KR20230017066A - Modified conjugated diene-based polymer and rubber composition comprising the same - Google Patents

Abstract

The present invention relates to a modified conjugated diene-based polymer with well-balanced wet road resistance and abrasion resistance, and a rubber composition containing the same. The modified conjugated diene-based polymer comprises: a repeating unit derived from a conjugated diene-based monomer; a repeating unit derived from an aromatic vinyl monomer; and a functional group derived from a denaturant. When measured by differential scanning calorimetry (DSC) through control of the fine structure of the polymer, the difference between the glass transition start temperature (onset, T_(g-on)) at which the glass transition occurs and the glass transition end temperature (offset, T_(g-off)) is 10℃ or more to 30℃ or less. Thus, an excellent balance between wet road resistance and driving resistance can be provided with improved wear resistance.

Description

Modified conjugated diene-based polymer and rubber composition containing the same

The present invention relates to a modified conjugated diene-based polymer having excellent wet road resistance and driving resistance in a well-balanced manner and improved abrasion resistance, and a rubber composition comprising the same.

In accordance with the recent demand for low fuel consumption for automobiles, conjugated diene-based polymers with low rolling resistance, excellent abrasion resistance and tensile properties, and control stability represented by wet road surface resistance are required as rubber materials for tires. there is.

In order to reduce the running resistance of a tire, there is a method of reducing the hysteresis loss of vulcanized rubber, and as an evaluation index of such vulcanized rubber, rebound elasticity at 50 ° C to 80 ° C, tan δ, Goodrich heat generation, etc. are used. That is, a rubber material having high rebound resilience at the above temperature or low tan δ and Goodrich heat generation is preferable.

Natural rubber, polyisoprene rubber, polybutadiene rubber and the like are known as rubber materials with low hysteresis loss, but these have a problem of low wet road surface resistance. Recently, conjugated diene-based polymers or copolymers such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) are produced by emulsion polymerization or solution polymerization and are used as rubber for tires. . Among them, the greatest advantage of solution polymerization over emulsion polymerization is that the vinyl structure content and styrene content that define rubber properties can be arbitrarily controlled, and molecular weight and physical properties can be changed by coupling or modification. that it can be controlled. Therefore, it is easy to change the structure of the finally manufactured SBR or BR, reduce the movement of the chain ends by linking or modifying the chain ends, and increase the binding force with fillers such as silica or carbon black. It is widely used as a rubber material for

The solution polymerization SBR is prepared using an anionic polymerization initiator, and a technique of combining or modifying the chain ends of the formed polymer using various denaturants to introduce functional groups into the ends is used. For example, U.S. Patent No. 4,397,994 suggests a technique in which active anions at the chain ends of a polymer obtained by polymerizing styrene-butadiene in a non-polar solvent using alkyllithium, a monofunctional initiator, are bonded using a binder such as a tin compound. did

In addition, when the solution polymerized SBR is used as a rubber material, it is possible to adjust the required tire properties such as driving resistance by increasing the vinyl content in the SBR, but when the vinyl content is high, braking performance and abrasion resistance are disadvantageous. Although the styrene content in SBR should be maintained at a certain level or higher, in this case, there is a problem in that the effect expressed from the high vinyl content does not appear.

Due to these problems, an attempt was made to improve driving resistance and wet road resistance in a balanced way by using a block copolymer SBR comprising two block copolymer units having a gradient in styrene and vinyl content as a solution polymerized SBR, but the improvement was not successful. It was only a minor level, and wet road resistance tends to deteriorate when SBR with a low glass transition temperature is applied to improve wear resistance.

Therefore, it is necessary to develop a polymer capable of simultaneously improving wet road surface resistance and abrasion resistance while basically meeting the required product performance in terms of tensile properties and fuel consumption properties.

US 4,397,994 A (1983. 08. 09.)

The present invention has been made to solve the problems of the prior art, and in order to implement a tire having improved wet road resistance and abrasion resistance in a balanced state while maintaining excellent tensile properties and fuel economy properties, Through structural control, it is an object to provide a modified conjugated diene-based polymer having a gap in a specific range between the onset temperature and the end temperature in the glass transition temperature.

In addition, an object of the present invention is to provide a rubber composition containing the modified conjugated diene-based polymer.

According to one embodiment of the present invention for solving the above problems, the present invention is a conjugated diene-based monomer-derived repeating unit; Repeating units derived from aromatic vinyl monomers; And a functional group derived from a denaturant, and when measured by Differential Scanning Calorimetry (DSC), a glass transition initiation temperature (onset, T _g-on ) and a glass transition termination temperature (offset, T g-on ) at which glass transition occurs. _g-off ) is 10 ° C. or more and less than 30 ° C., and a modified conjugated diene-based polymer having a styrene bond content of more than 30% by weight is provided.

In addition, the present invention provides a rubber composition comprising the modified conjugated diene-based polymer and a filler.

In the modified conjugated diene-based polymer according to the present invention, the gap between the onset temperature and the end temperature of the glass transition is controlled to a specific range by controlling the microstructure of the polymer, so that despite having a low glass transition temperature, wet road resistance and driving resistance are balanced. At the same time, it has the effect of improving wear resistance.

In addition, the modified conjugated diene-based polymer according to the present invention can realize excellent wear resistance and wet road resistance through microstructure control, and in addition, wear resistance is further improved by having a styrene bond content of more than 30% by weight, introducing a modifier and branching Excellent workability, fuel efficiency and tensile properties can also be realized through the control of the degree of curing.

The following drawings attached to this specification illustrate specific embodiments of the present invention, and serve to further understand the technical spirit of the present invention together with the contents of the above-described invention, so the present invention is limited to those described in the drawings. should not be construed as limiting.
1 is an example of a graph of tan δ versus temperature derived from dynamic viscoelasticity analysis by an Advanced Rheometric Expansion System (ARES).

Hereinafter, the present invention will be described in more detail to aid understanding of the present invention.

The terms or words used in the description and claims of the present invention should not be construed as being limited to ordinary or dictionary meanings, and the inventors use the concept of terms appropriately to describe their invention in the best way. Based on the principle that it can be defined, it should be interpreted as meaning and concept consistent with the technical spirit of the present invention.

Definition of Terms

As used herein, the term 'polymer' refers to a polymer compound prepared by polymerizing monomers, whether of the same or different types. The generic term polymer thus encompasses the term homopolymer, commonly used to refer to a polymer prepared from one type of monomer, and the term copolymer, as defined below.

The term 'copolymer' used herein refers to a polymer prepared by polymerization of at least two different monomers. Thus, the generic term copolymer includes polymers made from two or more different monomers, as well as binary copolymers, which are commonly used to refer to polymers made from two different types of monomers.

In the present specification, the term '1,2-vinyl bond content' refers to the conjugated diene monomer (butadiene, etc.) in the polymer based on the portion (total amount of polymerized butadiene) derived from the 1,2-position in the polymer chain of the polymer. Refers to the mass (or weight) percent of contained butadiene.

In this specification, the term 'styrene bond content' refers to the mass (or weight) percentage of styrene contained in the polymer chain of the polymer derived from an aromatic vinyl-based monomer (styrene, etc.).

In this specification, the term 'room temperature' refers to the temperature in its natural state without heating or cooling, and is a temperature of 20 ± 5 °C.

In this specification, the term 'substitution' may mean that hydrogen of a functional group, atomic group, or compound is substituted with a specific substituent, and when hydrogen of a functional group, atomic group, or compound is substituted with a specific substituent, the functional group, atomic group, or compound One or two or more substituents may be present according to the number of hydrogen present, and when a plurality of substituents are present, each substituent may be the same as or different from each other.

In this specification, the term 'alkyl group' may mean a monovalent aliphatic saturated hydrocarbon, and includes 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 two or more unsaturated bonds.

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

In the present invention, the term 'cycloalkyl group' may mean a cyclic saturated hydrocarbon.

In the present specification, the term 'aryl group' may mean an aromatic hydrocarbon, and may also refer to a monocyclic aromatic hydrocarbon in which one ring is formed, or a polycyclic aromatic hydrocarbon in which two or more rings are bonded. It may mean including all.

In this specification, the term 'aralkyl' is also called aralkyl, and may refer to a combination group 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.

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

In the present specification, the terms 'derived unit', 'derived repeating unit' and 'derived functional group' may refer to a component, structure derived from a certain material, or the material itself.

The terms 'comprising', 'having' and their derivatives herein are not intended to exclude the presence of any additional component, step or procedure, whether or not they are specifically disclosed. . For the avoidance of any doubt, all compositions claimed through use of the term "comprising", unless stated to the contrary, contain any additional additives, adjuvants, or compounds, whether polymeric or otherwise. can include In contrast, the term 'consisting essentially of' excludes from the scope of any succeeding recitation any other component, step or procedure, excepting those not essential to operability. The term 'consisting of' excludes any ingredient, step or procedure not specifically delineated or listed.

Measurement method and conditions

In the present specification, '1,2-vinyl bond content' and 'styrene bond content' are measured and analyzed by using Varian VNMRS 500 MHz NMR for vinyl content and styrene content in polymer units. In NMR measurement, 1,1,2,2-tetrachloroethane was used as the solvent, the solvent peak was calculated as 6.0 ppm, 7.2~6.9 ppm was random styrene, 6.9~6.2 ppm was block styrene, and 5.8~5.1 ppm was 1,4-vinyl and 1,2-vinyl, 5.1 to 4.5 ppm are measured by calculating the 1,2-vinyl bond content and the styrene bond content in the entire polymer, respectively, as the peak of 1,2-vinyl.

In the present specification, 'weight average molecular weight (Mw)', 'molecular weight distribution (MWD)' and 'unimodal properties' are gel permeation chromatograph (GPC) (PL GPC220, Agilent Technologies) under the following conditions: weight average molecular weight (Mw) , The number average molecular weight (Mn) was measured, and a molecular weight distribution curve was obtained, and the molecular weight distribution (PDI, MWD, Mw/Mn) was calculated and obtained from the measured molecular weights.

