KR20220088102A - Modified conjugated diene-based polymer, preparing method thereof and rubber composition comprising the same - Google Patents

Abstract

The present invention relates to a modified conjugated diene-based polymer having excellent processability and excellent tensile strength and viscoelastic properties and a rubber composition comprising the same, comprising: a hydrocarbon chain including a repeating unit derived from a conjugated diene-based monomer; and a macromonomer and an alkoxysilane-based modifier-derived unit coupled to any one terminal of the hydrocarbon chain and including a repeating unit derived from an N-functional group-containing monomer, wherein the N content according to NSX analysis is 100 ppm or more functional moiety Including;, wherein the functional moiety provides a modified conjugated diene-based polymer in which the ratio of the number average molecular weight of the functional moiety to the number average molecular weight of the entire polymer is 0.15 or less.

Description

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

The present invention relates to a modified conjugated diene-based polymer having excellent processability and excellent tensile strength and viscoelastic properties and a rubber composition comprising the same.

In response to the recent demand for fuel economy reduction in automobiles, a conjugated diene-based polymer having low rolling resistance, excellent abrasion resistance and tensile properties, and adjustment stability typified by wet road resistance is required as a rubber material for tires.

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

As a rubber material with a small hysteresis loss, natural rubber, polyisoprene rubber, polybutadiene rubber, etc. are known, but these have a problem of small wet road resistance. Accordingly, 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) have been manufactured by emulsion polymerization or solution polymerization and are used as rubber for tires. . Among them, the greatest advantage of solution polymerization compared to emulsion polymerization is that the content of vinyl structure and styrene content defining rubber properties can be arbitrarily adjusted, and molecular weight and physical properties can be adjusted by coupling or modification. that it can be adjusted. Therefore, it is easy to change the structure of the finally manufactured SBR or BR, and it is possible to reduce the movement of the chain ends by bonding or modifying the chain ends, and to increase the binding force with fillers such as silica or carbon black. It is widely used as a rubber material for

When this solution-polymerized SBR is used as a rubber material for a tire, by increasing the vinyl content in the SBR, the glass transition temperature of the rubber can be increased to adjust the required physical properties of the tire such as running resistance and braking force, as well as lower the glass transition temperature. By properly adjusting it, fuel consumption can be reduced. The solution polymerization SBR is prepared by using an anionic polymerization initiator, and a technique for introducing a functional group at the end by binding or modifying the chain end of the formed polymer using various modifiers is used. For example, U.S. Patent No. 4,397,994 discloses a technique in which an active anion at the chain end of a polymer obtained by polymerizing styrene-butadiene in a non-polar solvent using alkyllithium, a monofunctional initiator, is combined using a binder such as a tin compound. did

On the other hand, as a modifier for introducing a functional group to the chain end of the polymer, a technique of applying an aminoalkoxysilane modifier containing an alkoxysilane group and an amine group in a molecule at the same time in order to maximize the dispersibility and reactivity of the filler is widely known. However, as the number of amine groups in the modifier increases, the solubility in the hydrocarbon solvent used for preparing the polymer decreases, and thus there is a problem in that it is difficult to easily perform the modification reaction.

US 4397994 A

The present invention has been devised to solve the problems of the prior art, wherein the functional moiety is intensively distributed at any one end of the modified conjugated diene-based polymer, and the number average molecular weight ratio is controlled so that the affinity with the filler is excellent. An object of the present invention is to provide a modified conjugated diene-based polymer having excellent processability.

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

According to one embodiment of the present invention for solving the above problems, the present invention is a hydrocarbon chain comprising a repeating unit derived from a conjugated diene-based monomer; and a macromonomer and an alkoxysilane-based modifier-derived unit bonded to any one terminal of the hydrocarbon chain and including a repeating unit derived from an N-functional group-containing monomer, and a functional moiety having an N content of 100 ppm or more according to NSX analysis It provides a modified conjugated diene-based polymer that includes; and the ratio of the number average molecular weight of the functional moiety to the number average molecular weight of the entire polymer is 0.15 or less.

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 functional groups interacting with the filler are distributed only at one end, and the number average molecular weight ratio of the functional moiety to the number average molecular weight of the entire polymer is 0.15 or less. This may be excellent, and mechanical properties may be excellent.

together. The rubber composition according to the present invention has excellent processability as well as tensile properties and viscoelastic properties by including the modified conjugated diene-based polymer.

Hereinafter, the present invention will be described in more detail to help the 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 their ordinary or dictionary meanings, and the inventor must properly understand the concept of the term in order to best describe his invention. Based on the principle that can be defined, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.

Definition of Terms

As used herein, the term 'macromonomer' is a unit in which two or more polymerization-reactive monomer units are repeated, and refers to a unit capable of bonding to another polymer chain or a reactive compound through a terminal group.

As used herein, the term 'polymer' refers to a polymer compound prepared by polymerizing monomers, whether of the same or different type. The generic term polymer thus encompasses the terms homopolymer and copolymer, which are commonly used to refer to polymers prepared from only one monomer.

As used herein, the term 'hydrocarbon chain' may mean a molecular chain of a main backbone constituting a polymer, and may mean a chain mainly including a conjugated diene-based monomer or a repeating unit of a conjugated diene-based monomer and an aromatic vinyl-based monomer. .

As used herein, the term 'moiety' refers to a part in a macromolecule or polymer, and is a unit in which derived units or derived repeating units are aggregated, and is a part constituting a part of a macromolecule or polymer.

As used herein, the term 'functionality' includes a functional group and thus may mean having a characteristic capable of reacting with other functional groups or active sites, and in addition to a carbon-to-carbon bond or a carbon-to-hydrogen bond, N, O, S Alternatively, it may mean a property having a functional group including Si.

As used herein, the term 'vinyl content' refers to the mass (or weight) of butadiene contained in positions 1 and 2 in the polymer chain, based on the portion (total amount of polymerized butadiene) of the conjugated diene monomer (butadiene, etc.) in the polymer. ) refers to the percentage.

As used herein, the term 'monovalent hydrocarbon group' refers to a monovalent atomic group in which carbon and hydrogen are bonded, such as a monovalent alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkyl group containing one or more unsaturated bonds, and an aryl group. and the minimum number of carbon atoms of the substituent represented by the monovalent hydrocarbon may be determined according to the type of each substituent.

As used herein, the term 'divalent hydrocarbon group' refers to a divalent alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, a cycloalkylene group including one or more unsaturated bonds, and an arylene group, such as carbon and hydrogen bonded 2 It may mean a valent atomic group, and the minimum number of carbon atoms of the substituent represented by the divalent hydrocarbon may be determined according to the type of each substituent.

As used herein, the term 'alkyl group' may refer to a monovalent aliphatic saturated hydrocarbon, and linear alkyl groups such as methyl, ethyl, propyl and butyl and isopropyl, sec-butyl, ter It may mean including all branched alkyl groups such as tert-butyl and neopentyl.

As used herein, the term 'alkenyl group' may refer to a monovalent aliphatic unsaturated hydrocarbon including one or two or more double bonds.

As used herein, the term 'alkynyl group' may mean a monovalent aliphatic unsaturated hydrocarbon including one or two or more triple bonds.

As used herein, the term 'alkylene group' may refer to a divalent aliphatic saturated hydrocarbon such as methylene, ethylene, propylene, and butylene.

In the present specification, the term 'aryl group' may mean an aromatic hydrocarbon, and also a monocyclic aromatic hydrocarbon in which one ring is formed, or a polycyclic aromatic hydrocarbon in which two or more rings are bonded (polycyclic aromatic hydrocarbon) may be meant to include all of the

As used herein, the term 'heterocyclic group' refers to a carbon atom in a cycloalkyl group or an aryl group in which one or more hetero atoms are substituted, for example, it may mean including both a heterocycloalkyl group or a heteroaryl group.

As used herein, 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, within the functional group, atomic group or compound One or two or more plural substituents may be present depending on the number of hydrogens present, and when plural substituents are present, each substituent may be the same or different from each other.

As used herein, the term 'single bond' may refer to a single covalent bond itself that does not include a separate atom or molecular group.

As used herein, the terms 'derived unit', 'derived repeating unit' and 'derived functional group' may refer to a component, structure, or material itself derived from a certain material.

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. may include In contrast, the term 'consisting essentially of' excludes from the scope of any subsequent description any other component, step or procedure, except as not essential to operability. The term 'consisting of' excludes any component, step or procedure not specifically described or listed.

