Conjugated diene polymer and rubber composition containing the same

Abstract

The present invention relates to a conjugated diene polymer or a modified conjugated diene polymer having excellent wet skid resistance and wear resistance in a balanced manner, and a rubber composition containing the same, and by controlling the microstructure of the polymer, in a tan δ diagram according to temperature obtained by dynamic viscoelastic analysis of an advanced rheological extension system (ARES), the full width at half maximum (FWHM) value of the tan δ peak shown in the temperature range of ‑100° C. to 100° C. is 20° C. or more, and excellent viscoelastic behavior performance can be exhibited, and therefore, improvement in overall physical properties can be expected.

Description

[Technical field]

[0004] The present invention relates to a conjugated diene-based polymer having excellent wet skid resistance and abrasion resistance in a balanced manner, and a rubber composition comprising the conjugated diene-based polymer. Background Art

[0005] According to recent demands for automobiles with low fuel consumption rates, conjugated diene-based polymers having modulation stability represented by wet skid resistance and low rolling resistance as well as excellent wear resistance and tensile properties are required as rubber materials for tires.

[0006] In order to reduce the running resistance of the tire, there is a method of reducing the hysteresis loss of the vulcanized rubber, and the rebound resilience, tanδ, Goodrich heating, etc. at 50°C to 80°C are used as evaluation indicators of the vulcanized rubber. That is, it is desirable to use a rubber material having high rebound resilience or low tanδ or Goodrich heating at the above temperature.

[0007] Natural rubber, polyisoprene rubber or polybutadiene rubber are known as rubber materials with low hysteresis loss, but these rubbers have the limitation of low wet skid resistance. Therefore, recently, conjugated diene polymers or copolymers such as styrene-butadiene rubber (hereinafter referred to as "SBR") and butadiene rubber (hereinafter referred to as "BR") are prepared by emulsion polymerization or solution polymerization to be used as tire rubber. Among these polymerization methods, the greatest advantage of solution polymerization compared with emulsion polymerization is that the vinyl structure content and styrene content that determine the physical properties of the rubber can be arbitrarily adjusted, and its molecular weight and physical properties can be controlled by coupling or modification. Therefore, since it is easy to change the structure of the SBR or BR finally prepared, and the movement of the chain end can be reduced by coupling or modification of the chain end and the coupling force with fillers such as silica and carbon black can be increased, the SBR prepared by solution polymerization is widely used as a tire rubber material.

[0008] Solution-polymerized SBR is prepared by using an anionic polymerization initiator and is used by coupling or modifying the chain end of the polymer thus formed using various modifiers. For example, U.S. Pat. No. 4,397,994 discloses a method of coupling the active anion at the chain end of a polymer obtained by polymerizing styrene-butadiene in a nonpolar solvent using an alkyl lithium as a monofunctional initiator, using a coupling agent such as a tin compound.

[0009] In addition, if solution-polymerized SBR is used as the rubber material, the physical properties required for the tire, such as running resistance, can be controlled by increasing the vinyl content in the SBR, but if the vinyl content is high, the braking performance and wear resistance tend to become unfavorable, and therefore, the styrene content in the SBR needs to be above a certain level, but in this case, the effect expressed by the high vinyl content will not be manifested.

[0010] Due to these problems, attempts have been made to improve running resistance and wet skid resistance in a balanced manner by using solution-polymerized SBR, using a block copolymer SBR including two block copolymer units having gradients in styrene and vinyl contents, but the improvement is not significant, and in the case of applying SBR having a low glass transition temperature to improve wear resistance, wet skid resistance tends to become worse.

[0011] Therefore, it is necessary to develop a polymer that can simultaneously improve wet skid resistance and abrasion resistance while substantially satisfying the properties required of products in terms of tensile properties and fuel consumption performance.

[0012] [Prior art literature]

[0013] (Patent Document 1) US 4,397,994 A (August 9, 1983) Summary of the invention

[0014] Technical issues

[0015] The present invention is designed to solve the above-mentioned problems of the related art, and one object is to provide a conjugated diene polymer having a specific tan δ peak by controlling the microstructure of the polymer, thereby achieving a tire with improved wet skid resistance and wear resistance in a balanced manner while maintaining excellent tensile properties and fuel consumption performance.

[0016] In addition, another object of the present invention is to provide a modified conjugated diene-based polymer having improved wear resistance and wet skid resistance by controlling the microstructure of the polymer itself, and additionally having even further improved fuel consumption performance and processability by introducing a modifier.

[0017] In addition, the present invention provides a rubber composition comprising the conjugated diene polymer and / or the modified conjugated diene polymer.

[0018] Technical Solution

[0019] In order to solve the above-mentioned task, according to one embodiment of the present invention, there is provided a conjugated diene polymer, comprising repeating units derived from a conjugated diene monomer, wherein, in a tan δ diagram according to temperature obtained by dynamic viscoelastic analysis of an advanced rheological extension system (ARES), the full width at half maximum (FWHM) value of the tan δ peak shown in the temperature range of -100°C to 100°C is 20°C or more, and the advanced rheological extension system uses a dynamic mechanical analyzer to measure in a torsional mode under the conditions of a frequency of 10 Hz, a strain of 0.5% and a heating rate of 5°C / min.

[0020] In addition, the present invention provides a rubber composition comprising the conjugated diene polymer and a filler.

[0021] Beneficial Effects

[0022] The conjugated diene-based polymer according to the present invention can improve wet skid resistance while maintaining excellent wear resistance even at a low glass transition temperature by controlling the microstructure of the polymer.

[0023] In addition, since the conjugated diene polymer according to the present invention can achieve wear resistance and anti-skid properties by controlling the microstructure through the additional introduction of a modifier, excellent processing performance, fuel consumption performance and tensile properties can be obtained by using an alkoxysilane modifier and controlling the degree of branching, independent of the microstructure of the polymer. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] The accompanying drawings of the present disclosure illustrate specific embodiments of the present invention and are included together with the above description to provide a further understanding of the inventive concept. However, the inventive concept should not be construed as being limited to the accompanying drawings.

[0025] Figure 1 is an embodiment of a stress variation diagram according to temperature obtained by dynamic viscoelastic analysis using the Advanced Rheological Extension System (ARES). DETAILED DESCRIPTION

[0026] Hereinafter, the present invention will be described in more detail to help understanding of the present invention.

[0027] It should be understood that the words or terms used in the specification and claims of the present invention should not be understood as the meanings defined in commonly used dictionaries. It should also be understood that these words or terms should be understood to have the same meanings as they are in the technical concept of the present invention based on the principle that the inventor can appropriately define the meanings of words or terms to best illustrate the invention.

[0028] definition

[0029] The term "polymer" as used in this disclosure refers to a polymer compound prepared by polymerizing monomers, whether the monomers are the same or different types. Likewise, the generic term polymer includes the term homopolymer, which is usually used to refer to polymers prepared from one type of monomer, and the term copolymer, which is defined below.

[0030] The term "copolymer" used in this disclosure refers to a polymer prepared by polymerizing at least two different types of monomers. Likewise, the general term copolymer refers to: polymers prepared from two different types of monomers and including commonly used binary copolymers; and polymers prepared from two or more different types of monomers.

[0031] In the present disclosure, the term "1,2-vinyl bond content" refers to the mass (or weight) percentage of butadiene included in the 1,2-position in the polymer chain of a polymer based on the portion (total amount of polymerized butadiene) derived from a conjugated diene monomer (butadiene, etc.) in the polymer.

[0032] In the present disclosure, the term "styrene bond content" refers to the mass (or weight) percentage of styrene contained in a polymer chain of a polymer derived from an aromatic vinyl-based monomer (styrene, etc.) in a polymer.

[0033] In the present disclosure, the term "room temperature" refers to a temperature in a natural state without heating or cooling, and is a temperature of 20±5°C.

[0034] In the present disclosure, the term "substituted" may refer to that a hydrogen of a functional group, an atomic radical or a compound is replaced by a specific substituent, and if a hydrogen of a functional group, an atomic radical or a compound is replaced by a specific substituent, there may be one or a plurality including two or more substituents depending on the number of hydrogens present in the functional group, the atomic radical or the compound, and if there are multiple substituents, each substituent may be the same or different.

[0035] In the present disclosure, the term "alkyl" may refer to a monovalent aliphatic saturated hydrocarbon, and may include: a straight chain alkyl group such as methyl, ethyl, propyl and butyl; a branched chain alkyl group such as isopropyl, sec-butyl, tert-butyl and neopentyl; and a cyclic saturated hydrocarbon, or a cyclic unsaturated hydrocarbon containing one or two or more unsaturated bonds.

[0036] In the present disclosure, the term "alkylene" may refer to a divalent aliphatic saturated hydrocarbon such as methylene, ethylene, propylene, and butylene.

[0037] In the present invention, the term "cycloalkyl group" may refer to a cyclic saturated hydrocarbon.

[0038] In the present disclosure, the term “aryl group” may refer to an 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.

[0039] In the present disclosure, the term “aralkyl group” is also referred to as an aralkyl group, and may refer to a combination of an alkyl group and an aryl group, which is formed by substituting a hydrogen atom bonded to carbon constituting the alkyl group with an aryl group.

[0040] In the present disclosure, the term "single bond" may refer to a single covalent bond itself, not including separate atoms or molecular groups.

[0041] In the present disclosure, the terms "unit derived from", "repeating unit derived from", and "functional group derived from" may refer to a component or structure derived from a specific substance, or the substance itself.

[0042] In the present disclosure, the terms "comprising" and "having" and their derivatives, although these terms are specifically disclosed or not specifically disclosed, are not intended to exclude the presence of optional additional components, steps or methods. In order to avoid any uncertainty, all compositions claimed by using the term "comprising" may include optional additional additives, adjuvants or compounds, including polymers or any other substances, unless otherwise stated to the contrary. In contrast, the term "essentially consisting of excludes elements that are not necessary for operation and excludes optional other components, steps or methods from the scope of the optional continuous description. The term "consisting of excludes optional components, steps or methods that are not specifically described or shown.

[0043] Measurement methods and conditions

[0044] In the present disclosure, "1,2-vinyl bond content" and "styrene bond content" are the vinyl content and styrene content in the polymer unit, which are measured and analyzed using Varian VNMRS 500MHz NMR. For NMR measurement, 1,1,2,2-tetrachloroethane is used as a solvent, 6.0 ppm is calculated as a solvent peak, and a peak of 7.2 ppm to 6.9 ppm is considered as random styrene, a peak of 6.9 ppm to 6.2 ppm is considered as block styrene, a peak of 5.8 ppm to 5.1 ppm is considered as 1,4-vinyl and 1,2-vinyl, and a peak of 5.1 ppm to 4.5 ppm is considered as 1,2-vinyl, to calculate and measure the 1,2-vinyl content and styrene bond content in the whole polymer, respectively.

[0045] In the present disclosure, "weight average molecular weight (Mw)", "number average molecular weight (Mn)", "molecular weight distribution (MWD)" and "unimodal properties" are obtained by measuring the weight average molecular weight (Mw) and the number average molecular weight (Mn) by gel permeation chromatography (GPC) (PL GPC220, Agilent Technologies), obtaining a molecular weight distribution curve, and calculating the molecular weight distribution (PDI, MWD, Mw / Mn) from the measured individual molecular weights.

[0046] - Column: A combination of two PLgel Olexis columns (Polymer Laboratories Co.) and one PLgelmixed-C column (Polymer Laboratories Co.)

[0047] -Solvent: A mixture of tetrahydrofuran and 2% by weight of an amine compound

[0048] -Flow rate: 1ml / min

[0049] - Sample concentration: 1-2 mg / ml (diluted in THF)

[0050] -Injection volume: 100μl

[0051] - Column temperature: 40℃

[0052] -Detector: Refractive index detector

[0053] -Standard: Polystyrene (calibrated by cubic function)

[0054] In the present disclosure, "glass transition temperature (Tg)" is obtained based on ISO 22768:2006 using differential scanning calorimetry (DSCQ100, TA Co.). Under a nitrogen circulation of 50 ml / min, a differential scanning calorimetry (DSC) curve was recorded while increasing the temperature from -100°C at a rate of 20°C / min, and the peak top (inflection point) of the DSC differential curve was regarded as the glass transition temperature.

