KR20210031261A - Modified conjugated diene 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 remarkable processability and excellent tensile strength and viscoelastic properties, and a rubber composition comprising the same. The modified conjugated diene-based polymer comprises: a polymer chain comprising a repeating unit derived from a conjugated diene-based monomer; a modified monomer-derived unit represented by chemical formula 1; and a denaturant-derived functional group, wherein the modified monomer-derived unit is bonded to the polymer chain at least at one end thereof, and the denaturant-derived functional group is bonded to the modified monomer-derived unit bonded to the end of the polymer chain.

Description

Modified conjugated diene-based polymer, a method for producing the same, and a rubber composition containing the same TECHNICAL FIELD {MODIFIED CONJUGATED DIENE POLYMER, PREPARING METHOD THEREOF AND RUBBER COMPOSITION COMPRISING THE SAME}

The present invention relates to a modified conjugated diene polymer having excellent processability and excellent tensile strength and viscoelastic properties, a method for preparing the same, and a rubber composition including the same.

In recent years, in accordance with the demand for low fuel consumption for automobiles, a conjugated diene-based polymer having low rolling resistance, excellent abrasion resistance, and tensile properties as a rubber material for tires, and also having adjustment stability typified by wet road surface resistance is required.

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

As a rubber material having a low hysteresis loss, natural rubber, polyisoprene rubber, polybutadiene rubber, and the like are known, but these have a problem of low resistance to wet road surfaces. 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) are 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 vinyl structure content and styrene content that define rubber properties can be arbitrarily adjusted, and molecular weight and physical properties can be adjusted by coupling or modification. Is that it can be adjusted. Therefore, it is easy to change the structure of the final manufactured SBR or BR, reduce the movement of the chain ends by bonding or denaturation of the chain ends, and increase the bonding strength with fillers such as silica or carbon black. It is widely used as a rubber material.

When such a solution-polymerized SBR is used as a rubber material for a tire, the glass transition temperature of the rubber can be increased by increasing the vinyl content in the SBR, so that the required properties of the tire such as running resistance and braking force can be adjusted, as well as the glass transition temperature. Fuel consumption can be reduced by appropriate control. The solution polymerization SBR is prepared using an anionic polymerization initiator, and a technique of introducing a functional group at the terminal by bonding or denaturing the chain ends of the formed polymer using various modifiers is used. For example, U.S. Patent No. 4,397,994 proposes a technique in which the 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 bound using a binder such as a tin compound. I did.

On the other hand, as a modifier for introducing a functional group at the end of the polymer chain, a technique of applying an aminoalkoxysilane group modifier including an alkoxysilane group and an amine group in the molecule at the same time in order to maximize the powdery properties 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 polymer production decreases, and thus it is difficult to easily perform the modification reaction.

US 4397994 A

The present invention was conceived to solve the problems of the prior art, including a unit derived from a modified monomer containing an amine group in the polymer chain and at least at one end, and bonded to the end of the polymer chain to which the unit derived from the modified monomer is bonded. An object of the present invention is to provide a modified conjugated diene polymer having more excellent affinity with a filler containing a functional group derived from a denaturing agent.

In addition, the present invention polymerizes in the presence of a polymerization initiator and a modified monomer to prepare an active polymer chain including a unit derived from a modified monomer at one end, and the other end of the active polymer chain with a modified monomer before the reaction with a modifying agent. An object of the present invention is to provide a method of preparing the modified conjugated diene-based polymer comprising the step of capping.

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

According to an embodiment of the present invention for solving the above problems, the present invention is a polymer chain comprising a repeating unit derived from a conjugated diene-based monomer; A unit derived from a modified monomer represented by the following formula (1); And a functional group derived from a denaturant, wherein the unit derived from the modified monomer is bonded to the polymer chain and at least one end thereof, and the functional group derived from the modifying agent is bonded to a unit derived from the modified monomer bonded to the end of the polymer chain. Based polymers are provided:

[Formula 1]

In Formula 1,

R ₁ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,

R ₂ is a single bond or a substituted or unsubstituted C 1 to C 20 alkylene group with a substituent,

R ₃ and R ₄ are each independently a substituent substituted or unsubstituted C 1 to C 20 alkyl group, a C 3 to C 20 cycloalkyl group or a C 6 to C 30 aryl group,

The substituent is one or more selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms.

In addition, the present invention is a step of polymerizing a first modified monomer and a conjugated diene-based monomer or a conjugated diene-based monomer and an aromatic vinyl-based monomer in a carbon solvent in the presence of a polymerization initiator to prepare an active polymer chain containing a unit derived from a modified monomer ( S1); Adding and reacting a second modified monomer to the active polymer chain to prepare a capped polymer chain by capping the end with a unit derived from the second modified monomer (S2); And adding and reacting a denaturant to the capped polymer chain (S3), wherein the step (S1); Step (S2); Step (S3) is carried out continuously, the second modified monomer is added at the time when the polymerization conversion rate in step (S1) is 90% or more, and the modifying agent is added at the time when the polymerization conversion rate in step (S2) is 90% or more. And the first and second modified monomers are compounds represented by the following formula (1), and a method of preparing the modified conjugated diene-based polymer is provided.

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

The modified conjugated diene-based polymer according to the present invention includes a functional group derived from a denaturant, and a unit derived from a modified monomer is included in the polymer chain and at least at one end separately from the functional group derived from the denaturant, thereby having excellent affinity with a filler. .

The method for preparing a modified conjugated diene-based polymer according to the present invention comprises the step of carrying out a polymerization reaction by using a modified monomer containing an amine group during the polymerization reaction, and capping the polymer chain before the reaction with a modifying agent with a modified monomer. Separately, an amine group can be introduced into the polymer, thereby solving the difficulty of the denaturation reaction due to the amine group in the denaturant, and as a result, a highly modified modified conjugated diene-based polymer can be prepared.

In addition, the rubber composition according to the present invention has excellent tensile properties and viscoelastic properties by including the modified conjugated diene-based polymer.

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

Terms and words used in the description and claims of the present invention should not be construed as being limited to their usual or dictionary meanings, and the inventors appropriately explain the concept of terms in order to explain their own invention in the best way. Based on the principle that it can be defined, it should be interpreted as a meaning and concept consistent with the technical idea of the present invention.

In the present invention, the term'polymer chain' may mean that units derived from monomers are repeatedly linked by polymerization of one or more monomers.