Measurement method and conditions

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

In the present specification, 'weight average molecular weight (Mw)', 'number average molecular weight (Mn)' and 'molecular weight distribution (MWD)' are measured through gel permeation chromatohraph (GPC) analysis, and measured by checking the molecular weight distribution curve. will be. Molecular weight distribution (PDI, MWD, Mw/Mn) is calculated from each of the measured molecular weights. Specifically, the GPC uses a combination of two PLgel Olexis (Polymer Laboratories) columns and one PLgel mixed-C (Polymer Laboratories) column, and when calculating molecular weight, the GPC standard material (Standard material) is PS (polystyrene) GPC measurement solvent is prepared by mixing tetrahydrofuran with 2 wt% of an amine compound, sample concentration of 1-2 mg/mL (diluted in THF), flow rate of 1 mL/min, injection volume 100 uL, column temperature The condition of 40℃ is applied, and the detector uses the Refractive index.

In the present specification, 'N atom content' may be, for example, measured through an NSX analysis method, and the NSX analysis method is measured using a trace nitrogen quantitative analyzer (NSX-2100H). Exemplarily, when using the trace nitrogen quantitative analyzer, turn on the trace nitrogen quantitative analyzer (Auto sampler, Horizontal furnace, PMT & Nitrogen detector), Ar at 250 ml/min, O ₂ at 350 ml/min, ozonizer 300 ml/ Set the carrier gas flow rate to min, set the heater to 800°C, and wait for about 3 hours to stabilize the analyzer. After the analyzer is stabilized, a calibration curve in the range of 5 ppm, 10 ppm, 50 ppm, 100 ppm and 500 ppm was prepared using Nitrogen standard (AccuStandard S-22750-01-5 ml), and the area corresponding to each concentration was obtained. Then, draw a straight line using the ratio of concentration to area. Thereafter, a ceramic boat containing 20 mg of the sample is placed on the auto sampler of the analyzer to obtain an area, and the N content is calculated using the area of the sample obtained and the calibration curve. At this time, the sample is a modified conjugated diene-based polymer in which the solvent is removed by putting it in hot water heated with steam and stirring, and the residual monomer, residual modifier, and oil are removed.

In the present specification, 'Si atom content' was measured using an inductively coupled plasma emission analyzer (ICP-OES; Optima 7300DV) as an ICP analysis method. Specifically, about 0.7 g of the sample is placed in a platinum crucible (Pt crucible), and about 1 mL of concentrated sulfuric acid (98 wt%, Electronic grade) is added, heated at 300° C. for 3 hours, and the sample is heated in an electric furnace (Thermo Scientific, Lindberg Blue M), after conducting conversation with the program of steps 1 to 3 below,

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 wt%) and 20 μl of concentrated hydrofluoric acid (50 wt%) were added to the residue, sealed in a platinum crucible and shaken for at least 30 minutes, and then 1 mL of boric acid was added to the sample. and stored at 0° C. for 2 hours or more, diluted in 30 mL of ultrapure water, and measured by incineration.

Modified conjugated diene-based polymer

The present invention provides a modified conjugated diene-based polymer capable of providing a rubber composition having excellent affinity with a filler and, as a result, excellent processability, tensile properties and viscoelastic properties.

A modified conjugated diene-based polymer according to an embodiment of the present invention includes a hydrocarbon chain including a repeating unit derived from a conjugated diene-based monomer; and a macromonomer and an alkoxysilane-based modifier-derived unit bonded to any one terminal of the hydrocarbon chain and including a repeating unit derived from an N-functional group-containing monomer, and a functional moiety having an N content of 100 ppm or more according to NSX analysis and; and the ratio of the number average molecular weight of the functional moiety to the number average molecular weight of the entire polymer is 0.15 or less.

The modified conjugated diene-based polymer according to an embodiment of the present invention comprises the steps of preparing an active hydrocarbon chain through a polymerization reaction, preparing a macromonomer by oligomerization of an N-functional group-containing monomer, and modifying the active macromonomer and the modifier. It may be prepared by the method described below, which includes preparing a functional moiety and reacting the active hydrocarbon chain with the functional moiety.

Ratio of the number average molecular weight of the functional moiety in the modified conjugated diene-based polymer

According to an embodiment of the present invention, the modified conjugated diene-based polymer includes a hydrocarbon chain and a functional moiety, and the ratio of the number average molecular weight of the functional moiety to the number average molecular weight of the entire polymer is 0.15 or less do it with

The functional moiety includes a macromonomer including a repeating unit derived from an N-functional group-containing monomer and an alkoxysilane-based modifier, and refers to a portion in which all functional groups are gathered in the modified conjugated diene-based polymer, and according to the present invention , this functional moiety has a number average molecular weight ratio of 0.15 or less to the number average molecular weight of the entire polymer, preferably 0.10 or less, more preferably 0.07 or less, even more preferably 0.05 or less. can have rain.

On the other hand, the modified conjugated diene-based polymer according to an embodiment of the present invention may include one or more hydrocarbon chains and may include one or more macromonomers of a functional moiety. That is, one or more hydrocarbon chains may be bonded to each other and one or more macromonomers may be bonded to the functional moiety based on the unit derived from the modifier. For example, 1 and 1, 1 and 2, 1 and 3, 2 and 1, 2 and 2 of a hydrocarbon chain and a functional moiety, respectively, centering on a unit derived from an alkoxysilane-based modifier , may be combined in combinations of 3 and 1, etc., and hydrocarbon chains and functional moieties may be formed in more various combinations depending on the number of functional groups present in the modifier, provided that, functional groups in the modified conjugated diene-based polymer All of these are present within the functional moiety and may have a structure concentrated at either end.

As such, when all of the functional groups are intensively distributed at one end of the modified conjugated diene-based polymer, only one end of the polymer binds to the silica and the other end is free when interacting with silica, so the existing terminal end-modified polymer Similarly, the processability can be remarkably improved by showing an excellent effect on the dispersibility of the filler and the prevention of agglomeration. In addition, the functional moiety includes a repeating unit derived from a monomer containing an N-functional group and a unit derived from a modifier to achieve an effect by interaction with a filler at a level equal to or higher than that of the conventional modified polymer at both ends, and thus tensile properties and viscoelastic properties may be excellent.

However, when the number average molecular weight ratio of the functional moiety exceeds 0.15 with respect to the number average molecular weight of the entire polymer, it means that the distribution of the functional groups becomes relatively long, that is, they are widely distributed. It is not a characteristic, but the characteristic of a modified polymer that is a human body in which functional groups are distributed in the middle of the chain. For this reason, there may occur a problem in that the compounding properties, particularly the viscoelastic properties are deteriorated.

That is, in the modified conjugated diene-based polymer, the length of the hydrocarbon chain is shortened, which means that the overall number average molecular weight is reduced, or the length of the functional moiety is increased. It is difficult to satisfy, and a decrease in tensile properties occurs, and when the length of the functional moiety is increased, the dispersibility of the filler is rather reduced, leading to a decrease in workability, and the viscoelastic properties may be deteriorated together.

In addition, in the modified conjugated diene-based polymer according to an embodiment of the present invention, the number average molecular weight ratio of the functional moiety is 0.15 or less relative to the total polymer number average molecular weight, which corresponds to 15% of the total polymer, and the functional groups are widely distributed It may have a different effect from the case where it is used. Theoretically, when functional groups are widely or intensively distributed in the entire chain, if the number of functional groups is similar, tensile properties and viscoelastic properties may appear similar, but viscoelastic properties and processability are concentrated as in the present invention. distribution shows a remarkably excellent effect.

That is, the modified conjugated diene-based polymer according to an embodiment of the present invention is a functional moiety such that a macromonomer including a repeating unit derived from a monomer containing a functional group and a unit derived from an alkoxysilane-based modifier are intensively arranged. do it with As such, by distributing the functional group group only at one end of the entire polymer chain, the existing terminal-end-modified conjugated diene-based polymers, both ends-modified conjugated diene-based polymers and human-modified conjugated diene-based polymers have advantages, but their problems are was able to solve it.

On the other hand, the coupling of the hydrocarbon chain and the functional moiety in the modified conjugated diene-based polymer may be made through the alkoxysilane group of the alkoxysilane-based modifier of the functional moiety.

A hydrocarbon chain comprising a repeating unit derived from a conjugated diene-based monomer

According to an embodiment of the present invention, the hydrocarbon chain serving as the main backbone of the modified conjugated diene-based polymer has a repeating unit derived from a conjugated diene-based monomer 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 is It may be at least one selected from the group consisting of halogen atoms).

In addition, the hydrocarbon chain may include an aromatic vinyl-based monomer in addition to the conjugated diene-based monomer and further include a repeating unit derived therefrom. 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)- It may be at least one selected from the group consisting of α-methylstyrene (3-(2-pyrrolidino-1-methyl ethyl)styrene).