[0055] In the present disclosure, the "tan δ peak" is a peak shown in a tan δ graph according to temperature obtained by dynamic viscoelastic analysis of an advanced rheological extension system (ARES), and is measured using a dynamic mechanical analyzer (TA Co., ARES-G2) in a torsional mode under the conditions of a frequency of 10 Hz, a strain of 0.5%, and a heating rate of 5°C / min.

[0056] In the present disclosure, the "Si content" is measured by an ICP analysis method using inductively coupled plasma optical emission spectrometry (ICP-OES; Optima 7300DV), and is measured by using inductively coupled plasma optical emission spectrometry in the following manner: about 0.7 g of a sample is added to a platinum (Pt) crucible, about 1 mL of concentrated sulfuric acid (98 wt %, electronic grade) is added thereto, heated at 300° C. for 3 hours, and the sample is incinerated in an electric furnace (ThermoScientific, Lindberg Blue M) by the following procedure of steps 1 to 3:

[0057] 1) Step 1: Initial temperature is 0°C, rate (temperature / hour) is 180°C / hour, temperature (holding time) is 180°C (1 hour),

[0058] 2) Step 2: Initial temperature is 180°C, rate (temperature / hour) is 85°C / hour, temperature (holding time) is 370°C (2 hours),

[0059] 3) Step 3: Initial temperature is 370°C, rate (temperature / hour) is 47°C / hour, temperature (holding time) is 510°C (3 hours),

[0060] Add 1 mL of concentrated nitric acid (48 wt %) and 20 μl of concentrated hydrofluoric acid (50 wt %) to the residue, seal the platinum crucible and shake for more than 30 minutes, add 1 mL of boric acid to the sample, store at 0°C for more than 2 hours, dilute in 30 mL of ultrapure water, and incinerate.

[0061] In the present disclosure, "N content" can be measured by the NSX analysis method, and the measurement by the NSX analysis method can use a quantitative analyzer of trace nitrogen (NSX-2100H). Specifically, the quantitative analyzer of trace nitrogen (autosampler, horizontal furnace, PMT & Nitrogen detector) is turned on, the carrier gas flow rate is set to 250 ml / min for Ar, 350 ml / min for O2, 300 ml / min for the ozone generator, the heater is set to 800 ° C, and the analyzer is left to stand for about 3 hours to stabilize. After the analyzer is stabilized, a calibration curve within the calibration curve range of 5ppm, 10ppm, 50ppm, 100ppm and 500ppm is made using a nitrogen standard (AccuStandard S-22750-01-5ml), and the area corresponding to each concentration is obtained. Then, a straight line is made using the ratio of concentration to area. Afterwards, a ceramic boat containing 20 mg of the sample is placed in the autosampler of the analyzer and measured to obtain the area. By using the area of ​​the sample thus obtained and the calibration curve, the N content was calculated.

[0062] In this case, the sample used in the NSX analysis method may be a modified conjugated diene polymer from which the solvent is removed by placing the sample in hot water heated by steam and stirring, and may be a sample from which the remaining monomer and the remaining modifier are removed. In addition, if oil is added to the sample, the sample may be a sample from which the oil is extracted (removed).

[0063] Conjugated diene polymers

[0064] The conjugated diene polymer according to the present invention is characterized in that it contains repeating units derived from conjugated diene monomers, wherein, in a tan δ diagram according to temperature obtained by dynamic viscoelastic analysis by an advanced rheological extension system (ARES), a full width at half maximum (FWHM) value of a tan δ peak shown in a temperature range of -100°C to 100°C is 20°C or more, and the advanced rheological extension system uses a dynamic mechanical analyzer in a torsional mode under the conditions of a frequency of 10 Hz, a strain of 0.5% and a heating rate of 5°C / min.

[0065] According to one embodiment of the present invention, since the conjugated diene polymer is achieved by applying a specific preparation method to be described later to achieve a polymer having a specific structure, the dynamic viscoelastic behavior can be controlled to have a specific tanδ peak, and in this way, the tensile properties can be made excellent, and the anti-slip and abrasion resistance can be excellent in a balanced manner.

[0066] Dynamic Viscoelastic Behavior of Polymers

[0067] According to one embodiment of the present invention, the conjugated diene-based polymer is characterized in that, in a tan δ diagram according to temperature obtained by dynamic viscoelastic analysis of an advanced rheological expansion system (ARES), a full width at half maximum (FWHM) value of a tan δ peak shown in a temperature range of -100°C to 100°C is 20°C or more.

[0068] In the case of a polymer prepared by a conventional polymerization method and whose microstructure is not controlled, two or more tan δ peaks are exhibited, or the width of the peak is formed to be very narrow, and the width of the formed peak is not wide. This may be related to the glass transition temperature, and in the case where the units are segmented in the polymer as in a block copolymer, and there is a glass transition temperature difference between the blocks, the tan δ peak may have a narrow width and may exhibit two or more peaks. In addition, in the case of a random copolymer, if the vinyl content or the styrene content in the final polymer is controlled without finely controlling the microstructure, the width of the peak is generally shown to be very narrow.

[0069] In this case, the glass transition temperature of the block copolymer and the random copolymer may be the same, but the difference in wet skid resistance is large. In order to solve this defect, efforts have been made to improve wet skid resistance while reducing the change in glass transition temperature. However, if the glass transition temperature changes, there is a problem of change in wear resistance and change in the basic physical properties of the polymer, and there is still a problem of obtaining a polymer with improved performance. That is, it is difficult to adjust the balance between wear resistance and wet skid resistance, and considering that these two properties are difficult to improve by modification process, this is still a difficult problem to solve. However, the conjugated diene polymer according to one embodiment of the present invention is prepared by a preparation method for controlling the microstructure of the polymer, and although it has the same glass transition temperature as the conventional modified conjugated diene polymer, it can show a specific tan δ peak, and the effect of improving wet skid resistance and wear resistance can be obtained at the same time.

[0070] In this case, the tan δ peak is characterized in that, in a tan δ diagram according to temperature obtained by dynamic viscoelastic analysis of an advanced rheological expansion system (ARES), it appears in a temperature range of -100°C to 100°C, and the half-maximum width of the tan δ peak is 20°C or more. The number of tan δ peaks expressed in the temperature range may generally be 1, or 2 or more, and in the case where 2 or more peaks are expressed, it may refer to that the half-maximum width of one peak among the plurality of peaks is 20°C or more.

[0071] The full width at half maximum of the tanδ peak may be 20°C or more, preferably 25°C or more, and more preferably 30°C or more. In addition, the full width at half maximum may be 80°C at most, preferably 70°C or less. If the full width at half maximum is less than 20°C, there is a defect that the wet skid resistance is significantly reduced at the same glass transition temperature, and it is unlikely to achieve a full width at half maximum of more than 80°C. Even if it is achieved, phase separation will occur, which is inevitably accompanied by the defect of increased hysteresis at high temperatures, and there will be a defect that the fuel consumption performance is deteriorated.

[0072] In addition, the tan δ peak may be expressed at -100° C. to 100° C., preferably, -80° C. to 20° C., more preferably, -70° C. to 0° C. If the peak is expressed within the range, a more favorable effect of wear resistance can be expected.

[0073] The dynamic viscoelastic analysis of the Advanced Rheology Extension System corresponds to measuring tan δ according to temperature in the temperature range of -100°C to 100°C using a dynamic mechanical analyzer (TA Co., ARES-G2) in torsion mode at a frequency of 10 Hz, a strain of 0.5% and a heating rate of 5°C / min. In this case, the resulting graph is the tan δ value relative to temperature.

[0074] Repeating units from monomers

[0075] According to one embodiment of the present invention, the conjugated diene polymer has a repeating unit from a conjugated diene monomer as a main unit, and the conjugated diene monomer can be, for example, one or more selected from 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, isoprene, 3-butyl-1,3-octadiene, isoprene, 2-phenyl-1,3-butadiene and 2-halo-1,3-butadiene (halogen refers to a halogen atom).

[0076] In addition, in addition to the conjugated diene monomer, the conjugated diene polymer also contains an aromatic vinyl monomer, and may also contain repeating units derived therefrom, and the aromatic vinyl monomer may be, for example, selected from one or more of styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, 1-vinyl-5-hexylnaphthalene, 3-(2-pyrrolidinylethyl)styrene, 4-(2-pyrrolidinylethyl)styrene and 3-(2-pyrrolidinyl-1-methylethyl)-α-methylstyrene.

[0077] In another embodiment, the conjugated diene polymer may be a copolymer further comprising repeating units of diene monomers of 1 to 10 carbon atoms and repeating units of conjugated diene monomers. The repeating units from diene monomers may be repeating units from diene monomers different from the conjugated diene monomers, and the diene monomers different from the conjugated diene monomers may be, for example, 1,2-butadiene. If the conjugated diene polymer is a copolymer further comprising diene monomers, the conjugated diene polymer may comprise repeating units from diene monomers in an amount of greater than 0% by weight to 1% by weight, greater than 0% by weight to 0.1% by weight, greater than 0% by weight to 0.01% by weight, or greater than 0% by weight to 0.001% by weight, and within this range, the effect of preventing gel formation may be obtained.

[0078] According to one embodiment of the present invention, if two or more monomers are included in the chain of the conjugated diene polymer, a chain structure of an intermediate type of a random copolymer and a block copolymer can be formed, and in this case, the microstructure can be easily controlled and the effect of a balance between excellent physical properties can be obtained. A random copolymer may refer to a random arrangement of repeating units forming the copolymer.

[0079] Glass transition temperature of polymers

[0080] According to one embodiment of the present invention, the glass transition temperature of the modified conjugated diene-based polymer may be -100° C. to 20° C. The glass transition temperature is a value that varies according to the microstructure of the polymer, but in order to improve wear resistance, the polymer is preferably prepared to satisfy the range, more preferably, -100° C. to 0° C., more preferably, -90° C. to -10° C., and still more preferably, -80° C. to -20° C.

[0081] The glass transition temperature can be flexibly controlled according to the polymerization method and polymerization conditions by the bonding method (1,2-bonding or 1,4-bonding) of the conjugated diene monomer in the polymer unit, the presence or absence of repeating units derived from the aromatic vinyl monomer, the content of repeating units derived from the aromatic vinyl monomer, and the microstructure in each unit (1,2-vinyl bond content and styrene bond content).

[0082] For example, the conjugated diene polymer may contain 0% to 50% by weight, specifically, 0% to 45% by weight, preferably, 0% to 30% by weight of repeating units from aromatic vinyl monomers, where 0% by weight of repeating units from aromatic vinyl monomers means that repeating units from aromatic vinyl monomers are not included, and the polymer is composed only of conjugated diene monomers. In addition, relative to 100 parts by weight of the modified conjugated diene polymer, the 1,2-vinyl bond content may be 10 to 80 parts by weight, preferably, 20 to 60 parts by weight, and more preferably, 20 to 50 parts by weight. If the microstructure is controlled like this, it can be expected to improve wear resistance and wet skid resistance in a balanced manner, and have excellent tensile properties and fuel consumption performance.

[0083] Modified conjugated diene polymers

[0084] According to one embodiment of the present invention, there is provided a modified conjugated diene polymer, comprising a repeating unit derived from a conjugated diene monomer and a functional group derived from a modifier, wherein, in a tan δ diagram according to temperature obtained by dynamic viscoelastic analysis of an advanced rheological extension system (ARES), the full width at half maximum (FWHM) value of the tan δ peak exhibited in the temperature range of -100°C to 100°C is 20°C or more, and the advanced rheological extension system uses a dynamic mechanical analyzer to measure in a torsional mode under the conditions of a frequency of 10 Hz, a strain of 0.5% and a heating rate of 5°C / min.

