Oil-extended conjugated diene polymer and rubber composition containing the same

Abstract

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

Description

[Technical field]

[0004] The present invention relates to an oil-extended conjugated diene polymer having excellent tensile properties, running resistance and processability in a balanced manner and having improved wear resistance and wet skid resistance, and a rubber composition comprising the same. 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 running 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 or Goodrich heat generation 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 heat generation at the above temperature.

[0007] Natural rubber, polyisoprene rubber or polybutadiene rubber are known as rubber materials with low hysteresis loss, but these rubbers are limited in that they have 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 rubbers for tires. Among these polymerization methods, the biggest advantage of solution polymerization compared with emulsion polymerization is that the vinyl structure content and styrene content that specify 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, SBR prepared by solution polymerization is widely used as a rubber material for tires, because 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.

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

[0009] In addition, if solution-polymerized SBR is used as a 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 exhibited by the high vinyl content may not be exhibited.

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

[0011] Therefore, it is necessary to develop a polymer that can improve wet skid resistance and wear resistance while substantially satisfying the performance requirements of the product for 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 problems of the above-mentioned prior art, and one object is to provide an oil-extended conjugated diene polymer, which has a specific viscoelastic tanδ peak by controlling the microstructure of the polymer to achieve a tire with improved wet skid resistance and wear resistance in a balanced manner while maintaining excellent tensile properties and running resistance (fuel consumption performance), and which contains vegetable oil.

[0016] Furthermore, another object of the present invention is to provide an oil-extended modified conjugated diene-based polymer having improved wear resistance and wet skid resistance by controlling the microstructure of the polymer itself, and having even further improved running resistance and processability by introducing a modifier.

[0017] Furthermore, another object of the present invention is to provide a rubber composition comprising the conjugated diene-based polymer and / or the modified conjugated diene-based polymer.

[0018] Technical Solution

[0019] In order to solve the above-mentioned task, according to one embodiment of the present invention, there is provided an oil-extended conjugated diene polymer, comprising: a polymer unit comprising a repeating unit derived from a conjugated diene monomer; and a vegetable oil, wherein, in a tan δ diagram according to temperature obtained by dynamic viscoelastic analysis performed by an advanced rheological extension system (ARES), a full width at half maximum (FWHM) value of a tan δ peak displayed in a temperature range of -100°C to 100°C is 20°C or higher, 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 an oil-extended modified conjugated diene polymer, comprising: a modified polymer unit comprising a repeating unit derived from a conjugated diene monomer and a functional group derived from a modifier; and a vegetable oil, wherein, in a tan δ diagram according to temperature obtained by dynamic viscoelastic analysis performed 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.

[0021] Furthermore, the present invention provides a rubber composition comprising a polymer and a filler, wherein the polymer is an oil-extended conjugated diene polymer or an oil-extended modified conjugated diene polymer.

[0022] In addition, the present invention provides a rubber composition comprising a conjugated diene-based polymer and a filler, wherein, in a tan δ diagram according to temperature obtained by dynamic viscoelasticity analysis performed 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 31°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, and the conjugated diene-based polymer comprises a vegetable oil.

[0023] Beneficial Effects

[0024] The oil-extended conjugated diene polymer according to the present invention can exhibit excellent tensile properties and running resistance, and can exhibit significantly improved wet skid resistance and abrasion resistance by controlling the microstructure of the polymer, and can also exhibit excellent processability by containing vegetable oil.

[0025] In addition, since the conjugated diene polymer according to the present invention can achieve excellent wear resistance and wet skid resistance by controlling the microstructure, can achieve excellent processability by containing vegetable oil, and can further achieve excellent running resistance (fuel consumption performance) and tensile properties by introducing a modifier. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] The accompanying drawings in this disclosure illustrate certain 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.

[0027] Figure 1 is one embodiment of a tan delta plot as a function of temperature obtained by dynamic viscoelastic analysis performed by the Advanced Rheological Extension System (ARES). DETAILED DESCRIPTION

[0028] Hereinafter, the present invention will be described in more detail to help understanding of the present invention.

[0029] It is to be understood that the words or terms used in the specification and claims of the present invention should not be interpreted as the meanings defined in commonly used dictionaries. It is also to be understood that, based on the principle that the inventor can appropriately define the meanings of words or terms to best explain the invention, the words or terms should be interpreted as having meanings consistent with their inventive technical ideas.

[0030] Definition of terms

[0031] In the present disclosure, the term "polymer" refers to a polymer compound prepared by polymerization of monomers (whether of the same or different types). Similarly, the general term polymer encompasses 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.

[0032] In the present disclosure, the term "1,2-vinyl bond content" refers to the mass (or weight) percentage of butadiene contained at 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.

[0033] 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.

[0034] 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.

[0035] In the present disclosure, the term "substituted" may mean 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, then one or more (including two or more) substituents may be present depending on the number of hydrogens present in the functional group, the atomic radical or the compound, and if multiple substituents are present, each substituent may be the same or different.

[0036] 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 1 or 2 or more unsaturated bonds.

[0037] In the present disclosure, the term "alkylene" may refer to a divalent aliphatic saturated hydrocarbon, such as methylene, ethylene, propylene, and butylene.

[0038] In the present invention, the term "cycloalkyl group" may refer to a cyclic saturated hydrocarbon.

[0039] In the present disclosure, the term “aryl group” may refer to aromatic hydrocarbons, and may include monocyclic aromatic hydrocarbons in which one ring is formed and polycyclic aromatic hydrocarbons in which two or more rings are combined.

[0040] 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 formed by substituting a hydrogen atom bonded to carbon constituting an alkyl group with an aryl group.

[0041] In the present disclosure, the term "single bond" may refer to a single covalent bond itself that does not include separate atoms or molecular groups.

[0042] 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 certain material, or the material itself.

[0043] In the present disclosure, the term "polymer unit" refers to a polymer chain formed by polymerizing one monomer or a plurality of monomers.

[0044] In the present disclosure, the term "modified polymer unit" refers to a modified polymer chain further including a functional group derived from a modifier in a polymer chain formed by polymerizing one monomer or a plurality of monomers.

[0045] In the present disclosure, the terms "comprising" and "having" and their derivatives, whether or not these terms are specifically disclosed, are not intended to exclude the presence of optional additional ingredients, steps or processes. 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 materials) unless otherwise stated to the contrary. In contrast, the term "essentially consisting of excludes ingredients, steps or processes that are not necessary for the operation and excludes optional other ingredients, steps or processes from the scope of the optional continuous description. The term "consisting of" excludes optional ingredients, steps or processes that are not specifically described or illustrated.

[0046] Measurement methods and conditions

[0047] In the present disclosure, "1,2-vinyl bond content" and "styrene bond content" are the vinyl content and styrene content in a polymer unit, measured and analyzed using Varian VNMRS 500MHz NMR. For NMR measurement, 1,1,2,2-tetrachloroethane was used as a solvent, 6.0 ppm was calculated as a solvent peak, and the 1,2-vinyl content and styrene bond content in the total polymer were calculated and measured, respectively, taking into account the peaks of 7.2-6.9 ppm for atactic styrene, 6.9-6.2 ppm for block styrene, 5.8-5.1 ppm for 1,4-vinyl and 1,2-vinyl, and 5.1-4.5 ppm for 1,2-vinyl.

[0048] In the present disclosure, the "weight average molecular weight (Mw)", "molecular weight distribution (MWD)" and "unimodal properties" are obtained by measuring the weight average molecular weight (Mw) and the number average molecular weight (Mn) using a gel permeation chromatograph (GPC) (PL GPC220, Agilent Technologies), obtaining a molecular weight distribution curve, and calculating the molecular weight distribution (PDI, MWD, Mw / Mn) from each measured molecular weight.

[0049] – Column: A combination of two PLgel Olexis (Polymer Laboratories Co.) and one PLgelmixed-C (Polymer Laboratories Co.)

[0050] -Solvent: A mixture of tetrahydrofuran and 2 wt% of an amine compound was used

[0051] -Flow rate: 1ml / min

[0052] -Sample concentration: 1-2 mg / ml (diluted in THF)

[0053] -Injection volume: 100μl

[0054] - Column temperature: 40℃

[0055] -Detector: Refractive index

[0056] -Standard sample: polystyrene (calibrated with cubic function)

[0057] In the present disclosure, "glass transition temperature (Tg)" is obtained using differential scanning calorimetry (DSCQ100, TA Co.) based on ISO 22768:2006. A differential scanning calorimetry (DSC) curve was recorded under a nitrogen circulation at a flow rate of 50 ml / min while increasing the temperature from -100°C at a rate of 10°C / min, and the peak top (inflection point) of the DSC differential curve was considered to be the glass transition temperature.

[0058] In the present disclosure, the "tan δ peak" is a peak shown in a tan δ graph according to temperature obtained by dynamic viscoelasticity analysis performed by 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.