In the present invention, the term'substitution' may mean that a functional group, an atomic group, or hydrogen of a compound is substituted with a specific substituent. When a functional group, an atomic group, or hydrogen of a compound is substituted with a specific substituent, the functional group, atomic group, or compound Depending on the number of hydrogens present, one or two or more of a plurality of substituents may be present, and when a plurality of substituents are present, each of the substituents may be the same or different from each other.

In the present invention, the term'alkyl group' may mean a monovalent saturated aliphatic hydrocarbon, and may include linear alkyl groups such as methyl, ethyl, propyl, and butyl; Branched alkyl groups such as isopropyl, sec-butyl, tert-butyl, and neo-pentyl; And a cyclic saturated hydrocarbon, or a cyclic unsaturated hydrocarbon containing one or two or more unsaturated bonds.

In the present invention, the term'alkylene group' may mean a divalent saturated aliphatic hydrocarbon such as methylene, ethylene, propylene, and butylene.

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

In the present invention, the term'aryl group' may mean a cyclic aromatic hydrocarbon, and also a monocyclic aromatic hydrocarbon having one ring formed, or a polycyclic aromatic hydrocarbon having two or more rings bonded thereto. hydrocarbon) may be included.

In the present invention, the term'aralkyl' is also called aralkyl and may mean a combination of an alkyl group and an aryl group formed by replacing a hydrogen atom bonded to a carbon constituting an alkyl group with an aryl group.

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

In the present invention, the terms "derived unit", "derived repeating unit" and "derived functional group" may refer to a component, structure, or the substance itself derived from a substance.

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

The modified conjugated diene-based polymer according to an embodiment of the present invention includes a polymer chain including a repeating unit derived from a conjugated diene-based monomer; A unit derived from a modified monomer represented by the following formula (1); And a functional group derived from a modifier, wherein the unit derived from the modified monomer is bonded to the polymer chain and at least at one end thereof, and the functional group derived from the modifying agent is bonded to a unit derived from the modified monomer bonded to an end of the polymer chain.

[Formula 1]

In Formula 1,

R ₁ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,

R ₂ is a single bond or a substituted or unsubstituted C 1 to C 20 alkylene group with a substituent,

R ₃ and R ₄ are each independently a substituent substituted or unsubstituted C 1 to C 20 alkyl group, a C 3 to C 20 cycloalkyl group or a C 6 to C 30 aryl group,

The substituent is one or more selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms.

The modified conjugated diene-based polymer according to an embodiment of the present invention is prepared by a method described below including reacting a modified monomer containing an amine group during polymerization and before a modification reaction through a reaction with a denaturant. Through this, a modified monomer-derived unit is bonded to the polymer chain including the conjugated diene-based monomer-derived repeating unit and at least at one end, and the modifier-derived functional group is bonded to the modified monomer-derived unit bonded to the polymer chain end. It may be a highly modified copolymer.

The modified monomer is a compound represented by Formula 1, in Formula 1, R ₁ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ₂ is a single bond or an unsubstituted alkylene group having 1 to 10 carbon atoms, and R ₃ And R ₄ may be independently of each other an unsubstituted alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and more specifically, in Formula 1, R ₁ is a hydrogen atom, R ₂ is a single bond, and R ₃ and R ₄ may each independently be an unsubstituted alkyl group having 1 to 10 carbon atoms.

According to an embodiment of the present invention, the modified conjugated diene-based polymer is a polymer chain including a repeating unit derived from a conjugated diene-based monomer, a unit derived from a modified monomer bonded to the polymer chain, and a functional group derived from a modifying agent bonded to the unit derived from the modified monomer. In this case, the modified monomer-derived unit is bonded to at least one end of the polymer chain and the polymer chain, and the functional group derived from the modifying agent is bonded to a unit derived from a modified monomer bonded to the polymer chain end, Here, the repeating unit derived from the conjugated diene-based monomer may mean a repeating unit formed when the conjugated diene-based monomer is polymerized, and the functional group derived from the denaturant and the unit derived from the modified monomer are functional groups derived from the denaturant and units derived from the modified monomer, respectively. Can mean

In addition, according to another embodiment of the present invention, the modified conjugated diene-based polymer is a copolymer comprising a repeating unit derived from a conjugated diene-based monomer, a repeating unit derived from an aromatic vinyl-based monomer, a functional group derived from a modifying agent, and a unit derived from a modified monomer. In this case, the modified monomer-derived unit is bonded to and at least one end of a polymer chain including a repeating unit derived from a conjugated diene-based monomer and a repeating unit derived from an aromatic vinyl-based monomer, and the functional group derived from the modifier is at the end of the polymer chain. It may be bonded to the unit derived from the modified monomer to be bonded.

That is, the modified conjugated diene-based polymer according to an embodiment of the present invention includes a unit derived from a modified monomer in the polymer chain and at least at one end, and a unit derived from a modified monomer and a functional group derived from a modifying agent are included at at least one end of the polymer chain. It can be. Accordingly, the modified conjugated diene-based polymer according to an embodiment of the present invention may further include an amine group derived from a modified monomer in addition to a functional group derived from a modifying agent.

According to an embodiment of the present invention, the conjugated diene-based monomer is 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, 2 -Phenyl-1,3-butadiene and 2-halo-1,3-butadiene (halo means a halogen atom) may be one or more selected from the group consisting of.

The aromatic vinyl 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-pyrrolidino ethyl) styrene (3-(2-pyrrolidino ethyl) styrene), 4-(2-pyrrolidino ethyl) styrene (4-(2-pyrrolidino) ethyl)styrene) and 3-(2-pyrrolidino-1-methyl ethyl)-α-methylstyrene (3-(2-pyrrolidino-1-methyl ethyl)styrene).

As another example, 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 a repeating unit derived from the conjugated diene-based monomer. The diene-based monomer-derived repeating unit 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 a diene-based monomer-derived repeating unit in excess of 0% to 1% by weight, more than 0% to 0.1% by weight, It may be included in an amount exceeding 0% by weight to 0.01% by weight, or exceeding 0% by weight to 0.001% by weight, and there is an effect of preventing gel formation within this range.

According to an embodiment of the present invention, the polymer chain may be a random copolymer chain, and in this case, there is an effect of having an excellent balance between physical properties. The random copolymer may mean that the repeating units constituting the copolymer are randomly arranged.