[0085] The description about the tan δ peak has been provided in the above-mentioned conjugated diene-based polymer, and the description thereof will be omitted.

[0086] Si content and N content of polymer

[0087] Meanwhile, the modified conjugated diene polymer according to one embodiment of the present invention is based on the gross weight of polymer, and Si content and N content can be 50ppm or more, or 50ppm to 1000ppm respectively. The lower limit can be preferably 100ppm or more and 150ppm or more, and the upper limit can be preferably 700ppm or less, preferably 500ppm or less. Within these ranges, the mechanical properties such as tensile properties and viscoelastic properties of the rubber composition comprising the modified conjugated diene polymer can be excellent. Meanwhile, due to the introduction of compounds with modified functional groups, such as modifiers, modified initiators and modified monomers to be described later, therefore, Si and N can come from them.

[0088] Alkoxysilane modifiers

[0089] According to one embodiment of the present invention, the modified conjugated diene polymer contains a functional group from a modifier, and the modifier is used to modify the terminal of the polymer, and specifically, it can be an alkoxysilane modifier as a modifier with affinity to silica. The modifier with affinity to silica can refer to a modifier containing a functional group with affinity to silica in a compound used as a modifier, and the functional group with affinity to silica can refer to a functional group with excellent affinity to a filler, specifically, a silica filler, and can interact with the silica filler and the functional group from the modifier.

[0090] The modifier can be an alkoxysilane modifier, specifically, an alkoxysilane modifier comprising one or more heteroatoms including nitrogen atoms, oxygen atoms and sulfur atoms. If an alkoxysilane compound is used as a modifier, then by the substitution reaction between the anion active part at one end of the active polymer and the alkoxy group of the alkoxysilane modifier, one end of the active polymer can be modified to a state bonded with a silyl group, thus, the affinity of the modified conjugated diene polymer and the inorganic filler can be increased by the functional group from the modifier present at one end of the polymer unit, and the viscoelastic properties of the rubber composition comprising the modified conjugated diene polymer can be improved. In addition, if the alkoxysilane compound includes a nitrogen atom, then in addition to the effect of the silyl group, the additional effect of the improved physical properties due to the nitrogen atom can also be expected. In order to best embody this effect, it is preferred to apply a compound comprising a N-functional group.

[0091] According to one embodiment of the present invention, the modifier may include a compound represented by Formula 1 below.

[0092] [Formula 1]

[0093]

[0094] In formula 1, R 1 It can be a single bond or an alkylene group of 1 to 10 carbon atoms, R 2 and R 3 may be independently an alkyl group of 1 to 10 carbon atoms, R 4 can be hydrogen; an alkyl group of 1 to 10 carbon atoms; a divalent, trivalent or tetravalent alkylsilyl group substituted by an alkyl group of 1 to 10 carbon atoms; or a heterocyclic ring of 2 to 10 carbon atoms, R 21 It may be a single bond, an alkylene group of 1 to 10 carbon atoms, or -[R 42 O] j -, where R 42 The alkylene group may be an alkylene group of 1 to 10 carbon atoms, a and m may each independently be an integer selected from 1 to 3, n may be an integer of 0, 1 or 2, and j may be an integer selected from 1 to 30.

[0095] In a specific embodiment, in Formula 1, R 1 It can be a single bond or an alkylene group of 1 to 5 carbon atoms, R 2 and R 3 can be independently hydrogen or an alkyl group of 1 to 5 carbon atoms, R 4 It can be hydrogen, an alkyl group of 1 to 5 carbon atoms, a tetravalent alkylsilyl group substituted by an alkyl group of 1 to 5 carbon atoms, or a heterocyclic group of 2 to 5 carbon atoms, R 21 It can be a single bond, an alkylene group of 1 to 5 carbon atoms, or -[R 42 O] j -, where R 42 It can be an alkylene group with 1 to 5 carbon atoms, a can be an integer of 2 or 3, m can be an integer selected from 1 to 3, n can be an integer of 0, 1 or 2, wherein m+n=3 can be satisfied, and j can be an integer selected from 1 to 10.

[0096] In formula 1, if R 4 is a heterocyclic group, the heterocyclic group may be unsubstituted or substituted by a trisubstituted alkoxysilyl group, if the heterocyclic ring is substituted by a trisubstituted alkoxysilyl group, the trisubstituted alkoxysilyl group may be substituted by connecting the heterocyclic ring to an alkylene group having 1 to 10 carbon atoms, and the trisubstituted alkoxysilyl group may refer to an alkoxysilyl group substituted by an alkoxy group having 1 to 10 carbon atoms.

[0097] In a more specific embodiment, the compound represented by Formula 1 can be selected from 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)propyl)-methyl-1-amine, N,N-bis(3-(triethoxysilyl)propyl)-methyl-1-amine, N,N-diethyl-3-(trimethoxysilyl)propyl)-methyl-1-amine, 1-trimethylsilylamine, N,N-bis(3-(1H-imidazol-1-yl)propyl)-(triethoxysilyl)methan-1-amine, N,N-diethyl-3-(triethoxysilyl)propan-1-amine, tris(trimethoxysilyl)amine, tris(3-(trimethoxysilyl)propyl)amine, N,N-bis(3-(diethoxy(methyl)silyl)propyl)-1,1,1-trimethylsilylamine, N,N-bis(3-(1H-imidazol-1-yl)propyl)-(triethoxysilyl)methan-1-amine, N-(3-(1H-1,2,4-triazol-1-yl)propyl)- 3-(Trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine, 3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)-N-(3-(1-(3-(trimethoxysilyl)propyl)-1H-1,2,4-triazol-3-yl)propyl)propan-1-amine, N,N-bis(2-(2-methoxyethoxy)ethyl)-3-(triethoxysilyl)propan-1-amine, N,N-bis(3-(triethoxysilyl)ethyl) The invention can be selected from the group consisting of N-(2,5,8,11,14-pentaoxahexadecan-16-yl)-N-(3-(triethoxysilyl)propyl)-2,5,8,11,14-pentaoxahexadecan-16-amine, N-(2,5,8,11,14-pentaoxahexadecan-16-yl)-N-(3-(triethoxysilyl)propyl)-2,5,8,11,14-pentaoxahexadecan-16-amine and N-(3,6,9,12-tetraoxahexadecan-1-amine)-N-(3-(triethoxysilyl)propyl)-3,6,9,12-tetraoxahexadecan-1-amine.

[0098] In another embodiment, the modifier may include a compound represented by Formula 2 below.

[0099] [Formula 2]

[0100]

[0101] In formula 2, R 5 , R 6 and R 9 may be independently an alkylene group having 1 to 10 carbon atoms, R 7 , R 8 , R 10 and R 11 may be independently an alkyl group of 1 to 10 carbon atoms, R 12It can be hydrogen or an alkyl group of 1 to 10 carbon atoms, b and c can each independently be 0, 1, 2 or 3, wherein b+c≥1 can be satisfied, and A can be Among them, R 13 , R 14 , R 15 and R 16 Each independently may be hydrogen or an alkyl group of 1 to 10 carbon atoms.

[0102] In a specific embodiment, the compound represented by Formula 2 can be one selected from N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine and 3-(4,5-dihydro-1H-imidazol-1-yl)-N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine.

[0103] In another embodiment, the modifier may include a compound represented by Formula 3 below.

[0104] [Formula 3]

[0105]

[0106] In formula 3, A 1 and A 2 may be each independently a divalent hydrocarbon group of 1 to 20 carbon atoms containing or not containing an oxygen atom, R 17 To R 20 may be each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms, L 1 To L 4 may be each independently a divalent, trivalent or tetravalent alkylsilyl group substituted by an alkyl group having 1 to 10 carbon atoms, or a monovalent hydrocarbon group having 1 to 20 carbon atoms, wherein L 1 and L 2 and L 3 and L 4 may each be combined with each other to form a ring of 1 to 5 carbon atoms, and if L 1 and L 2 and L 3 and L 4 Each is combined with each other to form a ring, and the ring thus formed may include one to three kinds of one or more types of hetero atoms selected from N, O and S.

[0107] In a specific embodiment, in Formula 3, A 1 and A 2 may be independently an alkylene group having 1 to 10 carbon atoms, R 17 To R 20may be independently an alkyl group of 1 to 10 carbon atoms, L 1 To L 4 may be each independently a tetravalent alkylsilyl group substituted by an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 10 carbon atoms, wherein L 1 and L 2 and L 3 and L 4 can each be combined with each other to form a ring of 1 to 3 carbon atoms, and if L 1 and L 2 and L 3 and L 4 Each is combined with each other to form a ring, and the ring thus formed may include one to three kinds of one or more types of hetero atoms selected from N, O and S.

[0108] In a more specific embodiment, the compound represented by Formula 3 may be selected from 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropane-1-amine), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropane-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropane-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropane-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropane-1-amine), ,N-dipropylpropane-1-amine), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropane-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diethylpropane-1-amine), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropane-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropane-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropane-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-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-diethylmethane-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethane-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-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), -tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethane-1-amine), 3,3'-(1,1,3,3-tetraethoxydisiloxane-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)silaneamine, N,N'-((1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1-Trimethyl-N-(trimethylsilyl)silaneamine, N,N'-((1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silaneamine, N,N'-((1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilaneamine), N,N'-((1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1 ,1-trimethyl-N-phenylsilaneamine), N,N'-((1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilaneamine), 1,3-bis(3-(1H-imidazol-1-yl)propyl)-1,1,3,3-tetramethoxydisiloxane, 1,3-bis(3-(1H-imidazol-1-yl)propyl)-1,1,3,3-tetraethoxydisiloxane and 1,3-bis(3-(1H-imidazol-1-yl)propyl)-1,1,3,3-tetrapropoxydisiloxane. ,

[0109] In another embodiment, the modifier may include a compound represented by Formula 4 below.

[0110] [Formula 4]

[0111]

[0112] In formula 4, R 22 and R 23 may be each independently an alkylene group having 1 to 20 carbon atoms or -R 28 [OR 29 ] f -, R 24 To R 27 may be each independently an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, R 28 and R 29 may be independently an alkylene group having 1 to 20 carbon atoms, R 47 and R 48 may each independently be a divalent hydrocarbon group of 1 to 6 carbon atoms, d and e may each independently be 0 or an integer selected from 1 to 3, wherein d+e may be an integer greater than 1, and f may be an integer of 1 to 30.

[0113] Specifically, in Formula 4, R 22 and R 23 may be each independently an alkylene group of 1 to 10 carbon atoms or -R 28 [OR 29 ]f -, R 24 To R 27 may be independently an alkyl group of 1 to 10 carbon atoms, R 28 and R 29 may each independently be an alkylene group of 1 to 10 carbon atoms, d and e may each independently be 0 or an integer selected from 1 to 3, wherein d+e may be an integer greater than 1, and f may be an integer of 1 to 30.

[0114] More specifically, the compound represented by Formula 4 may be a compound represented by the following Formula 4a, Formula 4b, or Formula 4c.

[0115] [Formula 4a]

[0116]

[0117] [Formula 4b]

[0118]

[0119] [Formula 4c]

[0120]

[0121] In Formula 4a, Formula 4b and Formula 4c, R 22 To R 27 , d and e are the same as described above.

[0122] In a more specific embodiment, the compound represented by Formula 4 may be selected from 1,4-bis(3-(3-(triethoxysilyl)propoxy)propyl)piperazine, 1,4-bis(3-(triethoxysilyl)propyl)piperazine, 1,4-bis(3-(trimethoxysilyl)propyl)piperazine, 1,4-bis(3-(dimethoxymethylsilyl)propyl)piperazine, 1-(3-(ethoxydimethylsilyl)propyl)-4-(3-(triethoxysilyl)propyl)piperazine, 1-(3-(ethoxydimethylsilyl)propyl)-4-(3-(triethoxysilyl)propyl)piperazine, One of 1-(triethoxysilyl)methyl)piperazine, 1-(3-(ethoxydimethyl)methyl)-4-(3-(triethoxysilyl)propyl)piperazine, 1,3-bis(3-(triethoxysilyl)propyl)imidazolidine, 1,3-bis(3-(dimethoxyethylsilyl)propyl)imidazolidine, 1,3-bis(3-(trimethoxysilyl)propyl)hexahydropyrimidine, 1,3-bis(3-(triethoxysilyl)propyl)hexahydropyrimidine and 1,3-bis(3-(tributoxysilyl)propyl)-1,2,3,4-tetrahydropyrimidine.

