Conjugated diene-based polymer and rubber composition comprising the same

Abstract

The present invention relates to a conjugated diene polymer or a modified conjugated diene polymer having excellent wet road resistance and wear resistance in a balanced manner, and to a rubber composition comprising these polymers. In the tanδ graph according to temperature derived from dynamic viscoelasticity analysis by the Advanced Rheometric Expansion System (ARES), the full width at half maximum (FWHM) value of the tanδ peak appearing in the temperature range of -100℃ to 100℃ is 25 or higher, and by adding hydrogen, excellent viscoelastic behavior characteristics are exhibited, and accordingly, an improvement in overall physical properties can be expected.

Description

Technology Field

[0001] The present invention relates to a conjugated diene polymer having balanced excellent wet road resistance and driving resistance and improved wear resistance, and a rubber composition containing the same. Background Technology

[0003] Recently, in response to the demand for lower fuel consumption in automobiles, conjugated diene polymers are required as rubber materials for tires that possess low driving resistance, excellent wear resistance and tensile properties, and handling stability represented by wet road resistance.

[0004] In order to reduce the driving resistance of a tire, there is a method to minimize the hysteresis loss of vulcanized rubber, and indicators for evaluating such vulcanized rubber include rebound elasticity at 50°C to 80°C, tan δ, and Goodrich heat generation. That is, a rubber material with high rebound elasticity at the above temperature or low tan δ and Goodrich heat generation is preferred.

[0005] Natural rubber, polyisoprene rubber, or polybutadiene rubber are known as rubber materials with low hysteresis loss, but they have the problem of low wet road resistance. Accordingly, recently, conjugated diene polymers or copolymers such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) are manufactured by emulsion polymerization or solution polymerization and are used as rubber for tires. Among these, the greatest advantage of solution polymerization compared to emulsion polymerization is that the vinyl structure content and styrene content, which define rubber properties, can be arbitrarily controlled, and molecular weight and properties can be controlled through coupling or modification. Therefore, since structural changes in the final manufactured SBR or BR are easy, and chain end movement can be reduced through chain end bonding or modification, and bonding strength with fillers such as silica or carbon black can be increased, SBR produced by solution polymerization is widely used as rubber material for tires.

[0006] The above solution polymerization SBR is manufactured using an anionic polymerization initiator, and techniques are used to introduce functional groups to the chain ends of the formed polymer by bonding or modifying them using various modifying agents. For example, U.S. Patent No. 4,397,994 discloses a technique in which active anions at the chain ends of a polymer obtained by polymerizing styrene-butadiene under a non-polar solvent using alkyllithium, a monofunctional initiator, are bonded using a binder such as a tin compound.

[0007] In addition, when the above solution polymerized SBR is used as a rubber material, the vinyl content in the SBR can be increased to control the required properties of the tire, such as driving resistance. However, when the vinyl content is high, the braking performance and wear resistance become unfavorable, and therefore, the styrene content in the SBR must be maintained above a certain level, but in this case, there is a problem that the effects resulting from the high vinyl content do not appear.

[0008] Due to these problems, attempts were made to improve driving resistance and wet road resistance in a balanced manner by using a block copolymer SBR containing two block copolymer units with a gradient of styrene and vinyl content as a solution polymerization SBR, but the improvement was only minimal, and when an SBR with a low glass transition temperature is applied to improve wear resistance, wet road resistance tends to deteriorate.

[0009] Accordingly, there is a need to develop polymers that can simultaneously improve wet road resistance and wear resistance while fundamentally meeting product requirements for tensile and fuel efficiency characteristics. Prior art literature

[0011] US 4,397,994 A (1983. 08. 09.) The problem to be solved

[0012] The present invention was devised to solve the problems of the prior art described above, and aims to provide a conjugated diene polymer, which is a hydrogenated polymer, having a characteristic viscoelastic tanδ peak through the control of the polymer's microstructure, in order to realize a tire having balancedly improved wet road resistance and wear resistance while maintaining excellent tensile and fuel efficiency characteristics.

[0013] In addition, the present invention aims to provide a modified conjugated diene polymer that improves wear resistance and wet road resistance through the control of the polymer's own microstructure and hydrogenation, as well as further enhances fuel efficiency characteristics and processability through the introduction of a modifying agent.

[0014] In addition, the present invention aims to provide a rubber composition comprising the conjugated diene polymer and / or a modified conjugated diene polymer. means of solving the problem

[0016] According to one embodiment of the present invention for solving the above problem, the present invention provides a conjugated diene polymer comprising repeating units derived from conjugated diene monomers, wherein in a graph of stress change according to temperature derived from dynamic viscoelasticity analysis by an Advanced Rheometric Expansion System (ARES), the full width at half maximum (FWHM) value of the tanδ peak appearing in the temperature range of -100℃ to 100℃ is 25 or higher, and the rheometric system is measured using a dynamic mechanical analyzer in torsional mode under conditions of a frequency of 10 Hz, a strain of 0.5%, and a heating rate of 5℃ / min, and the hydrogenation rate of the conjugated diene monomer-derived units is 60 mol% or higher.

[0017] In addition, the present invention provides a modified conjugated diene polymer comprising repeating units derived from conjugated diene monomers and functional groups derived from a modifying agent, wherein, in a stress change graph according to temperature derived from dynamic viscoelasticity analysis by an Advanced Rheometric Expansion System (ARES), the full width at half maximum (FWHM) value of the tanδ peak appearing in the temperature range of -100℃ to 100℃ is 25 or higher, and the rheometric system is measured using a dynamic mechanical analyzer in torsional mode under conditions of a frequency of 10 Hz, a strain of 0.5%, and a heating rate of 5℃ / min, and the hydrogenation rate of the conjugated diene monomer-derived units is 60 mol% or higher.

[0018] In addition, the present invention provides a rubber composition comprising a polymer and a filler, wherein the polymer is a conjugated diene polymer or a modified conjugated diene polymer.

[0019] In addition, the present invention provides a rubber composition comprising a conjugated diene polymer and a filler, wherein, in a stress change graph according to temperature derived from dynamic viscoelasticity analysis by an Advanced Rheometric Expansion System (ARES), the full width at half maximum (FWHM) value of the tanδ peak appearing in the temperature range of -100℃ to 100℃ is 31 or higher, the rheometric system is measured using a dynamic mechanical analyzer in torsional mode under conditions of a frequency of 10 Hz, a strain of 0.5%, and a heating rate of 5℃ / min, and the conjugated diene polymer has a hydrogenation rate of a unit derived from a conjugated diene monomer of 60 mol% or higher. Effects of the invention

[0021] The conjugated diene polymer according to the present invention has the effect of improving wear resistance while maintaining a balanced excellent wet road resistance and driving resistance by controlling the microstructure of the polymer, and has the effect of further improving wear resistance by having a hydrogenation rate of 60 mol% or more.

[0022] In addition, the conjugated diene polymer according to the present invention can achieve excellent wear resistance and wet road resistance through microstructure control and hydrogenation, and furthermore, excellent processability, fuel efficiency, and tensile properties can also be achieved through the introduction of an alkoxysilane-based modifier and control of the degree of branching. Brief explanation of the drawing

[0024] The following drawings attached to this specification illustrate specific embodiments of the present invention and serve to further enhance understanding of the technical concept of the present invention together with the aforementioned description; therefore, the present invention should not be interpreted as being limited only to the matters described in such drawings. Figure 1 is an example of a tanδ graph as a function of temperature derived from dynamic viscoelasticity analysis by the Advanced Rheometric Expansion System (ARES). Specific details for implementing the invention

[0025] Hereinafter, the present invention will be described in more detail to aid in understanding the invention.

[0026] Terms and words used in the description and claims of the present invention should not be interpreted as being limited to their ordinary or dictionary meanings, but should be interpreted in a meaning and concept consistent with the technical spirit of the present invention, based on the principle that the inventor can appropriately define the concept of the terms to best describe his invention.

[0028] Definition of Terms

[0029] In this specification, the term "polymer" refers to a polymer compound produced by polymerizing monomers, whether of the same or different types. Thus, the general term polymer encompasses the term homopolymer, which is commonly used to refer to a polymer produced from a single type of monomer, and the term copolymer, as defined below.

[0030] In this specification, the term 'copolymer' refers to a polymer produced by the polymerization of at least two different monomers. Thus, the general term copolymer includes binary copolymers, which are commonly used to refer to polymers produced from two different monomers, and polymers produced from two or more different monomers.

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

[0032] In this specification, the term 'styrene bond content' refers to the mass (or weight) percentage of styrene contained in the polymer chains of the polymer derived from an aromatic vinyl monomer (styrene, etc.) among the polymers.

[0033] In this specification, the term 'room temperature' means a temperature in its natural state without heating or cooling, and is a temperature of 20±5℃.

[0034] In this specification, the term 'hydrogenation rate' refers to the molar ratio of units in which unsaturated bonds among the conjugated diene monomer-derived units have been hydrogenated to become saturated bonds, relative to the total number of conjugated diene monomer-derived units within the copolymer. Specifically, the following structural units (a), (b), (c), and (d) derived from conjugated diene monomers exist within the copolymer, and the hydrogenation rate is the molar ratio of the sum of structural units (b) and (d) relative to the total number of structural units (a) through (d). Here, the hydrogenation rate is of the copolymer 1 It can be obtained by H NMR measurement.

[0035]

[0036] In this specification, the term 'substitution' may mean that a hydrogen of a functional group, atomic group, or compound is substituted with a specific substituent, and when a hydrogen of a functional group, atomic group, or compound is substituted with a specific substituent, one or more substituents may exist depending on the number of hydrogens present in the functional group, atomic group, or compound, and when multiple substituents exist, each substituent may be the same or different from one another.

[0037] In this specification, the term 'alkyl group' may mean a monovalent aliphatic saturated hydrocarbon and may include linear alkyl groups such as methyl, ethyl, propyl, and butyl; branched alkyl groups such as isopropyl, sec-butyl, tert-butyl, and neo-pentyl; and cyclic saturated hydrocarbons, or cyclic unsaturated hydrocarbons containing one or more unsaturated bonds.

[0038] In this specification, the term 'alkylene group' may refer to divalent aliphatic saturated hydrocarbons such as methylene, ethylene, propylene, and butylene.

[0039] In the present invention, the term 'cycloalkyl group' may refer to a cyclic saturated hydrocarbon.

[0040] In this specification, the term 'aryl group' may mean an aromatic hydrocarbon, and may also include both a monocyclic aromatic hydrocarbon with one ring formed and a polycyclic aromatic hydrocarbon with two or more rings formed.

[0041] In this specification, the term 'aralkyl group', also called aralkyl, may refer to a combination of an alkyl group and an aryl group formed by substituting a hydrogen atom bonded to a carbon constituting an alkyl group with an aryl group.

[0042] In this specification, the term 'single bond' may mean a single covalent bond itself that does not include a separate atom or molecular group.

[0043] In this specification, the terms 'derived unit', 'derived repeating unit', and 'derived functional group' may refer to a component, structure, or the substance itself derived from a substance.

[0044] In this specification, the terms “comprising,” “having,” and their derivatives are not intended to exclude the presence of any additional components, steps, or procedures, whether or not they are specifically disclosed. To avoid any uncertainty, any composition claimed by the use of the term “comprising” may include any additional additives, adjuvants, or compounds, whether polymers or otherwise, unless otherwise stated. In contrast, the term “essentially composed of” excludes any other components, steps, or procedures from the scope of any subsequent description, except those not essential to operability. The term “composed of” excludes any components, steps, or procedures that are not specifically described or enumerated.

[0046] Measurement methods and conditions

[0047] In this specification, '1,2-vinyl bond content' and 'styrene bond content' refer to the vinyl and styrene content within polymer units measured and analyzed using Varian VNMRS 500 MHz NMR. For NMR measurement, 1,1,2,2-tetrachloroethane was used as the solvent, and the solvent peak was calculated as 6.0 ppm. The peaks were set as random styrene (7.2–6.9 ppm), blocked styrene (6.9–6.2 ppm), 1,4-vinyl and 1,2-vinyl (5.8–5.1 ppm), and 1,2-vinyl (5.1–4.5 ppm), and the 1,2-vinyl bond content and styrene bond content within the total polymer were calculated and measured, respectively.

[0048] In this specification, 'weight-average molecular weight (Mw)', 'molecular weight distribution (MWD)', and 'unimodal characteristics' were obtained by measuring the weight-average molecular weight (Mw) and number-average molecular weight (Mn) under the following conditions 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 of the measured molecular weights.

[0049] - Columns: Use a combination of two PLgel Olexis columns (Polymer Laboratories) and one PLgel mixed-C column (Polymer Laboratories).

[0050] - Solvent: Use a mixture of 2 wt% amine compound with tetrahydrofuran

[0051] - Flow rate: 1 ml / min

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

[0053] - Injection volume: 100 µl

[0054] - Column temperature: 40℃

[0055] - Detector: Refractive index

[0056] - Standard: Polystyrene (corrected by a cubic function)

[0057] In this specification, the 'glass transition temperature (Tg)' is defined as the glass transition temperature by using a Differential Scanning Calorimetry (DSCQ100, TA) in accordance with ISO 22768:2006, recording a differential scanning calorimetry curve (DSC curve) while increasing the temperature from -100℃ to 10℃ / min under a flow of 50 ml / min of nitrogen, and taking the inflection point of the DSC differential curve as the glass transition temperature.