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 /mol, a weight average molecular weight (Mw) of 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, and a peak average molecular weight (Mp) may be 1,000 g/mol to 3,000,000 g/mol, 10,000 g/mol to 2,000,000 g/mol, or 100,000 g/mol to 2,000,000 g/mol. Within this range, there are excellent effects of rolling resistance and wet road surface resistance.

In another example, the modified conjugated diene-based polymer may have a molecular weight distribution (PDI; MWD; Mw/Mn) of 1.0 or more and less than 1.7, or 1.1 or more and less than 1.7, or 1.2 or more and 1.6 or less, and within this range, tensile properties and viscoelasticity It has excellent properties and has an excellent balance between physical properties.

As another example, the modified conjugated diene-based polymer may have a Mooney relaxation rate measured at 100°C of 0.7 or more, 0.7 or more and 3.0 or less, 0.7 or more and 2.5 or less, or 0.7 or more and 2.0 or less.

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

On the other hand, the Mooney relaxation rate can be used as an index of the branched structure of the polymer. For example, when a polymer having an equivalent Mooney viscosity is compared, the Mooney relaxation rate decreases as the number of branches increases, so it can be used as an index of branching.

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

Here, the Mooney viscosity may be measured using a Mooney viscometer. Specifically, using a large rotor of Monsanto's MV2000E, under the conditions of 100°C and a rotor speed of 2±0.02 rpm, leave the polymer at room temperature (23±5°C) for 30 minutes or more, and then collect 27±3 g to the inside of the die cavity. It was measured while filling in and applying torque by operating a platen.

As another example, the modified conjugated diene-based polymer may have an N content of 200 ppm or more, 200 ppm to 10,000 ppm, or 100 ppm to 5,000 ppm, based on the total weight, and including a modified conjugated diene-based polymer within this range. The rubber composition has excellent mechanical properties such as tensile properties and viscoelastic properties. The N content may mean the content of N atoms present in the modified conjugated diene-based polymer, wherein the N atom may be derived from a modified monomer and a denaturant.

The N content may be measured using an NSX analysis method as an example, and the NSX analysis method may be measured using a trace nitrogen quantitative analyzer (NSX-2100H).

For example, when using the trace nitrogen quantitative analyzer, turn on the trace nitrogen quantitative analyzer (Auto sampler, Horizontal furnace, PMT & Nitrogen detector), Ar 250 ml/min, O ₂ 350 ml/min, ozonizer 300 ml/ After setting the carrier gas flow rate in min, and setting the heater to 800°C, wait for about 3 hours to stabilize the analyzer. After the analyzer is stabilized, use the Nitrogen standard (AccuStandard S-22750-01-5 ml) to prepare calibration curves for the ranges of 5 ppm, 10 ppm, 50 ppm, 100 ppm and 500 ppm, and obtain the area corresponding to each concentration. After that, a straight line was created using the ratio of the density to the area. Thereafter, a ceramic boat containing 20 mg of a sample was placed on the auto sampler of the analyzer and measured to obtain an area. The N content was calculated using the obtained sample area and the calibration curve.

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

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

In addition, the modifier according to the present invention may be a modifier for modifying at least one end of a polymer chain including a repeating unit derived from a conjugated diene-based monomer, and a specific example may be a silica affinity modifier. The silica-affinity modifier may mean a modifier containing a silica-affinity functional group in a compound used as a modifier, and the silica-affinity functional group has excellent affinity with a filler, particularly a silica-based filler, It may mean a functional group capable of interaction between the functional groups derived from the denaturant.

Specifically, according to an embodiment of the present invention, the denaturant may be one or more selected from compounds represented by the following Chemical Formula 2 or Chemical Formula 3.

[Formula 2]

In Chemical Formula 2,

R _a1 and R _a4 are each independently a single bond or an alkylene group having 1 to 10 carbon atoms, R _a2 and R _a3 are each independently an alkyl group _{having 1 to 10 carbon atoms, and R a5} is a hydrogen atom, a C 1 to C 10 alkyl group. An alkyl group or a divalent, trivalent or tetravalent alkylsilyl group substituted with an alkyl group or an alkyl group having 1 to 10 carbon atoms, n ₁ is an integer of 1 to 3, n ₂ is an integer of 0 to 2,

[Formula 3]

In Formula 3, A ₁ and A ₂ are each independently an alkylene group having 1 to 20 carbon atoms, R _b1 to R _b4 are each independently an alkyl group having 1 to 20 carbon atoms, and L ₁ to L ₄ are independently of each other It is a divalent, trivalent, or tetravalent alkylsilyl group substituted with an alkyl group having 1 to 20, an aryl group having 6 to 20 carbon atoms, or an alkyl group having 1 to 10 carbon atoms.

Specifically, the modifier according to an embodiment of the present invention may be a compound represented by Formula 2, and in Formula 2, R _a1 and R _a4 are each independently a single bond or an alkylene group having 1 to 5 carbon atoms, R _a2 and R _a3 are each independently an alkyl group having 1 to 5 carbon atoms, Ra ₅ may be a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a tetravalent alkylsilyl group substituted with an alkyl group having 1 to 5 carbon atoms, and n ₁ is It is an integer of 2 or 3, and n ₂ may be an integer of 0 to 2.

More specifically, the compound represented by Formula 2 is N,N-bis(3-(dimethoxy(methyl)silyl)propyl)-methyl-1-amine (N,N-bis(3-(dimethoxy(methyl) silyl)propyl)-methyl-1-amine), N,N-bis(3-(diethoxy(methyl)silyl)propyl)-methyl-1-amine (N,N-bis(3-(diethoxy(methyl)) silyl)propyl)-methyl-1-amine), N,N-bis(3-(trimethoxysilyl)propyl)-methyl-1-amine (N,N-bis(3-(trimethoxysilyl)propyl)-methyl -1-amine), N,N-bis(3-(triethoxysilyl)propyl)-methyl-1-amine (N,N-bis(3-(triethoxysilyl)propyl)-methyl-1-amine), N,N-diethyl-3-(trimethoxysilyl)propan-1-amine (N,N-diethyl-3-(trimethoxysilyl)propan-1-amine), N,N-diethyl-3-(tri Ethoxysilyl) propan-1-amine (N,N-diethyl-3-(triethoxysilyl)propan-1-amine), tri(trimethoxysilyl)amine, tri(3-(tri Methoxysilyl)propyl)amine (tri-(3-(trimethoxysilyl)propyl)amine) and N,N-bis(3-(diethoxy(methyl)silyl)propyl)-1,1,1-trimethylsilaneamine ( It may be one or more selected from the group consisting of N,N-bis(3-(diethoxy(methyl)silyl)propyl)-1,1,1-trimethlysilanamine).