[0123] In another embodiment, the modifier may include a compound represented by Formula 5 below.

[0124] [Formula 5]

[0125]

[0126] In Formula 5, R 30 It can be a monovalent hydrocarbon group having 1 to 30 carbon atoms, R 31 To R 33 may be independently an alkylene group having 1 to 10 carbon atoms, R 34 To R 37 Each may independently be an alkyl group of 1 to 10 carbon atoms, and g and h may each independently be 0 or an integer selected from 1 to 3, wherein g+h may be an integer of 1 or more.

[0127] In another embodiment, the modifier may include a compound represented by Formula 6 below.

[0128] [Formula 6]

[0129]

[0130] In formula 6, A 3 and A 4 may be independently an alkylene group having 1 to 10 carbon atoms, R 38 To R 41 Each independently may be an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and i may be an integer of 1 to 30.

[0131] In another embodiment, the modifier may include one or more selected from 3,4-bis(2-methoxyethoxy)-N-(4-(triethoxysilyl)butyl)aniline, N,N-diethyl-3-(7-methyl-3,6,8,11-tetraoxa-7-silatridec-7-yl)propane-1-amine, 2,4-bis(2-methoxyethoxy)-6-((trimethylsilyl)methyl)-1,3,5-triazine and 3,14-dimethoxy-3,8,8,13-tetramethyl-2,14-dioxa-7,9-dithia-3,8,13-trisilopentadecane.

[0132] In another embodiment, the modifier may include a compound represented by Formula 7 below.

[0133] [Formula 7]

[0134]

[0135] In formula 7, R 43 , R 45 and R 46may be independently an alkyl group of 1 to 10 carbon atoms, R 44 The alkylene group may be an alkylene group having 1 to 10 carbon atoms, and k may be an integer selected from 1 to 4.

[0136] In a more specific embodiment, the compound represented by Formula 7 may be selected from 8,8-dibutyl-3,13-dimethoxy-3,13-dimethyl-2,14-dioxa-7,9-dithia-3,13-disila-8-stanpentadecane, 8,8-dimethyl-3,13-dimethoxy-3,13-dimethyl-2,14-dioxa-7,9-dithia-3,13-disila-8 -Stannum pentadecane, 8,8-dibutyl-3,3,13,13-tetramethoxy-2,14-dioxa-7,9-dithia-3,13-disila-8-stannum pentadecane and 8-butyl-3,3,13,13-tetramethoxy-8-((3-(trimethoxysilyl)propyl)thio)-2,14-dioxa-7,9-dithia-3,13-disila-8-stannum pentadecane.

[0137] In another embodiment, the modifier may include a compound represented by Formula 8 below.

[0138] [Formula 8]

[0139]

[0140] In formula 8, R b2 To R b4 are each independently an alkylene group having 1 to 10 carbon atoms, R b5 To R b8 are each independently an alkyl group having 1 to 10 carbon atoms, R b13 and R b14 are each independently an alkylene group having 1 to 10 carbon atoms, R b15 To R b18 Each is independently an alkyl group of 1 to 10 carbon atoms, and m1, m2, m3 and m4 are each independently an integer of 1 to 3.

[0141] In another embodiment, the modifier may include a compound represented by Formula 9 below.

[0142] [Formula 9]

[0143]

[0144] In formula 9, R e1 and R e2 are each independently an alkylene group having 1 to 10 carbon atoms, R e3 To R e6 are each independently hydrogen, an alkyl group of 1 to 10 carbon atoms, or -Re7 S i e8 R e9 R e10 , where R e3 To R e6 At least one of them is -R e7 S i e8 R e9 R e10 , where R e7 is a single bond or an alkylene group of 1 to 10 carbon atoms, R e8 To R e10 are each independently an alkyl group of 1 to 10 carbon atoms or an alkoxy group of 1 to 10 carbon atoms, wherein R e8 To R e10 At least one of the groups is an alkoxy group having 1 to 10 carbon atoms.

[0145] In another embodiment, the modifier may include a compound represented by Formula 10 below.

[0146] [Formula 10]

[0147]

[0148] In Formula 10, X is O or S, R f1 and R f2 are each independently a single bond or an alkylene group of 1 to 10 carbon atoms,

[0149] R f3 To R f8 are each independently hydrogen, an alkyl group of 1 to 10 carbon atoms, an alkoxy group of 1 to 10 carbon atoms, an aryl group of 6 to 10 carbon atoms, a cycloalkyl group of 5 to 10 carbon atoms, or an aralkyl group of 7 to 14 carbon atoms, and p is an integer of 0 or 1, wherein if p is 0, then R f1 It is an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

[0150] In another embodiment, the modifier may include a compound represented by Formula 11 below.

[0151] [Formula 11]

[0152]

[0153] In formula 11, R g1 To R g4 are each independently hydrogen, an alkyl group of 1 to 10 carbon atoms, an alkoxy group of 1 to 10 carbon atoms, an aryl group of 6 to 12 carbon atoms, or -R g5 S O g6 , where R g1 To R g4At least one of them is -R g5 S O g6 , where R g5 is a single bond or an alkylene group of 1 to 10 carbon atoms, R g6 is an alkyl radical of 1 to 10 carbon atoms, Y is C or N, wherein, if Y is N, then R g4 Does not exist.

[0154] In another embodiment, the modifier may include a compound represented by Formula 12 below.

[0155] [Formula 12]

[0156]

[0157] In formula 12, R h1 and R h2 are each independently an alkyl group of 1 to 10 carbon atoms or an alkoxy group of 1 to 10 carbon atoms, R h3 is a single bond or an alkylene group of 1 to 10 carbon atoms, A3 is -Si(R h4 R h5 R h6 ) or -N[Si(R h7 R h8 R h9 )]2, where R h4 To R h9 Each is independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

[0158] In another embodiment, the modifier may include a compound represented by Formula 13 below.

[0159] [Formula 13]

[0160]

[0161] In formula 13, R g1 To R g3 are each independently an alkyl group of 1 to 10 carbon atoms or an alkoxy group of 1 to 10 carbon atoms, R g4 is an alkoxy group having 1 to 10 carbon atoms, and q is an integer of 2 to 100.

[0162] Shrinkage Factor

[0163] The conjugated diene-based polymer according to one embodiment of the present invention has a shrinkage factor (g′) of 0.1 or more, preferably 0.1 to 1.0, and more specifically 0.3 to 0.9, as measured by gel permeation chromatography-light scattering method equipped with a viscosity detector.

[0164] Here, the shrinkage factor (g') measured by the gel permeation chromatography-light scattering method is the ratio of the intrinsic viscosity of the branched polymer with the same absolute molecular weight to the intrinsic viscosity of the linear polymer, and can be used as an index of the branched structure of the branched polymer, that is, an index of the ratio occupied by the branch. For example, according to the decrease in the shrinkage factor, the number of branches of the corresponding polymer tends to increase, and therefore, in the case of comparing polymers with the same absolute molecular weight, as the branch increases, the shrinkage factor decreases, and the shrinkage factor can be used as an index of the degree of branching.

[0165] In addition, the shrinkage factor is obtained by measuring a chromatogram using a gel chromatography-light scattering measuring device equipped with a viscosity detector, and calculating based on solution viscosity and light scattering method, specifically, using a GPC-light scattering measuring device equipped with a light scattering detector, in which two columns using a polystyrene-based gel as a filler are connected, and a viscosity detector to obtain an absolute molecular weight and an intrinsic viscosity corresponding to each absolute molecular weight, calculating the intrinsic viscosity of a linear polymer corresponding to the absolute molecular weight, and obtaining the ratio of the intrinsic viscosity corresponding to each absolute molecular weight as the shrinkage factor. For example, the shrinkage factor is shown in the following manner: the absolute molecular weight is obtained by the light scattering detector by injecting a sample into a GPC-light scattering measuring device (Viscotek TDAmax, Malvern Co.) equipped with a light scattering detector and a viscosity detector, the intrinsic viscosity [η] for the absolute molecular weight is obtained by the light scattering detector and the viscosity detector, the intrinsic viscosity [η]0 of the linear polymer for the absolute molecular weight is calculated by the following mathematical equation 1, and the average value of the ratio of the intrinsic viscosity corresponding to each absolute molecular weight ([η] / [η]0) is shown as the shrinkage factor. In this case, a mixed solution of tetrahydrofuran and N,N,N',N'-tetramethylethylenediamine (controlled by mixing 20 mL of N,N,N',N'-tetramethylethylenediamine with 1 L of tetrahydrofuran) was used as an eluent, PL Olexis (Agilent Co.) was used as a column, and measurement was performed under the conditions of an oven temperature of 40°C and a flow rate of 1.0 mL / min, and a sample was prepared by dissolving 15 mg of a polymer in 10 mL of THF.

[0166] [Mathematical equation 1]

[0167] [η]0=10 -3.883 M 0.771

[0168] In mathematical equation 1, M is the absolute molecular weight.

[0169] In addition, the vinyl content of the modified conjugated diene polymer may be 5 wt % or more, 10 wt % or more, or 10 wt % to 60 wt %. Here, the vinyl content may refer to the amount of the conjugated diene monomer that is not 1,4-added but 1,2-added based on 100 wt % of the conjugated diene polymer composed of the monomer having a vinyl group and the aromatic vinyl monomer.

[0170] Mooney stress relaxation rate

[0171] In another embodiment, the Mooney stress relaxation rate of the modified conjugated diene polymer measured at 100° C. may be less than 0.7, and may be 0.7 to 3.0. Specifically, in the case of a branched polymer with a large degree of branching, the Mooney stress relaxation rate may be less than 0.7, preferably, 0.6 or less, more preferably, 0.5 or less, and optimally 0.4 or less, and in the case of a linear polymer with a small degree of branching, the Mooney stress relaxation rate may preferably be 0.7 to 2.5, more preferably, 0.7 to 2.0.

[0172] Here, the Mooney stress relaxation rate represents the stress change shown as a response to the same amount of strain, and can be measured using a Mooney viscometer. Specifically, the Mooney stress relaxation rate is obtained as follows: using a large rotor of Monsanto Co.'s MV2000E at 100°C and a rotor speed of 2±0.02rpm, by placing the polymer at room temperature (23±5°C) for more than 30 minutes, collecting 27±3g of the polymer and placing it in a mold cavity, applying torque by operating a platen and measuring the Mooney viscosity, and measuring the slope value of the change in the Mooney viscosity exhibited when the torque is released.

[0173] At the same time, the Mooney stress relaxation rate can be used as an index of the branched structure of the corresponding polymer. For example, in the case of comparing polymers having the same Mooney viscosity, as branching increases, the Mooney stress relaxation rate decreases and can be used as an index of the degree of branching.

[0174] Other properties of polymers

[0175] The (modified) conjugated diene polymer according to one embodiment of the present invention may include a functional group derived from a modified initiator at another terminal other than the terminal including the functional group derived from the modifier, and in this case, the modified initiator may be a reaction product of an N-functional group-containing compound and an organic metal compound.

[0176] Specifically, the N-functional group-containing compound can be a substituted or unsubstituted aromatic hydrocarbon compound containing an N-functional group, wherein the N-functional group includes an amino group, an amide group, an imidazole group, an imidazolyl group, a pyrimidine group or a cyclic amino group, and the substituent can be an alkyl group of 1 to 20 carbon atoms, a cycloalkyl group of 3 to 20 carbon atoms, an aryl group of 6 to 20 carbon atoms, an alkylaryl group of 7 to 20 carbon atoms, an arylalkyl group of 7 to 20 carbon atoms or an alkoxysilyl group of 1 to 10 carbon atoms.