[0059] In the present disclosure, “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 as follows: 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 (Thermo Scientific, Lindberg Blue M) by the procedure of steps 1 to 3 below:

[0060] 1) Step 1: initial temperature 0°C, rate (temperature / hour) 180°C / hour, temperature (holding time) 180°C (1 hour),

[0061] 2) Step 2: initial temperature 180°C, rate (temperature / hour) 85°C / hour, temperature (holding time) 370°C (2 hours), and

[0062] 3) Step 3: initial temperature 370°C, rate (temperature / hour) 47°C / hour, temperature (holding time) 510°C (3 hours),

[0063] 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 with 30 mL of ultrapure water, and incinerate.

[0064] In the present disclosure, "N content" can be measured by NSX analysis, and the measurement by NSX analysis can use a trace nitrogen quantitative analyzer (NSX-2100H). In particular, the trace nitrogen quantitative analyzer (autosampler, horizontal furnace, PMT & Nitrogen detector) is turned on, the carrier gas flow is set to Ar 250ml / min, O2 350ml / min and the ozone generator is 300ml / min, the heater is set to 800°C, and the analyzer is placed for about 3 hours to stabilize. After stabilizing the analyzer, a calibration curve with a 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, and then, by using the ratio of concentration to area, a straight line is obtained. After that, a ceramic boat containing 20mg of sample is placed in the autosampler of the analyzer and measured to obtain the area. By using the sample area and calibration curve thus obtained, the N content is calculated.

[0065] In this case, the sample used in the NSX analysis method may be a modified conjugated diene-based polymer from which a solvent has been removed by placing the sample in hot water heated by steam and stirring, and may be a sample from which residual monomers and a remaining modifier have been removed. In addition, if oil is added to the sample, the sample may be a sample from which the oil has been extracted (removed).

[0066] Oil-extended conjugated diene polymers

[0067] The present invention provides an oil-extended conjugated diene polymer having a specific viscoelastic tan δ peak by controlling the microstructure to achieve a tire having improved wet skid resistance and wear resistance and improved processability in a balanced manner while maintaining excellent tensile properties and running resistance (fuel consumption performance), and which contains vegetable oil.

[0068] The oil-extended conjugated diene polymer according to the present invention is characterized in that it contains: a polymer unit containing a repeating unit derived from a conjugated diene monomer; and a vegetable oil, wherein, in a tan δ diagram according to temperature obtained by dynamic viscoelastic analysis performed 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.

[0069] According to one embodiment of the present invention, since the oil-extended conjugated diene polymer is achieved by applying a specific preparation method (which will be described later) to obtain a polymer having a specific microstructure, the dynamic viscoelastic behavior of the polymer can be controlled to have a specific tan δ peak, whereby the tensile properties and running resistance can become excellent, and the wet skid resistance and wear resistance can be improved.

[0070] Furthermore, according to one embodiment of the present invention, by applying a preparation method (which will be described later), the conjugated diene-based polymer includes vegetable oil, and can achieve the effects of having excellent properties and improved processability.

[0071] Dynamic viscoelastic behavior of polymers

[0072] 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 viscoelasticity analysis performed by 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.

[0073] In the case of a polymer prepared by a general polymerization method and without controlling its microstructure, two or more tan δ peaks are shown, 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 unit is distributed in a polymer such as a block copolymer and there is a large glass transition temperature difference between the blocks, the tan δ peak may have a narrow width and may show two or more peaks. In addition, in the case of a random copolymer, if the vinyl content or 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.

[0074] In this case, the glass transition temperature may be the same for both block copolymers and random copolymers, but the wet skid resistance is very different, and in order to solve these defects, efforts have been made to improve the wet skid resistance when subjected to changes in the glass transition temperature. However, if the glass transition temperature changes, the problem is that the wear resistance changes, and the basic physical properties of the polymer change, and there is still a task to achieve 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 through modification processes, this is still a difficult task to solve. However, the conjugated diene polymer according to one embodiment of the present invention is prepared by a preparation method that controls the polymer microstructure, and although it has the same glass transition temperature as a conventional modified conjugated diene polymer, it can show a specific tan δ peak, which can achieve the effect of improving wet skid resistance and wear resistance at the same time.

[0075] In this case, the tan δ peak is characterized in that, in a tan δ diagram according to temperature obtained by dynamic viscoelastic analysis performed by an advanced rheological expansion system (ARES), the tan δ peak is shown in a temperature range of -100°C to 100°C, and the half-maximum full width of the tan δ peak is 20°C or more. The number of tan δ peaks shown in this temperature range is usually 1, or 2 or more, and in the case of showing 2 or more peaks, it may mean that the half-maximum full width of 1 peak among the plurality of peaks is 20°C or more.

[0076] The half-maximum full width value of the tanδ peak may be 20°C or higher, preferably 30°C or higher. In addition, the half-maximum full width value may be a maximum of 80°C, preferably 70°C or lower. In another embodiment, the half-maximum full width value of the tanδ peak may be 30°C to 80°C, or 35°C to 60°C. If the half-maximum full width is less than 20°C, the defect of significantly reduced wet skid resistance will occur at the same glass transition temperature, and it is unlikely to achieve a half-maximum full width of the peak greater than 80°C, and although it is achieved, phase separation may occur, which may inevitably be accompanied by the defect of increased hysteresis at high temperatures, and the defect of deteriorating fuel consumption performance may occur.

[0077] Furthermore, the tan δ peak may be shown at -100° C. to 100° C., preferably -80° C. to 20° C., more preferably -70° C. to 0° C. If the peak is shown in this range, a more favorable wear resistance effect can be expected.

[0078] The dynamic viscoelastic analysis performed by the Advanced Rheology Extension System corresponds to measuring tan δ as a function of temperature using a dynamic mechanical analyzer (TACo., 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 the temperature range of -100°C to 100°C, in which case the resulting graph is the tan δ value as a function of temperature.

[0079] Vegetable oil

[0080] According to one embodiment of the present invention, the conjugated diene-based polymer may be an oil-extended polymer comprising: a polymer unit comprising a repeating unit derived from a conjugated diene-based monomer; and a vegetable oil.

[0081] Generally, oil-extended rubber is a rubber prepared by mixing a synthetic rubber with a petroleum-based oil to improve the flexibility, elasticity and compounding properties of the synthetic rubber (e.g., a conjugated diene polymer). The conjugated diene polymer according to the present invention is prepared using a plant oil from a plant, which is an environmentally friendly material, and contains the plant oil in the polymer, and therefore, environmental friendliness and improved flexibility, elasticity and compounding properties can be expected.

[0082] Meanwhile, in the present invention, "vegetable oil" is an oil component derived from (ie, extracted from) a plant, and is generally a triglyceride molecule represented by Formula 14 below.

[0083] [Formula 14]

[0084]

[0085] In formula 14, R 14a To R 14c Each of is a group derived from an ester of a fatty acid, and is an unsaturated or saturated hydrocarbon group.

[0086] Here, R 14a To R 14c The relative proportions of may vary depending on the type of vegetable oil, for example, as shown in Table 1 below.

[0087] [Table 1]

[0088] Vegetable oil <![CDATA[Saturation (wt%, R 14a )]]> <![CDATA[Monounsaturated (wt%, R 14b )]]> <![CDATA[Polyunsaturated (wt%, R 14c )]]> Soybean Oil 17 23 60 Sunflower Oil 10 45 40 Canola Oil 7 63 28 Flaxseed Oil 10 45 40 olive oil 14 73 11 Peanut Oil 17 46 32 Cottonseed oil 26 18 52 Palm Oil 49 37 9 olive oil 14 73 11

[0089] In another embodiment, the iodine value of the vegetable oil may be 70 to 150, in particular 110 to 140.

[0090] In addition, the vegetable oil may have a glass transition temperature of -110°C to -100°C, and within this range, the wear resistance of the rubber composition may be more improved.

[0091] In another embodiment, as the vegetable oil, the present invention may include oils derived from plants without particular limitation, and in particular, the vegetable oil may be one or more selected from soybean oil, rapeseed oil, canola oil, sunflower seed oil, linseed oil, rice bran oil, palm oil, olive oil, peanut oil, oil palm oil, cottonseed oil and coconut oil. More particularly, in terms of more advantageously achieving the desired effect, the vegetable oil may be soybean oil.

[0092] In addition, the conjugated diene polymer may include 10 to 60 parts by weight or 20 to 37.5 parts by weight of vegetable oil based on 100 parts by weight of the polymer unit. In this case, even better effects of flexibility, elasticity and processability of the conjugated diene polymer may be achieved.

[0093] Repeating units from monomers

[0094] According to one embodiment of the present invention, the conjugated diene polymer comprises a polymer unit comprising a repeating unit from a conjugated diene monomer, and the conjugated diene monomer can be, for example, one or more selected from 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, 2-phenyl-1,3-butadiene and 2-halogeno-1,3-butadiene (halogeno refers to a halogen atom).

[0095] In addition, the polymer unit also contains repeating units from aromatic vinyl monomers, and the aromatic vinyl monomers can 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.