As another example, the hydrocarbon chain of the modified conjugated diene-based polymer may be a copolymer further comprising a repeating unit derived from a diene-based monomer having 1 to 10 carbon atoms together with the 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 modified conjugated diene-based polymer is a copolymer further comprising a diene-based monomer, the modified conjugated diene-based polymer contains more than 0% by weight and 1% by weight or less of the repeating unit derived from the diene-based monomer, more than 0% by weight and 0.1% by weight. Below, more than 0% by weight and 0.01% by weight or less, or more than 0% by weight and 0.001% by weight or less, there is an effect of preventing gel formation within this range.

According to an embodiment of the present invention, when two or more monomers are included in the hydrocarbon chain constituting the backbone of the modified conjugated diene-based polymer, it may be a random copolymer chain, and in this case, there is an excellent balance between the physical properties. The random copolymer may mean that the repeating units constituting the copolymer are disorderly arranged.

The hydrocarbon chain of the modified conjugated diene-based polymer according to an embodiment of the present invention may not include a functional group, wherein the functional group is an N-containing functional group, an S-containing functional group, an O-containing functional group, or a Si-containing functional group. can As described above, by not distributing a functional group in one hydrocarbon chain, the effect of disposing the functional moiety at one end as described above can be achieved.

Functional moieties of units derived from micromonomers and alkoxysilane-based modifiers

According to an embodiment of the present invention, the functional moiety of the modified conjugated diene-based polymer includes a repeating unit derived from an N-functional group-containing monomer and a unit derived from an alkoxysilane-based modifier.

In the functional moiety, the content of N atoms in the polymer according to NSX analysis may be 100 ppm or more by weight, preferably 150 ppm or more, more preferably 170 ppm or more. The modified conjugated diene-based polymer may have a relatively high content of N atoms by introducing a macromonomer in which an N-functional group is repeatedly present through a functional moiety, and the N-functional group is a polymer main chain and the main chain By having a structure bonded to a unit derived from an alkoxysilane-based compound bonded to at least one terminal, affinity and dispersibility with a filler, such as silica, during the compounding process are significantly improved, thereby providing excellent viscoelastic properties and greatly improved processability. can On the other hand, when the content of N atoms is applied to the alkoxysilane-based modifier as containing an amine, N atoms derived from the modifier may also be present.

According to an embodiment of the present invention, in the functional moiety of the modified conjugated diene-based polymer, the content of Si atoms in the polymer according to ICP analysis may be 180 ppm or more based on weight, preferably 190 ppm or more, more preferably It may be 200 ppm or more.

The content of Si atoms may be derived from a modifier, which is an alkoxysilane-based compound, and may be derived from Si incidentally included in the N-functional group-containing monomer in addition to being derived from the modifier. The content of Si atoms is a functional group present in the modified conjugated diene-based polymer, that is, it can be expected to improve affinity with a filler, and can be a major factor as well as improvement of processability.

In addition, due to the high content of N atoms, the modified conjugated diene-based polymer according to an embodiment of the present invention may satisfy the condition that the molar ratio (N/Si) of N atoms and Si atoms is 0.75 or more. In general, in the case of a polymer modified by a modifier, it may contain Si atoms and N atoms due to a modified polymerization initiator, a modified monomer, etc., but as described above, in the case of a polymer according to an embodiment of the present invention, an N-functional group Since the monomer is included as a repeating unit, the content of N atoms may be relatively large, and as a symbolic meaning accordingly, the molar ratio of N atoms to Si atoms may be 0.75 or more, preferably 0.77 or more, or 0.78 or more , more preferably 0.8 or more, and most optimally 0.9 or more. Through this, it is possible to optimize the effect of improving processability according to the improvement of dispersibility during mixing.

According to an embodiment of the present invention, the main unit constituting the macromonomer of the functional moiety is an N-functional group-containing monomer, and the N-functional group may be basically an amino group, an aliphatic cyclic amino group, an aliphatic chain type amino group, It may be an aromatic amino group or the like.

In addition, the functional moiety may be one unit bonded to one macromonomer through an alkoxysilyl group in the alkoxysilane-based modifier, and the macromonomer is a macromonomer, wherein two or more units are present in the alkoxysilane-based modifier through two or more alkoxysilyl groups. may be coupled.

The macromonomer of the functional moiety is a form in which an N-functional group-containing monomer is repeatedly bonded, and the number of repeating units may be 2 to 80. When the number of repeating units is 2 to 80, the number average molecular weight ratio occupied by the functional moiety in the entire polymer can be satisfied, and an appropriate level of functional groups can be secured, so that both processability and compounding properties can be achieved.

The functional moiety may further include a unit derived from a conjugated diene-based monomer in the macromonomer. That is, macromonomers can be polymerized (low polymerization) only with N-functional group-containing monomers, but may be prepared by polymerization (low polymerization) of N-functional group-containing monomers and conjugated diene-based monomers together for the purpose of increasing molecular weight or length. have. In this case, the macromonomer may be in the form of a random copolymer in which the conjugated diene-based monomer and the N-functional group-containing monomer are arbitrarily arranged, or may be in the form of a block copolymer in which the same units are gathered and arranged, and the form is not limited thereto.

According to an exemplary embodiment of the present invention, the N-functional group-containing monomer may be, for example, a compound represented by Formula 1 below.

[Formula 1]

In Formula 1,

X is N or CH;

R _8a to R _8c are each independently a hydrogen atom; an alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 20 carbon atoms; an alkynyl group having 2 to 20 carbon atoms; A heteroalkyl group having 1 to 20 carbon atoms, a heteroalkenyl group having 2 to 20 carbon atoms; a heteroalkynyl group having 2 to 20 carbon atoms; a cycloalkyl group having 5 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms; Or a heterocyclic group having 3 to 20 carbon atoms,

R _8d is a single bond, a substituted or unsubstituted C 1 to C 20 alkylene group; a cycloalkylene group having 5 to 20 carbon atoms that is unsubstituted or substituted with a substituent; Or an arylene group having 6 to 20 carbon atoms substituted or unsubstituted with a substituent, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms,

R _8e is an alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 20 carbon atoms; an alkynyl group having 2 to 20 carbon atoms; a heteroalkyl group having 1 to 20 carbon atoms; a heteroalkenyl group having 2 to 20 carbon atoms; a heteroalkynyl group having 2 to 20 carbon atoms; a cycloalkyl group having 5 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms; a heterocyclic group having 3 to 20 carbon atoms; Or a functional group represented by the following formula (1a),

O is an integer of 0 to 5, at least one of R _8e is a functional group represented by the following formula 1a, and when o is an integer of 2 to 5, a plurality of R _8e may be the same or different from each other,

[Formula 1a]

In Formula 1a,

R _8f is a single bond, a C 1 to C 20 alkylene group unsubstituted or substituted with a substituent; a cycloalkylene group having 5 to 20 carbon atoms that is unsubstituted or substituted with a substituent; Or an arylene group having 6 to 20 carbon atoms substituted or unsubstituted with a substituent, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms,

R _8g and R _8h are each independently an alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 20 carbon atoms; an alkynyl group having 2 to 20 carbon atoms; a heteroalkyl group having 1 to 20 carbon atoms; a heteroalkenyl group having 2 to 20 carbon atoms; a heteroalkynyl group having 2 to 20 carbon atoms; a cycloalkyl group having 5 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms; A mono-, di- or trisubstituted alkylsilyl group substituted with a heterocyclic group having 3 to 20 carbon atoms or an alkyl group having 1 to 10 carbon atoms, or R _8g and R _8h are connected to each other and together with N a heterocyclic group having 2 to 10 carbon atoms to form a ring.

In addition, the N-functional group-containing monomer may be a compound represented by the following formula (2).

[Formula 2]

In Formula 2,

X ₁ -X ₂ is CH ₂ -CH ₂ or CH=CH,

X ₃ -X ₄ is CH ₂ -CH ₂ , CH=N or N=N.

In addition, the N-functional group-containing monomer may be a compound represented by the following formula (3).