[0177] According to one embodiment of the present invention, the weight average molecular weight (Mw) of the (modified) conjugated diene polymer measured by gel permeation chromatography (GPC) can be 300,000 g / mol to 3,000,000 g / mol, 400,000 g / mol to 2,500,000 g / mol or 500,000 g / mol to 2,000,000 g / mol, within this range, running resistance and anti-skid properties can be more excellent in a balanced manner.

[0178] In addition, the (modified) conjugated diene polymer according to one embodiment of the present invention can be a high molecular weight polymer with a weight average molecular weight of 800,000 g / mol or more, preferably, 1,000,000 g / mol or more, and therefore, a polymer with excellent tensile properties can be obtained, and if prepared by the above-mentioned preparation method, the extension effect of the polymer chain length and the control of the microstructure can be achieved.

[0179] The number average molecular weight (Mn) of the (modified) conjugated diene polymer can be 1,000 g / mol to 2,000,000 g / mol, 10,000 g / mol to 1,500,000 g / mol or 100,000 g / mol to 1,200,000 g / mol, and the number average molecular weight can be preferably 400,000 g / mol or more, more preferably 500,000 g / mol or more. In addition, the peak molecular weight (Mp) can be 1,000 g / mol to 3,000,000 g / mol, 10,000 g / mol to 2,000,000 g / mol or 100,000 g / mol to 2,000,000 g / mol. Within these ranges, excellent rolling resistance and anti-slip properties can be obtained.

[0180] In addition, the (modified) conjugated diene polymer may have a unimodal molecular weight distribution curve by gel permeation chromatography (GPC) and the molecular weight distribution may be 1.0 to 3.0, preferably, 1.0 to 2.5, more preferably, 1.0 to 2.0, and still more preferably, 1.0 to less than 1.7, and here, the unimodal curve shape and the molecular weight distribution can be satisfied simultaneously by continuous polymerization to be described later.

[0181] Generally, there is a problem that in continuous polymerization, the molecular weight distribution shows a single peak and is wide, the processing property is excellent, but the tensile property and viscoelastic properties are poor, and in batch polymerization, the molecular weight distribution shows a bimodal and narrow, the tensile property and viscoelastic properties are excellent, but the processing property is poor, and the productivity is low. However, if the preparation method according to one embodiment of the present invention to be described later is applied, the molecular weight distribution can be selectively reduced to the maximum even by continuous preparation, and therefore, the control of the balance between physical properties such as processing property, tensile property and viscoelastic property becomes easy.

[0182] In addition, the (modified) conjugated diene-based polymer according to one embodiment of the present invention needs to satisfy a Mooney viscosity measured under the conditions of ASTM D1646 of 40 to 140, preferably, 45 to 120. There may be many metrics for evaluating processability, but if the Mooney viscosity satisfies the above range, the processability may be very excellent.

[0183] The (modified) conjugated diene polymer according to one embodiment of the present invention specifies the polymer structure so that by controlling the microstructure of the polymer such as the above-mentioned styrene bond content and 1,2-vinyl bond content, there is a difference between the glass transition starting temperature and the end temperature, and by selectively controlling the weight-average molecular weight, the shape of the molecular weight distribution curve, the molecular weight distribution, the N and Si atom contents and the Mooney viscosity, the effect of improving the wear resistance and the wet skid resistance in a balanced manner can be expected while maintaining excellent tensile properties, fuel consumption performance and processing performance.

[0184] Preparation method of conjugated diene polymer

[0185] In order to prepare the conjugated diene-based polymer, the present invention provides a method for preparing the conjugated diene-based polymer as follows.

[0186] The method for preparing a conjugated diene polymer is characterized in that it is a continuous preparation method and comprises: polymerizing a conjugated diene monomer, or a conjugated diene monomer and an aromatic vinyl monomer, in the presence of a hydrocarbon solvent, a polymerization initiator and a polar additive (S1), wherein step (S1) is carried out in two or more polymerization reactors, when the polymerization conversion rate of the first reactor is 70% to 85%, the polymer is transported to the second reactor, and a polar additive, or a polar additive and a conjugated diene monomer, are additionally added to the second reactor.

[0187] The physical properties of the conjugated diene polymer, such as the viscoelastic behavior, have been described above, and the following description will focus mainly on the preparation method.

[0188] The hydrocarbon solvent is not particularly limited but may be, for example, one or more selected from n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene and xylene.

[0189] Based on 1.0 equivalent of monomer, the amount of the polymerization initiator can be 0.1 equivalent to 3.0 equivalents, preferably, 0.1 equivalent to 2.0 equivalents, more preferably, 0.5 equivalent to 1.5 equivalents. In another embodiment, based on a total of 100g of monomer, the amount of the polymerization initiator can be 0.01mmol to 10mmol, 0.05mmol to 5mmol, 0.1mmol to 2mmol, 0.1mmol to 1mmol or 0.15mmol to 0.8mmol. Here, a total of 100g of monomer can be a conjugated diene monomer, or the sum of a conjugated diene monomer and an aromatic vinyl monomer.

[0190] Meanwhile, the polymerization initiator may be an organic metal compound, for example, one or more selected from an organic lithium compound, an organic sodium compound, an organic potassium compound, an organic rubidium compound, and an organic cesium compound.

[0191] Specifically, the organometallic compound can be one or more selected from methyllithium, ethyllithium, propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, hexyllithium, n-decyllithium, tert-octyllithium, phenyllithium, 1-naphthyllithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, sodium naphthyl, potassium naphthyl, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide and isopropyl lithium amide.

[0192] In another embodiment, the polymerization initiator may be a modified initiator, and the modified initiator may be a reaction product of a compound containing an N functional group and an organic metal compound.

[0193] Step S1

[0194] According to one embodiment of the present invention, step (S1) in the preparation method is a step of carrying out the polymerization reaction of conjugated diene monomers, or conjugated diene monomers and aromatic vinyl monomers by, for example, anionic polymerization. In a specific embodiment, the anionic polymerization can be an active anionic polymerization in which an anionic active part is formed at the polymerization end by an anionic growth reaction. In addition, the polymerization of step (S1) can be heating polymerization, isothermal polymerization or constant temperature polymerization (adiabatic polymerization). Constant temperature polymerization may refer to a polymerization method including a step of polymerization using the heat generated by the reaction itself without optional heat supply after adding a polymerization initiator, heating polymerization may refer to a polymerization method including adding a polymerization initiator and then raising the temperature by optional heat supply, and isothermal polymerization may refer to a polymerization method in which the temperature of the polymer is kept constant by increasing heat or removing heat by heat supply after adding a polymerization initiator.

[0195] In addition, according to one embodiment of the present invention, the polymerization of step (S1) can be carried out by adding a diene compound of 1 to 10 carbon atoms in addition to the conjugated diene monomer, and in this case, the effect of preventing the formation of gel on the reactor wall during long-term operation can be achieved. The diene compound can be, for example, 1,2-butadiene.

[0196] In addition, according to one embodiment of the present invention, the polymerization of step (S1) is carried out in two or more polymerization reactors, and the polymerization conversion rate in the first polymerization reactor of the polymerization reactors may be 70% to 85%, 70% to 80%, or 70% to less than 80%. That is, the polymerization of step (S1) can only be carried out until the polymerization conversion rate in the first polymerization reactor becomes 70% or more, 70% to 85%, 70% to 80%, or 70% to less than 80%.

[0197] Within this range, side reactions occurring when a polymer is formed after initiating a polymerization reaction can be suppressed and the microstructure of the polymer can be easily controlled, so the half-maximum full width of the glass transition temperature peak in dynamic mechanical analysis becomes broad, thereby providing a basis for improving wear resistance.

[0198] The polymerization in the first reactor can be carried out, for example, at a temperature range of below 80°C, -20°C to 80°C, 0°C to 80°C, 0°C to 70°C or 10°C to 70°C, within which the molecular weight distribution of the polymer can be controlled to be narrow and an excellent effect of improving physical properties can be obtained.

[0199] According to one embodiment of the present invention, step (S1) is carried out in two or more reactors, and after polymerization is carried out until the above-mentioned conversion rate in the first reactor is reached, the polymer is transported to the second reactor, and a polar additive or a conjugated diene monomer may be further added to the second reactor.

[0200] In this case, the polar additive or the polar additive and the conjugated diene monomer added additionally may be injected at once or sequentially, and may be added in batches at different points in the range, or continuously in the range.

[0201] The additional addition of polar additives, or polar additives and conjugated diene monomers, can be a means for achieving glass transition temperature properties of the prepared polymer and for controlling the conversion rate in the first reactor. By additionally adding polar additives, energy can be further applied to the polymerization reaction after a certain conversion rate, thereby producing deformation of the microstructure.

[0202] Specifically, in the case of homopolymerizing conjugated diene monomers, the polar additive can control the ratio of 1,2-bonds and 1,4-bonds by controlling the reaction rate, and in the case of copolymerizing conjugated diene monomers and aromatic vinyl monomers, the reaction rate difference between the monomers can be corrected to show an induction effect that easily forms a random copolymer.

[0203] In this case, the polar additive added can be used in an appropriate amount in a direction in which the half-maximum full width of the stress change peak can be widened. For example, based on a total of 100g of the monomer used when initiating polymerization, the polar additive added can be used in a ratio of 0.001g to 10g, or 0.01g to 1.0g, more preferably, 0.02g to 0.5g.

[0204] In addition, based on 100g of the monomer used when initiating polymerization, the amount of the conjugated diene monomer optionally added can be 5g to 25g, or 5g to 20g. If the polar additive or conjugated diene monomer added is controlled to the above amount, there are the following advantages: the control of the glass transition temperature peak during dynamic mechanical analysis can be easy, more refined control can be performed, and the full width at half maximum of the peak can be widened.

[0205] The total amount of the polar additive used in the polymerization of step (S1) may be 0.001 g to 50 g, or 0.002 g to 1.0 g, based on a total of 100 g of monomer. In another embodiment, the total amount of the polar additive may be greater than 0 g to 1 g, 0.01 g to 1 g, or 0.1 g to 0.9 g, based on a total of 100 g of polymerization initiator. Here, the total amount of the polar additive includes the additional amount of the polar additive.

[0206] The polymerization in the second reactor can be carried out in the temperature range of below 80°C, -20°C to 80°C, 0°C to 80°C, 0°C to 70°C or 10°C to 70°C, and within this range, the molecular weight distribution of the polymer can be controlled to be narrow and an excellent effect of improving physical properties can be obtained.

[0207] Meanwhile, when the full width at half maximum of the glass transition temperature peak is additionally controlled by dynamic mechanical analysis, the polymerization temperatures in the first reactor and the second reactor are also affected, and in this case, the polymerization temperature of the second reactor is preferably controlled to be lower than the polymerization temperature of the first reactor, and the polymerization temperature of the second reactor is preferably above 60°C.

[0208] The polar additive may be, for example, one or more selected from tetrahydrofuran, 2,2-bis(2-tetrahydrofuranyl)propane, diethyl ether, cyclopentyl ether, dipropyl ether, ethylene glycol methyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tert-butoxyethoxyethane, bis(3-dimethylaminoethyl)ether, (dimethylaminoethyl)ethyl ether, trimethylamine, triethylamine, tripropylamine, N,N,N',N'-tetramethylethylenediamine, sodium menthol and 2-ethyltetrahydrofuranyl ether, and may preferably be 2,2-bis(2-tetrahydrofuranyl)propane, triethylamine, tetramethylethylenediamine, sodium menthol or 2-ethyltetrahydrofuranyl ether.

