N,N-diethylpropane- 1-amine.

[00179] Experimental Example 1

[00180] Styrene unit content and vinyl content of each polymer, weight average molecular weight (Mw, ×10 ³ g/mol), number average molecular weight (Mn, ×10 ³ g/mol), molecular weight distribution indicated by the index polydispersity (PPD), binding number, Mooney viscosity (MV), Mooney stress relaxation rate, shrinkage ratio, Si content, and N content were measured respectively for modified or unmodified conjugated diene-based polymers in the Examples and Comparative Examples. The results are presented below in table 1.

[00181] 1) Content of styrene units and content of vinyl (% wt.)

[00182] The content of styrene units (SM (SM)) and the content of vinyl in each polymer is measured and analyzed using a Varian VNMRS 500 MHz nuclear magnetic resonance (NMR (NMR)).

[00183] In NMR measurements, 1,1,2,2-tetrachloroethane is used as the solvent, the solvent signal is calculated to be 5.97 ppm, and the styrene content and vinyl content are calculated by determining the statistical styrene peak at 7.2-6.9 ppm, styrene block peak at 6.9-6.2 ppm, 1,4-vinyl peak at 5.8-5.1 ppm. and a 1,2-vinyl peak at 5.1-4.5 ppm.

[00184] (2) Weight average molecular weight (Mw, ×10 ³ g/mol), number average molecular weight (Mn, ×10 ³ g/mol), polydispersity index (PPD) and binding number (CN)

[00185] Weight average molecular weight (Mw) and number average molecular weight (Mn) are measured by gel permeation chromatography (GPC) and a molecular weight distribution curve is obtained. In addition, the polydispersity index (PPD), Mw/Mn) is obtained by calculation using each of the measured molecular weights. More specifically, for GPC, two PLgel Olexis columns (Polymer Laboratories Ltd) and one PLgel mixed-C column (Polymer Laboratories Ltd) are combined and used, and polystyrene (PS) is used as the GPC standard material for calculation molecular weight. The solvent for carrying out GPC is obtained by mixing 2% of the mass. amine compound in tetrahydrofuran. In this case, the resulting molecular weight distribution curves are shown in FIG. 1-4.

[00186] In addition, a number of polymers are selected before injection of the modifier or coupling agent in each of the examples and comparative examples to obtain the maximum molecular weight (Mp ₁ ) of the polymer, and thereafter obtain the maximum molecular weight (Mp ₂ ) of each modified polymer per conjugated diene basis to calculate the binding number according to Equation 3 below.

[00187] [Equation 3]

Binding number (CN) = Mp ₂ /Mp ₁

[00188] 3) Mooney Viscosity and Mooney Stress Relaxation Rate

[00189] Mooney viscosity (MV, (ML1+4 at 100°C) MU) was measured with a large rotor at a rotor speed of 2±0.02 rpm at 100°C using an MV-2000 instrument (ALPHA Technologies, Ltd. ). After keeping the used samples at rest for 30 minutes or more at room temperature (23 ± 3°C), 27 ± 3 g of each sample is taken and filled in the cavity of the die, and the Mooney viscosity is measured for 4 minutes due to the operation of the plate.

[00190] After measuring the Mooney viscosity, the slope of the change in the obtained Mooney viscosity when the torque is released is determined to obtain the Mooney stress relaxation rate, the absolute value of the slope.

[00191] 4) Si content

[00192] The Si content is measured by inductively coupled plasma (ICP) analysis using an inductively coupled plasma optical emission spectrometer (ICP-OES; Optima 7300DV). More specifically, the Si content can be measured as follows. Approximately 0.7 g of the sample is placed in a platinum (Pt) crucible, approximately 1 ml of concentrated sulfuric acid (98% wt., electronic purity) is added and heated at 300°C for 3 hours, the sample is burned in an electric furnace (Thermo Scientific, Lindberg Blue M) with a program that includes the following steps 1 to 3:

[00193] 1) step 1: start temperature 0°C, rate (temperature/hour) 180°C/hour, temperature (hold time) 180°C (1 hour);

[00194] 2) step 2: start temperature 180°C, rate (temperature/hour) 85°C/hour, temperature (hold time) 370°C (2 hours);

[00195] 3) step 3: start temperature 370°C, rate (temperature/hour) 47°C/hour, temperature (hold time) 510°C (3 hours).