[Formula 3]

In Formula 3,

R _11a and R _11b are each independently an alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 20 carbon atoms; an alkynyl group having 2 to 20 carbon atoms; a heteroalkyl group having 1 to 20 carbon atoms; a heteroalkenyl group having 2 to 20 carbon atoms; a heteroalkynyl group having 2 to 20 carbon atoms; a cycloalkyl group having 5 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms; a heterocyclic group having 3 to 20 carbon atoms; Or a functional group represented by the following formula 3a,

R _11c is an alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 20 carbon atoms; an alkynyl group having 2 to 20 carbon atoms; a heteroalkyl group having 1 to 20 carbon atoms; a heteroalkenyl group having 2 to 20 carbon atoms; a heteroalkynyl group having 2 to 20 carbon atoms; a cycloalkyl group having 5 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms; a heterocyclic group having 3 to 20 carbon atoms; vinyl group; Or a functional group represented by the following formula 3a,

At least one of R _11a , R _11b and R _11c is a functional group represented by Formula 3a,

[Formula 3a]

In Formula 3a,

R _11d is a single bond or an alkylene group having 1 to 20 carbon atoms that is unsubstituted or substituted with a single bond; a cycloalkylene group having 5 to 20 carbon atoms that is unsubstituted or substituted with a substituent; Or an arylene group having 6 to 20 carbon atoms substituted or unsubstituted with a substituent, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms,

R _11e and R _11f are each independently an alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 20 carbon atoms; an alkynyl group having 2 to 20 carbon atoms; a heteroalkyl group having 1 to 20 carbon atoms; a heteroalkenyl group having 2 to 20 carbon atoms; a heteroalkynyl group having 2 to 20 carbon atoms; a cycloalkyl group having 5 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms; a heterocyclic group having 3 to 20 carbon atoms; or a mono-, di-, or tri-substituted alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms.

In addition, the N-functional group-containing monomer may be a compound represented by the following formula (4).

[Formula 4]

In Formula 4,

R _12a is a single bond or an alkylene group having 1 to 20 carbon atoms that is unsubstituted or substituted with a single bond; a cycloalkylene group having 5 to 20 carbon atoms that is unsubstituted or substituted with a substituent; Or an arylene group having 6 to 20 carbon atoms substituted or unsubstituted with a substituent, wherein the substituent is an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms,

R _12b and R _12c are each independently an alkyl group having 1 to 20 carbon atoms; an alkenyl group having 2 to 20 carbon atoms; an alkynyl group having 2 to 20 carbon atoms; a heteroalkyl group having 1 to 20 carbon atoms; a heteroalkenyl group having 2 to 20 carbon atoms; a heteroalkynyl group having 2 to 20 carbon atoms; a cycloalkyl group having 5 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms; a heterocyclic group having 3 to 20 carbon atoms; or a mono-, di-, or tri-substituted alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms.

Modifier: Alkoxysilane-based compound

In addition, the modified conjugated diene-based polymer may be in a form in which a macromonomer is coupled by an alkoxysilane-based modifier, and the alkoxysilane-based modifier of the functional moiety serves as a hub to which not only the macromonomer but also the hydrocarbon chain is coupled, Here, the alkoxysilane-based modifier may include at least three Si functional groups, that is, alkoxy groups bonded to silicon. Here, three alkoxy groups bonded to silicon means three Si-O bonds and does not mean three Si.

According to an embodiment of the present invention, the alkoxysilane-based compound included in the modified conjugated diene-based polymer may be an amine-containing alkoxysilane-based compound or an amine-free alkoxysilane-based compound.

In addition, the amine-containing alkoxysilane-based compound among the alkoxysilane-based compounds may be exemplarily a compound represented by the following Chemical Formula 5.

[Formula 5]

In Formula 5, 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, an epoxy group, or an alkylene group having 1 to 10 carbon atoms. It may be a monosubstituted, disubstituted or trisubstituted alkylsilyl group substituted with an alkyl group having 1 to 10 carbon atoms, an allyl group having 2 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a heterocyclic group having 2 to 10 carbon atoms, R ²¹ may be a single bond, an alkylene group having 1 to 10 carbon atoms, or -[R ⁴² O] _j -, R ⁴² may be an alkylene group having 1 to 10 carbon atoms, and a and m are each independently from 1 to 3 It may be an integer selected from, n may be an integer from 0 to 2, and j may be an integer selected from 1 to 30.

As a specific example, the compound represented by Formula 5 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), tri (trimethoxysilyl)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- (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-(trimethoxysilyl)propyl)propan-1-amine), 3-(trimethoxysilyl) )-N-(3-trimethoxysilyl)propyl)-N-(3-(1-(3-(trimethoxysilyl)propyl)-1H-1,2,4-triazol-3-yl) Propyl)propan-1-amine(3-(trimethoxysilyl)-N-(3-(trimethoxysilyl)propyl)-N-(3-(1-(3-(trimehtoxysilyl)propyl)-1H-1,2,4- triazol-3-yl)propyl)propan-1-amine), N-allyl-N-(3-(trimethoxysilyl)prop Phil)prop-2-en-1amine (N-allyl-N-(3-(trimethoxysilyl)propyl)prop-2-en-1-amine), N,N-bis(oxiran-2-ylmethyl) )-3-(trimethoxysilyl)propan 1-amine (N,N-bis(oxiran-2-ylmethyl)-3-(trimethoxysilyl)propan-1-amine), 1,1,1-trimethyl-N- (3- (triethoxysilyl) propyl) -N- (trimethylsilyl) silanamine (1,1,1-trimethyl-N- (3- (triethoxysilyl) propyl) -N- (trimethylsilyl) silanamine) and N; N-bis(3-(triethoxysilyl)propyl)-2,5,8,11,14-pentaoxahexadecan-16-amine (N,N-bis(3-(triethoxysilyl)propyl)-2, 5,8,11,14-pentaoxahexadecan-16-amine) may be one selected from the group consisting of.

As another example, the amine-containing alkoxysilane-based compound among the alkoxysilane-based compounds may include a compound represented by the following formula (6).

[Formula 6]

또는

일 수 있으며, 이 때, R¹³, R¹⁴, R¹⁵ 및 R¹⁶은 각각 독립적으로 수소, 또는 탄소수 1 내지 10의 알킬기일 수 있다.In Formula 6, 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 are each independently 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 1, 2 or 3, b+c≥4, and A is

or

may be, and 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 6 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-imidazol) It may be one selected from the group consisting of -1-yl)-N,N-bis(3-(triethoxysilyl)propyl)propan-1-amine).

As another example, the amine-containing alkoxysilane-based compound among the alkoxysilane-based compounds may include a compound represented by the following formula (7).

[Formula 7]

In Formula 7, A ¹ and A ² may each independently be a divalent hydrocarbon group having 1 to 20 carbon atoms including or not including an oxygen atom, and R ¹⁷ to R ²⁰ are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms. may be a hydrocarbon group, and L ¹ to L ⁴ are each independently a monosubstituted, disubstituted or trisubstituted 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 formed may include 1 to 3 at least one hetero atom selected from the group consisting of N, O and S.

As a specific example, the compound represented by Formula 7 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-tetra Ethoxydisiloxane-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-tetra Methoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine)(3,3′-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N ,N-diethylpropan-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine) ( 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimpropylpropan-1-amine), 3,3'-(1,1,3,3-tetra Ethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine)(3,3′-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis( N,N-diethylpropan-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine )(3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine), 3,3'-(1,1,3,3 -tetraethoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine) (3, 3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine), 3,3'-(1,1,3,3-tetrapropoxy Cydisiloxane-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-tetrae Toxydisiloxane-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-dimethylmethane-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-tetra Propoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethan-1-amine)(3,3′-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N ,N-dimethylmethan-1-amine), 3,3'-(1,1,3, 3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dipropylmethan-1-amine)(3,3′-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl) )bis(N,N-dipropylmethan-1-amine), 3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis(N,N-dimethylmethane-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-dipropylmethane-1-amine)(3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-) diyl)bis(N,N-dipropylmethan-1-amine), N,N'-((1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(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)silanamine(N,N'-((1,1,3,3-tetraethoxydisiloxane-1,3) -diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-(trimethylsilyl)silanamine), N,N'-((1,1,3,3-tetraprotoxy) Cydisiloxane-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-phenylsilaneamine(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-phenylsilaneamine (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-phenylsilaneamine (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- It may be one selected from the group consisting of bis(3-(1H-imidazol-1-yl)propyl)-1,1,3,3-tetrapropoxydisiloxane).

As another example, the amine-containing alkoxysilane-based compound among the alkoxysilane-based compounds may include a compound represented by the following Chemical Formula 8.

[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 number an alkylene group of 1 to 10, 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 amine-containing alkoxysilane-based compound among the alkoxysilane-based compounds may include a compound represented by the following Chemical Formula 9.

[Formula 9]

In Formula 9, R _e1 and R _e2 are each independently an alkylene group having 1 to 10 carbon atoms, and _Re3 to R _e6 are each 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 _Re3 to _Re6 is —R _e7 SiR _e8 Re9 _{Re9 Re10} , wherein _Re7 is a single bond or an alkylene group having 1 to 10 carbon atoms, and _Re8 to _Re10 are independently of each other 1 carbon number an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, wherein at least one of R _e8 to _Re10 is an alkoxy group having 1 to 10 carbon atoms.

As another example, the amine-free alkoxysilane-based compound among the alkoxysilane-based compounds may include a compound represented by the following Chemical Formula 10.