[0058] In this specification, the 'tanδ peak' is a peak appearing in the stress change graph according to temperature derived from dynamic viscoelastic analysis by the Advanced Rheometric Expansion System (ARES), and is measured in torsional mode using a dynamic mechanical analyzer (TA, ARES-G2) under conditions of a frequency of 10 Hz, a strain of 0.5%, and a heating rate of 5℃ / min.

[0059] In this specification, 'Si content' is measured using an inductively coupled plasma emission analyzer (ICP-OES; Optima 7300DV) as an ICP analysis method. Using the said inductively coupled plasma emission analyzer, approximately 0.7 g of the sample is placed in a platinum crucible (Pt crucible), approximately 1 mL of concentrated sulfuric acid (98 wt%, Electronic grade) is added, and the sample is heated at 300°C for 3 hours. After incineration of the sample in an electric furnace (Thermo Scientific, Lindberg Blue M) according to the program of steps 1 to 3 below,

[0060] 1) step 1: initial temp 0℃ rate (temp / hr) 180℃ / hr, temp(holdtime) 180℃ (1hr);

[0061] 2) step 2: initial temp 180℃ rate (temp / hr) 85℃ / hr, temp(holdtime) 370℃ (2hr);

[0062] 3) step 3: initial temp 370℃ rate (temp / hr) 47℃ / hr, temp(holdtime) 510℃ (3hr);

[0063] 1 mL of concentrated nitric acid (48 wt%) and 20 µL of concentrated hydrofluoric acid (50 wt%) were added to the residue, and the platinum crucible was sealed and shaken for at least 30 minutes. Then, 1 mL of boric acid was added to the sample and stored at 0°C for at least 2 hours. Afterward, the sample was diluted with 30 mL of ultrapure water and subjected to incineration for measurement.

[0064] In the present invention, 'N content' may be measured using the NSX analysis method, and the NSX analysis method may be measured using a micronitrogen quantitative analyzer (NSX-2100H). Specifically, the micronitrogen quantitative analyzer (Auto sampler, Horizontal furnace, PMT & Nitrogen detector) was turned on, and the carrier gas flow rates were set to Ar 250 ml / min, O2 350 ml / min, and ozonizer 300 ml / min. The heater was set to 800℃, and the analyzer was stabilized by waiting for about 3 hours. After the analyzer was stabilized, calibration curves for the ranges of 5 ppm, 10 ppm, 50 ppm, 100 ppm, and 500 ppm were constructed using a Nitrogen standard (AccuStandard S-22750-01-5 ml). After obtaining the area corresponding to each concentration, a straight line was constructed using the ratio of concentration to area. Afterwards, a ceramic boat containing 20 mg of the sample was placed in the Auto sampler of the analyzer and measured to obtain the area. The nitrogen atomic content was calculated using the obtained sample area and the calibration curve.

[0065] In this case, the sample used in the above NSX analysis method may be a modified conjugated diene polymer sample from which the solvent has been removed by placing it in hot water heated with steam and stirring, and from which residual monomers and residual modifying agents have been removed. Additionally, if oil has been added to the above sample, it may be a sample from which the oil has been extracted (removed).

[0067] Conjugated diene polymer

[0068] The present invention provides a conjugated diene polymer, which is a hydrogenated polymer, having a characteristic viscoelastic tanδ peak, through microstructural control capable of realizing a tire having balancedly improved wet road resistance and wear resistance while maintaining excellent tensile and fuel efficiency characteristics.

[0069] The conjugated diene polymer according to the present invention comprises repeating units derived from conjugated diene monomers, and in the stress change graph according to temperature derived from dynamic viscoelasticity analysis by the Advanced Rheometric Expansion System (ARES), the full width at half maximum (FWHM) value of the tanδ peak appearing in the temperature range of -100℃ to 100℃ is 25 or higher, the rheometric system is measured using a dynamic mechanical analyzer in torsional mode under conditions of a frequency of 10 Hz, a strain of 0.5%, and a heating rate of 5℃ / min, and the hydrogenation rate of the conjugated diene monomer-derived units is 60 mol% or higher.

[0070] According to one embodiment of the present invention, the conjugated diene polymer is realized as a hydrogenated polymer with a specific microstructure by applying a characteristic manufacturing method described below, thereby controlling the dynamic viscoelastic behavior of the polymer to have a characteristic tanδ peak, and through this, excellent tensile properties and balanced excellent wet road resistance and wear resistance can be achieved.

[0072] Dynamic viscoelastic behavior of polymers

[0073] According to one embodiment of the present invention, the conjugated diene polymer is characterized by having a full width at half maximum (FWHM) value of the tanδ peak appearing in the temperature range of -100℃ to 100℃ in a stress change graph according to temperature derived from dynamic viscoelasticity analysis by the Advanced Rheometric Expansion System (ARES), which is 25 or higher.

[0074] In general, for polymers produced by polymerization methods in which the microstructure is not controlled, the tanδ peak does not appear with two or more peaks, or the peak width is formed very narrowly. This may also be related to the glass transition temperature; in cases where the units within the polymer are compartmentalized, such as in block copolymers, and there is a large difference in glass transition temperatures between these blocks, the tanδ peak may appear with a narrow width and two or more peaks. Furthermore, in the case of random copolymers, if only the vinyl or styrene content in the final polymer is controlled without precise control of the microstructure, it is common for the peak width to appear very narrow.

[0075] In this case, although the glass transition temperature may be the same for both the block copolymer and the random copolymer, they exhibit significant differences in wet road resistance. To address this issue, efforts have been made to improve wet road resistance while accepting changes in the glass transition temperature. However, since changes in the glass transition temperature lead to changes in wear resistance and alterations in the fundamental properties of the polymer, realizing a polymer with improved performance remains a challenge. In other words, it remains a more difficult problem to solve because it is difficult to balance wear resistance and wet road resistance, and these two characteristics tend not to be improved simultaneously through modification processes. However, since the conjugated diene polymer according to one embodiment of the present invention is manufactured by a method that controls the microstructure of the polymer, it possesses a characteristic tanδ peak even if it has the same glass transition temperature as conventional modified conjugated diene polymers, thereby enabling the realization of an effect in which wet road resistance and wear resistance are simultaneously increased.

[0076] At this time, the tanδ peak is characterized by appearing in a temperature range of -100℃ to 100℃ in a stress change graph according to temperature derived from dynamic viscoelastic analysis by the Advanced Rheometric Expansion System (ARES), and having a full width at half maximum of 25 or more of the tanδ peak. The number of tanδ peaks appearing in the above temperature range may usually be one, but may be two or more, and if two or more peaks appear, it may mean that the full width at half maximum of one of the multiple peaks is 25 or more.

[0077] The full width at half maximum of the tanδ peak may be 25 or more, preferably 30 or more. Additionally, the full width at half maximum may be up to 80, preferably 70 or less. As another example, the full width at half maximum of the tanδ peak may be 30 or more and 80 or less, or 35 or more and 60 or less. If the full width at half maximum is less than 25, a problem occurs in which wet road resistance significantly decreases at the same glass transition temperature. If the full width at half maximum of the peak is greater than 80, it is unlikely to be realized, but even if it is realized, problems such as phase separation or increased hysteresis at high temperatures are inevitably accompanied, and consequently, problems such as poor fuel efficiency characteristics may occur.

[0078] In addition, the tanδ peak may appear at -100°C to 100°C, preferably at -80°C to 20°C, and more preferably at -70°C to 0°C. When the peak appears within the above range, a more advantageous effect in terms of wear resistance can be expected.

[0079] The dynamic viscoelasticity analysis using the above rheometric system is performed by using a dynamic mechanical analyzer (TA, ARES-G2) in torsional mode with a frequency of 10 Hz, a strain of 0.5%, and a heating rate of 5℃ / min to measure tanδ as a function of temperature in a temperature range of -100℃ to 100℃, and the graph derived therefrom is the tanδ value as a function of temperature.

[0081] Hydrogenation rate of polymer

[0082] According to one embodiment of the present invention, the conjugated diene polymer may be a hydrogenated polymer having a hydrogenation rate of a unit derived from a conjugated diene monomer of 60 mol% or more. As another example, the conjugated diene polymer may have a hydrogenation rate of a unit derived from a conjugated diene monomer of 80 mol% or more.

[0083] Meanwhile, the hydrogenation rate of the polymer may be influenced by the hydrogenation catalyst used during the hydrogenation reaction, the amount used, the reaction temperature, pressure conditions, and the reaction time. A conjugated diene polymer according to one embodiment of the present invention can satisfy the aforementioned hydrogenation rate by being manufactured by a manufacturing method including the hydrogenation reaction described below. Furthermore, by satisfying the above hydrogenation rate, the conjugated diene polymer has the effect of exhibiting excellent wet road resistance and driving resistance, while further improving wear resistance.

[0085] Monomer-derived repeating unit

[0086] According to one embodiment of the present invention, the conjugated diene polymer has repeating units derived from conjugated diene monomers as its main unit, and the conjugated diene monomers may be one or more selected from the group consisting of, for example, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, 2-phenyl-1,3-butadiene, and 2-halo-1,3-butadiene (halo means halogen atom).

[0087] In addition, the conjugated diene polymer may additionally include aromatic vinyl monomers in addition to conjugated diene monomers and further include repeating units derived therefrom. Examples of the aromatic vinyl monomers include styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, 1-vinyl-5-hexylnaphthalene, 3-(2-pyrrolidino ethyl)styrene, 4-(2-pyrrolidino ethyl)styrene, and 3-(2-pyrrolidino-1-methyl ethyl)-α-methylstyrene. It may be one or more selected from the group consisting of ethyl)-α-methylstyrene).

[0088] As another example, the conjugated diene polymer may be a copolymer further comprising repeating units derived from a diene monomer having 1 to 10 carbon atoms together with repeating units derived from the conjugated diene monomer. The repeating units derived from the diene monomer may be repeating units derived 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. When the conjugated diene polymer is a copolymer further comprising a diene monomer, the conjugated diene polymer may contain repeating units derived from the diene monomer in an amount greater than 0 weight% to 1 weight%, greater than 0 weight% to 0.1 weight%, greater than 0 weight% to 0.01 weight%, or greater than 0 weight% to 0.001 weight%, and within this range, it has the effect of preventing gel formation.

[0089] According to one embodiment of the present invention, when two or more monomers are included in the chain of the conjugated diene-based polymer, the chain structure may have an intermediate form between a random copolymer and a block copolymer, and in this case, the control of the microstructure may be easy, and thus there is an effect of excellent balance between each physical property. The random copolymer may mean that the repeating units forming the copolymer are arranged in a disordered manner.

[0091] Glass transition temperature of a polymer

[0092] According to one embodiment of the present invention, the modified conjugated diene polymer may have a glass transition temperature of -100°C to 20°C. Although the glass transition temperature varies depending on the microstructure of the polymer, it is desirable to manufacture the polymer to satisfy the above range for improved wear resistance, and more preferably -100°C to 0°C, more preferably -90°C to -10°C, and even more preferably -80°C to -20°C.

[0093] The above glass transition temperature can be flexibly controlled by the bonding method of conjugated diene monomers within the polymer unit (1,2-bond or 1,4-bond), the presence or absence of aromatic vinyl-derived repeating units, the content of aromatic vinyl-derived repeating units, and the microstructure within each unit (1,2-vinyl bond content and styrene bond content) according to the polymerization method and polymerization conditions.

[0094] For example, the conjugated diene polymer may contain repeating units derived from aromatic vinyl monomers in an amount of 0% to 50% by weight, specifically 0% to 45% by weight, and preferably more than 0% and less than or equal to 30% by weight. In this context, containing 0% by weight of repeating units derived from aromatic vinyl monomers means that the polymer is composed solely of conjugated diene monomers without including repeating units derived from aromatic vinyl monomers. Additionally, the 1,2-vinyl bond content may be 10% to 80% by weight relative to 100% by weight of the modified conjugated diene polymer, preferably 20% to 60% by weight, and more preferably 20% to 50% by weight. When the microstructure is controlled in this manner, excellent tensile strength and fuel efficiency characteristics can be expected, along with balanced improvements in wear resistance and wet road resistance.

[0096] Modified conjugated diene polymer

[0097] According to one embodiment of the present invention, a modified conjugated diene polymer is provided, comprising repeating units derived from a conjugated diene monomer and functional groups derived from a modifying agent, wherein in a tanδ graph according to temperature derived from dynamic viscoelasticity analysis by an Advanced Rheometric Expansion System (ARES), the full width at half maximum (FWHM) value of the tanδ peak appearing in the temperature range of -100℃ to 100℃ is 25 or higher, and the rheometric system is measured using a dynamic mechanical analyzer in torsional mode under conditions of a frequency of 10 Hz, a strain of 0.5%, and a heating rate of 5℃ / min, and the hydrogenation rate of the conjugated diene monomer-derived unit is 60 mol% or higher.

[0098] The description regarding the above tanδ peak and hydrogenation rate has been explained in the aforementioned conjugated diene polymer, so it is omitted.

[0100] Si and N content of the polymer

[0101] Meanwhile, the modified conjugated diene polymer according to one embodiment of the present invention may have Si and N contents of 50 ppm or more, or 50 ppm to 1000 ppm, based on the total weight of the polymer, and in the case of the lower limit, preferably 100 ppm or more and 150 ppm or more, respectively, and in the case of the upper limit, preferably 700 ppm or less and preferably 500 ppm or less. Within this range, the mechanical properties, such as tensile properties and viscoelastic properties of the rubber composition containing the modified conjugated diene polymer, are excellent. Meanwhile, the Si and N may be derived from compounds having modified functional groups, such as the modifying agent, modification initiator, or modification monomer described later, as a result of introducing these compounds.