[0209] Meanwhile, the polymerization conversion rate can be determined by, for example, measuring the solid concentration in the polymer solution phase containing the polymer during the polymerization process. In a specific embodiment, in order to ensure the polymer solution, a cylindrical container is installed at the outlet of each polymerization reactor to fill a certain amount of polymer solution in the cylindrical container, and then, the cylindrical container is separated from the reactor, the weight (A) of the cylinder filled with the polymer solution is measured, the polymer solution filled in the cylindrical container is transferred to an aluminum container, for example, an aluminum pan, the weight (B) of the cylindrical container from which the polymer solution is removed is measured, the aluminum container containing the polymer solution is dried in an oven at 140° C. for 30 minutes, the weight (C) of the dried polymer is measured, and the calculation is performed according to the following mathematical equation 2:

[0210] [Mathematical equation 2]

[0211]

[0212] In mathematical equation 2, the total solid content is the total solid (monomer) content in the polymer solution separated from each reactor, and is the weight percentage of the solid content relative to 100% of the polymer solution. For example, if the total solid content is 20% by weight, it can be calculated by substituting 20 / 100, that is, 0.2 in mathematical equation 2.

[0213] At the same time, the polymer polymerized in the second reactor can be sequentially transported to the final polymerization reactor, and polymerization can be performed until the final polymerization conversion becomes more than 95%. After polymerization in the second reactor, the polymerization conversion of each reactor from the third reactor to the final polymerization reactor can be appropriately controlled to control the molecular weight distribution. Afterwards, a reaction terminator that deactivates the activated part can be injected, and in the case of preparing a modified conjugated diene polymer, the active polymer can be transported to the modification reaction process, and the reaction terminator can use any material commonly used in this technical field without limitation.

[0214] In addition, the living polymer prepared by step (S1) may refer to a polymer in which a polymer anion is bonded to an organic metal cation of a polymerization initiator.

[0215] Preparation method of modified conjugated diene polymer

[0216] According to one embodiment of the present invention, a method for preparing a modified conjugated diene polymer is provided, characterized in that it also includes step (S2): in the method for preparing a conjugated diene polymer, a polymer that maintains the activity of the polymer prepared in step (S1) is reacted with a modifier.

[0217] In the method for preparing the modified conjugated diene-based polymer, the method for preparing the living polymer is the same as step (S1) of the conjugated diene-based polymer, and the description thereof will be omitted.

[0218] Step S2

[0219] Step (S2) is a modification step in which the active polymer is reacted with a modifier while the active state of the polymer prepared in step (S1) is maintained, and the anionic active part of the active polymer and the alkoxy group bonded to the silane of the modifier can react. Based on a total of 100g of monomer, the amount of the modifier can be 0.01mmol to 10mmol. In another embodiment, based on 1mol of the polymerization initiator in step (S1), the modifier can be used in a molar ratio of 1:0.1 to 10, 1:0.1 to 5 or 1:0.1 to 1:3.

[0220] In addition, according to one embodiment of the present invention, the modifier can be injected into the modification reactor, and step (S2) can be carried out in the modification reactor. In another embodiment, the modifier can be injected into the delivery section for delivering the active polymer prepared in step (S1) to the modification reactor for carrying out step (S2), and the active polymer can be reacted by mixing the modifier in the delivery section. In this case, the reaction can be a modification reaction for making the modifier and the active polymer simply coupled, or a coupling reaction for connecting the active polymer based on the modifier.

[0221] At the same time, in the preparation method of the modified conjugated diene polymer, before the modification reaction of step (S2), a step of injecting a conjugated diene monomer into the active polymer prepared in step (S1) and reacting the conjugated diene monomer may also be performed. In this case, the subsequent modification reaction may become more favorable. In this case, based on 1 mol of the active polymer, 1 mol to 100 mol of the conjugated diene monomer may be injected.

[0222] The preparation method of the modified conjugated diene polymer according to one embodiment of the present invention is a method that can satisfy the properties of the above-mentioned modified conjugated diene polymer, and as mentioned above, if the properties are satisfied, the effects to be achieved in the present invention can be achieved, but by differently controlling other polymerization conditions, the physical properties of the modified conjugated diene polymer according to the present invention can be obtained.

[0223] Rubber composition

[0224] According to the present invention, there is provided a rubber composition comprising the conjugated diene-based polymer or the modified conjugated diene-based polymer.

[0225] The rubber composition may contain 10 wt % or more, 10 wt % to 100 wt % or 20 wt % to 90 wt % of the (modified) conjugated diene polymer, and within this range, mechanical properties such as tensile strength and wear resistance are excellent, and an effect of excellent balance between physical properties can be achieved.

[0226] In addition, in addition to the (modified) conjugated diene polymer, the rubber composition may further include other rubber components as required, and in this case, based on the total weight of the rubber composition, the rubber component may be included in an amount of 90% by weight or less. In a specific embodiment, based on 100 parts by weight of the (modified) conjugated diene copolymer, the content of other rubber components may be 1 part by weight to 900 parts by weight.

[0227] The rubber component may be, for example, a natural rubber or a synthetic rubber, and may specifically be a natural rubber (NR), including cis-1,4-polyisoprene; a modified natural rubber obtained by modifying or purifying a conventional natural rubber, such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR) and hydrogenated natural rubber; and a synthetic rubber, such as styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, polyisobutylene-co-isoprene, chloroprene rubber, 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, polyurethane rubber, silicone rubber, epichlorohydrin rubber and halogenated butyl rubber, and any one of them or a mixture of two or more thereof may be used.

[0228] Based on 100 parts by weight of the (modified) conjugated diene polymer of the present invention, the rubber composition may contain 0.1 to 200 parts by weight or 10 to 120 parts by weight of filler. The filler may be, for example, a silica filler, specifically, wet silica (hydrated silicate), dry silica (anhydrous silicate), calcium silicate, aluminum silicate, colloidal silica, etc., and preferably, the filler may be wet silica having the most significant improvement effect on damage characteristics and a compatible effect on wet road adhesion. In addition, as required, the rubber composition may also contain a carbon filler.

[0229] In another embodiment, if silica is used as a filler, a silane coupling agent can be used together to improve the reinforcement and low exothermic properties. Specific examples of the silane coupling agent may include: bis(3-triethoxysilylpropyl)tetrasulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, Formyl tetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzoyl tetrasulfide, 3-triethoxysilylpropylmethacrylate monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, bis(3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide or dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide, and any one of them or a mixture of two or more thereof may be used. Preferably, bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazolyl tetrasulfide may be used in consideration of the improvement effect of reinforcing properties.

[0230] In addition, in the rubber composition according to one embodiment of the present invention, since a modified conjugated diene polymer having a functional group having a high affinity with silica is introduced into an active site as a rubber component, the mixing amount of the silane coupling agent can be smaller than in conventional cases. Therefore, the amount of the silane coupling agent can be 1 to 20 parts by weight or 5 to 15 parts by weight based on 100 parts by weight of silica, and within the above range, the effect as a coupling agent can be fully exhibited, and the effect of preventing gelation of the rubber component can be obtained.

[0231] The rubber composition according to one embodiment of the present invention may be sulfur cross-linkable and may further include a vulcanizing agent. The vulcanizing agent may specifically be sulfur powder, and the content may be 0.1 to 10 parts by weight based on 100 parts by weight of the rubber component. Within the above range, the elasticity and strength required for the vulcanized rubber composition may be ensured, and at the same time, excellent low fuel consumption may be obtained.

[0232] In addition to the above ingredients, the rubber composition according to one embodiment of the present invention may further contain various additives used in the conventional rubber industry, specifically, a vulcanization accelerator, a processing oil, a plasticizer, an anti-aging agent, a scorch retarder, zinc white, stearic acid, a thermosetting resin or a thermoplastic resin.

[0233] The vulcanization accelerator may include, for example, thiazole compounds such as 2-mercaptobenzothiazole (M), dibenzothiazolyl disulfide (DM) and N-cyclohexyl-2-benzothiazolesulfenamide (CZ); or guanidine compounds such as diphenylguanidine (DPG), and the content may be 0.1 to 5 parts by weight based on 100 parts by weight of the rubber component.

[0234] The processing oil serves as a softener in the rubber composition, and can include, for example, paraffins, cycloalkanes or aromatic compounds. Considering tensile strength and wear resistance, aromatic processing oils can be used, considering hysteresis loss and low temperature performance, cycloalkanes or paraffin processing oils can be used. Based on the rubber component of 100 weight portions, the content of processing oil can be below 100 weight portions. Within the above range, the tensile strength of vulcanized rubber and low heat release performance (low fuel consumption rate) can be prevented from deteriorating.

[0235] The anti-aging agent may include, for example, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, or a condensate of diphenylamine and acetone at high temperature, and the content is 0.1 to 6 parts by weight based on 100 parts by weight of the rubber component.

[0236] The rubber composition according to one embodiment of the present invention can be obtained by mixing according to a mixing formula using a mixing device such as a Banbury mixer, a roll and an internal mixer, and through a vulcanization process after a molding process, a rubber composition with low heat release performance and good wear resistance can be obtained.

[0237] Therefore, the rubber composition can be used to manufacture various components of a tire, such as a tire tread, a base tread, a sidewall, a carcass coating rubber, a belt coating rubber, a bead core, a chafer and a bead coating rubber, or to manufacture rubber products in various industries, such as anti-vibration rubber, a conveyor belt and a hose.

[0238] In addition, the present invention provides a tire produced using the rubber composition.

[0239] The tire may be a tire or include a tire tread.

[0240] Example

[0241] Hereinafter, the present invention will be described in more detail with reference to embodiments. Embodiments according to the present invention can be modified into various other types, and the scope of the present invention should not be limited to the embodiments described below. Embodiments of the present invention are provided to fully illustrate the present invention to those of ordinary skill in the art.

[0242] Experimental Data I

[0243] Example 1

[0244] Into the first reactor of the three continuously stirred liquid phase reactors (CSTR), n-hexane was continuously injected at a flow rate of 5 kg / hr, a monomer solution in which 60 wt% of 1,3-butadiene was dissolved in n-hexane was continuously injected at a flow rate of 1.16 kg / h, a monomer solution in which 60 wt% of styrene was dissolved in n-hexane was continuously injected at a flow rate of 0.31 kg / hr, an initiator solution in which 6.6 wt% of n-butyl lithium was dissolved in n-hexane was continuously injected at a flow rate of 8.33 g / hr, and a polar additive solution in which 2 wt% of di(tetrahydrofuryl)propane as a polar additive was dissolved in n-hexane was continuously injected at a flow rate of 2.25 g / hr. In this case, the internal temperature of the reactor was maintained at 60° C., and when the polymerization conversion rate reached 72%, the polymerization reactant was transported from the first reactor to the second reactor through a transport pipe.

[0245] Then, the temperature of the second reactor was maintained at 60°C, and into the second reactor, a solution in which 60 wt% of 1,3-butadiene was dissolved in n-hexane was continuously injected at a flow rate of 0.2 kg / hr, and a polar additive solution in which 10 wt% of di(tetrahydrofuranyl)propane was dissolved in n-hexane as a polar additive was continuously injected at a flow rate of 6 g / hr to participate in the reaction. When the polymerization conversion rate reached more than 95%, the reaction was terminated. Afterwards, the polymer reactant was transported from the second reactor to the third reactor through a delivery pipe, and a solution in which 4.5 wt% of silicon tetrachloride was dissolved in n-hexane as a coupling agent was injected at a flow rate of 3.7 g / hr, and the reaction was carried out for 30 minutes.

[0246] Then, a solution of IR1520 (BASF Co.) in which 30% by weight of an antioxidant was dissolved was injected at a rate of 100 g / h and stirred. The polymer thus obtained was injected into hot water heated with steam, stirred to remove the solvent, and tumble dried to remove the remaining solvent and water, thereby preparing an unmodified conjugated diene copolymer.

[0247] Example 2

[0248] An unmodified conjugated diene-based polymer was prepared by performing the same method as in Example 1, except that in Example 1, the polymerization reactant was transferred from the first reactor to the second reactor when the polymerization conversion rate in the first reactor reached 70%.

[0249] Example 3

[0250] An unmodified conjugated diene polymer was prepared by carrying out the same method as in Example 1, except that in Example 1, the temperature of the first reactor was maintained at 70° C., the temperature of the second reactor was maintained at 65° C., and the polymerization reactant was transferred from the first reactor to the second reactor when the polymerization conversion rate in the first reactor reached 80%.