In addition, the modifier according to another embodiment of the present invention may be a compound represented by Formula 3, in Formula 3, A ₁ and A ₂ are independently of each other an alkylene group having 1 to 10 carbon atoms, and R _b1 to R _b4 are each independently an alkyl group having 1 to 10 carbon atoms, and L ₁ to L ₄ are independently of each other a tetravalent alkyl substituted with an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms It may be a silyl group.

More specifically, the compound represented by Formula 3 is 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine) (3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine), 3,3'-(1,1,3,3- Tetraethoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine)(3,3'-(1,1,3,3-tetraethoxydisiloxane-1,3-diyl)bis( N,N-dimethylpropan-1-amine), 3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine) (3,3'-(1,1,3,3-tetrapropoxydisiloxane-1,3-diyl)bis(N,N-dimethylpropan-1-amine), 3,3'-(1,1,3,3- Tetramethoxydisiloxane-1,3-diyl)bis(N,N-diethylpropan-1-amine)(3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis( N,N-diethylpropan-1-amine), 3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,N-dipropylpropan-1-amine) (3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(N,Ndimpropylpropan-1-amine), 3,3'-(1,1,3,3-tetrae Oxydisiloxane-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-diethylmethane-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 Oxydisiloxane-1,3-diyl)bis(N,N-diethylmethane-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-dipropylmethane-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-dimethylmethane-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-dipropylmethane-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- Amin)(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-tetraprotooxide 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), and 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 It may be one or more selected from the group consisting of -1,3-diyl)bis(propan-3,1-diyl))bis(1,1,1-trimethyl-N-phenylsilanamine).

The modified conjugated diene-based polymer according to an embodiment of the present invention may have more excellent affinity with the filler by including a large number of amine groups having excellent affinity with the filler in the polymer molecule. Processability, tensile properties and viscoelastic properties can be excellent in balance.

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

The method for preparing the modified conjugated diene-based polymer according to an embodiment of the present invention is a modified monomer by polymerizing a first modified monomer and a conjugated diene-based monomer or a conjugated diene-based monomer and an aromatic vinyl-based monomer in a carbon solvent in the presence of a polymerization initiator. Preparing an active polymer chain containing the derived unit (S1); Adding and reacting a second modified monomer to the active polymer chain to prepare a capped polymer chain by capping the end with a unit derived from the second modified monomer (S2); And adding and reacting a denaturant to the capped polymer chain (S3), wherein the step (S1); Step (S2); Step (S3) is carried out continuously, the second modified monomer is added at the time when the polymerization conversion rate in step (S1) is 90% or more, and the modifying agent is added at the time when the polymerization conversion rate in step (S2) is 90% or more. The first and second modified monomers are characterized in that they are compounds represented by the following formula (1).

[Formula 1]

In Formula 1, R ₁ to R ₄ are as defined above, and the modifier is as described above.

In the first and second modified monomers,'first' and'second' are used to distinguish the input point of the modified monomer in the manufacturing method, and the first and second modified monomers are the same modified monomer. Is to mean.

The first modified monomer and the second modified monomer may be used in an amount of 0.1 to 50 mol relative to 1 mol of the polymerization initiator, respectively.

The hydrocarbon solvent is not particularly limited, but may be, for example, one or more 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-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium , Naphthyl sodium, naphthyl potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide and lithium isopropylamide It can be more than that.

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

The polymerization in step (S1) may be an anionic polymerization as an example, and a specific example may be a living anionic polymerization having an anionic active site at the polymerization end by a growth polymerization reaction by an anion. In addition, the polymerization in step (S1) may be elevated temperature polymerization, isothermal polymerization, or constant temperature polymerization (insulation polymerization), and the constant temperature polymerization includes polymerization by self-reaction heat without optionally applying heat after the polymerization initiator is added. It may mean a polymerization method, and the elevated-temperature polymerization may mean a polymerization method in which heat is arbitrarily applied after the polymerization initiator is added to increase the temperature, and the isothermal polymerization is heated by applying heat after the polymerization initiator is added. It may mean a polymerization method in which the temperature of the polymerized product is kept constant by increasing or taking away heat.

In addition, according to an embodiment of the present invention, the polymerization in step (S1) may further include a diene-based compound having 1 to 10 carbon atoms in addition to the conjugated diene-based monomer. There is an effect of preventing this formation. As an example of the diene-based compound, it may be 1,2-butadiene.

The polymerization of step (S1) may be carried out in a temperature range of 80° C. or less, -20° C. to 80° C., 0° C. to 80° C., 0° C. to 70° C., or 10° C. to 70° C., for example, and this range By narrowly controlling 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 include the unit derived from the modified monomer, and in another example, the active polymer chain includes a unit derived from the modified monomer at one end, and the polymer anion and organic at the other end. It may be a polymer to which a metal cation is bound.

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

The polar additives include, 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. , Tertiary butoxyethoxyethane, bis(3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine, N,N,N',N'-tetramethyl It may be one or more selected from the group consisting of ethylenediamine, sodium mentholate, and 2-ethyl tetrahydrofurfuryl ether, preferably 2,2-di(2-tetrahydro Furyl) propane, triethylamine, tetramethylethylenediamine, sodium mentholate, or 2-ethyl tetrahydrofurfuryl ether, and when the polar additive is included, a conjugated diene-based When a monomer and an aromatic vinyl-based monomer are copolymerized, there is an effect of inducing a random copolymer to be easily formed by compensating for a difference in reaction rate thereof.

In addition, the step (S2) is to prepare a capped active polymer chain by reacting the active polymer chain including the unit derived from the first modified monomer with the second modified monomer to cap the end of the polymer chain with the unit derived from the second modified monomer. As a step for, by adding and reacting a second modified monomer to the active polymer chain, an active polymer chain in which the other end of the active polymer chain is capped with a unit derived from the second modified monomer may be prepared.

The step (S3) is a step for preparing a modified conjugated diene-based polymer by reacting the capped active polymer chain with a denaturant, wherein the reaction may be a denaturation or a coupling reaction, wherein the denaturant is a total of 100 g of monomers It can be used in an amount of 0.01 mmol to 10 mmol based on. As another example, the modifier may be used in a molar ratio of 1:0.1 to 10, 1: 0.1 to 5, or 1:0.1 to 1:3, based on 1 mole of the polymerization initiator in step (S1).