[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 0 or an integer of 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 amine-free alkoxysilane-based compound among the alkoxysilane-based compounds may include a compound represented by the following Chemical Formula 11.

[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 , but 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, Y is C or N, wherein Y is For N, R _g4 is absent.

As another example, the amine-containing alkoxysilane-based compound among the alkoxysilane-based compounds may include a compound represented by the following Chemical Formula 12.

[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. to be.

As another example, the amine-free alkoxysilane-based compound among the alkoxysilane-based compounds may include a compound represented by the following Chemical Formula 13.

[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 from 2 to 100 .

Normal

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 1,000,000 g/mol, or 100,000 g/mol to 800,000 g It may be / mol, the weight average molecular weight (Mw) 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, the peak average molecular weight (Mp) may be from 1,000 g/mol to 3,000,000 g/mol, from 10,000 g/mol to 2,000,000 g/mol, or from 100,000 g/mol to 2,000,000 g/mol. Within this range, there is an excellent effect of rolling resistance and wet road resistance. As another example, the modified conjugated diene-based polymer may have a molecular weight distribution (PDI; MWD; Mw/Mn) of 1.0 or more to 3.0 or less, or 1.1 or more to 2.5 or less, or 1.1 or more and 2.0 or less, and tensile properties within this range and excellent viscoelastic properties, and excellent balance between physical properties.

In addition, the modified conjugated diene-based polymer may have a Mooney viscosity of 30 or more, 40 to 150, or 40 to 140 at 100° C., and has excellent processability and productivity within this range.

Here, the Mooney viscosity may be measured using a Mooney viscometer. Specifically, using Monsanto's MV2000E Large Rotor, under the conditions of 100°C and Rotor Speed 2±0.02 rpm, the polymer was left at room temperature (23±5°C for more than 30 minutes, then 27±3 g was collected and stored inside the die cavity) It was measured while filling and applying a torque by operating a platen.

In addition, the modified conjugated diene-based polymer may have a vinyl content of 5 wt% or more, 10 wt% or more, or 10 wt% to 60 wt%. Here, the vinyl content means the content of the 1,2-added conjugated diene-based monomer, not the 1,4-added, based on 100% by weight of the conjugated diene-based copolymer consisting of a monomer having a vinyl group and an aromatic vinyl-based monomer. can

Method for producing a modified conjugated diene-based polymer

In addition, the present invention provides a method for producing the modified conjugated diene-based polymer.

The method for producing the modified conjugated diene-based polymer according to an embodiment of the present invention comprises the steps of polymerizing a conjugated diene-based monomer or a conjugated diene-based monomer and an aromatic vinyl-based monomer in a hydrocarbon solvent in the presence of a polymerization initiator to prepare an active hydrocarbon chain (S1); preparing a functional moiety by reacting a macromonomer including a repeating unit derived from an N-functional group-containing monomer with an alkoxysilane-based modifier (S2); and reacting the active hydrocarbon chain with a functional moiety (S3).

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 is not particularly limited, for example, methyllithium, ethyllithium, propyllithium, isopropyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octyl Lithium, phenyllithium, 1-naphthyllithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolylylithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium , sodium naphthyl, potassium naphthyl, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide and lithium isopropylamide. may be more than

According to an embodiment of the present invention, the polymerization initiator is 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 monomer. can be used Here, the total amount of 100 g of the monomer may represent a conjugated diene-based monomer or a total amount of a conjugated diene-based monomer and an aromatic vinyl-based monomer.

Step S1

The polymerization in step (S1) may be, for example, anionic polymerization, and as a specific example, living anionic polymerization having an anionic active site at the polymerization end by an anion-based growth polymerization reaction. 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 the step of polymerizing by its own heat of reaction without optionally applying heat after the polymerization initiator is added. may refer to a polymerization method, wherein the temperature-rising polymerization may refer to a polymerization method in which the temperature is increased by optionally applying heat after the polymerization initiator is added, and the isothermal polymerization is heat by adding heat after the polymerization initiator is added It may refer to a polymerization method in which the temperature of the polymer is kept constant by increasing the temperature or taking heat away.

In addition, according to an 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. This has the effect of preventing its formation. An example of the diene-based compound may be 1,2-butadiene.

The polymerization of step (S1) may be carried out in a temperature range of, for example, less than 80 ℃, -20 ℃ to 80 ℃, 0 ℃ to 80 ℃, 0 ℃ to 70 ℃, or 10 ℃ to 70 ℃, this range By narrowing the molecular weight distribution of the polymer within, there is an excellent effect of improving physical properties.

The active polymer chain prepared by the step (S1) may refer to a polymer in which a polymer anion and an organometallic cation are bound.

Meanwhile, the polymerization in step (S1) may be carried out including a polar additive, and the polar additive is added in a proportion of 0.001 g to 50 g, 0.001 g to 10 g, or 0.005 g to 0.1 g based on 100 g of the total monomer. can do. As another example, the polar additive may be added in a proportion of 0.001 g to 10 g, 0.005 g to 5 g, 0.005 g to 4 g based on 1 mmol of the polymerization initiator in total.

The polar additive is, for example, tetrahydrofuran, 2,2-di (2-tetrahydrofuryl) propane, diethyl ether, cyclopentyl ether, dipropyl ether, ethylene methyl ether, ethylene dimethyl ether, diethyl glycol, dimethyl ether , tert-butoxyethoxyethane, bis (3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine, N,N,N',N'-tetra It may be at least one selected from the group consisting of methylethylenediamine, sodium mentholate, and 2-ethyl tetrahydrofurfuryl ether, preferably 2,2-di(2-tetra). It may be hydrofuryl) propane, triethylamine, tetramethylethylenediamine, sodium mentholate, or 2-ethyl tetrahydrofurfuryl ether, and if the polar additive is included, it may be a conjugated diene In the case of copolymerizing the monomer-based monomer and the aromatic vinyl-based monomer, there is an effect of compensating for the difference in their reaction rate, thereby inducing the easy formation of a random copolymer.

Step S2

Step (S2) is a step for preparing a functional moiety by reacting a macromonomer including a repeating unit derived from an N-functional group-containing monomer with an alkoxysilane-based modifier.

Here, the reaction may be a modification or a coupling reaction, and in this case, the modifier may be used in an amount of 0.01 mmol to 10 mmol based on 100 g of the N-functional group-containing monomer in total. 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.

On the other hand, the manufacturing method according to an embodiment of the present invention may further include the step of preparing a macromonomer before step (S2), and the step of preparing the macromonomer is N in the presence of an organolithium compound in a hydrocarbon solvent. - It may be carried out by polymerizing a functional group-containing monomer or an N-functional group-containing monomer and a conjugated diene-based monomer. In this case, the polymerization reaction may be a living anionic polymerization having an anionic active site at the polymerization terminal by growth polymerization reaction by an anion, and thus the macromonomer may be a living anionic terminal in which one terminal can function as a monomer.

Here, the organolithium compound may be an alkyllithium compound, and specifically, methyllithium, ethyllithium, propyllithium, isopropyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n -decyllithium, t-octyllithium, phenyllithium, 1-naphthyllithium, n-eicosyllithium, 4-butylphenyllithium, 4-tolylithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyl lithium or 4-cyclopentyllium, more specifically n-butyllithium.

As an example, the macromonomer may be prepared through Scheme 1 below, and may be a compound having a structure represented by Formula M1 below.

[Scheme 1]

As another example, the macromonomer may be prepared through the following Reaction Scheme 2, and may be a compound having a structure represented by the following Chemical Formula M2.

[Scheme 2]

As another example, the macromonomer may be prepared through Scheme 3 below, and may be a compound having a structure represented by Formula M3 below.

[Scheme 3]

As another example, the macromonomer may be prepared through the following Reaction Scheme 4, and may be a compound having a structure represented by the following Chemical Formula M4.

[Scheme 4]

In Schemes 1 to 4, R _8d , R ₈ , X, X ₁ -X ₂ , X ₃ -X ₄ , R _11a to R _11c , R _12a to R _12c , and o are as defined in Formulas 1 to 4 above, R-Li is an alkyllithium compound, and R is an alkyl group derived from the alkyllithium. to be.

In addition, the macromonomer includes 2 to 80, 2 to 60, or 2 to 50 repeating units derived from an N-functional group-containing monomer, which is one selected from compounds represented by Formulas 1 to 4, for example, the above formula In M1 to Formula M4, each of r ₁ to r ₄ may be 2 to 80, 2 to 60, or 2 to 50. In this case, the functional moiety including the macromonomer may be included in the modified conjugated diene-based polymer and may have the aforementioned Si and N contents derived therefrom, and the workability, tensile properties and viscoelastic properties will be excellent in a balanced way. can

Meanwhile, the step (S2) may be to prepare a functional moiety by reacting the alkoxysilane-based modifier with the living anion terminal of the macromonomer. Specifically, the alkoxysilane-based modifier may include an alkoxy group bonded to Si, and the modified conjugated diene-based polymer may be prepared by reacting the living anion terminal of the macromonomer with the alkoxy group. In this case, in the macromonomer, two units may react with two alkoxy groups, respectively, or more units may react with an alkoxy group.