- Column: Two PLgel Olexis (Polymer Laboratories) columns and one PLgel mixed-C (Polymer Laboratories) column are used in combination

- Solvent: 2% by weight of amine compound mixed with tetrahydrofuran

- Flow rate: 1 ml/min

- Sample concentration: 1~2 mg/ml (diluted in THF)

- Injection amount: 100 μl

- Column temperature: 40 ℃

-Detector: Refractive index

- Standard: Polystyrene (correction with cubic function)

In the present specification, the 'glass transition temperature (Tg)' is measured from -100 ° C to 10 ° C / min under the flow of nitrogen 50 ml / min using a differential scanning calorimetry (DSCQ100, TA) according to ISO 22768: 2006. A differential scanning calorimetry curve (DSC curve) is recorded while the temperature is raised at min, and the peak top (Inflection point) of the DSC differential curve is taken as the glass transition temperature.

In the present specification, 'glass transition start temperature (onset, T _g-on )' and 'glass transition end temperature (offset, T _g-off )' are measured from -100 ° C. under the flow of nitrogen at 50 ml / min in accordance with ISO 22768: 2006 While raising the temperature at 10 ° C./min, a differential scanning calorimetry curve (DSC curve) is recorded, and the temperature at which the glass transition starts in this curve is set as the glass transition start temperature, and the temperature at which the glass transition ends is set as the glass transition end temperature.

In the present specification, the 'tan δ peak' is a peak appearing in a tan δ graph according to temperature derived from dynamic viscoelasticity analysis by an Advanced Rheometric Expansion System (ARES), a dynamic mechanical analyzer (TA, ARES-G2 ) is used in torsional mode and measured under the conditions of a frequency of 10 Hz, a strain of 0.5%, and a heating rate of 5° C./min.

In the present specification, 'Si content' is measured using an inductively coupled plasma emission spectrometer (ICP-OES; Optima 7300DV) as an ICP analysis method, and about 0.7 g of a sample is placed in a platinum crucible (Pt crucible), put about 1 mL of concentrated sulfuric acid (98% by weight, electronic grade), heated at 300 ° C. for 3 hours, and the sample in an electric furnace (Thermo Scientific, Lindberg Blue M), following step 1 After conducting a conversation with the program of 3 to 3,

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

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

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

1 mL of concentrated nitric acid (48% by weight) and 20 μl of concentrated hydrofluoric acid (50% by weight) were added to the residue, and after sealing a platinum crucible and shaking for 30 minutes or more, 1 mL of boric acid was added to the sample. After putting it in and storing it at 0 ° C. for more than 2 hours, it was diluted in 30 mL of ultrapure water and measured by incineration.

In the present invention, 'N content' may be measured through the NSX analysis method, and the NSX analysis method may be measured using a trace nitrogen quantitative analyzer (NSX-2100H). Specifically, turn on the trace nitrogen quantitative analyzer (Auto sampler, Horizontal furnace, PMT & Nitrogen detector), set the carrier gas flow rate to 250 ml/min for Ar, 350 ml/min for O ₂ and 300 ml/min for ozonizer, and set the heater After setting to 800 ° C., the analyzer was stabilized by waiting for about 3 hours. After the analyzer is stabilized, a calibration curve of 5 ppm, 10 ppm, 50 ppm, 100 ppm and 500 ppm is prepared using a nitrogen standard (AccuStandard S-22750-01-5 ml), and the area corresponding to each concentration is obtained. Then, a straight line was drawn using the ratio of concentration to area. Thereafter, a ceramic boat containing 20 mg of the sample was placed on the auto sampler of the analyzer and measured to obtain an area. The nitrogen atom content was calculated using the area of the obtained sample and the calibration curve.

At this time, the sample used in the NSX analysis method may be a modified conjugated diene-based polymer sample in which the solvent is removed by stirring in hot water heated with steam, and residual monomer and residual modifier are removed. In addition, if oil is added to the above sample, it may be a sample after oil is extracted (removed).

Modified conjugated diene polymer

The present invention is a specific range of glass transition initiation temperature and glass transition termination through microstructure control that can implement a tire with balanced improved characteristics of wet road surface resistance and abrasion resistance while maintaining excellent tensile characteristics and fuel economy characteristics. A modified conjugated diene-based polymer having a temperature gap and a high styrene bond content is provided.

The modified conjugated diene-based polymer according to an embodiment of the present invention includes a repeating unit derived from a conjugated diene-based monomer; Repeating units derived from aromatic vinyl monomers; And a functional group derived from a denaturant, and when measured by Differential Scanning Calorimetry (DSC), a glass transition initiation temperature (onset, T _g-on ) and a glass transition termination temperature (offset, T g-on ) at which glass transition occurs. It is characterized in that the difference in _g-off ) is 10 ° C or more and less than 30 ° C, and the styrene bond content is more than 30% by weight.

According to one embodiment of the present invention, the modified conjugated diene-based polymer realizes a polymer having a specific microstructure through the application of a characteristic manufacturing method described later, and thus, in the glass transition temperature of the polymer, the glass transition initiation temperature and the glass transition end The temperature difference is controlled to be 10 ° C or more and less than 30 ° C, so that the tensile properties are excellent, and the wet road resistance and abrasion resistance can be excellent in balance.

Glass transition onset and glass transition end temperatures of polymers

According to one embodiment of the present invention, the modified conjugated diene-based copolymer is measured by differential scanning calorimetry (DSC), the glass transition onset temperature (onset, T _g-on ) and the glass transition end temperature The difference in (offset, T _g-off ) is 10 ° C or more and less than 30 ° C.

In general, in the case of a modified polymer prepared by a polymerization method and having an uncontrolled microstructure, the glass transition start temperature and the glass transition end temperature are substantially the same as the glass transition temperature and within a range of less than ± 10 ° C from the glass transition temperature, The difference between the starting temperature and the ending temperature cannot be greater than 10°C. In this case, it is possible to have wear resistance properties that can be improved due to the low glass transition temperature, but there is a problem accompanied by deterioration of physical properties in wet road resistance, and in the case of applying a polymer with a high glass transition temperature, the opposite is true. There is a problem in which the phenomenon appears, and it is difficult to easily control abrasion resistance and wet road resistance through structural transformation of the modifier, type of functional group, and control of branching degree.

However, since the modified conjugated diene-based polymer according to an embodiment of the present invention is produced by a manufacturing method for controlling the microstructure of the polymer, it is advantageous even if it has the same glass transition temperature as the existing modified conjugated diene-based polymer. By controlling the difference between the transition start temperature and the glass transition end temperature within a specific range, the effect of simultaneously increasing wet road resistance and abrasion resistance can be realized.

At this time, if the difference between the glass transition start temperature and the end temperature is less than 10 ° C, it is impossible to realize the effect of simultaneously improving wet road resistance and abrasion resistance, and the difference between the glass transition start temperature and end temperature is large at 30 ° C or more. When widened, two or more glass transition temperatures may appear, problems of deterioration in processability may occur, and problems of deterioration in tensile properties and fuel consumption characteristics may occur. Therefore, it is necessary to control the difference between the glass transition start temperature and the glass transition end temperature to be more than 10 ° C and less than 30 ° C. And, it may be more preferably 10 ℃ to 23 ℃, even more preferably 13 ℃ to 20 ℃.

Styrene binding content

According to one embodiment of the present invention, the modified conjugated diene-based polymer may have a styrene bond content of greater than 30% by weight. Here, the styrene bond content refers to the mass or weight percent of styrene contained in a polymer chain derived from an aromatic vinyl monomer in the polymer, and the modified conjugated diene-based polymer according to the present invention has a styrene bond content of the above With this range, further improvements in workability, wear resistance and tensile properties can be expected while maintaining excellent wet road resistance.

Specifically, the modified conjugated diene-based polymer may have a styrene bond content of more than 30% by weight and less than 45% by weight, and in this case, it may be more advantageous to improve abrasion resistance and tensile properties in a balanced manner.

Dynamic viscoelastic behavior of polymers

According to one embodiment of the present invention, the modified conjugated diene-based polymer is derived from dynamic viscoelasticity analysis by a rheometric system (Advanced Rheometric Expansion System, ARES) while satisfying the glass transition onset temperature and end temperature difference In a tan δ graph according to temperature, a full width at half maximum (FWHM) value of a tan δ peak appearing in a temperature range of -100 °C to 100 °C may be 20 °C or more.

In general, in the case of a polymer prepared by a polymerization method and having an uncontrolled microstructure, two or more tan δ peaks appear or the peak width is not wide, such as a very narrow peak width. This may be related to the glass transition temperature. When the units in the polymer are partitioned and the glass transition temperature difference between the blocks is large, such as in block copolymers, the tan δ peak is narrow and two or more peaks may appear. . Also, in the case of a random copolymer, when only the vinyl content or styrene content in the final polymer is adjusted without precise control of the microstructure, it is common that the peak width appears very narrow.

In this case, the glass transition temperature may be the same for both the block copolymer and the random copolymer, but there is a large difference in wet road resistance. There is an effort to However, when the glass transition temperature is changed, a change in abrasion resistance and a problem in that the physical properties of the basic polymer are changed, so implementing a polymer having improved performance still exists as a challenge. In other words, it is difficult to balance abrasion resistance and wet road resistance, and these two characteristics remain a more difficult task in that simultaneous improvement through the modification process does not tend to be achieved. However, in that the conjugated diene-based polymer according to an embodiment of the present invention is produced by a manufacturing method for controlling the microstructure of the polymer, even if it has the same glass transition temperature as the conventional modified conjugated diene-based polymer, it has a unique It has a tan δ peak of , and it is possible to realize the effect of simultaneously increasing wet road resistance and abrasion resistance.

At this time, the tan δ peak is a graph of stress change according to temperature derived from dynamic viscoelasticity analysis by an Advanced Rheometric Expansion System (ARES), in the temperature range of -100 ° C to 100 ° C It is characterized in that the full width at half maximum of the tan δ peak is 20 ° C or higher. The number of tan δ peaks appearing in the above temperature range can usually be one, but can also be two or more, and when two or more peaks appear, the full width at half maximum of one of the plurality of peaks is 20 ° C. or more.

The full width at half maximum of the tan δ peak may be 20°C or more, preferably 30°C or more. In addition, the value of the full width at half maximum may be 80°C at most, and may be preferably 70°C or less. As another example, the full width at half maximum of the tan δ peak may be 30°C or more and 80°C or less, or 35°C or more and 60°C or less. If the full width at half maximum is less than 20 ° C, there is a problem that the wet road resistance is significantly lowered at the same glass transition temperature, and if the full width at half maximum of the peak is greater than 80 ° C, it is unlikely to be implemented, but even if it is implemented, phase separation occurs or at high temperature An increase in hysteresis is inevitably accompanied, and accordingly, a problem of deterioration in fuel efficiency may occur.