In addition, according to an embodiment of the present invention, the method for preparing the modified conjugated diene-based polymer may be carried out by a continuous polymerization method in a plurality of reactors including two or more polymerization reactors and a modification reactor. As a specific example, the (S1) step, (S2) step a and (S3) step are continuously carried out, the modified monomer is added at a time when the polymerization conversion rate of step (S1) is 90% or more, and the modifier is (S2) It may be added and performed at the time when the polymerization conversion rate of the step) is 90% or more.

Meanwhile, the number of polymerization reactors may be flexibly determined according to reaction conditions and environments. The continuous polymerization method may refer to a reaction process in which a reactant is continuously supplied to a reactor and the produced reaction product is continuously discharged. In the case of the above-described continuous polymerization method, there is an effect of excellent productivity and processability, and excellent uniformity of the polymer to be produced.

At this time, the polymerization conversion rate may be adjusted according to the reaction temperature, the residence time of the reactor, and the like.

The polymerization conversion rate may be determined by measuring the solid concentration in the polymer solution containing the polymer, for example, during polymerization of the polymer.For example, in order to secure the polymer solution, a cylindrical container is mounted at the outlet of each polymerization reactor to A positive polymer solution was filled in a cylindrical container, the cylindrical container was separated from the reactor, and the weight (A) of the cylinder filled with the polymer solution was measured, and then the polymer solution filled in the cylindrical container was added to an aluminum container, For example, transfer to an aluminum dish and measure the weight (B) of a cylindrical container from which the polymer solution has been removed, and dry the aluminum container containing the polymer solution in an oven at 140° C. for 30 minutes, and determine the weight (C) of the dried polymer. After measurement, it may be calculated according to Equation 1 below.

[Equation 1]

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

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

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

The rubber component may be, for example, natural rubber or synthetic rubber, and specific examples include natural rubber (NR) including cis-1,4-polyisoprene; Modified natural rubber such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), hydrogenated natural rubber, etc. obtained by modifying or purifying the general natural rubber; Styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, polyisobutylene-co-isoprene, neoprene, poly(ethylene-co- Propylene), poly(styrene-co-butadiene), poly(styrene-co-isoprene), poly(styrene-co-isoprene-co-butadiene), poly(isoprene-co-butadiene), poly(ethylene-co-propylene -Co-diene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, halogenated butyl rubber, and the like, and any one or a mixture of two or more of them 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 a silica-based filler as an example, and a specific example may be wet silica (hydrous silicic acid), dry silica (silicic anhydride), calcium silicate, aluminum silicate, or colloidal silica, and preferably, the effect of improving fracture properties and wet It may be wet-type silica that has the best effect of both 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 properties may be used together, and as a specific example, the silane coupling agent is bis(3-triethoxysilylpropyl)tetrasulfide. , Bis(3-triethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis(2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilyl) Propyl) tetrasulfide, bis(2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide Feed, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilylpropylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzolyltetrasulfide, 3-triethoxysilylpropylmethacrylate monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, bis(3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethyl Silane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, dimethoxymethylsilylpropylbenzothiazolyltetrasulfide, and the like, and any one or a mixture of two or more of them may be used. Preferably, when considering the effect of improving reinforcing properties, it may be bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide.

In addition, in the rubber composition according to an embodiment of the present invention, since a modified conjugated diene-based polymer in which a functional group having high affinity with silica is introduced as a rubber component is used, the amount of the silane coupling agent is usually It may be less 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 While sufficiently exerted, there is an effect of preventing the gelation of the rubber component.

The rubber composition according to an embodiment of the present invention may be sulfur crosslinkable, and may further include a vulcanizing agent. The vulcanizing agent may specifically be a sulfur powder, and may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the rubber component, within this range, while securing the required elastic modulus and strength of the vulcanized rubber composition, and at the same time having low fuel economy. It has an excellent effect.

In addition to the above components, the rubber composition according to an embodiment of the present invention includes various additives commonly used in the rubber industry, specifically, a vulcanization accelerator, a process oil, an antioxidant, a plasticizer, an anti-aging agent, an anti-scorch agent, and zinc. white), stearic acid, a thermosetting resin, or a thermoplastic resin.

The vulcanization accelerator is, for example, a thiazole compound such as M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazylsulfenamide), or DPG A guanidine-based compound such as (diphenylguanidine) may be used, and may be included in an amount of 0.1 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, and when considering tensile strength and abrasion resistance, when considering aromatic process oil price, hysteresis loss, and low-temperature characteristics Naphthenic or paraffinic process oil may be used. For example, 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, and within this range, there is an effect of preventing a decrease in tensile strength and low heat generation (low fuel economy) of the vulcanized rubber.

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 anti-aging agent 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 condensation product of diphenylamine and acetone, and the like, and may be used in an amount of 0.1 to 6 parts by weight based on 100 parts by weight of the rubber component.

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

Accordingly, the rubber composition is a tire tread, under tread, side wall, carcass coated rubber, belt coated rubber, bead filler, pancreas, or bead coated rubber, and other tire members, anti-vibration rubber, belt conveyor, hose, etc. It may be useful in the manufacture of various industrial rubber products.

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

The tire may include a tire or a tire tread.

Hereinafter, examples will be described in detail to illustrate the present invention in detail. However, the embodiments 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 embodiments described below. The embodiments of the present invention are provided to more completely describe the present invention to those of ordinary skill in the art.

Manufacturing Example 1

0.51 mol of 4-methyl benzaldehyde and dimethylformamide were added to a 2 L round-bottom flask, the 4-methyl benzaldehyde was dissolved, and 240 g (1.73 mol) of potassium carbonate was added, followed by stirring at 80° C. for 1 hour. . Then, 0.62 mol of N-chloro-N,N-methylmethanamine hydrochloride was slowly added dropwise and reacted at the same temperature for 15 hours. After the reaction was completed, the solid was removed using a filter, ethyl acetate was added, and then washed several times with a saturated NaCl aqueous solution. Thereafter, the organic layer was dried over anhydrous magnesium sulfate, and the solid was removed using a filter, and the organic solvent was removed under reduced pressure to prepare 4-(dimethylamino)benzaldehyde.