In this case, the macromonomer needs to be prepared by controlling the ratio between the monomer used in preparing the hydrocarbon chain in step (S1) and the N-functional group-containing monomer used in preparing the macromonomer. The number of repeating units of the N-functional group-containing monomer included in the macromonomer may be a factor in determining the number average molecular weight ratio to the number average molecular weight of the entire polymer in relation to the hydrocarbon chain, which is a modified conjugated diene according to the present invention It can be said that it is a factor that makes it possible to achieve the effect of the type polymer.

Here, the precedence relationship between the steps (S1) and (S2) is irrelevant, and the step (S2) may be performed before the step (S1), or vice versa, and it is also possible to perform it in a separate reactor at the same time.

Step S3

Step (S3) is a step for preparing a modified conjugated diene-based polymer by reacting the functional moiety prepared in step (S2) with the active hydrocarbon chain prepared in step (S1).

The functional moiety prepared in step (S2) includes a unit derived from an alkoxysilane-based modifier, and the living anion terminal of the macromonomer reacts with an alkoxy group bonded to Si of the modifier, but an alkoxy moiety is present, and thus active The living anionic end of the hydrocarbon chain can react with this site to form a bond with silicon, and through this, a modified conjugated diene-based polymer having a functional moiety corresponding to a ratio of the number average molecular weight to the entire polymer is 0.15 or less. can

In addition, the macromonomer may be used in an amount of 0.1 to 4.0 moles, 0.1 to 2.0 moles, or 0.5 to 1.5 moles relative to 1 mole of the polymerization initiator.

In the case of the modified conjugated diene-based polymer prepared in this way, the proportion of the number average molecular weight of the functional moiety to the total is less than 15%, and the functional groups are intensively distributed to improve the compounding properties by improving dispersibility and affinity with the filler It can be expected greatly, and processability can also be improved.

rubber composition

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

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

In addition, the rubber composition may further include other rubber components as needed in addition to the modified conjugated diene-based polymer, wherein 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 thereof 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 that are modified or refined of 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, or a synthetic rubber such as halogenated butyl rubber, and any one or a mixture of two or more thereof may be used.

The rubber composition may include, for example, 0.1 parts 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 include wet silica (hydrous silicic acid), dry silica (anhydrous silicic acid), calcium silicate, aluminum silicate or colloidal silica, and preferably, the effect of improving fracture properties and wet It may be wet silica that has the best effect of compatibility with wet grip. In addition, the rubber composition may further include a carbon black-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 may be used together, and in 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-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilylpropylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzolyltetrasulfide, 3-triethoxysilylpropylmethacrylate monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, bis(3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethyl It may be silane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide or dimethoxymethylsilylpropylbenzothiazolyltetrasulfide, and any one or a mixture of two or more thereof may be used. Preferably, in consideration of the reinforcing improvement effect, it may be bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide.

In addition, in the rubber composition according to an embodiment of the present invention, as a rubber component, a modified conjugated diene-based polymer in which a functional group with high affinity for silica is introduced is used as a rubber component, so the compounding amount of the silane coupling agent is conventional. may be reduced than the case, and accordingly, the silane coupling agent may be used in an amount of 1 to 20 parts by weight, or 5 to 15 parts by weight, based on 100 parts by weight of silica, and the effect as a coupling agent within this range is It has the effect of preventing the gelation of the rubber component while being sufficiently exhibited.

The rubber composition according to an embodiment of the present invention may be crosslinkable with sulfur, and may further include a vulcanizing agent. The vulcanizing agent may be specifically 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, and within this range, the vulcanized rubber composition has a low fuel efficiency while securing the required elasticity modulus and strength. It has an excellent effect.

The rubber composition according to an embodiment of the present invention includes, in addition to the above components, various additives commonly used in the rubber industry, specifically, a vulcanization accelerator, process oil, antioxidant, plasticizer, anti-aging agent, scorch inhibitor, 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-benzothiazyl sulfenamide), or DPG A guanidine-based compound such as (diphenylguanidine) may be used, and may be included in an amount of 0.1 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. Naphthenic or paraffinic process oils may be used. The process oil may be included in an amount of 100 parts by weight or less based on 100 parts by weight of the rubber component, for example, and has an effect of preventing deterioration of the tensile strength and low heat generation (low fuel efficiency) of the vulcanized rubber within this range.

The antioxidant is, for example, 2,6-di-t-butylparacresol, dibutylhydroxytoluenyl, 2,6-bis((dodecylthio)methyl)-4-nonylphenol (2,6-bis( (dodecylthio)methyl)-4-nonylphenol) or 2-methyl-4,6-bis((octylthio)methyl)phenol (2-methyl-4,6-bis((octylthio)methyl)phenol), It 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 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 high-temperature condensate of diphenylamine and acetone, etc., 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, an internal mixer, etc. according to the compounding prescription, and has low heat generation and wear resistance by a vulcanization process after molding processing. This excellent rubber composition can be obtained.

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

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, in order to describe the present invention in detail, examples will be described in detail. However, the embodiment according to the present invention may be modified in various other forms, and the scope of the present invention should not be construed as being limited to the embodiment described in detail below. The embodiments of the present invention are provided to more completely explain the present invention to those of ordinary skill in the art.

Preparation Example 1

Put 100 ml of tetrahydrofuran, 10 g of 1,3-butadiene and 0.001 mol of active n-butyllithium in a 2L pressure reactor, and 1-vinyl imidazole (1-vinyl imidazole) ([act. Li] 1 mole to 2 mole ratio ) ) was added, and reacted at 10° C. for 30 minutes to prepare a solution containing a macromonomer, and 0.2 g of tetramethoxy silane as a denaturant was added to this solution and reacted for 15 minutes. A solution containing the sexual moiety was prepared ([act. Li]:[macromonomer] = 1:2 molar ratio, [denaturant]:[act. Li] = 1:1 molar ratio). Thereafter, the reaction was stopped using ethanol, and it was confirmed that 1-vinyl imidazole and tetramethoxysilane were not detected after the reaction through GC analysis.

Preparation 2

In Preparation Example 1, instead of tetramethoxysilane, N,N-dimethyl (3-trimethoxysilyl) propanamine (N,N-dimethyl(3-trimethoxysilyl) propanamine) ([act. Li] 1 mole to 2 mole ratio ) was added, and 20 g of 1,3-butadiene was added and reacted, except that a solution containing a functional moiety was prepared in the same manner as in Preparation Example 1, and after reaction through GC analysis It was confirmed that the reaction was carried out through the fact that the reactant was not detected.

Preparation 3

In Preparation Example 1, 0.1 g of 2-vinylpridine (2 molar ratio to 1 molar ratio of [act. Li]) was added instead of 1-vinyl imidazole, and N,N-bis ( 3-(triethoxysilyl)propyl)-3,6,9,12,15-pentaoxanonadecan-1-amine (N,N-bis(3-(triethoxysilyl)propyl)-3,6,9, A solution containing a functional moiety through the same method as in Preparation Example 1, except that 0.7 g of 12,15-pentaoxanonadecan-1-amine) ([act. Li] 1 mole to 2 mole ratio) was added and reacted. was prepared, and it was confirmed that the reaction was achieved through the fact that the reactant was not detected after the reaction through GC analysis.

Preparation 4

In Preparation Example 2, instead of 1-vinyl imidazole, N,N,N',N'-tetraethyl-1-methyl-1-vinylsilanediamine (N,N,N',N'-tetraethyl-1-methyl -1-vinylsilanediamine) ([act. Li] 1 mol to 2 mol ratio) 0.16 g was added, and 10 g of 1,3-butadiene was added and reacted, except for reaction in the same manner as in Preparation Example 2 above. A solution containing the moiety was prepared, and it was confirmed through GC analysis that the reactant was not detected after the reaction.

Preparation 5

In Preparation Example 1, instead of 1-vinyl imidazole, N,N,N',N'-tetramethyl-1-methyl-1-vinylsilanediamine (N,N,N',N'-tetramethyl-1-methyl A solution containing a functional moiety was prepared in the same manner as in Preparation Example 1, except that 0.16 g of -1-vinylsilanediamine) ([act. Li] 1 mole to 2 mole ratio) was added and reacted, and GC Through analysis, it was confirmed that the reaction occurred through the fact that the reactant was not detected after the reaction.