[0251] Example 4

[0252] An unmodified conjugated diene polymer was prepared by carrying out the same method as in Example 1, except that in Example 1, the polymerization reactant was transported from the first reactor to the second reactor when the polymerization conversion rate in the first reactor reached 73%, and a polar additive solution in which 10 wt % of di(tetrahydrofuryl)propane was dissolved in n-hexane was further injected into the second reactor and continuously injected at a flow rate of 15 g / hr.

[0253] Example 5

[0254] An unmodified conjugated diene polymer was prepared by carrying out the same method as in Example 1, except that in Example 1, the polymerization reactant was transported from the first reactor to the second reactor when the polymerization conversion rate in the first reactor reached 77%, and a polar additive solution in which 10 wt % of di(tetrahydrofuryl)propane was dissolved in n-hexane was further injected into the second reactor and continuously injected at a flow rate of 1 g / hr.

[0255] Example 6

[0256] An unmodified conjugated diene polymer was prepared by the same method as in Example 1, except that in Example 1, a monomer solution in which 60 wt% of 1,3-butadiene was dissolved in n-hexane was injected into the first reactor at a flow rate of 1.13 kg / hr, a monomer solution in which 60 wt% of styrene was dissolved in n-hexane was injected at a flow rate of 0.28 kg / hr, a polar additive solution in which 2 wt% of di(tetrahydrofuryl)propane as a polar additive was dissolved in n-hexane was injected at a flow rate of 4.0 g / hr, and the polymerization reactant was transported to the second reactor when the polymerization conversion rate in the first reactor reached 75%.

[0257] Comparative Example 1

[0258] An unmodified conjugated diene-based polymer was prepared by performing the same method as in Example 1, except that in Example 1, the polymerization reactant was transferred to the second reactor when the polymerization conversion rate in the first reactor reached 66%.

[0259] Comparative Example 2

[0260] An unmodified conjugated diene-based polymer was prepared by performing the same method as in Example 1, except that in Example 1, the polymerization reactant was transferred to the second reactor when the polymerization conversion rate in the first reactor reached 83%.

[0261] Comparative Example 3

[0262] An unmodified conjugated diene polymer was prepared by the same method as in Example 1, except that in Example 1, a polar additive solution in which 2 wt % of di(tetrahydrofuryl)propane was dissolved in n-hexane was injected into the first reactor at a flow rate of 5 g / hr, the polymerization reactant was transported to the second reactor when the polymerization conversion rate in the first reactor reached 75%, and the polar additive solution was not additionally injected into the second reactor.

[0263] Comparative Example 4

[0264] An unmodified conjugated diene polymer was prepared by the same method as in Example 1, except that in Example 1, a polar additive solution in which 2 wt% of di(tetrahydrofuryl)propane was dissolved in n-hexane was injected into the first reactor at a flow rate of 5 g / hr, the polymerization reactant was transported to the second reactor when the polymerization conversion rate in the first reactor reached 75%, and the 1,3-butadiene solution and the polar additive solution were not additionally injected into the second reactor.

[0265] Experimental Example 1. Evaluation of polymer performance

[0266] For each unmodified conjugated diene polymer prepared in the Examples and Comparative Examples, the styrene bond content and 1,2-vinyl bond content, weight average molecular weight (Mw, × 10 3 g / mol), number average molecular weight (Mn, ×10 3 g / mol), molecular weight distribution (PDI, MWD), Mooney viscosity (MV) and half maximum full width of tan δ peak. The results are shown in Table 1 below.

[0267] 1) Styrene bond content and 1,2-vinyl bond content (wt%)

[0268] The styrene bond content (SM) and 1,2-vinyl bond content in each polymer were measured and analyzed using Varian VNMRS 500 MHz NMR.

[0269] When NMR was measured, 1,1,2,2-tetrachloroethane was used as a solvent, and the styrene unit and vinyl content were calculated by calculating 5.97 ppm as a solvent peak, and considering 7.2 ppm to 6.9 ppm as a random styrene peak, 6.9 ppm to 6.2 ppm as a block styrene peak, 5.8 ppm to 5.1 ppm as 1,4-vinyl and 1,2-vinyl peaks, and 5.1 ppm to 4.5 ppm as a 1,2-vinyl peak.

[0270] 2) Weight average molecular weight (Mw, ×10 3 g / mol), number average molecular weight (Mn, ×10 3 g / mol) and molecular weight distribution (PDI, MWD)

[0271] The number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured by gel permeation chromatography (GPC) (PL GPC220, Agilent Technologies), and the molecular weight distribution was calculated by dividing the weight average molecular weight by the number average molecular weight.

[0272] - Column: A combination of two PLgel Olexis columns (Polymer Laboratories Co.) and one PLgel mixed-C column (Polymer Laboratories Co.)

[0273] -Solvent: A mixture of tetrahydrofuran and 2% by weight of an amine compound

[0274] -Flow rate: 1ml / min

[0275] - Sample concentration: 1-2 mg / ml (diluted in THF)

[0276] -Injection volume: 100μl

[0277] - Column temperature: 40℃

[0278] -Detector: Refractive index detector

[0279] -Standard: Polystyrene (calibrated by cubic function)

[0280] 3) Mooney viscosity

[0281] Mooney viscosity (MV, (ML1+4, @100°C) MU) was measured by using MV-2000 (Alpha Technologies Co.) using a large rotor at a rotor speed of 2±0.02 rpm at 100°C. In this case, the sample used was left at room temperature (23±3°C) for more than 30 minutes, and 27±3 g of the sample was collected and put into the mold cavity, and then, the press plate was operated for 4 minutes for measurement.

[0282] 4) Full width at half maximum (FWHM) of tanδ peak

[0283] For the polymers prepared in Examples and Comparative Examples, in order to perform dynamic viscoelastic analysis by an advanced rheological expansion system (ARES), a dynamic mechanical analyzer (TA Co., ARES-G2) was used to measure tan δ according to temperature in the temperature range of -100°C to 100°C at a frequency of 10 Hz, a strain of 0.5% and a heating rate of 5°C / min in a torsional mode. The results are as follows: Figure 1 The tan δ graph shown in FIG. 1 is used to obtain the full width at half maximum of the peak from the graph.

[0284] [Table 1]

[0285]

[0286] Referring to Table 1, in the case of the polymer prepared by the preparation method according to the present invention, all the half-maximum full width values ​​of the tan δ peak showed 20° C. or more, but it can be confirmed that all the comparative examples that did not follow the preparation method according to the present invention showed values ​​less than 20° C. That is, it can be found that according to the preparation method of the present invention, the microstructure of the polymer can be finely controlled, and the half-maximum full width value of the tan δ peak can be increased.

[0287] Experimental Example 2. Evaluation of the performance of the rubber composition

[0288] In order to compare and analyze the physical properties of the rubber compositions containing each unmodified conjugated diene-based polymer prepared in Examples and Comparative Examples and the molded articles made therefrom, viscoelastic properties and abrasion resistance were measured, respectively, and the results are shown in Table 3 below.

[0289] 1) Preparation of rubber samples

[0290] Each modified or unmodified conjugated diene-based polymer of Examples, Comparative Examples and Reference Examples was used as a raw material rubber and mixed under the mixing conditions shown in the following Table 2. The raw materials in Table 2 are expressed in parts by weight based on 100 parts by weight of the raw material rubber.

[0291] [Table 2]

[0292]

[0293] Specifically, the rubber sample was kneaded by first-stage kneading and second-stage kneading. In the first-stage kneading, a Banbury mixer equipped with a temperature control device was used to knead the raw rubber, silica (filler), organic silane coupling agent (X50S, Evonik), process oil (TADE oil), zinc oxide (ZnO), stearic acid, antioxidant (TMQ (RD)) (2,2,4-trimethyl-1,2-dihydroquinoline polymer), anti-aging agent (6PPD ((dimethylbutyl) -N-phenyl-phenylenediamine) and wax (microcrystalline wax). In this case, the initial temperature of the kneading device was controlled to 70°C, and after the mixing was completed, the first compounded mixture was obtained at a discharge temperature of 145°C. In the second stage kneading, the first compounded mixture was cooled to room temperature, and the first compounded mixture, sulfur, rubber accelerator (DPG (diphenylguanidine)) and vulcanization accelerator (CZ (N-cyclohexyl-2-benzothiazolesulfonamide)) were added to the kneading device and mixed at a temperature below 100°C to obtain a second compounded mixture. Then, the rubber specimen was formed by curing at 160°C for 20 minutes.

[0294] 2) Viscoelastic properties

[0295] For the rubber specimens made by including the polymers prepared in the embodiments and comparative examples, in order to perform dynamic viscoelastic analysis by an advanced rheological expansion system (ARES), a dynamic mechanical analyzer (TACo., ARES-G2) was used in a torsional mode at a frequency of 10 Hz, a strain of 0.5%, and a heating rate of 5°C / min to measure tanδ according to temperature in a temperature range of -100°C to 100°C, and a tanδ graph was obtained. In the obtained tanδ graph, the tanδ value at 0°C and the tanδ value at 60°C were confirmed. In this case, if the tanδ value at a low temperature of 0°C increases, the anti-skid property becomes better, and if the tanδ value at a high temperature of 60°C decreases, the hysteresis loss decreases, and the driving resistance (fuel consumption rate) becomes better. The result values ​​in Table 3 are indicated by setting the result value of Comparative Example 3 to 100, so the higher the numerical value, the better the result.

[0296] 3) Wear resistance (DIN wear test)

[0297] For each rubber sample, a DIN wear test was performed based on ASTM D5963 and represented by DIN loss index (loss volume index): abrasion resistance index (ARIA, method A). In Table 3 below, the result values ​​are indicated based on the measured result values ​​of Comparative Example 3, and therefore, the higher the value, the better the result.

[0298] [Table 3]

[0299]

[0300]

[0301] Referring to Table 3, it can be confirmed that in the case of the rubber sample containing the polymer having a tan δ peak full width at half maximum of 20°C or more according to the present invention, the improvement effects of wet skid resistance and running resistance are exhibited in a balanced manner while exhibiting significantly improved wear resistance.

[0302] In contrast, it was confirmed that the rubber sample including the polymer having a tan δ peak half maximum width of less than 20° C. of the comparative example exhibited significantly deteriorated wet skid resistance and running resistance compared with the examples and exhibited very poor wear resistance.

[0303] Experimental Data II

[0304] Example 7

[0305] Into the first reactor of the three continuously stirred liquid phase reactors (CSTR), n-hexane was continuously injected at a flow rate of 5 kg / hr, a monomer solution in which 60 wt% of 1,3-butadiene was dissolved in n-hexane was continuously injected at a flow rate of 1.16 kg / h, a monomer solution in which 60 wt% of styrene was dissolved in n-hexane was continuously injected at a flow rate of 0.31 kg / hr, an initiator solution in which 6.6 wt% of n-butyl lithium was dissolved in n-hexane was continuously injected at a flow rate of 8.33 g / hr, and a polar additive solution in which 2 wt% of di(tetrahydrofuryl)propane as a polar additive was dissolved in n-hexane was continuously injected at a flow rate of 2.25 g / hr. In this case, the internal temperature of the reactor was maintained at 60° C., and when the polymerization conversion rate reached 70%, the polymerization reactant was transported from the first reactor to the second reactor through a transport pipe.

[0306] Then, the temperature of the second reactor was maintained at 60° C., and into the second reactor, a solution in which 60 wt % of 1,3-butadiene was dissolved in n-hexane was continuously injected at a flow rate of 0.2 kg / hr, and a polar additive solution in which 10 wt % of di(tetrahydrofuranyl)propane was dissolved in n-hexane as a polar additive was continuously injected at a flow rate of 6 g / hr to participate in the reaction. When the polymerization conversion rate reached 95% or more, the polymerization reactant was transported from the second reactor to the third reactor through a transport pipe, and a solution in which 5 wt % of N,N-dimethyl-3-(trimethoxysilyl)propane-1-amine was dissolved in n-hexane as a modifier was injected at a flow rate of 11.6 g / hr, and the reaction was carried out for 30 minutes.