Then, 300 g (0.84 mol) of methyl triphenylphosphonium bromide and tetrahydrofuran (THF) were added, and 190 g (1.69 mol) of porassium t-butoxide was added dropwise in an ice bath. After stirring at room temperature for 30 minutes, 0.67 mol of 4-(dimethylamino)benzaldehyde prepared above was dissolved in THF, slowly added dropwise, and reacted at room temperature for 3 hours. After completion of the reaction, THF was distilled under reduced pressure, water was added, and extracted with methylene chloride, the organic layer was dried over anhydrous magnesium sulfate, and the solid was removed using a filter. The organic solvent was removed under reduced pressure, and 4-(dimethylamino)styrene (N,N-dimethyl-4-vinylaniline) was prepared.

Manufacturing Example 2

(3-chloropropyl) dimethoxymethylsilane (CAS No. 18171-19-2@Sigma-Aldrich, 1.83 g, 10 mmol) and diethylamine (0.8 g, 11 mmol) at room temperature (23℃±3℃) After completely dissolving by stirring in 100 ml of toluene, 3-(dimethoxy(methyl)silyl)N,N-diethylpropan-1-amine (3-(dimethoxy(methyl)silyl) was stirred under reflux for 2 hours at 110°C. -N,N-diethylpropane-1-amine) was prepared (yield: 2.5 g, >98%)

Manufacturing Example 3

33.9 g (0.2 mol) of diallyl trimethylsilylamine and 0.26 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyl disiloxane complex (platinum content 3% by mass) were added, and It was heated to 70°C. After the temperature in the reactor was stabilized, 53.7 g (0.4 mol) of methyldiethoxysilane was added dropwise for 4 hours, and reacted at this temperature for 1 hour to produce N,N-bis(3-(diethoxy(methyl)silyl)propyl )-1,1,1-trimethylsilaneamine (N,N-bis(3-(diethoxy(methyl)silyl)propyl)-1,1,1-trimethylsilamine) 58.1g was prepared.

Manufacturing Example 4

3,3'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(propan-1-amine) (CAS No. 76712-65-7@LookChem, 3.13 g, 10 mmol ) Was completely dissolved by stirring in 100 ml of toluene at room temperature (23° C.±3° C.), and then trimethylsilyl chloride (1.14 g, 10.5 mmol) and 2 at 40° C. in the presence of triethylamine (1.11 g, 11 mmol) as a base Reaction for a period of time N,N'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethylsilyl )Silanamine (N,N'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1,1,1-trimethyl-N-( trimethylsilyl)silanamine)) was prepared (yield: 5.6 g, >98%).

Example 1

0.375 kg/h of a styrene solution in which 60% by weight of styrene is dissolved in n-hexane and 60% by weight of 1,3-butadiene in n-hexane in the first reactor among the continuous reactors in which the three reactors are connected in series 1,3-butadiene solution dissolved in 1.4 kg/h, a modified monomer solution 31.8 g/h in which 4-(dimethylamino) styrene prepared in 1 was dissolved in 4 wt% in n-hexane as a modified monomer , n-hexane 5.1 kg/h, a solution in which 2,2-(di-2(tetrahydrofuryl)propane was dissolved in 1.2% by weight in n-hexane as a polar additive was 100.0 g/h, n- in n-hexane An n-butyllithium solution in which 1.1% by weight of butyllithium was dissolved was injected at a rate of 39.8 g/h At this time, the temperature of the first reactor was maintained at 50°C, and the polymerization conversion rate reached 100%. , Through the transfer pipe, the polymer was transferred from the first reactor to the second reactor.

Subsequently, a modified monomer solution in which 4% by weight of the modified monomer was dissolved in n-hexane was injected into the second reactor at a rate of 31.8 g/h. At this time, the temperature of the second reactor was maintained at 50°C, and when the polymerization conversion rate reached 100%, the polymer was transferred from the second reactor to the third reactor through a transfer pipe.

The polymer was transferred from the second reactor to the third reactor, and 3-(dimethoxy(methyl)silyl)-N,N-diethylpropan-1-amine (3-(dimethoxy(methyl)) prepared in Preparation Example 1 as a denaturant. )silyl)-N,N-diethylpropane-1-amine) dissolved in 2% by weight was added to the third reactor at a rate of 100.0 g/h. The temperature of the third reactor was maintained at 65°C.

Thereafter, a solution of IR1520 (BASF) dissolved in 30% by weight as an antioxidant was injected into the polymerization solution discharged from the third reactor at a rate of 17 g/h, followed by stirring. The resulting polymer was put in hot water heated with steam and stirred to remove the solvent to prepare a modified conjugated diene-based polymer.

Example 2

In Example 1, N,N-bis(3-(diethoxy(methyl)silyl)propyl)-1,1,1-trimethylsilaneamine (N,N-bis(3) prepared in Preparation Example 2 as a modifier) -(diethoxy(methyl)silyl)propyl)-1,1,1-trimethylsilamine) was added to the third reactor at a rate of 64.0 g/h, except that a solution in which 20% by weight was dissolved was added to the third reactor. In the same manner, a modified styrene-butadiene copolymer was prepared.

Example 3

In Example 1, N,N'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(propane-3,1-diyl) prepared in Preparation Example 3 as a denaturing agent) Bis(1,1,1-trimethylsilyl)silanamine (N,N'-(1,1,3,3-tetramethoxydisiloxane-1,3-diyl)bis(propane-3,1-diyl))bis(1 ,1,1-trimethyl-N-(trimethylsilyl)silanamine)) was added to the third reactor at a rate of 64.0 g/h, except that a solution in which 20% by weight was dissolved was added to the third reactor. , A modified styrene-butadiene copolymer was prepared.

Comparative Example 1

In Example 1, a modified conjugated diene-based polymer was prepared in the same manner as in Example 1, except that a modified monomer was not used.

Comparative Example 2

In Example 1, except that a 1,3-butadiene solution in which 60% by weight of 1,3-butadiene was dissolved in n-hexane was injected into the second reactor at a rate of 2.96 kg/h instead of the modified monomer solution. Was carried out in the same manner as in Example 1 to prepare a modified conjugated diene-based polymer.

Comparative Example 3

In Example 1, a modified conjugated diene-based polymer was prepared in the same manner as in Example 1, except that the modified monomer solution was not added to the first reactor.

Reference example

In Example 1, an Example except that 0.410 kg/h of a 1,3-butadiene solution in which 60% by weight of 1,3-butadiene was dissolved in n-hexane was injected into the second reactor together with a modified monomer solution. In the same manner as in 1, a modified conjugated diene-based polymer was prepared.