[0103] Alkoxysilane-based modifiers

[0104] According to one embodiment of the present invention, the modified conjugated diene-based polymer comprises a functional group derived from a modifying agent, and the modifying agent is intended to modify the ends of the polymer, and as a specific example, may be a silica-affinity modifying agent, which may be an alkoxysilane-based modifying agent. The silica-affinity modifying agent may refer to a modifying agent containing a silica-affinity functional group within a compound used as a modifying agent, and the silica-affinity functional group may refer to a functional group having excellent affinity with a filler, particularly a silica-based filler, so that interaction between the silica-based filler and the functional group derived from the modifying agent is possible.

[0105] The above-mentioned modifying agent may be an alkoxysilane-based modifying agent, and as a specific example, it may be an alkoxysilane-based compound containing one or more heteroatoms such as nitrogen atoms, oxygen atoms, or sulfur atoms. When the above-mentioned alkoxysilane-based compound is used as a modifying agent, modification can be performed in which one end of the active polymer is bonded to a silyl group through a substitution reaction between the anionic active site located at one end of the active polymer and the alkoxy group of the alkoxysilane-based compound. Accordingly, the affinity of the modified conjugated diene-based polymer with inorganic fillers, etc., from the functional group derived from the modifying agent present at one end of the polymer unit can be improved, and thus the viscoelastic properties of the rubber composition containing the modified conjugated diene-based polymer are further improved. In addition, if the above-mentioned alkoxysilane-based compound contains a nitrogen atom, additional physical property enhancement effects derived from the nitrogen atom can be expected in addition to the effects derived from the silyl group. To optimally realize these effects, it is desirable to apply a compound containing an N-containing functional group.

[0106] According to one embodiment of the present invention, the modifying agent may comprise a compound represented by the following chemical formula 1.

[0107] [Chemical Formula 1]

[0108]

[0109] In the above chemical formula 1, R 1 can be a single bond, or an alkylene group having 1 to 10 carbon atoms, and R 2 and R 3 Each can independently be an alkyl group having 1 to 10 carbon atoms, and R 4 may be hydrogen, an alkyl group having 1 to 10 carbon atoms, a monosubstituted, disubstituted, or trisubstituted alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, or a heterocyclic group having 2 to 10 carbon atoms, and R 21 silver single bond, an alkylene group having 1 to 10 carbon atoms, or -[R 42 O] j -It can be, R 42 can be an alkylene group having 1 to 10 carbon atoms, a and m can each be an integer selected independently from 1 to 3, n can be an integer of 0, 1, or 2, and j can be an integer selected from 1 to 30.

[0110] As a specific example, in the above Chemical Formula 1, R 1 can be a single bond, or an alkylene group having 1 to 5 carbon atoms, and R 2 and R 3 Each can independently be hydrogen, an alkyl group having 1 to 5 carbon atoms, and R 4 may be hydrogen, an alkyl group having 1 to 5 carbon atoms, a trialkylsilyl group substituted with an alkyl group having 1 to 5 carbon atoms, or a heterocyclic group having 2 to 5 carbon atoms, and R 21 silver single bond, or an alkylene group having 1 to 5 carbon atoms, or -[R 42 O] j -It can be, R 42 α can be an alkylene group having 1 to 5 carbon atoms, a can be an integer of 2 or 3, m can be an integer selected from 1 to 3, n can be an integer of 0, 1, or 2, where m+n=3, and j can be an integer selected from 1 to 10.

[0111] In the above chemical formula 1, R 4 In the case where the heterocyclic group is a heterocyclic group, the heterocyclic group may be substituted or unsubstituted with a trisubstituted alkoxysilyl group, and in the case where the heterocyclic group is substituted with a trisubstituted alkoxysilyl group, the trisubstituted alkoxysilyl group may be substituted by being connected to the heterocyclic group by an alkylene group having 1 to 10 carbon atoms, and the trisubstituted alkoxysilyl group may mean an alkoxysilyl group substituted with an alkoxy group having 1 to 10 carbon atoms.

[0112] As a more specific example, the compound represented by the above chemical formula 1 is 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-(diethoxy(methyl)silyl)propyl)-methyl-1-amine, N,N-bis(3-(trimethoxysilyl)propyl)-methyl-1-amine, N,N-bis(3-(trimethoxysilyl)propyl)-methyl-1-amine, N,N-diethyl-3-(trimethoxysilyl)propan-1-amine), N,N-diethyl-3-(triethoxysilyl)propan-1-amine), tri(trimethoxysilyl)amine), tri(3-(trimethoxysilyl)propyl)amine), N,N-bis(3-(diethoxy(methyl)silyl)propyl)-1,1,1-trimethylsilanamine, N,N-bis(3-(1H-imidazol-1-yl)propyl)-(triethoxysilyl)methan-1-amine(N,N-bis(3-(1H-imidazol-1-yl)propyl)-(triethoxysilyl)methan-1-amine), N-(3-(1H-1,2,4-triazole-1-yl)propyl)-3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)propan-1-amine(N-(3-(1H-1,2,4-triazole-1-yl)propyl)-3-(trimethoxysilyl)-N-(trimethoxysilyl)propyl)propan-1-amine), 3-(trimethoxysilyl)-N-(3-trimethoxysilyl)propyl)-N-(3-(1-(3-(trimethoxysilyl)propyl)-1H-1,2,4-triazole-3-yl)propyl)propan-1-amine(3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)-N-(3-(1-(3-(trimethoxysilyl)propyl)-1H-1,2,4-triazol-3-yl)propyl)propan-1-amine), N,N-bis(2-(2-methoxyethoxy)ethyl)-3-(triethoxysilyl)propna-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 (N-(2,5,8,11,14-pentaoxahexadecan-16-yl)-N-(3-(triethoxysilyl)propyl)-2,5,8,11,14-pentaoxahexadecan-16-amine) and It may be one selected from the group consisting of N-(3,6,9,12-tetraoxahexadecyl)-N-(3-(triethoxysilyl)propyl)-3,6,9,12-tetraoxahexadecan-1-amine.

[0113] As another example, the above-mentioned denaturant may include a compound represented by the following chemical formula 2.

[0114] [Chemical Formula 2]

[0115]

[0116] In the above chemical formula 2, R 5 , R 6 and R 9 Each can independently be an alkylene group having 1 to 10 carbon atoms, and R 7 , R 8 , R 10 and R 11 Each can independently be an alkyl group having 1 to 10 carbon atoms, and R 12 can be hydrogen or an alkyl group having 1 to 10 carbon atoms, b and c are each independently 0, 1, 2, or 3, and b+c ≥ 1, and A is or It can be, and in this case, R 13 , R 14 , R 15 and R 16 Each can independently be hydrogen or an alkyl group having 1 to 10 carbon atoms.

[0117] As a specific example, the compound represented by the above chemical formula 2 may be one selected from the group consisting of N-(3-(1H-imidazole-1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propylpropan-1-amine)(N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine)) and 3-(4,5-dihydro-1H-imidazole-1-yl)-N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine(3-(4,5-dihydro-1H-imidazol-1-yl)-N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine).

[0118] As another example, the above-mentioned denaturant may include a compound represented by the following chemical formula 3.

[0119] [Chemical Formula 3]

[0120]

[0121] In the above chemical formula 3, A 1 and A 2 Each may independently be a divalent hydrocarbon group having 1 to 20 carbon atoms, which may or may not contain an oxygen atom, and R 17 to R 20 Each can independently be a monovalent hydrocarbon group having 1 to 20 carbon atoms, and L 1 to L 4 is a monosubstituted, disubstituted, or trisubstituted alkylsilyl group independently substituted with an alkyl group having 1 to 10 carbon atoms, or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or L 1 and L 2 Wow, L 3 and L 4 They can be connected to each other to form a ring having 1 to 5 carbon atoms, and L 1 and L 2 Wow, L 3 and L 4 When connected to each other to form a ring, the formed ring may contain one to three heteroatoms selected from the group consisting of N, O, and S.

[0122] As a specific example, in the above chemical formula 3, A 1 and A 2 Each can independently be 1 to 10 alkylene groups, and R 17 to R 20 Each can independently be an alkyl group having 1 to 10 carbon atoms, and L 1 to L 4 Each is independently a trialkylsilyl group substituted with an alkyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or L 1 and L 2 Wow, L 3 and L 4 They can be connected to each other to form a ring having 1 to 3 carbon atoms, and L1 and L 2 Wow, L 3 and L 4 When connected to each other to form a ring, the formed ring may contain one to three heteroatoms selected from the group consisting of N, O, and S.

[0123] As a more specific example, the compound represented by the above chemical formula 3 is 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine)(3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine)), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine)(3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine)), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine)(3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine)), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine)(3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine)), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine)(3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimpropylpropan-1-amine)), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine)(3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine)), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine)(3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine)), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-Dipropylpropan-1-amine)(3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine)), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine)(3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine)), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1-amine)(3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1-amine)), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1-amine)(3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1-amine)), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1-amine)(3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diethylmethan-1-amine)), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethan-1-amine)(3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethan-1-amine)), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethan-1-amine)(3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethan-1-amine)), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethan-1-amine)(3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethan-1-amine)), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethan-1-amine)(3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethan-1-amine), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethan-1-amine)(3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethan-1-amine)), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethan-1-amine)(3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethan-1-amine)), N,N'-((1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine)(N,N'-((1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine)), N,N'-((1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine)(N,N'-((1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine)), N,N'-((1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine)(N,N'-((1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine)), N,N'-((1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilanamine)(N,N'-((1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilanamine)), N,N'-((1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilanamine)(N,N'-((1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilanamine)), N,N'-((1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilanamine)(N,N'-((1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilanamine)), 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-tetramethoxydisiloxane), It may be one selected from the group consisting of 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.

[0125] As another example, the above-mentioned denaturant may include a compound represented by the following chemical formula 4.

[0126] [Chemical Formula 4]

[0127]

[0128] In the above chemical formula 4, R 22 and R 23 Each independently has an alkylene group having 1 to 20 carbon atoms, or -R 28 [OR 29 ] f - and, R 24 to R 27 Each can independently be an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and R 28 and R 29 Each can independently be an alkylene group having 1 to 20 carbon atoms, and R 47 and R 48 Each may independently be a divalent hydrocarbon group having 1 to 6 carbon atoms, and d and e may each independently be an integer selected from 0 or 1 to 3, where d+e is an integer of 1 or more, and f may be an integer of 1 to 30.

[0129] Specifically, in the above chemical formula 4, R 22 and R 23 Each independently has an alkylene group having 1 to 10 carbon atoms, or -R 28 [OR 29 ] f -It could be, R 24 to R 27 Each can independently be an alkyl group having 1 to 10 carbon atoms, and R 28 and R 29 Each can independently be an alkylene group having 1 to 10 carbon atoms, and d and e can each independently be an integer selected from 0 or 1 to 3, where d+e can be an integer of 1 or more, and f can be an integer selected from 1 to 30.

[0130] More specifically, the compound represented by the above chemical formula 4 may be a compound represented by the following chemical formula 4a, chemical formula 4b, or chemical formula 4c.

[0131] [Chemical Formula 4a]

[0132]

[0133] [Chemical Formula 4b]

[0134]

[0135] [Chemical Formula 4c]

[0136]

[0137] In the above chemical formulas 4a, 4b, and 4c, R 22 to R 27 , d and e are as described above.

[0138] As a more specific example, the compound represented by the above chemical formula 4 is 1,4-bis(3-(3-(triethoxysilyl)propoxy)propyl)piperazine, 1,4-bis(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-(ethoxydimethyl)propyl)-4-(3-(triethoxysilyl)propyl)piperazine), 1-(3-(ethoxydimethyl)propyl)-4-(3-(triethoxysilyl)methyl)piperazine(1-(3-(ethoxydimethyl)methyl)-4-(3-(triethoxysilyl)propyl)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-(trimethoxysilyl)propyl)hexahydropyrimidine, 1,3-bis(3-(triethoxysilyl)propyl)hexahydropyrimidine (1,It may be one selected from the group consisting of 3-bis(3-(triethoxysilyl)propyl)hexahydropyrimidine) and 1,3-bis(3-(tributoxysilyl)propyl)-1,2,3,4-tetrahydropyrimidine.

[0139] As another example, the above-mentioned denaturant may include a compound represented by the following chemical formula 5.

[0140] [Chemical Formula 5]

[0141]

[0142] In the above chemical formula 5, R 30 can be a monovalent hydrocarbon group having 1 to 30 carbon atoms, and R 31 to R 33 Each can independently be an alkylene group having 1 to 10 carbon atoms, and R 34 to R 37 Each can independently be an alkyl group having 1 to 10 carbon atoms, and g and h can each independently be an integer selected from 0 or 1 to 3, and g+h can be an integer of 1 or more.

[0143] As another example, the above-mentioned denaturant may include a compound represented by the following chemical formula 6.

[0144] [Chemical Formula 6]

[0145]

[0146] In the above chemical formula 6, A 3 and A 4 Each can independently be 1 to 10 alkylene groups, and R 38 to R 41 Each can independently be an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and i can be an integer selected from 1 to 30.