In addition, the tan δ peak may be a peak appearing at -100°C to 100°C, preferably at -80°C to 20°C, and more preferably at -70°C to 0°C. When a peak appears in the above range, a more advantageous effect in wear resistance can be expected.

Dynamic viscoelasticity analysis by the rheometer system was performed in a torsional mode using a dynamic mechanical analyzer (TA, ARES-G2) at a frequency of 10 Hz, a strain of 0.5%, and a heating rate of 5° C./min. , tan δ is measured according to the temperature in the temperature range -100 ° C to 100 ° C, and the graph derived at this time is the tan δ value against the temperature.

Monomer-derived repeating unit

According to one embodiment of the present invention, the modified conjugated diene-based polymer has a conjugated diene-based monomer-derived repeating unit as a main unit, and the conjugated diene-based monomer is, 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) It may be one or more selected from the group consisting of

In addition, the modified conjugated diene-based polymer includes a repeating unit derived from an aromatic vinyl-based monomer, and the aromatic vinyl-based monomer is, for example, styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl)styrene, 1-vinyl-5-hexylnaphthalene, 3-(2-pyrrolidinoethyl)styrene (3-(2-pyrrolidino ethyl)styrene ), 4- (2-pyrrolidino ethyl) styrene (4- (2-pyrrolidino ethyl) styrene) and 3- (2-pyrrolidino-1-methyl ethyl) -α-methyl styrene (3- (2- pyrrolidino-1-methyl ethyl) -α-methylstyrene) may be one or more selected from the group consisting of.

As another example, the conjugated diene-based polymer may be a copolymer that further includes a repeating unit derived from a diene-based monomer having 1 to 10 carbon atoms together with a repeating unit derived from the conjugated diene-based monomer. The repeating unit derived from the diene-based monomer may be a repeating unit derived from a diene-based monomer different from the conjugated diene-based monomer, and the diene-based monomer different from the conjugated diene-based monomer may be, for example, 1,2-butadiene. . When the conjugated diene-based polymer is a copolymer further containing a diene-based monomer, the conjugated diene-based polymer contains a diene-based monomer-derived repeating unit in an amount greater than 0% by weight to 1% by weight, greater than 0% by weight to 0.1% by weight, greater than 0% by weight. It may be included in weight% to 0.01% by weight, or more than 0% by weight to 0.001% by weight, and there is an effect of preventing gel formation within this range.

According to one embodiment of the present invention, when two or more monomers are included in the chain of the conjugated diene-based polymer, it may have a chain structure intermediate between a random copolymer and a block copolymer, and in this case, it is easy to control the microstructure. It can be done, and there is an effect of excellent balance between each physical property. The random copolymer may mean that repeating units constituting the copolymer are randomly arranged.

glass transition temperature of polymers

According to one embodiment of the present invention, the modified conjugated diene-based polymer may have a glass transition temperature of -100 °C to 20 °C. The glass transition temperature is a value that varies depending on the microstructure of the polymer, but in order to improve wear resistance, it is preferable to manufacture a polymer to satisfy the above range, more preferably -100 ℃ to 0 ℃, more preferably -90 ℃ to It may be -10 °C, even more preferably -80 °C to -20 °C.

The glass transition temperature is the microstructure in each unit according to the bonding method (1,2-bond or 1,4-bond) of the conjugated diene-based monomer in the polymer unit, the content of the repeating unit derived from the aromatic vinyl-based monomer, the polymerization method, and the polymerization conditions. (1,2-vinyl bond content and styrene bond content) can be flexibly adjusted.

Si and N content of the polymer

On the other hand, the modified conjugated diene-based polymer according to an embodiment of the present invention may have Si and N contents of 50 ppm or more, or 50 ppm to 1000 ppm, respectively, based on the total weight of the polymer, and the lower limit is preferably each of 100 It may be ppm or more, may be 150 ppm or more, and the upper limit may be preferably 700 ppm or less, preferably 500 ppm or less. Within this range, mechanical properties such as tensile properties and viscoelastic properties of the rubber composition containing the modified conjugated diene-based polymer have excellent effects. On the other hand, Si and N may be derived from compounds having a modified functional group such as a modifier, a modification initiator, or a modified monomer, which will be described later, introduced.

denaturant

According to one embodiment of the present invention, the modified conjugated diene-based polymer includes a functional group derived from a modifier, and the modifier is for modifying the terminal of the polymer. Specifically, it may be a silica affinity modifier or an alkoxysilane-based modifier. . The silica-affinity modifier may mean a modifier containing a silica-affinity functional group in a compound used as a modifier, and the silica-affinity functional group has excellent affinity with fillers, particularly silica-based fillers, It may mean a functional group capable of interaction between functional groups derived from the denaturant.

The modifier may be, for example, an alkoxysilane-based modifier, and as a specific example, may be an alkoxysilane-based compound containing at least one heteroatom such as a nitrogen atom, an oxygen atom, or a sulfur atom. When the alkoxysilane-based compound is used as a modifier, modification is performed in a form in which one end of the active polymer is bonded to a silyl group through a substitution reaction between an anion active site located at one end of the active polymer and an alkoxy group of the alkoxysilane-based compound. Accordingly, the affinity of the modified conjugated diene-based polymer with an inorganic filler or the like can be improved from the modifier-derived functional group present at one end of the polymer unit, thereby improving the viscoelasticity of the rubber composition containing the modified conjugated diene-based polymer. There is an effect of further improving the characteristics. In addition, when the alkoxysilane-based compound contains a nitrogen atom, in addition to the effect derived from the silyl group, an additional physical property synergistic effect derived from the nitrogen atom can be expected. In order to optimally implement these effects, it is preferable to apply an alkoxysilane-based compound containing an N-containing functional group.

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

[Formula 1]

In Formula 1, R ¹ may be a single bond or an alkylene group having 1 to 10 carbon atoms, R ² and R ³ may each independently be an alkyl group having 1 to 10 carbon atoms, and R ⁴ is hydrogen, or an alkylene group having 1 to 10 carbon atoms. It may be an alkyl group having 10 carbon atoms, a monosubstituted, disubstituted or trisubstituted alkylsilyl group having 1 to 10 carbon atoms, or a heterocyclic group having 2 to 10 carbon atoms, and R ²¹ is a single bond, an alkyl group having 1 to 10 carbon atoms It may be a rene group, or -[R ⁴² O] _j -, R ⁴² may be an alkylene group having 1 to 10 carbon atoms, a and m may each independently be an integer selected from 1 to 3, and n is 0, 1 , or an integer of 2, and j may be an integer selected from 1 to 30.

As a specific example, in Formula 1, R ¹ may be a single bond or an alkylene group having 1 to 5 carbon atoms, R ² and R ³ may each independently be hydrogen or an alkyl group having 1 to 5 carbon atoms, and R ⁴ is It 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, R ²¹ is a single bond, or an alkylene group having 1 to 5 carbon atoms, or -[R ⁴² O] _j -, R ⁴² may be an alkylene group having 1 to 5 carbon atoms, a may be an integer of 2 or 3, m may be an integer selected from 1 to 3, and n is It may be an integer of 0, 1, or 2, where m+n=3, and j may be an integer selected from 1 to 10.

In Formula 1, when R ⁴ is a heterocyclic group, the heterocyclic group may be substituted or unsubstituted with a 3-substituted alkoxy silyl group, and when the hetero cyclic group is substituted with a 3-substituted alkoxy silyl group, the 3-substituted alkoxy silyl group It may be substituted by being connected to the heterocyclic group by an alkylene group having 1 to 10 carbon atoms, and the trisubstituted alkoxy silyl group may mean an alkoxy silyl group substituted with an alkoxy group having 1 to 10 carbon atoms.

As a more specific example, the compound represented by Formula 1 is N,N-bis(3-(dimethoxy(methyl)silyl)propyl)-methyl-1-amine (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-bis (3- (triethoxysilyl) propyl) -methyl-1-amine (N, N-bis (3- (triethoxysilyl) propyl) -methyl-1-amine), N,N-diethyl-3-(trimethoxysilyl)propan-1-amine (N,N-diethyl-3-(trimethoxysilyl)propan-1-amine), N,N-diethyl-3-(trimethoxysilyl)propan-1-amine Ethoxysilyl) propan-1-amine (N, N-diethyl-3- (triethoxysilyl) propan-1-amine), tri (trimethoxysilyl) amine (tri (trimethoxysilyl) amine), tri (3- (tri Methoxysilyl) propyl) amine (tri- (3- (trimethoxysilyl) propyl) amine), N, N-bis (3- (diethoxy (methyl) silyl) propyl) -1,1,1-trimethylsilanamine ( N,N-bis(3-(diethoxy(methyl)silyl)propyl)-1,1,1-trimethlysilanamine), N,N-bis(3-(1H-imidazol-1-yl)propyl)-(trimethly) Ethoxysilyl)methan-1-amine (N,N-bis(3-(1H-imidazol-1-yl)propyl)-(triethoxysilyl)methan-1-amine), N-(3-(1H-1, 2,4-triazol-1-yl) propyl) -3- (trimethoxysilyl) -N- (3- (trimethoxysilyl) propyl) propan-1-amine (N- (3- (1H- 1,2,4-triazole-1-yl)propyl)-3-(trimethoxysilyl)-N-(trimethoxysil 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 (3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)-N-(3-(1 -(3-(trimethoxysilyl)propyl)-1H-1,2,4-triazol-3-yl)propyl)propan-1-amine), N,N-bis(2-(2-methoxyethoxy)ethyl ) -3- (triethoxysilyl) propan-1-amine (N, N-bis (2- (2-methoxyethoxy) ethyl) -3- (triethoxysilyl) propna-1-amine), N, N-bis ( 3-(triethoxysilyl)propyl)-2,5,8,11,14-pentaoxahexadecane-16-amine (N,N-bis(3-(triethoxysilyl)propyl)-2,5,8, 11,14-pentaoxahexadecan-16-amine), N-(2,5,8,11,14-pentaoxahexadecane-16-yl)-N-(3-(triethoxysilyl)propyl)-2, 5,8,11,14-pentaoxahexadecane-16-amine (N-(2,5,8,11,14-pentaoxahexadecan-16-yl)-N-(3-(triethoxysilyl)propyl)-2, 5,8,11,14-pentaoxahexadecan-16-amine) and N-(3,6,9,12-tetraoxahexadecyl)-N-(3-(triethoxysilyl)propyl)-3,6, 9,12-tetraoxahexadecane-1-amine (N-(3,6,9,12-tetraoxahexadecyl)-N-(3-(triethoxysilyl)propyl)-3,6,9,12-tetraoxahexadecan-1- amine) may be one selected from the group consisting of.