[00196] 1 ml of concentrated nitric acid (48 wt. %) and 20 μl of concentrated hydrofluoric acid (50 wt. %) are added to the residue, the platinum crucible is sealed and shaken for 30 minutes or more, a sample is obtained, 1 ml of boric acid and the mixture is kept at 0°C for 2 hours or more, and then diluted with 30 ml of ultrapure water to measure the Si content.

[00197] 5) N content

[00198] The N content is measured by NSX analysis using a nitrogen trace analyzer (NSX-2100H). More specifically, the trace nitrogen analyzer (autosampler, horizontal oven, PMT detector and nitrogen detector) is switched on, the carrier gas flow rates are set to 250 ml/min for Ar, 350 ml/min for O ₂ and 300 ml/min for the ozonator , the heater is set to 800°C, and the analyzer is stabilized by waiting approximately 3 hours. After the analyzer is stabilized, a calibration curve is generated at 5 ppm, 10 ppm, 50 ppm, 100 ppm, and 500 ppm h using a nitrogen standard (AccuStandard VTOR-22750-01-5 ml), get the area corresponding to each concentration, and then get a straight line using the ratio of concentration to area. After that, a ceramic boat containing 20 mg of the sample is placed in the autosampler of the analyzer and the area is measured. The N content is calculated using the obtained sample area and the calibration curve.

[00199] 6) Shrink ratio (g')

[00200] After injecting the sample into a (gel permeation chromatography)-light scattering instrument (Viscotek TDAmax, Malvern Panalytical Ltd.) equipped with a light scattering detector and a viscosity detector, to obtain the absolute molecular weight from the light scattering detector and obtain the intrinsic viscosity [ƞ] relative to of the absolute molecular weight from the light scattering detector and the viscosity detector, the intrinsic viscosity [ƞ] ₀ of the linear polymer relative to the absolute molecular weight is calculated using Equation 2 below, and the average value of the ratios ([ƞ]/[ƞ] ₀ ) of the intrinsic viscosities corresponding to each absolute molecular weight, expressed as a shrinkage factor. In this case, a mixed solution of tetrahydrofuran and N,N,N',N'-tetramethylethylenediamine (adjusted by mixing 20 ml of N,N,N',N'-tetramethylethylenediamine with 1 liter of tetrahydrofuran) is used as the eluent, as a column a PL Olexis column (Agilent Technologies, Inc.) was used, measurements were made at an oven temperature of 40° C. and a THF flow rate of 1.0 ml/min, and a sample was prepared by dissolving 15 mg of polymer in 10 ml of THF.

[00201] [Equation 2]

[ƞ] ₀ = 10 ^-3.883 M ^0.771 .

[00202] In Equation 2, M is the absolute molecular weight.

[00203] Table 1

Category Examples Comparative examples Reference examples 1 2 3 1 2 3 4 5 1 2 Reaction conditions Modified monomer M1 M1 M1 M1 - - M1 M1 M1 M1 modifier or binding agent F1 F2 F3 F1 - F1 C1 F1 F1 F1 Temperature of the first reactor (°C) 50 50 50 50→80 55 50 50 75 50→80 50→80 Conversion rate in the first polymerization reactor (%) 40 43 41 - 48 41 47 70 - - NMR (% mass) SM (SM) 10 10 10 10 10 10 10 10 10 10 Vinyl 38 38 38 38 38 38 38 38 38 38 GPC Mw(Ch10 ³ g/mol) 482 510 455 361 448 475 514 690 374 428 Mn(Ch10 ³ g/mol) 311 324 304 298 320 305 325 312 325 310 PPD 1.55 1.57 1.50 1.21 1.40 1.56 1.58 2.21 1.15 1.38 C.N. 1.21 1.80 1.90 1.40 - 1.21 2.90 1.19 1.00 2.00 Molecular weight distribution curve Unimodal Unimodal Unimodal bimodal Unimodal Unimodal Unimodal Unimodal Unimodal Unimodal Mooney Viscosity (MV) 58 60 56 50 55 58 60 71 51 54 Mooney stress relaxation rate 1.0613 0.9299 0.8866 1.1346 0.8440 1.0077 0.4543 0.5440 1.3462 0.8172 Shrink factor (g') 1.112 1.010 0.959 1.214 0.918 1.101 0.449 0.512 1.417 0.908 Si content (ppm) 155 291 303 91 - 153 20 90 120 79 N content (ppm) 212 234 290 120 - 69 110 150 60 60

[00204] In Table 1, the specific materials of the modified monomer, modifier, and coupling agent are as follows.