[0147] As another example, the above-mentioned modifying agents are 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)propan-1-amine, 2,4-bis(2-methoxyethoxy)-6-((trimethylsilyl)methyl)-1,3,5-triazine and It may include one or more selected from the group consisting of 3,14-dimethoxy-3,8,8,13-tetramethyl-2,14-dioxa-7,9-dithia-3,8,13-trisilapentadecane.

[0148] As another example, the above-mentioned denaturant may include a compound represented by the following chemical formula 7.

[0149] [Chemical Formula 7]

[0150]

[0151] In the above chemical formula 7, R 43 , R 45 and R 46 Each can independently be an alkyl group having 1 to 10 carbon atoms, and R 44 can be an alkylene group having 1 to 10 carbon atoms, and k can be an integer selected from 1 to 4.

[0152] As a more specific example, the compound represented by the above chemical formula 7 is 8,8-dibutyl-3,13-dimethoxy-3,13-dimethyl-2,14-dioxa-7,9-dithia-3,13-disila-8-stannapentadecane, 8,8-dimethyl-3,13-dimethoxy-3,13-dimethyl-2,14-dioxa-7,9-dithia-3,13-disila-8-stannpentadecane, 8,8-dibutyl-3,3,13,13-tetramethoxy-2,14-dioxa-7,9-dithia-3,13-disila-8-stannpentadecane and It may be one selected from the group consisting of 8-butyl-3,3,13,13-tetramethoxy-8-((3-(trimethoxysilyl)propyl)thio)-2,14-dioxa-7,9-dithia-3,13-disila-8-stannpentadecane.

[0153] As another example, the above-mentioned denaturant may include a compound represented by the following chemical formula 8.

[0154] [Chemical Formula 8]

[0155]

[0156] In the above chemical formula 8, R b2 to R b4 are independently alkylene groups having 1 to 10 carbon atoms, and R b5 to Rb8 ☐ are independently alkyl groups having 1 to 10 carbon atoms, and R b13 and R b14 are independently alkylene groups having 1 to 10 carbon atoms, and R b15 to R b18 are independently alkyl groups having 1 to 10 carbon atoms, and m 1, m2, m3, and m4 are independent integers from 1 to 3.

[0157] As another example, the above-mentioned denaturant may include a compound represented by the following chemical formula 9.

[0158] [Chemical Formula 9]

[0159]

[0160] In the above chemical formula 9, R e1 and R e2 are independently alkylene groups having 1 to 10 carbon atoms, and R e3 to R e6 are independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or -R e7 SiR e8 R e9 R e10 but, R e3 to R e6 At least one of them is -R e7 SiR e8 R e9 R e10 and, here R e7 is a single bond or an alkylene group having 1 to 10 carbon atoms, and R e8 to R e10 ☐ are independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, wherein R e8 to R e10 At least one of them is an alkoxy group having 1 to 10 carbon atoms.

[0161] As another example, the above-mentioned denaturant may include a compound represented by the following chemical formula 10.

[0162] [Chemical Formula 10]

[0163]

[0164] In the above chemical formula 10, X is O or S, and R f1 and R f2 are independently single bonds or are alkylene groups having 1 to 10 carbon atoms, and

[0165] R f3 to R f8 ☐ are independently hydrogen, a C1 to C10 alkyl group, a C1 to C10 alkoxy group, a C6 to C10 aryl group, a C5 to C10 cycloalkyl group, or a C7 to C14 aralkyl group, p is an integer of 0 or 1, and if 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.

[0166] As another example, the above-mentioned denaturant may include a compound represented by the following chemical formula 11.

[0167] [Chemical Formula 11]

[0168]

[0169] In the above chemical formula 11, R g1 to R g4 are independently hydrogen, a C1 to C10 alkyl group, a C1 to C10 alkoxy group, a C6 to C12 aryl group, or -R g5 SiOR g6 but, R g1 to R g4 At least one of them is -R g5 SiOR g6 and, here R g5 is a single bond or an alkylene group having 1 to 10 carbon atoms, and R g6 is an alkyl group having 1 to 10 carbon atoms, and Y is C or N, wherein if Y is N, R g4 does not exist.

[0170] As another example, the above-mentioned denaturant may include a compound represented by the following chemical formula 12.

[0171] [Chemical Formula 12]

[0172]

[0173] In the above chemical formula 12, R h1 and R h2 is independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and R h3 is a single bond or an alkylene group having 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, and here R h4 to R h9 They are independently alkyl groups having 1 to 10 carbon atoms or alkoxy groups having 1 to 10 carbon atoms.

[0174] As another example, the above-mentioned denaturant may include a compound represented by the following chemical formula 13.

[0175] [Chemical Formula 13]

[0176]

[0177] In the above chemical formula 13, R g1 to R g3 is independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and R g4 is an alkoxy group having 1 to 10 carbon atoms, and q is an integer from 2 to 100.

[0179] Contraction factor

[0180] The conjugated diene polymer according to one embodiment of the present invention may have a shrinkage factor (g') obtained by measuring a gel permeation chromatography-light scattering method equipped with a viscosity detector of 0.1 or more, preferably 0.1 or more and 1.0 or less, more specifically 0.3 or more and 0.9 or less.

[0181] Here, the shrinkage factor (g') obtained by the gel permeation chromatography-photonic acid method measurement is the ratio of the intrinsic viscosity of a branched polymer to the intrinsic viscosity of a linear polymer having the same absolute molecular weight, and can be used as an indicator of the branched structure of the branched polymer, that is, an indicator of the proportion occupied by branches. For example, as the shrinkage factor decreases, the number of branches of the corresponding polymer tends to increase. Therefore, when comparing polymers with equivalent absolute molecular weights, the shrinkage factor becomes smaller as the number of branches increases, so it can be used as an indicator of the degree of branching.

[0182] In addition, the above shrinkage factor was calculated based on solution viscosity and light scattering methods by measuring a chromatogram using a gel chromatography-light scattering measuring device equipped with a viscosity detector. Specifically, the absolute molecular weight and the intrinsic viscosity corresponding to each absolute molecular weight were obtained using a GPC-light scattering measuring device equipped with a light scattering detector and a viscosity detector connected to two columns packed with polystyrene-based gel, and after calculating the intrinsic viscosity of the linear polymer corresponding to the absolute molecular weight, the shrinkage factor was obtained as the ratio of the intrinsic viscosity corresponding to each absolute molecular weight. For example, the above shrinkage factor was obtained by injecting a sample into a GPC-light scattering measuring device (Viscotek TDAmax, Malvern) equipped with a light scattering detector and a viscosity detector to obtain the absolute molecular weight from the light scattering detector and the intrinsic viscosity [η] for the absolute molecular weight from the light scattering detector and the viscosity detector, and then calculating the intrinsic viscosity [η]0 of the linear polymer for the absolute molecular weight through the following Equation 1, and representing the average value of the ratio of intrinsic viscosity ([η] / [η]0) corresponding to each absolute molecular weight as the shrinkage factor. At this time, the eluent used was a mixed solution of tetrahydrofuran and N,N,N',N'-tetramethylethylenediamine (adjusted by mixing 20 mL of N,N,N',N'-tetramethylethylenediamine with 1 L of tetrahydrofuran), the column used was PL Olexix (Agilent), measurements were taken under conditions of an oven temperature of 40℃ and a THF flow rate of 1.0 mL / min, and the sample was prepared by dissolving 15 mg of polymer in 10 mL of THF.

[0183] [Mathematical Formula 1]

[0184] [η]0=10 -3.883 M 0.771

[0185] In the above mathematical formula 1, M is the absolute molecular weight.

[0186] In addition, the modified conjugated diene polymer may have a vinyl content of 5% or more by weight, 10% or more by weight, or 10% to 60% by weight. Here, the vinyl content may refer to the content of a 1,2-added conjugated diene monomer rather than a 1,4-added conjugated diene monomer with respect to 100% by weight of a conjugated diene polymer composed of a monomer having a vinyl group and an aromatic vinyl monomer.

[0188] Mooney stress relaxation rate

[0189] As another example, the modified conjugated diene polymer may have a Mooney stress relaxation rate of less than 0.7 measured at 100°C and may be between 0.7 and 3.0. Specifically, the Mooney stress relaxation rate may be less than 0.7, preferably 0.6 or less, more preferably 0.5 or less, and optimally 0.4 or less in the case of a branched polymer with a large degree of branching, and may be preferably 0.7 to 2.5, more preferably 0.7 to 2.0 in the case of a linear polymer with a small degree of branching.

[0190] Here, the above Mooney stress relaxation rate represents the change in stress that appears in response to an equal amount of strain, and may be measured using a Mooney viscometer. Specifically, the above Mooney stress relaxation rate was obtained by using the Large Rotor of a Monsanto MV2000E under conditions of 100°C and Rotor Speed ​​2±0.02 rpm, taking 27±3 g of the polymer after leaving it at room temperature (23±5°C) for more than 30 minutes, filling it into the die cavity, operating the platen to apply torque while measuring the Mooney viscosity, and then measuring the slope value of the change in Mooney viscosity that appears as the torque is released.

[0191] Meanwhile, the Mooney stress relaxation rate can be used as an indicator of the branched structure of the polymer; for example, when comparing polymers with equivalent Mooney viscosity, the Mooney stress relaxation rate decreases as the number of branches increases, so it can be used as an indicator of branching.

[0193] Other properties of polymers

[0194] According to one embodiment of the present invention, the (modified) conjugated diene polymer may include a functional group derived from a modification initiator at one end in addition to a functional group derived from a modification agent at the other end, wherein the modification initiator may be a reaction product of an N-functional group-containing compound and an organometallic compound.

[0195] Specifically, the N-functional group-containing compound may be an aromatic hydrocarbon compound containing an N-functional group including an amino group, an amide group, an amino group, an imidazole group, a pyrimidyl group, or a cyclic amino group that is substituted or unsubstituted with a substituent, and the substituent may be an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or an alkoxysilyl group having 1 to 10 carbon atoms.

[0196] According to one embodiment of the present invention, the (modified) conjugated diene polymer may have a weight-average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 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, and within this range, the driving resistance and wet road surface resistance are more balanced and excellent.

[0197] In addition, the (modified) conjugated diene polymer according to one embodiment of the present invention may be a high molecular weight polymer having a weight-average molecular weight of 800,000 g / mol or more, preferably 1,000,000 g / mol or more, and accordingly, a polymer with excellent tensile properties can be realized, which can be achieved by controlling the microstructure and simultaneously realizing the effect of extending the polymer chains when manufactured according to the aforementioned manufacturing method.

[0198] According to one embodiment of the present invention, the (modified) conjugated diene polymer may have a number average molecular weight (Mn) of 1,000 g / mol to 2,000,000 g / mol, 10,000 g / mol to 1,500,000 g / mol, or 100,000 g / mol to 1,200,000 g / mol, and the number average molecular weight may preferably be 400,000 g / mol or more, more preferably 500,000 g / mol or more. In addition, the peak-top 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 this range, driving resistance and wet road resistance are excellent.

[0199] In addition, the (modified) conjugated diene polymer may have a unimodal molecular weight distribution curve by gel permeation chromatography (GPC), and the molecular weight distribution may be 1.0 to 3.0, preferably 1.0 to 2.5, more preferably 1.0 to 2.0, and even more preferably 1.0 or more and less than 1.7, wherein the unimodal curve shape and molecular weight distribution can be simultaneously satisfied by the continuous polymerization described below.

[0200] Generally, in continuous polymerization, the molecular weight distribution is broad and unimodal, resulting in excellent processability but poor tensile and viscoelastic properties; conversely, in batch polymerization, the molecular weight distribution is narrow and bimodal, resulting in excellent tensile and viscoelastic properties but poor processability and low productivity. However, by applying the manufacturing method described below according to one embodiment of the present invention, the molecular weight distribution can be selectively narrowed as much as possible even while manufacturing continuously, and accordingly, it is easy to control the balance of physical properties between processability, tensile properties, and viscoelastic properties.

[0201] In addition, the (modified) conjugated diene polymer according to one embodiment of the present invention must satisfy a Mooney viscosity of 40 to 120 as measured under ASTM D1646 conditions, preferably 45 to 100. Although there may be various measures to evaluate processability, processability may be significantly excellent when the Mooney viscosity satisfies the above range.

[0202] According to one embodiment of the present invention, the (modified) conjugated diene polymer has a polymer structure that has a difference between the glass transition initiation temperature and the termination temperature through the control of the polymer microstructure, such as the styrene bond content and 1,2-vinyl bond content, as described above, and optionally controls the weight-average molecular weight, the shape of the molecular weight distribution curve, the molecular weight distribution, the content of N and Si atoms, and the Mooney viscosity, thereby allowing for the effective balanced improvement of wear resistance and wet road resistance while maintaining excellent tensile properties, fuel efficiency, and processability.

[0204] Method for manufacturing conjugated diene polymers

[0205] The present invention provides a method for manufacturing a conjugated diene polymer as follows in order to manufacture the above conjugated diene polymer.

[0206] The above method for manufacturing a conjugated diene polymer comprises a step (S1) of polymerizing a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer in the presence of a hydrocarbon solvent, a polymerization initiator, and a polar additive; and a hydrogenation reaction step (S2), wherein the step (S1) is performed continuously in two or more polymerization reactors, and is transferred to a second reactor when the polymerization conversion rate of the first reactor is 70% to 85%, and further adds a polar additive, or a polar additive and a conjugated diene monomer to the second reactor.