As another example, the denaturant may include a compound represented by Formula 2 below.

[Formula 2]

또는

일 수 있으며, 이 때, R¹³, R¹⁴, R¹⁵ 및 R¹⁶은 각각 독립적으로 수소, 또는 탄소수 1 내지 10의 알킬기일 수 있다.In Formula 2, R ⁵ , R ⁶ and R ⁹ may each independently be an alkylene group having 1 to 10 carbon atoms, and R ⁷ , R ⁸ , R ¹⁰ and R ¹¹ may each independently be an alkyl group having 1 to 10 carbon atoms. may be, R ¹² may be hydrogen or an alkyl group having 1 to 10 carbon atoms, b and c are each independently 0, 1, 2 or 3, may be b+c≥1, and A is

or

In this case, R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ may each independently be hydrogen or an alkyl group having 1 to 10 carbon atoms.

As a specific example, the compound represented by Formula 2 is N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl Propan-1-amine) (N-(3-(1H-imidazol-1-yl)propyl)-3-(triethoxysilyl)-N-(3-(triethoxysilyl)propyl)propan-1-amine)) and 3- (4,5-dihydro-1H-imidazol-1-yl)-N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine (3-(4,5-dihydro-1H It may be one selected from the group consisting of -imidazol-1-yl)-N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine).

As another example, the modifier may include a compound represented by Formula 3 below.

[Formula 3]

In Chemical Formula 3, A ¹ and A ² may each independently be a divalent hydrocarbon group having 1 to 20 carbon atoms with or without an oxygen atom, and R ¹⁷ to R ²⁰ may each independently be a monovalent hydrocarbon group having 1 to 20 carbon atoms. It may be a hydrocarbon group, L ¹ to L ⁴ are each independently a 1-, 2-, or 3-substituted alkylsilyl group 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 and L ³ and L ⁴ may be connected to each other to form a ring having 1 to 5 carbon atoms, and when L ¹ and L ² and L ³ and L ⁴ are connected to each other to form a ring, a ring is formed. may include 1 to 3 heteroatoms selected from the group consisting of N, O and S.

As a specific example, in Formula 3, A ¹ and A ² may each independently be an alkylene group having 1 to 10, R ¹⁷ to R ²⁰ may each independently be an alkyl group having 1 to 10 carbon atoms, and L ¹ to L ⁴ is each 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 and L ³ and L ⁴ are connected to each other to form a ring having 1 to 3 carbon atoms When L ¹ and L ² and L ³ and L ⁴ are connected to each other to form a ring, the formed ring contains 1 to 3 heteroatoms selected from the group consisting of N, O and S. dogs may be included.

As a more specific example, the compound represented by 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-dipropylpropane- 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-dipropylpropanol Ropan-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-am ine)), 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-tetramethoxy Cidisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine)(N,N'-((1,1 ,3,3-tetramethoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine)), N,N'-(( 1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silaneamine) (N,N'-((1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl) silanamine)), N,N'-((1,1,3,3-tetraprooxydisiloxane-1,3-diyl)bis(propane-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(propane-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(propane-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilane Amine)(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(propane-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), 1,3-bis(3-(1H-imidazol-1-yl)propyl)-1,1,3, 3-tetraethoxydisiloxane (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 (1,3-bis(3-(1H-imidazol-1-yl)propyl)-1,1,3 ,3-tetrapropoxydisiloxane) may be selected from the group consisting of.

As another example, the modifier may include a compound represented by Formula 4 below.

[Formula 4]

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

Specifically, in Formula 4, R ²² and R ²³ may each independently be an alkylene group having 1 to 10 carbon atoms or -R ²⁸ [OR ²⁹ ] _f -, and R ²⁴ to R ²⁷ each independently have 1 carbon atom to 10 alkyl groups, R ²⁸ and R ²⁹ may each independently be an alkylene group having 1 to 10 carbon atoms, and d and e are each independently 0 or an integer selected from 1 to 3, but d+e is It may be an integer greater than or equal to 1, and f may be an integer selected from 1 to 30.

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

[Formula 4a]

[Formula 4b]

[Formula 4c]

In Chemical Formulas 4a, 4b, and 4c, R ²² to R ²⁷ , d and e are as described above.

As a more specific example, the compound represented by Formula 4 is 1,4-bis (3- (3- (triethoxysilyl) propoxy) propyl) piperazine (1,4-bis (3- (3- (triethoxysilyl) )propoxy)propyl)piperazine, 1,4-bis(3-(triethoxysilyl)propyl)piperazine(1,4-bis(3-(triethoxysilyl)propyl)piperazine), 1,4-bis(3- (trimethoxysilyl) propyl) piperazine (1,4-bis (3- (trimethoxysilyl) propyl) piperazine), 1,4-bis (3- (dimethoxymethylsilyl) propyl) piperazine (1,4- bis(3-(dimethoxymethylsilyl)propyl)piperazine), 1-(3-(ethoxydimethylsilyl)propyl)-4-(3-(triethoxysilyl)propyl)piperazine(1-(3-(ethoxydimethylsilyl) propyl)-4-(3-(triethoxysilyl)propyl)piperazine), 1-(3-(ethoxydimethyl)propyl)-4-(3-(triethoxysilyl)methyl)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 -(triethoxysilyl)propyl)imidazolidine), 1,3-bis(3-(dimethoxyethylsilyl)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) hexa Hydropyrimidine (1,3-bis(3-(triethoxysilyl)prop yl)hexahydropyrimidine) and 1,3-bis(3-(tributoxysilyl)propyl)-1,2,3,4-tetrahydropyrimidine (1,3-bis(3-(tributoxysilyl)propyl)-1 ,2,3,4-tetrahydropyrimidine) may be one selected from the group consisting of.

As another example, the modifier may include a compound represented by Formula 5 below.

[Formula 5]

In Formula 5, R ³⁰ may be a monovalent hydrocarbon group having 1 to 30 carbon atoms, R ³¹ to R ³³ may each independently be an alkylene group having 1 to 10 carbon atoms, and R ³⁴ to R ³⁷ may each independently have a carbon number It may be an alkyl group of 1 to 10, g and h are each independently an integer selected from 0 or 1 to 3, but g + h may be an integer of 1 or more.

As another example, the modifier may include a compound represented by Formula 6 below.

[Formula 6]

In Formula 6, A ³ and A ⁴ may each independently be an alkylene group having 1 to 10, and R ³⁸ to R ⁴¹ may each independently be an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, , i may be an integer selected from 1 to 30.

In another example, the denaturant is 3,4-bis (2-methoxyethoxy) -N- (4- (triethoxysilyl) butyl) aniline (3,4-bis (2-methoxyethoxy) -N- ( 4-(trimethylsilyl)butyl)aniline), N,N-diethyl-3-(7-methyl-3,6,8,11-tetraoxa-7-silatridecan-7-yl)propan-1-amine (N,N-diethyl-3-(7-methyl-3,6,8,11-tetraoxa-7-silatridecan-7-yl)propan-1-amine), 2,4-bis(2-methoxy Toxy)-6-((trimethylsilyl)methyl)-1,3,5-triazine (2,4-bis(2-methoxyethoxy)-6-((trimethylsilyl)methyl)-1,3,5-triazine) and 3,14-dimethoxy-3,8,8,13-tetramethyl-2,14-dioxa-7,9-dithia-3,8,13-trisilapentadecane (3,14-dimtehosy- 3,8,8,13-tetramethyl-2,14-dioxa-7,9-dithia-3,8,13-trisilapentadecane).

As another example, the denaturant may include a compound represented by Formula 7 below.

[Formula 7]

In Formula 7, R ⁴³ , R ⁴⁵ and R ⁴⁶ may each independently be an alkyl group having 1 to 10 carbon atoms, R ⁴⁴ may be an alkylene group having 1 to 10 carbon atoms, and k may be an integer selected from 1 to 4. there is.

As a more specific example, the compound represented by Formula 7 is 8,8-dibutyl-3,13-dimethoxy-3,13-dimethyl-2,14-dioxa-7,9-dithia-3,13- Disila-8-stanpentadecane (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-stanpentadecane (8,8- dimethyl-3,13-dimethoxy-3,13-dimethyl-2,14-dioxa-7,9-dithia-3,13-disila-8-stannapentadecane), 8,8-dibutyl-3,3,13, 13-tetramethoxy-2,14-dioxa-7,9-dithia-3,13-disilla-8-stanpentadecane (8,8-dibutyl-3,3,13,13-tetramethoxy-2 ,14-dioxa-7,9-dithia-3,13-disila-8-stannapentadecane) and 8-butyl-3,3,13,13-tetramethoxy-8-((3-(trimethoxysilyl) Propyl) thio) -2,14-dioxa-7,9-dithia-3,13-disilla-8-stanpentadecane (8-butyl-3,3,13,13-tetramethoxy-8-(( 3-(trimethoxysilyl)propyl)thio)-2,14-dioxa-7,9-dithia-3,13-disila-8-stannapentadecane).

As another example, the modifier may include a compound represented by Formula 8 below.

[Formula 8]

In Formula 8, R _b2 to R _b4 are each independently an alkylene group having 1 to 10 carbon atoms, R _b5 to R _b8 are each independently an alkyl group having 1 to 10 carbon atoms, and R _b13 and R _b14 are each independently a carbon atom group. 1 to 10 alkylene group, R _b15 to R _b18 are each independently an alkyl group having 1 to 10 carbon atoms, and m _{1 ,} m ₂ , m ₃ and m ₄ are each independently an integer of 1 to 3.

As another example, the modifier may include a compound represented by Formula 9 below.