[0096] In another embodiment, the polymer unit may be a copolymer further comprising a repeating unit from a diene monomer having 1 to 10 carbon atoms and a repeating unit from a conjugated diene monomer. The repeating unit from the diene monomer may be a repeating unit from a diene monomer different from the conjugated diene monomer, and the diene monomer different from the conjugated diene monomer may be, for example, 1,2-butadiene. If the conjugated diene polymer is a copolymer further comprising a diene monomer, the conjugated diene polymer may comprise a repeating unit from a diene monomer of greater than 0wt% to 1wt%, greater than 0wt% to 0.1wt%, greater than 0wt% to 0.01wt%, or greater than 0wt% to 0.001wt%, and within this range, the effect of preventing gel formation may be achieved.

[0097] According to one embodiment of the present invention, if two or more monomers are included in the polymer unit of the conjugated diene polymer, a chain structure intermediate between a random copolymer and a block copolymer can be formed, in which case the microstructure can be easily controlled and an excellent physical property balance effect can be achieved. A random copolymer may refer to a disordered arrangement of the repeating units forming the copolymer.

[0098] Glass transition temperature of polymers

[0099] According to one embodiment of the present invention, the glass transition temperature of the conjugated diene polymer may be -100° C. to 20° C. The glass transition temperature is a value that varies depending on the microstructure of the polymer, but in order to improve wear resistance, the polymer is preferably prepared to satisfy the above range, more preferably -100° C. to 0° C., more preferably -90° C. to -10° C., and even more preferably -80° C. to -20° C.

[0100] The glass transition temperature can be flexibly controlled according to the polymerization method and polymerization conditions by the bonding method (1,2-bond or 1,4-bond) of the conjugated diene monomer in the polymer unit, the presence or absence of repeating units derived from aromatic vinyl monomers, the content of repeating units derived from aromatic vinyl monomers, and the microstructure in each unit (1,2-vinyl bond content and styrene bond content).

[0101] In addition, the 1,2-vinyl bond content of the conjugated diene polymer may be 10 to 80 parts by weight, preferably 20 to 60 parts by weight, and more preferably 20 to 50 parts by weight, relative to 100 parts by weight of the polymer. If the microstructure is controlled in this way, balanced improvement in wear resistance and wet skid resistance can be expected, while having excellent tensile properties and running resistance.

[0102] Oil-extended modified conjugated diene polymers

[0103] According to one embodiment of the present invention, there is provided an oil-extended modified conjugated diene polymer, comprising: a modified polymer unit comprising a repeating unit derived from a conjugated diene monomer and a functional group derived from a modifier; and a vegetable oil, wherein, in a tan δ diagram according to temperature obtained by dynamic viscoelastic analysis performed by an advanced rheological extension system (ARES), a full width at half maximum (FWHM) value of a tan δ peak displayed in a temperature range of -100°C to 100°C is 20°C or higher, 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.

[0104] The description about the tan δ peak, the vegetable oil, and the unit derived from the monomer has been provided in the above-mentioned conjugated diene-based polymer, and the description thereof will be omitted.

[0105] Si content and N content of polymer

[0106] Meanwhile, based on the gross weight of polymer, Si content and N content of the modified conjugated diene polymer according to one embodiment of the present invention can be 50ppm or more, or 50ppm to 1000ppm respectively. The lower limit can preferably be 100ppm or more, 150ppm or more respectively, and the upper limit can preferably be 700ppm or less respectively, preferably 500ppm or less respectively. Within these scopes, the mechanical properties (such as tensile properties and viscoelastic properties) of the rubber composition comprising the modified conjugated diene polymer can be excellent. Meanwhile, owing to the introduction of compounds with modified functional groups, such as modifiers (which will be described later), modified initiators and modified monomers, Si and N can be from these compounds.

[0107] Alkoxysilane modifiers

[0108] According to one embodiment of the present invention, the modified conjugated diene polymer includes a functional group from a modifier, and the modifier is used to modify the terminal of the polymer, and in particular, 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 make the silica filler interact with the functional group from the modifier.

[0109] The modifier can be an alkoxysilane modifier, particularly an alkoxysilane modifier containing one or more heteroatoms including nitrogen atoms, oxygen atoms and sulphur atoms. If alkoxysilane compounds are used as modifiers, 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 bonding state 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 compounds contain nitrogen atoms, then in addition to the effect due to the silyl group, the effect of the physical property improvement due to the nitrogen atoms can also be expected. In order to best embody this effect, preferably the compound containing the N functional group is applied.

[0110] According to one embodiment of the present invention, the modifier may include a compound represented by Formula 1 below.

[0111] [Formula 1]

[0112]

[0113] In formula 1, R 1 It can be a single bond or an alkylene group with 1 to 10 carbon atoms, R 2 and R 3 may be independently an alkyl group of 1 to 10 carbon atoms, R 4 may be hydrogen, an alkyl group having 1 to 10 carbon atoms, a mono-, di- or tri-substituted alkylsilyl group having an alkyl group having 1 to 10 carbon atoms, or a heterocyclic ring having 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.

[0114] In a specific embodiment, in Formula 1, R 1 It can be a single bond or an alkylene group with 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 trialkylsilyl group substituted by an alkyl group of 1 to 5 carbon atoms, or a heterocyclic group of 2 to 5 carbon atoms. 21It may be a single bond, an alkylene group of 1 to 5 carbon atoms, or -[R 42 O] j -, where R 42 It may be an alkylene group of 1 to 5 carbon atoms, a may be an integer of 2 or 3, m may be an integer selected from 1 to 3, n may be an integer of 0, 1 or 2, wherein m+n=3 may be satisfied, and j may be an integer selected from 1 to 10.

[0115] In formula 1, if R 4 is a heterocyclic group, the heterocyclic group may be unsubstituted or substituted by a trisubstituted alkoxysilyl group, and if the heterocyclic group is substituted by a trisubstituted alkoxysilyl group, the trisubstituted alkoxysilyl group may be substituted by connecting the heterocyclic group 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.

[0116] In a more specific embodiment, the compound represented by Formula 1 may be one selected from the group consisting of N,N-bis(3-(dimethoxy(methyl)silyl)propyl)-methyl-1-amine, N,N-bis(3-(diethoxy(methyl)silyl)propyl)-methyl-1-amine, N,N-bis(3-(trimethoxysilyl)propyl)-methyl-1-amine, N,N-bis(3-(triethoxysilyl)propyl)-methyl-1-amine, N,N-diethyl-3-(trimethoxysilyl)propyl)-methyl-1-amine, N,N-diethyl-3-(triethoxysilyl)propane-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)methane-1-amine, N-(3-(1H-1,2,4-triazole-1-yl)propyl)-1,1,1-trimethylsilylamine 1-(trimethoxysilyl)propyl)-3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propane-1-amine, 3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)-N-(3-(1-(3-(trimethoxysilyl)propyl)-1H-1,2,4-triazol-3-yl)propyl)propane-1-amine, N,N-bis(2-(2-methoxyethoxy)ethyl)-3-(triethoxysilyl)propane-1-amine, N,N- Bis(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.

[0117] In another embodiment, the modifier may include a compound represented by Formula 2 below.

[0118] [Formula 2]

[0119]

[0120] 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, R12 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 Where R 13 , R 14 , R 15 and R 16 Each independently may be hydrogen or an alkyl group of 1 to 10 carbon atoms.

[0121] In a specific embodiment, the compound represented by Formula 2 can be one selected from the following groups: N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propane-1-amine and 3-(4,5-dihydro-1H-imidazol-1-yl)-N,N-bis(3-(triethoxysilyl)propyl)propane-1-amine.

[0122] In another embodiment, the modifier may include a compound represented by Formula 3 below.

[0123] [Formula 3]

[0124]

[0125] 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, 1 To L 4 may be each independently a mono-substituted, di-substituted or tri-substituted alkylsilyl group of 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 Each may 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 of them is combined with each other to form a ring, and the ring thus formed may include 1 to 3 one or more heteroatoms selected from N, O and S.

[0126] 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 trialkylsilyl 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 Each may 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 of them is combined with each other to form a ring, and the ring thus formed may include 1 to 3 one or more heteroatoms selected from N, O and S.

[0127] In a more specific embodiment, the compound represented by Formula 3 may be one selected from the group consisting of 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), 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-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-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), 3,3-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.

[0128] In another embodiment, the modifier may include a compound represented by Formula 4 below.

[0129] [Formula 4]

[0130]

[0131] 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 of 1 or more, and f may be an integer of 1 to 30.

[0132] Specifically, in Formula 4, R 22 and R 23 may be each independently an alkylene group having 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 of 1 or more, and f may be an integer of 1 to 30.

[0133] More specifically, the compound represented by Formula 4 may be a compound represented by the following Formula 4a, Formula 4b, or Formula 4c.

[0134] [Formula 4a]

[0135]

[0136] [Formula 4b]

[0137]

[0138] [Formula 4c]

[0139]

[0140] In Formula 4a, Formula 4b and Formula 4c, R 22 To R 27 , d and e are the same as above.

[0141] In a more specific embodiment, the compound represented by Formula 4 can be one selected from the group consisting of 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)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.