[0207] As the characteristics of conjugated diene polymers have been described above, the following description will focus on the manufacturing method.

[0209] The above hydrocarbon solvent is not particularly limited, but may be one or more selected from the group consisting of, for example, n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene, and xylene.

[0210] The polymerization initiator may be used in an amount of 0.1 to 3.0 equivalents based on 1.0 equivalent of monomer, preferably 0.1 to 2.0 equivalents, and more preferably 0.5 to 1.5 equivalents. In another example, the polymerization initiator may be used in an amount of 0.01 mmol to 10 mmol, 0.05 mmol to 5 mmol, 0.1 mmol to 2 mmol, 0.1 mmol to 1 mmol, or 0.15 to 0.8 mmol based on 100 g of total monomer. Here, 100 g of total monomer may be a conjugated diene monomer, or may represent the total amount of a conjugated diene monomer and an aromatic vinyl monomer.

[0211] Meanwhile, the polymerization initiator may be an organometallic compound, and may be one or more selected from, for example, organolithium compounds, organosodium compounds, organopotassium compounds, organorubidium compounds and organocesium compounds.

[0212] Specifically, the organometallic compound may be one or more selected from the group consisting of methyllithium, ethyllithium, propyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octyllithium, phenyllithium, 1-naphthyllithium, n-eicosillithium, 4-butylphenyllithium, 4-tolylithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naphthyl sodium, naphthyl potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide, and lithium isopropylamide.

[0213] As another example, the polymerization initiator may be a modification initiator, and the modification initiator may be a reaction product of an N-functional group-containing compound and the organometallic compound.

[0215] S1 stage

[0216] According to one embodiment of the present invention, in the manufacturing method, step (S1) is a step in which a polymerization reaction between a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer is performed, for example, by anionic polymerization. A specific example may be a living anionic polymerization having an anionic active site at the polymerization end by an anionic growth polymerization reaction. Furthermore, the polymerization in step (S1) may be a temperature-increasing polymerization, an isothermal polymerization, or a constant-temperature polymerization (adiabatic polymerization). The constant-temperature polymerization may refer to a polymerization method that includes a step of polymerizing using its own reaction heat without arbitrarily applying heat after adding a polymerization initiator; the temperature-increasing polymerization may refer to a polymerization method in which the temperature is increased by arbitrarily applying heat after adding the polymerization initiator; and the isothermal polymerization may refer to a polymerization method in which the temperature of the polymer is maintained constant by increasing or removing heat after adding the polymerization initiator.

[0217] In addition, according to one embodiment of the present invention, the polymerization of step (S1) may be carried out by including a diene compound having 1 to 10 carbon atoms in addition to the conjugated diene monomer, and in this case, it has the effect of preventing the formation of a gel on the reactor wall during long-term operation. The diene compound may be, for example, 1,2-butadiene.

[0218] In addition, according to one embodiment of the present invention, the polymerization in step (S1) is carried out in two or more polymerization reactors, wherein the polymerization conversion rate in the first polymerization reactor among the polymerization reactors may be 70% or more and 85% or less, or 70% to 80%. That is, the polymerization in step (S1) is characterized by being carried out only until the polymerization conversion rate in the first polymerization reactor becomes 70% or more, 70% or more and 85% or less, or 70% or more and 80% or less.

[0219] Within this range, after the polymerization reaction is initiated, side reactions occurring as the polymer is formed are suppressed, making it easier to control the microstructure of the polymer during polymerization. Consequently, the full width at half maximum of the tan δ peak in dynamic viscoelastic analysis is widened, thereby providing a basis for improving wear resistance.

[0220] Polymerization in the first reactor above can be carried out, for example, in a 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, and within this range, the molecular weight distribution of the polymer is narrowly controlled, which has an excellent effect of improving physical properties.

[0221] According to one embodiment of the present invention, the step (S1) is performed in two or more reactors, and after polymerization is carried out in the first reactor to the aforementioned polymerization conversion rate, it is transferred to the second reactor, and additionally, a polar additive or a conjugated diene monomer is added to the second reactor.

[0222] At this time, the additionally added polar additive, or the polar additive or conjugated diene monomer, may be added simultaneously or sequentially, and may be added at one point in time within the aforementioned polymerization conversion rate range, added in divided portions at multiple points in time within the range, or added continuously within the range.

[0223] The additional addition of polar additives or polar additives and conjugated diene monomers can serve as a means to control the polymerization conversion rate in the first reactor and to realize the glass transition temperature characteristics of the polymer being produced, as the addition of polar additives can provide additional power to the polymerization reaction after a specific polymerization conversion rate, thereby causing deformation of the microstructure.

[0224] In particular, the above polar additive has the effect of controlling the ratio of 1,2-links and 1,4-links by controlling the reaction rate when homopolymerizing conjugated diene monomers, and inducing the easy formation of random copolymers by compensating for the difference in reaction rates between these monomers when copolymerizing conjugated diene monomers and aromatic vinyl monomers.

[0225] At this time, an appropriate amount of the additionally added polar additive can be used so that the full width at half maximum of the tanδ peak widens. For example, the additionally added 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, based on a total of 100 g of monomer used at the start of polymerization.

[0226] In addition, the optionally added conjugated diene monomer can be used in an amount of 5 g to 25 g or 5 g to 20 g based on 100 g of the monomer used at the start of polymerization. When the additionally added polar additive or conjugated diene monomer is controlled in the above amounts, it is easy to control the glass transition temperature of the polymer and allows for finer adjustment, and there is an advantage that the full width at half maximum of the tanδ peak in dynamic viscoelasticity analysis can be widened.

[0228] The total amount of polar additive used in the polymerization of step (S1) above may be used in a ratio of 0.001 g to 50 g or 0.002 g to 1.0 g based on a total of 100 g of monomer. As another example, the total amount of polar additive may be used in a ratio of more than 0 g to 1 g, 0.01 g to 1 g, or 0.1 g to 0.9 g based on a total of 100 g of polymerization initiator. Here, the total amount of polar additive refers to the content including additionally added polar additive.

[0229] Polymerization in the second reactor above can be carried out, for example, in a 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, and within this range, the molecular weight distribution of the polymer is narrowly controlled, which has an excellent effect of improving physical properties.

[0230] Meanwhile, additionally, in controlling the full width at half maximum of the tan δ peak obtained from the dynamic viscoelasticity analysis, the polymerization temperature in the first reactor and the second reactor may also have an effect. In this case, it is preferable to control the polymerization temperature of the second reactor to be lower than or equal to the polymerization temperature of the first reactor, and it is preferable that the polymerization temperature of the second reactor be 60°C or higher.

[0231] The above polar additive may be, for example, one or more selected from the group consisting of tetrahydrofuran, 2,2-di(2-tetrahydrofuryl)propane, diethyl ether, cyclopentyl ether, dipropyl ether, ethylenemethyl ether, ethylene glycol dimethyl ether, diethylene glycol, dimethyl ether, tertiary-butoxyethoxyethane, bis(3-dimethylaminoethyl)ether, (dimethylaminoethyl)ethyl ether, trimethylamine, triethylamine, tripropylamine, N,N,N',N'-tetramethylethylenediamine, sodium mentholate, and 2-ethyltetrahydrofurfuryl ether, and preferably 2,2-di(2-tetrahydrofuryl)propane, triethylamine, tetramethylethylenediamine, sodium mentholate, or 2-ethyltetrahydrofurfuryl It may be ether (2-ethyl tetrahydrofurfuryl ether).

[0232] Meanwhile, the polymerization conversion rate may be determined, for example, by measuring the solid concentration in the polymer solution containing the polymer during polymerization. As a specific example, to obtain the polymer solution, a cylindrical container is installed at the outlet of each polymerization reactor and a certain amount of polymer solution is filled into the cylindrical container. Then, the cylindrical container is separated from the reactor and the weight (A) of the cylinder filled with the polymer solution is measured. Afterward, the polymer solution filled in the cylindrical container is transferred to an aluminum container, for example, an aluminum dish, and the weight (B) of the cylindrical container from which the polymer solution has been removed is measured. Then, the aluminum container containing the polymer solution is dried in an oven at 140°C for 30 minutes, and the weight (C) of the dried polymer is measured. The result may then be calculated according to the following mathematical formula 2.

[0233] [Mathematical Formula 2]

[0234]

[0235] In the above mathematical formula 2, the total solid content is the total solid content in the polymer solution separated in each reactor, which is the weight percentage of solids relative to 100% of the polymer solution. For example, if the total solid content is 20 weight%, when applying this to the above mathematical formula 2, it may be calculated by substituting 20 / 100, i.e., 0.2.

[0236] Meanwhile, the polymer produced in the second reactor may be sequentially transferred to the final polymerization reactor, and polymerization may proceed until the final polymerization conversion rate reaches 95% or more. After polymerization in the second reactor, the polymerization conversion rate for each reactor, from the third reactor to the final polymerization reactor, may be appropriately controlled for each reactor to control the molecular weight distribution. Subsequently, a reaction stopper may be introduced to deactivate the active site. If a modified conjugated diene polymer is to be produced, the active polymer may be transferred to a modification reaction process. The reaction stopper may be applied without limitation as long as it is a material that can be generally used in this technical field.

[0237] In addition, the active polymer produced by the above step (S1) may refer to a polymer in which the polymer anion and the organometallic cation of the polymerization initiator are combined.

[0239] S2 stage

[0240] According to one embodiment of the present invention, in the manufacturing method, step (S2) is a step of performing a hydrogenation reaction by contacting the active polymer prepared in step (S1) with hydrogen, and can be performed by contacting hydrogen gas with the active polymer under an inert atmosphere in the presence of a hydrogenation catalyst.

[0241] Here, the inert atmosphere may be composed using an inert gas, and the inert gas may be one or more selected from, for example, helium, nitrogen, and argon, which does not react with any reactants during the hydrogenation reaction. In this case, air is undesirable because it can oxidize or decompose the hydrogenation catalyst, causing a decrease in activity.

[0242] In addition, the above hydrogenation catalyst is not specifically limited and may be applied as a catalyst for the hydrogenation reaction of conjugated diene polymers, but, for example, a supported heterogeneous catalyst in which a metal such as Ni, Pt, Pd, or Ru is supported on carbon, silica, alumina, diatomaceous earth, etc.; a Ziegler-type catalyst in which a transition metal salt of an organic acid salt or acetylacetone salt of Ni, Co, Fe, or Cr is used together with a reducing agent such as an organoaluminum; or a homogeneous catalyst in which Ti, Ru, Rh, or Zr, etc. are organometallic complexes.

[0243] As a preferred example, the hydrogenation catalyst may be a titanocene compound or a mixture thereof with a reducing organometallic compound, and the titanocene compound may be a compound having a (substituted) cyclopentadienyl backbone, an indenyl backbone, or a fluorenyl backbone, such as biscyclopentadienyl titanium chloride or monopentamethylcyclopentadienyl titanium trichloride, and the reducing organometallic compound may be an organoalkali metal compound such as organolithium, an organomagnesium compound, an organoaluminum compound, an organoboron compound, or an organozinc compound.

[0244] In addition, the above hydrogenation catalyst may be 0.01 mmol to 20 mmol or 0.05 mmol to 5 mmol based on 100 g of active polymer, and in this case, the hydrogenation reaction can occur easily.

[0245] As another example, the above hydrogenation catalyst can be used in an amount such that the metallic component in the catalyst is 100 ppm or more, 150 ppm or more, or 150 ppm to 300 ppm based on 100 parts by weight of the active polymer, and in this case, the polymer produced may be advantageous in satisfying the aforementioned hydrogenation rate.

[0246] In addition, the above hydrogenation reaction is not specifically limited, but may be performed for 3 minutes to 10 hours or 10 minutes to 5 hours at a temperature range of, for example, 0°C to 200°C or 30°C to 150°C and a pressure range of 0.1 MPa to 15 MPa, 0.2 MPa to 10 MPa, or 0.3 MPa to 5 MPa, and in this case, the polymer produced may be more advantageous in satisfying the aforementioned hydrogenation rate. If the above temperature is lower than 0°C, the activity of the catalyst is reduced and at the same time the hydrogenation rate is reduced, requiring a large amount of catalyst, which is not only uneconomical but may also cause problems such as polymer precipitation due to the insolubilization of the hydrogenated polymer. If the above temperature is higher than 200°C, the activity of the catalyst is reduced and may cause gelation or decomposition of the polymer, and hydrogenation may occur in aromatic double bonds, which may cause problems such as reduced selectivity of hydrogenation.

[0248] Method for manufacturing a modified conjugated diene polymer

[0249] The present invention provides a method for manufacturing a modified conjugated diene polymer as follows, in order to manufacture the above-mentioned modified conjugated diene polymer.

[0250] The above method for manufacturing a modified conjugated diene-based polymer comprises a step (S1-1) of manufacturing an active polymer by polymerizing a conjugated diene monomer or a conjugated diene monomer and an aromatic vinyl monomer in the presence of a hydrocarbon solvent, a polymerization initiator, and a polar additive; a modification reaction step (S2-1) of reacting the active polymer with a modifying agent; and a hydrogenation reaction step (S2), wherein the step (S1) is performed continuously in two or more polymerization reactors, and is transferred to a second reactor when the polymerization conversion rate of the first reactor is 70% to 85%, and further adds a polar additive, or a polar additive and a conjugated diene monomer to the second reactor.