[Formula 9]

In Formula 9, R _e1 and R _e2 are each independently an alkylene group 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 However, at least one of R _e3 to R _e6 is -R _e7 SiR _e8 R _e9 R _e10 , wherein R _e7 is a single bond or an alkylene group having 1 to 10 carbon atoms, and R _e8 to R _e10 independently of each other have 1 carbon atom. to 10 alkyl groups or C1 to 10 alkoxy groups, but at least one of R _e8 to R _e10 is a C 1 to 10 alkoxy group.

As another example, the modifier may include a compound represented by Formula 10 below.

[Formula 10]

In Formula 10, X is O or S, R _f1 and R _f2 are each independently a single bond or an alkylene group having 1 to 10 carbon atoms,

R _f3 to R _f8 are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aralkyl group having 7 to 14 carbon atoms, , p is an integer of 0 or 1, and when p is 0, R _f1 is an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms.

As another example, the modifier may include a compound represented by Formula 11 below.

[Formula 11]

In Formula 11, R _g1 to R _g4 are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or -R _g5 SiOR _g6 , wherein R _g1 to R At least one of _g4 is -R _g5 SiOR _g6 , wherein R _g5 is a single bond or an alkylene group having 1 to 10 carbon atoms, R _g6 is an alkyl group having 1 to 10 carbon atoms, and Y is C or N, wherein Y is In case of N, R _g4 does not exist.

As another example, the modifier may include a compound represented by Formula 12 below.

[Formula 12]

In Formula 12, R _h1 and R _h2 are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, R _h3 is a single bond or an alkylene group having 1 to 10 carbon atoms, and A ₃ is -Si (R _h4 R _h5 R _h6 ) or -N[Si(R _h7 R _h8 R _h9 )] ₂ , wherein R _h4 to R _h9 are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms am.

As another example, the modifier may include a compound represented by Formula 13 below.

[Formula 13]

In Formula 13, R _g1 to R _g3 are each independently an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, R _g4 is an alkoxy group having 1 to 10 carbon atoms, and q is an integer of 2 to 100. .

Other characteristics

The conjugated diene-based polymer according to an embodiment of the present invention has a shrinkage factor (g') of 0.1 or more, preferably 0.1 or more and 1.0 or less, more specifically, obtained by gel permeation chromatography-light scattering method measurement with a viscosity detector. may be greater than or equal to 0.3 and less than or equal to 0.9.

Here, the shrinkage factor (g') obtained by the gel permeation chromatography-photolysis 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, It can be used as an indicator of the branching structure of a polymer, that is, as an indicator of the proportion occupied by branches. For example, as the shrinkage factor decreases, the branching number of the polymer tends to increase, and therefore, it is possible to compare polymers having equivalent absolute molecular weights. In this case, the more branching, the smaller the shrinkage factor, so it can be used as an index of branching degree.

In addition, the shrinkage factor is calculated based on the solution viscosity and light scattering method by measuring the chromatogram using a gel chromatography-light scattering measuring device equipped with a viscosity detector, specifically, a column using a polystyrene-based gel as a filler. After obtaining the absolute molecular weight and the intrinsic viscosity corresponding to each absolute molecular weight using a GPC-light scattering measuring device equipped with a light scattering detector and a viscosity detector connected to two heads, and calculating the intrinsic viscosity of the linear polymer corresponding to the absolute molecular weight, , The shrinkage factor was obtained as the ratio of intrinsic viscosities corresponding to each absolute molecular weight. Illustratively, the shrinkage factor is obtained by injecting a sample into a GPC-light scattering measuring device (Viscotek TDAmax, Malvern Co.) equipped with a light scattering detector and a viscosity detector, obtaining an absolute molecular weight from the light scattering detector, and measuring the absolute molecular weight from the light scattering detector and the viscosity detector. After obtaining the intrinsic viscosity [η] for the absolute molecular weight, the intrinsic viscosity [η] ₀ of the linear polymer with respect to the absolute molecular weight is calculated through Equation 1 below, and the ratio of the intrinsic viscosity corresponding to each absolute molecular weight ([η]/[ η] The average value of ₀ ) was expressed as a shrinkage factor. At this time, the eluent is a mixed solution of tetrahydrofuran and N,N,N',N'-tetramethylethylenediamine (20 mL of N,N,N',N'-tetramethylethylenediamine is mixed with 1L of tetrahydrofuran adjusted) was used, the column was used by PL Olexix (Agilent Co.), and the measurement was performed under conditions of an oven temperature of 40 ° C and a THF flow rate of 1.0 mL / min. Samples were prepared by dissolving 15 mg of polymer in 10 mL of THF. .

[Equation 1]

[η] ₀ =10 ^-3.883 M ^0.771

In Equation 1, M is an absolute molecular weight.

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

As another example, the modified conjugated diene-based polymer may have a Mooney stress relaxation rate measured at 100 °C of less than 0.7, and may be 0.7 to 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 having a high branching degree, and in the case of a linear polymer having a small branching degree. It may be preferably 0.7 to 2.5, more preferably 0.7 to 2.0.

Here, the Mooney stress relaxation rate indicates a change in stress in response to the same amount of strain, and may be measured using a Mooney viscometer. Specifically, the Mooney stress relaxation rate is 27 ± 3 g after leaving the polymer at room temperature (23 ± 5 ° C) for 30 minutes or more under conditions of 100 ° C and a rotor speed of 2 ± 0.02 rpm using a large rotor of Monsanto MV2000E. was collected and filled into the die cavity, the Mooney viscosity was measured while a torque was applied by operating a platen, and then the slope value of the Mooney viscosity change that appeared as the torque was released was measured and obtained.

On the other hand, the Mooney stress relaxation rate can be used as an indicator of the branching structure of the polymer. For example, when comparing polymers having equivalent Mooney viscosity, the Mooney stress relaxation rate decreases as the number of branches increases, so it can be used as an indicator of the degree of branching.

The modified conjugated diene-based polymer according to an embodiment of the present invention may include a denaturation initiator-derived functional group at the other end in addition to one end containing a denaturant-derived functional group, wherein the denaturation initiator is an N-functional group-containing compound. It may be a reaction product of and an organometallic compound.

Specifically, the N-functional group-containing compound may be an aromatic hydrocarbon compound including 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 unsubstituted or substituted with a substituent, The substituent is 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 having 1 to 10 carbon atoms. it can be

According to one embodiment of the present invention, the modified conjugated diene-based polymer has a weight average molecular weight (Mw) of 300,000 g/mol to 3,000,000 g/mol, 400,000 g as measured by gel permeation chromatography (GPC). / mol to 2,500,000 g / mol or 500,000 g / mol to 2,000,000 g / mol, and within this range, driving resistance and wet road resistance are more well-balanced and excellent.

In addition, the modified conjugated diene-based polymer according to an 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, thereby realizing a polymer having excellent tensile properties. In the case of manufacturing according to the above-described manufacturing method, this can be achieved as the effect of extending the chain of the polymer is also implemented together with the control of the microstructure.

The modified conjugated diene-based polymer according to an embodiment of the present invention has 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 be preferably 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, there is an excellent effect in driving resistance and wet road resistance.

In addition, the modified conjugated diene-based polymer has a unimodal molecular weight distribution curve by gel permeation chromatography (GPC), and may have a molecular weight distribution of 1.0 to 3.0, preferably 1.0 to 2.5, and more It may be preferably 1.0 to 2.0, 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 continuous polymerization described later.

In general, in continuous polymerization, the molecular weight distribution is wide in unimodal, so processability is excellent, but the tensile and viscoelastic properties are poor, and in batch polymerization, the molecular weight distribution is bimodal and narrow, so the tensile and viscoelastic properties are excellent. Although there is a problem of poor processability and low productivity, if the manufacturing method described below according to an embodiment of the present invention is applied, the molecular weight distribution can be selectively narrowed to the maximum even when manufactured in a continuous manner, and accordingly, processability and tensile properties and It may be easy to control the physical balance between viscoelastic properties.

In addition, the modified conjugated diene-based polymer according to an embodiment of the present invention should satisfy the Mooney viscosity of 40 to 140, preferably 45 to 120, measured under ASTM D1646 conditions. There may be various criteria for evaluating processability, but when the Mooney viscosity satisfies the above range, processability may be considerably excellent.

As described above, the modified conjugated diene-based polymer according to an embodiment of the present invention is a polymer having a difference in glass transition initiation temperature and termination temperature through control of the polymer microstructure such as styrene bond content and 1,2-vinyl bond content. By specifying the structure and optionally controlling 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, wear resistance and wettability are maintained while maintaining excellent tensile properties, fuel economy properties, and processability. A balanced improvement in road surface resistance can be expected as an effect.

Manufacturing method of modified conjugated diene-based polymer

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

The modified conjugated diene-based polymer production method is a continuous production method, comprising the steps of polymerizing a conjugated diene-based monomer and an aromatic vinyl-based monomer in the presence of a hydrocarbon solvent, a polymerization initiator, and a polar additive to prepare an active polymer (S1); And a step (S2) of reacting the active polymer prepared in step (S1) with a modifier, wherein step (S1) is continuously performed in two or more polymerization reactors, and the polymerization conversion rate of the first reactor is 70% to 85%, it is transferred to the second reactor, and a polar additive or a polar additive and a conjugated diene-based monomer are additionally added to the second reactor.

Hereinafter, since the description of the modified conjugated diene-based polymer and the modifier used in the reaction have been described above, the manufacturing method will be mainly described.

On the other hand, the aromatic vinyl-based monomer may be used for polymerization by appropriately adjusting the content of styrene bonds in the polymer to the above-mentioned range, for example, it may be used in excess of 30% by weight based on 100% by weight of the total monomers .

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

The polymerization initiator may be used in an amount of 0.1 equivalent to 3.0 equivalent based on 1.0 equivalent of the monomer, preferably 0.1 equivalent to 2.0 equivalent, and more preferably 0.5 equivalent to 1.5 equivalent. 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 the total monomers. Here, the total of 100 g of the monomers may be conjugated diene-based monomers or represent the total amount of conjugated diene-based monomers and aromatic vinyl-based monomers.

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

Specifically, the organometallic compound is methyllithium, ethyllithium, propyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octyllithium, phenyllithium, 1- Naphthyllithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naphthyl sodium, naphthyl It may be at least one selected from the group consisting of potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide and lithium isopropylamide.