Preparation 6

In Preparation Example 1, instead of 1-vinyl imidazole, N,N-dimethyl-1-(4-vinylphenyl)methanamine (N,N,-dimethyl-1-(4-vinylphenyl)methanamine) ([act. Li ] A solution containing a functional moiety was prepared in the same manner as in Preparation Example 1, except that 0.16 g of 1 mole to 2 mole ratio) was reacted, and no reactant was detected after the reaction through GC analysis. It was confirmed that the reaction was through.

Examples 1 to 6

In a 5 L autoclave reactor, 14 kg of n-hexane, 52 g of styrene, 188 g of 1,3-butadiene and 0.001 mol of active n-butyllithium were added, and then 2,2-di(2-tetrahydrofuryl) as a polar additive was added. ) Propane was added at a molar ratio of 1.5 to 1 mol of the active n-butyllithium, and the temperature inside the reactor was adjusted to 60° C. and an adiabatic temperature rising reaction was performed.

After about 30 minutes, 10 g of 1,3-butadiene was added to cap the end of the polymer with butadiene, and after about 10 minutes, the functional moieties prepared in Preparation Examples 1 to 6 were respectively added and reacted for 15 minutes. ([functional moiety]:[act. Li]=1:1 molar ratio).

Thereafter, the reaction was stopped using ethanol, and 2 g of a solution in which 30 wt% of an antioxidant, Wingstay K, was dissolved in hexane was added. The resulting polymer was put into hot water heated with steam, stirred to remove the solvent, and then roll-dried to remove the remaining solvent and water, thereby preparing a modified conjugated diene-based polymer.

Comparative Example 1

Put 100 ml of tetrahydrofuran and 0.001 mol of active n-butyllithium in a 2L pressure reactor, and N,N,N',N'-tetraethyl-1-methyl-1-vinylsilanediamine (N,N,N', After adding 0.24 g of N'-tetraethyl-1-methyl-1-vinylsilanediamine) (3 molar ratio to 1 mol of [act. Li]), it was reacted at 10° C. for 30 minutes to prepare a solution containing a denaturation initiator.

After adding 14 kg of n-hexane, 52 g of styrene, 188 g of 1,3-butadiene and 0.001 mol of the active modification initiator to a 5 L autoclave reactor, 2,2-di(2-tetrahydro) as a polar additive Furyl) propane was added in an amount of 1.5 moles relative to 1 mole of the modification initiator, the temperature inside the reactor was adjusted to 60° C., and an adiabatic temperature rising reaction was performed. After about 30 minutes, 10 g of 1,3-butadiene was added, the end of the polymer was capped with butadiene, and the reaction was carried out for 10 minutes.

Thereafter, the reaction was stopped using ethanol, and 2 g of a solution in which 30 wt% of an antioxidant, Wingstay K, was dissolved in hexane was added. The resulting polymer was put into hot water heated with steam, stirred to remove the solvent, and then roll-dried to remove the remaining solvent and water, thereby preparing a modified conjugated diene-based polymer.

Comparative Example 2

In a 5 L autoclave reactor, 14 kg of n-hexane, 52 g of styrene, 188 g of 1,3-butadiene and 0.001 mol of active n-butyllithium were added, and then 2,2-di(2-tetrahydrofuryl) as a polar additive was added. ) Propane was added at a molar ratio of 1.5 to 1 mol of the active n-butyllithium, and the temperature inside the reactor was adjusted to 60° C. and an adiabatic temperature rising reaction was performed.

After about 30 minutes, 39 g of 1,3-butadiene was added to cap the end of the polymer with butadiene, and after about 10 minutes, tetramethoxysilane was added as a modifier and reacted for 15 minutes ([modifier]:[ act. Li] = 1:1 molar ratio).

Thereafter, the reaction was stopped using ethanol, and 2 g of a solution in which 30 wt% of an antioxidant, Wingstay K, was dissolved in hexane was added. The resulting polymer was put into hot water heated with steam, stirred to remove the solvent, and then roll-dried to remove the remaining solvent and water, thereby preparing a modified conjugated diene-based polymer.

Comparative Example 3

Put 100 ml of tetrahydrofuran and 0.001 mol of active n-butyllithium in a 2L pressure reactor, and N,N,N',N'-tetraethyl-1-methyl-1-vinylsilanediamine (N,N,N', After adding 0.24 g of N'-tetraethyl-1-methyl-1-vinylsilanediamine) (3 molar ratio to 1 mol of [act. Li]), it was reacted at 10° C. for 30 minutes to prepare a solution containing a denaturation initiator.

After adding 14 kg of n-hexane, 52 g of styrene, 188 g of 1,3-butadiene and 0.001 mol of the active modification initiator to a 5 L autoclave reactor, 2,2-di(2-tetrahydro) as a polar additive Furyl) propane was added in an amount of 1.5 moles relative to 1 mole of the modification initiator, the temperature inside the reactor was adjusted to 60° C., and an adiabatic temperature rising reaction was performed.

After the reaction was performed in the same manner as in Comparative Example 2, a modified conjugated diene-based polymer was prepared.

Comparative Example 4

In a 5 L autoclave reactor, 14 kg of n-hexane, 52 g of styrene, 188 g of 1,3-butadiene, N,N,N',N'-tetraethyl-1-methyl-1-vinylsilanediamine (N,N After adding 0.24 g of ,N',N'-tetraethyl-1-methyl-1-vinylsilanediamine) (3 mole ratio to 1 mole of [act. Li]) and 0.001 mol of active n-butyllithium, 2,2- as a polar additive Di(2-tetrahydrofuryl)propane was added in an amount of 1.5 moles relative to 1 mole of the active n-butyllithium, the temperature inside the reactor was adjusted to 60° C., and an adiabatic temperature rising reaction was performed.

After the reaction was performed in the same manner as in Comparative Example 2, a modified conjugated diene-based polymer was prepared.

Comparative Example 5

Put 100 ml of tetrahydrofuran and 0.001 mol of active n-butyllithium in a 2L pressure reactor, and N,N,N',N'-tetraethyl-1-methyl-1-vinylsilanediamine (N,N,N', After adding 0.24 g of N'-tetraethyl-1-methyl-1-vinylsilanediamine) (3 molar ratio to 1 mol of [act. Li]), it was reacted at 10° C. for 30 minutes to prepare a solution containing a denaturation initiator.

In a 5 L autoclave reactor, 14 kg of n-hexane, 52 g of styrene, 188 g of 1,3-butadiene, N,N,N',N'-tetraethyl-1-methyl-1-vinylsilanediamine (N,N 0.24 g of ,N',N'-tetraethyl-1-methyl-1-vinylsilanediamine) (3 molar ratio to 1 mol of [act. Li]) and 0.001 mol of the above modification initiator were added and 2,2-di( 2-tetrahydrofuryl) propane was added in an amount of 1.5 moles relative to 1 mole of the active modification initiator, the temperature inside the reactor was adjusted to 60° C., and an adiabatic temperature rising reaction was performed.

After the reaction was performed in the same manner as in Comparative Example 2, a modified conjugated diene-based polymer was prepared.

Experimental Example 1

For each modified conjugated diene-based polymer prepared in Examples and Comparative Examples, the styrene unit content and vinyl content in the polymer, the weight average molecular weight (Mw, X10 ³ g/mol), and the number average molecular weight (Mn, X10 ³ g/mol) mol), molecular weight distribution (PDI, MWD), number average molecular weight of functional moieties (Mn, X10 ³ g/mol), and N content were respectively measured. The results are shown in Table 1 below.

1) Styrene units and vinyl content (wt%)

Styrene unit (SM) and vinyl (Vinyl) contents in each polymer were measured and analyzed using Varian VNMRS 500 MHz NMR.

For NMR measurement, 1,1,2,2-tetrachloroethane was used as the solvent, and the solvent peak was calculated as 5.97 ppm, 7.2~6.9 ppm is random styrene, 6.9~6.2 ppm is block styrene, and 5.8~5.1 ppm is 1,4-vinyl, 5.1-4.5 ppm was calculated as the peak of 1,2-vinyl, and the styrene unit and vinyl content were calculated.

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

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

- Column: A combination of two PLgel Olexis (Polymer Laboratories) columns and one PLgel mixed-C (Polymer Laboratories) column is used.

- Solvent: tetrahydrofuran mixed with 2 wt% of an amine compound

- Flow rate: 1 mL/min

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

- Injection volume: 100 uL

- Column temperature: 40℃

- Detector: Refractive index

- Standard: Polystyrene (corrected by cubic function)

3) N content

The N content was measured using a trace nitrogen quantitative analyzer (NSX-2100H) as an NSX analysis method. 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 the ozonizer, and heater was set to 800°C and then waited for about 3 hours to stabilize the analyzer. After the analyzer is stabilized, a calibration curve in the range of 5 ppm, 10 ppm, 50 ppm, 100 ppm and 500 ppm was prepared using Nitrogen standard (AccuStandard S-22750-01-5 ml), and the area corresponding to each concentration was obtained. Afterwards, 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 N content was calculated using the area of the obtained sample and the calibration curve.