[0307] Then, a solution of IR1520 (BASF Co.) in which 30% by weight of an antioxidant was dissolved was injected at a rate of 100 g / h and stirred. The polymer thus obtained was injected into hot water heated with steam, stirred to remove the solvent, and tumble dried to remove the remaining solvent and water, thereby preparing a modified conjugated diene copolymer.

[0308] Example 8

[0309] A modified conjugated diene polymer was prepared by the same method as in Example 7, except that in Example 7, a monomer solution in which 60 wt% of 1,3-butadiene was dissolved in n-hexane was continuously injected at a flow rate of 1.13 kg / hr, a monomer solution in which 60 wt% of styrene was dissolved in n-hexane was continuously injected at a flow rate of 0.28 kg / hr, a polar additive solution in which 2 wt% of di(tetrahydrofuryl)propane as a polar additive was dissolved in n-hexane was continuously injected at a flow rate of 4.0 g / hr, and the polymerization reactant was transported from the first reactor to the second reactor when the polymerization conversion rate in the first reactor reached 72%.

[0310] Example 9

[0311] A modified conjugated diene polymer was prepared by carrying out the same method as in Example 7, except that in Example 7, the temperature of the first reactor was maintained at 70°C, the temperature of the second reactor was maintained at 65°C, and the polymerization reactant was transported to the second reactor when the polymerization conversion rate in the first reactor reached 80%.

[0312] Example 10

[0313] A modified conjugated diene-based polymer was prepared by performing the same method as in Example 7, except that in Example 7, the polymerization reactant was transported from the first reactor to the second reactor when the polymerization conversion rate in the first reactor reached 77%, and the 1,3-butadiene solution additionally injected into the second reactor was not injected.

[0314] Embodiment 11

[0315] A modified conjugated diene polymer was prepared by the same method as in Example 7, except that in Example 7, a monomer solution in which 60 wt% of 1,3-butadiene was dissolved in n-hexane was continuously injected at a flow rate of 1.13 kg / hr, a monomer solution in which 60 wt% of styrene was dissolved in n-hexane was continuously injected at a flow rate of 0.28 kg / hr, an initiator solution in which 6.6 wt% of n-butyllithium was dissolved in n-hexane was continuously injected at a flow rate of 6.06 g / hr, and the polymerization reactant was transported from the first reactor to the second reactor when the polymerization conversion rate in the first reactor reached 72%.

[0316] Example 12

[0317] A modified conjugated diene polymer was prepared by the same method as in Example 7, except that in Example 7, a monomer solution in which 60 wt% of 1,3-butadiene was dissolved in n-hexane was continuously injected at a flow rate of 1.08 kg / hr, a monomer solution in which 60 wt% of styrene was dissolved in n-hexane was continuously injected at a flow rate of 0.35 kg / hr, a polar additive solution in which 2 wt% of di(tetrahydrofuryl)propane as a polar additive was dissolved in n-hexane was continuously injected at a flow rate of 3.0 g / hr, the polymerization reactant was transported from the first reactor to the second reactor when the polymerization conversion rate in the first reactor reached 75%, and the 1,3-butadiene solution additionally injected into the second reactor was continuously injected at a flow rate of 0.24 kg / hr.

[0318] Embodiment 13

[0319] A modified conjugated diene polymer was prepared by carrying out the same method as in Example 7, except that in Example 7, the polymerization reactants were transported from the first reactor to the second reactor when the polymerization conversion rate in the first reactor reached 73%, and a polar additive solution in which 10 wt % of di(tetrahydrofuryl)propane was dissolved in n-hexane was further injected into the second reactor and continuously injected at a flow rate of 15.0 g / hr.

[0320] Embodiment 14

[0321] A modified conjugated diene polymer was prepared by carrying out the same method as in Example 7, except that in Example 7, the polymerization reactants were transported from the first reactor to the second reactor when the polymerization conversion rate in the first reactor reached 73%, and a polar additive solution in which 10 wt % of di(tetrahydrofuryl)propane was dissolved in n-hexane was further injected into the second reactor and continuously injected at a flow rate of 1 g / hr.

[0322] Embodiment 15

[0323] A modified conjugated diene-based polymer was prepared by performing the same method as in Example 7, except that in Example 7, a monomer solution in which 60 wt% of 1,3-butadiene was dissolved in n-hexane was continuously injected at a flow rate of 1.06 kg / hr, the polymer was transported from the first reactor to the second reactor when the polymerization conversion rate in the first reactor reached 75%, and the 1,3-butadiene solution additionally injected into the second reactor was continuously injected at a flow rate of 0.30 kg / hr.

[0324] Comparative Example 5

[0325] A modified conjugated diene polymer was prepared by the same method as in Example 7, except that in Example 7, a polar additive solution in which 2 wt % of di(tetrahydrofuryl)propane was dissolved in n-hexane was injected into the first reactor at a flow rate of 17.5 g / hr, the polymerization reactants were transported to the second reactor when the polymerization conversion rate in the first reactor reached 78%, and 1,3-butadiene and the polar additive were not injected into the second reactor.

[0326] Comparative Example 6

[0327] A modified conjugated diene polymer was prepared by the same method as in Example 12, except that in Example 12, a polar additive solution in which 2 wt % of di(tetrahydrofuryl)propane was dissolved in n-hexane was injected into the first reactor at a flow rate of 6.0 g / hr, the polymerization reactants were transported to the second reactor when the polymerization conversion rate in the first reactor reached 73%, and the polar additive was not injected into the second reactor.

[0328] Comparative Example 7

[0329] A modified conjugated diene polymer was prepared by carrying out the same method as in Example 8, except that in Example 8, a polar additive solution in which 2 wt % of di(tetrahydrofuryl)propane was dissolved in n-hexane was injected into the first reactor at a flow rate of 17.5 g / hr, and the polar additive was not injected into the second reactor.

[0330] Comparative Example 8

[0331] A modified conjugated diene polymer was prepared by the same method as in Example 12, except that in Example 12, a polar additive solution in which 2 wt% of di(tetrahydrofuryl)propane was dissolved in n-hexane was injected into the first reactor at a flow rate of 12.0 g / hr, the polymerization reactants were transported to the second reactor when the polymerization conversion rate in the first reactor reached 76%, a solution in which 60 wt% of 1,3-butadiene was dissolved in n-hexane was injected into the second reactor at a flow rate of 0.24 kg / hr, and no polar additive was injected.

[0332] Comparative Example 9

[0333] A modified conjugated diene-based polymer was prepared by performing the same method as in Example 7, except that in Example 7, the polymerization reactant was transferred to the second reactor when the polymerization conversion rate in the first reactor reached 65%.

[0334] Comparative Example 10

[0335] A modified conjugated diene-based polymer was prepared by performing the same method as in Example 7, except that in Example 7, the polymerization reactant was transferred to the second reactor when the polymerization conversion rate in the first reactor reached 87%.

[0336] Comparative Example 11

[0337] An unmodified conjugated diene polymer was prepared by the same method as in Example 7, except that in Example 7, a polar additive solution in which 2 wt % of di(tetrahydrofuryl)propane was dissolved in n-hexane was injected into the first reactor at a flow rate of 5.0 g / hr, the polymerization reactants were transported to the second reactor when the polymerization conversion rate in the first reactor reached 75%, the polar additive solution was not injected into the second reactor, and a coupling reaction was carried out by continuously supplying a solution in which 4.5 wt % of silicon tetrachloride was dissolved in n-hexane as a coupling agent instead of a modifier at a flow rate of 3.7 g / hr.

[0338] Experimental Example 3. Evaluation of polymer performance

[0339] For each modified and unmodified conjugated diene-based polymer prepared in Examples 7 to 15 and Comparative Examples 5 to 11, the styrene bond content and 1,2-vinyl bond content, weight average molecular weight (Mw, × 10 3 g / mol), number average molecular weight (Mn, ×10 3 g / mol), molecular weight distribution (PDI, MWD) and the half maximum width of the tan δ peak. The results are shown in Table 4 below.

[0340] [Table 4]

[0341]

[0342]

[0343] Referring to Table 4 above, it can be confirmed that all polymers prepared by the preparation method according to the present invention showed a half-maximum full width value of the tan δ peak of 20° C. or more, but all comparative examples that did not follow the preparation method according to the present invention showed a value of less than 20° C. Thus, according to the preparation method of the present invention, it can be found that the microstructure of the polymer can be finely controlled, and the half-maximum full width value of the tan δ peak is increased.

[0344] Experimental Example 4. Evaluation of the performance of rubber molded products

[0345] In order to compare and analyze the physical properties of the rubber compositions containing each modified and unmodified conjugated diene-based polymer prepared in the Examples and Comparative Examples and the molded articles made therefrom, the viscoelastic properties and the wear resistance were measured by the same method as in Experimental Example 2 of Experimental Data 1. The results are shown in Table 5 below.

[0346] Meanwhile, in Table 5 below, the viscoelastic properties and abrasion resistance of Examples 7 to 15 and Comparative Examples 5 to 11 are indicated based on the measurement result values ​​of Comparative Example 11, and the higher the numerical value, the better the result.

[0347] [Table 5]

[0348]

[0349]

[0350] Referring to Table 5, in the case of the rubber sample containing the polymer having a half-maximum width of tan δ peak of 20°C or more according to the present invention, it can be confirmed that the wet skid resistance and the running resistance show improved performance in a balanced manner, and at the same time, the wear resistance is significantly improved. In contrast, in the case of the rubber sample containing the polymer of the comparative example having a half-maximum width of tan δ peak of less than 20°C, it can be confirmed that the wet skid resistance and the running resistance are significantly reduced compared with the examples, and the wear resistance is very poor.

Claims

1. A conjugated diene polymer comprising repeating units derived from a conjugated diene monomer, in, In the tan δ graph according to temperature obtained by dynamic viscoelastic analysis of the Advanced Rheological Extension System (ARES), the full width at half maximum (FWHM) value of the tan δ peak shown in the temperature range of -100°C to 100°C is 20°C to 43°C, and The Advanced Rheology Extension System uses a dynamic mechanical analyzer in torsion mode at a frequency of 10 Hz, a strain of 0.5%, and a heating rate of 5°C / min.

2. The conjugated diene polymer according to claim 1, wherein The tan δ peak is shown in the temperature range of -80°C to 20°C. 3 . The conjugated diene polymer according to claim 1 , further comprising a repeating unit derived from an aromatic vinyl monomer.

4. The conjugated diene polymer according to claim 1, wherein The molecular weight distribution curve by gel permeation chromatography was unimodal, and the molecular weight distribution was 1.0 to 3.

0.

5. A modified conjugated diene polymer comprising repeating units derived from a conjugated diene monomer and functional groups derived from a modifier, in, In the tan δ graph according to temperature obtained by dynamic viscoelastic analysis of the Advanced Rheological Extension System (ARES), the full width at half maximum (FWHM) value of the tan δ peak shown in the temperature range of -100°C to 100°C is 20°C to 42°C, and The Advanced Rheology Extension System uses a dynamic mechanical analyzer in torsion mode at a frequency of 10 Hz, a strain of 0.5%, and a heating rate of 5°C / min.

6. The modified conjugated diene polymer according to claim 5, wherein The modifier is an alkoxysilane modifier, and The modified conjugated diene-based polymer has a Si content and a N content of 50 ppm or more, respectively, based on the total weight of the polymer.

7. The modified conjugated diene polymer according to claim 5, wherein The molecular weight distribution curve by gel permeation chromatography was unimodal, and the molecular weight distribution was 1.0 to 3.

0.

8. A rubber composition comprising: a polymer and a filler, wherein: The polymer is the conjugated diene polymer according to claim 1 or the modified conjugated diene polymer according to claim 5 .

9. The rubber composition according to claim 8, wherein The filler may be included in an amount of 0.1 to 200 parts by weight based on 100 parts by weight of the polymer.

Images