As another example, the polymerization initiator may be a modified initiator, and the modified initiator may be a reaction product between an N-functional group-containing compound and the organometallic compound.

S1 phase

According to one embodiment of the present invention, step (S1) in the above production method is a step in which a polymerization reaction of a conjugated diene-based monomer and an aromatic vinyl-based monomer is performed, for example, by anionic polymerization. As a specific example, it may be a living anionic polymerization having an anionic active site at a polymerization end by a growth polymerization reaction by anions. In addition, the polymerization in step (S1) may be elevated temperature polymerization, isothermal polymerization or constant temperature polymerization (adiabatic polymerization), and the constant temperature polymerization includes polymerization with its own reaction heat without optionally applying heat after the polymerization initiator is added. It may mean a polymerization method, the elevated temperature polymerization may mean a polymerization method in which the temperature is increased by arbitrarily applying heat after the polymerization initiator is added, and the isothermal polymerization is a polymerization method in which heat is applied after the polymerization initiator is added. It may mean a polymerization method in which the temperature of the polymer is kept constant by increasing or taking away heat.

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

In addition, according to one embodiment of the present invention, the polymerization of step (S1) is carried out in two or more polymerization reactors, but the polymerization conversion rate in the first polymerization reactor of the polymerization reactors is 70% or more, 85% or less, 70% to 80% or more than 70% and up to 80%. That is, the polymerization in the step (S1) is carried out only until the polymerization conversion rate in the first polymerization reactor is 70% or more, 70% or more and 85% or less, 70% or more and 80% or less, or more than 70% and 80% or less. characterized by

After the polymerization reaction is initiated within this range, the full width at half maximum of the tan δ peak of the dynamic viscoelasticity analysis widens as the microstructure of the polymer is easily controlled during polymerization by suppressing side reactions occurring while the polymer is formed, and accordingly, the wear resistance is improved. It can lay the groundwork for improvement.

Polymerization in the first reactor may be carried out in a temperature range of, for example, 80 ° C or less, -20 ° C to 80 ° C, 0 ° C to 80 ° C, 0 ° C to 70 ° C or 10 ° C to 70 ° C, within this range By narrowly controlling the molecular weight distribution of the polymer, there is an excellent effect of improving physical properties.

According to one embodiment of the present invention, the step (S1) is carried out in two or more reactors, and after polymerization is performed in the first reactor to the polymerization conversion rate described above, it is transferred to the second reactor, and the polar additive is transferred to the second reactor. Alternatively, additional input of the conjugated diene-based monomer is performed.

At this time, the additionally added polar additive, polar additive, or conjugated diene-based monomer may be added simultaneously or sequentially, and may be added at one time in the polymerization conversion range or divided at several times in the range. It may be injected or continuously injected within the above range.

The addition of polar additives or polar additives and conjugated diene-based monomers can be a means for implementing the glass transition temperature characteristics of the polymer produced along with control of the polymerization conversion rate in the first reactor, which is achieved by adding polar additives. After a certain polymerization conversion rate, the polymerization reaction can be further energized to cause deformation of the microstructure.

In particular, in the case of homopolymerization of the conjugated diene-based monomer, the polar additive can control the ratio of 1,2-bond and 1,4-bond through reaction rate control, and the conjugated diene-based monomer and aromatic vinyl monomer In the case of copolymerization, there is an effect of inducing easy formation of a random copolymer by correcting the reaction rate difference between these monomers.

At this time, an appropriate amount of the additionally added polar additive may be used so that the full width at half maximum of the tan δ peak is widened. For example, the polar additive added may be used in an amount 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 100 g of the total monomers used in the polymerization initiation.

In addition, the conjugated diene-based monomer optionally added may 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 in the polymerization initiation. When the amount of additionally added polar additive or conjugated diene monomer is controlled as described above, it is easy to control the glass transition temperature of the polymer and finer adjustment is possible, and the full width at half maximum of the tan δ peak can be further widened in the dynamic viscoelasticity analysis. There is an advantage to being

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

The polymerization in the second reactor may be carried out in a temperature range of, for example, 80 ° C or less, -20 ° C to 80 ° C, 0 ° C to 80 ° C, 0 ° C to 70 ° C or 10 ° C to 70 ° C, within this range By narrowly controlling the molecular weight distribution of the polymer, there is an excellent effect of improving physical properties.

Meanwhile, 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, the polymerization temperature in the second reactor is set to the first reactor. It is preferable to control the polymerization temperature of the reactor below, and the polymerization temperature of the second reactor is preferably 60°C or higher.

The polar additive is, for example, tetrahydrofuran, 2,2-di (2-tetrahydrofuryl) propane, diethyl ether, cyclopentyl ether, dipropyl ether, ethylene methyl ether, ethylene glycol dimethyl ether, diethylene glycol, dimethyl Ether, tertiary-butoxyethoxyethane, bis(3-dimethylaminoethyl)ether, (dimethylaminoethyl)ethylether, trimethylamine, triethylamine, tripropylamine, N,N,N',N'- It may be at least one selected from the group consisting of tetramethylethylenediamine, sodium mentholate, and 2-ethyl tetrahydrofurfuryl ether, preferably 2,2-di(2- tetrahydrofuryl)propane, triethylamine, tetramethylethylenediamine, sodium mentholate or 2-ethyl tetrahydrofurfuryl ether.

On the other hand, the polymerization conversion rate can be determined, for example, by measuring the solid concentration of the polymer solution containing the polymer during polymerization, and as a specific example, in order to secure the polymer solution, a cylindrical container is installed at the outlet of each polymerization reactor to ensure a constant After filling a cylindrical container with an amount of polymer solution, separating the cylindrical container from the reactor and measuring the weight (A) of the cylinder filled with the polymer solution, the polymer solution filled in the cylindrical container was placed in an aluminum container, As an example, transfer to an aluminum dish, measure the weight (B) of the cylindrical container from which the polymer solution is removed, dry the aluminum container containing the polymer solution in an oven at 140 ° C. for 30 minutes, and measure the weight (C) of the dried polymer. After measurement, it may be calculated according to Equation 2 below.

[Equation 2]

In Equation 2, the total solids content is the total solids (monomers) content in the polymer solution separated in each reactor, and is the weight percentage of the solid content with respect to 100% of the polymer solution. Illustratively, when the total solid content is 20% by weight, when applied to Equation 2, it may be calculated by substituting 20/100, that is, 0.2.

Meanwhile, the polymerized material polymerized in the second reactor is sequentially transferred to the final polymerization reactor, and polymerization may proceed until the polymerization conversion rate is 95% or more. After polymerization in the second reactor, the third reactor, or The polymerization conversion rate for each reactor from the third reactor to the last polymerization reactor may be appropriately adjusted for each reactor to control the molecular weight distribution, and then a reaction terminator for inactivating the active site may be introduced, and modified conjugated diene In the case of preparing a based polymer, the active polymer may be transferred through a denaturation reaction process, and the reaction terminator may be applied without limitation as long as it is a material that can be generally used in this technical field.

In addition, the active polymer prepared by step (S1) may refer to a polymer in which a polymer anion and an organometallic cation of a polymerization initiator are bound.

S2 phase

Step (S2) is a denaturation step in which the active polymer prepared in step (S1) is reacted with a modifier, and an alkoxy group bound to silane of the modifier may react with an anionic active site of the active polymer. The modifier may be used in an amount of 0.01 mmol to 10 mmol based on 100 g of the total monomer. As another example, the modifier 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).

In addition, according to one embodiment of the present invention, the denaturant may be introduced into the denaturation reactor, and the step (S2) may be performed in the denaturation reactor. As another example, the denaturant may be introduced into a transfer unit for transporting the active polymer prepared in step (S1) to a denaturation reactor for performing step (S2), and the active polymer and the denaturant may be mixed in the transfer unit. In this case, the reaction may be a denaturation reaction in which the denaturant is simply bonded to the active polymer or a coupling reaction in which the active polymer is connected based on the denaturant.

On the other hand, the method for producing the modified conjugated diene-based polymer may further perform a step of reacting by adding a conjugated diene-based monomer to the active polymer prepared in the step (S1) before the modification reaction of the step (S2), , In this case, it may be more advantageous for the subsequent denaturation reaction. In this case, the conjugated diene-based monomer may be added in an amount of 1 to 100 moles based on 1 mole of the active polymer.

The method for producing the modified conjugated diene-based polymer according to an embodiment of the present invention is a method capable of satisfying the characteristics of the above-described modified conjugated diene-based polymer, and as described above, the effect to be achieved in the present invention is the above characteristics can be achieved, but in the case of polymerization conditions other than this, by controlling variously, the physical properties of the modified conjugated diene-based polymer according to the present invention can be implemented.

rubber composition

According to the present invention, a rubber composition comprising the modified conjugated diene-based polymer and a filler is provided.

The rubber composition may include the modified conjugated diene-based polymer in an amount of 10 wt% or more, 10 wt% to 100 wt%, or 20 wt% to 90 wt%, and within this range, tensile strength, abrasion resistance, etc. It has excellent mechanical properties and has an excellent balance between each physical property.

In addition, the rubber composition may further include other rubber components as needed in addition to the modified conjugated diene-based polymer, and in this case, the rubber component may be included in an amount of 90% by weight or less based on the total weight of the rubber composition. As a specific example, the other rubber component may be included in an amount of 1 to 900 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer.

The rubber component may be, for example, natural rubber or synthetic rubber, and specific examples include natural rubber (NR) including cis-1,4-polyisoprene; Modified natural rubbers such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber obtained by modifying or refining the general natural rubber; 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, halogenated butyl rubber, and the like, and any one or a mixture of two or more of these may be used.

The rubber composition may include, for example, 0.1 part by weight to 200 parts by weight, or 10 parts by weight to 120 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene-based polymer of the present invention. The filler may be, for example, a silica-based filler, and specific examples may include wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate, or colloidal silica. It may be a wet silica that has the most excellent wet grip effect. In addition, the rubber composition may further include a carbon-based filler, if necessary.