[0251] In the method for manufacturing the above-mentioned modified conjugated diene polymer, the step (S1-1) of manufacturing the active polymer is identical to the step (S1) of the above-mentioned conjugated diene polymer, and the step (S2) of performing the hydrogenation reaction is identical to the step (S2) of the above-mentioned conjugated diene polymer except that it is performed by contacting the modified active polymer with hydrogen, so the description thereof is omitted.

[0253] S1-2 stage

[0254] Step (S1-2) above is a modification step in which the active polymer prepared in Step (S1-1) reacts with a modifying agent, and the anionic active site of the active polymer and the alkoxy group bonded to the silane of the modifying agent can react. The modifying agent may be used in an amount of 0.01 mmol to 10 mmol based on 100 g of total monomer. As another example, the modifying agent may be used in a molar ratio of 1:0.1 to 10, 1:0.1 to 5, or 1:0.1 to 1:3 based on 1 mole of the polymerization initiator in Step (S1).

[0255] Additionally, according to one embodiment of the present invention, the modifying agent may be introduced into a modification reactor, and step (S1-2) may be carried out in the modification reactor. As another example, the modifying agent may be introduced into a transfer unit for transferring the active polymer prepared in step (S1-1) to a modification reactor for carrying out step (S1-2), and the reaction may proceed by mixing the active polymer and the modifying agent within the transfer unit, wherein the reaction may be a modification reaction in which the modifying agent is simply bonded to the active polymer, or a coupling reaction in which the active polymer is connected based on the modifying agent.

[0257] Meanwhile, the method for preparing the modified conjugated diene polymer may further perform a step of reacting by additionally adding a conjugated diene monomer to the active polymer prepared in step (S1-1) before the modification reaction in step (S1-2), and in this case, it may be more advantageous for the subsequent modification reaction. At this time, the conjugated diene monomer may be added in an amount of 1 mole to 100 moles relative to 1 mole of the active polymer.

[0259] The method for manufacturing the (modified) conjugated diene polymer according to one embodiment of the present invention is a method capable of satisfying the characteristics of the (modified) conjugated diene polymer described above. As described above, the effect intended to be achieved in the present invention can be achieved when the above characteristics are satisfied, but other polymerization conditions can be controlled in various ways to realize the physical properties of the (modified) conjugated diene polymer according to the present invention.

[0261] Rubber composition

[0262] According to the present invention, a rubber composition comprising the above-mentioned conjugated diene polymer or modified conjugated diene polymer is provided.

[0263] As another example, according to one embodiment of the present invention, a rubber composition is provided comprising a conjugated diene polymer and a filler, wherein in a stress change graph according to temperature derived from dynamic viscoelastic analysis by an Advanced Rheometric Expansion System (ARES), the full width at half maximum (FWHM) value of the tanδ peak appearing in the temperature range of -100℃ to 100℃ is 31 or higher, the rheometric system is measured using a dynamic mechanical analyzer in torsional mode under conditions of a frequency of 10 Hz, a strain of 0.5%, and a heating rate of 5℃ / min, and the conjugated diene polymer has a hydrogenation rate of a unit derived from a conjugated diene monomer of 60 mol% or higher.

[0264] The full width at half maximum of the tanδ peak may be 31 or greater, preferably 35 or greater, and more preferably 40 or greater. Additionally, the full width at half maximum may be up to 100, preferably 80 or less. If the full width at half maximum is less than 31, a problem arises where wet road resistance significantly decreases at the same glass transition temperature. If the full width at half maximum of the peak is greater than 100, it is unlikely to be realized, but even if it is realized, problems such as phase separation or increased hysteresis at high temperatures are inevitably accompanied, and consequently, problems such as poor fuel efficiency characteristics may occur.

[0265] In addition, the tanδ peak may appear at -100°C to 100°C, preferably at -80°C to 20°C, and more preferably at -70°C to 0°C. When the peak appears within the above range, a more advantageous effect in terms of wear resistance can be expected. Here, the conjugated diene polymer may be unmodified or modified by a modifying agent.

[0266] The above rubber composition may contain the above (modified) conjugated diene polymer in an amount of 10% or more by weight, 10% to 100% by weight, or 20% to 90% by weight, and within this range, mechanical properties such as tensile strength and wear resistance are excellent, and there is an excellent balance between each property.

[0267] In addition, the rubber composition may further include other rubber components as needed in addition to the (modified) conjugated diene polymer, wherein the rubber components may be included in an amount of 90% by weight or less relative to the total weight of the rubber composition. As a specific example, the other rubber components may be included in an amount of 1 to 900 parts by weight per 100 parts by weight of the (modified) conjugated diene polymer.

[0268] The above rubber component may be, for example, natural rubber or synthetic rubber, and specifically examples include natural rubber (NR) containing cis-1,4-polyisoprene; modified natural rubber such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber, which are obtained by modifying or purifying the above general natural rubber; It may be synthetic rubber such as styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, polyisobutylene-co-isoprene, neoprene, poly(ethylene-co-propylene), poly(styrene-co-butadiene), poly(styrene-co-isoprene), poly(styrene-co-isoprene-co-butadiene), poly(isoprene-co-butadiene), poly(ethylene-co-propylene-co-diene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, butyl halogenated rubber, etc., and any one or more of these may be used.

[0269] The above rubber composition may, for example, comprise 0.1 to 200 parts by weight, or 10 to 120 parts by weight, of a filler per 100 parts by weight of the (modified) conjugated diene-based polymer of the present invention. The filler may, for example, be a silica-based filler, and specific examples may include wet silica (hydrated silica), dry silica (anhydrous silica), calcium silicate, aluminum silicate, or colloidal silica, and preferably, it may be wet silica, which has the best effect of improving fracture characteristics and achieving the same effect as wet grip. In addition, the above rubber composition may further comprise a carbon-based filler as needed.

[0270] As another example, when silica is used as the above-mentioned filler, a silane coupling agent may be used together to improve reinforcement and low heat generation, and as specific examples, the above-mentioned silane coupling agent is 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. It may be 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilylpropylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzolyltetrasulfide, 3-triethoxysilylpropylmethacrylate monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, bis(3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, or dimethoxymethylsilylpropylbenzothiazolyltetrasulfide, and any one or a mixture of two or more of these may be used. Preferably, considering the effect of improving reinforcement, it may be bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide.

[0271] In addition, since the rubber composition according to one embodiment of the present invention uses a modified conjugated diene polymer in which a functional group with high affinity for silica is introduced to the active site as a rubber component, the amount of silane coupling agent can be reduced compared to the usual case, and accordingly, the silane coupling agent can be used in an amount of 1 to 20 parts by weight or 5 to 15 parts by weight per 100 parts by weight of silica, and within this range, the effect as a coupling agent is sufficiently exhibited while preventing gelation of the rubber component.

[0272] The rubber composition according to one embodiment of the present invention may be sulfur-crosslinkable and may further include a vulcanizing agent. Specifically, the vulcanizing agent may be sulfur powder and may be included in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the rubber component, and within this range, the necessary elastic modulus and strength of the vulcanized rubber composition are secured while having excellent low fuel consumption.

[0273] In addition to the above-mentioned components, the rubber composition according to one embodiment of the present invention may further include various additives commonly used in the rubber industry, specifically vulcanization accelerators, process oils, plasticizers, anti-aging agents, anti-scotch agents, zinc white, stearic acid, thermosetting resins, or thermoplastic resins.

[0274] The above vulcanization accelerator may be a thiazole-based compound such as M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), or CZ (N-cyclohexyl-2-benzothiazylsulfenamide), or a guanidine-based compound such as DPG (diphenylguanidine), and may be included in an amount of 0.1 to 5 parts by weight per 100 parts by weight of rubber component.

[0275] The above process oil acts as a softening agent within the rubber composition and may be, for example, a paraffinic, naphthenic, or aromatic compound; aromatic process oil may be used when considering tensile strength and wear resistance, while naphthenic or paraffinic process oil may be used when considering hysteresis loss and low-temperature characteristics. The above process oil may be included, for example, in an amount of 100 parts by weight or less per 100 parts by weight of the rubber component, and within this range, it has the effect of preventing a decrease in the tensile strength and low heat generation (low fuel consumption) of the vulcanized rubber.

[0276] The above anti-aging agent may be, 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 high-temperature condensation product of diphenylamine and acetone, and may be used in an amount of 0.1 to 6 parts by weight per 100 parts by weight of rubber component.

[0277] The rubber composition according to one embodiment of the present invention can be obtained by mixing using a mixer such as a Banbury mixer, a roll mixer, or an internal mixer according to the above formulation, and a rubber composition with low heat generation and excellent wear resistance can be obtained by a vulcanization process after molding.

[0278] Accordingly, the above rubber composition can be useful for manufacturing various components of a tire, such as tire treads, undertreads, sidewalls, carcass coating rubber, belt coating rubber, bead fillers, choppers, or bead coating rubber, or various industrial rubber products such as anti-vibration rubber, belt conveyors, and hoses.

[0280] In addition, the present invention provides a tire manufactured using the above rubber composition.

[0281] The above tire may include a tire or a tire tread.

[0283] Examples

[0284] Hereinafter, the present invention will be described in detail with reference to examples in order to specifically explain the invention. However, the embodiments according to the present invention may be modified in various different forms, and the scope of the present invention should not be interpreted as being limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the invention to those with average knowledge in the art.

[0286] Preparation Example: Preparation of a hydrogenation catalyst

[0287] 1 liter of purified cyclohexane was added to a nitrogen-substituted dry reaction vessel, 100 mmol of bis(η5-cyclopentadienyl)titanium dichloride was added, and an n-hexane solution containing 200 mmol of trimethylaluminum was added while stirring sufficiently, and the reaction was carried out at room temperature for about 3 days to obtain a hydrogenation catalyst.

[0289] Experimental Data I

[0290] Example 1

[0291] In the first reactor of three continuous stirred liquid-phase reactors (CSTR), n-hexane was continuously fed at a flow rate of 5 kg / hr, a monomer solution dissolved in n-hexane at 60 wt% 1,3-butadiene at 1.16 kg / hr, a monomer solution dissolved in n-hexane at 60 wt% styrene at 0.31 kg / hr, an initiator solution dissolved in n-hexane at 6.6 wt% n-butyllithium at 8.33 g / hr, and a polar additive solution dissolved in n-hexane at 2 wt% ditetrahydrofurylpropane at 2.25 g / hr. At this time, the internal temperature of the reactor was maintained at 60°C, and when the polymerization conversion rate reached 72%, the polymer was transferred from the first reactor to the second reactor through a transfer pipe.

[0292] Next, the temperature of the second reactor was maintained at 60°C, and a solution of 1,3-butadiene dissolved in n-hexane at 60 wt% was continuously introduced into the second reactor at 0.2 kg / hr, and a polar additive solution of ditetrahydrofurylpropane dissolved in n-hexane at 10 wt% was continuously introduced at 6 g / hr to participate in the reaction. When the polymerization conversion rate reached 95% or higher, the polymer was transferred from the second reactor to the third reactor through a transfer pipe, and a denaturant solution of N,N-dimethyl-3-(trimethoxysilyl)propane-1-amine dissolved in n-hexane at 5 wt% was introduced at 11.6 g / hr, and the reaction was carried out for 30 minutes.

[0293] After the reaction was finished, the hydrogenation catalyst prepared in the above preparation example and hydrogen were introduced into the third reactor, and a hydrogenation reaction was carried out at a temperature of 80°C and a hydrogen pressure of 0.7 MPa. At this time, 200 ppm of titanium was added as the hydrogenation catalyst per 100 parts by weight of polymer.

[0294] After that, a solution of IR1520 (BASF) dissolved at 30 wt% as an antioxidant was injected at a rate of 100 g / h and stirred. The resulting polymer was placed in hot water heated with steam and stirred to remove the solvent, and then roll-dried to remove the remaining solvent and water to produce a modified conjugated diene copolymer.

[0296] Example 2

[0297] A modified conjugated diene polymer was prepared in the same manner as in Example 1, except that the polymer was transferred from the first reactor to the second reactor when the polymerization conversion rate of the first reactor was 70%.

[0299] Example 3

[0300] A modified conjugated diene polymer was prepared in the same manner as in Example 1, except that the temperature of the first reactor was maintained at 70°C and the temperature of the second reactor at 65°C, and the polymerization was transferred to the second reactor when the polymerization conversion rate of the first reactor was 80%.

[0302] Example 4

[0303] A modified conjugated diene polymer was prepared in the same manner as in Example 1, except that the 1,3-butadiene solution additionally introduced into the second reactor in Example 1 was not introduced into the second reactor.

[0305] Example 5

[0306] A modified conjugated diene polymer was prepared in the same manner as in Example 1, except that a polar additive solution in which 10 wt% of ditetrahydrofurylpropane was dissolved in n-hexane added to the second reactor in Example 1 was continuously added at a rate of 15 g / hr.

[0308] Example 6

[0309] A modified conjugated diene polymer was prepared in the same manner as in Example 1, except that a polar additive solution in which 10 wt% of ditetrahydrofurylpropane was dissolved in n-hexane added to the second reactor in Example 1 was continuously added at a rate of 1 g / hr.