[00205] *Modified monomer M1: 1-vinylimidazole

[00206] *F1 modifier:

[00207] 3-(dimethoxy(methyl)silyl)-N,N-diethylpropan-1-amine

[00208] *F2 modifier:

[00209] N,N-bis(3-(diethoxy(methyl)silyl)propyl)-1,1,1-trimethylsilamine

[00210] *Modifier F3: N, N'-((1,1,3,3-tetramethoxy-disiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1 -trimethyl-N-(trimethylsilyl)silanamine)

[00211] *Coupling agent C1: Dichlorodimethylsilane

[00212] As shown in Table 1, it can be confirmed that the modified conjugated diene-based polymers of Examples 1-3 according to an embodiment of the present invention have a MDP (molecular weight distribution) of 1.0 or more and less than 1 ,7, a Mooney stress relaxation rate of 0.7 or more and a shrinkage ratio of 0.8 or more, while having a unimodal shape of the molecular weight distribution curve by gel permeation chromatography (see FIG. 1). On the other hand, it can be confirmed that the unmodified or modified conjugated diene based polymers of Comparative Examples 1 to 5 and Reference Examples 1 and 2 have a bimodal shape of the molecular weight distribution curve by gel permeation chromatography (see FIG. 2) or have a relaxation rate the Mooney stress is less than 0.7 and the shrinkage factor is less than 0.8, and especially with respect to Comparative Example 5, which was obtained by continuous polymerization, but the polymerization conversion rate in the first reactor was outside the scope of the present invention, the SPD value is greater than 1.7, and the Mooney stress relaxation rate and the shrinkage ratio are less than 0.7 and less than 0.8, respectively, and it can be confirmed that such values are significantly lower than those of the examples.

[00213] In addition, with respect to Comparative Example 1, in which the polymer was produced by the batch polymerization method of the present invention, the molecular weight distribution curve by gel permeation chromatography has a bimodal shape (see FIG. 2). Even if a batch polymerization method is used, as in reference examples 1 and 2, the molecular weight distribution curves can be adjusted so that they have a unimodal shape (see FIGS. 3 and 4), but in this case, any of the polymer binding numbers is 1.0 or 2.0, and since only a polymer in which the entire polymer is not bound by a modifier (Reference Example 1) and a polymer in which most of the polymer is bound by a modifier (Reference Example 2) can be present, there is a difference in structure and unimodal properties of polymers according to the continuous polymerization method of the present invention, and therefore, it can be confirmed that processability, tensile properties, and viscoelastic properties are significantly reduced compared to these characteristics of examples, as shown in Table 3, which is described below.

[00214] The modified conjugated diene based polymers of Comparative Examples 3 and 4 were obtained at the same level as the examples according to the present invention, except for the type of modifier and whether or not the modified monomer is used during polymerization, and the physical properties of the polymer such as molecular weight distribution, binding number, Mooney stress relaxation rate and shrinkage ratio show levels similar to those of examples, but since the functional group contemplated in the present invention derived from the modified monomer or modifier is not included, the filler affinity is poor, which can be confirmed by the fact that the tensile properties and viscoelastic properties of comparative examples 3 and 4 in table 3, which is described below, are significantly reduced in comparison with these properties of the examples.

[00215] Experimental Example 2

[00216] For a comparative analysis of the physical properties of rubber compositions comprising any of the modified or unmodified conjugated diene-based polymers obtained in the Examples, Comparative Examples, and Reference Examples, as well as the molded articles obtained therefrom, tensile mechanical properties and viscoelastic properties are respectively measured , and the results are shown in Table 3 below.

[00217] 1) Preparation of rubber samples

[00218] Any of the modified or unmodified conjugated diene-based polymers of Examples and Comparative Example were used as a raw material for rubber and mixed under the mixing conditions shown in Table 2 below. 100 wt.h. rubber.