[0142] In another embodiment, the modifier may include a compound represented by Formula 5 below.

[0143] [Formula 5]

[0144]

[0145] In Formula 5, R 30 It can be a monovalent hydrocarbon group with 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.

[0146] In another embodiment, the modifier may include a compound represented by Formula 6 below.

[0147] [Formula 6]

[0148]

[0149] 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 selected from 1 to 30.

[0150] In another embodiment, the modifier may include one or more selected from the group consisting of 3,4-bis(2-methoxyethoxy)-N-(4-(triethoxysilyl)butyl)aniline, N,N-diethyl-3-(7-methyl-3,6,8,11-tetraoxa-7-silatridecan-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-trisilapentadecane.

[0151] In another embodiment, the modifier may include a compound represented by Formula 7 below.

[0152] [Formula 7]

[0153]

[0154] In formula 7, R 43 , R 45 and R 46may be independently an alkyl group of 1 to 10 carbon atoms, R 44 May be an alkylene group having 1 to 10 carbon atoms, and k may be an integer selected from 1 to 4.

[0155] In a more specific embodiment, the compound represented by Formula 7 may be one selected from the group consisting of 8,8-dibutyl-3,13-dimethoxy-3,13-dimethyl-2,14-dioxa-7,9-dithia-3,13-disila-8-stannapentadecane, 8,8-dibutyl-3,13-dimethoxy-3,13-dimethyl-2,14-dioxa-7,9-dithia-3,13-disila-8-stannapentadecane, 8-Dimethyl-3,13-dimethoxy-3,13-dimethyl-2,14-dioxa-7,9-dithia-3,13-disila-8-stannapentadecane, 8,8-dibutyl-3,3,13,13-tetramethoxy-2,14-dioxa-7,9-dithia-3,13-disila-8-stannapentadecane and 8-butyl-3,3,13,13-tetramethoxy-8-((3-(trimethoxysilyl)propyl)thio)-2,14-dioxa-7,9-dithia-3,13-disila-8-stannapentadecane.

[0156] In another embodiment, the modifier may include a compound represented by Formula 8 below.

[0157] [Formula 8]

[0158]

[0159] 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 having 1 to 10 carbon atoms, and m1, m2, m3 and m4 are each independently an integer of 1 to 3.

[0160] In another embodiment, the modifier may include a compound represented by Formula 9 below.

[0161] [Formula 9]

[0162]

[0163] 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 -R e7 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 Each independently represents 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.

[0164] In another embodiment, the modifier may include a compound represented by Formula 10 below.

[0165] [Formula 10]

[0166]

[0167] 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,

[0168] R f3 To R f8 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aralkyl group having 7 to 14 carbon atoms, and p is an integer of 0 or 1, wherein when p is 0, R f1 It is an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

[0169] In another embodiment, the modifier may include a compound represented by Formula 11 below.

[0170] [Formula 11]

[0171]

[0172] In formula 11, R g1 To R g4Each is independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or -R g5 S O g6 , where R g1 To R g4 At 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 group of 1 to 10 carbon atoms, and Y is C or N, wherein when Y is N, R g4 Does not exist.

[0173] In another embodiment, the modifier may include a compound represented by Formula 12 below.

[0174] [Formula 12]

[0175]

[0176] In formula 12, R h1 and R h2 Each independently represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, R h3 is a single bond or an alkylene group of 1 to 10 carbon atoms, and 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.

[0177] In another embodiment, the modifier may include a compound represented by Formula 13 below.

[0178] [Formula 13]

[0179]

[0180] In formula 13, R g1 To R g3 Each independently represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 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.

[0181] Shrinkage Factor

[0182] The oil-extended modified 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, more specifically, 0.3 to 0.9, as measured by gel permeation chromatography-light scattering method equipped with a viscosity detector.

[0183] 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 indicator of the branched structure of the branched polymer, that is, an indicator of the proportion of the branch. For example, as the shrinkage factor decreases, 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, the shrinkage factor decreases as the number of branches increases, and thus the shrinkage factor can be used as an indicator of the degree of branching.

[0184] 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, an absolute molecular weight and an intrinsic viscosity corresponding to each absolute molecular weight are obtained using a GPC-light scattering measuring device equipped with a light scattering detector (in which two chromatographic columns using a polystyrene-based gel as a filler are connected) and a viscosity detector, the intrinsic viscosity of the linear polymer corresponding to the absolute molecular weight is calculated, and then the shrinkage factor is obtained as a ratio of the intrinsic viscosity corresponding to each absolute molecular weight. For example, the shrinkage factor is shown as follows: the absolute molecular weight is obtained from 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] with respect to the absolute molecular weight is obtained from the light scattering detector and the viscosity detector, the intrinsic viscosity [η]0 of the linear polymer with respect to the absolute molecular weight is calculated by the following mathematical formula 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 chromatographic column, and measurement was performed under the conditions of an oven temperature of 40°C and a THF flow rate of 1.0 mL / min, and a sample was prepared by dissolving 15 mg of a polymer in 10 mL of tetrahydrofuran.

[0185] [Mathematical formula 1]

[0186] [η]0=10 -3.883 M 0.771

[0187] In mathematical formula 1, M is the absolute molecular weight.

[0188] In addition, the vinyl content of the oil-extended modified conjugated diene polymer may be 5wt% or more, 10wt% or more, or 10wt% to 60wt%. 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 100wt% of the conjugated diene polymer composed of the monomer having a vinyl group and the aromatic vinyl monomer.

[0189] Mooney relaxation rate

[0190] In another embodiment, the Mooney relaxation rate of the oil-extended 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 relaxation rate may be less than 0.7, preferably 0.6 or less, more preferably 0.5 or less, and most preferably 0.4 or less, and in the case of a linear polymer with a small degree of branching, the Mooney relaxation rate may preferably be 0.7 to 2.5, more preferably 0.7 to 2.0.

[0191] Here, the Mooney relaxation rate indicates the stress change shown as a response to the same amount of strain, and can be measured using a Mooney viscometer. Specifically, the Mooney relaxation rate is obtained as follows using the large rotor of Monsanto Co.'s MV2000E at 100°C and a rotor speed of 2±0.02rpm: the polymer is placed at room temperature (23±5°C) for more than 30 minutes, 27±3g of the polymer is collected and placed in a mold cavity, a torque is applied by operating the Platen and the Mooney viscosity is measured, and the slope value of the Mooney viscosity change displayed is measured while the torque is released.

[0192] At the same time, the Mooney relaxation rate can be used as an indicator of the branched structure of the corresponding polymer. For example, when comparing polymers with the same Mooney viscosity, the Mooney relaxation rate decreases as the branching increases, and thus can be used as an indicator of the degree of branching.

[0193] Other properties of polymers

[0194] The oil-extended (modified) conjugated diene polymer according to one embodiment of the present invention may contain a functional group from a modified initiator at the other end in addition to one end containing a functional group from a modifier, wherein the modified initiator may be a reaction product of a compound containing an N functional group and an organic metal compound.

[0195] Specifically, the compound containing an N functional group can be a substituted or unsubstituted aromatic hydrocarbon compound, which contains an N functional group, and the N functional group includes an amino group, an amide group, an amino group, an imidazolyl group, an imidazolyl group, a pyrimidinyl 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 aralkyl group of 7 to 20 carbon atoms or an alkoxysilyl group of 1 to 10 carbon atoms.

[0196] According to one embodiment of the present invention, the weight average molecular weight (Mw) of the oil-extended (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, the running resistance and wet skid resistance can be more balanced and excellent.

[0197] In addition, the oil-extended (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, so that a polymer with excellent tensile properties can be obtained, and if prepared by the above-mentioned preparation method, the effects of extending the polymer chain length and controlling the microstructure can be achieved.

[0198] The number average molecular weight (Mn) of the oil-extended (modified) conjugated diene polymer may 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 may be preferably 400,000 g / mol or greater, more preferably 500,000 g / mol or greater. In addition, the peak molecular weight (Mp) may 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 wet skid resistance effects may be obtained.

[0199] In addition, the oil-extended (modified) conjugated diene polymer may have a unimodal molecular weight distribution curve obtained by gel permeation chromatography (GPC) and a molecular weight distribution of 1.0 to 3.0, preferably 1.0 to 2.5, more preferably 1.0 to 2.0, and further more preferably 1.0 to less than 1.7, wherein the unimodal curve shape and the molecular weight distribution may be satisfied simultaneously by continuous polymerization (which will be described later).

[0200] Generally speaking, there is a problem that in continuous polymerization, the molecular weight distribution is unimodal and wide, the processability is excellent, but the tensile properties and viscoelastic properties are poor, while in batch polymerization, the molecular weight distribution is bimodal and narrow, the tensile properties and viscoelastic properties are excellent, but the processability is poor and the productivity is low. However, if the preparation method according to one embodiment of the present invention (which will be described later) is applied, the molecular weight distribution can be selectively reduced to the greatest extent through continuous preparation, thereby making it easy to control the balance between physical properties such as processability, tensile properties and viscoelastic properties.