[0311] Comparative Example 1

[0312] A modified conjugated diene polymer was prepared in the same manner as in Example 1, except that in Example 1 above, a monomer solution dissolved in n-hexane at 60 wt% 1,3-butadiene at 13 kg / hr, a monomer solution dissolved in n-hexane at 60 wt% styrene at 0.28 kg / hr, and a polar additive solution at 17.5 g / hr were introduced into the first reactor, and when the polymerization conversion rate of the first reactor was 78%, the polymer was transferred to the second reactor, and 1,3-butadiene and polar additives were not introduced into the second reactor.

[0314] Comparative Example 2

[0315] A modified conjugated diene polymer was prepared in the same manner as in Example 1, except that in Example 1, the temperature of the first reactor was maintained at 50°C and the temperature of the second reactor was maintained at 40°C, the polymer was transferred to the second reactor when the polymerization conversion rate of the first reactor was 57%, and 1,3-butadiene was not additionally added to the second reactor.

[0317] Comparative Example 3

[0318] A modified conjugated diene polymer was prepared in the same manner as in Example 1, except that the temperature of the first reactor was maintained at 50°C and the temperature of the second reactor at 40°C, and the polymer was transferred to the second reactor when the polymerization conversion rate of the first reactor was 53%.

[0320] Comparative Example 4

[0321] A modified conjugated diene polymer was prepared in the same manner as Comparative Example 1, except that in Comparative Example 1 above, a monomer solution dissolved in n-hexane at 60 wt% of 1,3-butadiene was introduced into the first reactor at a rate of 1.08 kg / hr, a monomer solution dissolved in n-hexane at 60 wt% of styrene was introduced at a rate of 0.35 kg / hr, and a polar additive solution was introduced at a rate of 12.0 g / hr; when the polymerization conversion rate of the first reactor was 72%, the polymer was transferred to the second reactor, and a solution dissolved in n-hexane at 60 wt% of 1,3-butadiene was introduced into the second reactor at a rate of 0.2 kg / hr to perform the polymerization reaction, and a hydrogenation reaction was not performed after the modification reaction.

[0323] Comparative Example 5

[0324] A modified conjugated diene polymer was prepared in the same manner as Comparative Example 1, except that the hydrogenation reaction was not performed in Comparative Example 1.

[0326] Comparative Example 6

[0327] An unmodified conjugated diene polymer was prepared by carrying out the same procedure as Comparative Example 1, except that in Comparative Example 1 above, a monomer solution dissolved in n-hexane at 60 wt% with 1,3-butadiene was introduced into the first reactor at a rate of 1.16 kg / hr, a monomer solution dissolved in n-hexane at 60 wt% with styrene was introduced at a rate of 0.31 kg / hr, and a polar additive solution was introduced at a rate of 5.0 g / hr; when the polymerization conversion rate of the first reactor was 72%, the polymer was transferred to the second reactor, and a coupling reaction was carried out by continuously supplying a coupling agent in which silicon tetrachloride was dissolved in n-hexane at a rate of 4.5 wt% with 4.5 wt% with hexane instead of a modifying agent.

[0329] Comparative Example 7

[0330] A modified conjugated diene polymer was prepared by carrying out the same procedure as Comparative Example 1, except that the hydrogenation catalyst was added as titanium at a concentration of 30 ppm per 100 parts by weight of the polymer.

[0332] Comparative Example 8

[0333] In the above Example 1, a modified conjugated diene polymer was prepared by carrying out the same procedure as in Example 1, except that no hydrogenation reaction was performed.

[0335] Experimental Example 1. Evaluation of Polymer Characteristics

[0336] For each modified or unmodified conjugated diene polymer prepared in the above examples and comparative examples, the styrene unit content, vinyl content, and weight-average molecular weight (Mw, X10) within the polymer, respectively 3 g / mol), number average molecular weight (Mn, X10⁻⁶ 3 g / mol), molecular weight distribution (PDI, MWD), hydrogenation rate, and full width at half maximum of the tan δ peak were measured, respectively. The results are shown in Table 1 below.

[0337] 1) Styrene Units and Vinyl Content (Weight%)

[0338] The styrene unit (SM) and vinyl content in each of the above polymers were measured and analyzed using Varian VNMRS 500 MHz NMR.

[0339] For NMR measurement, 1,1,2,2-tetrachloroethane was used as the solvent, and the solvent peak was calculated as 6.00 ppm, while the peaks were 7.2–6.9 ppm for random styrene, 6.9–6.2 ppm for blocked styrene, 5.8–5.1 ppm for 1,4-vinyl, and 5.1–4.5 ppm for 1,2-vinyl, and the styrene units and vinyl content were calculated.

[0341] 2) Weight-average molecular weight (Mw, X10) 3 g / mol), number average molecular weight (Mn, X10⁻⁶ 3 g / mol), and molecular weight distribution (PDI, MWD)

[0342] The number average molecular weight (Mn) and weight average molecular weight (Mw) were measured under the following conditions using 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.

[0343] - Columns: Use a combination of two PLgel Olexis columns (Polymer Laboratories) and one PLgel mixed-C column (Polymer Laboratories).

[0344] - Solvent: Use a mixture of 2 wt% amine compound with tetrahydrofuran

[0345] - Flow rate: 1 mL / min

[0346] - Sample concentration: 1–2 mg / mL (diluted in THF)

[0347] - Infusion volume: 100 uL

[0348] - Column temperature: 40℃

[0349] - Detector: Refractive index

[0350] - Standard: Polystyrene (corrected by a cubic function)

[0352] 3) Full Width Half Maximum (FWHM) of the tanδ peak

[0353] For the polymers prepared in the above examples and comparative examples, to analyze dynamic viscoelasticity using the Advanced Rheometric Expansion System (ARES), a dynamic mechanical analyzer (TA, ARES-G2) was used to measure tanδ as a function of temperature in the temperature range of -100℃ to 100℃ in torsional mode with a frequency of 10 Hz, a strain of 0.5%, and a heating rate of 5℃ / min, and a tanδ graph as shown in Fig. 1 was obtained, and the full width at half maximum of the peak was calculated from this graph.

[0355] 4) Hydrogenation rate (mol%)

[0356] With respect to the polymers prepared in the above examples and comparative examples, 1 The spectra of the following structural units (a) to (d) were obtained by H NMR analysis, and the relative molar ratio of the sum of structural unit (b) and structural unit (d) to the total structural unit was calculated using the integral values ​​of each peak area.

[0357] Specifically, NMR spectra were obtained using Varian VNMRS 500 MHz NMR, and structural units (a) and (c) were defined as 4.0–6.0 ppm and structural units (b) and (d) as 0.5–2.5 ppm, and the relative molar ratio of the sum of structural units (b) and (d) to the total structural units was calculated. Meanwhile, 1,1,2,2-tetrachloroethane was used as the solvent for NMR measurement, and the solvent peak was calculated as 6.00 ppm.

[0358]

[0359] division Examples Comparative example 1 2 3 4 5 6 1 2 3 4 5 6 7 8 NMR (wt%) SM 17 17 17 17 15 17 15 17 17 20 17 17 15 17 Vinyl 13 13 13 13 20 13 25 13 13 20 13 13 25 13 GPC Mn(X10 3 g / mol) 351 365 341 378 350 425 376 385 405 410 430 378 389 403 Mw(X10 3 g / mol) 581 608 577 616 577 705 608 620 689 658 721 685 623 650 PDI 1.66 1.67 1.69 1.63 1.65 1.66 1.62 1.61 1.70 1.60 1.68 1.81 1.60 1.61 FWHM of the tanδ peak 38 36 42 45 40 36 17 19 16 12 14 17 19 35 Hydrogenation rate (mol%) 95 95 94 95 95 94 95 93 94 - - 95 20 -

[0360] Referring to Table 1 above, it is confirmed that the polymers produced by the manufacturing method according to the present invention all have full width at half maximum (FWHM) values ​​of the tanδ peak at 25 or higher and a hydrogenation rate of 60 mol% or higher, whereas the comparative examples not produced by the manufacturing method according to the present invention have full width at half maximum (FWHM) values ​​of the tanδ peak at less than 25, a hydrogenation rate of less than 60 mol%, or are not hydrogenated polymers. In other words, it can be seen that when using the manufacturing method of the present invention, precise control of the polymer microstructure is possible, which allows for a larger full width at half maximum (FWHM) value of the tanδ peak and satisfies the hydrogenation rate.

[0362] Experimental Example 2. Evaluation of Characteristics of Molded Rubber Products

[0363] In order to compare and analyze the physical properties of the rubber composition containing each modified conjugated diene polymer prepared in the above examples and comparative examples and the molded article prepared therefrom, the full width at half maximum of the tanδ peak, tensile properties, viscoelastic properties, and wear resistance were measured, respectively, and the results are shown in Table 3 below.

[0364] 1) Preparation of rubber specimens

[0365] Each modified or unmodified conjugated diene polymer of the examples and comparative examples was used as the raw rubber and formulated under the formulation conditions shown in Table 2 below. The content of each raw material in Table 2 is a portion by weight based on 100 parts by weight of the raw rubber.

[0366] division raw material Content (parts by weight) 1st stage mixed training rubber 100 silica 70 Coupling agent (X50S) 11.2 Process oil 37.5 zinc oxide 3 stearic acid 2 antioxidants 2 Anti-aging agent 2 wax 1 Second stage mixed training sulfur 1.5 rubber accelerator 1.75 vulcanization accelerator 2

[0367] Specifically, the above rubber specimen is mixed through a first stage of mixing and a second stage of mixing. In the first stage of mixing, raw rubber, silica (filler), organosilane coupling agent (X50S, Evonik), process oil (TDAE oil), zinc oxide (ZnO), stearic acid, antioxidant (TMQ(RD) (2,2,4-trimethyl-1,2-dihydroquinoline polymer), anti-aging agent (6PPD ((dimethylbutyl)-N-phenyl-phenylenediamine)), and wax (microcrystaline wax) were mixed using a Banbury mixer equipped with a temperature control device. At this time, the initial temperature of the mixer was controlled to 70°C, and a primary mixture was obtained at an discharge temperature of 145°C to 155°C after the mixing was completed. In the second stage of mixing, the primary mixture was cooled to room temperature, and then the primary mixture, sulfur, rubber accelerator (DPG (diphenylguanidine)) and A vulcanization accelerator (CZ(N-cyclohexyl-2-benzothiazylsulfenamide)) was added, and the mixture was mixed at a temperature of 100°C or lower to obtain a secondary mixture. Subsequently, a rubber specimen was prepared by undergoing a curing process at 160°C for 20 minutes.

[0369] 2) Full Width Half Maximum (FWHM) of the tanδ peak

[0370] For rubber specimens prepared including the polymers prepared in the above examples and comparative examples, for dynamic viscoelasticity analysis using the Advanced Rheometric Expansion System (ARES), a dynamic mechanical analyzer (TA, ARES-G2) was used to measure tanδ as a function of temperature in the temperature range of -100℃ to 100℃ in torsional mode with a frequency of 10 Hz, a strain of 0.5%, and a heating rate of 5℃ / min, and a tanδ graph was obtained, and the full width at half maximum of the tanδ peak was calculated from this graph.

[0371] In addition, the tanδ values ​​at 0°C and 60°C were checked in the obtained tanδ graph. At this time, a higher tanδ value at low temperature 0°C indicates superior wet road resistance, and a higher tanδ value at high temperature 60°C indicates less hysteresis loss and superior driving resistance (fuel efficiency). However, since the results in Table 3 below are expressed as an index based on the measurement results of Comparative Example 6, a higher value indicates superior performance.

[0373] 3) Tensile strength

[0374] Tensile strength was measured by preparing each test specimen in accordance with the tensile test method of ASTM 412 and measuring the tensile strength at the time of cutting of the test specimen. Specifically, tensile properties were measured at room temperature at a speed of 50 cm / min using a Universal Test Machine 4204 (Instron) tensile testing machine.

[0376] 4) Wear resistance (DIN wear test)

[0377] For each rubber specimen, a DIN abrasion test was conducted in accordance with ASTM D5963, and the results were expressed as the DIN loss index (loss volume index): ARIA (Abration Resistance Index, Method A). A higher value indicates superior performance.

[0378] division Examples Comparative example 1 2 3 4 5 6 1 2 3 4 5 6 7 8 FWHM of the tanδ peak 43 41 49 49 45 41 22 23 20 18 20 22 24 41 tensile strength 100 101 100 101 98 100 101 100 101 53 55 100 60 55 Viscoelastic properties tan δ at 0℃ 118 119 115 114 113 116 100 100 99 90 92 100 92 103 tan δ at 60℃ 108 108 108 109 107 109 107 108 108 109 108 100 107 107 Wear resistance 119 11 122 124 119 117 95 99 98 69 73 100 77 80

[0379] Referring to Table 3 above, in the case of rubber specimens containing a polymer that satisfies the full width at half maximum of the tanδ peak and the hydrogenation rate according to the present invention, the full width at half maximum of the tanδ peak was all 31 or higher, and it can be confirmed that tensile strength, wet road resistance, and driving resistance are excellent, while wear resistance is significantly improved at the same time.

[0380] On the other hand, in the case of rubber specimens containing polymers of comparative examples that do not satisfy the full width at half maximum of the tanδ peak and / or hydrogenation rate, the full width at half maximum of the tanδ peak all show values ​​less than 31, and the tensile strength, wet road resistance, driving resistance, and wear resistance are not balanced and excellent, and the wear resistance is significantly reduced or the tensile strength or wet road resistance is significantly reduced, and it can be confirmed that even if the full width at half maximum of the tanδ peak has a value of 31 or more, the tensile strength, wet road resistance, driving resistance, and wear resistance are reduced.