As another example, when silica is used as the filler, a silane coupling agent for improving reinforcing properties and low heat generation properties may be used together. As a specific example, the silane coupling agent is bis(3-triethoxysilylpropyl) tetrasulfide , Bis (3-triethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilyl propyl) tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide Feed, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-trimethoxysilylpropylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzolyltetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide, bis(3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethyl silane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide or dimethoxymethylsilylpropylbenzothiazolyltetrasulfide, and the like, and any one or a mixture of two or more of these may be used. Preferably, considering the effect of improving reinforcing property, it may be bis(3-triethoxysilylpropyl) polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide.

In addition, since the rubber composition according to an embodiment of the present invention uses a modified conjugated diene-based polymer in which a functional group having high affinity for silica is introduced into an active site as a rubber component, the amount of the silane coupling agent is usually may be reduced than the case, and accordingly, the silane coupling agent may be used in an amount of 1 part by weight to 20 parts by weight, or 5 parts by weight to 15 parts by weight based on 100 parts by weight of silica, and within this range, the effect as a coupling agent is There is an effect of preventing gelation of the rubber component while sufficiently exhibiting.

The rubber composition according to an embodiment of the present invention may be sulfur crosslinkable and may further include a vulcanizing agent. The vulcanizing agent may be a sulfur powder, and may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the rubber component. It has an excellent effect.

The rubber composition according to an embodiment of the present invention, in addition to the above components, various additives commonly used in the rubber industry, specifically, vulcanization accelerators, process oils, plasticizers, anti-aging agents, anti-scorch agents, zinc white, Stearic acid, a thermosetting resin, or a thermoplastic resin may be further included.

The vulcanization accelerator is, for example, a thiazole-based compound such as M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazylsulfenamide), or DPG A guanidine-based compound such as (diphenylguanidine) may be used, and may be included in an amount of 0.1 part by weight to 5 parts by weight based on 100 parts by weight of the rubber component.

The process oil acts as a softener in the rubber composition, and may be, for example, a paraffinic, naphthenic, or aromatic compound, considering tensile strength and wear resistance, aromatic process oil considering hysteresis loss and low-temperature characteristics. Naphthenic or paraffinic process oils may be used. The process oil may be included in an amount of, for example, 100 parts by weight or less based on 100 parts by weight of the rubber component, and within this range, there is an effect of preventing deterioration of tensile strength and low heat generation (low fuel consumption) of vulcanized rubber.

The antioxidant is, 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 hot condensate of diphenylamine and acetone, or the like, and may be used in an amount of 0.1 to 6 parts by weight based on 100 parts by weight of the rubber component.

The rubber composition according to an embodiment of the present invention can be obtained by kneading using a kneader such as a Banbury mixer, a roll, or an internal mixer according to the above compounding prescription, and has low heat generation and wear resistance by a vulcanization process after molding. This excellent rubber composition can be obtained.

Accordingly, the rubber composition may be used for each member of a tire such as a tire tread, under tread, side wall, carcass coated rubber, belt coated rubber, bead filler, cheifer, or bead coated rubber, anti-vibration rubber, belt conveyor, hose, etc. It can be useful in the manufacture of various industrial rubber products.

In addition, the present invention provides a tire manufactured using the rubber composition.

The tire may include a tire or a tire tread.

Example

Hereinafter, examples will be described in detail to explain the present invention in detail. However, the embodiments according to the present invention can be modified in many different forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

Example 1

In the first reactor of the three continuous stirred liquid phase reactors (CSTR), a monomer solution dissolved in 5 kg/hr of n-hexane and 60% by weight of 1,3-butadiene in n-hexane was added to 0.74 kg/hr of n-hexane. 0.42 kg/hr of a monomer solution in which 60% by weight of styrene was dissolved, 6.07 g/hr of an initiator solution in which 6.6% by weight of n-butyllithium was dissolved in n-hexane, ditetrahydrofuryl in n-hexane as a polar additive A polar additive solution in which 2% by weight of propane was dissolved was continuously introduced at a flow rate of 4.6 g/hr. At this time, the temperature inside the reactor was maintained at 70° 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.

Subsequently, the temperature of the second reactor was maintained at 70° C., and a solution in which 60% by weight of 1,3-butadiene was dissolved in n-hexane was added to the second reactor at 0.13 kg/hr as a polar additive in n-hexane. The polar additive solution in which 10% by weight of tetrahydrofuryl propane was dissolved was continuously added at 7.7 g/hr to participate in the reaction, and when the polymerization conversion rate reached 95% or more, the third The polymer was transferred to a reactor, and a solution in which 5% by weight of N,N-dimethyl-3-(trimethoxysilyl)propan-1-amine was dissolved in n-hexane as a denaturant was added at 11.6 g/hr for 30 minutes. while the reaction proceeded.

Thereafter, a solution of IR1520 (BASF Co.) dissolved at 30% by weight as an antioxidant was injected at a rate of 100 g/h and stirred. The polymer obtained as a result was put in hot water heated with steam, stirred to remove the solvent, and then roll dried to remove the residual amount of solvent and water to prepare a modified conjugated diene-based copolymer.

Example 2

In Example 1, when the polymerization conversion rate in the first reactor was 78%, the polymer was transferred from the first reactor to the second reactor, and the temperature of the second reactor was maintained at 65 ° C. In the same manner, a modified conjugated diene-based polymer was prepared.

Example 3

A modified conjugated diene-based polymer was prepared in the same manner as in Example 1, except that the transfer to the second reactor was carried out when the polymerization conversion rate in the first reactor was 70%.

Example 4

A modified conjugated diene-based polymer was prepared in the same manner as in Example 1, except that the transfer to the second reactor was carried out when the polymerization conversion rate in the first reactor was 80%.

Example 5

In Example 1, when the polymerization conversion rate in the first reactor was 76%, the polymer was transferred from the first reactor to the second reactor, and the 1,3-butadiene solution additionally introduced into the second reactor was not introduced into the second reactor. A modified conjugated diene-based polymer was prepared in the same manner as in Example 1 except that it was not.

Example 6

In Example 1, when the polymerization conversion rate in the first reactor was 75%, the polymer was transferred from the first reactor to the second reactor, and 10% by weight of ditetrahydrofuryl propane was added to n-hexane added to the second reactor. A modified conjugated diene-based polymer was prepared in the same manner as in Example 1, except that the dissolved polar additive solution was continuously added at 15.4 g/hr.

Example 7

In Example 1, when the polymerization conversion rate in the first reactor was 75%, the polymer was transferred from the first reactor to the second reactor, and 10% by weight of ditetrahydrofuryl propane was added to n-hexane added to the second reactor. A modified conjugated diene-based polymer was prepared in the same manner as in Example 1, except that the dissolved polar additive solution was continuously added at 2.3 g/hr.

Example 8

In Example 1, the polar additive solution in which 2% by weight of ditetrahydrofurylpropane was dissolved in n-hexane was continuously introduced into the first reactor at a rate of 2.7 g/hr, and the polymerization conversion rate in the first reactor was 77%. When the polymer is transferred from the first reactor to the second reactor, 1,1,1-trimethyl-N-(3-(triethoxysilyl)propyl)-N-(trimethyl A solution in which 1,1,1-trimethyl-N-(3-(triethoxysilyl)propyl)-N-(trimethylsilyl)silanamine) was dissolved at 5% by weight was added at 16.6 g/hr and stirred for 30 minutes. A modified conjugated diene-based polymer was prepared in the same manner as in Example 1, except that the reaction was performed.

Example 9

In Example 1, the polar additive solution in which 2% by weight of ditetrahydrofurylpropane was dissolved in n-hexane was continuously added to the first reactor at 6.6 g/hr, and 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)) was added at 19.3 g/hr to a solution in which 5% by weight was dissolved and the reaction proceeded for 30 minutes. Then, a modified conjugated diene-based polymer was prepared in the same manner as in Example 1.

Comparative Example 1

In Example 1, in the first reactor, 0.87 kg/hr of a monomer solution in which 60% by weight of 1,3-butadiene was dissolved in n-hexane and 2% by weight of ditetrahydrofurylpropane in n-hexane were dissolved as polar additives. The solution was continuously introduced at 13.5 g/hr, and when the polymerization conversion rate in the first reactor was 75%, the polymer was transferred to the second reactor, except that 1,3-butadiene and polar additives were not added to the second reactor. Then, a modified conjugated diene-based polymer was prepared in the same manner as in Example 1.

Comparative Example 2

In Example 1, the monomer solution dissolved in n-hexane at 60% by weight of 1,3-butadiene was continuously introduced into the first reactor at a rate of 0.87 kg/hr, and when the polymerization conversion rate of the first reactor was 61%, the polymer was produced. Transfer to the second reactor, and a modified conjugated diene-based polymer was prepared in the same manner as in Example 1, except that 1,3-butadiene was not added to the second reactor.

Comparative Example 3

A modified conjugated diene-based polymer was prepared in the same manner as in Example 1, except that the polymer was transferred to the second reactor when the polymerization conversion rate in the first reactor was 66%.

Comparative Example 4

In Comparative Example 1, a solution in which 4.5% by weight of silicon tetrachloride was dissolved in n-hexane as a coupling agent instead of a denaturant was continuously supplied at 3.7 g/hr to carry out the coupling reaction. An unmodified conjugated diene-based polymer was prepared in the same manner as in Example 1.

Comparative Example 5

In Example 1, a monomer solution in which 60% by weight of styrene was dissolved in n-hexane was added to the first reactor at 0.36 kg/hr, and the polymer was transferred to the second reactor when the polymerization conversion rate of the first reactor was 65% Example 1, except that a monomer solution in which 60% by weight of styrene was dissolved in n-hexane was continuously introduced into the second reactor at a rate of 0.06 kg/hr and the temperature of the second reactor was maintained at 80° C. A modified conjugated diene-based polymer was prepared in the same manner as above.

Experimental Example 1. Evaluation of polymer properties

Styrene bond content and 1,2-vinyl content in the polymer, weight average molecular weight (Mw, X10 ³ g / mol), and number average molecular weight for each modified or unmodified conjugated diene-based polymer prepared in the above Examples and Comparative Examples (Mn, X10 ³ g/mol), molecular weight distribution (PDI, MWD), glass transition temperature, glass transition onset temperature, glass transition end temperature, and full width at half maximum of the tan δ peak were respectively measured. The results are shown in Table 1 below.