[0201] Furthermore, the oil-extended (modified) conjugated diene-based polymer according to one embodiment of the present invention needs to satisfy a Mooney viscosity measured under ASTM D1646 of 40 to 140, preferably 45 to 120. There may be many measures for evaluating processability, but if the Mooney viscosity satisfies the above range, processability is remarkably excellent.

[0202] The oil-extended (modified) conjugated diene polymer according to one embodiment of the present invention determines the polymer structure to have a difference between the glass transition starting temperature and the end temperature by controlling the microstructure of the polymer, such as the aforementioned styrene bond content and 1,2-vinyl bond content, 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, and can be expected to achieve the effects of balanced improvement in wear resistance and wet skid resistance while maintaining excellent tensile properties, fuel consumption performance and processability.

[0203] Preparation method of oil-extended conjugated diene polymer

[0204] In order to prepare the oil-extended conjugated diene-based polymer, the present invention provides a method for preparing the conjugated diene-based polymer as follows.

[0205] The method for preparing oil-extended conjugated diene polymers is characterized in that it is a continuous preparation method, and comprises: polymerizing conjugated diene monomers and aromatic vinyl monomers (S1) in the presence of a hydrocarbon solvent, a polymerization initiator and a polar additive; mixing vegetable oil (S2) after step (S1), wherein step (S1) is continuously carried out in two or more polymerization reactors, the polymer is transported to the second reactor when the polymerization conversion rate in the first reactor is 70% to 85%, and the polar additive, or the polar additive and the conjugated diene monomer are additionally added to the second reactor.

[0206] Hereinafter, the description of the physical properties (eg, viscoelastic behavior) of the oil-extended conjugated diene-based polymer is as provided above, and the description of the preparation method will be mainly given.

[0207] Furthermore, the explanation about the conjugated diene-based monomer and the aromatic vinyl-based monomer used for the polymerization is provided above, and the description thereof will be omitted.

[0208] 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.

[0209] Based on 1.0 equivalent of monomer, the consumption of polymerization initiator can be 0.1 equivalent to 3.0 equivalent, preferably 0.1 equivalent to 2.0 equivalent, more preferably 0.5 equivalent to 1.5 equivalent.In another embodiment, based on 100g monomer in total, the consumption of 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, 100g monomer in total can be conjugated diene monomer, or the sum of conjugated diene monomer and aromatic vinyl monomer.

[0210] 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.

[0211] 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.

[0212] 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.

[0213] Step S1

[0214] According to one embodiment of the present invention, step (S1) in the preparation method is a step of carrying out a polymerization reaction of conjugated diene monomers and aromatic vinyl monomers by, for example, anionic polymerization. In a specific embodiment, the anionic polymerization may be a living anionic polymerization, whereby an anionic active portion is formed at the polymerization end by the growth reaction of the anion. In addition, the polymerization of step (S1) may be heating polymerization, isothermal polymerization or constant temperature polymerization (adiabatic polymerization). Constant temperature polymerization may refer to a polymerization method comprising the step of using the reaction heat generated by itself without optionally applying heat to polymerize after adding a polymerization initiator; heating polymerization may refer to a polymerization method comprising: injecting a polymerization initiator and then raising the temperature by optionally applying heat; isothermal polymerization may refer to a polymerization method by which the temperature of the polymer is kept constant by applying heat to increase heat or removing heat after injecting a polymerization initiator.

[0215] In addition, according to one embodiment of the present invention, the polymerization of step (S1) can be carried out by further 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.

[0216] 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 can be 70% to 85%, or 70% to 80%. That is, the polymerization of step (S1) can be carried out only until the polymerization conversion rate in the first polymerization reactor reaches 70% or more, 70% to 85%, or 70% to 80%.

[0217] 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. Therefore, the half-maximum full width of the tan δ peak obtained by dynamic mechanical analysis becomes wider, thereby providing a basis for improving wear resistance.

[0218] The polymerization in the first reactor can be carried out, for example, in the temperature range of 80°C or lower, -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 narrower and an excellent effect of improving physical properties can be obtained.

[0219] 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 conversion rate is reached in the first reactor, the polymer is transported to the second reactor, and a polar additive or a conjugated diene monomer can be additionally injected into the second reactor.

[0220] In this case, the additionally injected polar additive or the polar additive and the conjugated diene-based monomer may be injected at once or in sequence, and may be injected in batches at each of the points within the range, or may be continuously injected within the points within the range.

[0221] The additional injection of polar additives or polar additives and conjugated diene monomers together with controlling the conversion rate in the first reactor can be a means for achieving glass transition temperature properties of the prepared polymer. By additionally injecting polar additives, further power can be applied to the polymerization reaction after a certain conversion rate, thereby producing deformation of the microstructure.

[0222] In particular, in the case of copolymerizing a conjugated diene-based monomer and an aromatic vinyl-based monomer, the difference in reaction rate between the monomers may be corrected by a polar additive, thereby achieving an induction effect of easily forming a random copolymer.

[0223] In this case, the additionally injected polar additive can be used in a suitable amount in a direction in which the half maximum width of the tan δ peak can be increased. For example, based on a total of 100 g of the monomer used when initiating the polymerization, the additionally injected polar additive can be used in a ratio of 0.001 g to 10 g, or 0.01 g to 1.0 g, more preferably 0.02 g to 0.5 g.

[0224] In addition, based on 100g of the monomer used in initiating the polymerization, the amount of the conjugated diene monomer selectively injected can be 5g to 25g, or 5g to 20g. If the polar additive or conjugated diene monomer injected is controlled within the above amount, it has the advantage that the glass transition temperature of the polymer can be easily controlled, more precise adjustment can be made, and the half-maximum full width of the tanδ peak obtained by dynamic viscoelastic analysis can be widened.

[0225] Based on a total of 100 g of monomer, the total amount of the polar additive used in the polymerization of step (S1) may be in a ratio of 0.001 g to 50 g, or 0.002 g to 1.0 g. In another embodiment, based on a total of 100 g of polymerization initiator, the total amount of the polar additive may be in a ratio of greater than 0 g to 1 g, 0.01 g to 1 g, or 0.1 g to 0.9 g. Here, the total amount of the polar additive includes an additional injection amount of the polar additive.

[0226] The polymerization in the second reactor can be carried out in the temperature range of 80°C or lower, -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 narrower and excellent effect of improving physical properties can be achieved.

[0227] Meanwhile, when the full width at half maximum of the tan δ peak obtained by dynamic mechanical analysis is additionally controlled, the polymerization temperature in the first reactor and the second reactor may also have an effect, and in this case, it is preferred to control the polymerization temperature of the second reactor to be lower than the polymerization temperature of the first reactor, and the polymerization temperature of the second reactor is preferably 60° C. or higher.

[0228] The polar additive may be, for example, one or more selected from tetrahydrofuran, 2,2-bis(2-tetrahydrofuranyl)propane, ethyl 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.

[0229] Meanwhile, the polymerization conversion rate can be determined, for example, by measuring the solid concentration in the polymer solution phase containing the polymer during the polymerization. In a specific embodiment, in order to ensure the polymer solution, a cylindrical container is installed at the outlet of each polymerization reactor to charge a certain amount of polymer solution into 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 (e.g., an aluminum pan), the weight (B) of the cylindrical container from which the polymer solution is removed is measured, the aluminum container filled with the polymer solution is dried in an oven at 140° C. for 30 minutes, the weight (C) of the dried polymer is measured, and calculated according to the following Mathematical Formula 2.

[0230] [Mathematical formula 2]

[0231]

[0232] In Mathematical Formula 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 amount relative to the 100% polymer solution. For example, if the total solid content is 20wt%, it can be calculated by substituting 20 / 100, i.e. 0.2, in Mathematical Formula 2.

[0233] 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 95% or higher. 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 when preparing the 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 the art without limitation.

[0234] In addition, the living polymer prepared through step (S1) may refer to a polymer in which a polymer anion and an organic metal cation of a polymerization initiator are bonded.

[0235] Step S2

[0236] Step (S2) may be performed by adding and mixing the vegetable oil before drying the polymer after step (S1).

[0237] Preparation method of modified conjugated diene polymer

[0238] The present invention provides a method for preparing a modified conjugated diene-based polymer as follows to prepare the modified conjugated diene-based polymer.

[0239] The method for preparing modified conjugated diene polymers is a continuous preparation method, and is characterized in that it includes: polymerizing conjugated diene monomers and aromatic vinyl monomers in the presence of a hydrocarbon solvent, a polymerization initiator and a polar additive to prepare an active polymer (S3); performing a modification reaction by reacting the active polymer with a modifier (S4); adding and mixing vegetable oil (S5), wherein step (S3) is continuously carried out in two or more polymerization reactors, and when the polymerization conversion rate in 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.

[0240] In the method for preparing the modified conjugated diene polymer, the step (S3) of preparing the active polymer and the step (S5) of mixing the vegetable oil are respectively the same as the step (S1) and the step (S2) of preparing the conjugated diene polymer, and their description will be omitted.