[00219] Table 2

Category raw material Quantity (wt.h.) First stage of mixing Rubber 100 Silica 70 Coupling agent (X50S) 11.2 Process oil 37.5 Zinc white 3 Stearic acid 2 Antioxidant 2 Antioxidant 2 Wax 1 Second stage of mixing Sulfur 1.5 Rubber Vulcanization Accelerator 1.75 Vulcanization accelerator 2

[00220] More specifically, the rubber samples are kneaded by a first kneading step and a second kneading step. In the first kneading step, rubber raw material, silica (filler), organosilane coupling agent (X50S, Evonik), process oil (TDAE oil), zinc oxide (ZnO), stearic acid, antioxidant (TMQ(RD), 2.2 ,4-trimethyl-1,2-dihydroquinoline polymer), antioxidant (6PPD ((dimethylbutyl)-N-phenylphenylenediamine)), and wax (microcrystalline wax) are kneaded using a Banbury mixer equipped with a temperature control device. so that it is 70 ° C, and at the end of mixing, a primary recipe is obtained at a discharge temperature from 145 to 155 ° C. In the second stage of mixing, after cooling the primary recipe to room temperature, the primary recipe, sulfur, rubber vulcanization accelerator (DPD (diphenylguanine)) and the vulcanization accelerator (CZ (N-cyclohexyl-2-benzothiazylsulfonamide) is added to the mixer and mixed at a temperature of 100°C or less, a secondary formulation is obtained. Then, a curing process is carried out at 160° C. for 20 minutes to obtain each rubber sample.

[00221] 2) Tensile properties

[00222] Each sample is prepared in accordance with the ASTM 412 tensile test method and the tensile strength at break of the sample and tensile stress at 300% elongation (300% modulus) are measured to evaluate tensile mechanical properties. More specifically, tensile properties are measured at a speed of 50 cm/min at room temperature using a tensile testing machine Universal Test Machine 4204 (Instron).

[00223] 3) Viscoelastic properties

[00224] With regard to viscoelastic properties, the tan δ value is confirmed by measuring the viscoelastic behavior for dynamic deformation at each measurement temperature (-60 to 60°C) and at a frequency of 10 Hz in film tension mode using a force analyzer (GABO Qualimeter Testanlagen GmbH). For the measured values, the higher tan δ at a low temperature of 0°C, the better the wet handling, and the lower the tan δ at a high temperature of 60°C, the lower the hysteresis loss and the better the running resistance (fuel economy), but in Table 3, since the viscoelastic properties are expressed by indexing (%) after determining the reference value, the higher the value, the better the viscoelastic properties.

[00225] 4) Processability characteristics

[00226] Measure the Mooney viscosity (MV, (ML1+4 at 100°C) MU) of the secondary formulation obtained in section 1) "Obtaining rubber samples" in order to comparatively analyze the processing characteristics of each polymer, and in this case, the lower the measured value of Mooney viscosity, the better the processability characteristics.

[00227] More specifically, the Mooney viscosity is measured with a large rotor at a rotor speed of 2±0.02 rpm at 100°C using an MV-2000 instrument (ALPHA Technologies). After resting each secondary formulation for 30 minutes or more at room temperature (23±3°C), 27±3 g of each sample is taken and the die cavity is filled. The Mooney viscosity is measured within 4 minutes by operating the plate.

[00228] Table 3

Category Examples Comparative examples Reference examples 1 2 3 1 2 3 4 5 1 2 Tensile properties Tensile strength (kg ^. s / cm ² ) 160 165 161 160 160 158 165 155 154 150 300% modulus (kg ^. s/cm ² ) 109 111 115 108 83 95 89 99 87 92 Viscoelastic Properties (Indicator) tan δ (at 0°C) 101 103 103 100 100 101 98 99 100 99 tan δ (at 60°C) 131 130 135 119 100 113 103 118 110 105 Processability characteristics 79 78 81 90 69 80 78 92 100 95

[00229] In Table 3, the obtained viscoelastic property values of Examples 1-3, Comparative Example 1, Comparative Examples 3-5, and Reference Examples 1 and 2 are expressed as exponents (%) based on the measured value for Comparative Example 2.

[00230] As shown in Table 3, with regard to Examples 1-3 according to the embodiment of the present invention, tensile properties, viscoelastic properties, and processability characteristics are improved compared to those properties of Comparative Examples 1-5 and Reference Examples 1 and 2.

[00231] For viscoelastic properties, it is known that it is generally very difficult to have properties in which the tan δ value at 60°C improves simultaneously with the improvement in the tan δ value at 0°C. Thus, it can be understood that the viscoelastic properties of Examples 1 to 3, in which the tan δ values at 60°C are remarkably improved, while the tan δ values at 0°C were at the same level or higher than those of the Comparative Examples, are wonderful.