[0382] Experimental Data II

[0383] Example 7

[0384] In the first reactor of three continuous stirred liquid-phase reactors (CSTR), n-hexane was continuously fed at a flow rate of 5 kg / hr, a monomer solution dissolved in n-hexane at 60 wt% 1,3-butadiene at 1.16 kg / hr, a monomer solution dissolved in n-hexane at 60 wt% styrene at 0.31 kg / hr, an initiator solution dissolved in n-hexane at 6.6 wt% n-butyllithium at 8.33 g / hr, and a polar additive solution dissolved in n-hexane at 2 wt% ditetrahydrofurylpropane at 2.25 g / hr. At this time, the internal temperature of the reactor was maintained at 60°C, and when the polymerization conversion rate reached 72%, the polymer was transferred from the first reactor to the second reactor through a transfer pipe.

[0385] Next, the temperature of the second reactor was maintained at 60°C, and a solution of 1,3-butadiene dissolved in n-hexane at 60 wt% was continuously fed into the second reactor at 0.2 kg / hr, and a polar additive solution of ditetrahydrofurylpropane dissolved in n-hexane at 10 wt% was continuously fed at 6 g / hr to participate in the reaction, and when the polymerization conversion rate reached 95% or more, the reaction was terminated and the polymer was transferred from the second reactor to the third reactor.

[0386] Next, the hydrogenation catalyst prepared in the above preparation example and hydrogen were introduced into the third reactor, and a hydrogenation reaction was carried out at a temperature of 80°C and a hydrogen pressure of 0.7 MPa. At this time, 200 ppm of titanium was added as the hydrogenation catalyst per 100 parts by weight of polymer.

[0387] After that, a solution of IR1520 (BASF) dissolved at 30 wt% as an antioxidant was injected at a rate of 100 g / h and stirred. The resulting polymer was placed in hot water heated with steam and stirred to remove the solvent, and then roll-dried to remove the remaining solvent and water to produce an unmodified conjugated diene copolymer.

[0389] Example 8

[0390] An unmodified conjugated diene polymer was prepared in the same manner as in Example 7, except that the polymer was transferred from the first reactor to the second reactor when the polymerization conversion rate of the first reactor was 70%.

[0392] Example 9

[0393] An unmodified conjugated diene polymer was prepared in the same manner as in Example 7, except that the temperature of the first reactor was maintained at 70°C and the temperature of the second reactor at 65°C, and the polymerization conversion rate of the first reactor was transferred to the second reactor when it was 80%.

[0395] Example 10

[0396] An unmodified conjugated diene polymer was prepared in the same manner as in Example 7, except that the 1,3-butadiene solution additionally introduced into the second reactor in Example 7 was not introduced into the second reactor.

[0398] Example 11

[0399] An unmodified conjugated diene polymer was prepared in the same manner as in Example 7, except that a polar additive solution in which 10 wt% of ditetrahydrofurylpropane was dissolved in n-hexane added to the second reactor in Example 7 was continuously added at a rate of 15 g / hr.

[0401] Example 12

[0402] An unmodified conjugated diene polymer was prepared in the same manner as in Example 7, except that a polar additive solution in which 10 wt% of ditetrahydrofurylpropane was dissolved in n-hexane added to the second reactor in Example 7 was continuously added at a rate of 1 g / hr.

[0404] Comparative Example 9

[0405] An unmodified conjugated diene polymer was prepared in the same manner as in Example 7, except that in Example 7, a monomer solution dissolved in n-hexane at 60 wt% 1,3-butadiene was introduced into the first reactor at a rate of 1.13 kg / hr, a monomer solution dissolved in n-hexane at 60 wt% styrene was introduced at a rate of 0.28 kg / hr, and a polar additive solution was introduced at a rate of 17.5 g / hr, and when the polymerization conversion rate of the first reactor was 78%, the polymer was transferred to the second reactor, and 1,3-butadiene and the polar additive were not introduced into the second reactor.

[0407] Comparative Example 10

[0408] An unmodified conjugated diene polymer was prepared in the same manner as in Example 7, except that in Example 7, the temperature of the first reactor was maintained at 50°C and the temperature of the second reactor was maintained at 40°C, the polymer was transferred to the second reactor when the polymerization conversion rate of the first reactor was 57%, and 1,3-butadiene was not additionally added to the second reactor.

[0410] Comparative Example 11

[0411] An unmodified conjugated diene polymer was prepared in the same manner as in Example 7, except that the temperature of the first reactor was maintained at 50°C and the temperature of the second reactor at 40°C, and the polymer was transferred to the second reactor when the polymerization conversion rate of the first reactor was 53%.

[0413] Comparative Example 12

[0414] In Comparative Example 9 above, a monomer solution dissolved in n-hexane at 60 wt% with 1,3-butadiene was introduced into the first reactor at a rate of 1.08 kg / hr, a monomer solution dissolved in n-hexane at 60 wt% with styrene was introduced at a rate of 0.35 kg / hr, and a polar additive solution was introduced at a rate of 12.0 g / hr. When the polymerization conversion rate of the first reactor was 72%, the polymer was transferred to the second reactor, and a solution dissolved in n-hexane at 60 wt% with 1,3-butadiene was introduced into the second reactor at a rate of 0.2 kg / hr to perform the polymerization reaction. An unmodified conjugated diene polymer was prepared in the same manner as Comparative Example 9, except that a hydrogenation reaction was not performed after the modification reaction.

[0416] Comparative Example 13

[0417] An unmodified conjugated diene polymer was prepared in the same manner as Comparative Example 9, except that the hydrogenation reaction was not performed in Comparative Example 9.

[0419] Comparative Example 14

[0420] A modified conjugated diene polymer was prepared by carrying out the same procedure as Comparative Example 9, except that the hydrogenation catalyst was added as titanium at a concentration of 30 ppm per 100 parts by weight of the polymer.

[0422] Comparative Example 15

[0423] In the above Example 7, a modified conjugated diene polymer was prepared by carrying out the same procedure as in Example 7, except that no hydrogenation reaction was performed.

[0425] Experimental Example 3. Evaluation of Polymer Characteristics

[0426] For each unmodified conjugated diene polymer prepared in the above examples and comparative examples, the styrene unit content, vinyl content, and weight-average molecular weight (Mw, X10) within the polymer, respectively 3 g / mol), number average molecular weight (Mn, X10⁻⁶ 3 g / mol), molecular weight distribution (PDI, MWD), hydrogenation rate, and full width at half maximum of the tan δ peak were measured using the same method as in Experimental Example 1 of the aforementioned Experimental Data I. The results are shown in Table 4 below.

[0427] division Examples Comparative example 7 8 9 10 11 12 9 10 11 12 13 14 15 NMR (wt%) SM 17 17 17 17 15 17 15 17 17 20 17 15 17 Vinyl 13 13 13 13 20 13 25 13 13 20 13 25 13 GPC Mn(X10 3 g / mol) 352 333 310 348 326 407 356 375 379 396 403 352 368 Mw(X10 3 g / mol) 565 542 539 587 536 581 569 591 639 618 672 598 604 PDI 1.61 1.63 1.74 1.69 1.64 1.43 1.60 1.58 1.69 1.56 1.67 1.70 1.64 FWHM of the tanδ peak 37 35 40 44 38 35 15 17 15 11 13 17 32 Hydrogenation rate (mol%) 96 95 94 95 95 94 95 93 94 - - 20 -

[0428] Referring to Table 4 above, in the case of modified conjugated diene polymers produced by the manufacturing method according to the present invention, the full width at half maximum of the tanδ peak is 25 or higher and the hydrogenation rate is 60 mol% or higher. However, comparative examples not produced by the manufacturing method according to the present invention have a full width at half maximum of the tanδ peak of less than 25, a hydrogenation rate of less than 60 mol%, or are not hydrogenated polymers. In other words, it can be seen that when using the manufacturing method of the present invention, precise control of the polymer microstructure is possible, which allows for a larger full width at half maximum of the tanδ peak and satisfies the hydrogenation rate.

[0430] Experimental Example 4. Evaluation of Characteristics of Molded Rubber Products

[0431] In order to compare and analyze the physical properties of the rubber composition containing each unmodified conjugated diene polymer prepared in the above examples and comparative examples and the molded article prepared therefrom, the full width at half maximum of the tan δ peak, tensile properties, viscoelastic properties, and wear resistance were measured in the same manner as in Experimental Example 2 of Experimental Data I described above, and the results are shown in Table 5 below.

[0432] Meanwhile, in Table 5 below, tensile strength, viscoelastic properties, and wear resistance are expressed as indices based on the measured values ​​of Comparative Example 9, and a higher value indicates superiority.

[0433] division Examples Comparative example 7 8 9 10 11 12 9 10 11 12 13 14 15 FWHM of the tanδ peak 43 40 46 48 43 40 19 22 21 17 19 22 37 tensile strength 100 100 99 100 98 98 100 99 101 51 54 60 55 Viscoelastic properties tan δ at 0℃ 115 115 111 113 112 114 100 98 97 84 89 91 103 tan δ at 60℃ 100 100 100 101 99 101 100 100 100 101 100 99 99 Wear resistance 115 116 120 121 118 115 100 99 97 68 69 75 80

[0434] Referring to Table 5 above, in the case of rubber specimens containing a polymer that satisfies the full width at half maximum of the tanδ peak and the hydrogenation rate according to the present invention, the full width at half maximum of the tanδ peak was all 31 or higher, and it can be confirmed that tensile strength, wet road resistance, and driving resistance are excellent, while wear resistance is significantly improved at the same time.

[0435] On the other hand, in the case of rubber specimens containing polymers of comparative examples that do not satisfy the full width at half maximum of the tanδ peak and / or hydrogenation rate, the full width at half maximum of the tanδ peak all show values ​​less than 31, and the tensile strength, wet road resistance, driving resistance, and wear resistance are not balanced and excellent, and the wear resistance is significantly reduced or the tensile strength or wet road resistance is significantly reduced, and it can be confirmed that even if the full width at half maximum of the tanδ peak has a value of 31 or more, the tensile strength, wet road resistance, driving resistance, and wear resistance are reduced.

Claims

Claim 1 A conjugated diene polymer comprising repeating units derived from conjugated diene monomers, wherein, in a stress change graph according to temperature derived from dynamic viscoelastic analysis by an Advanced Rheometric Expansion System (ARES), the full width at half maximum (FWHM) value of the tanδ peak appearing in the temperature range of -100℃ to 100℃ is 30 or more and 80 or less, and said rheometric system is measured using a dynamic mechanical analyzer in torsional mode under conditions of a frequency of 10 Hz, a strain of 0.5%, and a heating rate of 5℃ / min, and the hydrogenation rate of the conjugated diene monomer-derived units is 60 mol% or more. Claim 2 delete Claim 3 A conjugated diene polymer according to claim 1, wherein the full width at half maximum of the tanδ peak is 35 or more and 60 or less. Claim 4 A conjugated diene polymer according to claim 1, wherein the hydrogenation rate of the conjugated diene monomer-derived unit is 80 mol% or more. Claim 5 A conjugated diene polymer according to claim 1, wherein the tan δ peak appears in a temperature range of -80℃ to 20℃. Claim 6 A conjugated diene polymer according to claim 1, further comprising repeating units derived from aromatic vinyl monomers. Claim 7 A modified conjugated diene polymer comprising repeating units derived from conjugated diene monomers and functional groups derived from a modifying agent, wherein, in a stress change graph according to temperature derived from dynamic viscoelastic analysis by an Advanced Rheometric Expansion System (ARES), the full width at half maximum (FWHM) value of the tanδ peak appearing in the temperature range of -100℃ to 100℃ is 30 or more and 80 or less, wherein the rheometric system is measured using a dynamic mechanical analyzer in torsional mode under conditions of a frequency of 10 Hz, a strain of 0.5%, and a heating rate of 5℃ / min, and the hydrogenation rate of the conjugated diene monomer-derived units is 60 mol% or more. Claim 8 In claim 7, the modifying agent is an alkoxysilane-based modifying agent, and the modified conjugated diene-based polymer is a modified conjugated diene-based polymer having Si and N contents of 50 ppm or more each based on the total weight of the polymer. Claim 9 A rubber composition comprising a polymer and a filler, wherein the polymer is a conjugated diene polymer according to claim 1 or a modified conjugated diene polymer according to claim 7. Claim 10 A rubber composition according to claim 9, comprising 0.1 to 200 parts by weight of a filler based on 100 parts by weight of the polymer. Claim 11 A rubber composition comprising a conjugated diene polymer and a filler, wherein, in a stress change graph according to temperature derived from dynamic viscoelasticity analysis by an Advanced Rheometric Expansion System (ARES), the full width at half maximum (FWHM) value of the tan δ peak appearing in the temperature range of -100℃ to 100℃ is 31 or more and 100 or less, the rheometric system is measured using a dynamic mechanical analyzer in torsional mode under conditions of a frequency of 10 Hz, a strain of 0.5%, and a heating rate of 5℃ / min, and the conjugated diene polymer has a hydrogenation rate of a unit derived from a conjugated diene monomer of 60 mol% or more. Claim 12 A rubber composition according to claim 11, wherein the conjugated diene polymer is an unmodified conjugated diene polymer. Claim 13 A rubber composition according to claim 11, wherein the conjugated diene polymer is a modified conjugated diene polymer comprising a functional group derived from a modifying agent.

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