[0241] Step S4

[0242] Step (S4) is a modification step by reacting the active polymer prepared in step (S3) with a modifier, 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 of 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.

[0243] In addition, according to one embodiment of the present invention, the modifier can be injected into the modification reactor, and step (S4) can be performed in the modification reactor. In another embodiment, the modifier can be injected into the delivery section for delivering the active polymer prepared in step (S3) to the modification reactor for performing step (S4), and the active polymer and the modifier can be mixed in the delivery section to react. In this case, the reaction can be a modification reaction in which only the modifier is coupled to the active polymer, or a coupling reaction for connecting the active polymer based on the modifier.

[0244] Meanwhile, in the preparation method of the modified conjugated diene polymer, before the modification reaction in step (S4), a step of additionally injecting a conjugated diene monomer into the active polymer prepared in step (S3) and reacting the conjugated diene monomer may be further performed, in which 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.

[0245] The preparation method of the oil-extended (modified) conjugated diene polymer according to one embodiment of the present invention is a method that can meet the performance requirements of the above-mentioned oil-extended (modified) conjugated diene polymer, and as mentioned above, if the performance requirements are met, the effects to be achieved in the present invention can be achieved, but by diversified control of other polymerization conditions, the physical properties of the oil-extended (modified) conjugated diene polymer according to the present invention can be achieved.

[0246] Rubber composition

[0247] According to the present invention, a rubber composition is provided, which comprises the oil-extended conjugated diene polymer or the oil-extended modified conjugated diene polymer.

[0248] In another embodiment, according to an embodiment of the present invention, there is provided a rubber composition comprising a conjugated diene polymer and a filler, wherein, in a tan δ diagram according to temperature obtained by dynamic viscoelastic analysis performed by an advanced rheological extension system (ARES), a full width at half maximum (FWHM) value of a tan δ peak displayed in a temperature range of -100°C to 100°C is 31°C or higher, wherein 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, and the conjugated diene polymer comprises a vegetable oil.

[0249] The full width at half maximum of the tanδ peak may be 31°C or higher, preferably 35°C or higher, and more preferably 40°C or higher. In addition, the full width at half maximum may be a maximum of 100°C, preferably 80°C or lower. If the full width at half maximum is less than 31°C, there will be a problem of significantly reducing the wet skid resistance at the same glass transition temperature, and it is unlikely to achieve a full width at half maximum of more than 100°C, but even if it is achieved, phase separation may occur, inevitably accompanied by the defect of increased hysteresis at high temperatures, and the defect of deteriorating fuel consumption performance may occur.

[0250] In addition, the tan δ peak may be shown at -100°C to 100°C, preferably -80°C to 20°C, and more preferably -70°C to 0°C. If the peak is shown in this range, a more favorable wear resistance effect can be expected. Here, the conjugated diene-based polymer may be unmodified or modified with a modifier.

[0251] 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 excellent balance between physical properties can be achieved.

[0252] In addition, in addition to the (modified) conjugated diene polymer, the rubber composition may also include other rubber components as required, and in this case, based on the total weight of the rubber composition, the content of the rubber component may be 90wt% or less. In a specific embodiment, based on 100 parts by weight of the (modified) conjugated diene polymer, the content of other rubber components may be 1 part by weight to 900 parts by weight.

[0253] The rubber component may be, for example, a natural rubber or a synthetic rubber, and in particular may be: a natural rubber (NR) including cis-1,4-polyisoprene; a modified natural rubber obtained by modifying or purifying ordinary 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.

[0254] 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 filler based on silica, in particular wet silica (hydrated silicate), dry silica (anhydrous silicate), calcium silicate, aluminum silicate, colloidal silica, etc., and preferably, the filler may be wet silica, which has the most significant effect of improving damage characteristics and the compatibility effect of wet road adhesion. In addition, as required, the rubber composition may also contain a carbon-based filler.

[0255] In another embodiment, if silica is used as a filler, a silane coupling agent may be used together to improve 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-dimethylthiocarbamoyl 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.

[0256] In addition, in the rubber composition according to one embodiment of the present invention, since the modified conjugated diene polymer used as the rubber component introduces a functional group having a high affinity with silica in the active part, the mixing amount of the silane coupling agent can be less than that of the usual case. 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 the rubber component from gelling can be achieved.

[0257] 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 be particularly sulfur powder, and the content may be 0.1 to 10 parts by weight based on 100 parts by weight of the rubber component, and within the above range, the elasticity and strength required for the vulcanized rubber composition may be ensured, while achieving excellent low fuel consumption.

[0258] The rubber composition according to one embodiment of the present invention may further contain various additives used in the general rubber industry in addition to the above components, particularly vulcanization accelerators, processing oils, plasticizers, anti-aging agents, scorch retardants, zinc white, stearic acid, thermosetting resins or thermoplastic resins.

[0259] The vulcanization accelerator may include, for example, a thiazole-based compound such as 2-mercaptobenzothiazole (M), dibenzothiazolyl disulfide (DM) and N-cyclohexyl-2-benzothiazolylsulfenamide (CZ), or a guanidine-based compound such as diphenylguanidine (DPG), in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the rubber component.

[0260] 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 the deterioration of low heat release performance (low fuel consumption rate) can be prevented.

[0261] 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 may be used in an amount of 0.1 to 6 parts by weight based on 100 parts by weight of the rubber component.

[0262] 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 roller 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.

[0263] 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.

[0264] Furthermore, the present invention provides a tire manufactured using the rubber composition.

[0265] The tire may be a tire or include a tire tread.

[0266] Example

[0267] Hereinafter, the present invention will be explained in more detail with reference to embodiments. Embodiments according to the present invention can be changed into various other types, and the scope of the present invention should not be limited to the embodiments described below. Embodiments of the present invention are provided to fully explain the present invention to those with general knowledge in the art.

[0268] Experimental Data I

[0269] Example 1

[0270] Into the first reactor of the three continuously stirred liquid phase reactors (CSTR), n-hexane at a flow rate of 5 kg / hour, a monomer solution in which 60 wt% of 1,3-butadiene was dissolved in n-hexane at a flow rate of 1.6 kg / hour, a monomer solution in which 60 wt% of styrene was dissolved in n-hexane at a flow rate of 0.31 kg / hour, an initiator solution in which 6.6 wt% of n-butyl lithium was dissolved in n-hexane at a flow rate of 8.33 g / hour, and a polar additive solution in which 2 wt% of di(tetrahydrofuryl)propane as a polar additive was dissolved in n-hexane at a flow rate of 2.25 g / hour. 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.

[0271] Then, the temperature of the second reactor was maintained at 60°C, and into the second reactor, a solution of 60wt% of 1,3-butadiene dissolved in n-hexane at a flow rate of 0.2kg / hour and a polar additive solution of 10wt% of di(tetrahydrofuranyl)propane dissolved in n-hexane at a flow rate of 6g / hour were continuously injected 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 delivery pipe, and a solution of 5wt% of N,N-dimethyl-3-(trimethoxysilyl)propane-1-amine dissolved in n-hexane as a modifier was injected at a flow rate of 17.8g / hour, and then reacted for 30 minutes.

[0272] Thereafter, soybean oil was continuously injected into the third reactor at a flow rate of 200 g / hour and mixed.

[0273] Then, IR1520 (BASF Co.) solution in which 30 wt% of an antioxidant was dissolved was injected at a rate of 100 g / hour and stirred. The polymer thus obtained was injected into hot water heated with steam, stirred to remove the solvent, and roller dried to remove the residual solvent and water, thereby preparing a modified conjugated diene polymer.

[0274] Example 2

[0275] A modified 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 at a flow rate of 1.13 kg / hour, a monomer solution in which 60 wt% of styrene was dissolved in n-hexane at a flow rate of 0.28 kg / hour, and a polar additive solution at a flow rate of 4.0 g / hour were continuously injected into the first reactor, the polymer was transported from the first reactor to the second reactor when the polymerization conversion rate in the first reactor reached 72%, and a solution in which 5 wt% of N,N-bis(oxiran-2-ylmethyl)-3-(trimethoxysilyl)propan-1-amine as a modifier was dissolved in n-hexane at a flow rate of 29.0 g / hour was injected into the third reactor.

[0276] Example 3

[0277] A modified 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 at a flow rate of 1.08 kg / hour, a monomer solution in which 60 wt% of styrene was dissolved in n-hexane at a flow rate of 0.35 kg / hour, and a polar additive solution at a flow rate of 3.0 g / hour were continuously injected into the first reactor, a solution in which 60 wt% of 1,3-butadiene was dissolved in n-hexane at a flow rate of 0.24 kg / hour was injected into the second reactor, and a solution in which 5 wt% of 3,3'-(piperazine-1,3-diyl)bis(N,N-bis(3-triethoxysilyl)propyl)propane-1-amine as a modifier was dissolved in n-hexane at a flow rate of 60.0 g / hour was injected into the third reactor.