4) molecular weight ratio of functional moieties

After obtaining each of the number average molecular weight (Mn) of the functional moiety prepared in each Preparation Example and the number average molecular weight (Mn) of the modified conjugated diene-based polymer prepared in each Example by the measuring method described above, the modified conjugate The ratio of the number average molecular weight of the functional moiety to the number average molecular weight of the diene-based polymer was obtained.

division Example comparative example One 2 3 4 5 6 One 2 3 4 5 NMR
(weight%) SM 21 21 21 21 21 21 21 21 21 21 21 Vinyl 49 48 50 49 49 50 50 50 50 49 50 final
polymer Mn (X10 ³ g/mol) 320 332 342 342 356 345 365 403 395 375 373 Mw (X10 ³ g/mol) 560 398 592 393 598 583 402 544 545 506 492 MWD 1.75 1.20 1.73 1.15 1.68 1.69 1.10 1.35 1.38 1.35 1.32 N content (ppm) 221 280 168 280 232 115 234 - 332 339 670 Mn of the functional moiety (X10 ³ g/mol) 25 24 16 12 26 26 - - - - - molecular weight ratio 0.08 0.08 0.05 0.04 0.07 0.08 - - - - -

As shown in Table 1, in Examples 1 to 6, it was confirmed that the N atom content was 100 ppm or more and the number average molecular weight ratio of the functional moiety was 0.15 or less. On the other hand, the polymers of Comparative Examples 1-5 have a high N content similar to that of the polymers of Examples, but unlike the polymers of Examples, the functional groups are dispersed at the beginning and end of the polymer or are dispersed in the chain. It can be known through the manufacturing method.

Experimental Example 2

In order to compare and analyze the physical properties of the rubber composition containing each modified conjugated diene-based polymer prepared in Examples and Comparative Examples and molded articles prepared therefrom, tensile properties, viscoelastic properties and processability were measured respectively, and the results are shown in the table below 3 is shown.

1) Preparation of rubber specimens

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

division Raw material Content (parts by weight) 1st stage kneading rubber 100 silica 70 Coupling agent (X50S) 11.2 fair oil 37.5 Zincizing agent 3 stearic acid 2 antioxidant 2 anti-aging agent 2 wax One 2nd stage kneading sulfur 1.5 rubber accelerator 1.75 vulcanization accelerator 2

Specifically, the rubber specimen is kneaded through the first stage kneading and the second stage kneading. In the first stage kneading, raw rubber, silica (filler), organosilane coupling agent (X50S, Evonik), process oil (TDAE oil), zincating agent (ZnO), stearic acid using a Banbari mixer equipped with a temperature controller is used. , 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 completion of mixing, a first formulation was obtained at a discharge temperature of 145° C. to 155° C. In the second stage of kneading, the first formulation was cooled to room temperature. After mixing, the primary compound, sulfur, rubber accelerator (DPD (diphenylguanine)) and vulcanization accelerator (CZ (N-cytlohexyl-2-benzothiazylsulfenamide)) are added to the kneader, and the temperature is below 100 ° C. A secondary formulation was obtained by mixing in. Then, a rubber specimen was prepared through a curing process at 160° C. for 20 minutes.

2) Tensile properties

For tensile properties, each test piece was prepared according to the tensile test method of ASTM 412, and the tensile stress (300% modulus) at 300% elongation of the test piece was measured. Specifically, the tensile properties were measured at room temperature at a speed of 50 cm/min using a Universal Test Machin 4204 (Instron Co., Ltd.) tensile tester.

3) Viscoelastic properties

For the viscoelastic properties, the tan δ value was confirmed by measuring the viscoelastic behavior against dynamic deformation at a frequency of 10 Hz and each measurement temperature (-60°C to 60°C) in Film Tension mode using a dynamic mechanical analyzer (GABO). In the measurement result, the higher the low temperature 0℃ tanδ value, the better the wet road resistance, and the lower the high temperature 60℃ tanδ value, the less the hysteresis loss and the better the low running resistance (fuel efficiency). Since the value is expressed as an Index (%) based on the result value of Comparative Example 1, the higher the numerical value, the better.

4) Machinability characteristics

1) The Mooney viscosity (MV, (ML1+4, @100℃) MU) of the primary compound obtained during the manufacture of 1) rubber specimen was measured to compare and analyze the processability characteristics of each polymer. In this case, the lower the Mooney viscosity measurement value, the more This indicates that the workability characteristics are excellent, and in Table 3 below, it is expressed as an Index (%) based on the result value of Comparative Example 2, and the higher the number, the better.

Specifically, using MV-2000 (ALPHA Technologies) at 100°C, using a Rotor Speed of 2±0.02 rpm, and a Large Rotor, each secondary compound was left at room temperature (23±3°C for at least 30 minutes and then 27± 3 g was collected and filled in the die cavity, and the platen was operated for 4 minutes.

division Example comparative example One 2 3 4 5 6 One 2 3 4 5 Tensile properties 300% modulus 165 169 165 168 171 160 148 152 165 164 167 Viscoelastic properties tan δ0℃ 102 104 100 99 102 101 100 102 99 100 102 tan δ60℃ 116 118 120 119 121 119 100 91 112 108 115 Machinability characteristics (Index) 102 105 108 105 112 103 92 100 86 105 87

As shown in Table 3, Examples 1 to 6 showed superior processability properties compared to Comparative Examples 1 to 5, and at the same time, it was confirmed that the tensile properties and viscoelastic properties were also excellent.

In particular, in the case of Comparative Example 1 using only the modification initiator and Comparative Example 2 using only the modifier, it was confirmed that the tensile properties were inferior and the tan δ at 60 ° C was also very poor due to the rotational resistance, and the workability was also poor. can

In addition, in the case of Comparative Example 3 in which both ends were modified, both ends of the filler and the polymer chain interacted, and it was confirmed that the processability was very poor due to the drop in fluidity of one side of the chain, and to overcome this In the case of Comparative Example 4, in which a functional group was positioned in the chain by using a modified monomer instead of a modification initiator, processability was improved compared to Comparative Example 3, but it was confirmed that the damage of relatively poor rotation resistance occurred.

Accordingly, Comparative Example 5 using both the modification initiator, the modification monomer and the modification agent showed relatively high rotation resistance compared to other comparative examples, but it was not seen that there was an improvement as in the Example, and it was confirmed that the workability was very poor.

Claims (11)

a hydrocarbon chain including a repeating unit derived from a conjugated diene-based monomer; and
A functional moiety coupled to any one terminal of the hydrocarbon chain, comprising a macromonomer and an alkoxysilane-based modifier-derived unit including a repeating unit derived from an N-functional group-containing monomer, and having an N content of 100 ppm or more according to NSX analysis; including,
The ratio of the number average molecular weight of the functional moiety to the number average molecular weight of the entire polymer is 0.15 or less of the modified conjugated diene-based polymer.
The method according to claim 1,
The modified conjugated diene-based polymer is a modified conjugated diene-based polymer having an N atom content of 150 ppm or more by weight.
The method according to claim 1,
The ratio of the number average molecular weight of the functional moiety to the number average molecular weight of the entire polymer is 0.08 or less of the modified conjugated diene-based polymer.
The method according to claim 1,
The functional moiety is a modified conjugated diene-based polymer in which one or more macromonomers are bonded to a silyl group of an alkoxysilane-based modifier.
The method according to claim 1,
The macromonomer is a modified conjugated diene-based polymer further comprising a unit derived from a conjugated diene-based monomer.
The method according to claim 1,
The alkoxysilane-based modifier is an amine-containing alkoxysilane-based compound or an amine-free alkoxysilane-based compound, and a modified conjugated diene-based polymer comprising three or more alkoxy groups bonded to silicon.
The method according to claim 1,
The hydrocarbon chain is bonded to the silyl group of the alkoxysilane-based modifier in the functional moiety, and one or more hydrocarbon chains are bonded to the modified conjugated diene-based polymer.
The method according to claim 1,
The hydrocarbon chain is a modified conjugated diene-based polymer further comprising a repeating unit derived from an aromatic vinyl-based monomer.
The method according to claim 1,
A modified conjugated diene-based polymer having a number average molecular weight (Mn) of 1,000 g/mol to 2,000,000 g/mol.
A rubber composition comprising the modified conjugated diene-based polymer according to claim 1 and a filler.
11. The method of claim 10,
The rubber composition is a rubber composition comprising 0.1 parts by weight to 200 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene-based polymer.