[00232] In addition, as shown in Table 3 with respect to Reference Examples 1 and 2, which are obtained by batch polymerization but have a unimodal molecular weight distribution curve shape, the poor processability inherent in batch polymerization is not only not improved, but mixing properties, such as tensile properties and viscoelastic properties realized in conventional batch polymerization are also significantly worse than these properties in the examples. Here, the poor processability inherent in batch polymerization can be confirmed by the results of Comparative Example 1 having a bimodal molecular weight distribution curve, which was obtained by conventional batch polymerization.

Claims (39)

1. A modified conjugated diene polymer having a unimodal gel permeation chromatography (GPC) molecular weight distribution curve and a molecular weight distribution (MWD; polydispersity index (PPD)) of 1.0 or more and less than 1.7 , where the modified conjugated diene-based polymer contains a functional group derived from the modified monomer represented by formula 2, and contains a functional group derived from an aminoalkoxysilane-based modifier at least at one end thereof, where the aminoalkoxysilane-based modifier includes at least , one selected from the compounds represented by formulas 4 and 5; [Formula 2]

where in formula 2 R ₂ is an alkenyl group having 2 to 10 carbon atoms; [Formula 4]

, where in formula 4 R _a1 and R _a4 are each independently a single bond or an alkylene group having 1 to 10 carbon atoms, R _a2 and R _a3 are each independently an alkyl group having 1 to 10 carbon atoms, R _a5 represents an alkyl group having 1 to 10 carbon atoms, or an alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, n1 means an integer from 1 to 3, and n2 means an integer from 0 to 2; [Formula 5]

, where in formula 5 A ₁ and A ₂ are each independently an alkylene group having 1 to 20 carbon atoms, R _b1 -R _b4 are each independently an alkyl group having 1 to 20 carbon atoms, and L ₁ -L ₄ are each independently an alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms. 2. The modified conjugated diene polymer according to claim 1, wherein the modified monomer represented by formula 2 is a compound represented by formula 3: [Formula 3]

. 3. A modified polymer based on a conjugated diene according to claim 1, in which in formula 4 R _a1 and R _a4 are each independently a single bond or an alkylene group having 1 to 5 carbon atoms, R _a2 and R _a3 are each independently an alkyl group having 1 to 5 carbon atoms, and R _a5 represents an alkyl group having 1 to 5 carbon atoms or an alkylsilyl group substituted with an alkyl group having 1 to 5 carbon atoms. 4. A modified polymer based on a conjugated diene according to claim 1, in which in formula 5 A ₁ and A ₂ are each independently an alkylene group having 1 to 10 carbon atoms, R _b1 -R _b4 are each independently an alkyl group having 1 to 10 carbon atoms, and L ₁ -L ₄ are each independently an alkylsilyl group substituted with an alkyl group having 1 to 5 carbon atoms. 5. The modified conjugated diene based polymer according to claim 1, wherein the modified conjugated diene based polymer has a number average molecular weight (Mn) of 1,000 to 2,000,000 g/mol, a weight average molecular weight (Mw) of 1,000 to 3,000,000 g/mol, and average maximum molecular weight (Mp) from 1000 to 3000000 g/mol. 6. The modified conjugated diene based polymer according to claim 1, wherein the silicon (Si) content and the nitrogen (N) content of the modified conjugated diene based polymer are 50 ppm or more based on the weight of the modified conjugated diene based polymer. diene. 7. The modified conjugated diene based polymer according to claim 1, wherein the modified conjugated diene based polymer has a Mooney stress relaxation rate measured at 100°C of 0.7 or more and 3.0 or less. 8. The modified conjugated diene based polymer according to claim 1, wherein the modified conjugated diene based polymer has a shrinkage coefficient, which is obtained by measurement using (gel permeation chromatography)-light scattering with a viscosity detector, from 0.8 to 3.0. 9. The modified conjugated diene based polymer according to claim 1, wherein the binding number (C.N.) of the modified conjugated diene based polymer satisfies the condition 1<C.N.<F, where F is the number of functional groups of the modifier. 10. Rubber composition for elements of tires or rubber products, containing a modified polymer based on a conjugated diene according to claim 1 and a filler. 11. The rubber composition according to claim 10, in which the rubber composition contains from 0.1 to 200 wt.h. filler based on 100 mass.h. modified polymer based on conjugated diene. 12. The rubber composition of claim 10 wherein the filler is silica filler or carbon black filler.

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