[0278] Example 4

[0279] A modified conjugated diene polymer was prepared by the same method as in Example 1, except that in Example 1, the polymerization reactants were transported to the second reactor when the polymerization conversion rate in the first reactor reached 80%, and a solution of 5 wt % of 2,2-dimethoxy-1-(3-(trimethoxysilyl)propyl)-1,2-azasilolidine as a modifier dissolved in n-hexane was injected into the third reactor at a flow rate of 23.4 g / hour.

[0280] Example 5

[0281] A modified conjugated diene polymer was prepared by carrying out 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 75%, and cottonseed oil was continuously injected at a flow rate of 200 g / hour instead of soybean oil.

[0282] Example 6

[0283] A modified 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 continuously injected into the first reactor at a flow rate of 1.37 kg / hour, the internal temperature of the first reactor was maintained at 70°C, 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 monomer solution in which 60 wt% of 1,3-butadiene was dissolved in n-hexane was not injected into the second reactor.

[0284] Comparative Example 1

[0285] A modified 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 at a flow rate of 1.13 kg / hour and a monomer solution in which 60 wt% of styrene was dissolved in n-hexane at a flow rate of 0.28 kg / hour were injected into the first reactor, 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.

[0286] Comparative Example 2

[0287] A modified 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 at a flow rate of 1.08 kg / hour, a monomer solution in which 60 wt% of styrene was dissolved in n-hexane at a flow rate of 0.35 kg / hour, and a polar additive solution at a flow rate of 3.0 g / hour were injected into the first reactor, the polymerization reactants were transported to the second reactor when the polymerization conversion rate in the first reactor reached 64%, and 1,3-butadiene was not injected into the second reactor.

[0288] Comparative Example 3

[0289] A modified conjugated diene polymer was prepared by the same method as in Example 1, except that in Example 1, an initiator solution in which 6.6 wt % of n-butyl lithium was dissolved in n-hexane was continuously injected into the first reactor at a flow rate of 8.34 g / hour, and the polymerization reactant was transported to the second reactor when the polymerization conversion rate in the first reactor reached 55%.

[0290] Comparative Example 4

[0291] A modified conjugated diene polymer was prepared by 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 75%, and the step of injecting soybean oil into the third reactor and mixing was not performed.

[0292] Comparative Example 5

[0293] A modified conjugated diene polymer was prepared by 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 74%, 1,3-butadiene and the polar additive were not injected into the second reactor, and the coupling reaction was carried out by continuously supplying a solution in which 13.5 wt % of silicon tetrachloride as a coupling agent instead of a modifier was dissolved in n-hexane at a flow rate of 3.7 g / hour.

[0294] Experimental Example 1. Evaluation of polymer properties

[0295] For each modified or unmodified conjugated diene polymer prepared in the examples and comparative examples, the styrene unit content and vinyl 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 full width at half maximum of tan δ peak. The results are shown in Table 2 below.

[0296] 1) Styrene bond content and 1,2-vinyl bond content (wt%)

[0297] The styrene bond content (SM) and 1,2-vinyl bond content in each polymer were measured and analyzed using Varian VNMRS 500 MHz NMR.

[0298] 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 the solvent peak as 6.00 ppm, 7.2-6.9 ppm as a random styrene peak, 6.9-6.2 ppm as a block styrene peak, 5.8-5.1 ppm as 1,4-vinyl and 1,2-vinyl peaks, and 5.1-4.5 ppm as a 1,2-vinyl peak.

[0299] 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)

[0300] 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.

[0301] – Column: A combination of two PLgel Olexis (Polymer Laboratories Co.) and one PLgelmixed-C (Polymer Laboratories Co.)

[0302] -Solvent: A mixture of tetrahydrofuran and 2 wt% of an amine compound was used

[0303] -Flow rate: 1ml / min

[0304] -Sample concentration: 1-2 mg / ml (diluted in THF)

[0305] -Injection volume: 100μl

[0306] - Column temperature: 40℃

[0307] -Detector: Refractive index

[0308] -Standard sample: polystyrene (calibrated by cubic function)

[0309] 3) Full width at half maximum (FWHM) of tanδ peak

[0310] For the polymers prepared in the 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 the change of tanδ with 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 is plotted and the full width at half maximum of the peak is obtained from the graph.

[0311] [Table 2]

[0312]

[0313] Referring to Table 2, in the case of the polymers prepared by the preparation method according to the present invention, all tan δ peaks showed half-maximum full width values ​​of 20°C or higher, but it was confirmed that all comparative examples that did not follow the preparation method of the present invention showed values ​​lower than 20°C.

[0314] Thus, 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.

[0315] Experimental Example 2. Performance evaluation of rubber composition

[0316] In order to compare and analyze the physical properties of the rubber compositions containing the modified conjugated diene-based polymers prepared in the examples and comparative examples and the molded articles made therefrom, tensile properties, viscoelasticity, wear resistance and processability were measured respectively, and the results are shown in Table 4 below.

[0317] 1) Preparation of rubber samples

[0318] Each of the modified or unmodified conjugated diene-based polymers of Examples, Comparative Examples and Reference Examples was used as a raw material rubber and compounded under the compounding conditions shown in the following Table 3. The raw materials in Table 3 are expressed in parts by weight based on 100 parts by weight of the raw material rubber.

[0319] [Table 3]

[0320]

[0321] 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), processing 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 mixing device was controlled at 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 mixing, the first compounded mixture was cooled to room temperature, and then the first compounded mixture, sulfur, rubber accelerator (DPG (diphenylguanidine)) and vulcanization accelerator (CZ (N-cyclohexyl-2-benzothiazolylsulfenamide)) were added to the mixing device and mixed at a temperature of 100°C or less to obtain a second compounded mixture. Then, the rubber sample was formed by performing a curing process at 160°C for 20 minutes.

[0322] 2) Tensile strength (kgf / cm 2 )

[0323] The tensile strength was measured by manufacturing each sample according to the ASTM 412 tensile test method and measuring the tensile strength at break. Specifically, the tensile properties were measured at a rate of 50 cm / min at room temperature using a tensile tester of Universal Test Machin 4204 (Instron Co.). The result values ​​in Table 4 are indexed based on the measurement result values ​​of Comparative Example 5, and a higher value indicates a better result.

[0324] 3) Wear resistance (DIN wear test)

[0325] For each rubber sample, a DIN wear test was performed based on ASTM D5963 and expressed as DIN loss index (loss volume index): abrasion resistance index (ARIA, Method A). In Table 4 below, the result values ​​are indexed based on the measurement result values ​​of Comparative Example 5, so that higher values ​​indicate better results.

[0326] 4) Viscoelasticity

[0327] For the rubber sample, 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 the change in tanδ with temperature in the temperature range of -100°C to 100°C in torsion mode at a frequency of 10 Hz, a strain of 0.5%, and a heating rate of 5°C / min to obtain a tanδ graph. 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 wet skid resistance 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 ratio) becomes better. The result values ​​in Table 4 are indexed based on the measurement result values ​​of Comparative Example 5, and therefore, a higher value indicates a better result.

[0328] 5) Processing performance

[0329] By measuring the Mooney viscosity (MV, (ML1+4), @100°C MU) of the first compounded mixture obtained during the rubber sample preparation process in 1), the processing properties of each polymer were compared and analyzed. In this case, the lower the measured value of the Mooney viscosity, the better the processing properties. The result values ​​in Table 4 are indexed based on the result values ​​of Comparative Example 5, so that the higher the value, the better the result.

[0330] Specifically, each first compounded mixture was allowed to stand at room temperature (23±3° C.) for 30 minutes or longer using MV-2000 (ALPHA Technologies Co.) at 100° C. with a large rotor at a rotor speed of 2±0.02 rpm, 27±3 g was collected and put into a mold cavity, and then, the Platen was operated for 4 minutes for measurement.

[0331] [Table 4]

[0332]

[0333] Referring to Table 4, it can be confirmed that, when compared with Comparative Example 5, in the case of the rubber samples containing the polymers of Examples 1 to 6 satisfying the half-maximum full width value of the tan δ peak according to the present invention, well-balanced improvements in wet skid resistance and running resistance are exhibited while maintaining the same level of tensile strength and processability, and at the same time, significantly improved wear resistance is exhibited.

[0334] In contrast, it was confirmed that, in the case of the rubber samples including the polymers of Comparative Examples 1 to 3, wet skid resistance, running resistance, and wear resistance were not improved in a balanced manner, and significantly deteriorated wet skid resistance and wear resistance were exhibited, compared to Examples.

[0335] Furthermore, in the case of the rubber sample including the polymer of Comparative Example 4 (which does not include vegetable oil), it can be confirmed that the wear resistance and processability are significantly reduced compared with Examples.

[0336] From the above results, it can be confirmed that the oil-extended conjugated diene polymer of the present invention controls the half-maximum width of tan δ by controlling the microstructure, and achieves the effect of showing balanced excellent tensile properties, running resistance and processability, and at the same time significantly improving the wet skid resistance and wear resistance by adding vegetable oil.