1) Styrene bond content and 1,2-vinyl content (% by weight)

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

In the NMR measurement, 1,1,2,2-tetrachloroethane was used as the solvent, the solvent peak was calculated as 6.00 ppm, 7.2~6.9 ppm was random styrene, 6.9~6.2 ppm was block styrene, and 5.8~5.1 ppm was 1,4-vinyl and 1,2-vinyl, 5.1 to 4.5 ppm were calculated as styrene bonds and 1,2-vinyl content as the peak of 1,2-vinyl.

2) Weight average molecular weight (Mw, X10 ³ g/mol), number average molecular weight (Mn, X10 ³ g/mol), and molecular weight distribution (PDI, MWD)

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

- Column: Two PLgel Olexis (Polymer Laboratories) columns and one PLgel mixed-C (Polymer Laboratories) column are used in combination

- Solvent: 2% by weight of amine compound mixed with tetrahydrofuran

- Flow rate: 1 mL/min

- Sample concentration: 1~2 mg/mL (diluted in THF)

- Injection amount: 100 uL

- Column temperature: 40 ℃

-Detector: Refractive index

- Standard: Polystyrene (correction with cubic function)

3) Glass transition temperature (Tg, ℃), glass transition onset temperature (T _g-on, ℃) and glass transition termination temperature (T _g-off, ℃)

Differential Scanning Calorimetry (DSCQ100, TA Company) in accordance with ISO 22768: 2006, differential scanning calorimetry curve (DSC curve) while raising the temperature from -100 ° C to 10 ° C / min under the circulation of 50 ml / min nitrogen was recorded, and the temperature at which the glass transition began in this curve was set as the glass transition onset temperature, the temperature at which the glass transition ended was set as the glass transition end temperature, and the peak top (Inflection point) of the DSC differential curve was set as the glass transition temperature. did

4) Full Width Half Maximum (FWHM) of the tan δ peak

For the polymers prepared in the above Examples and Comparative Examples, for dynamic viscoelasticity analysis by a rheometric system (Advanced Rheometric Expansion System, ARES), a torsion mode using a dynamic mechanical analyzer (TA, ARES-G2) ( Torsional mode) at a frequency of 10 Hz, a strain of 0.5%, and a heating rate of 5°C/min, tan δ was measured according to temperature in the temperature range of -100°C to 100°C, and a tan δ graph as shown in FIG. 1 was obtained. was obtained, and the full width at half maximum of the peak was determined from this graph.

Referring to Table 1, in the case of the polymer prepared by the manufacturing method according to the present invention, the glass transition start temperature (onset, T _g-on ) and glass transition end temperature (offset, T _g-off ) at which glass transition occurs The difference is 10 ° C or more and less than 30 ° C, the styrene bond content exceeds 30% by weight, and the full width at half maximum value of the tan δ peak is all 20 ° C or more, but all comparative examples that are not prepared by the manufacturing method according to the present invention are glass The difference between the transition onset temperature (onset, T _g-on ) and the glass transition end temperature (offset, T _g-off ) is less than 10 ℃ or more than 30 ℃, and the full width at half maximum of the tan δ peak is less than 20 ℃ It can be confirmed that it has

Through this, in the case of the manufacturing method of the present invention, precise control of the polymer microstructure is possible, and the difference between the glass transition start temperature (onset, T _g-on ) and the glass transition end temperature (offset, T _g-off ) It can be seen that can be adjusted.

Experimental Example 2. Evaluation of characteristics of rubber molded articles

In order to compare and analyze the physical properties of the rubber composition containing each of the modified conjugated diene-based polymers prepared in the above Examples and Comparative Examples and molded articles prepared therefrom, viscoelastic properties and abrasion resistance were measured, respectively, and the results are shown in Table 3 below. was

1) Preparation of rubber specimen

Each of the modified or unmodified conjugated diene-based polymers of Examples and Comparative Examples was mixed under the compounding conditions shown in Table 2 below as raw material rubber. The content of the raw materials in Table 2 is each part by weight based on 100 parts by weight of raw rubber.

Specifically, the rubber specimen is kneaded through first-stage kneading and second-stage kneading. In the first stage kneading, raw material rubber, silica (filler), organosilane coupling agent (X50S, Evonik), process oil (TDAE oil), zincating agent (ZnO), stearic acid are mixed using a Banbari mixer equipped with a temperature controller , antioxidant (TMQ(RD) (2,2,4-trimethyl-1,2-dihydroquinoline polymer), antioxidant (6PPD ((dimethylbutyl)-N-phenyl-phenylenediamine) and wax (Microcrystaline Wax) ) Was kneaded. At this time, the initial temperature of the kneader was controlled to 70 ° C, and after mixing was completed, the first mixture was obtained at a discharge temperature of 145 ° C. In the second stage kneading, after cooling the first mixture to room temperature, The primary compound, sulfur, a rubber accelerator (DPG (diphenylguanidine)) and a vulcanization accelerator (CZ (N-cyclohexyl-2-benzothiazylsulfenamide)) were added to a kneading machine, and mixed at a temperature of 100 ° C or less to form a mixture of 2 After that, a rubber specimen was prepared through a curing process at 160° C. for 20 minutes.

2) Viscoelastic properties

For the rubber specimens manufactured including the polymers prepared in the above Examples and Comparative Examples, a frequency of 10 Hz and a strain of 0.5 in a torsional mode using a dynamic mechanical analyzer (TA, ARES-G2). %, at a heating rate of 5 °C/min, tan δ was measured according to temperature in the temperature range of -100 °C to 100 °C, and a tan δ graph was obtained. In the obtained tan δ graph, the tan δ value at 0°C and the tan δ value at 60°C were confirmed. At this time, the higher the low-temperature 0 ° C tan δ value, the better the wet road resistance, and the lower the high-temperature 60 ° C tan δ value, the lower the hysteresis loss and the better the driving resistance (fuel economy). Since the result value was expressed as an index based on the measurement result value of Comparative Example 4, the higher the number, the better.

3) Abrasion resistance (DIN abrasion test)

For each rubber specimen, a DIN abrasion test was performed according to ASTM D5963, and the DIN loss index (loss volume index) was expressed as ARIA (Abration resistance index, Method A). The higher the value, the better. .

Referring to Table 3, the difference between the glass transition onset temperature (onset, T _g-on ) and the glass transition end temperature (offset, T _g-off ) according to the present invention is 10 ° C or more and less than 30 ° C, and the styrene bond content In the case of the rubber specimen containing the polymer of more than 30% by weight, compared to Comparative Example 4, it can be seen that wet road resistance and driving resistance are improved in a balanced manner, and at the same time, abrasion resistance is remarkably improved.

On the other hand, in the case of rubber specimens containing the polymers of Comparative Examples 1 to 3 in which the difference between the glass transition onset temperature (onset, T _g-on ) and the glass transition end temperature (offset, T _g-off ) is less than 10 ° C, comparison is made. Compared to Example 4, wet road resistance, driving resistance and wear resistance were not improved in a balanced manner, and it can be seen that wet road resistance and abrasion resistance are significantly reduced compared to Example 4.

In addition, in the case of Comparative Example 5 in which the difference between the glass transition start temperature (onset, T _g-on ) and the glass transition end temperature (offset, T _g-off ) is 30 ° C or more, wet road resistance and wear resistance are improved compared to Comparative Example 4 It showed a tendency, but the driving resistance rapidly decreased, and as a result, it was confirmed that not only did it fail to exhibit excellent balanced characteristics of wet road resistance, driving resistance and wear resistance, but also poor driving resistance and abrasion resistance compared to the examples.

From the above results, the modified conjugated diene-based polymer of the present invention has a difference between the glass transition onset temperature (onset, T _g-on ) and the glass transition end temperature (offset, T _g-off ) within a specific range through microstructure control. It was confirmed that, despite having a low glass transition temperature, by adjusting the styrene bond content to more than 30% by weight, the wet road resistance and running resistance were well-balanced and the abrasion resistance was improved.

Claims (13)

Repeating units derived from conjugated diene-based monomers; Repeating units derived from aromatic vinyl monomers; And a denaturant-derived functional group,
When measured by Differential Scanning Calorimetry (DSC), the difference between the glass transition onset temperature (onset, T _g-on ) and glass transition termination temperature (offset, T _g-off ) at which glass transition occurs is 10 ℃ or more and less than 30 ℃,
A modified conjugated diene-based polymer having a styrene bond content of more than 30% by weight.
According to claim 1,
The glass transition onset temperature (T _g-on ) and glass transition end temperature (T _g-off ) The difference between 10 ℃ to 25 ℃ modified conjugated diene-based polymer.
According to claim 1,
A modified conjugated diene-based polymer having a glass transition temperature (Tg) of -100 ° C or more and 20 ° C or less.
According to claim 1,
In the tan δ change graph with temperature derived from the dynamic viscoelasticity analysis by the Advanced Rheometric Expansion System (ARES), the full width at half maximum of the tan δ peak appearing in the temperature range of -100 ° C to 100 ° C at half maximum, FWHM) value is 20 ℃ or more,
The rheometer system is a modified conjugated diene-based polymer that is measured under conditions of a frequency of 10 Hz, a strain of 0.5%, and a heating rate of 5 ° C. / min in torsion mode using a dynamic mechanical analyzer.
According to claim 4,
A modified conjugated diene-based polymer in which the full width at half maximum value of the tan δ peak is 30 ° C. or more and 80 ° C. or less.
According to claim 4,
The tan δ peak is a conjugated diene-based polymer that appears in the temperature range of -80 ℃ to 20 ℃.
According to claim 1,
A modified conjugated diene-based polymer having a unimodal molecular weight distribution curve by gel permeation chromatography and a molecular weight distribution of 1.0 to 3.0.
According to claim 1,
A modified conjugated diene-based polymer having a Si and N content of 50 ppm or more, respectively, based on the total weight of the polymer.
According to claim 1,
The styrene bond content is more than 30% by weight and less than 45% by weight of the modified conjugated diene-based polymer.
According to claim 1,
The modifier is a modified conjugated diene-based polymer that is an alkoxysilane-based compound containing an N-functional group.
A rubber composition comprising the modified conjugated diene-based polymer according to claim 1 and a filler.
According to claim 11,
A rubber composition comprising 0.1 part by weight to 200 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene-based polymer.
According to claim 11,
The filler is a rubber composition that is a silica-based filler or a carbon black-based filler.

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