Experimental Example 1

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

1) Styrene unit and vinyl content (% by weight)

The contents of styrene units (SM) and vinyl (Vinyl) in each of the polymers were measured and analyzed using Varian VNMRS 500 MHz NMR.

In the NMR measurement, 1,1,2,2-tetrachloroethane was used as the solvent, and the solvent peak was calculated as 5.97 ppm, 7.2 to 6.9 ppm was random styrene, 6.9 to 6.2 ppm was block styrene, and 5.8 to 5.1 ppm was 1,4-vinyl, 5.1 to 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 weight average molecular weight (Mw) and number average molecular weight (Mn) were measured through GPC (Gel permeation Chromatography) analysis, and a molecular weight distribution curve was obtained. In addition, the molecular weight distribution (PDI, MWD, Mw/Mn) was obtained by calculating from the measured molecular weights. Specifically, the GPC is used by combining two columns of PLgel Olexis (Polymer Laboratories) and one column of PLgel mixed-C (Polymer Laboratories), and when calculating the molecular weight, the GPC standard material is PS (polystyrene). It was carried out using. The GPC measurement solvent was prepared by mixing 2% by weight of an amine compound in tetrahydrofuran.

3) Mooney viscosity and Mooney relaxation rate

The Mooney viscosity (MV, (ML1+4, @100°C) MU) was measured using a Rotor Speed 2±0.02 rpm, Large Rotor at 100°C using MV-2000 (ALPHA Technologies). Samples were left at room temperature (23±3°C) for at least 30 minutes, and then 27±3 g was collected, filled in the die cavity, and platen was operated to measure for 4 minutes.

After the Mooney viscosity measurement, the slope value of the Mooney viscosity change that appears as the torque is released was measured to obtain the Mooney relaxation rate, which is its absolute value.

4) N content

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

division Example Reference example Comparative example One 2 3 One 2 3 NMR
(weight%) SM 21 21 21 21 21 21 21 Vinyl 50 50 50 50 50 50 50 GPC Mw(X10 ³ g/mol) 466 460 455 453 461 460 466 Mn(X10 ³ g/mol) 310 305 301 310 309 310 302 Mp(X10 ³ g/mol) 430 424 425 450 431 425 423 PDI 1.50 1.51 1.51 1.46 1.49 1.48 1.54 Mooney viscosity (MV) 64 68 67 57 53 60 58 Mooney mitigation rate 1.0024 1.0057 1.0088 1.0653 1.0022 1.1502 1.0091 N content (ppm) 264 288 287 268 126 149 151

As can be seen from Table 1 above, Examples 1 to 3 showed a significant increase in the N content in the molecule compared to Comparative Examples 1 to 3, and Example 1 applied the same denaturing agent as in Comparative Examples 1 to 3 In spite of that, compared to Comparative Example 1, it increased significantly to 2.1 times, 1.8 times compared to Comparative Example, and 1.7 times compared to Comparative Example 3. Through this, it can be seen that the modified conjugated diene-based polymer according to the present invention includes a unit derived from a modified monomer in the polymer chain and at least at one end, independently of the functional group derived from the modifying agent, and is highly modified thereto.

Experimental Example 2

In order to compare and analyze the physical properties of the rubber compositions including the modified conjugated diene-based copolymers prepared in Examples and Comparative Examples and molded articles prepared therefrom, tensile properties and viscoelastic properties were measured, respectively, and the results are shown in Table 3 below. Shown in.

1) Preparation of rubber specimen

Each modified or unmodified conjugated diene-based polymer of Examples, Comparative Examples and Reference Examples was used as a raw material rubber and was blended under the blending conditions shown in Table 2 below. The content of the raw materials 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 Zinc 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), zinc agent (ZnO), stearic acid are used by using a Banbari mixer attached with a temperature control device. , Antioxidant (TMQ(RD) (2,2,4-trimethyl-1,2-dihydroquinoline polymer), anti-aging agent (6PPD ((dimethylbutyl)-N-phenyl-phenylenediamine) and wax (Microcrystaline Wax) At this time, the initial temperature of the kneader was controlled at 70° C., and after completion of the blending, a first blend was obtained at a discharge temperature of 145° C. to 155° C. In the second stage kneading, the first blend was cooled to room temperature. After that, the first blend, sulfur, a rubber accelerator (DPD (diphenylguanine)) and a vulcanization accelerator (CZ (N-cyclohexyl-2-benzothiazylsulfenamide)) were added to the kneader, and a temperature of 100°C or less. The mixture was mixed at, to obtain a secondary compound, and then subjected to a curing process at 160° C. for 20 minutes to prepare a rubber specimen.

2) Tensile characteristics

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

3) Viscoelastic properties

For 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℃~60℃) in Film Tension mode using a dynamic mechanical analyzer (GABO). In the measurement result, the higher the low-temperature 0℃ tan value, the better the wet road surface resistance, and the lower the high-temperature 60℃ tan δ value, the lower the hysteresis loss and the better rolling resistance characteristics (fuel economy). Since the result value is expressed as an index based on the result value of Comparative Example 1, the higher the value, the better.

4) Processability characteristics

1) The Mooney viscosity (MV, (ML1+4, @100°C) MU) of the secondary compound obtained during the manufacture of the rubber specimen was measured to compare and analyze the processability characteristics of each polymer. It shows excellent processability characteristics.

Specifically, MV-2000 (ALPHA Technologies, Inc.) was used at 100°C with a Rotor Speed of 2±0.02 rpm, and a Large Rotor was used, and each secondary compound was left at room temperature (23±3°C) for 30 minutes or more, and then 27 ±3 g was collected, filled inside the die cavity, and measured for 4 minutes by operating the platen.

division Example Reference example Comparative example One 2 3 One 2 3 Tensile properties Tensile strength (kgf/cm ² ) 187 187 186 179 175 170 179 300% modulus (kgf/cm ² ) 121 123 121 110 105 100 105 Viscoelastic properties tan δ(at 0℃) 105 104 104 105 101 100 102 tan δ(at 60℃) 135 131 132 89 83 100 90 Processability characteristics 98 99 98 88 105 100 101

As shown in Table 3, Examples 1 to 3 exhibited equivalent processability characteristics compared to Comparative Examples 1 to 3 and Reference Examples, while at the same time remarkably excellent in tensile properties and viscoelastic properties.