[0337] Experimental Data II

[0338] Example 7

[0339] Into the first reactor of the three continuously stirred liquid phase reactors (CSTR), n-hexane at a flow rate of 5 kg / hour, a monomer solution in which 60 wt% of 1,3-butadiene was dissolved in n-hexane at a flow rate of 1.16 kg / hour, a monomer solution in which 60 wt% of styrene was dissolved in n-hexane at a flow rate of 0.31 kg / hour, an initiator solution in which 6.6 wt% of n-butyl lithium was dissolved in n-hexane at a flow rate of 8.33 g / hour, and a polar additive solution in which 2 wt% of di(tetrahydrofuryl)propane as a polar additive was dissolved in n-hexane at a flow rate of 2.25 g / hour. In this case, the internal temperature of the reactor was maintained at 60° C., and when the polymerization conversion rate reached 75%, the polymerization reactant was transported from the first reactor to the second reactor through a transport pipe.

[0340] Then, the temperature of the second reactor is maintained at 60° C., and a solution of 60 wt% of 1,3-butadiene dissolved in n-hexane at a flow rate of 0.2 kg / hour and a polar additive solution of 10 wt% of di(tetrahydrofuranyl)propane dissolved in n-hexane at a flow rate of 6 g / hour are continuously injected into the second reactor to participate in the reaction. When the polymerization conversion rate reaches 95% or more, the polymer reactant is transported from the second reactor to the third reactor through a transport pipe, and a solution of 13.5 wt% of silicon tetrachloride dissolved in n-hexane as a coupling agent is continuously supplied at a flow rate of 3.7 g / hour, and then a coupling reaction is carried out.

[0341] Thereafter, soybean oil was continuously injected into the third reactor at a flow rate of 200 g / hour and mixed.

[0342] Then, IR1520 (BASF Co.) solution in which 30 wt% of an antioxidant was dissolved was injected at a rate of 100 g / hour and stirred. The polymer thus obtained was injected into hot water heated with steam, stirred to remove the solvent and roller dried to remove the residual solvent and water, thereby preparing an unmodified conjugated diene polymer.

[0343] Example 8

[0344] An unmodified conjugated diene polymer was prepared by carrying out the same method as in Example 7, except that in Example 7, when the polymerization conversion rate in the first reactor reached 74%, the polymerization reactant was transported from the first reactor to the second reactor, and cottonseed oil was continuously injected at a flow rate of 200 g / hour instead of soybean oil.

[0345] Example 9

[0346] An unmodified conjugated diene-based polymer was prepared by performing the same method as in Example 7, except that in Example 7, when the polymerization conversion rate in the first reactor reached 70%, the polymerization reactant was transferred from the first reactor to the second reactor.

[0347] Example 10

[0348] An unmodified conjugated diene-based polymer was prepared by performing the same method as in Example 7, except that in Example 7, when the polymerization conversion rate in the first reactor reached 80%, the polymerization reactant was transferred to the second reactor.

[0349] Embodiment 11

[0350] An unmodified conjugated diene polymer was prepared by carrying out the same method as in Example 7, except that in Example 7, the internal temperature of the first reactor was maintained at 70° C., the polymerization reactant was transported from the first reactor to the second reactor when the polymerization conversion rate in the first reactor reached 76%, and the monomer solution in which 60 wt % of 1,3-butadiene was dissolved in n-hexane was not injected into the second reactor.

[0351] Comparative Example 6

[0352] An unmodified conjugated diene polymer was prepared by carrying out the same method as in Example 7, except that in Example 7, when the polymerization conversion rate in the first reactor reached 74%, the polymerization reactants were transported from the first reactor to the second reactor, and 1,3-butadiene and the polar additive were not injected into the second reactor.

[0353] Comparative Example 7

[0354] An unmodified 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 at a flow rate of 1.08 kg / hour and a monomer solution in which 60 wt% of styrene was dissolved in n-hexane at a flow rate of 0.35 kg / hour were injected into the first reactor, when the polymerization conversion rate in the first reactor reached 64%, the polymerization reactants were transported to the second reactor, and 1,3-butadiene was not injected into the second reactor.

[0355] Comparative Example 8

[0356] An unmodified conjugated diene-based polymer was prepared by performing the same method as in Example 7, except that in Example 7, when the polymerization conversion rate in the first reactor reached 55%, the polymerization reactant was transferred to the second reactor.

[0357] Comparative Example 9

[0358] An unmodified 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, a monomer solution in which 60 wt% of styrene was dissolved in n-hexane, and a polar additive solution in which 2 wt% of di(tetrahydrofuryl)propane was dissolved in n-hexane, were injected into the first reactor at a flow rate of 1.13 kg / hour, when the polymerization conversion rate in the first reactor reached 76%, the polymerization reactants were transported to the second reactor, and the step of injecting soybean oil into the third reactor and mixing was not performed.

[0359] Experimental Example 3. Evaluation of polymer properties

[0360] For each unmodified conjugated diene-based polymer prepared in the Examples and Comparative Examples, the styrene unit content and vinyl 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 full width at half maximum of tan δ peak. The results are shown in Table 5 below.

[0361] [Table 5]

[0362]

[0363] Referring to Table 5 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 tan δ peak of 20°C or higher, but all comparative examples not following the preparation method according to the present invention showed values ​​lower than 20°C.

[0364] Thus, 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 full width at half maximum of the tan δ peak is increased.

[0365] Experimental Example 4. Performance evaluation of rubber molded products

[0366] In order to compare and analyze the physical properties of the rubber compositions containing each unmodified conjugated diene polymer prepared in the embodiments and comparative examples and the molded articles made therefrom, the half-maximum full width of the tan δ peak, tensile properties, viscoelastic properties, wear resistance and processability were measured by the same method as Experimental Example 2 of Experimental Data I, and the results are shown in Table 6 below.

[0367] Meanwhile, in Table 6 below, the tensile strength, viscoelasticity, wear resistance and processability of Examples 7 to 11 and Comparative Examples 6 to 9 are indexed based on the measured result values ​​of Comparative Example 6, and a higher value indicates a better result.

[0368] [Table 6]

[0369]

[0370] Referring to Table 6, in the case of the rubber samples containing the polymers of Examples 7 to 11 satisfying the half-maximum full width value of tan δ according to the present invention, it can be confirmed that, when compared with Comparative Example 6, the tensile strength, processability, and running resistance are maintained at the same level, while the wet skid resistance and abrasion resistance are significantly improved.

[0371] On the contrary, in the case of the rubber samples containing the polymers of Comparative Examples 7 and 8, it was confirmed that the wet skid resistance and the running resistance were significantly reduced compared with the examples. In addition, it was confirmed that in the case of the rubber sample containing the polymer of Comparative Example 9 (which does not contain vegetable oil), the wet skid resistance and the wear resistance were greatly reduced, and the processability was significantly reduced compared with the examples.

[0372] From the above results, it can be confirmed that the oil-extended modified conjugated diene polymer of the present invention controls the half-maximum width of tan δ by controlling the microstructure, and exhibits balanced excellent tensile properties, running resistance and processability by containing vegetable oil, and at the same time shows the effect of significantly improving wet skid resistance and abrasion resistance.

Claims

1. An oil-extended conjugated diene polymer comprising: A polymer unit comprising a repeating unit derived from a conjugated diene monomer; and Vegetable oil, in, In a tan δ graph according to temperature obtained by dynamic viscoelastic analysis performed by an Advanced Rheological Extension System (ARES), a tan δ peak shown in a temperature range of -80°C to 20°C has a full width at half maximum (FWHM) value of 30°C to 80°C, and The Advanced Rheology Extension System was measured using 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 oil-extended conjugated diene polymer according to claim 1, wherein The full width at half maximum of the tan δ peak is 35°C to 60°C.

3. The oil-extended conjugated diene polymer according to claim 1, wherein The vegetable oil is one or more selected from soybean oil, rapeseed oil, canola oil, sunflower oil, linseed oil, rice bran oil, palm oil, olive oil, peanut oil, oil palm oil, cottonseed oil and coconut oil.

4. The oil-extended conjugated diene polymer according to claim 1, wherein The vegetable oil may be included in an amount of 10 to 60 parts by weight based on 100 parts by weight of the polymer unit.

5. The oil-extended conjugated diene polymer according to claim 1, wherein The polymer unit further comprises a repeating unit derived from an aromatic vinyl-based monomer.

6. An oil-extended modified conjugated diene polymer comprising: A modified polymer unit comprising a repeating unit derived from a conjugated diene monomer and a functional group derived from a modifier; and Vegetable oil, in, In a tan δ graph according to temperature obtained by dynamic viscoelastic analysis performed by an Advanced Rheological Extension System (ARES), a tan δ peak shown in a temperature range of -80°C to 20°C has a full width at half maximum (FWHM) value of 30°C to 80°C, and The Advanced Rheology Extension System was measured using 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.

7. The oil-extended modified conjugated diene polymer according to claim 6, 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.

8. A rubber composition comprising a polymer and a filler, wherein: The polymer is the oil-extended conjugated diene polymer according to claim 1 or the oil-extended modified conjugated diene polymer according to claim 6.

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.

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