Specifically, Examples 1 to 3 showed remarkably improved tensile properties and viscoelastic properties, particularly rolling resistance properties, compared to Comparative Examples 1 to 3, and at the same time, the processability properties were equally excellent. It is a modified conjugated diene-based polymer prepared without use, and Comparative Examples 2 and 3 are modified conjugated diene-based polymers prepared by using a modified monomer, respectively, but only at the beginning (or at the start) of polymerization or at the end of the polymerization.

From the results of Tables 1 and 3, the modified conjugated diene-based polymer according to the present invention contains a unit derived from a modified monomer in the polymer chain and at least at one end, apart from the functional group derived from the modifying agent, and thus affinity with the filler. It can be seen that it is more effective in improving tensile properties and viscoelastic properties by being better than this.

Claims (14)

A polymer chain containing a repeating unit derived from a conjugated diene-based monomer; A unit derived from a modified monomer represented by the following formula (1); And a functional group derived from a denaturant,
The modified monomer-derived unit is bonded to the polymer chain and at least one end,
The modified conjugated diene-based polymer, wherein the functional group derived from the modifier is bonded to a unit derived from a modified monomer bonded to the end of the polymer chain:
[Formula 1]

In Chemical Formula 1,
R ₁ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,
R ₂ is a single bond or a substituted or unsubstituted C 1 to C 20 alkylene group with a substituent,
R ₃ and R ₄ are each independently a substituent substituted or unsubstituted C 1 to C 20 alkyl group, a C 3 to C 20 cycloalkyl group or a C 6 to C 30 aryl group,
The substituent is one or more selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms.
The method according to claim 1,
In Formula 1, R ₁ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,
R ₂ is a single bond or an unsubstituted C 1 to C 10 alkylene group,
R ₃ and R ₄ are each independently an unsubstituted C 1 to C 10 alkyl group, a C 3 to C 10 cycloalkyl group, or a C 6 to C 12 aryl group.
The method according to claim 1,
The polymer 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,
The polymer chain includes a repeating unit derived from a conjugated diene-based monomer and a unit derived from a modified monomer,
At least one end of the polymer chain is a modified conjugated diene-based polymer in which a unit derived from a modified monomer and a functional group derived from a modifying agent are bonded to each other.
The method according to claim 1,
The number average molecular weight (Mn) is 1,000 g/mol to 2,000,000 g/mol, the weight average molecular weight (Mw) is 1,000 g/mol to 3,000,000 g/mol, and the peak average molecular weight (Mp) is 1,000 g/mol to 3,000,000 g /mol of modified conjugated diene-based polymer.
The method according to claim 1,
Modified conjugated diene polymer having a molecular weight distribution of 1.0 or more and less than 1.7.
The method according to claim 1,
A modified conjugated diene-based polymer having an N content of 200 ppm or more based on weight.
The method according to claim 1,
The modified conjugated diene polymer is one or more selected from compounds represented by the following formula (2) or (3):
[Formula 2]

In Chemical Formula 2,
R _a1 and R _a4 are each independently a single bond or an alkylene group having 1 to 10 carbon atoms,
R _a2 and R _a3 are each independently an alkyl group having 1 to 10 carbon atoms,
R _a5 is a hydrogen atom, a divalent, trivalent or tetravalent alkylsilyl group substituted with a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms,
n ₁ is an integer of 1 to 3,
n ₂ is an integer from 0 to 2,
[Formula 3]

In Chemical Formula 3,
A ₁ and A ₂ are each independently an alkylene group having 1 to 20 carbon atoms,
R _b1 to R _b4 are each independently an alkyl group having 1 to 20 carbon atoms,
L ₁ to L ₄ are each independently a divalent, trivalent or tetravalent alkylsilyl group substituted with an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkyl group having 1 to 10 carbon atoms.
The method of claim 8,
In Formula 2, R _a1 and R _a4 are each independently a single bond or an alkylene group having 1 to 5 carbon atoms, R _a2 and R _a3 are each independently an alkyl group having 1 to 5 carbon atoms, and R _a5 is a hydrogen atom, It is a tetravalent alkylsilyl group substituted with a C1-C5 alkyl group or a C1-C5 alkyl group,
In Formula 3, A ₁ and A ₂ are each independently an alkylene group having 1 to 10 carbon atoms, R _b1 to R _b4 are each independently an alkyl group having 1 to 10 carbon atoms, and L ₁ to L ₄ are independently of each other A modified conjugated diene-based polymer that is a tetravalent alkylsilyl group substituted with an alkyl group having 1 to 10, an aryl group having 6 to 12 carbon atoms, or an alkyl group having 1 to 5 carbon atoms.
Polymerizing a first modified monomer and a conjugated diene-based monomer or a conjugated diene-based monomer and an aromatic vinyl-based monomer in a carbon solvent in the presence of a polymerization initiator to prepare an active polymer chain including a modified monomer-derived unit (S1);
Adding and reacting a second modified monomer to the active polymer chain to prepare a capped polymer chain by capping the end with a unit derived from the second modified monomer (S2); And
Including the step (S3) of adding and reacting a denaturant to the capped polymer chain,
The step (S1); Step (S2); Step (S3) is carried out continuously, the second modified monomer is added at the time when the polymerization conversion rate in step (S1) is 90% or more, and the modifying agent is added at the time when the polymerization conversion rate in step (S2) is 90% or more. Is to perform,
The method for preparing the modified conjugated diene-based polymer of claim 1, wherein the first and second modified monomers are compounds represented by the following formula (1):
[Formula 1]

In Chemical Formula 1,
R ₁ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,
R ₂ is a single bond or a substituted or unsubstituted C 1 to C 20 alkylene group with a substituent,
R ₃ and R ₄ are each independently a substituent substituted or unsubstituted C 1 to C 20 alkyl group, a C 3 to C 20 cycloalkyl group or a C 6 to C 30 aryl group,
The substituent is one or more selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms.
The method of claim 10,
The method for producing a modified conjugated diene-based polymer to be used in an amount of 0.1 to 10 mol relative to 1 mol of the polymerization initiator.
The method of claim 10,
The method for producing a modified conjugated diene-based polymer, wherein the first modified monomer and the second modified monomer are each used in an amount of 0.1 to 50 mol relative to 1 mol of the polymerization initiator.
A rubber composition comprising the modified conjugated diene polymer and a filler according to claim 1.
The method of claim 13,
The rubber composition is a rubber composition containing 0.1 to 200 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene-based polymer.